Sample records for amphiphilic polyepsilon-caprolactone-b-polyacrylic acid

  1. Preparation and Properties of Vesicles from Condensable Amphiphilic Amino Acids

    Institute of Scientific and Technical Information of China (English)

    熊向源; 何巍; 李子臣; 李福绵


    Three double-chain amphiphiles with amino acid groups as hydrphilic moiety were synthesized. These amphiphiles can be easily dispersed in buffer solution to form transparent dispersion. Examination of the dispersion by transmission electron microscopy (TEM) showed the formation of stable vesicular aggregates, which was also confirmed by the ability to encapsulate water-soluble dyes. Since amino acid groups are located on the surface of the vesicles, water-soluble carbodiimide can induce the condensation of these groups to form peptide. The phase transition temperatures of these vesicles were estimated by differential scanning calorimetry (DSC), and a decrease of phase transition temperature was observed after polycondensation due to the disturbance of the ordered arrangement of the hydrophobic chains. The leakage rate of the vesicles before and after condensation was studied by monitoring the increase of fluorescence intensity of water-soluble dye. These vesicles belong to the least permeable ones and the leakage rate can be controlled by varying the degree of condensation or the temperature.

  2. Stable Vesicles Composed of Mono- or Dicarboxylic Fatty Acids and Trimethylammonium Amphiphiles

    DEFF Research Database (Denmark)

    Caschera, Filippo; Bernardino de la Serna, Jorge; Löffler, Philipp M. G.


    shown to be more stable than those formed by pure fatty acids. Those containing bola-amphiphile even showed encapsulation of a small hydrophilic solute (8-hydroxypyrene-1,3,6-trisulfonic-acid) suggesting a denser packing of the amphiphiles. Compression and kinetics analysis of monolayers composed...... of these amphiphiles mixtures at the air/water interface suggest that the stabilization of the structures can be attributed to two main interactions between headgroups, predominantly the formation of hydrogen bonds between protonated and deprotonated acids and then the additional electrostatic interactions between...

  3. Superior SWNT dispersion by amino acid based amphiphiles: designing biocompatible cationic nanohybrids. (United States)

    Brahmachari, Sayanti; Das, Dibyendu; Das, Prasanta Kumar


    Stable aqueous SWNT dispersion up to 92% was achieved using amino acid based amphiphiles through a structure-property investigation. The nanohybrids showed remarkable serum stability and biocompatibility to mammalian cells.

  4. Nucleic acid amphiphiles : synthesis and self-assembled nanostructures

    NARCIS (Netherlands)

    Kwak, Minseok; Herrmann, Andreas; Clever, Guido; Mao, Chengde; Shionoya, Mitsuhiko; Stulz, Eugen


    This review provides an overview of a relatively new class of bio-conjugates, DNA amphiphiles, which consist of oligonucleotides covalently bonded to synthetic hydrophobic units. The reader will find the basic principles for the structural design and preparation methods of the materials. Moreover, t

  5. Thermodynamics of micellization of cholic acid based facial amphiphiles carrying three permanent ionic head groups

    NARCIS (Netherlands)

    Willemen, H.M.; Marcelis, A.T.M.; Sudhölter, E.J.R.


    This paper describes a series of cholic acid based facial amphiphiles carrying three ionic headgroups. Their micellization behavior in water was studied as a function of spacer length and alkyl tail length: both were found to have a small influence on the critical micellization concentration (cmc).

  6. Hydrophilic modification of PVDF microfiltration membranes by adsorption of facial amphiphile cholic acid. (United States)

    Hu, Meng-Xin; Li, Ji-Nian; Zhang, Shi-Lin; Li, Liang; Xu, Zhi-Kang


    Amphiphilic molecules have been widely used in surface modification of polymeric materials. Bile acids are natural biological compounds and possess special facial amphiphilic structure with a unusual distribution of hydrophobic and hydrophilic regions. Based on the facial amphiphilicity, cholic acid (CA), one of the bile acids, was utilized for the hydrophilic modification of poly(vinylidene fluoride) (PVDF) microfiltration membranes via the hydrophobic interactions between the hydrophobic face of CA and the membrane surfaces. Ethanol, methanol, and water were respectively used as solvent during CA adsorption procedure. Their polarity affects the CA adsorption amount, as similar to CA concentration and adsorption time. There are no changes on the membrane surface morphology after CA adsorption. The hydrophilicity of PVDF membranes is greatly enhanced and the water drops permeates into the CA modified membranes quickly after modification. All these factors benefit to the permeation flux of membrane for water. When CA concentration is higher than 0.088 M, the water permeation flux is doubled as compared with the nascent PVDF membrane and shows a good stability during filtration procedure. These results reveal the promising potential of facial amphiphilic bile acids for the surface modification of polymeric materials.

  7. Gold Nanoparticles Protected with Thiol-Derivatized Amphiphilic Poly(epsilon-caprolactone)-b-poly(acrylic acid)

    DEFF Research Database (Denmark)

    Javakhishvili, Irakli; Hvilsted, Søren


    Amphiphilic poly(epsilon-caprolactone)-b-poly(acrylic acid) (HS-PCL-b-PAA) with a thiol functionality in the PCL terminal has been prepared in a novel synthetic cascade. Initially, living anionic ring-opening polymerization (ROP) of epsilon-caprolactone (epsilon-CL) employing the difunctional...

  8. Novel self-associative and multiphase nanostructured soft carriers based on amphiphilic hyaluronic acid derivatives

    DEFF Research Database (Denmark)

    Eenschooten, Corinne; Vaccaro, Andrea; Delie, Florence


    The purpose of the present study was to investigate the physicochemical properties in aqueous media of amphiphilic hyaluronic acid (HA) derivatives obtained by reaction of HA’s hydroxyl groups with octenyl succinic anhydride (OSA). The self-associative properties of the resulting octenyl succinic...... anhydridemodified hyaluronic acid (OSA-HA) derivatives were studied by fluorescence spectroscopy using Nile Red as fluorophore. The morphology, size and surface charge of the OSA-HA assemblies were determined by transmission electron microscopy, dynamic light scattering and by measuring their electrophoretic...

  9. Adsorption of phthalic acid esters (PAEs) by amphiphilic polypropylene nonwoven from aqueous solution: the study of hydrophilic and hydrophobic microdomain. (United States)

    Zhou, Xiangyu; Wei, Junfu; Zhang, Huan; Liu, Kai; Wang, Han


    A kind of amphiphilic polypropylene nonwoven with hydrophilic and hydrophobic microdomain was prepared through electron beam induced graft polymerization and subsequent ring opening reaction and then utilized in the adsorption of phthalic acid esters (PAEs). To elucidate the superiority of such amphiphilic microdomain, a unique structure without hydrophilic part was constructed as comparison. In addition, the adsorption behaviors including adsorption kinetics, isotherms and pH effect were systematically investigated. The result indicated that the amphiphilic structure and the synergy between hydrophilic and hydrophobic microdomain could considerably improve the adsorption capacities, rate and affinity. Particularly the existence of hydrophilic microdomain could reduce the diffusion resistance and energy barrier in the adsorption process. These adsorption results showed that the amphiphilic PP nonwoven have the potential to be used in environmental application.

  10. Preparation and Microbiological Evaluation of Amphiphilic Kanamycin-Lipoamino Acid Ion-Pairs

    Directory of Open Access Journals (Sweden)

    Rosario Pignatello


    Full Text Available Amphiphilic ion-pairs of kanamycin (KAN were prepared by evaporation of a water-ethanol co-solution of KAN base and a lipoamino acid bearing a 12-carbon atoms alkyl side chain (LAA12, at different molar ratios. Infrared spectroscopy confirmed the structure of ion-pairs, while differential scanning calorimetry (DSC and powder X-ray diffractometry (PXRD studies supported the formation of new saline species with a different crystalline structure than the starting components. The solubility pattern shown in a range of both aqueous and organic solvents confirmed that the ion-pairs possess an amphiphilic character. The LAA12 counter-ion showed not to improve the antibacterial activity of KAN, suggesting that such chemical strategy is not able to favor the penetration of this drug inside the bacteria cells. Nevertheless, a slight improving, i.e., a one-fold dilution, was observed in E. coli. The present study can also serve as the basis for a further evaluation of LAA ion-pairing of antibiotics, as a means to improve the loading of hydrophilic drugs into lipid-based nanocarriers.

  11. Preparation and structural characterisation of novel and versatile amphiphilic octenyl succinic anhydride-modified hyaluronic acid derivatives

    DEFF Research Database (Denmark)

    Eenschooten, Corinne Diane; Guillaumie, Fanny; Kontogeorgis, Georgios


    The purpose of the present study was to prepare amphiphilic hyaluronic acid (HA) derivatives and to study the influence of a selection of reaction parameters on the degree of substitution (DS) of the derivatives. Octenyl succinic anhydride (OSA)–modified HA (OSA–HA) derivatives were prepared...

  12. Acid-Labile Amphiphilic PEO-b-PPO-b-PEO Copolymers: Degradable Poloxamer Analogs. (United States)

    Worm, Matthias; Kang, Biao; Dingels, Carsten; Wurm, Frederik R; Frey, Holger


    Poly ((ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)) triblock copolymers commonly known as poloxamers or Pluronics constitute an important class of nonionic, biocompatible surfactants. Here, a method is reported to incorporate two acid-labile acetal moieties in the backbone of poloxamers to generate acid-cleavable nonionic surfactants. Poly(propylene oxide) is functionalized by means of an acetate-protected vinyl ether to introduce acetal units. Three cleavable PEO-PPO-PEO triblock copolymers (Mn,total = 6600, 8000, 9150 g·mol(-1) ; Mn,PEO = 2200, 3600, 4750 g·mol(-1) ) have been synthesized using anionic ring-opening polymerization. The amphiphilic copolymers exhibit narrow molecular weight distributions (Ð = 1.06-1.08). Surface tension measurements reveal surface-active behavior in aqueous solution comparable to established noncleavable poloxamers. Complete hydrolysis of the labile junctions after acidic treatment is verified by size exclusion chromatography. The block copolymers have been employed as surfactants in a miniemulsion polymerization to generate polystyrene (PS) nanoparticles with mean diameters of ≈200 nm and narrow size distribution, as determined by dynamic light scattering and scanning electron microscopy. Acid-triggered precipitation facilitates removal of surfactant fragments from the nanoparticles, which simplifies purification and enables nanoparticle precipitation "on demand."

  13. Spontaneous Polymerization of An Amino Acid Based Amphiphile at Air/water Interface Investigated by ESI-MS and Transmission IR Spectrometry

    Institute of Scientific and Technical Information of China (English)

    WANG Hai-Yan; XIAO Yi; LI Yan-Mei; WU Li-Xin; YU Zhi-Wu; ZHAO Yu-Fen


    @@ Self-assemblies of amphiphilic molecules are proposed to play a ubiquitous role at the early stages of evolution in the formation of primitive biopolymers. [1] As regard to the significance of N-phosphoryl amino acids as a model for the co-evolution of protein and nucleic acids at the prebiotic stage, [2] amphiphilic N-phosphoryl amino acids with two hydrophobic tails were synthesized. [3

  14. Amphiphilic poly(L-amino acids) - new materials for drug delivery. (United States)

    Lalatsa, Aikaterini; Schätzlein, Andreas G; Mazza, Mariarosa; Le, Thi Bich Hang; Uchegbu, Ijeoma F


    The formulation of drug compounds into medicines will increasingly rely on the use of specially tailored molecules, which fundamentally alter the drug's pharmacokinetics to enable its therapeutic activity. This is particularly true of the more challenging hydrophobic drugs or therapeutic biological molecules. The demand for such enabled medicines will translate into a demand for advanced highly functionalised drug delivery materials. Polymers have been used to formulate medicines for many decades and this is unlikely to change soon. Amphiphilic polymers based on amino acids are the subject of this review. These molecules, which present as either poly(L-amino acid) block copolymers or poly(L-amino acid) backbones with hydrophobic substituents, self assemble into micelles, vesicles, nanofibres and solid nanoparticles and such self assemblies, have drug delivery capabilities. The nature of the self-assembly depends on the chemistry of the constituent molecules, with the more hydrophilic molecules forming nanosized micellar aggregates including peptide nanofibres, molecules of intermediate hydrophobicity forming polymeric vesicles and the more hydrophobic variants forming amorphous polymeric nanoparticles of 100-1000 nm in diameter. The self-assemblies may be loaded with drugs or may present as micelle forming polymer-drug conjugates and the supramolecular aggregates have been employed as drug solubilisers, tumour targeting agents, gene delivery vectors and facilitators of intracellular drug uptake, with a more promising polymer-drug conjugate progressing to clinical testing.

  15. Nucleoside, nucleotide and oligonucleotide based amphiphiles: a successful marriage of nucleic acids with lipids. (United States)

    Gissot, Arnaud; Camplo, Michel; Grinstaff, Mark W; Barthélémy, Philippe


    Amphiphilic molecules based on nucleosides, nucleotides and oligonucleotides are finding more and more biotechnological applications. This Perspective highlights their synthesis, supramolecular organization as well as their applications in the field of biotechnology.

  16. A Comprehensive Study on Lyotropic Liquid-Crystalline Behavior of an Amphiphile in 20 Kinds of Amino Acid Ionic Liquids. (United States)

    Fujimura, Kanae; Ichikawa, Takahiro; Yoshio, Masafumi; Kato, Takashi; Ohno, Hiroyuki


    We examined the self-organization behavior of a designed amphiphilic molecule in 20 kinds of amino acid ionic liquids composed of 1-butyl-3-methylimidazolium cation and natural amino acid anion ([C4mim][AA]). Addition of [C4mim][AA], regardless of their anion species, to the amphiphile provided homogeneous mixtures showing lyotropic liquid-crystalline (LC) behavior. Upon increasing the component ratio of [C4mim][AA] in the mixtures, a successive change of the mesophase patterns from inverted hexagonal columnar, in some case via bicontinuous cubic, to layered phases was observed. By examining the LC properties at various temperatures and component ratios, we constructed lyotropic LC phase diagrams. Interestingly, the appearance of these phase diagrams is greatly different according to the selection of [AA]. Through comparison, we found that the self-organization behavior of an amphiphile in ionic liquids can be tuned by controlling their ability to form hydrogen-bond, van der Waals, and π-π interactions.

  17. Poly(trimethylene carbonate)/Poly(malic acid) Amphiphilic Diblock Copolymers as Biocompatible Nanoparticles. (United States)

    Barouti, Ghislaine; Khalil, Ali; Orione, Clement; Jarnouen, Kathleen; Cammas-Marion, Sandrine; Loyer, Pascal; Guillaume, Sophie M


    Amphiphilic polycarbonate-poly(hydroxyalkanoate) diblock copolymers, namely, poly(trimethylene carbonate) (PTMC)-b-poly(β-malic acid) (PMLA), are reported for the first time. The synthetic strategy relies on commercially available catalysts and initiator. The controlled ring-opening polymerization (ROP) of trimethylene carbonate (TMC) catalyzed by the organic guanidine base 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), associated with iPrOH as an initiator, provided iPrO-PTMC-OH, which served as a macroinitiator in the controlled ROP of benzyl β-malolactonate (MLABe) catalyzed by the neodymium triflate salt (Nd(OTf)3). The resulting hydrophobic iPrO-PTMC-b-PMLABe-OH copolymers were then hydrogenolyzed into the parent iPrO-PTMC-b-PMLA-OH copolymers. A range of well-defined copolymers, featuring different sizes of segments (Mn,NMR up to 9300 g mol(-1) ; ÐM =1.28-1.40), were thus isolated in gram quantities, as evidenced by NMR spectroscopy, size exclusion chromatography, thermogravimetric analysis, differential scanning calorimetry, and contact angle analyses. Subsequently, PTMC-b-PMLA copolymers with different hydrophilic weight fractions (11-75 %) self-assembled in phosphate-buffered saline upon nanoprecipitation into well-defined nano-objects with Dh =61-176 nm, a polydispersity index nanoparticles demonstrated no significant effect on cell viability at low concentrations, and a very low cytotoxicity at high concentrations only for PTMC-b-PMLA copolymers exhibiting hydrophilic fractions over 47 %, thus illustrating the potential of these copolymers as promising nanoparticles.

  18. Boronic acid-tethered amphiphilic hyaluronic acid derivative-based nanoassemblies for tumor targeting and penetration. (United States)

    Jeong, Jae Young; Hong, Eun-Hye; Lee, Song Yi; Lee, Jae-Young; Song, Jae-Hyoung; Ko, Seung-Hak; Shim, Jae-Seong; Choe, Sunghwa; Kim, Dae-Duk; Ko, Hyun-Jeong; Cho, Hyun-Jong


    (3-Aminomethylphenyl)boronic acid (AMPB)-installed hyaluronic acid-ceramide (HACE)-based nanoparticles (NPs), including manassantin B (MB), were fabricated for tumor-targeted delivery. The amine group of AMPB was conjugated to the carboxylic acid group of hyaluronic acid (HA) via amide bond formation, and synthesis was confirmed by spectroscopic methods. HACE-AMPB/MB NPs with a 239-nm mean diameter, narrow size distribution, negative zeta potential, and >90% drug encapsulation efficiency were fabricated. Exposed AMPB in the outer surface of HACE-AMPB NPs (in the aqueous environment) may react with sialic acid of cancer cells. The improved cellular accumulation efficiency, in vitro antitumor efficacy, and tumor penetration efficiency of HACE-AMPB/MB NPs, compared with HACE/MB NPs, in MDA-MB-231 cells (CD44 receptor-positive human breast adenocarcinoma cells) may be based on the CD44 receptor-mediated endocytosis and phenylboronic acid-sialic acid interaction. Enhanced in vivo tumor targetability, infiltration efficiency, and antitumor efficacies of HACE-AMPB NPs, compared with HACE NPs, were observed in a MDA-MB-231 tumor-xenografted mouse model. In addition to passive tumor targeting (based on an enhanced permeability and retention effect) and active tumor targeting (interaction between HA and CD44 receptor), the phenylboronic acid-sialic acid interaction can play important roles in augmented tumor targeting and penetration of HACE-AMPB NPs. STATEMENT OF SIGNIFICANCE: (3-Aminomethylphenyl)boronic acid (AMPB)-tethered hyaluronic acid-ceramide (HACE)-based nanoparticles (NPs), including manassantin B (MB), were fabricated and their tumor targeting and penetration efficiencies were assessed in MDA-MB-231 (CD44 receptor-positive human adenocarcinoma) tumor models. MB, which exhibited antitumor efficacies via the inhibition of angiogenesis and hypoxia inducible factor (HIF)-1, was entrapped in HACE-AMPB NPs in this study. Phenylboronic acid located in the outer surface

  19. Supramolecular amphiphiles. (United States)

    Zhang, Xi; Wang, Chao


    Supramolecular amphiphiles (SA), also named superamphiphiles, refer to amphiphiles that are formed by non-covalent interactions. This tutorial review focuses on the molecular architectures of SAs, including diversified topologies such as single chain, double chain, bolaform, gemini and rotaxane types. Non-covalent syntheses that have been employed to fabricate SAs are driven by hydrogen bonding, electrostatic attraction, host-guest recognition, charge transfer interaction, metal coordination and so on. It should be noted that SAs can be either small organic molecules or polymers. SAs allow for tuning of their amphiphilicity in a reversible fashion, leading to controlled self-assembly and disassembly. This line of research has been enriching traditional colloid chemistry and current supramolecular chemistry, and the application of SAs in the field of functional supramolecular materials is keenly anticipated.

  20. Amphiphilic chitosan-grafted-functionalized polylactic acid based nanoparticles as a delivery system for doxorubicin and temozolomide co-therapy. (United States)

    Di Martino, Antonio; Sedlarik, Vladimir


    The aim of this work was to investigate the potential of an amphiphilic system comprising chitosan-grafted polylactide and carboxyl-functionalized polylactide acid as a carrier for the controlled release and co-release of two DNA alkylating drugs: doxorubicin and temozolomide. Polylactide and carboxyl-functionalized polylactide acid were obtained through direct melt polycondensation reaction, using methanesulfonic acid as a non-toxic initiator, and subsequently these were grafted to the chitosan backbone through a coupling reaction, utilizing 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide as a condensing agent. ATR-FTIR analysis and conductometric titration confirmed that a reaction between CS and PLA, PLACA2% and PLACA5% occurred. Chitosan-grafted-polylactide and polylactide-citric acid nanoparticles were prepared via the polyelectrolyte complex technique, applying dextran sulphate as a polyanion, and loaded with doxorubicin and temozolomide. The diameter of particles, ζ-potential and their relationship to temperature and pH were analysed in all formulations. Encapsulation, co-encapsulation efficiency and release studies were conducted in different physiological simulated environments and human serum. Results showed the continuous release of drugs without an initial burst in different physiological media.

  1. Hexanoic acid and polyethylene glycol double grafted amphiphilic chitosan for enhanced gene delivery: influence of hydrophobic and hydrophilic substitution degree. (United States)

    Layek, Buddhadev; Haldar, Manas K; Sharma, Gitanjali; Lipp, Lindsey; Mallik, Sanku; Singh, Jagdish


    Gene therapy holds immense potential as a future therapeutic strategy for the treatment of numerous genetic diseases which are incurable to date. Nevertheless, safe and efficient gene delivery remains the most challenging aspects of gene therapy. To overcome this difficulty a series of hexanoic acid (HA) and monomethoxy poly(ethylene glycol) (mPEG) double grafted chitosan-based (HPC) nanomicelles were developed as nonviral gene carrier. HPC polymers with various HA and mPEG substitution degrees were synthesized, and their chemical structures were confirmed by (1)H NMR spectroscopy. HPC nanomicelles exhibited excellent blood compatibility and cell viability, as demonstrated by in vitro hemolysis and MTT assay, respectively. The cationic HPC nanomicelles retained the plasmid DNA (pDNA) binding capacity of chitosan and formed stable HPC/pDNA polyplexes with diameters below 200 nm. Both hydrophobic and hydrophilic substitution resulted in suppressed nonspecific protein adsorption on HPC/pDNA polyplexes and increased pDNA dissociation. However, resistance against DNase I degradation was enhanced by HA conjugation while being inhibited by mPEG substitution. Amphiphilic modification resulted in 3-4.5-fold higher cellular uptake in human embryonic kidney 293 cells (HEK 293) mainly through clathrin-mediated pathway. The optimal HPC/pDNA polyplexes displayed 50-fold and 1.2-fold higher gene transfection compared to unmodified chitosan and Fugene, respectively, in HEK 293 cells. Moreover, both the cellular uptake and in vitro transfection study suggested a clear dependence of gene expression on the extent of HA and mPEG substitution. These findings demonstrate that amphiphilic HPC nanomicelles with the proper combination of HA and mPEG substitution could be used as a promising gene carrier for efficient gene therapy.

  2. Synthesis and characterization of amphiphilic glycidol-chitosan-deoxycholic acid nanoparticles as a drug carrier for doxorubicin. (United States)

    Zhou, Huofei; Yu, Weiting; Guo, Xin; Liu, Xiudong; Li, Nan; Zhang, Ying; Ma, Xiaojun


    Novel amphiphilic chitosan derivatives (glycidol-chitosan-deoxycholic acid, G-CS-DCA) were synthesized by grafting hydrophobic moieties, deoxycholic acid (DCA), and hydrophilic moieties, glycidol, with the purpose of preparing carriers for poorly soluble drugs. Based on self-assembly, G-CS-DCA can form nanoparticles with size ranging from 160 to 210 nm, and G-CS-DCA nanoparticles maintained stable structure for about 3 months when stored in PBS (pH 7.4) at room temperature. The critical aggregation concentration decreased from 0.043 mg/mL to 0.013 mg/mL with the increase of degree of substitution (DS) of DCA. Doxorubicin (DOX) could be easily encapsulated into G-CS-DCA nanoparticles and keep a sustained release manner without burst release when exposed to PBS (pH 7.4) at 37 °C. Antitumor efficacy results showed that DOX-G-CS-DCA have significant antitumor activity when MCF-7 cells were incubated with different concentration of DOX-G-CS-DCA nanoparticles. The fluorescence imaging results indicated DOX-G-CS-DCA nanoparticles could easily be uptaken by MCF-7 cells. These results suggested that G-CS-DCA nanoparticles may be a promising carrier for DOX delivery in cancer therapy.

  3. TEM and SEM observations of super-structures constructed in organogel systems from a combination of boronic-acid-appended bola-amphiphiles with chiral diols (United States)

    Koumoto, Kazuya; Yamashita, Tadahiro; Kimura, Taro; Luboradzki, Roman; Shinkai, Seiji


    Two bola-amphiphilic α,ω-diboronic acids separated by a (CH2)11 or (CH2)12 group were synthesized. Complexation with chiral diols readily gave new amphiphiles end-capped with the chiral substituents. Some of these acted as good gelators of organic solvents. Transmission electron microscope and scanning electron microscope observations established that a variety of super-structures are created in the organogels, depending on the solvents and the structure of the chiral end-cap groups. In most cases, the fibrous aggregates, the network structure which is the driving-force for gelation, showed a helical higher-order structure reflecting the chirality of the end-cap groups. The results indicate that the combinatorial approach utilizing boronic acid functions and diol compounds is useful in creating a variety of new super-structures in the gel phase.

  4. Improvement of pulmonary surfactant activity by introducing D-amino acids into highly hydrophobic amphiphilic α-peptide Hel 13-5. (United States)

    Nakamura, Yoshihiro; Yukitake, Ko; Nakahara, Hiromichi; Lee, Sooyoung; Shibata, Osamu; Lee, Sannamu


    The high costs of artificial pulmonary surfactants, ranging in hundreds per kilogram of body weight, used for treating the respiratory distress syndrome (RDS) premature babies have limited their applications. We have extensively studied soy lecithins and higher alcohols as lipid alternatives to expensive phospholipids such as DPPC and PG. As a substitute for the proteins, we have synthesized the peptide Hel 13-5D3 by introducing D-amino acids into a highly lipid-soluble, basic amphiphilic peptide, Hel 13-5, composed of 18 amino acid residues. Analysis of the surfactant activities of lipid-amphiphilic artificial peptide mixtures using lung-irrigated rat models revealed that a mixture (Murosurf SLPD3) of dehydrogenated soy lecithin, fractionated soy lecithin, palmitic acid (PA), and peptide Hel 13-5D3 (40:40:17.5:2.5, by weight) superior pulmonary surfactant activity than a commercially available pulmonary surfactant (beractant, Surfacten®). Experiments using ovalbumin-sensitized model animals revealed that the lipid-amphiphilic artificial peptide mixtures provided significant control over an increase in the pulmonary resistance induced by premature allergy reaction and reduced the number of acidocytes and neutrophils in lung-irrigated solution. The newly developed low-cost pulmonary surfactant system may be used for treatment of a wide variety of respiratory diseases.

  5. Surface activity of new invertible amphiphilic polyesters based on poly(ethylene glycol) and aliphatic dicarboxylic acids. (United States)

    Voronov, A; Vasylyev, S; Kohut, A; Peukert, W


    The surface active properties of aqueous solutions of invertible amphiphilic alternated polyesters differing by hydrophilic-lipophilic balance (HLB) and molecular weight have been determined over the wide concentration range. The polyesters are based on poly(ethylene glycol) (PEG) of two molecular weights and aliphatic dicarboxylic acids (decanedioic and dodecanedioic). The surface activity of the polyesters and their ability to form micellar assemblies (which was recently shown for organic solvents) has been confirmed in water. The central role of the balance of hydrophilic to hydrophobic groups ratio in the formation of polymeric arrangements having hydrophobic pockets and external hydrophilic shell has been shown. The effect of molecular weight has been found considerable as well. Two changes in slope have been observed for the more hydrophobic polyesters in the surface tension vs log concentration curve. The change at low concentration is believed to originate from the formation of polyester assemblies with a hydrophobic interior and hydrophilic exterior due to the interaction of hydrophobic fragments and macromolecular flexibility. The higher concentration region exhibits behavior consistent with a cmc, which was confirmed by additional dye solubilization experiments. Molecular structure of the polyester micelles is determined by the solubilization of a solvatochromic dye. The experiment confirmed that micellization of polyesters is accompanied by the association of more hydrophobic (aliphatic) constituents forming the micelle interior. The hydrophilic fragments (ethylene oxide groups) are involved in the formation of micelle exterior.

  6. Anti-angiogenic activity and antitumor efficacy of amphiphilic twin drug from ursolic acid and low molecular weight heparin (United States)

    Cheng, Wenming; Zohra Dahmani, Fatima; Zhang, Juan; Xiong, Hui; Wu, Yuanyuan; Yin, Lifang; Zhou, Jianping; Yao, Jing


    Heparin, a potential blood anti-coagulant, is also known for its binding ability to several angiogenic factors through electrostatic interactions due to its polyanionic character. However, the clinical application of heparin for cancer treatment is limited by several drawbacks, such as unsatisfactory therapeutic effects and severe anticoagulant activity that could induce hemorrhaging. Herein, low molecular weight heparin (LMWH) was conjugated to ursolic acid (UA), which is also an angiogenesis inhibitor, by binding the amine group of aminoethyl-UA (UA-NH2) with the carboxylic groups of LMWH. The resulting LMWH-UA conjugate as an amphiphilic twin drug showed reduced anticoagulant activity and could also self-assemble into nanomicelles with a mean particle size ranging from 200-250 nm. An in vitro endothelial tubular formation assay and an in vivo Matrigel plug assay were performed to verify the anti-angiogenic potential of LMWH-UA. Meanwhile, the in vivo antitumor effect of LMWH-UA was also evaluated using a B16F10 mouse melanoma model. LMWH-UA nanomicelles were shown to inhibit angiogenesis both in vitro and in vivo. In addition, the i.v. administration of LMWH-UA to the B16F10 tumor-bearing mice resulted in a significant inhibition of tumor growth as compared to the free drug solutions. These findings demonstrate the therapeutic potential of LMWH-UA as a new therapeutic remedy for cancer therapy.

  7. Physicochemical characterization and tube-like structure formation of a novel amino acid-based zwitterionic amphiphile N-(2-hydroxydodecyl)-L-valine in water. (United States)

    Ghosh, Arjun; Dey, Joykrishna


    Surface activity and aggregation behavior of an amino acid-based zwitterionic amphiphile N-(2-hydroxydodecyl)-L-valine were studied in aqueous solutions (pH 13). The self-assembly formation was investigated by use of a number of techniques including surface tension, conductivity, viscosity, fluorescence spectroscopy, dynamic light scattering, and transmission electron microscopy. The amphiphile exhibits two breaks in the surface tension vs concentration plot indicating stepwise aggregate formation and thus results in two values of critical aggregation concentration. The amphiphile was found to be very surface active compared to fatty acid soaps. The average hydrodynamic diameter and size distribution of the aggregates were obtained from DLS measurements. Conductivity measurements suggested formation of vesicles or closed tubules. TEM pictures revealed the existence of spherical vesicles, separated tubules, and tubules with multiple Y-type junctions in going from dilute to moderately concentrated solution. However, in concentrated solution, the junctions break to form separate tubular structures which upon further increase of concentration are converted to rod-like micelles. The mechanism of branched tubule formation is discussed in light of the experimental observations.

  8. Supramolecular assemblies and molecular recognition of amphiphilic schiff bases with barbituric acid in organized molecular films. (United States)

    Jiao, Tifeng; Liu, Minghua


    A bolaform Schiff base, N,N'-bis(salicylidene)-1,10-decanediamine (BSC10), has been synthesized and its interfacial hydrogen bond formation or molecular recognition with barbituric acid was investigated in comparison with that of a single chain Schiff base, 2-hydroxybenzaldehyde-octadecylamine (HBOA). It has been found that while HBOA formed a monolayer at the air/water interface, the bolaform Schiff base formed a multilayer film with ordered layer structure on water surface. When the Schiff bases were spread on the subphase containing barbituric acid, both of the Schiff bases could form hydrogen bonds with barbituric acid in situ in the spreading films. As a result, an increase of the molecular areas in the isotherms was observed. The in situ H-bonded films could be transferred onto solid substrates, and the transferred multilayer films were characterized by various methods such as UV-vis and FT-IR spectrosopies. Spectral changes were observed for the films deposited from the barbituric acid subphase, which supported the hydrogen bond formation between the Schiff bases and barbituric acid. By measuring the MS-TOF of the deposited films dissolved in CHCl3 solution, it was concluded that a 2:1 complex of HBOA with barbituric acid and a 1:2 complex of BSC10 with barbituric acid were formed. On the other hand, when the multilayer films of both Schiff bases were immersed in an aqueous solution of barbituric acid, a similar molecular recognition through the hydrogen bond occurred. A clear conformational change of the alkyl spacer in the bolaform Schiff base was observed during the complex formation with the barbituric acid.

  9. Effect of pH and oxygen atom of the hydrophobic chain on the self-assembly property and morphology of the pyridyl boronic acid based amphiphiles. (United States)

    Maiti, Monali; Roy, Aparna; Roy, Sumita


    The surface activity and aggregation behavior of two synthesized boronic acid based anionic surfactants, sodium salt of 2-dodecyl pyridine-5-boronic acid (SDDPB) and sodium salt of 2-oxydodecyl pyridine-5-boronic acid (SODDPB), were studied in buffer solution at pH 9 and 13 containing carbohydrates. The self-assembly formation was investigated by use of a number of techniques including surface tension, conductivity, fluorescence spectroscopy, dynamic light scattering, X-ray diffraction, and transmission electron microscopy (TEM). Both of the amphiphiles exhibit a single break in the surface tension vs log(concentration) plots, indicating existence of one critical aggregation concentration. Steady state fluorescence spectroscopy was used to determine the polarity indexes using pyrene and the rigidity of the microenvironments of the aggregates using 1,6-diphenyl-1,3,5-hexatriene (DPH) as fluorescence probe molecules. The pKa's of both amphiphiles were determined in buffer solutions of different pH's. XRD studies were performed to shed light on the morphology of the self-assemblies. TEM micrographs revealed the existence of vesicles for both the amphiphiles in buffer solution of pH 9, but at pH 13, TEM pictures indicate the existence of closed vesicles in SDDPB solution and at concentrated solution the vesicles are fused to form sponge-like micelles. After aging the vesicular solution of pH 13 of SDDPB, the closed vesicles are destroyed. In contrast, for SODDPB at pH 13, TEM pictures suggest the existence of spherical and complex micelles in solution which were further transformed into crystal-like structure upon aging. The average hydrodynamic radii were determined by dynamic light scattering measurement. Therefore, for the first time, we have successfully synthesized two new surfactants containing pyridyl-boronic acid as a headgroup which shows remarkable tuning of morphology in two different pH's and in the presence of two different carbohydrates.

  10. Self-assembled nanoparticles based on amphiphilic chitosan derivative and hyaluronic acid for gene delivery. (United States)

    Liu, Ya; Kong, Ming; Cheng, Xiao Jie; Wang, Qian Qian; Jiang, Li Ming; Chen, Xi Guang


    The present work described nanoparticles (NPs) made of oleoyl-carboxymethy-chitosan (OCMCS)/hyaluronic acid (HA) using coacervation process as novel potential carriers for gene delivery. An N/P ratio of 5 and OCMCS/HA weight ratio of 4 were the optimal conditions leading to the smallest (164.94 nm), positive charged (+14.2 mV) and monodispersed NPs. OCMCS-HA/DNA (OHD) NPs showed higher in vitro DNA release rates and increased cellular uptake by Caco-2 cells due to the HA involved in NPs. The MTT survival assay indicated no significant cytotoxicity. The transfection efficiency of OHD NPs was 5-fold higher than OCMCS/DNA (OD) NPs; however, it decreased significantly in the presence of excess free HA. The results indicated that OHD NPs internalized in Caco-2 cells were mediated by the hyaluronan receptor CD44. The data obtained in the present research gave evidence of the potential of OHD NPs for the targeting and further transfer of genes to the epithelial cells.

  11. Establishing the ellipsoidal geometry of a benzoic acid-based amphiphile via dimer switching: insights from intramolecular rotation and facial H-bond torsion. (United States)

    Ramesh, Nivarthi; Sarangi, Nirod Kumar; Patnaik, Archita


    Soft molecular ellipsoids conceived from 3,4-di(dodecyloxy)benzoic acid (DDBA) amphiphile draw attention to monomer structure design, intramolecular -COOH headgroup twist (ϕ°) and cyclic-acyclic dimer switching through facial H-bond torsion (ψ°). Generically, precipitation in hydrogen bonded systems has been the prime phenomenon once the critical aggregation concentrations were reached in the bulk solution. DDBA was no exception to this generalization. It formed precipitates in chloroform and methanol with no specific geometry but with cyclic dimer motifs in them. On the contrary, surface pressure modulated interfacial aggregation with ellipsoidal geometry followed acyclic dimerization (catemer motif) with various levels of headgroup torsion, established through real-time polarization modulated infrared reflection-absorption spectroscopy (IRRAS) and density functional theory (DFT) calculations, that estimated the energy costs for these unexplored pathways. The reaction coordinates ϕ° and ψ° in consonance with 2D surface pressure modulation thus directed the shape anisotropy during the dynamic self-assembly of DDBA. Changes in subphase pH and metal ionic environment had a derogatory effect on the ellipsoid formation, the structural requirement for which strictly followed a stringent need for twin alkyl chains in an asymmetric unit cell, as 4-dodecyloxybenzoic acid (MABA) with a single alkyl chain formed exclusively spherical assemblies with no dimer modulation. The investigation thus reports unexplored energy pathways toward ellipsoidal geometry of the amphiphile in the course of its interfacial aggregation.

  12. Chiral Cyclobutane β-Amino Acid-Based Amphiphiles: Influence of Cis/Trans Stereochemistry on Solution Self-Aggregation and Recognition. (United States)

    Sorrenti, Alessandro; Illa, Ona; Pons, Ramon; Ortuño, Rosa M


    Novel diastereomeric anionic amphiphiles based on the rigid cyclobutane β-amino acid scaffold have been synthesized and deeply investigated with the aim of generating new functional supramolecular architectures on the basis of the rational design of original amphiphilic molecules and the control of their self-assembly. The main interest has been focused on the effect that cis/trans stereochemistry exerts on their molecular organization and recognition. In diluted solutions, the relative stereochemistry mainly influences the headgroup solvation and anionic-charge stabilization, i.e., better stabilized in the cis diastereoisomer due to intramolecular hydrogen-bonding and/or charge-dipole interactions. This provokes differences in their physicochemical behavior (pKa, cmc, conductivity) as well as in the structural parameters of the spherical micelles formed. Although both diastereoisomers form fibers that evolve with time from the spherical micelles, they display markedly different morphology and kinetics of formation. In the lyotropic liquid crystal domain, the greatest differences are observed at the highest concentrations and can be ascribed to different hydrogen-bonding and molecular packing imposed by the stereochemical constraints. Remarkably, the spherical micelles of the two anionic surfactants show dramatically diverse enantioselection ability for bilirubin enantiomers. In addition, both the surfactants form heteroaggregates with bilirubin at submicellar concentrations but with a different expression of supramolecular chirality. This points out that the unlike relative configuration of the two surfactants influences their chiral recognition ability as well as the fashion in which chirality is expressed at the supramolecular level by controlling the molecular organization in both micellar aggregates and surfactant/bilirubin heteroaggregates. All these differential features can be appropriate and useful for the design and development of new soft materials with

  13. The role of amphiphiles

    NARCIS (Netherlands)

    Hoekstra, F.A.; Golovina, E.A.


    This paper reviews our work on the partitioning of amphiphilic compounds from the cytoplasm into membranes during drying of plant systems, and discusses how relevant this phenomenon might be for anhydrobiosis. Amphiphilic guest molecules do partition into membranes and oil bodies, as demonstrated by

  14. Left or Right: How Does Amino Acid Chirality Affect the Handedness of Nanostructures Self-Assembled from Short Amphiphilic Peptides? (United States)

    Wang, Meng; Zhou, Peng; Wang, Jiqian; Zhao, Yurong; Ma, Hongchao; Lu, Jian R; Xu, Hai


    Peptide and protein fibrils have attracted an enormous amount of interests due to their relevance to many neurodegenerative diseases and their potential applications in nanotechnology. Although twisted fibrils are regarded as the key intermediate structures of thick fibrils or bundles of fibrils, the factors determining their twisting tendency and their handedness development from the molecular to the supramolecular level are still poorly understood. In this study, we have designed three pairs of enantiomeric short amphiphilic peptides: (L)I3(L)K and (D)I3(D)K, (L)I3(D)K and (D)I3(L)K, and (La)I3(L)K and (Da)I3(D)K, and investigated the chirality of their self-assembled nanofibrils through the combined use of atomic force microscopy (AFM), circular dichroism (CD) spectroscopy, scanning electron microscopy (SEM), and molecular dynamic (MD) simulations. The results indicated that the twisted handedness of the supramolecular nanofibrils was dictated by the chirality of the hydrophilic Lys head at the C-terminal, while their characteristic CD signals were determined by the chirality of hydrophobic Ile residues. MD simulations delineated the handedness development from molecular chirality to supramolecular handedness by showing that the β-sheets formed by (L)I3(L)K, (La)I3(L)K, and (D)I3(L)K exhibited a propensity to twist in a left-handed direction, while the ones of (D)I3(D)K, (Da)I3(D)K, and (L)I3(D)K in a right-handed twisting orientation.

  15. Facially amphiphilic thiol capped gold and silver nanoparticles

    Indian Academy of Sciences (India)

    Shreedhar Bhata; Uday Maitra


    A series of bile acid-derived facially amphiphilic thiols have been used to cap sliver and gold nanoparticles. The self-assembling properties of these steroid-capped nanoparticles have been investigated and reported in this article.

  16. Cellular recognition of synthetic peptide amphiphiles in supported bioartificial membranes (United States)

    Pakalns, Teika

    The goal of this study was to demonstrate that lipidated cell adhesion peptides could form well-ordered biomimetic surfaces that were capable of influencing cellular behavior in a controlled and specific manner. The first step taken was to covalently link synthetic dialkyl tails to the amino-termini of the collagen-derived peptide IV-H1 (amino acid sequence GVKGDKGNPGWPGAP) and the well-known tripeptide Arg-Gly-Asp (RGD) to produce amino-coupled peptide amphiphiles. Other spatial orientations of RGD were also generated by coupling tails to the carboxyl-terminus to give carboxyl-coupled RGD amphiphiles and to both the amino- and carboxyl-termini to give looped RGD amphiphiles. The next step taken was to let the peptide amphiphile self-assemble along with methyl ester-capped dialkyl tails into mixed films. It was found that all the peptide amphiphiles formed stable monolayers at the air-water interface in a Langmuir trough. IV-H1 amphiphiles and carboxyl-coupled and looped RGD amphiphiles deposited well as Langmuir-Blodgett mixed films on solid surfaces at all peptide concentrations, but aminocoupled RGD amphiphiles did not deposit well at high RGD concentrations. FT-IR studies of films containing RGD amphiphiles showed that amino-coupled RGD head groups formed the strongest lateral hydrogen bonds. The final step was to study cellular response to mixed films containing IV-H1 or RGD amphiphiles. The spreading of melanoma cells was influenced by both the molar concentration and spatial orientation of the amphiphilic peptides. Cells spread on IV-H1 and looped RGD films in a concentration-dependent manner, but spread indiscriminately on carboxyl-coupled RGD films and did not spread at all on well-deposited amino-coupled RGD films. The specificity of the cellular response to looped RGD amphiphiles was investigated. Control films of looped Arg-Gly-Glu (RGE) amphiphiles inhibited the adhesion and spreading of melanoma and endothelial cells, and antibody inhibition of the

  17. The role of amphiphiles. (United States)

    Hoekstra, Folkert A; Golovina, Elena A


    This paper reviews our work on the partitioning of amphiphilic compounds from the cytoplasm into membranes during drying of plant systems, and discusses how relevant this phenomenon might be for anhydrobiosis. Amphiphilic guest molecules do partition into membranes and oil bodies, as demonstrated by the results of in vivo electron paramagnetic resonance spectroscopy on incorporated spin probes. Arguments for the likelihood of endogenous cytoplasmic amphiphiles behaving similarly during dehydration and rehydration of plant systems are presented. Negative and positive aspects of the partitioning are summarized. Positive aspects are the automatic insertion of amphiphilic antioxidants into membranes of the dehydrating organism, and the control of membrane fluidity and the phase transition temperature. A negative aspect is the perturbation of membrane structure, leading to increased permeability and loss of function. The finding that after an initial fluidization during dehydration, the membrane surface becomes immobilized in desiccation-tolerant systems and not in desiccation-sensitive systems, is discussed in the light of a strict control of the effect of partitioning. The adaptive significance of amphiphile partitioning into the membranes of anhydrobiotes is discussed.

  18. Self-aggregated nanoparticles based on amphiphilic poly(lactic acid-grafted-chitosan copolymer for ocular delivery of amphotericin B

    Directory of Open Access Journals (Sweden)

    Zhou WJ


    Full Text Available Wenjun Zhou,1 Yuanyuan Wang,2 Jiuying Jian,2 Shengfang Song1 1Department of Ophthalmology, Yongchuan Hospital, Chongqing Medical University, Chongqing, People’s Republic of China; 2College of Life Science, Chongqing Medical University, Chongqing, People’s Republic of China Background: The purpose of this study was to develop a self-aggregated nanoparticulate vehicle using an amphiphilic poly(lactic acid-grafted-chitosan (PLA-g-CS copolymer and to evaluate its potential for ocular delivery of amphotericin B. Methods: A PLA-g-CS copolymer was synthesized via a “protection-graft-deprotection” procedure and its structure was confirmed by Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance, and X-ray diffraction spectra. Amphotericin B-loaded nanoparticles based on PLA-g-CS (AmB/PLA-g-CS were prepared by the dialysis method and characterized for particle size, zeta potential, and encapsulation efficiency. Studies of these AmB/PLA-g-CS nanoparticles, including their mucoadhesive strength, drug release properties, antifungal activity, ocular irritation, ocular pharmacokinetics, and corneal penetration were performed in vitro and in vivo. Results: Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance, and X-ray diffraction spectra showed that the PLA chains were successfully grafted onto chitosan molecules and that crystallization of chitosan was suppressed. The self-aggregated PLA-g-CS nanoparticles had a core-shell structure with an average particle size of approximately 200 nm and zeta potentials higher than 30 mV. Amphotericin B was incorporated into the hydrophobic core of the nanoparticles with high encapsulation efficiency. Sustained drug release from the nanoparticles was observed in vitro. The ocular irritation study showed no sign of irritation after instillation of the PLA-g-CS nanoparticles into rabbit eyes. The minimal inhibitory concentration of the AmB/PLA-g-CS nanoparticles showed antifungal

  19. Stimuli Responsive Amphiphilic Assemblies (United States)


    Amphiphilic Nanocontainers, Angewandte Chemie International Edition , (03 2011): 0. doi: 10.1002/anie.201006193 TOTAL: 4 Number of Papers published in... International Conference on Novel Materials and their Synthesis, Xi An, China, October 14-19, 2012 (Organizers: Anning Zhou, Min Zhang & Yuping Wu, Fudan...University) Plenary Lecture, PolyTech – 2012: International Conference on Advances in Polymeric Materials & Nanotechnology, Pune, India, Dec. 15

  20. Preparation and Characterization of Amphiphilic Triblock Terpolymer-Based Nanofibers as Antifouling Biomaterials

    KAUST Repository

    Cho, Youngjin


    Antifouling surfaces are critical for the good performance of functional materials in various applications including water filtration, medical implants, and biosensors. In this study, we synthesized amphiphilic triblock terpolymers (tri-BCPs, coded as KB) and fabricated amphiphilic nanofibers by electrospinning of solutions prepared by mixing the KB with poly(lactic acid) (PLA) polymer. The resulting fibers with amphiphilic polymer groups exhibited superior antifouling performance to the fibers without such groups. The adsorption of bovine serum albumin (BSA) on the amphiphilic fibers was about 10-fold less than that on the control surfaces from PLA and PET fibers. With the increase of the KB content in the amphiphilic fibers, the resistance to adsorption of BSA was increased. BSA was released more easily from the surface of the amphiphilic fibers than from the surface of hydrophobic PLA or PET fibers. We have also investigated the structural conformation of KB in fibers before and after annealing by contact angle measurements, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and coarse-grained molecular dynamics (CGMD) simulation to probe the effect of amphiphilic chain conformation on antifouling. The results reveal that the amphiphilic KB was evenly distributed within as-spun hybrid fibers, while migrated toward the core from the fiber surface during thermal treatment, leading to the reduction in antifouling. This suggests that the antifouling effect of the amphiphilic fibers is greatly influenced by the arrangement of amphiphilic groups in the fibers. © 2012 American Chemical Society.

  1. Amphiphilic dendritic peptides: Synthesis and behavior as an organogelator and liquid crystal

    Directory of Open Access Journals (Sweden)

    Xinwu Ba


    Full Text Available New amphiphilic dendritic peptides on dendritic polyaspartic acid were designed and synthesized. The organogel and liquid crystal properties of these amphiphilic dendritic peptides were fully studied by field-emission SEM, temperature dependent FT-IR, differential scanning calorimetry, polarization optical microscopy and X-ray diffraction experiments. Amphiphilic dendritic peptides G3 show good organogel properties with a minimum gelation concentration as low as 1 wt %. Furthermore, amphiphilic dendritic peptides G3 can form a hexagonal columnar liquid crystal assembly over a wide temperature range.

  2. Amphiphilic dendronized homopolymers

    Institute of Scientific and Technical Information of China (English)


    A series of second generation of amphiphilic dendronized homopolymers are efficiently synthesized,and their thermoresponsiveness in aqueous solutions and secondary structures in methanol solutions are described.These polymers are constructed in each repeat unit with various generations of hydrophobic 4-aminoproline and hydrophilic oligoethylene glycol (OEG)-based dendrons,and their over-all hydrophilicity is tuned by varying these dendron generations.Polymers with or without the first generation of proline dendron show good water solubility at room temperature,but exhibit typical thermoresponsive behaviors at elevated temperatures as characterized by turbidity measurements using UV-vis spectroscopy,while the polymer with the secondary generation of proline dendron is not soluble in water.All polymers show ordered secondary structures as evidenced by the optical rotation and circular dichroism experiments.Finally,assembly of these amphiphilic homopolymers into porous films via breath figure (BF) technique is described,and polymer structures are found to show significant influence on the morphology of porous film.

  3. In vivo pharmacokinetics, biodistribution and antitumor effect of amphiphilic poly(L-amino acids) micelles loaded with a novel all-trans retinoic acid derivative. (United States)

    Tang, Jihui; Wang, Xinqun; Wang, Ting; Chen, Feihu; Zhou, Jianping


    Poly(amino acid)s are well-known as biodegradable and environmentally acceptable materials. In this study, a series of poly(L-aspartic acid)-b-poly(L-phenylalanine) (PAA-PPA) compounds with different degrees of polymerization were used to prepare copolymer micelles for a poorly water-soluble drug 4-amino-2-trifluoromethyl-phenyl retinate (ATPR, a novel all-trans retinoic acid derivative) and in vivo pharmacokinetics, biodistribution and antitumor efficacy of ATPR delivered by PAA-PPA micelles were evaluated. The area under the plasma concentration time curve AUC0→∞ of ATPR-loaded PAA20PPA20 micelles was 2.23 and 1.97 times higher than that of ATPR solution and ATPR CrmEL solution, respectively; In addition, the mean residence time (MRT) was increased 1.67 and 1.97-fold, respectively and the total body clearance (CL) was reduced 2.25 and 1.98-fold, respectively. The biodistribution study indicated that most of the ATPR in the ATPR-M group was distributed in the liver and there was delayed liver aggregation compared with the ATPR solution and ATPR CrmEL solution groups. Furthermore, the antitumor efficacy of ATPR-loaded PAA20PPA20 micelles was demonstrated in in vivo antitumor models involving mice inoculated with the human gastric cancer cell line SGC-7901. At the same dose of 7mg/kg, the ATPR-loaded micelles group demonstrated a better tumor growth inhibition and induced differentiation than the groups given ATPR solution and ATPR CrmEL solution. Therefore, the ATPR-loaded PAA-PPA micelles appear to be a potentially useful drug delivery system for ATPR and suitable for the chemotherapy of gastric cancer.

  4. Amphiphilic poly-N-vinylpyrrolidone nanocarriers with incorporated model proteins (United States)

    Kuskov, A. N.; Villemson, A. L.; Shtilman, M. I.; Larionova, N. I.; Tsatsakis, A. M.; Tsikalas, I.; Rizos, A. K.


    New nanoscaled polymeric carriers have been prepared on the basis of different amphiphilic water-soluble derivatives of poly-N-vinylpyrrolidone (PVP). The polymer self-assembly and interaction with model proteins (Bowman-Birk soybean proteinase inhibitor (BBI) and its hydrophobized derivatives) were studied in aqueous media. The possibility of inclusion of both BBI and hydrophobized oleic acid derivatives of BBI in amphiphilic PVP aggregates was investigated. It was ascertained that polymeric particles of size 50-80 nm were formed in certain concentrations of amphiphilic PVP and poorly soluble dioleic acid derivatives of BBI. Such polymeric aggregates are capable of solubilization of dioleoyl BBI with a concomitant prevention of its inactivation at low pH values.

  5. Amphiphilic poly-N-vinylpyrrolidone nanocarriers with incorporated model proteins

    Energy Technology Data Exchange (ETDEWEB)

    Kuskov, A N [Department of Polymers, D I Mendeleyev University of Chemical Technology, 9 Miusskaya Square, Moscow 125047 (Russian Federation); Villemson, A L [Department of Chemistry, M V Lomonosov Moscow State University, 119992 Moscow (Russian Federation); Shtilman, M I [Department of Polymers, D I Mendeleyev University of Chemical Technology, 9 Miusskaya Square, Moscow 125047 (Russian Federation); Larionova, N I [Department of Chemistry, M V Lomonosov Moscow State University, 119992 Moscow (Russian Federation); Tsatsakis, A M [Medical School, University of Crete, Voutes, 71409 Heraklion, Crete (Greece); Tsikalas, I [Department of Chemistry and Foundation for Research and Technology-Hellas (FORTH), University of Crete, PO Box 2208, Heraklion 71003, Crete (Greece); Rizos, A K [Department of Chemistry and Foundation for Research and Technology-Hellas (FORTH), University of Crete, PO Box 2208, Heraklion 71003, Crete (Greece)


    New nanoscaled polymeric carriers have been prepared on the basis of different amphiphilic water-soluble derivatives of poly-N-vinylpyrrolidone (PVP). The polymer self-assembly and interaction with model proteins (Bowman-Birk soybean proteinase inhibitor (BBI) and its hydrophobized derivatives) were studied in aqueous media. The possibility of inclusion of both BBI and hydrophobized oleic acid derivatives of BBI in amphiphilic PVP aggregates was investigated. It was ascertained that polymeric particles of size 50-80 nm were formed in certain concentrations of amphiphilic PVP and poorly soluble dioleic acid derivatives of BBI. Such polymeric aggregates are capable of solubilization of dioleoyl BBI with a concomitant prevention of its inactivation at low pH values.

  6. H-shaped supra-amphiphiles based on a dynamic covalent bond. (United States)

    Wang, Guangtong; Wang, Chao; Wang, Zhiqiang; Zhang, Xi


    The imine bond, a kind of dynamic covalent bond, is used to bind two bolaform amphiphiles together with spacers, yielding H-shaped supra-amphiphiles. Micellar aggregates formed by the self-assembly of the H-shaped supra-amphiphiles are observed. When pH is tuned down from basic to slightly acidic, the benzoic imine bond can be hydrolyzed, leading to the dissociation of H-shaped supra-amphiphiles. Moreover, H-shaped supra-amphiphiles have a lower critical micelle concentration than their building blocks, which is very helpful in enhancing the stability of the benzoic imine bond being hydrolyzed by acid. The surface tension isotherms of the H-shaped supra-amphiphiles with different spacers indicate their twisty conformation at a gas-water interface. The study of H-shaped supra-amphiphiles can enrich the family of amphiphiles, and moreover, the pH-responsiveness may make them apply to controlled or targetable drug delivery in a biological environment.

  7. Biolabeling and Binding Evaluation of Amphiphilic Nanocrystallopolymers

    Directory of Open Access Journals (Sweden)

    Kwang-Suk Jang


    Full Text Available Surfactant-like inorganic-organic hybrid molecules named as nanocrystallopolymers were designed by conjugation of the hydrophilic synthetic poly(amino acid, poly-α,β-(N-(2-hydroxyethyll-aspartamide, with hydrophobic inorganic nanoparticles. In aqueous media, amphiphilic nanocrystallopolymers form self-aggregates with unique morphologies. Here, a simple biolabeling method of nanocrystallopolymers was developed. Biotin was selected as a model biomolecule. The specific binding of biotin-labeled nanocrystallopolymers to the targeted surface was evaluated with a surface plasmon resonance sensor.

  8. Drug release from hydrazone-containing peptide amphiphiles

    Energy Technology Data Exchange (ETDEWEB)

    Matson, John B.; Stupp, Samuel I. (NWU)


    Hydrolytically-labile hydrazones in peptide amphiphiles were studied as degradable tethers for release of the drug nabumetone from nanofiber gels. On-resin addition of the novel compound tri-Boc-hydrazido adipic acid to a lysine E-amine allowed for precise placement of a hydrazide in a peptide sequence.

  9. Blends of Amphiphilic, Hyperbranched Polyesters and Different Polyolefins

    NARCIS (Netherlands)

    Schmaljohann, D.; Pötschke, P.; Hässler, R.; Voit, B.I.; Froehling, P.E.; Mostert, B.; Loontjens, J.A.


    A hyperbranched polyester based on 3,5-dihydroxybenzoic acid was completely modified with dodecanoyl chloride to result in an amphiphilic, globular polymer, which has a polar core and a nonpolar outer sphere with the ability both to incorporate an organic dye and to interact with a nonpolar matrix.

  10. Competitive Binding of Natural Amphiphiles with Graphene Derivatives (United States)

    Radic, Slaven; Geitner, Nicholas K.; Podila, Ramakrishna; Käkinen, Aleksandr; Chen, Pengyu; Ke, Pu Chun; Ding, Feng


    Understanding the transformation of graphene derivatives by natural amphiphiles is essential for elucidating the biological and environmental implications of this emerging class of engineered nanomaterials. Using rapid discrete-molecular-dynamics simulations, we examined the binding of graphene and graphene oxide with peptides, fatty acids, and cellulose, and complemented our simulations by experimental studies of Raman spectroscopy, FTIR, and UV-Vis spectrophotometry. Specifically, we established a connection between the differential binding and the conformational flexibility, molecular geometry, and hydrocarbon content of the amphiphiles. Importantly, our dynamics simulations revealed a Vroman-like competitive binding of the amphiphiles for the graphene oxide substrate. This study provides a mechanistic basis for addressing the transformation, evolution, transport, biocompatibility, and toxicity of graphene derivatives in living systems and the natural environment.

  11. Tunable catalysts for solvent-free biphasic systems: pickering interfacial catalysts over amphiphilic silica nanoparticles. (United States)

    Zhou, Wen-Juan; Fang, Lin; Fan, Zhaoyu; Albela, Belén; Bonneviot, Laurent; De Campo, Floryan; Pera-Titus, Marc; Clacens, Jean-Marc


    Stabilization of oil/oil Pickering emulsions using robust and recyclable catalytic amphiphilic silica nanoparticles bearing alkyl and propylsulfonic acid groups allows fast and efficient solvent-free acetalization of immiscible long-chain fatty aldehydes with ethylene glycol.

  12. Membrane analysis with amphiphilic carbon dots. (United States)

    Nandi, Sukhendu; Malishev, Ravit; Parambath Kootery, Kaviya; Mirsky, Yelena; Kolusheva, Sofiya; Jelinek, Raz


    Newly-synthesized amphiphilic carbon dots were used for spectroscopic analysis and multicolour microscopic imaging of membranes and live cells. We show that Förster resonance energy transfer (FRET) occurred from the amphiphilic carbon dots to different membrane-associated fluorescence acceptors. The amphiphilic carbon dots enabled imaging of membrane disruption by the beta-amyloid peptide.

  13. Chiral Cyclobutane β-Amino Acid-Based Amphiphiles: Influence of Cis/Trans Stereochemistry on Condensed Phase and Monolayer Structure. (United States)

    Sorrenti, Alessandro; Illa, Ona; Ortuño, Rosa M; Pons, Ramon


    New diastereomeric nonionic amphiphiles, cis- and trans-1, based on an optically pure cyclobutane β-amino ester moiety have been investigated to gain insight into the influence exerted by cis/trans stereochemistry and stereochemical constraints on the physicochemical behavior, molecular organization, and morphology of their Langmuir monolayers and dry solid states. All these features are relevant to the rational design of functional materials. trans-1 showed a higher thermal stability than cis-1. For the latter, a higher fluidity of its monolayers was observed when compared with the films formed by trans-1 whose BAM images revealed the formation of condensed phase domains with a dendritic shape, which are chiral, and all of them feature the same chiral sign. Although the formation of LC phase domains was not observed by BAM for cis-1, compact dendritic crystals floating on a fluid subphase were observed beyond the collapse, which are attributable to multilayered 3D structures. These differences can be explained by the formation of hydrogen bonds between the amide groups of consecutive molecules allowing the formation of extended chains for trans-1 giving ordered arrangements. However, for cis-1, this alignment coexists with another one that allows the simultaneous formation of two hydrogen bonds between the amide and the ester groups of adjacent molecules. In addition, the propensity to form intramolecular hydrogen bonds must be considered to justify the formation of different patterns of hydrogen bonding and, consequently, the formation of less ordered phases. Those characteristics are congruent also with the results obtained from SAXS-WAXS experiments which suggest a more bent configuration for cis-1 than for trans-1.

  14. Phases and phase transition in insoluble and adsorbed monolayers of amide amphiphiles: Specific characteristics of the condensed phases. (United States)

    Vollhardt, D


    For understanding the role of amide containing amphiphiles in inherently complex biological processes, monolayers at the air-water interface are used as simple biomimetic model systems. The specific characteristics of the condensed phases and phase transition in insoluble and adsorbed monolayers of amide amphiphiles are surveyed to highlight the effect of the chemical structure of the amide amphiphiles on the interfacial interactions in model monolayers. The mesoscopic topography and/or two-dimensional lattice structures of selected amino acid amphiphiles, amphiphilic N-alkylaldonamide, amide amphiphiles with specific tailored headgroups, such as amide amphiphiles based on derivatized ethanolamine, e.g. acylethanolamines (NAEs) and N-,O-diacylethanolamines (DAEs) are presented. Special attention is devoted the dominance of N,O-diacylated ethanolamine in mixed amphiphilic acid amide monolayers. The evidence that a first order phase transition can occur in adsorption layers and that condensed phase domains of mesoscopic scale can be formed in adsorption layers was first obtained on the basis of the experimental characteristics of a tailored amide amphiphile. New thermodynamic and kinetic concepts for the theoretical description of the characteristics of amide amphiphile's monolayers were developed. In particular, the equation of state for Langmuir monolayers generalized for the case that one, two or more phase transitions occur, and the new theory for phase transition in adsorbed monolayers are experimentally confirmed at first by amide amphiphile monolayers. Despite the significant progress made towards the understanding the model systems, these model studies are still limited to transfer the gained knowledge to biological systems where the fundamental physical principles are operative in the same way. The study of biomimetic systems, as described in this review, is only a first step in this direction.

  15. Mimicking cell membrane-like structures on alkylated silicon surfaces by peptide amphiphiles

    Energy Technology Data Exchange (ETDEWEB)

    Shamsi, Fahimeh, E-mail: [Biophysics and Bioengineering, School of Chemical and Biomolecular Engineering, University of Sydney, Sydney, NSW 2006 (Australia); Coster, Hans G.L. [Biophysics and Bioengineering, School of Chemical and Biomolecular Engineering, University of Sydney, Sydney, NSW 2006 (Australia)


    Highlights: {yields} Lipidated peptide amphiphiles were hydrophobically attached onto an alkylated surface. {yields} Morphology of nanofibres of the peptide amphiles depended on the acyl chain length. {yields} We show that extended 2D analogues of the nanofibre surface can be constructed. {yields} Peptide amphiphiles with shorter acyl chains formed more homogeneous layers. - Abstract: We present a new strategy for flexible attachment of peptide amphiphiles on functionalized silicon surfaces. This method involves the production of an alkylated surface on which a lipidated peptide can then be attached through hydrophobic interaction. We applied this to two derivatives of amphiphilic peptide molecules with the same amino acid sequence (A-A-A-A-G-G-G-E-R-G-D) but different in alkyl chain lengths (palmitic acid, undecanoic acid). The basis of this work was to develop substrates which are more biocompatible and bioactive. The ultra-thin peptide amphiphile films were characterized using electrical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (ATR-FTIR) spectroscopy. The results demonstrated that the length of the alkyl chain in the peptide amphiphile affects the packing and coverage of the peptides on the silicon surface.

  16. 三条两亲性多肽的自组装行为及酸敏特性%Self-Assembly and Acid-Responsive Behavior of Three Amphiphilic Peptides

    Institute of Scientific and Technical Information of China (English)

    梁菊; 来丹玉; 吴文澜; 李国芝; 李军波; 方财林


    scattering (DLS) tests showed that their size distributions were uniform and narrow. In dilute hydrochloric acid (pH 5.0), peptide AP1 presented a sharp acid-dependent demicel ization transition, with no assembled particles found by TEM and no DLS peak in the range 1-1000 nm. However, the micel ar structures of the amphiphilic peptides AP2 and AP3 did not disappear at pH 5.0. TEM results showed that AP2 assembly appeared through aggregation and the shape of AP3 micel ar particles became non-spherical or irregular. AP2 assembly at pH 5.0 showed a multiple peak distribution and AP3 assembly showed a broad peak distribution in DLS, consistent with the TEM results. The changes in secondary structures of amphiphilic peptides AP1, AP2, and AP3 at pH 7.0 and 5.0 were confirmed by circular dichroism (CD) and Fourier transform infrared (FT-IR) spectroscopy. We then selected curcumin as a model drug to investigate the drug-loading capacity and in vitro release behavior of peptide AP1 micel es. As a result, AP1 is expected to comprise an ideal acid-responsive drug carrier for the intel igent delivery of anticancer drugs. The differences between AP1, AP2, and AP3 assembly behaviors in neutral and acidic conditions provide a novel and effective approach for regulating self-assembly of peptides. AP1 is expected to offer an ideal pH-responsive functional material.

  17. Grafting amphiphilic brushes onto halloysite nanotubes via a living RAFT polymerization and their Pickering emulsification behavior. (United States)

    Hou, Yifan; Jiang, Junqing; Li, Kai; Zhang, Yanwu; Liu, Jindun


    Amphiphilic brushes of poly(4-vinylpyridine)-block-polystyrene (P4VP-b-PS) and polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) are grafted onto halloysite nanotubes (HNTs) via a surface reversible addition-fragmentation chain transfer (RAFT) living polymerization through anchoring R group in RAFT agent S-1-dodecyl-S'-(R,R'-dimethyl-R″-acetic acid) trithiocarbonates (DDMAT). The characterization of TGA, TEM, and GPC show that amphiphilic brushes are successfully grafted onto HNTs in a living manner. To verify the amphiphilicity of HNTs grafted with block copolymers, their Pickering emulsification behavior in water/soybean oil diphase mixture is studied. The results show that modified HNTs can emulsify water/soybean oil diphase mixture and the emulsification performance is dependent on microstructure of amphiphilic brushes such as hydrophilic/hydrophobic segment size and sequence.

  18. Comb-like amphiphilic copolymers bearing acetal-functionalized backbones with the ability of acid-triggered hydrophobic-to-hydrophilic transition as effective nanocarriers for intracellular release of curcumin. (United States)

    Zhao, Junqiang; Wang, Haiyang; Liu, Jinjian; Deng, Liandong; Liu, Jianfeng; Dong, Anjie; Zhang, Jianhua


    The pH-responsive micelles have enormous potential as nanosized drug carriers for cancer therapy due to their physicochemical changes in response to the tumor intracellular acidic microenvironment. Herein, a series of comb-like amphiphilic copolymers bearing acetal-functionalized backbone were developed based on poly[(2,4,6-trimethoxybenzylidene-1,1,1-tris(hydroxymethyl) ethane methacrylate-co-poly(ethylene glycol) methyl ether methacrylate] [P(TTMA-co-mPEGMA)] as effective nanocarriers for intracellular curcumin (CUR) release. P(TTMA-co-mPEGMA) copolymers with different hydrophobic-hydrophilic ratios were prepared by one-step reversible addition fragmentation chain transfer (RAFT) copolymerization of TTMA and mPEGMA. Their molecular structures and chemical compositions were confirmed by (1)H NMR, Fourier transform infrared spectroscopy (FT-IR) and gel permeation chromatography (GPC). P(TTMA-co-mPEGMA) copolymers could self-assemble into nanosized micelles in aqueous solution and displayed low critical micelle concentration (CMC). All P(TTMA-co-mPEGMA) micelles displayed excellent drug loading capacity, due to the strong π-π conjugate action and hydrophobic interaction between the PTTMA and CUR. Moreover, the hydrophobic PTTMA chain could be selectively hydrolyzed into a hydrophilic backbone in the mildly acidic environment, leading to significant swelling and final disassembly of the micelles. These morphological changes of P(TTMA-co-mPEGMA) micelles with time at pH 5.0 were determined by DLS and TEM. The in vitro CUR release from the micelles exhibited a pH-dependent behavior. The release rate of CUR was significantly accelerated at mildly acidic pH of 4.0 and 5.0 compared to that at pH 7.4. Toxicity test revealed that the P(TTMA-co-mPEGMA) copolymers exhibited low cytotoxicity, whereas the CUR-loaded micelles maintained high cytotoxicity for HepG-2 and EC-109 cells. The results indicated that the novel P(TTMA-co-mPEGMA) micelles with low CMC, small and tunable

  19. Tandem Facial Amphiphiles for Membrane Protein Stabilization

    DEFF Research Database (Denmark)

    Chae, Pil Seok; Gotfryd, Kamil; Pacyna, Jennifer;


    We describe a new type of synthetic amphiphile that is intended to support biochemical characterization of intrinsic membrane proteins. Members of this new family displayed favorable behavior with four of five membrane proteins tested, and these amphiphiles formed relatively small micelles....

  20. Two-dimensional crystallography of amphiphilic molecules at the air-water interface

    DEFF Research Database (Denmark)

    Jacquemain, D.; Grayer Wolf, S.; Leveiller, F.;


    , and review recent results obtained from them for Langmuir films. The methods have been successfully applied in the elucidation of the structure of crystalline aggregates of amphiphilic molecules such as alcohols, carboxylic acids and their salts, alpha-amino acids, and phospholipids at the water surface...

  1. Amphiphilic NO-donor antioxidants. (United States)

    Chegaev, Konstantin; Lazzarato, Loretta; Rolando, Barbara; Marini, Elisabetta; Lopez, Gloria V; Bertinaria, Massimo; Di Stilo, Antonella; Fruttero, Roberta; Gasco, Alberto


    Models of amphiphilic NO-donor antioxidants 24-26 were designed and synthesized. The products were obtained by linking a lipophilic tail (C(6), C(8), C(10)) with a polar head constituted by the 2,6-dimethoxyphenol antioxidant joined to the NO-donor 3-furoxancarboxamide substructure through a bridge containing a quaternary ammonium group. Compound 23, containing the shortest C(2)-alkyl chain, was also studied as a reference. The antioxidant properties (TBARS and LDL oxidation assays) and the vasodilator properties of the compounds were studied in vitro. The ability of these products to interact with phospholipid vesicles was also investigated by NMR techniques. The results indicate that both activities are modulated by the ability of the compounds to accumulate on phospholipid layers.

  2. Selection of Prebiotic Molecules in Amphiphilic Environments

    Directory of Open Access Journals (Sweden)

    Christian Mayer


    Full Text Available A basic problem in all postulated pathways of prebiotic chemistry is the low concentration which generally is expected for interesting reactants in fluid environments. Even though compounds, like nucleobases, sugars or peptides, principally may form spontaneously under environmental conditions, they will always be rapidly diluted in an aqueous environment. In addition, any such reaction leads to side products which often exceed the desired compound and generally hamper the first steps of a subsequent molecular evolution. Therefore, a mechanism of selection and accumulation of relevant prebiotic compounds seems to be crucial for molecular evolution. A very efficient environment for selection and accumulation can be found in the fluid continuum circulating in tectonic fault zones. Vesicles which form spontaneously at a depth of approximately 1 km present a selective trap for amphiphilic molecules, especially for peptides composed of hydrophilic and hydrophobic amino acids in a suitable sequence. The accumulation effect is shown in a numeric simulation on a simplified model. Further, possible mechanisms of a molecular evolution in vesicle membranes are discussed. Altogether, the proposed scenario can be seen as an ideal environment for constant, undisturbed molecular evolution in and on cell-like compartments.

  3. Synthesis, Characterization, and Aqueous Lubricating Properties of Amphiphilic Graft Copolymers Comprising 2-Methoxyethyl Acrylate

    DEFF Research Database (Denmark)

    Javakhishvili, Irakli; Røn, Troels; Jankova Atanasova, Katja;


    of the corresponding monomers followed by deblocking reaction leads to well-defined amphiphiles with narrow molecular weight distributions (PDI ≤ 1.29) and varying content of methacrylic acid. The graft copolymers showed effective surface adsorption and lubrication for self-mated poly(dimethylsiloxane) (PDMS) contacts...

  4. Macroscopic alignment of graphene stacks by Langmuir-Blodgett deposition of amphiphilic hexabenzocoronenes

    DEFF Research Database (Denmark)

    Laursen, B.W.; Nørgaard, K.; Reitzel, N.;


    e present structural studies of Langmuir V and Langmuir-Blodgett (LB) films of new amphiphilic hexa-peri-hexabenzocoronene (HBC) discotics, carrying five branched alkyl side chains and one polar group. The polar group is either a carboxylic acid moiety or an electron acceptor moiety (anthraquinone...

  5. Mesomorphous structure change by tail chain number in ionic liquid crystalline complexes of linear polymer and amphiphiles

    Institute of Scientific and Technical Information of China (English)

    Zhi Yu Cheng; Bi Ye Ren; Shu Ying He; Xin Xing Liu; Zhen Tong


    Three polymer-amphiphile complexes were prepared by combining poly(allylamine hydrochloride) (PAH) with the potassium salt of mono-, di-, and trisubstituted benzoic acid dendrons (4-octyloxybenzoic acid, 3,5-dioctyloxybenzoic acid, and 3,4,5-trioctyloxybenzoic acid). The solid structure and properties were monitored with FT-IR, XRD, TG, DSC, and polarized optical microscope (POM). Difference in the tail chain number of the dendritic amphiphile induced two different mesomorphous structures: lamella for the mono-, disubstituted dendron containing complexes and hexagonal column for the trisubstituted dendron containing complexes. These corresponded to the ionic thermotropic liquid crystal SmA and φh phases, respectively. This finding is significant for design of functional nanostructures based on the ionic complexation of polymers and amphiphiles.

  6. Thermotropic organization of hydrogen-bond-bridged bolaform amphiphiles. (United States)

    Zhang, Jing; Zhou, Mingjun; Wang, Shan; Carr, Jessica; Li, Wen; Wu, Lixin


    A series of quaternary ammonium amphiphiles (A-n) bearing carboxylic acid groups were designed and synthesized. The branched bolaform structures can be constructed by dimerizations of carboxylic acid groups through intermolecular hydrogen bonding, as demonstrated by the Fourier transform infrared (FT-IR) spectra and the temperature-dependent FT-IR spectra. The thermotropic organizations of branched bolaform ammonium dimer complexes were characterized by differential scanning calorimetry, polarized optical microscopy, and X-ray diffraction. We investigated the influence of the spacer between the cationic group and the benzene ring on the thermotropic organization. A-6 with short lateral alkyl chains formed a simple layered structure at room temperature and exhibited smectic A mesophase above 145 °C, whereas A-8 with intermediate lateral chain length organized into smectic A phase over a wide temperature range. A further increase of the length (n = 10, 12) of the lateral chains resulted in the formation of lamellar structure with in-plane layered periodicity, which is rare in the organization of ionic compounds. A packing model of the quasi-2D lamellar was proposed on the basis of the experimental data of X-ray diffraction results. Notably, the quasi-2D lamellar structure could evolve into a simple layer with the increase of temperature. The present results showed a direct relationship in which the branched architecture can be applied to tune the self-assembly behavior of ionic amphiphiles and is allowed to construct new layered superstructure.

  7. Nanoassemblies from amphiphilic cytarabine prodrug for leukemia targeted therapy. (United States)

    Liu, Jing; Zhao, Dujuan; He, Wenxiu; Zhang, Huiyuan; Li, Zhonghao; Luan, Yuxia


    The anti-leukemia effect of cytarabine (Ara-C) is severely restricted by its high hydrophilic properties and rapid plasma degradation. Herein, a novel amphiphilic small molecular prodrug of Ara-C was developed by coupling a short aliphatic chain, hexanoic acid (HA) to 4-NH2 of the parent drug. Based on the amphiphilic nature, the resulting bioconjugate (HA-Ara) could spontaneously self-assemble into stable spherical nanoassemblies (NAs) with an extremely high drug loading (∼71wt%). Moreover, folate receptor (FR)-targeting NAs with high grafting efficient folic acid - bovine serum albumin (FA-BSA) conjugate immobilized on the surface (NAs/FA-BSA) was prepared. The results of MTT assays on FR-positive K562 cells and FR-negative A549 cells demonstrated higher cytotoxicity of HA-Ara NAs than the native drug. Especially, the IC50 values revealed that NAs/FA-BSA was 3 and 2-fold effective than non-targeted NAs after 24 and 48h treatment with K562 cells, respectively indicating FR-mediated enhanced anti-tumor efficacy. In vitro cellular uptake, larger accumulation of HA-Ara NAs were observed in comparative with the free FITC and the results further confirmed the selective uptake of NAs/FA-BSA in folate receptor enriched cancer cells. Above all, self-assembled HA-Ara NAs exhibited potential superiority for Ara-C delivery and FA-modified NAs would be an excellent candidate for targeting leukemia therapy.

  8. From bola-amphiphiles to supra-amphiphiles: the transformation from two-dimensional nanosheets into one-dimensional nanofibers with tunable-packing fashion of n-type chromophores. (United States)

    Liu, Kai; Yao, Yuxing; Wang, Chao; Liu, Yu; Li, Zhibo; Zhang, Xi


    With a rational design of the supra-amphiphiles, we have successfully demonstrated that not only the dimension of the self-assembled nanostructures, but also the packing fashion of the functional naphthalene diimide (a typical n-type chromophore), can be tuned in a noncovalent way in aqueous solution. Naphthalene diimide is incorporated into a bola-amphiphile as the rigid core, whereas viologen derivatives are used as the hydrophilic head. The bola-amphiphile self-assembles into two-dimensional nanosheets, in which naphthalene diimide adopts a "J-type" aggregation. Water-soluble supramolecular complexation between viologen derivatives and the 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt is used as a driving force for the formation of the supra-amphiphiles. Upon formation of the supra-amphiphiles, the nanosheets transform into ultralong nanofibers with a close packing of naphthalene diimide. Notably, just by mixing the two building blocks of the supra-amphiphiles in aqueous solution, a dimension-controlled evolution of the nanostructures is formed that leads to a different packing fashion of the n-type functional chromophores, which is facile and environmental friendly.

  9. Sunfish amphiphiles : Conceptually new carriers for DNA delivery

    NARCIS (Netherlands)

    Hulst, R; Muizebelt, [No Value; Oosting, P; van der Pol, C; Wagenaar, A; Smisterova, J; Bulten, E; Driessen, C; Hoekstra, D; Engberts, JBFN; Muizebelt, Inouk; Šmisterová, Jarmila


    A conceptually new class of cationic amphiphiles, Sunfish amphiphiles, designed for the delivery of genes into cells is introduced. Sunfish amphiphiles have two hydrophobic tails, connected at the 4- and the N-position to the cationic pyridinium headgroup. Two extreme morphologies visualised by back

  10. Prediction on amphiphilicity of hypocrellin derivatives

    Institute of Scientific and Technical Information of China (English)

    谢杰; 马江华; 赵井泉


    Hypocrellins are most suitable for photodynamic therapy (PDT) of the diseases occurring in the superficial layer, such as microvascular diseases, because of their special absorption spectral properties. However, hypocrellins and most of their derivatives are basically lipophilic, while the hydrophilic derivatives lose the PDT activity in vivo. Therefore, the key problem for practical application of PDT of microvascular diseases focuses on finding the derivatives which possess optimized amphiphilicity. Herein, we developed a theoretical method to estimate the amphiphilicity of a molecule by the calculated average polarity. Compared with the experimentally measured results, the method is proved to be applicable. Based on the computation and available experimental results, it can be concluded that the derivative must have the polarities around 0.22 for optimized amphiphilicity.

  11. Prediction on amphiphilicity of hypocrellin derivatives

    Institute of Scientific and Technical Information of China (English)

    谢杰; 马江华; 赵井泉


    Hypocrellins are most suitable for photodynamic therapy (PDT) of the diseases occurring in the superficial layer, such as microvascular diseases, because of their special absorption spectral properties. However, hypocrellins and most of their derivatives are basically lipophilic, while the hydrophilic derivatives lose the PDT activity in vivo. Therefore, the key problem for practical application of PDT of microvascular diseases focuses on finding the derivatives which possess optimized amphiphilicity. Herein, we developed a theoretical method to estimate the amphi-philicity of a molecule by the calculated average polarity. Compared with the experimentally measured results, the method is proved to be applicable. Based on the computation and available experimental results, it can be concluded that the derivative must have the polarities around C.22 for optimized amphiphilicity.

  12. Computational Amphiphilic Materials for Drug Delivery

    Directory of Open Access Journals (Sweden)

    Naresh eThota


    Full Text Available Amphiphilic materials can assemble into a wide variety of morphologies and have emerged as a novel class of candidates for drug delivery. Along with a large number of experiments reported, computational studies have been also conducted in this field. At an atomistic/molecular level, computations can facilitate quantitative understanding of experimental observations and secure fundamental interpretation of underlying phenomena. This review summarizes the recent computational efforts on amphiphilic copolymers and peptides for drug delivery. Atom-resolution and time-resolved insights are provided from bottom-up to microscopically elucidate the mechanisms of drug loading/release, which are indispensable in the rational screening and design of new amphiphiles for high-efficacy drug delivery.

  13. Bulk modification of PDMS microchips by an amphiphilic copolymer. (United States)

    Xiao, Yan; Yu, Xiao-Dong; Xu, Jing-Juan; Chen, Hong-Yuan


    A simple and rapid bulk-modification method based on adding an amphiphilic copolymer during the fabrication process was employed to modify PDMS microchips. Poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) was used as the additive substance. Compared to the native PDMS microchips, both the contact angle and the EOF of the bulk-modified PDMS microchips decreased. The effects of the additive loading and the pH on the EOF were investigated in detail. The bulk-modified PDMS microchips exhibited reproducible and stable EOF behavior. The application of the bulk-modified PDMS microchips was also studied and the results indicated that they could be successfully used to separate amino acids and to suppress protein adsorption.

  14. An Amylase-Responsive Bolaform Supra-Amphiphile. (United States)

    Kang, Yuetong; Cai, Zhengguo; Tang, Xiaoyan; Liu, Kai; Wang, Guangtong; Zhang, Xi


    An amylase-responsive bolaform supra-amphiphile was constructed by the complexation between β-cyclodextrin and a bolaform covalent amphiphile on the basis of host-guest interaction. The bolaform covalent amphiphile could self-assemble in solution, forming sheet-like aggregates and displaying weak fluorescence because of aggregation-induced quenching. The addition of β-cyclodextrin led to the formation of the bolaform supra-amphiphile, prohibiting the aggregation of the bolaform covalent amphiphile and accompanying with the significant recovery of fluorescence. Upon the addition of α-amylase, with the degradation β-cyclodextrin, the fluorescence of the supra-amphiphile would quench gradually and significantly, and the quenching rate linearly correlated to the concentration of α-amylase. This study enriches the field of supra-amphiphiles on the basis of noncovalent interactions, and moreover, it may provide a facile way to estimate the activity of α-amylase.

  15. Self-Assembly and Hydrogelation of Peptide Amphiphiles

    Directory of Open Access Journals (Sweden)

    Wahyudi Priyono Suwarso


    Full Text Available Seven peptide amphiphiles were successfully synthesized using solid phase peptide synthesis method. Peptide amphiphiles were characterized using matrix assisted laser desorption/ionization (MALDI. Atomic force microscopy (AFM study showed that peptide amphiphiles having glycine, valine, or proline as linker, self-assembled into 100-200 nm nanofibers structure. According to our research, both peptide amphiphile with positive and negative charges bear similar self-assembly properties. Peptide amphiphile also showed its capability as low molecular weight gelator (LMWG. Peptide amphiphiles bearing C-16 and C-12 as alkyl showed better hydrogelation properties than C-8 alkyl. Five out of seven peptide amphiphiles have minimum gelation concentration (MGC lower than 1% (w/v.

  16. Designing new symmetrical facial oligothiophene amphiphiles

    NARCIS (Netherlands)

    Janeliunas, Dainius; Eelkema, Rienk; Nieto-Ortega, Belén; Ramírez Aguilar, Francisco J; López Navarrete, Juan T; van der Mee, Lars; Stuart, Marc C A; Casado, Juan; van Esch, Jan H


    In this study we designed a new class of symmetrical facial oligothiophene amphiphiles, which could be obtained in fewer steps than for previously reported analogues, but still possess the specific substituent sequence to control their backbone curvature. This novel design allows the late-stage intr


    Institute of Scientific and Technical Information of China (English)


    Amphiphilic star-block copolymers composed of polystyrene and poly(acrylic acid) were synthesized by iodidemediated radical polymerization. Firstly, free radical polymerization of styrene was carried out with AIBN as initiator and 1,1,1-trimethyolpropane tri(2-iodoisobutyrate) as chain transfer agent, giving iodine atom ended star-shaped polystyrene with three arm chains, R(polystyrene)3. Secondly, tert-butyl acrylate was polymerization using polystyrene obtained as macro-chain transfer agent, and star-block copolymer, R(polystyrene-b-poly(tert-butyl acrylate))3 with controlled molecular weight was obtained. Finally, amphiphilic star-block copolymer, R(polystyrene-b-poly(acrylic acid))3 was obtained by hydrolysis of R(polystyrene-b-poly(tert-butyl acrylate))3 under acidic condition.

  18. Fundamental behavior of a model biomolecular amphiphile system (United States)

    Haverstick, Kraig Leonard

    An interest in the fundamental interactions between protein components, in the form of either single amino acids or peptides, unifies the work represented in this thesis. These fundamental interactions drive protein folding, enzyme-substrate binding, and cell adhesion to extracellular ligands. The technology of lipidation was used to isolate these protein interactions. Lipidation of a water-soluble amino acid or peptide sequence confined the protein component to the air-water interface or to a self-assembled structure in water. Compression of the molecules at the air-water interface ordered them into a solid-like monolayer, and Langmuir-Blodgett deposition produced a surface modification with protein component presented in a controlled, orderly manner. These molecules have potential applications as biomaterials coatings or drug delivery devices. A method for determination of specific hydrogen bonding interactions through cocrystallization of two complementary peptide sequences is also described. In order to understand the effect of lipidation and lipid structure on peptide behavior, a comprehensive study of tail designs was first undertaken. Tail length, linkage group, linker, spacer length, and headgroup chirality, orientation, and terminal group were systematically varied in simple amino acid amphiphiles. Monolayer assembly, thermal stability, and structure were studied with Langmuir isotherms and Fourier transform infrared spectroscopy. Each part of the tail structure was found to affect monolayer behavior. With lipid effects better understood, peptide amphiphiles were designed, synthesized, and studied using peptide sequences of importance for cell adhesion. The sequences [IV-H1] from type IV collagen and Arg-Gly-Asp (RGD) were lipidated and characterized in monolayers by Langmuir isotherms and Fourier transform infrared spectroscopy. Biological functionality was determined by melanoma cell spreading assays. Peptide presentation was found to be critical for

  19. The encapsulation of an amphiphile into polystyrene microspheres of narrow size distribution

    Directory of Open Access Journals (Sweden)

    Pellach Michal


    Full Text Available Abstract Encapsulation of compounds into nano- or microsized organic particles of narrow size distribution is of increasing importance in fields of advanced imaging and diagnostic techniques and drug delivery systems. The main technology currently used for encapsulation of molecules within uniform template particles while retaining their size distribution is based on particle swelling methodology, involving penetration of emulsion droplets into the particles. The swelling method, however, is efficient for encapsulation only of hydrophobic compounds within hydrophobic template particles. In order to be encapsulated, the molecules must favor the hydrophobic phase of an organic/aqueous biphasic system, which is not easily achieved for molecules of amphiphilic character. The following work overcomes this difficulty by presenting a new method for encapsulation of amphiphilic molecules within uniform hydrophobic particles. We use hydrogen bonding of acid and base, combined with a pseudo salting out effect, for the entrapment of the amphiphile in the organic phase of a biphasic system. Following the entrapment in the organic phase, we demonstrated, using fluorescein and (antibiotic tetracycline as model molecules, that the swelling method usually used only for hydrophobes can be expanded and applied to amphiphilic molecules.

  20. The encapsulation of an amphiphile into polystyrene microspheres of narrow size distribution. (United States)

    Pellach, Michal; Margel, Shlomo


    Encapsulation of compounds into nano- or microsized organic particles of narrow size distribution is of increasing importance in fields of advanced imaging and diagnostic techniques and drug delivery systems. The main technology currently used for encapsulation of molecules within uniform template particles while retaining their size distribution is based on particle swelling methodology, involving penetration of emulsion droplets into the particles. The swelling method, however, is efficient for encapsulation only of hydrophobic compounds within hydrophobic template particles. In order to be encapsulated, the molecules must favor the hydrophobic phase of an organic/aqueous biphasic system, which is not easily achieved for molecules of amphiphilic character.The following work overcomes this difficulty by presenting a new method for encapsulation of amphiphilic molecules within uniform hydrophobic particles. We use hydrogen bonding of acid and base, combined with a pseudo salting out effect, for the entrapment of the amphiphile in the organic phase of a biphasic system. Following the entrapment in the organic phase, we demonstrated, using fluorescein and (antibiotic) tetracycline as model molecules, that the swelling method usually used only for hydrophobes can be expanded and applied to amphiphilic molecules.

  1. A Peptide Amphiphile Organogelator of Polar Organic Solvents (United States)

    Rouse, Charlotte K.; Martin, Adam D.; Easton, Christopher J.; Thordarson, Pall


    A peptide amphiphile is reported, that gelates a range of polar organic solvents including acetonitrile/water, N,N-dimethylformamide and acetone, in a process dictated by β-sheet interactions and facilitated by the presence of an alkyl chain. Similarities with previously reported peptide amphiphile hydrogelators indicate analogous underlying mechanisms of gelation and structure-property relationships, suggesting that peptide amphiphile organogel design may be predictably based on hydrogel precedents. PMID:28255169

  2. Headgroup effects on the Krafft temperatures and self-assembly of ω-hydroxy and ω-carboxy hexadecyl quaternary ammonium bromide bolaform amphiphiles: micelles versus molecular clusters? (United States)

    Holder, Simon J; Sriskantha, Bruntha C; Bagshaw, Stephen A; Bruce, Ian J


    Eight bolaform amphiphiles were synthesised and characterised; 4 α,ω-hydroxy-alkane trialkyl (and pyridyl) ammonium bromides and 4 α,ω-carboxy-alkane trialkyl (and pyridyl) ammonium bromides where the alkyl groups were methyl, ethyl and propyl. Four of these represented new compounds. Overall the Krafft temperatures (T(K)) of the eight amphiphiles were high, with 6 of the eight possessing T(K)s greater than 45 °C. Thus most of the amphiphiles could only expect to find applications at raised temperatures limiting their potential utility. However in addition to the previously reported α,ω-hydroxy-hexadecyl triethylammonium bromide (2b) with a T(K) of 19.1 °C, another amphiphile, α,ω-carboxy-hexadecyl tripropylammonium bromide (2c) has been identified with a T(K) near ambient temperatures (T(K) of 22.1 °C). This provides an acid functional ammonium bolaform amphiphile that micellises at ambient temperatures to complement the hydroxyl derivative. A correlation between T(K) and the product of the enthalpies and T(m)s of the compounds was observed for 7 of the eight compounds. No correlation between the amphiphile critical micelle concentrations (cmc) and T(K)s was observed confirming previous reports that T(K) values are predominantly determined by crystalline stability rather than solubility. Considerable differences were observed between the various amphiphile T(K)s at different pHs but no clear trend was apparent for the various compounds (despite the degree to which the compounds' carboxylic acid and hydroxyl functionalities were likely to be ionised). The cmcs for the amphiphiles were an order of magnitude larger than those for analogous mono-ammonium amphiphiles with little difference in between the hydroxyl- and carboxy-functionalised compounds. The aggregation numbers (N(agg)) obtained for all compounds were very low (N(agg)bolaforms were in the range 1.0-1.4 nm whereas those for the carboxy-compounds were in the range 2.1-2.4 nm. These results

  3. Fluctuations and structure of amphiphilic films; Fluctuations et structure de films d`amphiphiles

    Energy Technology Data Exchange (ETDEWEB)

    Gourier, CH


    This thesis is divided in three parts.The first part exposes in a theoretical point of view, how the fluctuations spectrum of an amphiphilic film is governed by its properties and its bidimensional characteristics.The measurements of fluctuations spectra of an interface are accessible with the measurement of intensity that interface diffuses out of the specular angle, we present in the second chapter the principles of the X rays diffusion by a real interface and see how the diffuse diffusion experiments allow to determine the fluctuations spectrum of an amphiphilic film. The second part is devoted to the different experimental techniques that have allowed to realize the study of fluctuation as well as the structural study.The third part is devoted to experimental results concerning the measurements of fluctuations spectra and to the study of the structure of amphiphilic films. We show that it is possible by using an intense source of X rays (ESRF: European Synchrotron Radiation Facility) to measure the water and amphiphilic films fluctuations spectra until molecular scales. The last chapter is devoted to the structural study and film fluctuations made of di-acetylenic molecules. (N.C.)

  4. [Amphiphilic cyclodextrins and their applications. Preparation of nanoparticles based on amphiphilic cyclodextrins for biomedical applications]. (United States)

    Parrot-Lopez, H; Perret, F; Bertino-Ghera, B


    Solubilization of hydrophobic drugs at the molecular level as inclusion complexes inside cyclodextrins (CDs) offers a good alternative for improving their stability, solubility and bioavailability, and for preventing against their possible toxicity or controlling secondary effects. Therefore CDs are widely used as solubilizing excipients. However since dissociation takes place too readily upon dilution, inclusion complexes inside simple water-soluble CD appears ineffective for drug delivery applications. Chemical modifications of CDs allow them to self-organize as larger assemblies useful for resolving this lability issue. Depending on the position, the number and the nature of these groups, amphiphilic CDs can form assemblies such as vesicles, solid-lipid nanoparticles, nanospheres, liquid crystals, or micellar systems. This review deals with the synthesis of amphiphilic cyclodextrins leading to supramolecular assemblies and the physical properties of these assemblies. From the first sulfonated amphiphilic cyclodextrins isolated in our laboratory in 2003, to the latest ones being regioselectively functionalized by two or four fluoroalkyl chains, through the persubstituted fluorinated cyclodextrines, all these amphiphilic cyclodextrins have shown good abilities for encapsulation. Complexation of bioactive molecules (acyclovir) by these modified alpha-cyclodextrin derivatives, the encapsulation efficiency and release profile were measured as an assessment of the properties of such nanoparticles regarding drug delivery applications.

  5. Multilayers of Fluorinated Amphiphilic Polyions for Marine Fouling Prevention

    NARCIS (Netherlands)

    Zhu, X.; Guo, S.; Janczewski, D.; Parra-Velandia, F.J.; Teo, S.L-M.; Vancso, G.J.


    Sequential layer-by-layer (LbL) deposition of polyelectrolytes followed by chemical cross-linking was investigated as a method to fabricate functional amphiphilic surfaces for marine biofouling prevention applications. A novel polyanion, grafted with amphiphilic perfluoroalkyl polyethylene glycol (

  6. Confined supramolecular nanostructures of mesogen-bearing amphiphiles. (United States)

    Zou, Bo; Wang, Mingfeng; Qiu, Dengli; Zhang, Xi; Chi, Lifeng; Fuchs, Harald


    Stable surface nanostructures with different morphology have been successfully constructed by modifying the chemical structure of synthetic amphiphiles; by introducing mesogenic groups into bolaform amphiphiles, stable spaghetti-like or stripe-like nanostructures can be obtained; it is believed that such a kind of surface structure could be used for templating synthesis and assembly.

  7. Incorporation of Amphiphilic Cyclodextrins into Liposomes as Artificial Receptor Units

    NARCIS (Netherlands)

    Kauscher, Ulrike; Stuart, Marc C. A.; Druecker, Patrick; Galla, Hans-Joachim; Ravoo, Bart Jan


    In this article, we describe the introduction of amphiphilic beta-cyclodextrins into liposomes to act as artificial receptor units. Using dynamic light scattering, dye encapsulation, and cryogenic transmission electron microscopy, we show that amphiphilic beta-cyclodextrins can be mixed in any propo

  8. Amphiphile nanoarchitectonics: from basic physical chemistry to advanced applications. (United States)

    Ramanathan, Muruganathan; Shrestha, Lok Kumar; Mori, Taizo; Ji, Qingmin; Hill, Jonathan P; Ariga, Katsuhiko


    Amphiphiles, either synthetic or natural, are structurally simple molecules with the unprecedented capacity to self-assemble into complex, hierarchical geometries in nanospace. Effective self-assembly processes of amphiphiles are often used to mimic biological systems, such as assembly of lipids and proteins, which has paved a way for bottom-up nanotechnology with bio-like advanced functions. Recent developments in nanostructure formation combine simple processes of assembly with the more advanced concept of nanoarchitectonics. In this perspective, we summarize research on self-assembly of amphiphilic molecules such as lipids, surfactants or block copolymers that are a focus of interest for many colloid, polymer, and materials scientists and which have become increasingly important in emerging nanotechnology and practical applications, latter of which are often accomplished by amphiphile-like polymers. Because the fundamental science of amphiphiles was initially developed for their solution assembly then transferred to assemblies on surfaces as a development of nanotechnological techniques, this perspective attempts to mirror this development by introducing solution systems and progressing to interfacial systems, which are roughly categorized as (i) basic properties of amphiphiles, (ii) self-assembly of amphiphiles in bulk phases, (iii) assembly on static surfaces, (iv) assembly at dynamic interfaces, and (v) advanced topics from simulation to application. This progression also represents the evolution of amphiphile science and technology from simple assemblies to advanced assemblies to nanoarchitectonics.

  9. Synthesis of an amphiphilic dendrimer-like block copolymer and its application on drug delivery

    KAUST Repository

    Wang, Shuaipeng


    Dendrimer-like amphiphilic copolymer is a kind of three-dimensional spherical structure polymer. An amphiphilic dendrimer-like diblock copolymer, PEEGE-G2-b-PEO(OH)12, constituted of a hydrophobic poly(ethoxyethyl glycidol ether) inner core and a hydrophilic poly(ethylene oxide) outer layer, has been successfully synthesized by the living anionic ring-opening polymerization method. The intermediates and targeted products were characterized with 1H NMR spectroscopy and gel permeation chromatography. The application on drug delivery of dendrimer-like diblock copolymer PEEGE-G2-b-PEO(OH)12 using DOX as a model drug was also studied. The drug loading content and encapsulation efficiency were found at 13.07% and 45.75%, respectively. In vitro release experiment results indicated that the drug-loaded micelles exhibited a sustained release behavior under acidic media.

  10. Terpene and dextran renewable resources for the synthesis of amphiphilic biopolymers. (United States)

    Alvès, Marie-Hélène; Sfeir, Huda; Tranchant, Jean-François; Gombart, Emilie; Sagorin, Gilles; Caillol, Sylvain; Billon, Laurent; Save, Maud


    The present work shows the synthesis of amphiphilic polymers based on the hydrophilic dextran and the hydrophobic terpenes as renewable resources. The first step concerns the synthesis of functional terpene molecules by thiol-ene addition chemistry involving amino or carboxylic acid thiols and dihydromyrcenol terpene. The terpene-modified polysaccharides were subsequently synthesized by coupling the functional terpenes with dextran. A reductive amination step produced terpene end-modified dextran with 94% of functionalization, while the esterification step produced three terpene-grafted dextrans with a number of terpene units per dextran of 1, 5, and 10. The amphiphilic renewable grafted polymers were tested as emulsifiers for the stabilization of liquid miniemulsion of terpene droplets dispersed in an aqueous phase. The average hydrodynamic diameter of the stable droplets was observed at about 330 nm.

  11. Optimization of hypocrellin B derivative amphiphilicity and biological activity

    Institute of Scientific and Technical Information of China (English)

    LIU Xin; XIE Jie; ZHANG LuYong; CHEN HongXia; GU Ying; ZHAO JingQuan


    To satisfy the dual requirements of the fluent transportation in blood and the affinity to the target tissues of vascular diseases, hypocrellin derivatives with optimized amphiphilicity are expected. In this work, 3-amino-1-propanesulfonic acid and 4-amino-1-butanesulfonic acid substituted hypocrellin B,named compounds 1 and 2, were designed, synthesized in high yields and characterized. Besides greatly strengthened red absorption, the maximum solubility of compound 2 in phosphate buffered saline (PBS) is 4.2 mg/mL which is just enough to prepare an aqueous solution for intravenous injection in clinically acceptable concentration, while the partition coefficient between n-octanol and PBS,5.6, benefits the cell-uptake and biological activity as well. Furthermore, EPR measurements reveal that the photosensitization activities of the two compounds to generate semiquinone anion radicals, superoxide anion radicals and singlet oxygen are a little bit higher than those of taurine substituted hypocrellin B (THB), but the photodynamic activities to human lung cancer A549 cells are several times that of THB, mainly due to increases in lipophilicity and cell-uptake.

  12. Lipopolysaccharide Neutralization by Cationic-Amphiphilic Polymers through Pseudoaggregate Formation. (United States)

    Uppu, Divakara S S M; Haldar, Jayanta


    Synthetic polymers incorporating the cationic charge and hydrophobicity to mimic the function of antimicrobial peptides (AMPs) have been developed. These cationic-amphiphilic polymers bind to bacterial membranes that generally contain negatively charged phospholipids and cause membrane disintegration resulting in cell death; however, cationic-amphiphilic antibacterial polymers with endotoxin neutralization properties, to the best of our knowledge, have not been reported. Bacterial endotoxins such as lipopolysaccharide (LPS) cause sepsis that is responsible for a great amount of mortality worldwide. These cationic-amphiphilic polymers can also bind to negatively charged and hydrophobic LPS and cause detoxification. Hence, we envisaged that cationic-amphiphilic polymers can have both antibacterial as well as LPS binding properties. Here we report synthetic amphiphilic polymers with both antibacterial as well as endotoxin neutralizing properties. Levels of proinflammatory cytokines in human monocytes caused by LPS stimulation were inhibited by >80% when coincubated with these polymers. These reductions were found to be dependent on concentration and, more importantly, on the side-chain chemical structure due to variations in the hydrophobicity profiles of these polymers. These cationic-amphiphilic polymers bind and cause LPS neutralization and detoxification. Investigations of polymer interaction with LPS using fluorescence spectroscopy and dynamic light scattering (DLS) showed that these polymers bind but neither dissociate nor promote LPS aggregation. We show that polymer binding to LPS leads to sort of a pseudoaggregate formation resulting in LPS neutralization/detoxification. These findings provide an unusual mechanism of LPS neutralization using novel synthetic cationic-amphiphilic polymers.

  13. Tuning peptide amphiphile supramolecular structure for biomedical applications (United States)

    Pashuck, Eugene Thomas, III

    The use of biomaterials in regenerative medicine has been an active area of research for more than a decade. Peptide amphiphiles, which are short peptide sequences coupled to alkyl tails, have been studied in the Stupp group since the beginning of the decade and been used for a variety of biomedical applications. Most of the work has focused on the bioactive epitopes places on the periphery of the PA molecules, but the interior amino acids, known as the beta-sheet region, give the PA nanofiber gel much of its mechanical strength. To study the important parameters in the beta-sheet region, six PA molecules were constructed to determine the influence of beta-sheet length and order of the amino acids in the beta-sheet. It was found that having beta-sheet forming amino acids near the center of the fiber improves PA gel stiffness, and that having extra amino acids that have preferences for other secondary structures, like alpha-helix decreased the gels stiffness. Using FTIR and circular dichroism it was found that the mechanical properties are influenced by the amount of twist in the beta-sheet, and PAs that have more twisted beta-sheets form weaker gels. The effect amino acid properties have on peptide amphiphile self-assembly where studied by synthesizining molecules with varying side group size and hydrophobicity. It was found that smaller amino acids lead to stiffer gels and when two amino acids had the same size the amino acid with the larger beta-sheet propensity lead to a stiffer gel. Furthermore, small changes in peptide structure were found to lead to big changes in nanostructure, as leucine and isoleucine, which have the same size but slightly different structures, form flat ribbons and cylindrical nanofibers, respectively. Phenylalanine and alanine were studied more indepth because they represent the effects of adding an aromatic group to amino acids in the beta-sheet regon. These phenylalanine PAs formed short, twisted ribbons when freshly dissolved in water

  14. Langmuir and Langmuir-Blodgett films of hybrid amphiphiles with a polyoxometalate headgroup. (United States)

    Wang, Xiao-Le; Wang, Yong-Liang; Miao, Wen-Ke; Hu, Min-Biao; Tang, Jing; Yu, Wei; Hou, Zhan-Yao; Zheng, Ping; Wang, Wei


    A hybrid was at first synthesized by a postfunctionalization of an aminomethane trisalkoxo-functionalized Anderson-type polyoxometalate (POM) encapsulated by three tetrabutylammonium ions using a 3,5-bis(tetradecyloxy)benzoic acid by amidation. Then the three TBA(+) counter cations were programmatically replaced by protons (H(+)) following a molecule-to-amphiphile conversion. In this way one hybrid and three POM-containing hybrid amphiphiles (PCHAs) were acquired by adjusting the number (n) of TBA(+) ions and number (3 - n) of H(+) ions (n = 3, 2, 1, and 0). These compounds can be spread onto a water surface to form a Langmuir monolayer film at the air-water interface. Surface pressure-molecular area measurements exhibit the TBA(+) (H(+)) number playing an important role in the forming ability and stability of Langmuir monolayer films. Also, the Langmuir-Blodgett (LB) technique has been used to transfer the monolayer film onto solid supports to fabricate solid multilayer films. It was found that the PCHA with three H(+) ions had the best Langmuir film-forming ability and thus formed stable LB films with a two-dimensional ordered structure. Our findings are instructive in fabricating and using solid films of the amphiphiles with POM headgroups.

  15. Intrinsically disordered amphiphilic peptides as potential targets in drug delivery vehicles. (United States)

    Vincenzi, Marian; Accardo, Antonella; Costantini, Susan; Scala, Stefania; Portella, Luigi; Trotta, Annamaria; Ronga, Luisa; Guillon, Jean; Leone, Marilisa; Colonna, Giovanni; Rossi, Filomena; Tesauro, Diego


    Intrinsically disordered proteins/peptides play a crucial role in many physiological and pathological events and may assume a precise conformation upon binding to a specific target. Recently, we have described the conformational and functional properties of two linear ester peptides provided with the following sequences: Y-G-E-C-P-C-K-OAllyl (PepK) and Y-G-E-C-P-C-E-OAllyl (PepE). Both peptides are characterized by the presence of the "CPC" motif together with a few amino acids able to promote disorder. The CPC sequence is a binding motif for the CXCR4 receptor that represents a well-known target for cancer therapies. In this paper, we report on synthetic amphiphilic peptides that consist of lipophilic derivatives of PepE and PepK bearing two stearic alkyl chains and/or an ethoxylic spacer. These peptide amphiphiles form stable supramolecular aggregates; they present conformational features that are typical of intrinsically disordered molecules as shown by CD spectroscopy. Solution fluorescence and DLS studies have been performed to evaluate Critical Micellar Concentrations and the dimension of supramolecular aggregates. Moreover, preliminary in vitro cell-based assays have been conducted to investigate the molecular recognition processes involving the CXCR4 receptor. In the end, the results obtained have been compared with the previous data generated by the corresponding non-amphiphilic peptides (PepE and PepK).

  16. High Selective Performance of Designed Antibacterial and Anticancer Peptide Amphiphiles. (United States)

    Chen, Cuixia; Chen, Yucan; Yang, Cheng; Zeng, Ping; Xu, Hai; Pan, Fang; Lu, Jian Ren


    Short designed peptide amphiphiles are attractive at killing bacteria and inhibiting cancer cell growth, and the flexibility in their structural design offers a great potential for improving their potency and biocompatibility to mammalian host cells. Amino acid sequences such as G(IIKK)nI-NH2 (n≥3) have been shown to be membrane lytic, but terminal amino acid modifications could impose a huge influence on their performance. We report in this work how terminal amino acid modifications to G(IIKK)3I-NH2 influence its α-helical structure, membrane penetrating ability, and selective actions against different cell types. Deletion of an N-terminal Gly or a C-terminal Ile did not affect their antibacterial activity much, an observation consistent with their binding behavior to negatively charged membrane lipid monolayers. However, the cytotoxicity against mammalian cells was much worsened by the N-terminal Gly deletion, consistent with an increase in its helical content. Despite little impact on the antibacterial activity of G(IIKK)3I-NH2, deletion of both terminal amino acids greatly reduced its antitumor activity. Cholesterol present in tumor cell membrane-mimic was thought to constrain (IIKK)3-NH2 from penetrating into the cancerous membranes, evident from its lowest surface physical activity at penetrating model lipid membranes. On the other hand, its low toxicity to normal mammalian cells and high antibacterial activity in vitro and in vivo made it an attractive antibacterial agent. Thus, terminal modifications can help rebalance the different interactions involved and are highly effective at manipulating their selective membrane responses.

  17. Repurposing Cationic Amphiphilic Antihistamines for Cancer Treatment

    DEFF Research Database (Denmark)

    Ellegaard, Anne-Marie; Dehlendorff, Christian; Vind, Anna C.;


    Non-small cell lung cancer (NSCLC) is one of the deadliest cancers worldwide. In search for new NSCLC treatment options, we screened a cationic amphiphilic drug (CAD) library for cytotoxicity against NSCLC cells and identified several CAD antihistamines as inducers of lysosomal cell death. We...... then performed a cohort study on the effect of CAD antihistamine use on mortality of patients diagnosed with non-localized cancer in Denmark between 1995 and 2011. The use of the most commonly prescribed CAD antihistamine, loratadine, was associated with significantly reduced all-cause mortality among patients...... with non-localized NSCLC or any non-localized cancer when compared with use of non-CAD antihistamines and adjusted for potential confounders. Of the less frequently described CAD antihistamines, astemizole showed a similar significant association with reduced mortality as loratadine among patients with any...

  18. Phase behavior of an amphiphilic fluid. (United States)

    Schoen, Martin; Giura, Stefano; Klapp, Sabine H L


    We invoke mean-field density functional theory (DFT) to investigate the phase behavior of an amphiphilic fluid composed of a hard-sphere core plus a superimposed anisometric Lennard-Jones perturbation. The orientation dependence of the interactions consists of a contribution analogous to the interaction potential between a pair of "spins" in the classical, three-dimensional Heisenberg fluid and another one reminiscent of the interaction between (electric or magnetic) point dipoles. At fixed orientation both contributions are short-range in nature decaying as r-6 (r being the separation between the centers of mass of a pair of amphiphiles). Based upon two mean-field-like approximations for the pair correlation function that differ in the degree of sophistication we derive expressions for the phase boundaries between various isotropic and polar phases that we solve numerically by the Newton-Raphson method. For sufficiently strong coupling between the Heisenberg "spins" both mean-field approximations generate three topologically different and generic types of phase diagrams that are observed in agreement with earlier work [see, for example, Tavares et al., Phys. Rev. E 52, 1915 (1995)]. Whereas the dipolar contribution alone is incapable of stabilizing polar phases on account of its short-range nature it is nevertheless important for details of the phase diagram such as location of the gas-isotropic liquid critical point, triple, and tricritical points. By tuning the dipolar coupling constant suitably one may, in fact, switch between topologically different phase diagrams. Employing also Monte Carlo simulations in the isothermal-isobaric ensemble the general topology of the DFT phase diagrams is confirmed.

  19. Pancreatic beta cells express two autoantigenic forms of glutamic acid decarboxylase, a 65-kDa hydrophilic form and a 64-kDa amphiphilic form which can be both membrane-bound and soluble

    DEFF Research Database (Denmark)

    Christgau, S; Schierbeck, H; Aanstoot, H J;


    The 64-kDa pancreatic beta-cell autoantigen, which is a target of autoantibodies associated with early as well as progressive stages of beta-cell destruction, resulting in insulin-dependent diabetes (IDDM) in humans, has been identified as the gamma-aminobutyric acid-synthesizing enzyme glutamic...... acid decarboxylase. We have identified two autoantigenic forms of this protein in rat pancreatic beta-cells, a Mr 65,000 (GAD65) hydrophilic and soluble form of pI 6.9-7.1 and a Mr 64,000 (GAD64) component of pI 6.7. GAD64 is more abundant than GAD65 and has three distinct forms with regard to cellular...

  20. Amphiphilic vinyl polymers effectively prolong liposome circulation time in vivo. (United States)

    Torchilin, V P; Shtilman, M I; Trubetskoy, V S; Whiteman, K; Milstein, A M


    Newly synthesized amphiphilic polyacrylamide and poly(vinyl pyrrolidone), single terminus-modified with long-chain fatty acyl groups, are able to incorporate into the liposomal membrane, and similar to poly(ethylene glycol) prolong liposome circulation in vivo and decrease liposome accumulation in the liver. Protective efficacy of modified polymers increases with the increase in the length of acyl moiety and decreases for higher molecular weight polymers. The data on amphiphilic polymer-modified liposome biodistribution are presented.

  1. Perfluorocyclobutyl-containing Amphiphilic Block Copolymers Synthesized by RAFT Polymerization

    Institute of Scientific and Technical Information of China (English)

    LI, Yongjun; ZHANG, Sen; FENG, Chun; ZHANG, Yaqin; LI, Qingnuan; LI, Wenxin; HUANG, Xiaoyu


    Amphiphilic block copolymers containing hydrophobic perfluorocyclobutyl-based (PFCB) polyacrylate and hydrophilic poly(ethylene glycol) (PEG) segments were prepared via reversible addition-fragmentation chain transfer (RAP-T) polymerization. The PFCB-containing acrylate monomer, p-(2-(p-tolyloxy)perfluorocyclobutoxy)phenyl acrylate, was first synthesized from commercially available compounds in good yields, and this kind of acrylate monomer can be homopolymerized by free radical polymerization or RAFT polymerization. Kinetic study showed the 2,2'-azobis(isobutyronitrile) (AIBN) initiated and cumyl dithiobenzoate (CDB) mediated RAFT polymerization was in a living fashion, as suggested by the fact that the number-average molecular weights (M_n) increased linearly with the conversions of the monomer, while the polydispersity indices kept less than 1.10. The block polymers with narrow molecular weight distributions (M_w/M_n≤1.21) were prepared through RAFT polymerization using PEG monomethyl ether capped with 4-cyanopentanoic acid dithiobenzoate end group as the macro chain transfer agent (mPEG-CTA). The length of the hydrophobic segment can be tuned by the feed ratio of the PFCB-based acrylate monomer and the extending of the polymerization time. The micellization behavior of the block copolymers in aqueous media was investigated by the fluorescence probe technique.

  2. Revealing Amphiphilic Nanodornains of Anti-Biofouling Polymer Coatings

    Energy Technology Data Exchange (ETDEWEB)

    Amadei, CA; Yang, R; Chiesa, M; Gleason, KK; Santos, S


    Undesired bacterial adhesion and biofilm formation on wetted surfaces leads to significant economic and environmental costs in various industries. Amphiphilic coatings with molecular hydrophilic and hydrophobic patches can mitigate such biofouling effectively in an environmentally friendly manner. The coatings are synthesized by copolymerizing (Hydroxyethyl)methacrylate and perfluorodecylacrylate via initiated chemical vapor deposition (iCVD). In previous studies, the size of the patches was estimated to be similar to 1.4-1.75 nm by fitting protein adsorption data to a theoretical model. However, no direct observations of the molecular heterogeneity exist and therefore the origin of the fouling resistance of amphiphilic coatings remains unclear. Here, the amphiphilic nature is investigated by amplitude modulation atomic force microscopy (AM-AFM). High-resolution images obtained by penetrating and oscillating the AFM tip under the naturally present water layer with sub-nanometer amplitudes reveal, for the first time, the existence of amphiphilic nanodomains (1-2 nm(2)). Compositional heterogeneity at the nanoscale is further corroborated by a statistical analysis on the data obtained with dynamic AM-AFM force spectroscopy. Variations in the long range attractive forces, responsible for water affinity, are also identified. These nanoscopic results on the polymers wettability are also confirmed by contact angle measurements (i.e., static and dynamic). The unprecedented ability to visualize the amphiphilic nanodomains as well as sub-nanometer crystalline structures provides strong evidence for the existence of previously postulated nanostructures, and sheds light on the underlying antifouling mechanism of amphiphilic chemistry.

  3. Hemocompatibility of folic-acid-conjugated amphiphilic PEG-PLGA copolymer nanoparticles for co-delivery of cisplatin and paclitaxel: treatment effects for non-small-cell lung cancer. (United States)

    He, Zelai; Shi, Zengfang; Sun, Wenjie; Ma, Jing; Xia, Junyong; Zhang, Xiangyu; Chen, Wenjun; Huang, Jingwen


    In this study, we used folic-acid-modified poly(ethylene glycol)-poly(lactic-co-glycolic acid) (FA-PEG-PLGA) to encapsulate cisplatin and paclitaxel (separately or together), and evaluated their antitumor effects against lung cancer; this study was conducted in order to investigate the antitumor effects of the co-delivery of cisplatin and paclitaxel by a targeted drug delivery system. Blood compatibility assays and complement activation tests revealed that FA-PEG-PLGA nanoparticles did not induce blood hemolysis, blood clotting, or complement activation. The results also indicated that FA-PEG-PLGA nanoparticles had no biotoxic effects, the drug delivery system allowed controlled release of the cargo molecules, and the co-delivery of cisplatin and paclitaxel efficiently induces cancer cell apoptosis and cell cycle retardation. In addition, co-delivery of cisplatin and paclitaxel showed the ability to suppress xenograft lung cancer growth and prolong the survival time of xenografted mice. These results implied that FA-PEG-PLGA nanoparticles can function as effective carriers of cisplatin and paclitaxel, and that co-delivery of cisplatin and paclitaxel by FA-PEG-PLGA nanoparticles results in more effective antitumor effects than the combination of free-drugs or single-drug-loaded nanoparticles.

  4. Langmuir and Langmuir-Blodgett films of amphiphilic hexa-peri-hexabenzocoronene: New phase transitions and electronic properties controlled by pressure

    DEFF Research Database (Denmark)

    Reitzel, N.; Hassenkam, T.; Balashev, K.;


    We present the synthesis as well as the structural and electronic properties of an amphiphilic derivative of hexaalkylhexa-peri-hexabenzocoronene (HBC), which contains one alkyl substituent that is terminated with a carboxylic acid group. The molecules form well-defined Langmuir films when spread...

  5. Design of amphiphilic oligopeptides as models for fine tuning peptide assembly with plasmid DNA. (United States)

    Goparaju, Geetha N; Gupta, Pardeep K


    We discuss the design of novel amphiphilic oligopeptides with hydrophobic and cationic amino acids to serve as models to understand peptide-DNA assembly. Biophysical and thermodynamic characterization of interaction of these amphiphilic peptides with plasmid DNA is presented. Peptides with at least +4 charges favor stable complex formation. Surface potential is dependent on the type of hydrophobic amino acid for a certain charge. Thermodynamically it is a spontaneous interaction between most of the peptides and plasmid DNA. Lys(7) and Tyr peptides with +4/+5 charges indicate cooperative binding with pDNA without saturation of interaction while Val(2)-Gly-Lys(4), Val-Gly-Lys(5), and Phe-Gly-Lys(5) lead to saturation of interaction indicating condensed pDNA within the range of N/Ps studied. We show that the biophysical properties of DNA-peptide complexes could be modulated by design and the peptides presented here could be used as building blocks for creating DNA-peptide complexes for various biomedical applications, mainly nucleic acid delivery.

  6. Antibacterial Activity of Geminized Amphiphilic Cationic Homopolymers. (United States)

    Wang, Hui; Shi, Xuefeng; Yu, Danfeng; Zhang, Jian; Yang, Guang; Cui, Yingxian; Sun, Keji; Wang, Jinben; Yan, Haike


    The current study is aimed at investigating the effect of cationic charge density and hydrophobicity on the antibacterial and hemolytic activities. Two kinds of cationic surfmers, containing single or double hydrophobic tails (octyl chains or benzyl groups), and the corresponding homopolymers were synthesized. The antimicrobial activity of these candidate antibacterials was studied by microbial growth inhibition assays against Escherichia coli, and hemolysis activity was carried out using human red blood cells. It was interestingly found that the homopolymers were much more effective in antibacterial property than their corresponding monomers. Furthermore, the geminized homopolymers had significantly higher antibacterial activity than that of their counterparts but with single amphiphilic side chains in each repeated unit. Geminized homopolymers, with high positive charge density and moderate hydrophobicity (such as benzyl groups), combine both advantages of efficient antibacterial property and prominently high selectivity. To further explain the antibacterial performance of the novel polymer series, the molecular interaction mechanism is proposed according to experimental data which shows that these specimens are likely to kill microbes by disrupting bacterial membranes, leading them unlikely to induce resistance.

  7. Repurposing Cationic Amphiphilic Antihistamines for Cancer Treatment

    Directory of Open Access Journals (Sweden)

    Anne-Marie Ellegaard


    Full Text Available Non-small cell lung cancer (NSCLC is one of the deadliest cancers worldwide. In search for new NSCLC treatment options, we screened a cationic amphiphilic drug (CAD library for cytotoxicity against NSCLC cells and identified several CAD antihistamines as inducers of lysosomal cell death. We then performed a cohort study on the effect of CAD antihistamine use on mortality of patients diagnosed with non-localized cancer in Denmark between 1995 and 2011. The use of the most commonly prescribed CAD antihistamine, loratadine, was associated with significantly reduced all-cause mortality among patients with non-localized NSCLC or any non-localized cancer when compared with use of non-CAD antihistamines and adjusted for potential confounders. Of the less frequently described CAD antihistamines, astemizole showed a similar significant association with reduced mortality as loratadine among patients with any non-localized cancer, and ebastine use showed a similar tendency. The association between CAD antihistamine use and reduced mortality was stronger among patients with records of concurrent chemotherapy than among those without such records. In line with this, sub-micromolar concentrations of loratadine, astemizole and ebastine sensitized NSCLC cells to chemotherapy and reverted multidrug resistance in NSCLC, breast and prostate cancer cells. Thus, CAD antihistamines may improve the efficacy of cancer chemotherapy.

  8. Formation and antifouling properties of amphiphilic coatings on polypropylene fibers. (United States)

    Goli, Kiran K; Rojas, Orlando J; Genzer, Jan


    We describe the formation of amphiphilic polymeric assemblies via a three-step functionalization process applied to polypropylene (PP) nonwovens and to reference hydrophobic self-assembled n-octadecyltrichlorosilane (ODTS) monolayer surfaces. In the first step, denatured proteins (lysozyme or fibrinogen) are adsorbed onto the hydrophobic PP or the ODTS surfaces, followed by cross-linking with glutaraldehyde in the presence of sodium borohydride (NaBH(4)). The hydroxyl and amine functional groups of the proteins permit the attachment of initiator molecules, from which poly (2-hydroxyethyl methacrylate) (PHEMA) polymer grafts are grown directly through "grafting from" atom transfer radical polymerization. The terminal hydroxyls of HEMA's pendent groups are modified with fluorinating moieties of different chain lengths, resulting in amphiphilic brushes. A palette of analytical tools, including ellipsometry, contact angle goniometry, Fourier transform infrared spectroscopy in the attenuated total reflection mode, and X-ray photoelectron spectroscopy is employed to determine the changes in physicochemical properties of the functionalized surfaces after each modification step. Antifouling properties of the resultant amphiphilic coatings on PP are analyzed by following the adsorption of fluorescein isothiocyanate-labeled bovine serum albumin as a model fouling protein. Our results suggest that amphiphilic coatings suppress significantly adsorption of proteins as compared with PP fibers or PP surfaces coated with PHEMA brushes. The type of fluorinated chain grafted to PHEMA allows modulation of the surface composition of the topmost layer of the amphiphilic coating and its antifouling capability.

  9. Synthesis of Bioinspired Carbohydrate Amphiphiles that Promote and Inhibit Biofilms. (United States)

    Dane, Eric L; Ballok, Alicia E; O'Toole, George A; Grinstaff, Mark W


    The synthesis and characterization of a new class of bioinspired carbohydrate amphiphiles that modulate Pseudomonas aeruginosa biofilm formation are reported. The carbohydrate head is an enantiopure poly-amido-saccharide (PAS) prepared by a controlled anionic polymerization of β-lactam monomers derived from either glucose or galactose. The supramolecular assemblies formed by PAS amphiphiles are investigated in solution using fluorescence assays and dynamic light scattering. Dried samples are investigated using X-ray, infrared spectroscopy, and transmission electron microscopy. Additionally, the amphiphiles are evaluated for their ability to modulate biofilm formation by the Gram-negative bacterium Pseudomonas aeruginosa. Remarkably, from a library of eight amphiphiles, we identify a structure that promotes biofilm formation and two structures that inhibit biofilm formation. Using biological assays and electron microscopy, we relate the chemical structure of the amphiphiles to the observed activity. Materials that modulate the formation of biofilms by bacteria are important both as research tools for microbiologists to study the process of biofilm formation and for their potential to provide new drug candidates for treating biofilm-associated infections.

  10. Investigation on the ion pair amphiphiles and their in vitro release of amantadine drug based on PLGA–PEG–PLGA gel

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Xiaoxia, E-mail:; Ji, Xiaoqing; Shi, Chunhuan; Liu, Jing [Shandong University, School of Pharmaceutical Science and Center for Pharmaceutical Research & Drug Delivery Systems (China); Wang, Haiyang [Institute of Materia Medica Shandong Academy of Medical Sciences, Shandong Taitian Newdrug Discovery Co.Ltd (China); Luan, Yuxia, E-mail: [Shandong University, School of Pharmaceutical Science and Center for Pharmaceutical Research & Drug Delivery Systems (China)


    The amantadine drug and oleic acid surfactant are used to form amantadine-based ion pair amphiphiles based on proton transfer reaction between the drug and the surfactant molecules. The ion pair amphiphiles are characterized by {sup 1}H-nuclear magnetic resonance, Fourier transform infrared spectroscopy, and X-ray diffraction. Self-assembly properties of amantadine-based ion pair amphiphiles are studied by surface tension determination, transmission electron microscopy, zeta potential, and dynamic light scattering. The aggregation behavior studies indicate that the as-prepared ion pair amphiphiles can self-assemble into vesicles with the size of 200–300 nm in aqueous solution. The drug release results show that the amantadine release rate could be well controlled by incorporating the amantadine-based ion pair vesicles in poly (lactic-co-glycolic acid)-poly (ethylene glycol)-poly (lactic-co-glycolic acid) (PLGA–PEG–PLGA) copolymer hydrogel. The drug release from the AT–OA vesicle-loaded PLGA–PEG–PLGA hydrogel is significantly inhibited in comparison with the AT-loaded PLGA–PEG–PLGA hydrogel. The present work thus demonstrates that the vesicle-loaded hydrogel is a good candidate for the drug delivery system with long-term controlled drug release behavior.

  11. Photolabile plasmonic vesicles assembled from amphiphilic gold nanoparticles for remote-controlled traceable drug delivery (United States)

    Song, Jibin; Fang, Zheng; Wang, Chenxu; Zhou, Jiajing; Duan, Bo; Pu, Lu; Duan, Hongwei


    We have developed a new type of photo-responsive plasmonic vesicles that allow for active delivery of anticancer payloads to specific cancer cells and personalized drug release regulated by external photo-irradiation. Our results show that amphiphilic gold nanoparticles carrying hydrophilic poly(ethylene glycol) (PEG) and photo-responsive hydrophobic poly(2-nitrobenzyl acrylate) (PNBA) can assemble into plasmonic vesicles with gold nanoparticles embedded in the hydrophobic shell of PNBA, which can be converted into hydrophilic poly(acrylic acid) upon photo exposure. Benefiting from the interparticle plasmonic coupling of gold nanoparticles in close proximity, the plasmonic vesicles assembled from amphiphilic gold nanoparticles exhibit distinctively different optical properties from single nanoparticle units, which offer the opportunity to track the photo-triggered disassembly of the vesicles and the associated cargo release by plasmonic imaging. We have shown the dense layer of PEG grafts on the vesicles not only endow plasmonic vesicles with excellent colloidal stability, but also serve as flexible spacers for bioconjugation of targeting ligands to facilitate the specific recognition of cancer cells. The targeted delivery of model anticancer drug doxorubicin, investigated by dual-modality plasmonic and fluorescence imaging and toxicity studies, clearly demonstrated the potential of photolabile plasmonic vesicles as multi-functional drug carriers.We have developed a new type of photo-responsive plasmonic vesicles that allow for active delivery of anticancer payloads to specific cancer cells and personalized drug release regulated by external photo-irradiation. Our results show that amphiphilic gold nanoparticles carrying hydrophilic poly(ethylene glycol) (PEG) and photo-responsive hydrophobic poly(2-nitrobenzyl acrylate) (PNBA) can assemble into plasmonic vesicles with gold nanoparticles embedded in the hydrophobic shell of PNBA, which can be converted into


    Institute of Scientific and Technical Information of China (English)

    Jing Wang; Yuan Yao; Bing Ji; Wei Huang; Yong-feng Zhou; De-yue Yan


    The amphiphilic multiarm copolymers were synthesized through the modification of commercially available hyperbranched polyesters (Boltom H40) with N-ε-carbobenzoxy-L-Lysine N-carboxyanhydride (ZLys-NCA). After being condensed with N-Boc-phenylalanine (Boc-NPhe) and deprotected the Boc-groups in trifluoroacetic acid (TFA), the original terminal hydroxyl groups were transformed into the amino groups and then initiated the ring-opening polymerization of ZLys-NCA. The hydrophilic poly(L-lysine) was grafted to the surface of Boltorn H40 successfully after the protecting benzyl groups were removed by the HBr solution in glacial acetic acid (33 wt%). The resulting multiarm copolymers were characterized by the 1H-NMR, GPC and FTIR. The arm length calculated by NMR and GPC analysis was about 3 and 13 lysine-units for H40-Phe-PLysl and H40-Phe-PLys2 respectively. Due to the amphiphilic molecular structure, they displayed ability to self-assemble into spherical micelles in aqueous solution with the average diameter in the range from 70 nm to 250 nm. The CMC of H40-Phe-PLysl and H40-Phe-PLys2 was 0.013 mg/mL and 0.028 mg/mL, respectively,indicating that H40-Phe-PLysl with shorter arm length is easier to self-assemble than H40-Phe-PLys2 with longer arm length.

  13. Effects of hydrophobic and hydrophilic modifications on gene delivery of amphiphilic chitosan based nanocarriers. (United States)

    Wang, Bingqing; He, Chunbai; Tang, Cui; Yin, Chunhua


    The structure-activity relationships between hydrophobic and hydrophilic modification on chitosan and resultant physicochemical properties along with performances in dealing with critical gene delivery barriers were investigated through amphiphilic linoleic acid(LA) and poly (β-malic acid) (PMLA) double grafted chitosan (LMC)/plasmid DNA (pDNA) nanocomplexes. LMC polymers with various LA and PMLA substitution degrees were synthesized and their hydrophilicity/hydrophobicity was characterized. Compared to chitosan, LMC nanoparticles retained the pDNA binding ability at pH 5.5 when they formed nanocomplexes with pDNA encoding enhanced green fluorescence protein (pEGFP) and the resultant complexes showed diameters below 300 nm. Hydrophobic LA and hydrophilic PMLA substitution contributed to suppressed non-specific adsorption, reduced interactions inside LMC/pDNA nanocomplexes, and enhanced pDNA dissociation. However, enzymatic degradation resistance, cell adsorption, and cellular uptake through clathrin-mediated pathway were promoted by hydrophobic LA grafting while being inhibited by hydrophilic PMLA substitution. In vitro transfection assay suggested the optimal LMC/pEGFP nanocomplexes mediated an 8.0-fold improved transfection compared to chitosan/pEGFP nanocomplexes. The 4.2-fold and 2.2-fold higher intramuscular gene expression in mice compared to chitosan/pEGFP and polyethyleneimine (PEI)/pEGFP nanocomplexes further demonstrated the superiority of LMC/pDNA nanocomplexes. Therefore, amphiphilic chitosan derivates with appropriate combination of hydrophobic and hydrophilic modification would be promising gene delivery nanocarriers.

  14. Redox-controllable amphiphilic [2]rotaxanes. (United States)

    Tseng, Hsian-Rong; Vignon, Scott A; Celestre, Paul C; Perkins, Julie; Jeppesen, Jan O; Di Fabio, Alberto; Ballardini, Roberto; Gandolfi, M Teresa; Venturi, Margherita; Balzani, Vincenzo; Stoddart, J Fraser


    With the fabrication of molecular electronic devices (MEDs) and the construction of nanoelectromechanical systems (NEMSs) as incentives, two constitutionally isomeric, redox-controllable [2]rotaxanes have been synthesized and characterized in solution. Therein, they both behave as near-perfect molecular switches, that is, to all intents and purposes, these two rotaxanes can be switched precisely by applying appropriate redox stimuli between two distinct chemomechanical states. Their dumbbell-shaped components are composed of polyether chains interrupted along their lengths by i) two pi-electron rich recognition sites-a tetrathiafulvalene (TTF) unit and a 1,5-dioxynaphthalene (DNP) moiety-with ii) a rigid terphenylene spacer placed between the two recognition sites, and then terminated by iii) a hydrophobic tetraarylmethane stopper at one end and a hydrophilic dendritic stopper at the other end of the dumbbells, thus conferring amphiphilicity upon these molecules. A template-directed protocol produces a means to introduce the tetracationic cyclophane, cyclobis(paraquat-p-phenylene) (CBPQT(4+)), which contains two pi-electron accepting bipyridinium units, mechanically interlocked around the dumbbell-shaped components. Both the TTF unit and the DNP moiety are potential stations for CBPQT(4+), since they can establish charge-transfer and hydrogen bonding interactions with the bipyridinium units of the cyclophane, thereby introducing bistability into the [2]rotaxanes. In both constitutional isomers, (1)H NMR and absorption spectroscopies, together with electrochemical investigations, reveal that the CBPQT(4+) ring is predominantly located on the TTF unit, leading to the existence of a single translational isomer (co-conformation) in both cases. In addition, a model [2]rotaxane, incorporating hydrophobic tetraarylmethane stoppers at both ends of its dumbbell-shaped component, has also been synthesized as a point of reference. Molecular synthetic approaches were used to

  15. Rheological and phase behaviour of amphiphilic lipids

    Directory of Open Access Journals (Sweden)

    Alfaro, M. C.


    Full Text Available This chapter reviews the different association structures which are likely to be formed by amphiphilic lipids in the liquid-crystalline state and their corresponding shear flow properties. The structure and rheological behaviour of thermotropic liquid crystals, emphasizing the properties of smectic mesophases, and those of lyotropic liquid crystals such as: nematic, lamellar, diluted lamellar, lamellar dispersions, hexagonal and cubic mesophases are described. The importance of a comprehensive rheological characterisation, including rheo-optical techniques, is pointed out for their practical applications, development of formulations and as a useful technique to assist in the determination of phase diagrams. A historical approach has been used to discuss the evolving field of the rheology and structure identification of liquid crystals formed by amphiphilic lipids and surfactants. Non-Newtonian viscous shear flow, thixotropic and antithixotropic phenomena, linear viscoelastic properties -described by dynamic and creep compliance experiments- and non-linear viscoelastic properties - described by the difference of normal stresses and stress relaxation tests are interpreted on the basis of a microstructure-rheology relationship. The polycrystalline nature of liquid crystals turns out to be rather sensitive to shear due to the change of both size and orientation of the liquid-crystalline monodomains under flow.En este capítulo se realiza una revisión de las distintas estructuras coloidales de asociación que pueden formar los lípidos anfifílicos en estado líquido-cristalino y de sus correspondientes propiedades de flujo en cizalla. Se describe la estructura y comportamiento reológico de cristales líquidos termotrópicos, con énfasis en los de tipo esméctico, fases gel, y cristales líquidos liotrópicos: nemáticos, laminares, laminares diluidos, dispersiones de laminares, hexagonales y cúbicos. Se hace hincapié en la importancia de una

  16. Ga(III) chelates of amphiphilic DOTA-based ligands: synthetic route and in vitro and in vivo studies

    Energy Technology Data Exchange (ETDEWEB)

    Fontes, Andre [Centro de Quimica, Campus de Gualtar, Universidade do Minho, 4710-057, Braga (Portugal); Prata, M. Isabel M. [IBILI, Faculdade de Medicina, Universidade de Coimbra, 3548, Coimbra (Portugal); Geraldes, Carlos F.G.C. [Departamento de Ciencias da Vida, Faculdade de Ciencias e Tecnologia, Universidade de Coimbra, 3001-401, Coimbra (Portugal); Centro de Neurociencias e Biologia Celular, Universidade de Coimbra, 3001-401, Coimbra (Portugal); Andre, Joao P., E-mail: jandre@quimica.uminho.p [Centro de Quimica, Campus de Gualtar, Universidade do Minho, 4710-057, Braga (Portugal)


    In this work, we report on a synthetic strategy using amphiphilic DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid)-based chelators bearing a variable-sized {alpha}-alkyl chain at one of the pendant acetate arms (from 6 to 14 carbon atoms), compatible with their covalent coupling to amine-bearing biomolecules. The amphiphilic behavior of the micelles-forming Ga(III) chelates (critical micellar concentration), their stability in blood serum and their lipophilicity (logP) were investigated. Biodistribution studies with the {sup 67}Ga-labeled chelates were performed in Wistar rats, which showed a predominant liver uptake with almost no traces of the radiochelates in the body after 24 h.

  17. A New Class of Amphiphiles Bearing Rigid Hydrophobic Groups for Solubilization and Stabilization of Membrane Proteins

    DEFF Research Database (Denmark)

    Chae, Pil Seok; Rasmussen, Søren G F; Rana, Rohini R;


    Non-traditional amphiphiles: Conferring aqueous solubility on membrane proteins generally requires the use of a detergent or other amphiphilic agent. A new class of amphiphiles was synthesized, based on steroidal lipophilic groups, and evaluated with several membrane proteins. The results show th...

  18. Magnetic Amphiphilic Composites Applied for the Treatment of Biodiesel Wastewaters

    Directory of Open Access Journals (Sweden)

    Bruno R. S. Lemos


    Full Text Available In this work, new magnetic amphiphilic composites were prepared by chemical vapor deposition with ethanol on the surface of hydrophilic natural chrysotile matrix containing Fe catalyst. XRD, Raman, Mössbauer and SEM analyses suggest the formation of a complex nanostructured material composed of hydrophobic carbon nanotubes/nanofibers grown on the hydrophilic surface of the MgSi fiber mineral and the presence of Fe metallic nanoparticles coated by carbon. These nanostructured particles show amphiphilic properties and interact very well with both oil and aqueous phases. When added to emulsions the amphiphilic particles locate on the oil/water interface and, under a magnetic field, the oil droplets collapsed leading to the separation of the aqueous and oil phases. Preliminary work showed excellent results on the use of these particles to break wastewater emulsions in the biodiesel process.

  19. Amphiphilic phase-transforming catalysts for transesterification of triglycerides (United States)

    Nawaratna, Gayan Ivantha

    Heterogeneous catalytic reactions that involve immiscible liquid-phase reactants are challenging to conduct due to limitations associated with mass transport. Nevertheless, there are numerous reactions such as esterification, transesterification, etherification, and hydrolysis where two immiscible liquid reactants (such as polar and non-polar liquids) need to be brought into contact with a catalyst. With the intention of alleviating mass transport issues associated with such systems but affording the ability to separate the catalyst once the reaction is complete, the overall goal of this study is geared toward developing a catalyst that has emulsification properties as well as the ability to phase-transfer (from liquid-phase to solid-phase) while the reaction is ongoing and evaluating the effectiveness of such a catalytic process in a practical reaction. To elucidate this concept, the transesterification reaction was selected. Metal-alkoxides that possess acidic and basic properties (to catalyze the reaction), amphiphilic properties (to stabilize the alcohol/oil emulsion) and that can undergo condensation polymerization when heated (to separate as a solid subsequent to the completion of the reaction) were used to test the concept. Studies included elucidating the effect of metal sites and alkoxide sites and their concentration effects on transesterification reaction, effect of various metal alkoxide groups on the phase stability of the reactant system, and kinetic effects of the reaction system. The studies revealed that several transition-metal alkoxides, especially, titanium and yttrium based, responded positively to this reaction system. These alkoxides were able to be added to the reaction medium in liquid phase and were able to stabilize the alcohol/oil system. The alkoxides were selective to the transesterification reaction giving a range of ester yields (depending on the catalyst used). It was also observed that transition-metal alkoxides were able to be

  20. Preparation of pH-responsive membranes with amphiphilic copolymers by surface segregation method☆

    Institute of Scientific and Technical Information of China (English)

    Yanlei Su; Yuan Liu; Xueting Zhao; Yafei Li; Zhongyi Jiang


    Novel pH-responsive membranes were prepared by blending pH-responsive amphiphilic copolymers with pol-yethersulfone (PES) via a nonsolvent-induced phase separation (NIPS) technique. The amphiphilic copolymers bearing Pluronic F127 and poly(methacrylic acid) (PMAA) segments, abbreviated as PMAAn–F127–PMAAn, were synthesized by free radical polymerization. The physical and chemical properties of the blend membranes were evaluated by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectrum, water con-tact angle, Zeta potential and X-ray photoelectron spectroscopy (XPS). The enrichment of hydrophilic PMAA seg-ments on the membrane surfaces was attributed to surface segregation during the membrane preparation process. The blend membranes had significant pH-responsive properties due to the conformational changes of surface-segregated PMAA segments under different pH values of feed solutions. Fluxes of the blend membranes were larger at low pH values of feed solutions than that at high pH values. The pH-responsive ability of the mem-branes was enhanced with the increase of the degree of PMAA near-surface coverage.

  1. Hydrophobicity and thermodynamic response for aqueous solutions of amphiphiles (United States)

    Zemánková, Katerina; Troncoso, Jacobo; Cerdeiriña, Claudio A.; Romaní, Luis; Anisimov, Mikhail A.


    The anomalous behavior of aqueous solutions of amphiphiles in the water-rich region is analyzed via a phenomenological approach that utilizes the isobaric heat capacity Cp as an experimental probe. We report extensive data for solutions of 14 amphiphiles as a function of temperature at atmospheric pressure. Beyond that, Cp data but also isobaric thermal expansivities and isothermal compressibilities for three solutions of tert-butanol as a function of both temperature and pressure are presented. Results rule out the possibility that the observed phenomenology is associated with the anomalous thermodynamics of pure water. Indeed, our Cp data, quantitatively consistent with recent spectroscopic analyses, suggest that water-mediated interactions between the nonpolar parts of amphiphiles are at the origin of anomalies, with the effects of such "hydrophobic aggregation" being observed at mole fractions as small as 0.01. Physicochemical details like the size, the electronic charge distribution and the geometry of amphiphile molecules as well as third-order derivatives of the Gibbs energy and the associated Koga lines support the above claims while they further contribute to characterizing the role of hydrophobicity in these phenomena. Progress with a view to gain a deeper, more concrete understanding remains.

  2. Reinforcement of latex rubber by the incorporation of amphiphilic nanoparticles (United States)

    Latex rubbers are fabricated from latex suspensions. During the fabrication process, latex particles are bound together while water is removed from the suspension. This report shows the mechanical properties of latex rubbers can be improved by incorporating a small amount of amphiphilic nanoparticle...

  3. Loading of Vesicles into Soft Amphiphilic Nanotubes using Osmosis

    NARCIS (Netherlands)

    Erne, Petra M.; van Bezouwen, Laura S.; Stacko, Peter; van Dtjken, Derk Jan; Chen, Jiawen; Stuart, Marc C. A.; Boekema, Eghert J.; Feringa, Ben L.


    The facile assembly of higher-order nanoarchitectures from simple building blocks is demonstrated by the loading of vesicles into soft amphiphilic nanotubes using osmosis. The nanotubes are constructed from rigid interdigitated bilayers which are capped with vesicles comprising phospholipid-based fl

  4. Peptide amphiphiles and their use in supramolecular chemistry

    NARCIS (Netherlands)

    Versluis, Frank


    In this thesis the behavior and functionality of peptide amphiphiles at the surface of bilayer vesicles is examined. By controlling the behavior of the surface bound peptides, I was able to construct assemblies which could: 1) release their content (triggered by pH), 2) fuse in a targeted and contro

  5. Bio-based amphiphilic materials development and applications (United States)

    Farm-based raw materials are increasingly used in the development of amphiphilic materials that have potential applications in the production of a variety of consumer and industrial products, including lubricants. Raw materials of interest include: starches, proteins, fats, oils, and sugars. These ...

  6. Preparation and self-folding of amphiphilic DNA origami. (United States)

    Zhou, Chao; Wang, Dianming; Dong, Yuanchen; Xin, Ling; Sun, Yawei; Yang, Zhongqiang; Liu, Dongsheng


    Amphiphilic DNA origami is prepared by dressing multiple hydrophobic molecules on a rectangular single layer DNA origami, which is then folded or coupled in sandwich-like structures with two outer DNA origami layer and one inner hydrophobic molecules layer. The preference to form different kinds of structures could be tailored by rational design of DNA origami.

  7. Amphiphiles containing aromatic groups in the hydrophobic part

    NARCIS (Netherlands)

    Visscher, Inge


    Aggregation processes are essential for life on this planet. For example, the membranes of all living cells are bilayered aggregates, consisting of lipid molecules, proteins and steroids. In many biological processes, aggregates play a role. The main driving force for aggregation of amphiphiles is h

  8. Cationic amphiphiles as delivery system for genes into eukaryotic cells

    NARCIS (Netherlands)

    Oberle, Volker; Zuhorn, Inge S.; Audouy, Sandrine; Bakowsky, Udo; Smisterová, Jarmila; Engberts, Jan B.F.N.; Hoekstra, Dick; Gregoriadis, G; McCormack, B


    Cationic liposomes, consisting of synthetic amphiphiles and a so-called helper lipid, rapidly form complexes with DNA, known as lipoplexes. When incubated with cells in culture, the DNA can be delivered into the cell and becomes expressed. Because of these properties, lipoplexes are considered a use

  9. Self-assembly of fibronectin mimetic peptide-amphiphile nanofibers (United States)

    Rexeisen, Emilie Lynn

    Many therapeutic strategies incorporate peptides into their designs to mimic the natural protein ligands found in vivo. A few examples are the short peptide sequences RGD and PHSRN that mimic the primary and synergy-binding domains of the extracellular matrix protein, fibronectin, which is recognized by the cell surface receptor, alpha5beta 1 integrin. Even though scaffold modification with biomimetic peptides remains one of the most promising approaches for tissue engineering, the use of these peptides in therapeutic tissue-engineered products and drug delivery systems available on the commercial market is limited because the peptides are not easily able to mimic the natural protein. The design of a peptide that can effectively target the alpha5beta1 integrin would greatly increase biomimetic scaffold therapeutic potential. A novel peptide containing both the RGD primary binding domain and PHSRN synergy-binding domain for fibronectin joined with the appropriate linker should bind alpha 5beta1 integrin more efficiently and lead to greater cell adhesion over RGD alone. Several fibronectin mimetic peptides were designed and coupled to dialkyl hydrocarbon tails to make peptide-amphiphiles. The peptides contained different linkers connecting the two binding domains and different spacers separating the hydrophobic tails from the hydrophilic headgroups. The peptide-amphiphiles were deposited on mica substrates using the Langmuir-Blodgett technique. Langmuir isotherms indicated that the peptide-amphiphiles that contained higher numbers of serine residues formed a more tightly packed monolayer, but the increased number of serines also made transferring the amphiphiles to the mica substrate more difficult. Atomic force microscopy (AFM) images of the bilayers showed that the headgroups might be bent, forming small divots in the surface. These divots may help expose the PHSRN synergy-binding domain. Parallel studies undertaken by fellow group members showed that human

  10. Periodically Grafted Amphiphilic Copolymers: Effects of Steric Crowding and Reversal of Amphiphilicity. (United States)

    Mandal, Joydeb; Ramakrishnan, S


    Two series of periodically clickable polyesters were prepared; one of them carries alkylene segments along its backbone, whereas the other carries poly(ethylene glycol) (PEG) segments. These polyesters were clicked with either MPEG-350 azide or docosyl (C22) azide to yield periodically grafted amphiphilic copolymers (PGACs) carrying either flexible hydrophilic or crystallizable hydrophobic backbone segments. The immiscibility between hydrocarbon and PEG segments causes both of these systems to fold in either a zigzag or hairpin-like conformation; the hairpin-like conformation appears to be preferred when flexible PEG segments are present in the backbone. The folded chains further reorganize in the solid state to develop a lamellar morphology that permits the collocation of the PEG and hydrocarbon (HC) segments within alternate domains; evidence for the self-segregation was gained from DSC, SAXS, and AFM studies. SAXS studies revealed the formation of an extended lamellar structure, whereas AFM images showed uniform layered morphology with layer heights that matched reasonably well with the interlamellar spacing obtained from the SAXS study. Labeling one representative PGAC, carrying crystallizable long alkylene segments in the backbone and pendant PEG-350 side chains, with a small mole fraction of pyrene fluorophore permitted the examination of the conformational transition that occurs upon going from a good to a poor solvent; this single-chain folded conformation, we postulate, is the intermediate that organizes into the lamellar morphology.

  11. Self-Assembling Peptide Amphiphiles for Targeted Drug Delivery (United States)

    Moyer, Tyson

    The systemic delivery of therapeutics is currently limited by off-target side effects and poor drug uptake into the cells that need to be treated. One way to circumvent these issues is to target the delivery and release of therapeutics to the desired location while limiting systemic toxicity. Using self-assembling peptide amphiphiles (PAs), this work has investigated supramolecular nanostructures for the development of targeted therapies. Specifically, the research has focused on the interrelationships between presentation of targeting moeities and the control of nanostructure morphology in the context of systemic delivery for targeting cancer and vascular injuries. The self-assembly region of the PA was systematically altered to achieve control of nanostructure widths, from 100 nm to 10 nm, by the addition of valine-glutamic acid dimers into the chemical structure, subsequently increasing the degree of nanostructure twist. For the targeting of tumors, a homing PA was synthesized to include a dimeric, cyclic peptide sequence known to target the cancer-specific, death receptor 5 (DR5) and initiate apoptosis through the oligomerization of DR5. This PA presented a multivalent display of DR5-binding peptides, resulting in improved binding affinity measured by surface plasmon resonance. The DR5-targeting PA also showed enhanced efficacy in both in vitro and in vivo tumor models relative to non-targeted controls. Alternative modifications to the PA-based antitumor therapies included the use of a cytotoxic, membrane-lytic PA coassembled with a pegylated PA, which showed enhanced biodistribution and in vivo activity after coassembly. The functionalization of the hydrophobic core was also accomplished through the encapsulation of the chemotherapy camptothecin, which was shown to be an effective treatment in vivo. Additionally, a targeted PA nanostructure was designed to bind to the site of vascular intervention by targeting collagen IV. Following balloon angioplasty

  12. Amphiphilic semi-interpenetrating polymer networks using pulverized rubber (United States)

    Shahidi, Nima

    Scrap rubber materials provide a significant challenge to either reuse or safe disposal. Every year, millions of tires are discarded to landfills in the United States, consuming a staggering amount of land space, creating a high risk for large fires, breeding mosquitoes that spread diseases, and wasting the planet's natural resources. This situation cannot be sustained. The challenge of reusing scrap rubber materials is mainly due to the crosslinked structure of vulcanized rubber that prevent them from melting and further processing for reuse. The most feasible recycling approach is believed to be a process in which the vulcanized rubber is first pulverized into a fine powder and then incorporated into new products. The production of fine rubber particles is generally accomplished through the use of a cryogenic process that is costly. Therefore, development of a cost effective technology that utilizes a large quantity of the scrap rubber materials to produce high value added materials is an essential element in maintaining a sustainable solution to rubber recycling. In this research, a cost effective pulverization process, solid state shear extrusion (SSSE), was modified and used for continuous pulverization of the rubber into fine particles. In the modified SSSE process, pulverization takes place at high compressive shear forces and a controlled temperature. Furthermore, an innovative particle modification process was developed to enhance the chemical structure and surface properties of the rubber particles for manufacturing of high value added products. Modification of rubber particles was accomplished through the polymerization of a hydrophilic monomer mixture within the intermolecular structure of the hydrophobic rubber particles. The resulting composite particles are considered as amphiphilic particulate phase semi-interpenetrating polymer networks (PPSIPNs). The modified rubber particles are water dispersible and suitable for use in a variety of aqueous media

  13. Self-assembling peptide amphiphile nanostructures for cancer therapy (United States)

    Soukasene, Stephen

    The application of nanotechnology to cancer therapy shows great promise for reducing the burden of the disease. By virtue of their size, nanoscale objects preferentially accumulate in tumor tissue through an enhanced permeability and retention (EPR) effect. However, to fully overcome the issues that limit current cancer treatments, viable nanostructures must also impart multifunctionality and be fully compatible with their biological surrounds. The self-assembling peptide amphiphile (PA) materials studied extensively in the Stupp Research Group form very biocompatible high aspect ratio nanostructures that meet these criteria. This thesis investigates the development of PA nanostructures designed to treat cancer. We first look to use the PA as a drug delivery vehicle by entrapping a small hydrophobic anti-cancer drug, camptothecin, in the core of the nanostructures. Using a solvent evaporation technique to load the drug into the PA nanofibers, we are able to improve the aqueous solubility of the molecule by nearly 30-fold. TEM and AFM studies show that entrapment of drug molecules does not disrupt the self-assembled morphology of the nanofiber. In vitro and in vivo studies are also conducted to demonstrate the bioactivity of the drug after its entrapment. As a potential platform for novel therapeutics, we next develop techniques for using light irradiation to trigger self-assembly inside the confined space of liposomes. We encapsulate PA monomers that assemble under acidic conditions along with a photoacid generator inside liposomes. Upon exposure to 254 nm light, the PA monomers self assemble inside the liposome to form nanostructures, which we observe through a quick freeze/deep etch technique that allows us to look inside the liposomes by SEM and TEM. Last of all, the development and discovery of epitopes for targeting PA nanostructures to tumors are explored. Using phage display technology we generate two groups of peptide sequences, one of which can potentially

  14. Molecular dynamics simulation of {beta}-sheet formation in self-assembled peptide amphiphile fibers

    Energy Technology Data Exchange (ETDEWEB)

    Lee, One-Sun; Liu Yamei; Schatz, George C., E-mail: [Northwestern University, Department of Chemistry (United States)


    The influence of amino acid sequence on the secondary structure of peptide amphiphile (PAs) cylindrical micelles and fibers that are self-assembled in solution is studied using molecular dynamics simulations. Simulations for two choices of PAs were performed, starting with structures that have the correct overall shape, but which restructure considerably during the simulation, with one fiber being composed of valine rich PAs and the other of alanine rich PAs. Self-assembly is similar in both simulations, with stable fibers (diameter is 7.7-8 nm) obtained after 40 ns. We find that the valine rich PA fiber has a higher {beta}-sheet population than the alanine rich fiber, and that the number of hydrogen bonds is higher. This behavior of the valine rich fiber is consistent with experimental measurements of higher stiffness, and it shows that stiffness can be varied while still maintaining self-assembly.

  15. Amphiphile dependency of the monomeric and dimeric forms of acetylcholinesterase from human erythrocyte membrane. (United States)

    Ott, P; Brodbeck, U


    Human erythrocyte membrane-bound acetylcholinesterase was converted to a monomeric species by treatment of ghosts with 2-mercaptoethanol and iodoacetic acid. After solubilization with Triton X-100, the reduced and alkylated enzyme was partially purified by affinity chromatography and separated from residual dimeric enzyme by sucrose density gradient centrifugation in a zonal rotor. Monomeric and dimeric acetylcholinesterase showed full enzymatic activity in presence of Triton X-100 whereas in the absence of detergent, activity was decreased to approx. 20% and 15%, respectively. Preformed egg phosphatidylcholine vesicles fully sustained activity of the monomeric species whereas the dimer was only 80% active. The results suggest that a dimeric structure is not required for manifestation of amphiphile dependency of membrane-bound acetylcholinesterase from human erythrocytes. Furthermore, monomeric enzyme appears to be more easily inserted into phospholipid bilayers than the dimeric species.

  16. Amphiphilic γ-PGA nanoparticles administered on rat middle ear mucosa produce adjuvant-like immunostimulation in vivo

    DEFF Research Database (Denmark)

    Nilsson, Johan; Broos, Sissela; Akagi, Takami;


    CONCLUSION: Amphiphilic biodegradable nanoparticles (NPs) composed of poly(γ-glutamic acid) conjugated with L-phenylalanine ethylester (γ-PGA-Phe NPs) applied on the rat middle ear mucosa produce an inflammatory type 1 response. The observation is of relevance for the use of γ-PGA-Phe NPs...... as a concomitant antigen delivery system and adjuvant measure in the context of vaccinations. OBJECTIVES: To examine effects of topical mucosal administration of γ-PGA-Phe NPs as a potentially combined antigen delivery system and adjuvant. METHODS: γ-PGA-Phe NPs were administered on rat middle ear mucosa in a sham...

  17. Solid-supported biomimetic membranes based on amphiphilic block copolymers


    Kowal, Justyna


    Planar artificial membranes based on amphiphilic block copolymers are of high interest due to their potential applications in catalysis, drug screening, sensing, etc. Such polymeric membranes can successfully mimic biological membranes, providing high robustness and stability, which makes them good candidates to be developed in direction of applications. Even though solid-supported polymer membranes have been already investigated to a certain extent, it is still an emerging area. This thesis ...

  18. A defect mediated lamellar to isotropic transition of amphiphile bilayers


    Pal, Antara; Pabst, Georg; Raghunathan, V. A.


    We report the observation of a novel isotropic phase of amphiphile bilayers in a mixed system consisting of the ionic surfactant, sodium docecylsulphate (SDS), and the organic salt p-toludine hydrochloride (PTHC). This system forms a collapsed lamellar ($L_\\alpha$) phase over a wide range of water content, which transforms into an isotropic phase on heating. This transition is not observed in samples without excess water, where the $L_\\alpha$ phase is stable at higher temperatures. Our observ...

  19. Tuning Amphiphilicity of Particles for Controllable Pickering Emulsion


    Zhen Wang; Yapei Wang


    Pickering emulsions with the use of particles as emulsifiers have been extensively used in scientific research and industrial production due to their edge in biocompatibility and stability compared with traditional emulsions. The control over Pickering emulsion stability and type plays a significant role in these applications. Among the present methods to build controllable Pickering emulsions, tuning the amphiphilicity of particles is comparatively effective and has attracted enormous attent...

  20. Synthesis and evaluation of amphiphilic peptides as nanostructures and drug delivery tools (United States)

    Sayeh, Naser Ali

    conjugates although one limitation lies in the effort of controlling the rate of drug release. The encapsulated or complexed drugs tend to be released rapidly (before reaching the target site) and in the dendrimer--drug conjugates, it is the chemical linkage that controls the drug release. Thus, future studies in this field are urgently required to create more efficient and stable biomaterials. Peptides are considered as efficient vectors for achieving optimal cellular uptake. The potential use of peptides as drug delivery vectors received much attention by the discovery of several cell-penetrating peptides (CPPs). The first CPPs discovered in 1988, that were sequences from HIV-1 encoded TAT protein, TAT (48--60), and penetrated very efficiently through cell membranes of cultured mammalian cells. CPPs are a class of diverse peptides, typically with 8--25 amino acids, and unlike most peptides, they can cross the cellular membrane with more efficiency. CPPs have also shown to undergo self-assembly and generate nanostructures. The generation of self-assembled peptides and nanostructures occur through various types of interactions between functional groups of amino acid residues, such as electrostatic, hydrophobic, and hydrogen bonding. Appropriate design and functionalization of peptides are critical for generating nanostructures. Chemically CPPs are classified into two major groups: linear and cyclic peptides. It has been previously reported that linear peptides containing hydrophilic and hydrophobic amino acids could act as membrane protein stabilizers. These compounds are short hydrophilic or amphiphilic peptides that have positively charged amino acids, such as arginine, lysine or histidine, which can interact with the negative charge phospholipids layer on the cell membrane and translocate the cargo into the cells. Conjugation to cationic linear CPPs, such as TAT, penetratin, or oligoarginine efficiently improves the cellular uptake of large hydrophilic molecules, but the

  1. Interaction of multidrug-resistant Chinese hamster ovary cells with amphiphiles.


    Loe, D. W.; Sharom, F J


    The interaction of membrane-active amphiphiles with a series of MDR Chinese hamster ovary (CHO) cell lines was investigated. Cross-resistance to cationic amphiphiles was observed, which was effectively sensitised by verapamil. MDR cells showed collateral sensitivity to polyoxyethylene amphiphiles (Triton X-100/Nonidet P-40), which reached a maximum at 9-10 ethylene oxide units. Resistant lines were also highly collaterally sensitive (17-fold) to dibutylphthalate. mdrl transfectants showed cro...

  2. Dendronized multifunctional amphiphilic polymers as efficient nanocarriers for biomedical applications. (United States)

    Kumari, Meena; Gupta, Shilpi; Achazi, Katharina; Böttcher, Christoph; Khandare, Jayant; Sharma, Sunil K; Haag, Rainer


    To gain insight into the factors that affect stability and transport efficiency under dilution conditions, dendronized and hyperbranched multifunctional amphiphilic polymers are synthesized by following the "grafting to" approach using varied amounts of propargylated alkyl chain with perfect and hyperbranched polyglycerol dendrons on the base copolymer of PEG (Mn: 1000 g mol(-1)) diethylester and 2-azidopropane-1,3-diol following the "bio-catalytic method" and "click approach". The dendronized and hyperbranched polymeric systems form supramolecular aggregates and exhibit an efficient transport potential for the model dye "Nile red" in the low μm range in the core-shell-type architecture provided with distinct amphiphilicity as required for encapsulation. Cytotoxicity studies show the polymeric systems to be non-toxic over a wide concentration range. The cellular internalization of Nile-red-encapsulated supramolecular micellar structures is also studied using cellular fluorescence micro-scopy and fluorescence-activated cell sorting (FACS) measurements. A comparison of the data for the dendronized polymers (PEG Mn: 600/1000 g mol(-1)) with the respective low-molecular-weight amphiphile reveal that these polymeric systems are excellent nanotransporters.

  3. Incorporation of amphiphilic cyclodextrins into liposomes as artificial receptor units. (United States)

    Kauscher, Ulrike; Stuart, Marc C A; Drücker, Patrick; Galla, Hans-Joachim; Ravoo, Bart Jan


    In this article, we describe the introduction of amphiphilic β-cyclodextrins into liposomes to act as artificial receptor units. Using dynamic light scattering, dye encapsulation, and cryogenic transmission electron microscopy, we show that amphiphilic β-cyclodextrins can be mixed in any proportion with a typical mixture of phospholipids and cholesterol to provide stable, spherical, and unilamellar mixed vesicles. It is also possible to form giant unilamellar vesicles with mixtures of lipids and cyclodextrin. The permeability of the mixed vesicles increases with the percentage of cyclodextrin. The cyclodextrins can act as host molecules for hydrophobic guest molecules, even when they are dispersed at a low percentage in the vesicle membrane. It is shown that mixed vesicles can be decorated with carbohydrate-functionalized guest molecules, with photoresponsive guest molecules, and with dye-functionalized guest molecules. Taken together, it is demonstrated that the host-guest chemistry of amphiphilic cyclodextrins is fully compatible with a liposomal bilayer membrane and the advantages of each can be combined to give superior nanocontainers.

  4. Amphiphiles Self-Assembly: Basic Concepts and Future Perspectives of Supramolecular Approaches

    Directory of Open Access Journals (Sweden)

    Domenico Lombardo


    Full Text Available Amphiphiles are synthetic or natural molecules with the ability to self-assemble into a wide variety of structures including micelles, vesicles, nanotubes, nanofibers, and lamellae. Self-assembly processes of amphiphiles have been widely used to mimic biological systems, such as assembly of lipids and proteins, while their integrated actions allow the performance of highly specific cellular functions which has paved a way for bottom-up bionanotechnology. While amphiphiles self-assembly has attracted considerable attention for decades due to their extensive applications in material science, drug and gene delivery, recent developments in nanoscience stimulated the combination of the simple approaches of amphiphile assembly with the advanced concept of supramolecular self-assembly for the development of more complex, hierarchical nanostructures. Introduction of stimulus responsive supramolecular amphiphile assembly-disassembly processes provides particularly novel approaches for impacting bionanotechnology applications. Leading examples of these novel self-assembly processes can be found, in fact, in biosystems where assemblies of different amphiphilic macrocomponents and their integrated actions allow the performance of highly specific biological functions. In this perspective, we summarize in this tutorial review the basic concept and recent research on self-assembly of traditional amphiphilic molecules (such as surfactants, amphiphile-like polymers, or lipids and more recent concepts of supramolecular amphiphiles assembly which have become increasingly important in emerging nanotechnology.

  5. Edge-modified amphiphilic Laponite nano-discs for stabilizing Pickering emulsions. (United States)

    Yang, Ying; Liu, Zhi; Wu, Dayong; Wu, Man; Tian, Ye; Niu, Zhongwei; Huang, Yong


    We investigated the effect of amphiphilic Laponite nano-discs, which were edge-modified by hydrophobic chains, on the properties of Pickering emulsions and Pickering emulsions polymerization. Comparing to unmodified Laponites, these amphiphilic nano-discs can greatly reduce the surface tension, resulting in very stable Pickering emulsions. These particles uniquely combine the Pickering effect with amphiphilic properties similar to the surfactant. Taking advantage of these amphiphilic Pickering emulsifiers, miniemulsion polymerization of styrene was performed. Homogeneous polystyrene nanoparticles with size around 150 nm could thus be prepared.

  6. Hybrids of silver nanoparticles with amphiphilic hyperbranched macromolecules exhibiting antimicrobial properties


    Aymonier, Cyril; Schlotterbeck, Ulf; Antonietti, Lydie; Zacharias, Philipp; Thomann, Ralf; Till, Joerg C.; Mecking, Stefan


    Hybrids of silver particles of 1 to 2 nm in size with highly branched amphiphilically modified polyethyleneimines adhere effectively to polar substrates providing environmentally friendly antimicrobial coatings.

  7. Cationic amphiphiles with fatty acyl chain asymmetry of coconut oil deliver genes selectively to mouse lung. (United States)

    Chandrashekhar, Voshavar; Srujan, Marepally; Prabhakar, Rairala; Reddy, Rakesh C; Sreedhar, Bojja; Rentam, Kiran K R; Kanjilal, Sanjit; Chaudhuri, Arabinda


    Recent structure-activity studies have revealed a dramatic influence of hydrophobic chain asymmetry in enhancing gene delivery efficacies of synthetic cationic amphiphiles (Nantz, M. H. et al. Mol. Pharmaceutics2010, 7, 786-794; Koynova, R. et al. Mol. Pharmaceutics2009, 6, 951-958). The present findings demonstrate for the first time that such a transfection enhancing influence of asymmetric hydrocarbon chains observed in pure synthetic cationic amphiphiles also works for cationic amphiphiles designed with natural, asymmetric fatty acyl chains of a food-grade oil. Herein, we demonstrate that cationic amphiphiles designed with the natural fatty acyl chain asymmetry of food-grade coconut oil are less cytotoxic and deliver genes selectively to mouse lung. Despite lauroyl chains being the major fatty acyl chains of coconut oil, both the in vitro and In vivo gene transfer efficiencies of such cationic amphiphiles were found to be remarkably superior (>4-fold) to those of their pure dilauroyl analogue. Mechanistic studies involving the technique of fluorescence resonance energy transfer (FRET) revealed higher biomembrane fusibility of the cationic liposomes of the coconut amphiphiles than that of the symmetric dilauroyl analogue. AFM study revealed pronounced fusogenic nonlamellar structures of the liposomes of coconut amphiphiles. Findings in the FRET and cellular uptake study, taken together, support the notion that the higher cellular uptake resulting from the more fusogenic nature of the liposomes of coconut amphiphiles 1 are likely to play a dominant role in making the coconut amphiphiles transfection competent.

  8. Synthesis of apolipoprotein B lipoparticles to deliver hydrophobic/amphiphilic materials. (United States)

    Chu, Hsueh-Liang; Cheng, Tsai-Mu; Chen, Hung-Wei; Chou, Fu-Hsuan; Chang, Yu-Chuan; Lin, Hsin-Yu; Liu, Shih-Yi; Liang, Yu-Chuan; Hsu, Ming-Hua; Wu, Dian-Shyeu; Li, Hsing-Yuan; Ho, Li-Ping; Wu, Ping-Ching; Chen, Fu-Rong; Chen, Gong-Shen; Shieh, Dar-Bin; Chang, Chia-Seng; Su, Chia-Hao; Yao, Zemin; Chang, Chia-Ching


    To develop a drug delivery system (DDS), it is critical to address challenging tasks such as the delivery of hydrophobic and amphiphilic compounds, cell uptake, and the metabolic fate of the drug delivery carrier. Low-density lipoprotein (LDL) has been acknowledged as the human serum transporter of natively abundant lipoparticles such as cholesterol, triacylglycerides, and lipids. Apolipoprotein B (apo B) is the only protein contained in LDL, and possesses a binding moiety for the LDL receptor that can be internalized and degraded naturally by the cell. Therefore, synthetic/reconstituting apoB lipoparticle (rABL) could be an excellent delivery carrier for hydrophobic or amphiphilic materials. Here, we synthesized rABL in vitro, using full-length apoB through a five-step solvent exchange method, and addressed its potential as a DDS. Our rABL exhibited good biocompatibility when evaluated with cytotoxicity and cell metabolic response assays, and was stable during storage in phosphate-buffered saline at 4 °C for several months. Furthermore, hydrophobic superparamagnetic iron oxide nanoparticles (SPIONPs) and the anticancer drug M4N (tetra-O-methyl nordihydroguaiaretic acid), used as an imaging enhancer and lipophilic drug model, respectively, were incorporated into the rABL, leading to the formation of SPIONPs- and M4N- containing rABL (SPIO@rABL and M4N@rABL, respectively). Fourier transform infrared spectroscopy suggested that rABL has a similar composition to that of LDL, and successfully incorporated SPIONPs or M4N. SPIO@rABL presented significant hepatic contrast enhancement in T2-weighted magnetic resonance imaging in BALB/c mice, suggesting its potential application as a medical imaging contrast agent. M4N@rABL could reduce the viability of the cancer cell line A549. Interestingly, we developed solution-phase high-resolution transmission electron microscopy to observe both LDL and SPIO@rABL in the liquid state. In summary, our LDL-based DDS, rABL, has

  9. Dehydration-induced redistribution of amphiphilic molecules between cytoplasm and lipids is associated with desiccation tolerance in seeds

    NARCIS (Netherlands)

    Buitink, J.; Leprince, O.; Hoekstra, F.A.


    This study establishes a relationship between desiccation tolerance and the transfer of amphiphilic molecules from the cytoplasm into lipids during drying, using electron paramagnetic resonance spectroscopy of amphiphilic spin probes introduced into imbibed radicles of pea (Pisum sativum) and cucumb

  10. Screening nylon-3 polymers, a new class of cationic amphiphiles, for siRNA delivery. (United States)

    Nadithe, Venkatareddy; Liu, Runhui; Killinger, Bryan A; Movassaghian, Sara; Kim, Na Hyung; Moszczynska, Anna B; Masters, Kristyn S; Gellman, Samuel H; Merkel, Olivia M


    Amphiphilic nucleic acid carriers have attracted strong interest. Three groups of nylon-3 copolymers (poly-β-peptides) possessing different cationic/hydrophobic content were evaluated as siRNA delivery agents in this study. Their ability to condense siRNA was determined in SYBR Gold assays. Their cytotoxicity was tested by MTT assays, their efficiency of delivering Alexa Fluor-488-labeled siRNA intracellularly in the presence and absence of uptake inhibitors was assessed by flow cytometry, and their transfection efficacies were studied by luciferase knockdown in a cell line stably expressing luciferase (H1299/Luc). Endosomal release was determined by confocal laser scanning microscopy and colocalization with lysotracker. All polymers efficiently condensed siRNA at nitrogen-to-phosphate (N/P) ratios of 5 or lower, as reflected in hydrodynamic diameters smaller than that at N/P 1. Although several formulations had negative zeta potentials at N/P 1, G2C and G2D polyplexes yielded >80% uptake in H1299/Luc cells, as determined by flow cytometry. Luciferase knockdown (20-65%) was observed after transfection with polyplexes made of the high molecular weight polymers that were the most hydrophobic. The ability of nylon-3 polymers to deliver siRNA intracellularly even at negative zeta potential implies that they mediate transport across cell membranes based on their amphiphilicity. The cellular uptake route was determined to strongly depend on the presence of cholesterol in the cell membrane. These polymers are, therefore, very promising for siRNA delivery at reduced surface charge and toxicity. Our study identified nylon-3 formulations at low N/P ratios for effective gene knockdown, indicating that nylon-3 polymers are a new, promising type of gene delivery agent.

  11. Amphiphilic polymeric micelle as pseudostationary phase in electrokinetic chromatography for analysis of eight corticosteroids in cosmetics. (United States)

    Xu, Xiaojin; Ni, Xinjiong; Cao, Yuhua; Zhuo, Xiaolu; Yang, Xiaoxiao; Cao, Guangqun


    Amphiphilic polymeric micelle, as a novel pseudostationary phase in EKC was used to determine eight kinds of corticosteroids namely hydrocortisone, prednisolone, hydrocortisone acetate, prednisone, cortisone acetate, prednisolone acetate, dexamethasone, and triamcinolone acetonide in cosmetics. Amphiphilic random copolymer poly(methyl methacrylate-co-methacrylic acid) (P(MMA-co-MAA)) was micellizated via neutralization in alkaline aqueous solution. The influences of the molar ratio of monomer MMA to MAA, the concentration of polymer and pH on the polymeric micelle microstructure and EKC performances were investigated. As molar ratio of MMA to MAA in P(MMA-co-MAA) increased, both CMC and environmental polarity of the inner core in polymeric micelle decreased dramatically. With increasing monomer ratio, the size of polymeric micelles increased firstly, and then decreased, finally increased again. ζ potential of the micelle had a slight decline trend. As increment of polymer concentration, the size of the polymeric micelle increased steadily. By optimizing the monomer ratio, the polymer concentration, and pH of the running buffer, as well as operation conditions such as separation voltage and temperature, the eight analytes could be separated within 16.5 min using 7.5 mg/mL polymer with the monomer ratio of 7:3 dissolved in pH 9.2 borax buffer as the running buffer. The method has been used for analysis of corticosteroids in cosmetic samples with simple extraction; the recoveries for eight analytes were between 85.9 and 106%. This method was of accuracy, repeatability, pretreatment simplicity, and could be applied to the quality control of cosmetics.

  12. Drug-loading capacity and nuclear targeting of multiwalled carbon nanotubes grafted with anionic amphiphilic copolymers

    Directory of Open Access Journals (Sweden)

    Tsai HC


    Full Text Available Hsieh-Chih Tsai,1,* Jeng-Yee Lin,2,* Faiza Maryani,1 Chun-Chiang Huang,1 Toyoko Imae1,31Graduate Institute of Applied Science and Technology, 2Division of Plastic Surgery, Department of Surgery, Taipei Medical University Hospital, Taipei Medical University, 3Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei, Taiwan *These authors contributed equally to this work Abstract: In this study, three types of hybrid nanotubes (NTs, ie, oxidized multiwalled carbon NTs (COOH MWCNTs, heparin (Hep-conjugated MWCNTs (Hep MWCNTs, and diblock copolymer polyglycolic acid (PGA-co-heparin conjugated to MWCNTs (PGA MWCNTs, were synthesized with improved biocompatibility and drug-loading capacity. Hydrophilic Hep substituents on MWCNTs improved biocompatibility and acted as nucleus-sensitive segments on the CNT carrier, whereas the addition of PGA enhanced drug-loading capacity. In the PGA MWCNT system, the amphiphilic copolymer (PGA-Hep formed micelles on the side walls of CNTs, as confirmed by electron microscopy. The PGA system encapsulated the hydrophobic drug with high efficiency compared to the COOH MWCNT and Hep MWCNT systems. This is because the drug was loaded onto the PGA MWCNTs through hydrophobic forces and onto the CNTs by ∏–∏ stacking interactions. Additionally, most of the current drug-carrier designs that target cancer cells release the drug in the lysosome or cytoplasm. However, nuclear-targeted drug release is expected to kill cancer cells more directly and efficiently. In our study, PGA MWCNT carriers effectively delivered the active anticancer drug doxorubicin into targeted nuclei. This study may provide an effective strategy for the development of carbon-based drug carriers for nuclear-targeted drug delivery. Keywords: carbon nanotube, amphiphilic copolymer, drug loading, nucleus targeting, cancer therapy

  13. Synthesis and characteristics of biodegradable pyridinium amphiphiles used for in vitro DNA delivery

    NARCIS (Netherlands)

    Roosjen, Astrid; Smisterova, Jarmila; Driessen, Cecile; Anders, Joachim T.; Wagenaar, Anno; Hoekstra, Dirk; Hulst, Ron; Engberts, Jan B.F.N.


    Pyridinium amphiphiles have found practical application for the delivery of DNA into eukaryotic cells. A general synthetic method starting from (iso)nicotinoyl chloride has been devised for the preparation of pyridinium amphiphiles based on (bio)degradable esters, allowing structural variation both

  14. Self-assembly of peptide-amphiphile nanofibers under physiological conditions (United States)

    Stupp, Samuel I.; Hartgerink, Jeffrey D.; Beniash, Elia


    The present invention provides a method of promoting neuron growth and development by contacting cells with a peptide amphiphile molecule in an aqueous solution in the presence of a metal ion. According to the method, the peptide amphiphile forms a cylindrical micellar nanofiber composed of beta-sheets, which promote neuron growth and development.

  15. Composition and method for self-assembly and mineralization of peptide-amphiphiles (United States)

    Stupp, Samuel I [Chicago, IL; Beniash, Elia [Newton, MA; Hartgerink, Jeffrey D [Pearland, TX


    The present invention is directed to a composition useful for making homogeneously mineralized self assembled peptide-amphiphile nanofibers and nanofiber gels. The composition is generally a solution comprised of a positively or negatively charged peptide-amphiphile and a like signed ion from the mineral. Mixing this solution with a second solution containing a dissolved counter-ion of the mineral and/or a second oppositely charged peptide amphiphile, results in the rapid self assembly of the peptide-amphiphiles into a nanofiber gel and templated mineralization of the ions. Templated mineralization of the initially dissolved mineral cations and anions in the mixture occurs with preferential orientation of the mineral crystals along the fiber surfaces within the nanofiber gel. One advantage of the present invention is that it results in homogenous growth of the mineral throughout the nanofiber gel. Another advantage of the present invention is that the nanofiber gel formation and mineralization reactions occur in a single mixing step and under substantially neutral or physiological pH conditions. These homogeneous nanostructured composite materials are useful for medical applications especially the regeneration of damaged bone in mammals. This invention is directed to the synthesis of peptide-amphiphiles with more than one amphiphilic moment and to supramolecular compositions comprised of such multi-dimensional peptide-amphiphiles. Supramolecular compositions can be formed by self assembly of multi-dimensional peptide-amphiphiles by mixing them with a solution comprising a monovalent cation.

  16. Composition and method for self-assembly and mineralization of peptide amphiphiles (United States)

    Stupp, Samuel I.; Beniash, Elia; Hartgerink, Jeffrey D.


    The present invention is directed to a composition useful for making homogeneously mineralized self assembled peptide-amphiphile nanofibers and nanofiber gels. The composition is generally a solution comprised of a positively or negatively charged peptide-amphiphile and a like signed ion from the mineral. Mixing this solution with a second solution containing a dissolved counter-ion of the mineral and/or a second oppositely charged peptide amphiphile, results in the rapid self assembly of the peptide-amphiphiles into a nanofiber gel and templated mineralization of the ions. Templated mineralization of the initially dissolved mineral cations and anions in the mixture occurs with preferential orientation of the mineral crystals along the fiber surfaces within the nanofiber gel. One advantage of the present invention is that it results in homogenous growth of the mineral throughout the nanofiber gel. Another advantage of the present invention is that the nanofiber gel formation and mineralization reactions occur in a single mixing step and under substantially neutral or physiological pH conditions. These homogeneous nanostructured composite materials are useful for medical applications especially the regeneration of damaged bone in mammals. This invention is directed to the synthesis of peptide-amphiphiles with more than one amphiphilic moment and to supramolecular compositions comprised of such multi-dimensional peptide-amphiphiles. Supramolecular compositions can be formed by self assembly of multi-dimensional peptide-amphiphiles by mixing them with a solution comprising a monovalent cation.

  17. Adsorption of alkyltriphenylphosphonium amphiphiles on nafion membranes. X-ray photoelectron spectroscopy and static secondary ion mass spectrometry analysis

    NARCIS (Netherlands)

    Straaten-Nijenhuis, van Wilma F.; Sudholter, Ernst J.R.; Jong, de Feike; Reinhoudt, David N.; Mahy, Jan W.G.


    Conductivity, UV, and attenuated total reflectance IR measurements show that n-alkyltriphenylphosphonium amphiphiles adsorb on a Ndion 117 membrane. Approximately 20% of the Ndion protons are exchanged for a cationic amphiphile (n-hexadecyltriphenylphoephonium). Diffusion of amphiphile through the m

  18. Metal-free synthesis of amphiphilic functional polycarbonates

    Institute of Scientific and Technical Information of China (English)


    Amphiphilic block copolymers of poly(5-benzyloxy trimethylene carbonate) (PBTMC) and poly(ethylene glycol) (PEG) were synthesized through enzymatic polymerization using immobilized porcine pancreas lipase (IPPL). The obtained copolymers with different compositions were characterized by GPC and 1H NMR. The copolymer composition was in agreement with the feed ratio.The molecular weight of the copolymers showed an increasing trend with the decrease of PEG contents. Micelles of the copolymers were formed by dialysis procedure, and characterized by transmission electron microscopy (TEM).

  19. From Vesicles to Protocells: The Roles of Amphiphilic Molecules

    Directory of Open Access Journals (Sweden)

    Yuka Sakuma


    Full Text Available It is very challenging to construct protocells from molecular assemblies. An important step in this challenge is the achievement of vesicle dynamics that are relevant to cellular functions, such as membrane trafficking and self-reproduction, using amphiphilic molecules. Soft matter physics will play an important role in the development of vesicles that have these functions. Here, we show that simple binary phospholipid vesicles have the potential to reproduce the relevant functions of adhesion, pore formation and self-reproduction of vesicles, by coupling the lipid geometries (spontaneous curvatures and the phase separation. This achievement will elucidate the pathway from molecular assembly to cellular life.

  20. Micellar structure of amphiphilic poly(2-oxazoline) diblock copolymers

    DEFF Research Database (Denmark)

    Papadakis, C.M.; Ivanova, R.; Lüdtke, K.


    Amphiphilic diblock copolymers from poly(2-oxazoline)s in aqueous solution can form micelles. By means of small-angle neutron scattering, we have found that poly[(n-nonyl-2-oxazoline)-b-(methyl-2-oxazoline)] {P[(NOx)-b-(MOx)]} diblock copolymers in aqueous solution form micelles of core-shell type....... We have determined the core radius and the shell thickness of the micelles. Comparing the values obtained to the stretched lengths of the blocks leads to the conclusion that the P(NOx) core blocks are stretched, whereas the P(MOx) shell blocks are coiled....

  1. Bolaform supramolecular amphiphiles as a novel concept for the buildup of surface-imprinted films. (United States)

    Zhang, Jiawei; Liu, Yiliu; Wu, Guanglu; Schönhoff, Monika; Zhang, Xi


    Stable multilayer films were fabricated on the basis of the alternating layer-by-layer assembly of a two-component bolaform supramolecular amphiphile and diazoresins, followed by photochemical cross-linking of the structure. UV-visible spectroscopy and atomic force microscopy revealed a uniform deposition process. Moreover, one component of the supramolecular amphiphile can be removed from the multilayer films after cross-linking between the second component and the diazoresin. The release and uptake of the imprinted supramolecular amphiphile component are shown to be reversible. Furthermore, uptake experiments of different molecules show the selectivity of the imprinted sites for the template molecule. Thus, surface-imprinted films can be formed by employing dissociable two-component supramolecular amphiphiles. This research reveals that supramolecular amphiphiles can be used as a novel concept for the construction of multilayer films, and it also provides a new method of generating surface-imprinted multilayers.

  2. Amphiphilic biopolymers (amphibiopols) as new surfactants for membrane protein solubilization (United States)

    Duval-Terrié, Caroline; Cosette, Pascal; Molle, Gérard; Muller, Guy; Dé, Emmanuelle


    The aim of this study was to develop new surfactants for membrane protein solubilization, from a natural, biodegradable polymer: the polysaccharide pullulan. A set of amphiphilic pullulans (HMCMPs), differing in hydrophobic modification ratio, charge ratio, and the nature of the hydrophobic chains introduced, were synthesized and tested in solubilization experiments with outer membranes of Pseudomonas fluorescens. The membrane proteins were precipitated, and then resolubilized with various HMCMPs. The decyl alkyl chain (C10) was the hydrophobic graft that gave the highest level of solubilization. Decyl alkyl chain-bearing HMCMPs were also able to extract integral membrane proteins from their lipid environment. The best results were obtained with an amphiphilic pullulan bearing 18% decyl groups (18C10). Circular dichroism spectroscopy and membrane reconstitution experiments were used to test the structural and functional integrity of 18C10-solubilized proteins (OmpF from Escherichia coli and bacteriorhodopsin from Halobacterium halobium). Whatever their structure type (α or β), 18C10 did not alter either the structure or the function of the proteins analyzed. Thus, HMCMPs appear to constitute a promising new class of polymeric surfactants for membrane protein studies. PMID:12649425

  3. Lipophosphoramidate-based bipolar amphiphiles: their syntheses and transfection properties. (United States)

    Berchel, Mathieu; Le Gall, Tony; Lozach, Olivier; Haelters, Jean-Pierre; Montier, Tristan; Jaffrès, Paul-Alain


    Six new cationic bolaamphiphiles (also called bipolar amphiphiles, bolaform amphiphiles, or bolalipids) were readily prepared by a thiol-ene click reaction that engaged a mercapto-alcohol (mercapto-ethanol or mercapto-hexanol) and a cationic based lipophosphoramidate. The cationic lipophosphoramidates contain two lipid chains that end in an alkene group and a selected cationic polar head group (trimethylammonium, dimethyl hydroxyethyl ammonium, or methylimidazolium). These compounds were formulated in water (with or without DOPE as a colipid) to produce supramolecular aggregates. These aggregates, before (i.e. bolasomes) and after (i.e. bolaplexes) mixing with plasmid DNA (pDNA) at various charge ratios, were characterized with regard to their sizes and zeta potentials. In the case of bolasomes, the suspensions were unstable since precipitation occurred after only a few hours at room temperature. On the other hand, bolaplex formulations exhibited clearly a better colloidal stability. Then, the gene delivery properties of the cationic bolasomes were investigated using two human-derived epithelial cell lines (A549 and 16HBE). Compared to the commercially available lipofection reagent (Lipofectamine), most of the cationic bolaamphiphiles were able to efficiently transfect these cells when they were formulated with DOPE in a 1 : 1 molar ratio. We report herein that bolaamphiphiles possessing a trimethylammonium or a dimethyl hydroxyethyl ammonium head group were the most efficient in terms of transfection efficiency while exhibiting no significant cytotoxicity.


    Institute of Scientific and Technical Information of China (English)

    Xiao-chun Qin; Chun-lai Ren


    Combining self-consistent-field theory and density-functional theory,we systematically study the deformation of copolymer micelles induced by the presence of amphiphilic dimer particles.Due to the amphiphilic nature,dimer particles tend to accumulate onto the interface of the copolymer micelle.With increasing concentration of the symmetric dimer particles,which are made of two identical spherical particles,the micelle deforms from the initial sphere to ellipse,dumbbell,and finally separates into two micelles.Furthermore,asymmetric dimer particles,composed by two particles with different sizes,are considered to investigate the influence of geometry of dimer particles on the deformation of the micelle.It is found that the micelle inclines to deform into dumbbell due to the additional curvature originating in the gathering of asymmetric dimer particles onto the interface of the micelle.The present study on the deformation of micelles is useful to understand the possible shape variation in the course of cell division/fusion.

  5. Immobilization of amphiphilic polycations by catechol functionality for antimicrobial coatings. (United States)

    Han, Hua; Wu, Jianfeng; Avery, Christopher W; Mizutani, Masato; Jiang, Xiaoming; Kamigaito, Masami; Chen, Zhan; Xi, Chuanwu; Kuroda, Kenichi


    A new strategy for preparing antimicrobial surfaces by a simple dip-coating procedure is reported. Amphiphilic polycations with different mole ratios of monomers containing dodecyl quaternary ammonium, methoxyethyl, and catechol groups were synthesized by free-radical polymerization. The polymer coatings were prepared by immersing glass slides into a polymer solution and subsequent drying and heating. The quaternary ammonium side chains endow the coatings with potent antibacterial activity, the methoxyethyl side chains enable tuning the hydrophobic/hydrophilic balance, and the catachol groups promote immobilization of the polymers into films. The polymer-coated surfaces displayed bactericidal activity against Escherichia coli and Staphylococcus aureus in a dynamic contact assay and prevented the accumulation of viable E. coli, S. aureus, and Acinetobacter baumannii for up to 96 h. Atomic force microscopy (AFM) images of coating surfaces indicated that the surfaces exhibit virtually the same smoothness for all polymers except the most hydrophobic. The hydrophobic polymer without methoxyethyl side chains showed clear structuring into polymer domains, causing high surface roughness. Sum-frequency generation (SFG) vibrational spectroscopy characterization of the surface structures demonstrated that the dodecyl chains are predominantly localized at the surface-air interface of the coatings. SFG also showed that the phenyl groups of the catechols are oriented on the substrate surface. These results support our hypothesis that the adhesive or cross-linking functionality of catechol groups discourages polymer leaching, allowing the tuning of the amphiphilic balance by incorporating hydrophilic components into the polymer chains to gain potent biocidal activity.

  6. Amino acid-bile acid based molecules: extremely narrow surfactant nanotubes formed by a phenylalanine-substituted cholic acid. (United States)

    Travaglini, Leana; D'Annibale, Andrea; Schillén, Karin; Olsson, Ulf; Sennato, Simona; Pavel, Nicolae V; Galantini, Luciano


    An amino acid-substituted bile acid forms tubular aggregates with inner and outer diameters of about 3 and 6 nm. The diameters are unusually small for surfactant self-assembled tubes. The results enhance the spectrum of applications of supramolecular tubules and open up possibilities for investigating a novel class of biological amphiphiles.

  7. Amphiphilic Spider Silk-Like Block Copolymers with Tunable Physical Properties and Morphology for Biomedical Applications (United States)

    Huang, Wenwen; Krishnaji, Sreevidhya; Kaplan, David; Cebe, Peggy


    Silk-based materials are important candidates for biomedical applications because of their excellent biocompatibility and biodegradability. To generate silk amphiphilic biopolymers with potential use in guided tissue repair and drug delivery, a novel family of spider silk-like block copolymers was synthesized by recombinant DNA technology. Block copolymer thermal properties, structural conformations, protein-water interactions, and self-assembly morphologies were studied with respect to well controlled protein amino acid sequences. A theoretical model was used to predict the heat capacity of the protein and protein-water complex. Using thermal analysis, two glass transitions were observed: Tg1 is related to conformational changes caused by bound water removal, while Tg2 (>Tg1) is the glass transition of dry protein. Real-time infrared spectroscopy and X-ray diffraction confirmed that different secondary structural changes occur during the two Tg relaxations. Using scanning electron microscopy, fibrillar networks and hollow vesicles are observed, depending on protein block copolymer sequence. This study provides a deeper understanding of the relationship between protein physical properties and amino acid sequence, with implications for design of other protein-based materials. Support was provided from the NSF CBET-0828028 and the MRI Program under DMR-0520655 for thermal analysis instrumentation.

  8. A new drug carrier: Magnetite nanoparticles coated with amphiphilic block copolymer

    Institute of Scientific and Technical Information of China (English)

    CHANG Yu; BAI YunPeng; TENG Bao; Li ZhaoLong


    This paper reports on the synthesis and characterization of 4 nm magnetite nanoparticles coated with amphiphilic block copolymers of poly(ethyl methacrylate)-b-poly(2-hydroxyethyl methacrylate) (PEMA-b-PHEMA) by surface-initiated atom transfer radical polymerization (ATRP), which can act as new po-tential carriers for hydrophobic targeted drug delivery. Vibrating sample magnetometer analysis indi-cated that the magnetite nanoparticles were superparamagnetic at room temperature. Thermogravim-etric analysis (TGA) was applied to studying the property of surface of magnetite nanoparticles, and the surface density of macromolecules was calculated. The grafting density of oleic acid, BrMPA and PEMA was 5.8, 3.9, 0.16 chain/nm2 respectively, which indicates that the initiation efficiency decreases due to the influence of large space of oleic acid molecules. In vitro progesterone and (-)-isoproterenol hy-drochloride release in phosphate buffered saline (PBS) at pH 7.0 and 37℃ was conducted in order to demonstrate the function of drug loading and release. The results showed that the amount of drug carried into the core-shell Fe3O4@PEMA-b-PHEMA depends on the length of hydrophobic segment of block copolymer. The release of progesterone (37% after 22 h in our previous work) was compared with the release of (-)-isoproterenol hydrochloride (80% after 50 min), demonstrating that the strong hy-drophobic interaction between hydrophobic segment and drug can effectively control the release of hydrophobic drugs.

  9. Pd loaded amphiphilic COF as catalyst for multi-fold Heck reactions, C-C couplings and CO oxidation. (United States)

    Mullangi, Dinesh; Nandi, Shyamapada; Shalini, Sorout; Sreedhala, Sheshadri; Vinod, Chathakudath P; Vaidhyanathan, Ramanathan


    COFs represent a class of polymers with designable crystalline structures capable of interacting with active metal nanoparticles to form excellent heterogeneous catalysts. Many valuable ligands/monomers employed in making coordination/organic polymers are prepared via Heck and C-C couplings. Here, we report an amphiphilic triazine COF and the facile single-step loading of Pd(0) nanoparticles into it. An 18-20% nano-Pd loading gives highly active composite working in open air at low concentrations (Conc. Pd(0) couplings and C-C couplings using 'non-boronic acid' substrates, and exhibits good recyclability with no sign of catalyst leaching. As an oxidation catalyst, it shows 100% conversion of CO to CO2 at 150 °C with no loss of activity with time and between cycles. Both vapor sorptions and contact angle measurements confirm the amphiphilic character of the COF. DFT-TB studies showed the presence of Pd-triazine and Pd-Schiff bond interactions as being favorable.

  10. Synthesis of biodegradable amphiphilic Y-shaped block co-polymers via ring-opening polymerization for drug delivery. (United States)

    Jia, Lin; Yan, Lifeng; Li, Yang


    A series of novel Y-shaped biodegradable block co-polymers of poly(ε-caprolactone) (PCL) and poly(ethyl ethylene phosphate) (PEEP) (PCL-(PEEP)2) were synthesized via ring-opening polymerization (ROP) of EEP with bis-hydroxy-functional ROP initiator (init-PCL-(OH)2). The init-PCL-(OH)2 was synthesized by ROP of CL using 4-hydroxybutyl acrylate (HBA) as initiator and L-tartaric acid as catalyst in bulk, and subsequently the resulting vinyl-terminated PCL was end-capped by acetyl chloride, followed by Michael addition using excess diethanolamine. The Y-shaped co-polymers and their intermediates were characterized by (1)H-, (13)C-, (31)P-NMR, FT-IR and gel-permeation chromatography. The results indicated that the molecular weight of the Y-shaped co-polymers increased with the increasing of the molar ratios of EEP to init-PCL-(OH)2 in the feed, while the PCL chain length was kept constant. The amphiphilic block co-polymers could self-assemble into micelles in aqueous solution, which was demonstrated by dynamic light scattering, (1)H-NMR and atomic force microscopy. A study of controlled release of indomethacin indicated that the amphiphilic block co-polymers could potentially provide novel vehicles for drug delivery.

  11. Electron paramagnetic resonance study of amphiphiles partitioning behavior in desiccation-tolerant moss during dehydration

    Institute of Scientific and Technical Information of China (English)


    Desiccation tolerance is a crucial characteristic for desert moss surviving in arid regions. Desiccation procedure always induces amphiphiles transferring from the polar cytoplasm into lipid bodies. The behavior of amphiphiles transferring can contribute to the enhancement of desiccation tolerance and the reduction of plasma membrane integrity simultaneously. The effects of amphiphiles partitioning into the lipid phase during water loss has been studied for pollen and seeds using electron paramagnetic resonance (EPR) spectroscopy. However, desiccation-tolerant high plants occur among mosses, several angiosperms and higher plants seeds or pollens. They have different strategies for survival in dehydration and rehydration. A desiccation-tolerant moss Tortula desertorurn was used to investigate the behaviors of amphiphilic molecules during drying by spin label technology. There are small amount of amphiphilic probes partitioning into membrane during moss leaves dehydration, comparing with that in higher plants. Cytoplasm viscosity changed from 1.14 into glass state only dehydration less than 60 min. Moss leaves lost plasma membrane integrity slightly,from 0.115 to 0.237, occurred simultaneously with amphiphiles partition. The results showed the more advantages of mosses than higher plants in adapting fast dehydration. We propose that EPR spin label is feasible for studying the amphiphiles partitioning mechanisms in membrane protection and damage for desiccation-tolerant mosses.(C) 2007 Yan Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

  12. Self-assembly of phosphate amphiphiles in mixtures of prebiotically plausible surfactants. (United States)

    Albertsen, A N; Duffy, C D; Sutherland, J D; Monnard, P-A


    The spontaneous formation of closed bilayer structures from prebiotically plausible amphiphiles is an essential requirement for the emergence of early cells on prebiotic Earth. The sources of amphiphiles could have been both endo- and exogenous (accretion of meteorite carbonaceous material or interstellar dust particles). Among all prebiotic possible amphiphile candidates, those containing phosphate are the least investigated species because their self-assembly occurs in a seemingly too narrow range of conditions. The self-assembly of simple phosphate amphiphiles should, however, be of great interest, as contemporary membranes predominantly contain phospholipids. In contrast to common expectations, we show that these amphiphiles can be easily synthesized under prebiotically plausible environmental conditions and can efficiently form bilayer structures in the presence of various co-surfactants across a large range of pH values. Vesiculation was even observed in crude reaction mixtures that contained 1-decanol as the amphiphile precursor. The two best co-surfactants promoted vesicle formation over the entire pH range in aqueous solutions. Expanding the pH range where bilayer membranes self-assemble and remain intact is a prerequisite for the emergence of early cell-like compartments and their preservation under fluctuating environmental conditions. These mixed bilayers also retained small charged solutes, such as dyes. These results demonstrate that alkyl phosphate amphiphiles might have played a significant role as early compartment building blocks.

  13. Synthesis of Polymerizable Amphiphiles with Systematic Variation of Critical Packing Parameters

    Institute of Scientific and Technical Information of China (English)

    M. H. Li; W. L. Yang; J. Qian; C. C. Wang; S. K. Fu


    @@ 1Introduction An amphiphile is a molecule composed of hydrophilic part and hydrophobic part, which are incompatible and tend to separate from each other. The tendency of separation is often promoted by addition of water and sometimes also oil. Under balanced conditions the mixtures form macroscopically homogeneous phases, including isotropic solution phases and liquid crystalline phases. Correlation of the amphiphile structure with its preferred phases could be understood with a simple geometric model[1], which defines a dimensionless Critical Packing Parameter (CPP) to describe the relative bulkiness of the hydrophobic part and the hydrophilic part in an amphiphile. With CPP increasing from a small value to a high value the amphiphile changes from hydrophilic to hydrophobic, its preferred phase structure from direct structures via lamellar structure to reverse structures. This model provides a basis for the molecular design of amphiphiles. To immobilize the microstructure of the phases formed by amphiphiles is a challenge for current material chemists. Techniques of both inorganic polymerization[2] and organic polymerization[3] have been developed. With organic polymerization the molecular design of polymerizable amphiphiles is critical for the successful immobilization of the vulnerable precursor microstructures.

  14. Gd-DTPA-Dopamine-Bisphytanyl Amphiphile: Synthesis, Characterisation and Relaxation Parameters of the Nanoassemblies and Their Potential as MRI Contrast Agents. (United States)

    Gupta, Abhishek; Willis, Scott A; Waddington, Lynne J; Stait-Gardner, Tim; de Campo, Liliana; Hwang, Dennis W; Kirby, Nigel; Price, William S; Moghaddam, Minoo J


    Here, a new amphiphilic magnetic resonance imaging (MRI) contrast agent, a Gd(III)-chelated diethylenetriaminepentaacetic acid conjugated to two branched alkyl chains via a dopamine spacer, Gd-DTPA-dopamine-bisphytanyl (Gd-DTPA-Dop-Phy), which is readily capable of self-assembling into liposomal nanoassemblies upon dispersion in an aqueous solution, is reported. In vitro relaxivities of the dispersions were found to be much higher than Magnevist, a commercially available contrast agent, at 0.47 T but comparable at 9.40 T. Analysis of variable temperature (17)O NMR transverse relaxation measurements revealed the water exchange of the nanoassemblies to be faster than that previously reported for paramagnetic liposomes. Molecular reorientation dynamics were probed by (1)H NMRD profiles using a classical inner and outer sphere relaxation model and a Lipari-Szabo "model-free" approach. High payloads of Gd(III) ions in the liposomal nanoassemblies made solely from the Gd-DTPA-Dop-Phy amphiphiles, in combination with slow molecular reorientation and fast water exchange makes this novel amphiphile a suitable candidate to be investigated as an advanced MRI contrast agent.

  15. Asymmetric and symmetric bolaform supra-amphiphiles: formation of imine bond influenced by aggregation. (United States)

    Wang, Guangtong; Wu, Guanglu; Wang, Zhiqiang; Zhang, Xi


    A series of bolaform supra-amphilphiles with different symmetries were fabricated through dynamic benzoic imine bond formation. The pH dependence of imine formations of these supra-amphiphiles were characterazied. We found that the extent of the imine formation of these supra-amphiphies were different. The supra-amphiphiles with a poorer symmetry always exhibited a lower imine formation at a given pH. Therefore, the varied extent of imine bond formation indicate the different aggregations of these supra-amphilphiles, which are controlled by the molecular symmetry of the supra-amphiphiles.

  16. Surfactant Behavior of Amphiphilic Polymer-Tethered Nanoparticles. (United States)

    Zhang, Yue; Zhao, Hanying


    In recent years, an emerging research area has been the surfactant behavior of polymer-tethered nanoparticles. In this feature article, we have provided a general introduction to the synthesis, self-assembly, and interfacial activity of polymer-tethered inorganic nanoparticles, polymer-tethered organic nanoparticles, and polymer-tethered natural nanoparticles. In addition, applications of the polymer-tethered nanoparticles in colloidal and materials science are briefly reviewed. All research demonstrates that amphiphilic polymer-tethered nanoparticles exhibit surfactant behavior and can be used as elemental building blocks for the fabrication of advanced structures by the self-assembly approach. The polymer-tethered nanoparticles provide new opportunities to engineer materials and biomaterials possessing specific functionality and physical properties.

  17. Stabilizing bolaform amphiphile interfacial assemblies by introducing mesogenic groups. (United States)

    Wang, Mingfeng; Qiu, Dengli; Zou, Bo; Wu, Tao; Zhang, Xi


    We describe the synthesis and characterization of the mesogen-bearing bolaform amphiphile 4,4'-dihydroxybiphenylbis(11-pyridinium-N-yl-undecanoic ester) dibromide (BP-10) and its solid/liquid interfacial self-assembly. Cylindrical micelles are directly observed by atomic force microscopy (AFM) at the interface between mica and the aqueous solution above the critical micelle concentration (cmc). In situ and ex situ AFM studies indicate that the cylindrical micelles are stable both at the mica/solution interface and in the dry state. The enhanced stability of the micellar structures enables a detailed investigation of their self-assembly behavior and supramolecular structures at the interface. The adsorption model proposed here is supported by the variation of the interfacial self-assemblies on changing the solution concentration and substrate temperature.

  18. Self-Assembly of Charged Amphiphilic Diblock Copolymers with Insoluble Blocks of Decreasing Hydrophobicity: From Kinetically Frozen Colloids to Macrosurfactants

    Energy Technology Data Exchange (ETDEWEB)

    M Jacquin; P Muller; H Cottet; O Theodoly


    We have investigated the self-assembly properties in aqueous solution of amphiphilic diblock copolymers with insoluble blocks of different hydrophobicity and demonstrated that the condition to obtain dynamic micelles is to design samples with insoluble blocks of low enough hydrophobicity. We focus here on results with new water-soluble amphiphilic diblock copolymers poly(diethyleneglycol ethylether acrylate)-b-poly(acrylic acid), or PDEGA-b-PAA. The physical characteristics of PDEGA-b-PAA micelles at high ionization have been determined by small angle neutron scattering (SANS). We show that PDEGA-b-PAA samples form micelles at thermodynamic equilibrium. The critical micelle concentrations (CMCs) decrease strongly with ionic strength and temperature due to a solvent quality decrease for, respectively, the corona and the core. This behavior of reversible aggregation is remarkable as compared to the behavior of kinetically frozen aggregation that has been widely observed with samples of similar architecture and different hydrophobic blocks, for example, poly(styrene)-b-poly(acrylic acid), PS-b-PAA, and poly(butyl acrylate)-b-poly(acrylic acid), PBA-b-PAA. We have measured the interfacial tension between water and the homopolymers PDEGA and PBA at, respectively, 3 and 20 mN/m at room temperature, which permits one to estimate the energy cost to extract a unimer from a micelle. The results are consistent with a micelle association that is fast for PDEGA-b-PAA and kinetically frozen PBA-b-PAA. Hence, PDEGA-b-PAA samples form a new system of synthetic charged macrosurfactant with unique properties of fast dynamic association, tunable charge, and water solubility even at temperatures and NaCl concentrations as high as 65 C and 1 M.

  19. Non-Surface Activity of Cationic Amphiphilic Diblock Copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Nayak, Rati Ranjan; Yamada, Tasuku; Matsuoka, Hideki, E-mail:, E-mail: [Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)


    Cationic amphiphilic diblock copolymers containing quaternized poly (2-vinylpyridine) chain as a hydrophilic segment (PIp-b-PNMe2VP) were synthesized by living anionic polymerization. By IR measurement, we confirmed the quaternization of the polymer (PIp-b-PNMe2VP), and determined the degree of quaternization by conductometric titration. The surface tension experiment showed that the polymers are non-surface active in nature. The foam formation of the polymer solutions was also investigated with or without added salt. Almost no foam formation behavior was observed without added salt, while a little foam was observed in the presence of 1M NaCl. The critical micelle concentration (cmc) of the diblock copolymers with 3 different chain lengths was measured by the static light scattering method. The cmc values obtained in this study were much lower than the values obtained for anionic non-surface active diblock polymers studied previously. The hydrodynamic radii of the polymer micelle increased slightly in the presence of 1 M NaCl. The transmission electron microscopic images revealed spherical micelles in pure water. In the presence of salt, the cmc values increased as was the case for anionic polymers, which is unlike conventional surfactant systems but consistent with non-surface active anionic block copolymers. The microviscosity of the micelle core was evaluated using Coumarin-153 as a fluorescent anisotropy probe using steady-sate fluorescence depolarization. Non-surface activity has been proved to be universal for ionic amphiphilic block copolymers both for anionic and cationic. Hence, the origin of non-surface activity is not the charged state of water surface itself, but should be an image charge repulsion at the air/water interface.

  20. Aminoglycoside-derived amphiphilic nanoparticles for molecular delivery. (United States)

    Miryala, Bhavani; Godeshala, Sudhakar; Grandhi, Taraka Sai Pavan; Christensen, Matthew D; Tian, Yanqing; Rege, Kaushal


    The development of effective drug carriers can lead to improved outcomes in a variety of disease conditions. Aminoglycosides have been used as antibacterial therapeutics, and are attractive as monomers for the development of polymeric materials in various applications. Here, we describe the development of novel aminoglycoside-derived amphiphilic nanoparticles for drug delivery, with an eye towards ablation of cancer cells. The aminoglycoside paromomycin was first cross-linked with resorcinol diglycidyl ether leading to the formation of a poly (amino ether), PAE. PAE molecules were further derivatized with methoxy-terminated poly(ethylene glycol) or mPEG resulting in the formation of mPEG-PAE polymer, which self-assembled to form nanoparticles. Formation of the mPEG-PAE amphiphile was characterized using (1)H NMR, (13)C NMR, gel permeation chromatography (GPC) and FTIR spectroscopy. Self-assembly of the polymer into nanoparticles was characterized using dynamic light scattering, zeta potential analyses, atomic force microscopy (AFM) and the pyrene fluorescence assay. mPEG-PAE nanoparticles were able to carry significant amounts of doxorubicin (DOX), presumably by means of hydrophobic interactions between the drug and the core. Cell-based studies indicated that mPEG-PAE nanoparticles, loaded with doxorubicin, were able to induce significant loss in viabilities of PC3 human prostate cancer, MDA-MB-231 human breast cancer, and MB49 murine bladder cancer cells; empty nanoparticles resulted in negligible losses of cell viability under the conditions investigated. Taken together, our results indicate that the mPEG-PAE nanoparticle platform is attractive for drug delivery in different applications, including cancer.

  1. Antifungal amphiphilic aminoglycoside K20: bioactivities and mechanism of action

    Directory of Open Access Journals (Sweden)

    Sanjib K. Shrestha


    Full Text Available K20 is a novel amphiphilic antifungal aminoglycoside that is synthetically derived from the antibiotic kanamycin A. Reported here are investigations of K20’s antimicrobial activities, cytotoxicity, and fungicidal mechanism of action. In vitro growth inhibitory activities against a variety of human and plant pathogenic yeasts, filamentous fungi, and bacteria were determined using microbroth dilution assays and time-kill curve analyses, and hemolytic and animal cell cytotoxic activities were determined. Effects on Cryptococcus neoformans H-99 infectivity were determined with a preventive murine lung infection model. The antifungal mechanism of action was studied using intact fungal cells, yeast lipid mutants, and small unilamellar lipid vesicles. K20 exhibited broad-spectrum in vitro antifungal activities but not antibacterial activities. Pulmonary, single dose-administration of K20 reduced C. neoformans lung infection rates 4-fold compared to controls. Hemolysis and half-maximal cytotoxicities of mammalian cells occurred at concentrations that were 10 to 32-fold higher than fungicidal MICs. With fluorescein isothiocyanate, 20 to 25 mg/L K20 caused staining of >95% of C. neoformans and Fusarium graminearum cells and at 31.3 mg/L caused rapid leakage (30 to 80% in 15 min of calcein from preloaded small unilamellar lipid vesicles. K20 appears to be a broad-spectrum fungicide, capable of reducing the infectivity of C. neoformans, and exhibits low hemolytic activity and mammalian cell toxicity. It perturbs the plasma membrane by mechanisms that are lipid modulated. K20 is a novel amphiphilic aminoglycoside amenable to scalable production and a potential lead antifungal for therapeutic and crop protection applications.

  2. Self-Assembly and Headgroup Effect in Nanostructured Organogels via Cationic Amphiphile-Graphene Oxide Composites (United States)

    Jiao, Tifeng; Wang, Yujin; Zhang, Qingrui; Yan, Xuehai; Zhao, Xiaoqing; Zhou, Jingxin; Gao, Faming


    Self-assembly of hierarchical graphene oxide (GO)-based nanomaterials with novel functions has received a great deal of attentions. In this study, nanostructured organogels based on cationic amphiphile-GO composites were prepared. The gelation behaviors of amphiphile-GO composites in organic solvents can be regulated by changing the headgroups of amphiphiles. Ammonium substituted headgroup in molecular structures in present self-assembled composites is more favorable for the gelation in comparison to pyridinium headgroup. A possible mechanism for headgroup effects on self-assembly and as-prepared nanostructures is proposed. It is believed that the present amphiphile-GO self-assembled system will provide an alternative platform for the design of new GO nanomaterials and soft matters. PMID:24983466

  3. Branched peptide amphiphiles, related epitope compounds and self assembled structures thereof (United States)

    Stupp, Samuel I.; Guler, Mustafa O.


    Branched peptide amphiphilic compounds incorporating one or residues providing a pendant amino group for coupling one or more epitope sequences thereto, such compounds and related compositions for enhanced epitope presentation.

  4. Self-assembling peptide amphiphiles and related methods for growth factor delivery (United States)

    Stupp, Samuel I.; Donners, Jack J. J. M.; Silva, Gabriel A.; Behanna, Heather A.; Anthony, Shawn G.


    Amphiphilic peptide compounds comprising one or more epitope sequences for binding interaction with one or more corresponding growth factors, micellar assemblies of such compounds and related methods of use.

  5. Amphiphilic organoplatinum(II) complexes: Self-assembly in solution and at interfaces (United States)

    Maran, Umamageswaran

    Organoplatinum(II) gemini amphiphiles with three different chain lengths and a predefined angle of 60° are synthesized. Self-organization at the air-water interface is investigated as a function of chain length and reduction in surface area, by using Langmuir-trough techniques. The atomic force microscopy (AFM) images of the transferred Langmuir-Schaefer (LS) films reveals wormlike aggregates for the organoplatinum(II) gemini amphiphiles, possessing hexyloxy- and dodecyloxy-chains. A neutral crown ether functionalized [1+1] facial amphiphile was self-assembled from a flexible 32-membered dibenzo crown ether and a diplatinum acceptor clip. A homologous series of charged triangle-shaped amphiphilic metallomacrocyles was self-assembled from stoichiometric amounts of organoplatinum(II) gemini amphiphiles and bipyridyl donor molecules in quantitative yields. The amphiphilic triangular scaffolds were characterized by multinuclear NMR and ESI-MS. A new amphiphilic organoplatinum(II) precursor with a predefined angle of 90° was synthesized. The precursor was mixed in stoichiometric ratios with two different 3-substituted pyridines and a rigid bipyridyl ligand to construct three charged amphiphilic metallomacrocyles. The computational calculations on the assemblies constructed from flexible 3-substituted pyridines indicate that the assemblies exist largely as chair isomers. The self-organization of the hexacationic triangular amphiphiles at liquid-liquid, air-water and solid-air interfaces was studied using confocal microscopy, in situ Raman spectroscopy, Langmuir-trough techniques, fluorescence spectroscopy and AFM. The amphiphilic triangle with octadecyloxy-chains was found to form a bicontinuous coacervate with pores in a chloroform/water solvent mixture. The pressure-area isotherms revealed formation of surface aggregates at the air-water interface. Fluid AFM studies on the transferred LS layers reveal ridge-like patterns with a flat top. Models were constructed to

  6. Formation of polymer vesicles by amphiphilic fluorosiloxane graft copolymers in solution

    Institute of Scientific and Technical Information of China (English)

    Rui Gang Hou; Ling Min Yi; He Ming Lin; Jia Wei Li; Chuan Xia Huang


    Amphiphilic fluorosiloxane graft copolymers with a poly(dimethylsiloxane) (PDMS) backbone, a hydrophobic fluorosiloxane side-chain and three hydrophilic polyether side-chains were synthesized by hydrosilation reaction in this work. The micellization of amphiphilic graft copolymers in the water/ethanol solvent system was investigated, and vesicles with different size were formed after the self-assembly system was aged for different time.

  7. Self-assembly of a peptide amphiphile: transition from nanotape fibrils to micelles


    Miravet Celades, Juan Felipe; Escuder Gil, Beatriu; Segarra Maset, María Dolores; Tena Solsona, Marta; Hamley, Ian W; Dehsorkhi, Ashkan; Castelletto, Valeria


    A thermal transition is observed in the peptide amphiphile C16-KTTKS (TFA salt) from nanotapes at 20 °C to micelles at higher temperature (the transition temperature depending on concentration). The formation of extended nanotapes by the acetate salt of this peptide amphiphile, which incorporates a pentapeptide from type I procollagen, has been studied previously [V. Castelletto et al., Chem. Commun., 2010, 46, 9185]. Here, proton NMR and SAXS provide evidence for the TFA salt spherical micel...

  8. Platform Approach to Produce Polymer Nanoparticles with Modular Functionality from Amphiphilic Block Copolymer Stabilizers (United States)


    functionality, an amphiphilic BCP scaffold was devised to serve as an emulsion polymerization stabilizer. The PS-b-P(EO-co-AGE) BCP contained a PS...synthesized via emulsion polymerization using an amphiphilic block copolymer (BCP) surfactant. The polystyrene-block-poly(ethylene oxide-co-allyl...glycidyl ether) BCPs with various lengths and functional monomer incorporation were synthesized using anionic polymerization . Modification of the allyl

  9. Self-assembling Characteristics of Amphiphilic Star Block Copolymers with a Polyelectrolyte Shell

    Institute of Scientific and Technical Information of China (English)

    S.Strandman; A.Zarembo; V.Aseyev; S.J.Butcher; H.Tenhu


    1 Results Amphiphilic block copolymers are capable of forming supramolecular assemblies resembling those observed in nature,such as spherical micelles,worm micelles,and vesicles.Changing the solvent composition,ionic strength or pH of the polymer solution may induce the self-assembly of block copolymers or trigger the transition between the geometries of noncovalent assemblies.In the current work,we have synthesised starlike amphiphilic block copolymers having hydrophobic poly(methyl methacrylate),PMMA,...

  10. Surface functionalization of carbon nanotubes by direct encapsulation with varying dosages of amphiphilic block copolymers (United States)

    Yao, Xueping; Li, Jie; Kong, Liang; Wang, Yong


    Encapsulation of carbon nanotubes (CNTs) by amphiphilic block copolymers is an efficient way to stabilize CNTs in solvents. However, the appropriate dosages of copolymers and the assembled structures are difficult to predict and control because of the insufficient understanding on the encapsulation process. We encapsulate multiwalled CNTs with polystyrene-block-poly (4-vinyl pyridine) (PS-b-P4VP) by directly mixing them in acetic acid under sonication. The copolymer forms a lamellar structure along the surface of CNTs with the PS blocks anchoring on the tube wall and the P4VP blocks exposed to the outside. The encapsulated CNTs achieve good dispersibility in polar solvents over long periods. To increase our understanding of the encapsulation process we investigate the assembled structures and stability of copolymer/CNTs mixtures with changing mass ratios. Stable dispersions are obtained at high mass ratios between the copolymer and CNTs, i.e. 2 or 3, with the presence of free spherical micelles. Transmission electron microscopy and thermal gravimetric analysis determine that the threshold for the complete coverage of CNTs by the copolymer occurs at the mass ratio of 1.5. The coated copolymer layer activates the surface of CNTs, enabling further functionalization of CNTs. For instance, atomic layer deposition of TiO2 produces conformal thin layers on the encapsulated CNTs while isolated TiO2 bumps are produced on the pristine, inert CNTs.

  11. Solvent-free, molecular-level modeling of self-assembling amphiphiles in water (United States)

    Dey, Somajit; Saha, Jayashree


    Aggregation mesophases of self-assembling amphiphiles in water are highly important in the context of biology (biomembranes), therapy (liposomes), industry (polymer surfactants), and condensed-matter physics (lyotropic liquid crystals). Besides helping to increase fundamental understanding of collective molecular behavior, simulations of these lyotropic phases are pivotal to technological and medical developments such as smart drug carriers for gene therapy. Implicit-solvent, coarse-grained, low resolution modeling with a simple pair potential is the key to realizing the larger length and time scales associated with such mesoscopic phenomena during a computer simulation. Modeling amphiphiles by directed, soft, ellipsoidal cores interacting via a computationally simple yet tunable anisotropic pair potential, we have come to such a single-site model amphiphile that can rapidly self-assemble to give diverse lyotropic phases (such as fluid bilayers, micelles, etc.) without requiring the explicit incorporation of solvent particles. The model directly represents a tunable packing parameter that manifests in the spontaneous curvature of the amphiphile aggregates. Besides the all-important hydrophobic interaction, the hydration force is also treated implicitly. Thanks to the efficient solvent-free molecular-level coarse graining, this model is suitable for generic mesoscale studies of phenomena such as self-assembly, amphiphile mixing, domain formation, fusion, elasticity, etc., in amphiphile aggregates.

  12. Preparation of plasmonic vesicles from amphiphilic gold nanocrystals grafted with polymer brushes (United States)

    Song, Jibin; Huang, Peng; Chen, Xiaoyuan


    Gold nanovesicles contain multiple nanocrystals within a polymeric coating. The strong plasmonic coupling between adjacent nanoparticles in their vesicular shell makes ultrasensitive biosensing and bioimaging possible. In our laboratory, multifunctional plasmonic vesicles are assembled from amphiphilic gold nanocrystals (such as gold nanoparticles and gold nanorods) coated with mixed hydrophilic and hydrophobic polymer brushes or amphiphilic diblock co-polymer brushes. To fulfill the different requirements of biomedical applications, different polymers that are either pH=responsive, photoactive or biodegradable can be used to form the hydrophobic brush, while the hydrophilicity is maintained by polyethylene glycol (PEG). This protocol covers the preparation, surface functionalization and self-assembly of amphiphilic gold nanocrystals grafted covalently with polymer brushes. The protocol can be completed within 2 d. The preparation of amphiphilic gold nanocrystals, coated with amphiphilic diblock polymer brushes using a ‘grafting to’ method or mixed hydrophilic and hydrophobic polymer brushes using tandem ‘grafting to’ and ‘grafting from’ methods, is described. We also provide detailed procedures for the preparation and characterization of pH-responsive plasmonic gold nanovesicles from amphiphilic gold nanocrystals using a film-rehydration method that can be completed within ~3 d. PMID:27763624

  13. Self-assembly of amphiphilic molecules in organic liquids (United States)

    Tung, Shih-Huang


    Amphiphilic molecules are well-known for their ability to self-assemble in water to form structures such as micelles and vesicles. In comparison, much less is known about amphiphilic self-assembly in nonpolar organic liquids. Such "reverse" self assembly can produce many of the counterparts to structures found in water. In this dissertation, we focus on the formation and dynamics of such reverse structures. We seek to obtain fundamental insight into the driving forces for reverse self-assembly processes. Three specific types of reverse structures are studied: (a) reverse wormlike micelles, i.e., long, flexible micellar chains; (b) reverse vesicles, i.e., hollow containers enclosed by reverse bilayers; and (c) organogel networks. While our focus is on the fundamentals, we note that reverse structures can be useful in a variety of applications ranging from drug delivery, controlled release, hosts for enzymatic reactions, and templates for nanomaterials synthesis. In the first part of this study, we describe a new route for forming reverse wormlike micelles in nonpolar organic liquids. This route involves the addition of trace amounts of a bile salt to solutions of the phospholipid, lecithin. We show that bile salts, due to their unique "facially amphiphilic" structure, can promote the aggregation of lecithin molecules into these reverse micellar chains. The resulting samples are viscoelastic and show interesting rheological properties. Unusual trends are seen in the temperature dependence of their rheology, which indicates the importance of hydrogen-bonding interactions in the formation of these micelles. Another remarkable feature of their rheology is the presence of strain-stiffening, where the material becomes stiffer at high deformations. Strain-stiffening has been seen before for elastic gels of biopolymers; here, we demonstrate the same properties for viscoelastic micellar solutions. The second reverse aggregate we deal with is the reverse vesicle. We present a

  14. Synthesis of antibacterial amphiphilic elastomer based on polystyrene-block-polyisoprene-block-polystyrene via thiol-ene addition

    Energy Technology Data Exchange (ETDEWEB)

    Keleş, Elif, E-mail: [Department of Chemistry, Bülent Ecevit University, Zonguldak 67100 (Turkey); Hazer, Baki, E-mail: [Department of Chemistry, Bülent Ecevit University, Zonguldak 67100 (Turkey); Cömert, Füsun B. [Department of Microbiology, Faculty of Medicine, Bülent Ecevit University, 67600 Zonguldak (Turkey)


    A new type of amphiphilic antibacterial elastomer has been described. Thermoplastic elastomer, polystyrene–block-polyisoprene–block-polystyrene (PS–b-PI–b-PS) triblock copolymer was functionalized in toluene solution by free radical mercaptan addition in order to obtain an amphiphilic antibacterial elastomer. Thiol terminated PEG was grafted through the double bonds of PS–b-PI–b-PS via free radical thiol-ene coupling reaction. The antibacterial properties of the amphiphilic graft copolymers were observed. The original and the modified polymers were used to create microfibers in an electro-spinning process. Topology of the electrospun micro/nanofibers were studied by using scanning electron microscopy (SEM). The chemical structures of the amphiphilic comb type graft copolymers were elucidated by the combination of elemental analysis, {sup 1}H NMR, {sup 13}C NMR, GPC and FTIR. - Graphical abstract: Double bonds of polyisoprene units in polystyrene–block-polyisoprene–block-polystyrene triblock copolymer were partially capped with PEG containing mercapto end group via thiol-ene addition in order to obtain antibacterial amphiphilic elastomer. Nano fibers from amphiphilic graft polymers solution were produced by electrospinning. The PEG grafted copolymer inhibits very effectively bacterial growth. Highlights: ► A commercial synthetic elastomer was grafted with PEG to obtain amphiphilic elastomer. ► Amphiphilic elastomer shows antibacterial properties. ► Electrospun micro fibers of the amphiphilic elastomer tend to globular formation.

  15. Langmuir monolayer and Langmuir-Blodgett films formed by a melamine-headed azobenzene-derived amphiphile: interfacial assembly affected by host-guest interaction. (United States)

    Xu, Weihong; Wang, Yanhua; Xiao, Yunxia; Liu, Fang; Lu, Guo-Yuan


    A novel azobenzene-derived amphiphile with a melamine head, 2Azo-2C12H2-melamine, has been synthesized. pi-A isotherm measurements displayed that this amphiphile is able to form a stable Langmuir monolayer on both pure water and barbituric acid (BA)- or thymine (T)-containing subphases. The collapse surface pressure and limiting molecular area of its Langmuir monolayer on pure water are 40 mN/m and 0.56 nm2, respectively. However, when barbituric acid or thymine was introduced into the subphase, the corresponding pi-A isotherms of the monolayers exhibited a lower collapse surface pressure (22 mN/m for BA, 21 mN/m for T) and smaller limiting molecular area (0.54 nm2 for BA and 0.52 nm2 for T). UV-vis and FT-IR studies of the LB films formed by 2Azo-2C12H25-melamine have also been carried out. The results indicated that the LB films of 2Azo-2C12H25-melamine deposited from pure water undergo distinct collapse of the H-aggregate upon UV irradiation, while the LB films deposited from a BA- or T-containing subphase retain the H-aggregate. The host-guest-interaction-induced blockage of azobenzene photoisomerization should be responsible for the stabilized H-aggregate. A 1:1 host/guest binding mode to form a linear supramolecular polymeric chain has been proposed in the Langmuir monolayers formed on a BA- or T-containing subphase. The current results suggest that the host-guest interaction should be an effective means to manipulate the interfacial assembly of azobenzene-derived amphiphiles.

  16. Anti-biofouling properties of amphiphilic phosphorylcholine polymer films. (United States)

    Li, Yan; Liu, Cheng-Mei; Yang, Jin-Ying; Gao, Ya-Hui; Li, Xue-Song; Que, Guo-He; Lu, J R


    Surfaces of amphiphilic phosphorylcholine polymer (PC1036) prepared by spin-coating were characterized by spectroscopic ellipsometry, water contact angle and atomic force microscopy. The antifouling properties of the PC1036 films to marine benthic diatom Nitzschia closterium MMDL533 were also investigated. The results showed that the dry PC1036 film promoted the adhesion of N. closterium MMDL533 because the hydrophobic lauryl groups were present in the film surface. The 2 h-swelled PC1036 films had excellent anti-fouling properties with extremely low attachment densities and retention densities no matter what the annealing temperature was. The thickness of the coated films lower than 147 Å had a profound effect on the film anti-fouling properties. Otherwise, when the film thickness was higher than that value, there was no more improvement of diatom cell reduction observed. The annealing temperature had only a little effect on the film resistant to diatom adhesion, which might be attributed to two factors including the PC group packing densities in the outer PC layer and the equilibrated water volume fraction in the 2 h-swelled PC1036 films.

  17. Effect of Amphiphiles on the Rheology of Triglyceride Networks (United States)

    Seth, Jyoti


    Networks of aggregated crystallites form the structural backbone of many products from the food, cosmetic and pharmaceutical industries. Such materials are generally formulated by cooling a saturated solution to yield the desired solid fraction. Crystal nucleation and growth followed by aggregation leads to formation of a space percolating fractal-network. It is understood that microstructural hierarchy and particle-particle interactions determine material behavior during processing, storage and use. In this talk, rheology of suspensions of triglycerides (TAG, like tristearin) will be explored. TAGs exhibit a rich assortment of polymorphs and form suspensions that are evidently sensitive to surface modifying additives like surfactants and polymers. Here, a theoretical framework will be presented for suspensions containing TAG crystals interacting via pairwise potentials. The work builds on existing models of fractal aggregates to understand microstructure and its correlation with material rheology. Effect of amphiphilic additives is derived through variation of particle-particle interactions. Theoretical predictions for storage modulus will be compared against experimental observations and data from the literature and micro structural predictions against microscopy. Such a theory may serve as a step towards predicting short and long-term behavior of aggregated suspensions formulated via crystallization.

  18. Self-assembly of model amphiphilic Janus particles. (United States)

    Rosenthal, Gerald; Gubbins, Keith E; Klapp, Sabine H L


    We apply molecular dynamics simulations to investigate the structure formation of amphiphilic Janus particles in the bulk phase. The Janus particles are modeled as (soft) spheres composed of a hydrophilic and hydrophobic part. Their orientation is described by a vector representing an internal degree of freedom. Investigating energy fluctuations and cluster size distributions, we determine the aggregation line in a temperature-density-diagram, where the reduced temperature is an inverse measure for the anisotropic coupling. Below this aggregation line clusters of various sizes depending on density and reduced temperature are found. For low densities in the range ρ∗ ≤ 0.3, the cluster size distribution has a broad maximum, indicating simultaneous existence of various cluster sizes between 5 and 10. We find no hint of a condensation transition of these clustered systems. In the case of higher densities (ρ∗ = 0.5 and 0.6), the cluster size distribution shows an extremely narrow peak at clusters of size 13. In these icosahedrons, the particles are arranged in a closed-packed manner, thereby maximizing the number of bonds. Analyzing the translational mean-square displacement we also observe indications of hindered diffusion due to aggregation.

  19. Preparation and self-assembly of amphiphilic polylysine dendrons

    DEFF Research Database (Denmark)

    Mirsharghi, Sahar; Knudsen, Kenneth D.; Bagherifam, Shahla


    Polylysine dendrons with lipid tails prepared by divergent solid-phase synthesis showed self-assembling properties in aqueous solutions., Herein, we present the synthesis of new amphiphilic polylysine dendrons with variable alkyl chain lengths (C1–C18) at the C-terminal. The dendrons were synthes...... and 20 μM concentrations. The dendrons showed low cytotoxicity, displaying cell viability well above 80%....... were influenced by the length of the alkyl chain and the generation number (Gn). Increasing the temperature and concentration did not have significant impact on the hydrodynamic diameter, but the self-assembling properties were influenced by the pH value. This demonstrated the need for positively...... with alkyl chain lengths above C12 are ascribed to intermicellar aggregates stabilized by hydrophobic and electrostatic forces in accordance with the observed pH effect. Finally, the cytotoxicity of the dendrons was evaluated in mouse fibroblast (NIH/3T3) and human embryonic kidney (HEK 293T) cells at 5, 10...

  20. Tissue Regeneration through Self-Assembled Peptide Amphiphile Nanofibers

    Directory of Open Access Journals (Sweden)

    Hossein Hosseinkhani


    Full Text Available Introduction: In the present study, we hypothesized that a novelapproach to promote vascularization would be to create injectablethree dimensional (3-D scaffolds within growth factor that enhancethe sustained release of growth factor and induce the angiogenesis.Material and Methods: We demonstrate that a 3-D scaffold can beformed by mixing of peptide-amphiphile (PA aqueous solution withhepatocyte growth factor (HGF solution. PA was synthesized bystandard solid phase chemistry that ends with the alkylation of theNH2 terminus of the peptide. The sequence of arginine-glycineasparticacid (RGD was included in peptide design as well. A 3-Dnetwork of nanofibers was formed by mixing HGF suspensions withdilute aqueous solution of PA.Results: Scanning electron microscopy (SEM examination revealedthe formation of fibrous assemblies with an extremely high aspectratio and high surface areas with mean diameter of less than 200 nm.In vitro HGF release profile of 3-D nanofibers was investigated whileangiogenesis induced by the released HGF was being assessed. Invivo potential ability of PA nanofibers to induce angiogenesis wasassessed through subcutaneous injection of PA solution, HGFsolution, and PA in combination with HGF solutions. Injection of PAwith HGF induced significant angiogenesis around the injected site,in marked contrast to HGF injection alone and PA injection alone.Conclusion: The combination of HGF-induced angiogenesis is apromising procedure to improve tissue regeneration.

  1. Amphiphilic organic ion pairs in solution: a theoretical study. (United States)

    Pradines, Vincent; Poteau, Romuald; Pimienta, Veronique


    The macroscopic manifestation of hydrophobic interactions for amphiphilic organic ion pairs (tetraalkylammonium-anion) has been shown experimentally by measuring their association constants and their affinity with the organic phase. Beyond a certain size, there is a direct relation between association constants and chain lengths in tetraalkylammonium ions. We propose to cast a bridge between these results and geometrical properties considered at the level of a single ion pair by means of quantum chemistry calculations performed on model systems: trimethylalkylammonium-pentyl sulfate instead of tetraalkylammonium-dodecyl sulfate. Two limiting cases are considered: head-to-head configurations, which yield an optimal electrostatic interaction between polar heads, and parallel configurations with a balance between electrostatic and hydrophobic interactions. All properties (geometries, complexation energies, and atomic charges) were obtained at the MP2 level of calculation, with water described by a continuum model (CPCM). Dispersion forces link hydrocarbon chains of tetraalkylammonium ions and pentyl sulfate, thus yielding (for the largest ion pairs) parallel configurations favored with respect to head-to-head geometries by solute-solvent electrostatic interactions. Given the small experimental association energies, we probe the accuracy limit of the MP2 and CPCM methods. However, clear trends are obtained as a function of chain length, which agree with the experimental observations. The calculated monotonic stabilization of ion pairs when the hydrocarbon chain increases in length is discussed in terms of electrostatic interactions (between ions and between ion pairs and water), dispersion forces, and cavitation energies.

  2. Photochemical Isomerization and Topochemical Polymerization of the Programmed Asymmetric Amphiphiles (United States)

    Kim, Dae-Yoon; Lee, Sang-A.; Jung, Daseal; Jeong, Kwang-Un


    For the advancement in multi-stimuli responsive optical devices, we report the elaborate molecular engineering of the dual photo-functionalized amphiphile (abbreviated as AZ1DA) containing both a photo-isomerizable azobenzene and a photo-polymerizable diacetylene. To achieve the efficient photochemical reactions in thin solid films, the self-assembly of AZ1DA molecules into the ordered phases should be precisely controlled and efficiently utilized. First, the remote-controllable light shutter is successfully demonstrated based on the reversible trans-cis photo-isomerization of azobenzene group in the smectic A mesophase. Second, the self-organized monoclinic crystal phase allows us to validate the photo-polymerization of diacetylene moiety for the photo-patterned thin films and the thermo-responsible color switches. From the demonstrations of optically tunable thin films, it is realized that the construction of strong relationships between chemical structures, molecular packing structures and physical properties of the programmed molecules is the core research for the development of smart and multifunctional soft materials.

  3. Dynamic in vivo biocompatibility of angiogenic peptide amphiphile nanofibers. (United States)

    Ghanaati, Shahram; Webber, Matthew J; Unger, Ronald E; Orth, Carina; Hulvat, James F; Kiehna, Sarah E; Barbeck, Mike; Rasic, Angela; Stupp, Samuel I; Kirkpatrick, C James


    Biomaterials that promote angiogenesis have great potential in regenerative medicine for rapid revascularization of damaged tissue, survival of transplanted cells, and healing of chronic wounds. Supramolecular nanofibers formed by self-assembly of a heparin-binding peptide amphiphile and heparan sulfate-like glycosaminoglycans were evaluated here using a dorsal skinfold chamber model to dynamically monitor the interaction between the nanofiber gel and the microcirculation, representing a novel application of this model. We paired this model with a conventional subcutaneous implantation model for static histological assessment of the interactions between the gel and host tissue. In the static analysis, the heparan sulfate-containing nanofiber gels were found to persist in the tissue for up to 30 days and revealed excellent biocompatibility. Strikingly, as the nanofiber gel biodegraded, we observed the formation of a de novo vascularized connective tissue. In the dynamic experiments using the dorsal skinfold chamber, the material again demonstrated good biocompatibility, with minimal dilation of the microcirculation and only a few adherent leukocytes, monitored through intravital fluorescence microscopy. The new application of the dorsal skinfold model corroborated our findings from the traditional static histology, demonstrating the potential use of this technique to dynamically evaluate the biocompatibility of materials. The observed biocompatibility and development of new vascularized tissue using both techniques demonstrates the potential of these angiogenesis-promoting materials for a host of regenerative strategies.

  4. Self-assembly of ssDNA-amphiphiles into micelles, nanotapes and nanotubes (United States)

    Pearce, Timothy R.

    The field of DNA nanotechnology utilizes DNA as a construction material to create functional supramolecular and multi-dimensional structures like two-dimensional periodic lattices and three-dimensional polyhedrons with order on the nanometer scale for many nanotechnology applications including molecular templating, nanosensors, and drug delivery. Single-stranded DNA (ssDNA) is often used to create these nanostructures as the DNA bases provide an intrinsic molecular code that can be exploited to allow for the programmed assembly of structures based upon Watson-Crick base-pairing. However, engineering these complex structures from biopolymers alone requires careful design to ensure that the intrinsic forces responsible for organizing the materials can produce the desired structures. Additional control over supramolecular assembly can be achieved by chemically modifying the ssDNA with hydrophobic moieties to create amphiphilic molecules, which adds the hydrophobic interaction to the list of contributing forces that drive the self-assembly process. We first explored the self-assembly behavior of a set of ssDNA aptamer-amphiphiles composed of the same hydrophobic tail and hydrophilic ssDNA aptamer headgroup but with different spacer molecules linking these groups together. Through the use of cryo-transmission electron microscopy (cryo-TEM), small angle x-ray scattering (SAXS), and circular dichroism (CD) we show that the aptamer-amphiphiles can assemble into a variety of structures depending on the spacer used. We demonstrated, for the first time, the creation of self-assembled aptamer-amphiphile nanotape structures and show that the choice of the spacer used in the design of aptamer-amphiphiles can influence their supramolecular self-assembly as well as the secondary structure of the aptamer headgroup. We next explored the role of the ssDNA headgroup on the amphiphile self-assembly behavior by designing amphiphiles with headgroups of multiple lengths and nucleotides

  5. Bile acids, farnesoid X receptor, atherosclerosis and metabolic control

    NARCIS (Netherlands)

    Kuipers, Folkert; Stroeve, Johanna H. M.; Caron, Sandrine; Staels, Bart


    Purpose of review Bile acids are amphiphilic molecules synthesized from cholesterol exclusively in the liver that are essential for effective absorption of dietary fat. In addition to this classical role', bile acids act as signalling molecules that control their own metabolism by activating the nuc

  6. Amphiphilic Janus gold nanoparticles prepared by interface-directed self-assembly: synthesis and self-assembly. (United States)

    Liu, Guannan; Tian, Jia; Zhang, Xu; Zhao, Hanying


    Materials with Janus structures are attractive for wide applications in materials science. Although extensive efforts in the synthesis of Janus particles have been reported, the synthesis of sub-10 nm Janus nanoparticles is still challenging. Herein, the synthesis of Janus gold nanoparticles (AuNPs) based on interface-directed self-assembly is reported. Polystyrene (PS) colloidal particles with AuNPs on the surface were prepared by interface-directed self-assembly, and the colloidal particles were used as templates for the synthesis of Janus AuNPs. To prepare colloidal particles, thiol-terminated polystyrene (PS-SH) was dissolved in toluene and citrate-stabilized AuNPs were dispersed in aqueous solution. Upon mixing the two solutions, PS-SH chains were grafted to the surface of AuNPs and amphiphilic AuNPs were formed at the liquid-liquid interface. PS colloidal particles decorated with AuNPs on the surfaces were prepared by adding the emulsion to excess methanol. On the surface, AuNPs were partially embedded in the colloidal particles. The outer regions of the AuNPs were exposed to the solution and were functionalized through the grafting of atom-transfer radical polymerization (ATRP) initiator. Poly[2-(dimethamino)ethyl methacrylate] (PDMAEMA) on AuNPs were prepared by surface-initiated ATRP. After centrifugation and dissolving the colloidal particles in tetrahydrofuran (THF), Janus AuNPs with PS and PDMAEMA on two hemispheres were obtained. In acidic pH, Janus AuNPs are amphiphilic and are able to emulsify oil droplets in water; in basic pH, the Janus AuNPs are hydrophobic. In mixtures of THF/methanol at a volume ratio of 1:5, the Janus AuNPs self-assemble into bilayer structures with collapsed PS in the interiors and solvated PDMAEMA at the exteriors of the structures.

  7. Self-assembly of amphiphilic janus particles into monolayer capsules for enhanced enzyme catalysis in organic media. (United States)

    Cao, Wei; Huang, Renliang; Qi, Wei; Su, Rongxin; He, Zhimin


    Encapsulation of enzymes during the creation of an emulsion is a simple and efficient route for enhancing enzyme catalysis in organic media. Herein, we report a capsule with a shell comprising a monolayer of silica Janus particles (JPs) (referred to as a monolayer capsule) and a Pickering emulsion for the encapsulation of enzyme molecules for catalysis purposes in organic media using amphiphilic silica JPs as building blocks. We demonstrate that the JP capsules had a monolayer shell consisting of closely packed silica JPs (270 nm). The capsules were on average 5-50 μm in diameter. The stability of the JP capsules (Pickering emulsion) was investigated with the use of homogeneous silica nanoparticles as a control. The results show that the emulsion stabilized via amphiphilic silica JPs presented no obvious changes in physical appearance after 15 days, indicating the high stability of the emulsions and JP capsules. Furthermore, the lipase from Candida sp. was chosen as a model enzyme for encapsulation within the JP capsules during their formation. The catalytic performance of lipase was evaluated according to the esterification of 1-hexanol with hexanoic acid. It was found that the specific activity of the encapsulated enzymes (28.7 U mL(-1)) was more than 5.6 times higher than that of free enzymes in a biphasic system (5.1 U mL(-1)). The enzyme activity was further increased by varying the volume ratio of water to oil and the JPs loadings. The enzyme-loaded capsule also exhibited high stability during the reaction process and good recyclability. In particular, the jellification of agarose in the JP capsules further enhanced their operating stability. We believe that the monolayer structure of the JP capsules, together with their high stability, rendered the capsules to be ideal enzyme carriers and microreactors for enzyme catalysis in organic media because they created a large interfacial area and had low mass transfer resistance through the monolayer shell.

  8. DNA nanotubes and helical nanotapes via self-assembly of ssDNA-amphiphiles. (United States)

    Pearce, Timothy R; Kokkoli, Efrosini


    DNA nanotubes were created using molecular self-assembly of single-stranded DNA (ssDNA)-amphiphiles composed of a hydrophobic dialkyl tail and polycarbon spacer and a hydrophilic ssDNA headgroup. The nanotube structures were formed by bilayers of amphiphiles, with the hydrophobic components forming an inner layer that was shielded from the aqueous solvent by an outer layer of ssDNA. The nanotubes appeared to form via an assembly process that included transitions from twisted nanotapes to helical nanotapes to nanotubes. Amphiphiles that contained different ssDNA headgroups were created to explore the effect of the length and secondary structure of the ssDNA headgroup on the self-assembly behavior of the amphiphiles in the presence and absence of the polycarbon spacer. It was found that nanotubes could be formed using a variety of headgroup lengths and sequences. The ability to create nanotubes via ssDNA-amphiphile self-assembly offers an alternative to the other purely DNA-based approaches like DNA origami and DNA tile assembly for constructing these structures and may be useful for applications in drug delivery, biosensing, and electronics.

  9. Cationic Amphiphiles Increase Activity of Aminoglycoside Antibiotic Tobramycin in the Presence of Airway Polyelectrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Purdy Drew, Kirstin R.; Sanders, Lori K.; Culumber, Zachary W.; Zribi, Olena; Wong, Gerard C.L.; (UIUC)


    It is empirically known that anionic polyelectrolytes present in cystic fibrosis (CF) airways due to bacterial infection significantly decrease the activity of cationic antimicrobials via electrostatic binding. In this work, we use synchrotron small-angle X-ray scattering to investigate the interaction between tobramycin, an aminoglycoside antibiotic commonly administered to CF patients via inhalation, with DNA, which is found in high concentrations in the CF airway. We find that interactions between DNA and tobramycin are significantly modified by the presence of mixtures of amphiphilic molecules. We measure a hierarchy of self-assembled structures formed between tobramycin, DNA, and the amphiphile mixtures and show how interactions between these components can be controlled. Results indicate that mixtures of cationic and negative curvature amphiphiles optimized for DNA binding via charge matching and curvature matching can competitively displace bound tobramycin from DNA and thereby drastically suppress tobramycin-DNA binding and resultant antimicrobial inactivation. Growth inhibition assays confirm the increased activity of tobramycin in the presence of DNA with the addition of the amphiphiles. These results suggest that optimized cationic amphiphile solutions have the potential to enhance antimicrobial function in highly infected environments that contain increased concentrations of anionic inflammatory polymers.

  10. Cationic Amphiphiles Increase Activity of Aminoglycoside Antibiotic Tobramycin in the Presence of Airway Polyelectrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Drew, K.R.Purdy; Sanders, L.K.; Culumber, Z.W.; Zribi, O.; Wong, G.C.L.


    It is empirically known that anionic polyelectrolytes present in cystic fibrosis (CF) airways due to bacterial infection significantly decrease the activity of cationic antimicrobials via electrostatic binding. In this work, we use synchrotron small-angle X-ray scattering to investigate the interaction between tobramycin, an aminoglycoside antibiotic commonly administered to CF patients via inhalation, with DNA, which is found in high concentrations in the CF airway. We find that interactions between DNA and tobramycin are significantly modified by the presence of mixtures of amphiphilic molecules. We measure a hierarchy of self-assembled structures formed between tobramycin, DNA, and the amphiphile mixtures and show how interactions between these components can be controlled. Results indicate that mixtures of cationic and negative curvature amphiphiles optimized for DNA binding via charge matching and curvature matching can competitively displace bound tobramycin from DNA and thereby drastically suppress tobramycin-DNA binding and resultant antimicrobial inactivation. Growth inhibition assays confirm the increased activity of tobramycin in the presence of DNA with the addition of the amphiphiles. These results suggest that optimized cationic amphiphile solutions have the potential to enhance antimicrobial function in highly infected environments that contain increased concentrations of anionic inflammatory polymers.

  11. In vitro drug release and biological evaluation of biomimetic polymeric micelles self-assembled from amphiphilic deoxycholic acid–phosphorylcholine–chitosan conjugate

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Minming; Guo, Kai; Dong, Hongwei; Zeng, Rong, E-mail:; Tu, Mei; Zhao, Jianhao


    Novel biomimetic amphiphilic chitosan derivative, deoxycholic acid–phosphorylcholine–chitosan conjugate (DCA–PCCs) was synthesized based on the combination of Atherton–Todd reaction for coupling phosphorylcholine (PC) and carbodiimide coupling reaction for linking deoxycholic acid (DCA) to chitosan. The chemical structure of DCA–PCCs was characterized by {sup 1}H and {sup 31}P nuclear magnetic resonance (NMR). The self-assembly of DCA–PCCs in water was analyzed by fluorescence measurements, dynamic laser light-scattering (DLS), zeta potential and transmission electron microscopy (TEM) technologies. The results confirmed that the amphiphilic DCA–PCCs can self-assemble to form nanosized spherical micelles with biomimetic PC shell. In vitro biological evaluation revealed that DCA–PCCs micelles had low toxicity against NIH/3T3 mouse embryonic fibroblasts as well as good hemocompatibility. Using quercetin as a hydrophobic model drug, drug loading and release study suggested that biomimetic DCA–PCCs micelles could be used as a promising nanocarrier avoiding unfavorable biological response for hydrophobic drug delivery applications. - Highlights: • DCA–PCCs with phosphorylcholine and deoxycholic acid was synthesized. • DCA–PCCs can self-assemble to form spherical micelles in aqueous system. • DCA–PCCs micelles had excellent cytocompatibility and hemocompatibility. • DCA–PCCs micelles loaded with quercetin exhibited a sustained drug release behavior.

  12. Membrane behavior as influenced by partitioning of amphiphiles during drying : a comparative study in anhydrobiotic plant systems

    NARCIS (Netherlands)

    Golovina, E.A.; Hoekstra, F.A.


    During cellular desiccation, reduction in volume can in principle cause amphiphilic compounds to partition from the cytoplasm into membranes, with structural perturbance as the result. Here, we studied the effect of partitioning of endogenous amphiphiles on membrane surface dynamics in desiccation-t

  13. Colloidosomes formed by nonpolar/polar/nonpolar nanoball amphiphiles. (United States)

    Chang, Hung-Yu; Tu, Sheng-Hung; Sheng, Yu-Jane; Tsao, Heng-Kwong


    Fullerene-based amphiphiles are able to form bilayer vesicles in aqueous solution. In this study, the self-assembly behavior of polymer-tethered nanoballs (NBs) with nonpolar/polar/nonpolar (n-p-n') motif in a selective solvent is investigated by dissipative particle dynamics. A model NB bears two hydrophobic polymeric arms (n'-part) tethered on an extremely hydrophobic NB (n-part) with hydrophilic patch (p-part) patterned on its surface. Dependent on the hydrophobicity and length of tethered arms, three types of aggregates are exhibited, including NB vesicle, core-shell micelle, and segmented-worm. NB vesicles are developed for a wide range of hydrophobic arm lengths. The presence of tethered arms perturbs the bilayer structure formed by NBs. The structural properties including the order parameter, membrane thickness, and area density of the inner leaflet decrease with increasing the arm length. These results indicate that for NBs with longer arms, the extent of interdigitation in the membrane rises so that the overcrowded arms in the inner corona are relaxed. The transport and mechanical properties are evaluated as well. As the arm length grows, the permeability increases significantly because the steric bulk of tethered arms loosens the packing of NBs. By contrast, the membrane tension decreases owing to the reduction of NB/solvent contacts by the polymer corona. Although fusion can reduce membrane tension, NB vesicles show strong resistance to fusion. Moreover, the size-dependent behavior observed in small liposomes is not significant for NB vesicles due to isotropic geometry of NB. Our simulation results are consistent with the experimental findings.

  14. Aggregation behaviour of amphiphilic cyclodextrins: the nucleation stage by atomistic molecular dynamics simulations (United States)

    Mazzaglia, Antonino; Ganazzoli, Fabio


    Summary Amphiphilically modified cyclodextrins may form various supramolecular aggregates. Here we report a theoretical study of the aggregation of a few amphiphilic cyclodextrins carrying hydrophobic thioalkyl groups and hydrophilic ethylene glycol moieties at opposite rims, focusing on the initial nucleation stage in an apolar solvent and in water. The study is based on atomistic molecular dynamics methods with a “bottom up” approach that can provide important information about the initial aggregates of few molecules. The focus is on the interaction pattern of amphiphilic cyclodextrin (aCD), which may interact by mutual inclusion of the substituent groups in the hydrophobic cavity of neighbouring molecules or by dispersion interactions at their lateral surface. We suggest that these aggregates can also form the nucleation stage of larger systems as well as the building blocks of micelles, vesicle, membranes, or generally nanoparticles thus opening new perspectives in the design of aggregates correlating their structures with the pharmaceutical properties. PMID:26734094

  15. Enthalpy of interaction and binding isotherms of non-ionic surfactants onto micellar amphiphilic polymers (amphipols). (United States)

    Diab, C; Winnik, F M; Tribet, C


    The interactions in water between short amphiphilic macromomolecules, known as amphipols, and three neutral surfactants (detergents), dodecylmaltoside (DM), n-octylthioglucoside (OTG), and n-octyltetraethyleneoxide (C8E4), have been assessed by static and dynamic light-scattering (SLS and DLS), capillary electrophoresis (CE), and isothermal titration calorimetry (ITC). The amphipols selected are random copolymers of the hydrophobic n-octylacrylamide (25-30 mol %), a charged hydrophilic monomer, either acrylic acid ( approximately 35 mol %) or a phosphorylcholine-modified acrylamide (40-70 mol %), and, optionally, N-isopropylacrylamide (30-40 mol %). In water, the copolymers form micelles of small size (hydrodynamic radius: approximately 5 nm). Neutral surfactants, below their critical micellar concentration (cmc), form mixed micelles with the amphipols irrespective of the chemical structure of the detergent or the polymer. The fraction of detergent in the surfactant/polymer complexes increases significantly (cooperatively) as the surfactant concentration nears the cmc. The ITC data, together with data gathered by CE, were fitted via a regular mixing model, which allowed us to predict the detergent concentration in equilibrium with complexes and the heat evolved upon transfer of detergent from water into a mixed surfactant/polymer complex. The enthalpy of transfer was found to be almost equal to the enthalpy of micellization, and the regular mixing model points to a near-ideal mixing behavior for all systems. Amphipols are promising tools in biochemistry where they are used, together with neutral surfactants, for the stabilization and handling of proteins. This study provides guidelines for the optimization of current protein purification protocols and for the formulations of surfactant/polymer systems used in pharmaceutics, cosmetics, and foodstuffs.

  16. Preparation of amphiphilic block copolymer containing triazene moieties and fluorescence study

    Indian Academy of Sciences (India)

    Emil C Buruiana; Andreea L Chibac; Violeta Melinte; Tinca Buruiana


    The present study describes the synthesis via microwave accelerated reversible additionfragmentation chain transfer (RAFT) polymerization of an amphiphilic block copolymer poly(acrylic acid)-b-poly(dodecylacrylamide-co-1-(phenyl)-3-(2-methacryloyloxyethyl carbamoyloxyethyl)-3-methyltriazene-1) [PAA-b-(PDA-co-PUMA-T)]. The structure and the chemical composition of the block copolymer were confirmed by spectral/thermal analysis. The photoreactivity of the triazene sequences from PAA-b-(PDA-co-PUMA-T) was quantified by UV/vis irradiation in chloroform/dimethylformamide solutions and in thin film, indicating that the solvent polarity modifies with an order of magnitude the rate constant values. The lower rate constant in film state (film = 1.3 × 10−3 s-1), shows that the higher mobility of polymeric chains in solution allow a more rapid orientation, favourable to the triazene bond cleavage. The capability of block copolymer to form micelles in aqueous environment and implicitly, its critical micelle concentration (CMC) was evidenced through fluorescence measurements using pyrene probe (10-6 M), the CMC value being of 4.64 × 10−3 g L-1 PAA--(PDA--PUMA-T) (3.27 × 10−7 M). Experiments of fluorescence quenching with various metal cations (UO$^{2+}_{2}$, Fe2+, Fe3+, Ni2+, Cu2+, Co2+, Pb2+ and Hg2+) suggested that such a block copolymer could find applications as fluorescence-based chemosensor for the detection of iron cations in homogeneous organic solutions or aqueous environments by thin films.

  17. Magnetic amphiphilic hybrid carbon nanotubes containing N-doped and undoped sections: powerful tensioactive nanostructures (United States)

    Purceno, Aluir D.; Machado, Bruno F.; Teixeira, Ana Paula C.; Medeiros, Tayline V.; Benyounes, Anas; Beausoleil, Julien; Menezes, Helvecio C.; Cardeal, Zenilda L.; Lago, Rochel M.; Serp, Philippe


    In this work, unique amphiphilic magnetic hybrid carbon nanotubes (CNTs) are synthesized and used as tensioactive nanostructures in different applications. These CNTs interact very well with aqueous media due to the hydrophilic N-doped section, whereas the undoped hydrophobic one has strong affinity for organic molecules. The amphiphilic character combined with the magnetic properties of these CNTs opens the door to completely new and exciting applications in adsorption science and catalysis. These amphiphilic N-doped CNTs can also be used as powerful tensioactive emulsification structures. They can emulsify water/organic mixtures and by a simple magnetic separation the emulsion can be easily broken. We demonstrate the application of these CNTs in the efficient adsorption of various molecules, in addition to promoting biphasic processes in three different reactions, i.e. transesterification of soybean oil, quinoline extractive oxidation with H2O2 and a metal-catalyzed aqueous oxidation of heptanol with molecular oxygen.In this work, unique amphiphilic magnetic hybrid carbon nanotubes (CNTs) are synthesized and used as tensioactive nanostructures in different applications. These CNTs interact very well with aqueous media due to the hydrophilic N-doped section, whereas the undoped hydrophobic one has strong affinity for organic molecules. The amphiphilic character combined with the magnetic properties of these CNTs opens the door to completely new and exciting applications in adsorption science and catalysis. These amphiphilic N-doped CNTs can also be used as powerful tensioactive emulsification structures. They can emulsify water/organic mixtures and by a simple magnetic separation the emulsion can be easily broken. We demonstrate the application of these CNTs in the efficient adsorption of various molecules, in addition to promoting biphasic processes in three different reactions, i.e. transesterification of soybean oil, quinoline extractive oxidation with H2O2 and

  18. Synthesis of amphiphilic aminated inulin via 'click chemistry' and evaluation for its antibacterial activity. (United States)

    Dong, Fang; Zhang, Jun; Yu, Chunwei; Li, Qing; Ren, Jianming; Wang, Gang; Gu, Guodong; Guo, Zhanyong


    Inulins are a group of abundant, water-soluble, renewable polysaccharides, which exhibit attractive bioactivities and natural properties. Improvement such as chemical modification of inulin is often performed prior to further utilization. We hereby presented a method to modify inulin at its primary hydroxyls to synthesize amphiphilic aminated inulin via 'click chemistry' to facilitate its chemical manipulation. Additionally, its antibacterial property against Staphylococcus aureus (S. aureus) was also evaluated and the best inhibitory index against S. aureus was 58% at 1mg/mL. As the amphiphilic aminated inulin is easy to prepare and exhibits improved bioactivity, this material may represent as an attractive new platform for chemical modifications of inulin.

  19. Monte Carlo simulation for the micellar behavior of amphiphilic comb-like copolymers

    Institute of Scientific and Technical Information of China (English)

    冯莺; 隋家贤; 赵季若; 陈欣方


    Micellar behaviors in 2D and 3D lattice models for amphiphilic comb-like copolymers in water phase and in water/oil mixtures were simulated. A dynamical algorithm together with chain reptation movements was used in the simulation. Three-dimension displaying program was pro-grammed and free energy was estimated by Monte Carlo technigue. The results demonstrate that reduced interaction energy influences morphological structures of micelle and emulsion ??stems greatly; 3D simulation showing can display more direct images of morphological structures; the amphiphilic comb-like polymers with a hydrophobic main chain and hydrophilic side chains have lower energy in water than in oil.

  20. Trapping of polycyclic aromatic hydrocarbons by amphiphilic cyclodextrin functionalized polypropylene nonwovens

    DEFF Research Database (Denmark)

    Lumholdt, Ludmilla; Nielsen, Ronnie Bo Højstrup; Larsen, Kim Lambertsen

    Recently, there has been an augmented focus on the increasing amount of pesticides, drug residues and endocrine disruptors present in waste and drinking water1. These pollutants represent a challenge in water purification since they may be hazardous to human health even in low doses2. Cyclodextrins...... of the textile fibers. In this study we present the ability of amphiphilic CD coated polypropylene nonwovens to trap 8 different polycyclic aromatic hydrocarbons/endocrine disruptors from aqueous solutions thus demonstrating the potential of using the amphiphilic cyclodextrins for water purification....

  1. Intra-chain organisation of hydrophobic residues controls inter-chain aggregation rates of amphiphilic polymers

    CERN Document Server

    Varilly, Patrick; Kirkegaard, Julius B; Knowles, Tuomas P J; Chandler, David


    Aggregation of amphiphiles through the action of hydrophobic interactions is a common feature in soft condensed matter systems and is of particular importance in the context of biophysics as it underlies both the generation of functional biological machinery as well as the formation of pathological misassembled states of proteins. Here we explore the aggregation behaviour of amphiphilic polymers using lattice Monte-Carlo calculations and show that the distribution of hydrophobic residues within the polymer sequence determines the facility with which dry/wet interfaces can be created and that such interfaces drive the aggregation process.

  2. Precisely Controlled 2D Free-Floating Nanosheets of Amphiphilic Molecules through Frame-Guided Assembly. (United States)

    Zhou, Chao; Zhang, Yiyang; Dong, Yuanchen; Wu, Fen; Wang, Dianming; Xin, Ling; Liu, Dongsheng


    2D assembly of amphiphilic molecules in aqueous solution is a challenging and intriguing topic as it is normally thermodynamically unfavorable. However, through frame-guided assembly strategy and using DNA origami as the frame, monodispersed and shape-defined nanosheets are prepared. As leading hydrophobic groups (LHGs) are anchored on the frames, amphiphilic molecules in aqueous solution are guided to assemble in the hydrophobic region. By adjusting the distribution of the LHGs, the size and shape of the assemblies can be controlled precisely.

  3. Charge-Transfer Supra-Amphiphiles Built by Water-Soluble Tetrathiafulvalenes and Viologen-Containing Amphiphiles: Supramolecular Nanoassemblies with Modifiable Dimensions. (United States)

    Lv, Zhong-Peng; Chen, Bin; Wang, Hai-Ying; Wu, Yue; Zuo, Jing-Lin


    In this study, multidimensional nanoassemblies with various morphologies such as nanosheets, nanorods, and nanofibers are developed via charge-transfer interaction and supra-amphiphile self-assembling in aqueous phase. The charge-transfer interactions between tetrathiafulvalene derivatives (TTFs) and methyl viologen derivatives (MVs) have been confirmed by the characteristic charger-transfer absorption. (1) H NMR and electrospray ionizsation mass spectrometry (ESI-MS) analyses also indicate supra-amphiphiles are formed by the combination of TTFs and MVs head group through charge-transfer interaction and Coulombic force. X-ray single crystal structural studies, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) reveal that both linkage pattern of TTFs in hydrophilic part and alkane chain structure in hydrophobic part have significant influence on nanoassemblies morphology and microstructure. Moreover, gold nanoparticles (AuNPs) are introduced in the above supramolecular nanoassemblies to construct a supra-amphiphile-driven organic-AuNPs assembly system. AuNPs could be assembled into 1D-3D structures by adding different amount of MVs.

  4. Nanoscale amphiphilic macromolecules with variable lipophilicity and stereochemistry modulate inhibition of oxidized low-density lipoprotein uptake. (United States)

    Poree, Dawanne E; Zablocki, Kyle; Faig, Allison; Moghe, Prabhas V; Uhrich, Kathryn E


    Amphiphilic macromolecules (AMs) based on carbohydrate domains functionalized with poly(ethylene glycol) can inhibit the uptake of oxidized low density lipoprotein (oxLDL) and counteract foam cell formation, a key characteristic of early atherogenesis. To investigate the influence of lipophilicity and stereochemistry on the AMs' physicochemical and biological properties, mucic acid-based AMs bearing four aliphatic chains (2a) and tartaric acid-based AMs bearing two (2b and 2l) and four aliphatic chains (2g and 2k) were synthesized and evaluated. Solution aggregation studies suggested that both the number of hydrophobic arms and the length of the hydrophobic domain impact AM micelle sizes, whereas stereochemistry impacts micelle stability. 2l, the meso analogue of 2b, elicited the highest reported oxLDL uptake inhibition values (89%), highlighting the crucial effect of stereochemistry on biological properties. This study suggests that stereochemistry plays a critical role in modulating oxLDL uptake and must be considered when designing biomaterials for potential cardiovascular therapies.

  5. Microfluidics-assisted generation of stimuli-responsive hydrogels based on alginates incorporated with thermo-responsive and amphiphilic polymers as novel biomaterials. (United States)

    Karakasyan, C; Mathos, J; Lack, S; Davy, J; Marquis, M; Renard, D


    We used a droplet-based microfluidics technique to produce monodisperse responsive alginate-block-polyetheramine copolymer microgels. The polyetheramine group (PEA), corresponding to a propylene oxide /ethylene oxide ratio (PO/EO) of 29/6 (Jeffamine(®) M2005), was condensed, via the amine link, to alginates with various mannuronic/guluronic acids ratios and using two alginate:jeffamine mass ratios. The size of the grafted-alginate microgels varied from 60 to 80 μm depending on the type of alginate used and the degree of substitution. The droplet-based microfluidics technique offered exquisite control of both the dimension and physical chemical properties of the grafted-alginate microgels. These microgels were therefore comparable to isolated grafted-alginate chains in retaining both their amphiphilic and thermo-sensitive properties. Amphiphilicity was demonstrated at the oil-water interface where grafted-alginate microgels were found to decrease interfacial tension by ∼ 50%. The thermo-sensitivity of microgels was clearly demonstrated and a 10 to 20% reduction in size between was evidenced on increasing the temperature above the lower critical solution temperature (TLCST) of Jeffamine. In addition, the reversibility of thermo-sensitivity was demonstrated by studying the oil-water affinity of microgels with temperature after Congo red labeling. Finally, droplet-based microfluidics was found to be a good and promising tool for generating responsive biobased hydrogels for drug delivery applications and potential new colloidal stabilizers for dispersed systems such as Pickering emulsions.

  6. pH-induced vesicle-to-micelle transition in amphiphilic diblock copolymer: investigation by energy transfer between in situ formed polymer embedded gold nanoparticles and fluorescent dye. (United States)

    Maiti, Chiranjit; Banerjee, Rakesh; Maiti, Saikat; Dhara, Dibakar


    The ability to regulate the formation of nanostructures through self-assembly of amphiphilic block copolymers is of immense significance in the field of biology and medicine. In this work, a new block copolymer synthesized by using reversible addition-fragmentation chain transfer (RAFT) polymerization technique from poly(ethylene glycol) monomethyl ether acrylate (PEGMA) and Boc-l-tryptophan acryloyloxyethyl ester (Boc-l-trp-HEA) was found to spontaneously form pH-responsive water-soluble nanostructures after removal of the Boc group. While polymer vesicles or polymerosomes were formed at physiological pH, the micelles were formed at acidic pH (transition. Formation of these nanostructures was confirmed by different characterization techniques, viz. transmission electron microscopy, dynamic light scattering, and steady-state fluorescence measurements. Further, these vesicles were successfully utilized to reduce HAuCl4 and stabilize the resulting gold nanoparticles (AuNPs). These AuNPs, confined within the hydrophobic shell of the vesicles, could participate in energy transfer process with fluorescent dye molecules encapsulated in the core of the vesicles, thus forming a nanometal surface energy transfer (NSET) pair. Subsequently, following the efficiency of energy transfer between this pair, it was possible to monitor the process of transition from vesicles to micelles. Thus, in this work, we have successfully demonstrated that NSET can be used to follow the transition between nanostructures formed by amphiphilic block copolymers.

  7. Improved surface property of PVDF membrane with amphiphilic zwitterionic copolymer as membrane additive (United States)

    Li, Jian-Hua; Li, Mi-Zi; Miao, Jing; Wang, Jia-Bin; Shao, Xi-Sheng; Zhang, Qi-Qing


    An attempt to improve hydrophilicity and anti-fouling properties of PVDF membranes, a novel amphiphilic zwitterionic copolymer poly(vinylidene fluoride)-graft-poly(sulfobetaine methacrylate) (PVDF-g-PSBMA) was firstly synthesized by atom transfer radical polymerization (ATRP) and used as amphiphilic copolymer additive in the preparation of PVDF membranes. The PVDF-g-PSBMA/PVDF blend membranes were prepared by immersion precipitation process. Fourier transform infrared attenuated reflection spectroscopy (FTIR-ATR) and X-ray photoelectronic spectroscopy (XPS) measurements confirmed that PSBMA brushes from amphiphilic additives were preferentially segregated to membrane-coagulant interface during membrane formation. The morphology of membranes was characterized by scanning electron microscopy (SEM). Water contact angle measurements showed that the surface hydrophilicity of PVDF membranes was improved significantly with the increasing of amphiphilic copolymer PVDF-g-PSBMA in cast solution. Protein static adsorption experiment and dynamic fouling resistance experiment revealed that the surface enrichment of PSBMA brush endowed PVDF blend membrane great improvement of surface anti-fouling ability.


    Institute of Scientific and Technical Information of China (English)

    Jian-hua Li; You-yi Xu; Jian-hua Wang; Chun-hui Du


    The synthesis of a novel amphiphilic comb-shaped copolymer consisting of a main chain of styrene-(N-(4-hydroxyphenyl) maleimide) (SHMI) copolymer and poly(ethylene glycol) methyl ether methacrylate (PEGMA) side groups was achieved by atom transfer radical polymerization (ATRP). The amphiphilic copolymers were characterized by ~1H-NMR, Fourier transform infrared (FTIR) spectroscopy and gel permeation chromatography (GPC). From thermogravimetric analysis (TGA), the decomposition temperature of SHMI-g-PEGMA is lower than that of SHMI, and the graft ratio of PEGMA in the SHMI is 18.6%. The experimental results of solubilities showed that SHMI, SHMI-Br and SHMI-g-PEGMA had excellent solubility in polar solvents, such as DMF, DMSO and NMP. SHMI-g-PEGMA had higher solubilities in H_2O and methanol, while lower solubility in CHCl_3 than SHMI and SHMI-Br. PVDF blend membranes were prepared via the standard immersion precipitation phase inversion process, using amphiphilic SHMI-g-PEGMA copolymer as additives. The morphology and hydrophilicity of the blend membrane surfaces were characterized by SEM and water contact angle. It is demonstrated that the blend membranes display enhanced hydrophilicity compared to unmodified PVDF membranes. Finally, the permeation and anti-fouling properties were investigated. The result shows that amphiphilic SHMI-g-PEGMA copolymer increases the permeatability and anti-fouling property of PVDF membranes greatly.

  9. Improved surface property of PVDF membrane with amphiphilic zwitterionic copolymer as membrane additive

    Energy Technology Data Exchange (ETDEWEB)

    Li Jianhua, E-mail: [Institute of Biomedical and Pharmaceutical Technology and College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350001 (China); Li Mizi; Miao Jing; Wang Jiabin; Shao Xisheng [Institute of Biomedical and Pharmaceutical Technology and College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350001 (China); Zhang Qiqing, E-mail: [Institute of Biomedical and Pharmaceutical Technology and College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350001 (China) and Institute of Biomedical Engineering, Chinese Academy of Medical Science, Peking Union Medical College, Tianjin 300192 (China)


    An attempt to improve hydrophilicity and anti-fouling properties of PVDF membranes, a novel amphiphilic zwitterionic copolymer poly(vinylidene fluoride)-graft-poly(sulfobetaine methacrylate) (PVDF-g-PSBMA) was firstly synthesized by atom transfer radical polymerization (ATRP) and used as amphiphilic copolymer additive in the preparation of PVDF membranes. The PVDF-g-PSBMA/PVDF blend membranes were prepared by immersion precipitation process. Fourier transform infrared attenuated reflection spectroscopy (FTIR-ATR) and X-ray photoelectronic spectroscopy (XPS) measurements confirmed that PSBMA brushes from amphiphilic additives were preferentially segregated to membrane-coagulant interface during membrane formation. The morphology of membranes was characterized by scanning electron microscopy (SEM). Water contact angle measurements showed that the surface hydrophilicity of PVDF membranes was improved significantly with the increasing of amphiphilic copolymer PVDF-g-PSBMA in cast solution. Protein static adsorption experiment and dynamic fouling resistance experiment revealed that the surface enrichment of PSBMA brush endowed PVDF blend membrane great improvement of surface anti-fouling ability.

  10. H-aggregation of azobenzene-substituted amphiphiles in vesicular membranes

    NARCIS (Netherlands)

    Kuiper, JM; Engberts, JBFN


    Photochemical switching has been studied of double-tailed phosphate amphiphiles containing azobenzene units in both tails in aqueous vesicular dispersions and in mixed vesicular systems with 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). Since the ease of switching depends on the strength of the b

  11. Amphiphile regulation of ion channel function by changes in the bilayer spring constant

    DEFF Research Database (Denmark)

    Lundbæk, Jens August; Koeppe, R.E.; Andersen, Oluf Sten


    Many drugs are amphiphiles that, in addition to binding to a particular target protein, adsorb to cell membrane lipid bilayers and alter intrinsic bilayer physical properties (e. g., bilayer thickness, monolayer curvature, and elastic moduli). Such changes can modulate membrane protein function b......-dependent sodium channels in living cells. The use of gA channels as molecular force probes provides a tool for quantitative, predictive studies of bilayer-mediated regulation of membrane protein function by amphiphiles....... by altering the energetic cost (Delta G(bilayer)) of bilayer deformations associated with protein conformational changes that involve the protein-bilayer interface. But amphiphiles have complex effects on the physical properties of lipid bilayers, meaning that the net change in Delta G(bilayer) cannot...... be predicted from measurements of isolated changes in such properties. Thus, the bilayer contribution to the promiscuous regulation of membrane proteins by drugs and other amphiphiles remains unknown. To overcome this problem, we use gramicidin A (gA) channels as molecular force probes to measure the net...

  12. Synthesis of Novel Amphiphilic Azobenzenes and X-ray Scattering Studies of Their Langmuir Monolayers

    DEFF Research Database (Denmark)

    Sørensen, Thomas Just; Kjær, Kristian; Breiby, Dag Werner;


    . At the air-water interface, the amphiphilic azobenzenes form noncrystalline but stable Langmuir films that display an unusual reversible monolayer collapse close to 35 mN/m. The structures and phase transitions were studied by X-ray reflectivity (XR) and grazing-incidence X-ray diffraction, both utilizing...

  13. Aggregation Properties of an Amphiphilic Methanofullerene Derivative in THF-H2O Solvent Mixtures

    Institute of Scientific and Technical Information of China (English)

    Guan Wu WANG; Li Juan JIAO; Er Hong HAO; Yong Ming LU; You Jun YANG


    Amphiphilic methanofullerene 1 exhibits strong tendency to form aggregates in THF-H2O solvent mixtures. Two different aggregation processes induced by either varying the solvent composition or upon standing have been found. Concentration has great influence on the aggregation process. Paralleling to the UV-Vis changes, an unusual solvatochromism has been observed in these two different processes.

  14. Transfection of small numbers of human endothelial cells by electroporation and synthetic amphiphiles

    NARCIS (Netherlands)

    van Leeuwen, E B; van der Veen, A Y; Hoekstra, D; Engberts, J B; Halie, M R; van der Meer, J; Ruiters, M H


    OBJECTIVES: This study compared the efficiency of electroporation and synthetic amphiphiles. (SAINT-2pp/DOPE) in transfecting small numbers of human endothelial cells. METHODS AND RESULTS: Optimal transfection conditions were tested and appeared to be 400 V and 960 microF for electroporation and a 1

  15. Preparation of Vesicles and Nanoparticles of Amphiphilic Cyclodextrins Containing Labile Disulfide Bonds

    NARCIS (Netherlands)

    Nolan, Darren; Darcy, Raphael; Ravoo, Bart Jan


    Amphiphilic cyclodextrin derivatives were prepared in which a disulfide bond connects the hydrophobic substituents to the macrocycle. These compounds were obtained by 1,3-dicyclohexylcarbodiimide-mediated coupling reactions of heptakis(6-amino-6-deoxy)-B-cyclodextrins and disulfide-containing carbox

  16. Bilayer Vesicles of Amphiphilic Cyclodextrins: Host Membranes That Recognize Guest Molecules

    NARCIS (Netherlands)

    Falvey, Patrick; Lim, Choon Woo; Darcy, Raphael; Revermann, Tobias; Karst, Uwe; Giesbers, Marcel; Marcelis, Antonius T.M.; Lazar, Adina; Coleman, Anthony W.; Reinhoudt, David N.; Ravoo, Bart Jan


    A family of amphiphilic cyclodextrins (6, 7) has been prepared through 6-S-alkylation (alkyl=n-dodecyl and n-hexadecyl) of the primary side and 2-O-PEGylation of the secondary side of a-, B-, and Y-cyclodextrins (PEG=poly(ethylene glycol)). These cyclodextrins form nonionic bilayer vesicles in aqueo

  17. Bilayer vesicles of amphiphilic cyclodextrines: host membranes that recognize guest molecules

    NARCIS (Netherlands)

    Falvey, P.; Lim, C.W.; Darcy, R.; Revermann, T.; Karst, U.; Marcelis, A.T.M.; Coleman, A.W.; Reinhoudt, D.N.; Ravoo, B.J.


    A family of amphiphilic cyclodextrins (6, 7) has been prepared through 6-S-alkylation (alkyl=n-dodecyl and n-hexadecyl) of the primary side and 2-O-PEGylation of the secondary side of alpha-, beta-, and gamma-cyclodextrins (PEG=poly(ethylene glycol)). These cyclodextrins form nonionic bilayer vesicl

  18. Tunable Hydrophobicity in DNA Micelles : Design, Synthesis, and Characterization of a New Family of DNA Amphiphiles

    NARCIS (Netherlands)

    Anaya, Milena; Kwak, Minseok; Musser, Andrew J.; Muellen, Klaus; Herrmann, Andreas; Müllen, Klaus


    This work describes the synthesis and characterization of a new family of DNA amphiphiles containing modified nucleobases. The hydrophobicity was imparted by the introduction of a dodec-1-yne chain at the 5-position of the uracil base, which allowed precise and simple tuning of the hydrophobic prope

  19. Oxidized potato starch based thermoplastic films : Effect of combination of hydrophilic and amphiphilic plasticizers

    NARCIS (Netherlands)

    Niazi, Muhammad Bilal Khan; Broekhuis, Antonius A.


    Different combinations of hydrophilic (glycerol and water) and amphiphilic (isoleucine) plasticizers were studied in the production of thermoplastic starch (TPS) powders and films from oxidized potato starch. All powder samples had an irregular and shrivelled morphology. In all mixtures containing i

  20. Non-amphiphilic carbohydrate liquid crystals containing an intact monosaccharide moiety

    NARCIS (Netherlands)

    Smits, E; Engberts, J.B.F.N.; Kellogg, R.M; van Doren, H.A.


    A chiral rigid moiety which forms the basis of a new class of non-amphiphilic carbohydrate liquid crystals has been developed. This moiety contains a fully intact glucopyranose ring embedded in a trans-decalin structure. The original carbohydrate is substituted so that only two hydroxyl groups are l


    Directory of Open Access Journals (Sweden)

    Christina Yacoob


    Full Text Available Amphiphilic molecules are challenging to be incorporatedinto polymeric particles for sustained release due to their significant solubility in both water and organic solvent used in the fabrication process. Here, we investigated an extensive panel of fabrication methods for the incorporation and release of amphiphilic molecules, in particular, novel amphiphilic bumped kinase inhibitors (BKIs. Previously, BKIswere shown to reduce malaria transmission by blocking of gametocyte exflagellation. Prolonged BKI bioavailability for effective transmission blocking is crucial since infectious gametocytes circulate for several weeks inthe mammalian host, well beyond the half-life of BKIs. So far, delivery systems for sustained release of those BKIs have not been successfully formulated yet. Here we demonstrate that out of several delivery vehicles the partition-optimized single emulsion particles are the ideal system for incorporation and sustained release of amphiphilic BKIs. They increased the incorporation greater than 90% through optimized partitioning of amphiphilic molecules to the polymer phase and sustained release of BKIs up to several weeks with a reduction in the initial burst release. Overall this work provides a method for the incorporation and sustained release of amphiphilic BKIs, and can be adapted for other amphiphilic molecules.

  2. Enhancing the protein resistance of silicone via surface-restructuring PEO-silane amphiphiles with variable PEO length


    Rufin, M. A.; Gruetzner, J. A.; Hurley, M. J.; Hawkins, M. L.; Raymond, E. S.; Raymond, J. E.; Grunlan, M. A.


    Silicones with superior protein resistance were produced by bulk-modification with poly(ethylene oxide) (PEO)-silane amphiphiles that demonstrated a higher capacity to restructure to the surface-water interface versus conventional non-amphiphilic PEO-silanes. The PEO-silane amphiphiles were prepared with a single siloxane tether length but variable PEO segment lengths: α-(EtO)3Si(CH2)2-oligodimethylsiloxane13-block-poly(ethylene oxide)n-OCH3 (n = 3, 8, and 16). Conventional PEO-silane analogu...

  3. Effect of stereochemistry, chain length and sequence pattern on antimicrobial properties of short synthetic β-sheet forming peptide amphiphiles. (United States)

    Ong, Zhan Yuin; Cheng, Junchi; Huang, Yuan; Xu, Kaijin; Ji, Zhongkang; Fan, Weimin; Yang, Yi Yan


    In the face of mounting global antibiotics resistance, the identification and development of membrane-active antimicrobial peptides (AMPs) as an alternative class of antimicrobial agent have gained significant attention. The physical perturbation and disruption of microbial membranes by the AMPs have been proposed to be an effective means to overcome conventional mechanisms of drug resistance. Recently, we have reported the design of a series of short synthetic β-sheet folding peptide amphiphiles comprised of recurring (X1Y1X2Y2)n-NH2 sequences where X: hydrophobic amino acids, Y: cationic amino acids and n: number of repeat units. In efforts to investigate the effects of key parameters including stereochemistry, chain length and sequence pattern on antimicrobial effects, systematic d-amino acid substitutions of the lead peptides (IRIK)2-NH2 (IK8-all L) and (IRVK)3-NH2 (IK12-all L) were performed. It was found that the corresponding D-enantiomers exhibited stronger antimicrobial activities with minimal or no change in hemolytic activities, hence translating very high selectivity indices of 407.0 and >9.8 for IK8-all D and IK12-all D respectively. IK8-all D was also demonstrated to be stable to degradation by broad spectrum proteases trypsin and proteinase K. The membrane disrupting bactericidal properties of IK8-all D effectively prevented drug resistance development and inhibited the growth of various clinically isolated MRSA, VRE, Acinetobacter baumanni, Pseudomonas aeruginosa, Cryptococcus. neoformans and Mycobacterium tuberculosis. Significant reduction in intracellular bacteria counts was also observed following treatment with IK8-all D in the Staphylococcus. aureus infected mouse macrophage cell line RAW264.7 (P < 0.01). These results suggest that the d-amino acids substituted β-sheet forming peptide IK8-all D with its enhanced antimicrobial activities and improved protease stability, is a promising therapeutic candidate with potential to combat

  4. Large organized surface domains self-assembled from nonpolar amphiphiles. (United States)

    Krafft, Marie Pierre


    For years, researchers had presumed that Langmuir monolayers of small C(n)F(2n+1)C(m)H(2m+1) (FnHm) diblock molecules (such as F8H16) consisted of continuous, featureless films. Recently we have discovered that they instead form ordered arrays of unusually large (~30-60 nm), discrete self-assembled surface domains or hemimicelles both at the surface of water and on solid substrates. These surface micelles differ in several essential ways from all previously reported or predicted molecular surface aggregates. They self-assemble spontaneously, even at zero surface pressure, depending solely on a critical surface concentration. They are very large (~100 times the length of the diblock) and involve thousands of molecules (orders of magnitude more than classical micelles). At the same time, the surface micelles are highly monodisperse and self-organize in close-packed hexagonal patterns (two-dimensional crystals). Their size is essentially independent from pressure, and they do not coalesce and are unexpectedly sturdy for soft matter (persisting even beyond surface film collapse). We and other researchers have observed large surface micelles for numerous diblocks, using Langmuir-Blodgett (LB) transfer, spin-coating and dip-coating techniques, or expulsion from mixed monolayers, and on diverse supports, establishing that hemimicelle formation and ordering are intrinsic properties of (perfluoroalkyl)alkanes. Notably, they involve "incomplete" surfactants with limited amphiphilic character, which further illustrates the outstanding capacity for perfluoroalkyl chains to promote self-assembly and interfacial film structuring. Using X-ray reflectivity, we determined a perfluoroalkyl-chain-up orientation. Theoretical investigations assigned self-assembly and hemimicelle stability to electrostatic dipole-dipole interactions at the interface between Fn- and Hm-sublayers. Grazing-incidence small-angle X-ray scattering (GISAXS) data collected directly on the surface of water

  5. Synthesis of antibacterial amphiphilic elastomer based on polystyrene-block-polyisoprene-block-polystyrene via thiol-ene addition. (United States)

    Keleş, Elif; Hazer, Baki; Cömert, Füsun B


    A new type of amphiphilic antibacterial elastomer has been described. Thermoplastic elastomer, polystyrene-block-polyisoprene-block-polystyrene (PS-b-PI-b-PS) triblock copolymer was functionalized in toluene solution by free radical mercaptan addition in order to obtain an amphiphilic antibacterial elastomer. Thiol terminated PEG was grafted through the double bonds of PS-b-PI-b-PS via free radical thiol-ene coupling reaction. The antibacterial properties of the amphiphilic graft copolymers were observed. The original and the modified polymers were used to create microfibers in an electro-spinning process. Topology of the electrospun micro/nanofibers were studied by using scanning electron microscopy (SEM). The chemical structures of the amphiphilic comb type graft copolymers were elucidated by the combination of elemental analysis, (1)H NMR, (13)C NMR, GPC and FTIR.

  6. Photophysical and photochemical studies of a novel amphiphilic zinc phthalocyanine and its interaction with calf thymus DNA. (United States)

    Yuan, Linxin; Gui, Li; Wang, Yue; Zhang, Quanquan; Zhou, Lin; Wei, Shaohua


    β-tetra (aminophenoxy) sulfonic substituted zinc phthalocyanines (SNZnPc), a novel amphiphilic zinc phthalocyanine (Pc), was synthesized. The photophysical, photochemical, and photobiology properties were studied. Results indicated that the synthesized SNZnPc has good amphiphilic property and high reactive oxygen species (ROSs) generation ability. Furthermore, SNZnPc has strong affinity to calf thymus DNA (CT-DNA) through intercalation ways and can effectively cleavage CT-DNA after irradiation by light with appropriate wavelength.

  7. Photophysical and photochemical studies of a novel amphiphilic zinc phthalocyanine and its interaction with calf thymus DNA (United States)

    Yuan, Linxin; Gui, Li; Wang, Yue; Zhang, Quanquan; Zhou, Lin; Wei, Shaohua


    β-tetra (aminophenoxy) sulfonic substituted zinc phthalocyanines (SNZnPc), a novel amphiphilic zinc phthalocyanine (Pc), was synthesized. The photophysical, photochemical, and photobiology properties were studied. Results indicated that the synthesized SNZnPc has good amphiphilic property and high reactive oxygen species (ROSs) generation ability. Furthermore, SNZnPc has strong affinity to calf thymus DNA (CT-DNA) through intercalation ways and can effectively cleavage CT-DNA after irradiation by light with appropriate wavelength.

  8. Synthesis of a new generation of amphiphiles with multi-cryptand headgroups: A comparative study at air–water interface

    Indian Academy of Sciences (India)

    B Sarkar; R K Gupta; R A Singh; P K Bharadwaj


    A laterally non-symmetric aza cryptand has been derivatized with two hydrophobic chains to afford amphiphiles with one cryptand headgroup and two hydrophobic tails. Three such units readily attach to 1,3,5-benzenetricarbonyl trichloride, to form a new generation of amphiphilic molecules with three cryptand headgroups and six hydrophobic chains. These molecules are studied at the air–water interface in a Langmuir trough. They readily form LB-films on a number of substrates that are characterized.

  9. The synthesis of spherical calcium carbonate composite in amphiphilic PS-b-PAA solution and its thermal dynamic characteristic

    Institute of Scientific and Technical Information of China (English)

    YUE Linhai; JIN Dalai


    Spherical calcium carbonate composite is synthesized in the solution of amphiphilic block copolymer of polystyrene(PS) and poly(acrylic acid)(PAA). SEM and XRD measurements show that the diameter of the particulates decreases with the augment of the PS-b-PAA concentration, crystalline in the composite is calcite and its morphology as well as the structure is changed too. TG-DTA together with IR analysis is applied to investigating the thermal dynamic behavior of the composite. The results show that the composite is mainly composed of two phases, that is, the nano- crystalline calcium carbonate and the PS-b-PA-Ca composites. PS phase decomposes first with a large heat release at about 330℃. However, the PAA chains have relatively high thermal stability, probably due to the structural Ca-O bond, and decomposes at above 400℃. Matching opinions are used to explain the possible reasons for the regular as well as the particular characteristics of the composite corresponding to a certain copolymer concentration.

  10. Enhancing the protein resistance of silicone via surface-restructuring PEO-silane amphiphiles with variable PEO length. (United States)

    Rufin, M A; Gruetzner, J A; Hurley, M J; Hawkins, M L; Raymond, E S; Raymond, J E; Grunlan, M A


    Silicones with superior protein resistance were produced by bulk-modification with poly(ethylene oxide) (PEO)-silane amphiphiles that demonstrated a higher capacity to restructure to the surface-water interface versus conventional non-amphiphilic PEO-silanes. The PEO-silane amphiphiles were prepared with a single siloxane tether length but variable PEO segment lengths: α-(EtO)3Si(CH2)2-oligodimethylsiloxane13-block-poly(ethylene oxide) n -OCH3 (n = 3, 8, and 16). Conventional PEO-silane analogues (n = 3, 8 and 16) as well as a siloxane tether-silane (i.e. no PEO segment) were prepared as controls. When surface-grafted onto silicon wafer, PEO-silane amphiphiles produced surfaces that were more hydrophobic and thus more adherent towards fibrinogen versus the corresponding PEO-silane. However, when blended into a silicone, PEO-silane amphiphiles exhibited rapid restructuring to the surface-water interface and excellent protein resistance whereas the PEO-silanes did not. Silicones modified with PEO-silane amphiphiles of PEO segment lengths n = 8 and 16 achieved the highest protein resistance.

  11. Passivation of nanocrystalline TiO2 junctions by surface adsorbed phosphinate amphiphiles enhances the photovoltaic performance of dye sensitized solar cells

    KAUST Repository

    Wang, Mingkui


    We report a new class of molecular insulators that electronically passivate the surface of nanocrystalline titania films for high performance dye sensitized solar cells (DSC). Using electrical impedance measurements we demonstrate that co-adsorption of dineohexyl bis-(3,3-dimethyl-butyl)-phosphinic acid (DINHOP), along with the amphiphilic ruthenium sensitizer Z907Na increased substantially the power output of the cells mainly due to a retardation of interfacial recombination of photo-generated charge carriers. The use of phosphinates as anchoring groups opens up new avenues for modification of the surface by molecular insulators, sensitizers and other electro-active molecules to realize the desired optoelectronic performance of devices based on oxide junctions. © 2009 The Royal Society of Chemistry.

  12. Characterization of Fe3O4/P(St-MPEO) Amphiphilic Magnetic Polymer Microspheres

    Institute of Scientific and Technical Information of China (English)


    Amphiphilic magnetic microspheres consisting of styrene and poly(ethylene oxide) macromonomer(MPEO) were prepared by dispersion copolymerization in the presence of Fe3O4 magnetic fluid in an ethanol/water medium. The sizes of the magnetic microspheres and their distribution were characterized by means of scanning electron microscopy(SEM). The surface morphology and the average surface roughness of the microspheres were investigated by virtue of atomic force microscopy(AFM). It was found that the microspheres exhibit microscopic phase-separate and the mean square surface roughness of the microspheres increases with increasing MPEO used in the copolymerization. The amphiphilic magnetic microspheres containing 0.4-3.5 mg/g hydroxyl groups could be prepared from MPEO with different concentrations and styrene.

  13. Removal of volatile organic compounds using amphiphilic cyclodextrin-coated polypropylene. (United States)

    Lumholdt, Ludmilla; Fourmentin, Sophie; Nielsen, Thorbjørn T; Larsen, Kim L


    Polypropylene nonwovens were functionalised using a self-assembled, amphiphilic cyclodextrin coating and the potential for water purification by removal of pollutants was studied. As benzene is one of the problematic compounds in the Water Framework Directive, six volatile organic compounds (benzene and five benzene-based substances) were chosen as model compounds. The compounds were tested as a mixture in order to provide a more realistic situation since the wastewater will be a complex mixture containing multiple pollutants. The volatile organic compounds are known to form stable inclusion complexes with cyclodextrins. Six different amphiphilic cyclodextrin derivatives were synthesised in order to elucidate whether or not the uptake abilities of the coating depend on the structure of the derivative. Headspace gas chromatography was used for quantification of the uptake exploiting the volatile nature of benzene and its derivatives. The capacity was shown to increase beyond the expected stoichiometries of guest-host complexes with ratios of up to 16:1.

  14. Structural mechanism of nuclear transport mediated by importin β and flexible amphiphilic proteins. (United States)

    Yoshimura, Shige H; Kumeta, Masahiro; Takeyasu, Kunio


    Karyopherin β family proteins mediate the nuclear/cytoplasmic transport of various proteins through the nuclear pore complex (NPC), although they are substantially larger than the size limit of the NPC.To elucidate the molecular mechanism underlying this paradoxical function, we focused on the unique structures called HEAT repeats, which consist of repetitive amphiphilic α helices. An in vitro transport assay and FRAP analyses demonstrated that not only karyopherin β family proteins but also other proteins with HEAT repeats could pass through the NPC by themselves, and serve as transport mediators for their binding partners. Biochemical and spectroscopic analyses and molecular dynamics simulations of purified HEAT-rich proteins revealed that they interact with hydrophobic groups, including phenyl and alkyl groups, and undergo reversible conformational changes in tertiary structures, but not in secondary structures. These results show that conformational changes in the flexible amphiphilic motifs play a critical role in translocation through the NPC.

  15. Monte Carlo study of the self-assembly of achiral bolaform amphiphiles into helical nanofibers. (United States)

    Wahab, M; Schiller, P; Schmidt, R; Mögel, H-J


    It is shown by coarse-grained off-lattice Monte Carlo simulations that a geometrically induced frustration of the parallel arrangement of rigid achiral bolaform amphiphiles can cause chirality in self-assembled nanostructures. The amphiphilic molecules are represented as rigid linear chains of 8 equally sized hydrophobic spheres (tail) and a hydrophilic sphere (head) at each end. The hydrophilic and hydrophobic spheres differ in size. A very simple interaction scheme consisting of only hard-core repulsion between all spheres and square-well attraction between hydrophobic spheres is sufficient for self-assembly into helical fibers for molecules with head/tail diameter ratios ranging from 1.3 to 1.8.

  16. Nose to Brain Delivery: New Trends in Amphiphile-Based "Soft" Nanocarriers. (United States)

    Marianecci, Carlotta; Rinaldi, Federica; Hanieh, Patrizia N; Paolino, Donatella; Marzio, Luisa Di; Carafa, Maria


    The aim of the present paper is to highlight the potential of nasal mucosa as an administration route for targeting the central nervous system, in particular, the brain. Among the formulation strategies for enhance nose to brain drug delivery, the use of colloidal carriers has became a revolutionary approach. These systems should be able to entrap drugs in the desired amount, to penetrate through anatomical barriers, to efficiently release the loaded drugs in the site of action and moreover to show a good physicochemical, biological stability and good biocompatibility. The use of vesicular systems (liposomes and niosomes) together with the use of micelles, in nose to brain delivery are here presented. Vesicle structure is characterized by the presence of a hydrophobic bilayer and an aqueous core that is absent in micelles. Amphiphilic molecules are responsible for soft nanocarriers formation, in particular: liposomes are formed by phospholipids, while niosomes by non-ionic surfactant and micelles by amphiphilic polymers.

  17. Amphiphilic block copolymers as efficiency boosters in microemulsions a SANS investigation of the role of polymers

    CERN Document Server

    Endo, H; Mihailescu, M; Monkenbusch, M; Gompper, G; Richter, D; Jakobs, B; Sottmann, T; Strey, R


    The effect of amphiphilic block copolymers on ternary microemulsions (water, oil and non-ionic surfactant) is investigated. Small amounts of PEP-PEO block copolymer lead to a dramatic expansion of the one-phase region where water and oil can be solubilized by the mediation of surfactant molecules. Small-angle neutron-scattering experiments employing a high-precision two-dimensional contrast-variation technique demonstrate that the polymer is distributed uniformly on the surfactant membrane, where it modifies the membrane curvature elasticity. Furthermore, a new approach to determine the bending rigidity of an amphiphilic membrane is proposed, which is precise enough to measure the logarithmic scale dependence of the bending rigidity and its universal prefactor in bicontinuous microemulsions. (orig.)

  18. Super-resolution microscopy reveals structural diversity in molecular exchange among peptide amphiphile nanofibres (United States)

    da Silva, Ricardo M. P.; van der Zwaag, Daan; Albertazzi, Lorenzo; Lee, Sungsoo S.; Meijer, E. W.; Stupp, Samuel I.


    The dynamic behaviour of supramolecular systems is an important dimension of their potential functions. Here, we report on the use of stochastic optical reconstruction microscopy to study the molecular exchange of peptide amphiphile nanofibres, supramolecular systems known to have important biomedical functions. Solutions of nanofibres labelled with different dyes (Cy3 and Cy5) were mixed, and the distribution of dyes inserting into initially single-colour nanofibres was quantified using correlative image analysis. Our observations are consistent with an exchange mechanism involving monomers or small clusters of molecules inserting randomly into a fibre. Different exchange rates are observed within the same fibre, suggesting that local cohesive structures exist on the basis of β-sheet discontinuous domains. The results reported here show that peptide amphiphile supramolecular systems can be dynamic and that their intermolecular interactions affect exchange patterns. This information can be used to generate useful aggregate morphologies for improved biomedical function.

  19. Preparation of Nano-porous Materials(Ⅰ) by Polymerization of Amphiphile Self-assemblies

    Institute of Scientific and Technical Information of China (English)


    The polymerization of amphiphilic self-assemblies is a promising method to synthesize nano-structured materials with novel properties. These materials have many attractive features for their application in biomedical area and materials science, such as catalysis, separation, surface modification, and therapeutics areas. A general review on the polymerization of lipids and surfactant self-assemblies to amphiphilic self-assemblies is given in this paper with 49 参考文献. The polymerization and the subsequently resulted structure of lipids in different morphologies are summarized. The polymerization of polymerizable surfactants(surfmers) in emulsion and liquid crystalline phases are also discussed. The potential application of new nano-porous materials is briefly described.

  20. Electron spin resonance study of chloroplast photosynthetic activity in the presence of amphiphilic amines. (United States)

    Sersen, F; Balgavý, P; Devínsky, F


    Electron spin resonance spectroscopy (ESR) was used to study the effects of amphiphilic amines of the carbamate, amide, and ester type and amine oxide on the photosynthetic system of spinach chloroplasts. The ESR signal II connected to the photosynthetic center PS II donor side was observed to diminish in the presence of amines, whereas that of PS I remained unchanged. The inhibition of PS II increased with the increasing of amine concentration. In the presence of amines, the light: dark chloroplast ESR signals ratio as well as the intensity of the ESR signal of unbound Mn2+ increased. It is suggested that the amphiphilic amines affect the structure of PS II and the electron transfer to PS I. The effects of the amines tested on the photosynthetic system correlate with their potency to perturb the lipid membrane structure.

  1. New synthetic amphiphilic polymers for steric protection of liposomes in vivo. (United States)

    Torchilin, V P; Trubetskoy, V S; Whiteman, K R; Caliceti, P; Ferruti, P; Veronese, F M


    Carboxy group-terminated synthetic polymers--branched poly(ethylene glycol), poly(acryloylmorpholine), and poly(vinylpyrrolidone)--were made amphiphilic by derivatization with phosphatidyl ethanolamine via the terminal carboxy group and then incorporated into lecithin-cholesterol liposomes prepared by the detergent dialysis method. Following the biodistribution of liposomes in mice, all three polymers were shown to be effective steric protectors for liposomes and were able to sharply increase liposome circulation times in a concentration-dependent manner. The accumulation of liposomes in the liver decreases. The effects observed are similar to those found for liposomes modified with linear poly(ethylene glycol). At low polymer concentration, amphiphilic branched poly(ethylene glycol) seems to be the most effective liposome protector, most probably, because at the same molar content of anchoring groups, each attachment point carries two polymeric chains and doubles the quantity of liposome-grafted polymer comparing to linear poly(ethylene glycol).

  2. Self-assembly of aromatic-functionalized amphiphiles: The role and consequences of aromatic-aromatic noncovalent interactions in building supramolecular aggregates and novel assemblies

    Energy Technology Data Exchange (ETDEWEB)

    Whitten, D.G.; Chen, L.; Geiger, H.C.; Perlstein, J.; Song, X. [Los Alamos National Lab., NM (United States). Chemical Science and Technology Div.]|[Univ. of Rochester, NY (United States)


    This feature article presents an overview of a study of several different aromatic-functionalized amphiphiles-fatty acid and phospholipid derivatives. These amphiphiles form organized assemblies when the fatty acids are spread as monolayers at the air-water interface or when the phospholipids are dispersed in aqueous solutions. For a wide range of aromatic chromophores--trans-stilbene derivatives and a series of vinylogues (1,4-diphenyl-1,3-butadiene and 1,6-diphenyl-1,3,5-hexatriene), diphenylacetylenes, and azobenzenes such as phenyl, biphenyl, and terphenyl derivatives and modified stilbenes (styryl thiophenes and styryl naphthalenes)--assembly formation is accompanied by formation of aggregates of the aromatic groups. Results of experimental studies and simulations indicate that in many cases the aromatics form a small, stable unit aggregate characterized by strong noncovalent edge-to-face interactions among adjacent aromatics. Although the unit aggregates exhibit characteristic spectral shifts and strong induced circular dichroism indicating a chiral pinwheel aggregate structure, they may be packed together in pure films or dispersions to form an extended glide or herringbone structure. Although the pinwheel unit aggregate and the extended glide or herringbone structure. Although the pinwheel unit aggregate and the extended glide structure is favored for the majority of aromatics studied, for certain aromatics (styrenes, styrylthiophenes, and {alpha}-styrylnaphthalenes) a translation layer, characterized by face-to-face noncovalent interactions, is preferred. The glide or herringbone aggregates are readily distinguished from the translation aggregates by different spectral signatures and different photochemical and photophysical behavior. Factors controlling the type of aggregate and hence extended structure formed from different aromatic functionalized aromatics include shape and steric factors and strength of the competing noncovalent edge-face and face


    Institute of Scientific and Technical Information of China (English)

    Kan Yue; Jinlin He; Chang Liu; Mingjun Huang; Xue-Hui Dong; Kai Guo; Peihong Ni


    "Click chemistry" is,by definition,a general functionalization methodology (GFM) and its marriage with living anionic polymerization is particularly powerful in precise macromolecular synthesis.This paper reports the synthesis of a "clickable" middle-chain azide-functionalized polystyrene (mPS-N3) by anionic polymerization and its application in the preparation of novel shape amphiphiles based on polyhedral oligomeric silsesquioxane (POSS).The mPS-N3 was synthesized by coupling living poly(styryl)lithium chains (PSLi) with 3-chloropropylmethyldichlorosilane and subsequent nucleophilic substitution of the chloro group in the presence of sodium azide.Excess PSLi was end-capped with ethylene oxide to facilitate its removal by flash chromatography.The mPS-N3 was then derived into a giant lipid-like shape amphiphile in two steps following a sequential "click" strategy.The copper(I)-catalyzed azide-alkyne cycloaddition between mPS-N3 and alkyne-functionalized vinyl-substituted POSS derivative (VPOSS-alkyne) ensured quantitative ligation to give polystyrene with VPOSS tethered at the middle of the chain (mPS-VPOSS).The thiol-ene reaction with 1-thioglycerol transforms the vinyl groups on the POSS periphery to hydroxyls,resulting in an amphiphilic shape amphiphile,mPS-DPOSS.This synthetic approach is highly efficient and modular.It demonstrates the "click" philosophy of facile complex molecule construction from a library of simple building blocks and also suggests that mPS-N3 can be used as a versatile "clickable" motif in polymer science for the precise synthesis of complex macromolecules.

  4. A synthetic strategy for novel nonsymmetrical bola amphiphiles based on carbohydrates

    NARCIS (Netherlands)

    Schuur, B; Wagenaar, Anno; Heeres, Andre; Heeres, Erik H. J.


    A number of novel nonionic bolaform amphiphiles with nonidentical aldityl head groups, 1-(1-deoxy-D-galactitol-l-ylamino)-6-(1-deoxy-D- galactitol-1-ylamino)hexane (4a), 1-(1-deoxy-D-mannitol-1-ylamino)-6-(1-deoxy-D-glucitol-1-ylamino)hexane (4b). and 1-(1-deoxy-D-tialactitol-1-ylamino)-6-(1-deoxy-D

  5. Amphiphilic Cellulose Ethers Designed for Amorphous Solid Dispersion via Olefin Cross-Metathesis. (United States)

    Dong, Yifan; Mosquera-Giraldo, Laura I; Taylor, Lynne S; Edgar, Kevin J


    The design of cellulose ether-based amphiphiles has been difficult and limited because of the harsh conditions typically required for appending ether moieties to cellulose. Olefin cross-metathesis recently has been shown to be a valuable approach for appending a variety of functional groups to cellulose ethers and esters, provided that an olefin handle for metathesis can be attached. This synthetic pathway gives access to these functional derivatives under very mild conditions and at high efficiency. Modification of ethyl cellulose by metathesis to prepare useful derivatives, for example, for solubility and bioavailability enhancement of drugs by amorphous solid dispersion (ASD), has been limited by the low DS(OH) of commercial ethyl cellulose derivatives. This is problematic because ethyl cellulose is otherwise a very attractive substrate for synthesis of amphiphilic derivatives by olefin metathesis. Herein we explore two methods for opening up this design space for ether-based amphiphiles, for example, permitting synthesis of more hydrophilic derivatives. One approach is to start with the more hydrophilic commercial methyl cellulose, which contains much higher DS(OH) and therefore is better suited for introduction of high DS of olefin metathesis "handles". In another approach, we explored a homogeneous one-pot synthesis methodology from cellulose, where controlled DS of ethyl groups was introduced at the same time as the ω-unsaturated alkyl groups, thereby permitting complete control of DS(OH), DS(Et), and ultimately DS of the functional group added by metathesis. We describe the functionalized derivatives available by these successful approaches. In addition, we explore new methods for reduction of the unsaturation in initial metathesis products to provide robust methods for enhancing product stability against further radical-catalyzed reactions. We demonstrate initial evidence that the products show strong promise as amphiphilic matrix polymers for amorphous

  6. Langmuir-Blodgett Films and Calcium Ion Coordination of Biliverdin and Its Amphiphilic Derivatives

    Institute of Scientific and Technical Information of China (English)


    Monolayer formation and LB film fabrication of amphiphilic derivative of biliverdin 1,diododecyl biliverdinamide [B(CONHC12H25)2,2] at an air-water interface on pure water subphase and subphase containing calcium ion were investigated and compared with 1.The coordination in ordered molecular films is much different from that in bulk solution.The formation of ligand-calcium complex was confirmed by X-ray photoelectron spectroscopy.

  7. A comparative study of the physicochemical properties of perfluorinated and hydrogenated amphiphiles. (United States)

    Blanco, Elena; González-Pérez, Alfredo; Ruso, Juan M; Pedrido, Rosa; Prieto, Gerardo; Sarmiento, Félix


    In this work we studied and compared the physicochemical properties of perfluorinated (sodium perfluoroheptanoate, C7FONa, and perfluorooctanoate, C8FONa) and hydrogenated (sodium octanoate, C8HONa, decanoate, C10HONa, and dodecanoate, C12HONa) amphiphiles. First, we determined their Krafft points to study the solubility and appropriate temperature range of micellization of these compounds. The critical micelle concentration (cmc) and ionization degree of micellization (beta) as a function of temperature (T) were estimated from conductivity data. Plots of cmc vs T appear to follow the typical U-shaped curve with a minimum T(min). The results show that the surfactants with CF2/CH2 ratio of 1.5 between alkyl chains (C12HONa-C8FONa and C10HONa-C7FONa) have nearly the same minimum value for cmc against temperature. The comparison between the cmc of hydrogenated amphiphiles and the corresponding perfluorinated amphiphiles must be done at this point. Thermodynamic functions of micellization were obtained by applying different theoretical models and choosing the one that best fit our experimental data. Although perfluorinated and hydrogenated amphiphiles present similar thermodynamic behavior, we have found a variation of 1.3 to 1.7 in the CF2/CH2 ratio, which did not remain constant with temperature. In the second part of this study the apparent molar volumes and adiabatic compressibilities were determined from density and ultrasound velocity measurements. Apparent molar volumes at infinite dilution presented the ratio 1.5 between alkyl chains again. However, apparent molar volumes upon micellization for sodium perfluoroheptanoate indicated a different aggregation pattern.

  8. Control of structure and growth of polymorphic crystalline thin films of amphiphilic molecules on liquid surfaces

    DEFF Research Database (Denmark)

    Weinbach, S.P.; Kjær, K.; Bouwman, W.G.;


    The spontaneous formation and coexistence of crystalline polymorphic trilayer domains in amphiphilic films at air-liquid interfaces is demonstrated by grazing incidence synchrotron x-ray diffraction. These polymorphic crystallites may serve as models for the early stages of crystal nucleation...... and growth, helping to elucidate the manner in which additives influence the progress of crystal nucleation, growth, and polymorphism and suggesting ways of selectively generating and controlling multilayers on liquid surfaces. Auxiliary molecules have been designed to selectively inhibit development...

  9. Structure and Dynamics in Amphiphilic Bilayers: NMR and MD simulation Studies



    Solid-state nuclear magnetic resonance (NMR) spectroscopy and molecular dynamics (MD) simulations were employed to study molecular structure and dynamics in amphiphilic bilayers. This thesis reports on method development and practical applications to two types of bilayer systems: simple cell membrane models composed of phosphatidylcholine lipids and cholesterol; and liquid crystals composed of ethyleneoxide-based surfactants often used in technological applications and in fundamental studies ...

  10. Novel Amphiphilic Polymer Gel Electrolytes Based on PEG-b-GMA-co-MMA

    Institute of Scientific and Technical Information of China (English)


    1 Results Gel polymer electrolytes for lithium battery have been widely investigated recently because of their high ion conductivity at room temperature. We synthesized and characterized novel gel electrolytes based on amphiphilic copolymethacrylates containing different lengths of ethylene oxide (EO) chain as ionophilic units and methyl methacrylate (MMA) chain as ionophobic units[1]. Their electrochemical properties were also measured.1H NMR and FTIR analysis results elucidated that PEG-b-glycidyl met...

  11. Elisapterosin F: a polycyclic gorgonian-derived diterpene with a facially amphiphilic structure (United States)

    Rodríguez, Ileana I.; Rodríguez, Abimael D.


    Analysis of the terpene metabolites of Pseudopterogorgia elisabethae collected in San Andrés island, Colombia has resulted in the discovery of a novel metabolite, elisapterosin F (1). The tangled molecular structure of 1, which was elucidated after extensive spectroscopic data interpretation, possesses hydrophilic and hydrophobic groups located on two opposite faces, rather than at two ends as in the more conventional head/tail amphiphiles. PMID:20161151

  12. Vortex-Induced Alignment of a Water Soluble Supramolecular Nanofiber Composed of an Amphiphilic Dendrimer

    Directory of Open Access Journals (Sweden)

    Akihiko Tsuda


    Full Text Available We have synthesized a novel amphiphilic naphthalene imide bearing a cationic dendrimer wedge (NID. NID molecules in water self-assemble to form a two-dimensional ribbon, which further coils to give a linear supramolecular nanofiber. The sample solution showed linear dichroism (LD upon stirring of the solution, where NID nanofibers dominantly align at the center of vortex by hydrodynamic interaction with the downward torsional flows.

  13. Vortex-induced alignment of a water soluble supramolecular nanofiber composed of an amphiphilic dendrimer. (United States)

    Yamamoto, Taiki; Tsuda, Akihiko


    We have synthesized a novel amphiphilic naphthalene imide bearing a cationic dendrimer wedge (NID). NID molecules in water self-assemble to form a two-dimensional ribbon, which further coils to give a linear supramolecular nanofiber. The sample solution showed linear dichroism (LD) upon stirring of the solution, where NID nanofibers dominantly align at the center of vortex by hydrodynamic interaction with the downward torsional flows.

  14. New synthesis of amphiphilic copolymers PE-g-PEO via esterfication

    Institute of Scientific and Technical Information of China (English)


    A new series of high molecular weight amphiphilic graft copolymers PE-g-PEO has been prepared. The esterifications between PE-p-MS-g-MA and PEO with OH group at the chain end are carried out under different conditions. The compositions of these graft copolymers are studied by NMR and FTIR. It is found to be a convenient and efficient way to prepare high molecular weight PE-g-PEO graft copolymers.

  15. Exploring single chain amphiphile self-assembly and their possible roles in light transduction

    DEFF Research Database (Denmark)

    Monnard, Pierre-Alain


    Self-assembled structures of single-chain amphiphiles have been used as hosts for biochemical, and chemical reactions. Their use as models for protocells (i.e., precursors to the first biological cells) has been extensively researched by various groups because the availability of single chain amp...... network. References 1 Cape, J., et al. (2011) Chem. Sci., 2 (4), 661-667. 2 Maurer, S. E., et al. (2009) Astrobiology, 9, 979-987. 3 Caschera, F., et al. Langmuir, In press....

  16. New Amphiphilic Polypyridyl Ruthenium(Ⅱ) Sensitizer and Its Application in Dye-Sensitized Solar Cells

    Institute of Scientific and Technical Information of China (English)

    KONG Fan-Tai; DAI Song-Yuan; WANG Kong-Jia


    Amphiphilic polypyridyl ruthenium(Ⅱ) complex cis-di(isothiocyanato)(4,4'-di-tert-butyl-2,2'-bipyridyl)(4,4'-dicarboxy-2,2'-bipyridyl)ruthenium(Ⅱ) (K005) has been synthesized and characterized by cyclic voltammetry, 1H NMR, UV-Vis, and FT-IR spectroscopies. The sensitizer sensitizes TiO2 over a notably broad spectral range due to its intense metal-to-ligand charge-transfer (MLCT) bands at 537 and 418 nm. The photophysical and photochemical studies of K005 were contrasted with those of cis-Ru(dcbpy)2(NCS)2, known as the N3 dye, and the amphiphilic ruthenium(Ⅱ) dye Z907. A reversible couple at E1/2=0.725 V vs. saturated calomel electrode (SCE) with a separation of 0.08 V between the anodic and cathodic peaks, was observed due to the RuⅡ/Ⅲ couple by cyclic voltammetry.Furthermore, this amphiphilic ruthenium complex was successfully used as sensitizers for dye-sensitized solar cells with the efficiency of 3.72% at the 100 mW·cm-2 irradiance of air mass 1.5 simulated sunlight without optimization of TiO2 films and the electrolyte.

  17. Self-Assembly of Discrete Metal Complexes in Aqueous Solution via Block Copolypeptide Amphiphiles

    Directory of Open Access Journals (Sweden)

    Timothy J. Deming


    Full Text Available The integration of discrete metal complexes has been attracting significant interest due to the potential of these materials for soft metal-metal interactions and supramolecular assembly. Additionally, block copolypeptide amphiphiles have been investigated concerning their capacity for self-assembly into structures such as nanoparticles, nanosheets and nanofibers. In this study, we combined these two concepts by investigating the self-assembly of discrete metal complexes in aqueous solution using block copolypeptides. Normally, discrete metal complexes such as [Au(CN2]−, when molecularly dispersed in water, cannot interact with one another. Our results demonstrated, however, that the addition of block copolypeptide amphiphiles such as K183L19 to [Au(CN2]− solutions induced one-dimensional integration of the discrete metal complex, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Transmission electron microscopy (TEM showed a fibrous nanostructure with lengths and widths of approximately 100 and 20 nm, respectively, which grew to form advanced nanoarchitectures, including those resembling the weave patterns of Waraji (traditional Japanese straw sandals. This concept of combining block copolypeptide amphiphiles with discrete coordination compounds allows the design of flexible and functional supramolecular coordination systems in water.

  18. Amphiphilic crescent-moon-shaped microparticles formed by selective adsorption of colloids. (United States)

    Kim, Shin-Hyun; Abbaspourrad, Alireza; Weitz, David A


    We use a microfluidic device to prepare monodisperse amphiphilic particles in the shape of a crescent-moon and use these particles to stabilize oil droplets in water. The microfluidic device is comprised of a tapered capillary in a theta (θ) shape that injects two oil phases into water in a single receiving capillary. One oil is a fluorocarbon, while the second is a photocurable monomer, which partially wets the first oil drop; silica colloids in the monomer migrate and adsorb to the interface with water but do not protrude into the oil interface. Upon UV-induced polymerization, solid particles with the shape of a crescent moon are formed; removal of fluorocarbon oil yields amphiphilic particles due to the selective adsorption of silica colloids. The resultant amphiphilic microparticles can be used to stabilize oil drops in a mixture of water and ethanol; if they are packed to sufficient surface density on the interface of the oil drop, they become immobilized, preventing direct contact between neighboring drops, thereby providing the stability.

  19. Complexation between a macromolecule and an amphiphile by Monte Carlo technique. (United States)

    Gharibi, Hussein; Behjatmanesh-Ardakani, Reza; Hashemianzadeh, Majid; Mousavi-Khoshdel, Morteza


    Using a simple modified version of Larson's model, we studied the complexation between a macromolecule and an amphiphile in a dilute range of concentrations. The main characteristic of amphiphile molecules, that is, the hydrophobicity of the tails and hydrophilicity of the heads, is used to model the self-assembling process. Contrary to the molecular thermodynamics approaches, no prior shape was considered for the aggregates and the system was allowed to choose the most stable structure. For true ensemble averaging, without any synthetic results, configurational bias Monte Carlo and reptation moves are used to produce a Markov chain of configurations. From the results, it is found that the macromolecule causes the clusters of surfactants to be formed at a concentration much lower than the critical micelle concentration. Furthermore, the shape of the clusters tends to be more spherical, which is in line with theory and experiments. From the results, it is learned how a polymer can change the behavior of an amphiphilic molecule. All of the results are in good qualitative agreement with experimental and molecular thermodynamics results. Furthermore, the model predicts network formation between bound clusters at high concentrations of the surfactant.

  20. Wet foams hydrophobized by amphiphiles to give Al2O3 porous ceramics (United States)

    Pokhrel, Ashish; Park, Jung Gyu; Kim, Ik Jin


    Wet chemical method to prepare ceramic foams with antecedent stability using inorganic particles (Al2O3,SiO2 etc.) which are in situ hydrophobized upon adsorption of short-chain amphiphilic molecules in the wet state and heightened mechanical property in the sintered state was developed. These wet foams are stable over several days and show no bubble coarsening nor drainage or creaming. This long-term stability is achieved through the irreversible adsorption of partially hydrophobized colloidal particles to the air-water interface using short-chain amphiphiles to in situ modify the wetting behavior of the particle surface based on the observations of Pickering emulsions. As a result, the suspension is foamed homogeneously throughout its entire volume and porous bulk materials can be produced upon drying and sintering. Wet foams featuring average bubble sizes between 30 and 300μm and sintered foams with porosity from 50 to 85% were obtained by adjusting the amphiphile - particle concentration, and additives in the initial suspension. Cells were mostly closed with an average size of approximately 150 μm. Single cells were separated by walls with minimum thicknesses of 1-3 μm.

  1. The search for new amphiphiles: synthesis of a modular, high-throughput library

    Directory of Open Access Journals (Sweden)

    George C. Feast


    Full Text Available Amphiphilic compounds are used in a variety of applications due to their lyotropic liquid-crystalline phase formation, however only a limited number of compounds, in a potentially limitless field, are currently in use. A library of organic amphiphilic compounds was synthesised consisting of glucose, galactose, lactose, xylose and mannose head groups and double and triple-chain hydrophobic tails. A modular, high-throughput approach was developed, whereby head and tail components were conjugated using the copper-catalysed azide–alkyne cycloaddition (CuAAC reaction. The tails were synthesised from two core alkyne-tethered intermediates, which were subsequently functionalised with hydrocarbon chains varying in length and degree of unsaturation and branching, while the five sugar head groups were selected with ranging substitution patterns and anomeric linkages. A library of 80 amphiphiles was subsequently produced, using a 24-vial array, with the majority formed in very good to excellent yields. A preliminary assessment of the liquid-crystalline phase behaviour is also presented.

  2. Binary-component micelle and vesicle: Free energy and asymmetric distributions of amphiphiles between vesicle monolayers

    Institute of Scientific and Technical Information of China (English)

    Zhang Qi-Yi; Xiang Xun


    The real-space two-dimensional self-consistent field theory (SCFT) is employed to study the free energies of micelles and vesicles constituted by binary amphiphilic diblock copolymer AB in homopolymer A.With an increasing volume fraction of copolymer AB,there are morphological transitions from circle micelles to oblate circle-like micelles,to a compound structure with inverted micelles in the inner center and micelles outer layer,and to vesicles.Special attention is paid to the role of the copolymer AB in controlling the free energies of the micelles and vesicles by examining the effect of the length ratio of A/B with the fixed whole chain length of the AB copolymer,the length effect of A or B block with the corresponding fixed length of B or A block,for one component of copolymer,and the effect of different amphiphile compositions for a binary-component copolymer system.The quantity η is provided to describe the asymmetric density distribution of amphiphiles between the inner and outer monolayers of vesicles,and to quantify the relative asymmetric extent of the density distribution between two species of copolymers in binary component vesicles.

  3. Precisely Size-Tunable Monodisperse Hairy Plasmonic Nanoparticles via Amphiphilic Star-Like Block Copolymers. (United States)

    Chen, Yihuang; Yoon, Young Jun; Pang, Xinchang; He, Yanjie; Jung, Jaehan; Feng, Chaowei; Zhang, Guangzhao; Lin, Zhiqun


    In situ precision synthesis of monodisperse hairy plasmonic nanoparticles with tailored dimensions and compositions by capitalizing on amphiphilic star-like diblock copolymers as nanoreactors are reported. Such hairy plasmonic nanoparticles comprise uniform noble metal nanoparticles intimately and perpetually capped by hydrophobic polymer chains (i.e., "hairs") with even length. Interestingly, amphiphilic star-like diblock copolymer nanoreactors retain the spherical shape under reaction conditions, and the diameter of the resulting plasmonic nanoparticles and the thickness of polymer chains situated on the surface of the nanoparticle can be readily and precisely tailored. These hairy nanoparticles can be regarded as hard/soft core/shell nanoparticles. Notably, the polymer "hairs" are directly and permanently tethered to the noble metal nanoparticle surface, thereby preventing the aggregation of nanoparticles and rendering their dissolution in nonpolar solvents and the homogeneous distribution in polymer matrices with long-term stability. This amphiphilic star-like block copolymer nanoreactor-based strategy is viable and robust and conceptually enables the design and synthesis of a rich variety of hairy functional nanoparticles with new horizons for fundamental research on self-assembly and technological applications in plasmonics, catalysis, energy conversion and storage, bioimaging, and biosensors.


    Institute of Scientific and Technical Information of China (English)

    Takeaki Miyamoto; Masahiko Minoda; Yoshinobu Tsujii


    Vinyl ether (VE)-based amphiphilic block copolymers with D-glucose residues as hydrophilic pendants were synthesized by CH3CH(OiBu)Cl/ZnI2-initiated sequential living cationic copolymerization of 3-O-(vinyloxy)ethyl-1, 2:5, 6-di-O-isopropylidene-D-glucofuranose (IGVE) and isobutyl VE (IBVE) and subsequent deprotection. The precursor block copolymers had a narrow molecular weight distribution(Mw/Mn~1.1) and a controlled segmental composition. The solubility characteristics of the amphiphilic copolymer depended strongly on composition. Their solvent-cast thin films were examined, under a transmission electron microscope, and could be seen to exhibit various microphase-separated surface morphologies such as spheres, cylinders, and lamellae, depending on composition. The amphiphilic copolymers with the appropriate segmental composition were found to form a stable monolayer at the airwater interface, which was successfully transferred onto a substrate by the Langmuir-Blodgett (LB)technique. The layered structure of the built-up LB films was controlled by blending the homopolymer.

  5. Gold Nanoparticles Protected with Thiol-Derivatized Amphiphilic Poly( -caprolactone)-b-poly(acrylic acid)

    DEFF Research Database (Denmark)

    Javakhishvili, Irakli; Hvilsted, Søren


    chromatography (SEC), nuclear magnetic resonance eR NMR) and infrared (FT IR) spectroscopy. The capacity of the resulting block copolymer in preparation of monolayer-protected gold nanoparticles has been examined by reduction of a gold salt in the presence of this macroligand under thiol-deficient conditions...

  6. Co-Delivery of Imiquimod and Plasmid DNA via an Amphiphilic pH-Responsive Star Polymer that Forms Unimolecular Micelles in Water

    Directory of Open Access Journals (Sweden)

    Wenjing Lin


    Full Text Available Dual functional unimolecular micelles based on a pH-responsive amphiphilic star polymer β-CD-(PLA-b-PDMAEMA-b-PEtOxMA21 have been developed for the co-delivery of imiquimod and plasmid DNA to dendritic cells. The star polymer with well-defined triblock arms was synthesized by combining activator regenerated by electron-transfer atom-transfer radical polymerization with ring-opening polymerization. Dissipative particle dynamics simulation showed that core-mesophere-shell-type unimolecular micelles could be formed. Imiquimod-loaded micelles had a drug loading of 1.6 wt % and a larger average size (28 nm than blank micelles (19 nm. The release of imiquimod in vitro was accelerated at the mildly acidic endolysosomal pH (5.0 in comparison to physiologic pH (7.4. Compared with blank micelles, a higher N:P ratio was required for imiquimod-loaded micelles to fully condense DNA into micelleplexes averaging 200–400 nm in size. In comparison to blank micelleplexes, imiquimod-loaded micelleplexes of the same N:P ratio displayed similar or slightly higher efficiency of gene transfection in a mouse dendritic cell line (DC2.4 without cytotoxicity. These results suggest that such pH-responsive unimolecular micelles formed by the well-defined amphiphilic star polymer may serve as promising nano-scale carriers for combined delivery of hydrophobic immunostimulatory drugs (such as imiquimod and plasmid DNA with potential application in gene-based immunotherapy.

  7. Micellar and vesicular nanoassemblies of triazole-based amphiphilic probes triggered by mercury(II) ions in a 100% aqueous medium. (United States)

    Kim, Inhye; Lee, Na-Eun; Jeong, Yoo-Jeong; Chung, Young-Ho; Cho, Byoung-Ki; Lee, Eunji


    ABA-type amphiphiles bearing a triazole-based aromatic block were easily synthesized using click chemistry, which act as fluorescent turn-off Hg(2+)-chemoprobes in an aqueous solution. Interestingly, the metal-binding process of amphiphiles induced nanoassemblies even below the CMCs, and the binding stoichiometry affected the morphologies of the resultant nanostructures.

  8. Construction of amphiphilic segments on polypropylene nonwoven surface and its application in removal of endocrine disrupting compounds (EDCs) from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Kai [State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Tianjin Polytechnic University, Tianjin 300160 (China); School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300160 (China); Wei, Junfu, E-mail: [State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Tianjin Polytechnic University, Tianjin 300160 (China); School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300160 (China); Zhou, Xiangyu [State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Tianjin Polytechnic University, Tianjin 300160 (China); School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300160 (China); School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300160 (China); Liu, Nana [State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Tianjin Polytechnic University, Tianjin 300160 (China); School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300160 (China)


    Highlights: • The amphiphilic segments on polypropylene nonwoven surface were constructed successfully. • The adsorption behavior for EDCs of the amphiphilic adsorption materials was systematically studied. • The novel amphiphilic adsorption materials have broad application prospects in EDCs removal from aqueous solution. - Abstract: The amphiphilic segments on polypropylene nonwoven (PP nonwoven) surface were constructed using the ultraviolet (UV) irradiation graft polymerization for the removal of endocrine disrupting compounds (EDCs) with different polarity from aqueous solution. The stearyl acrylate (SA) as hydrophobic functional monomer was introduced onto the surface of PP nonwoven fabric at first stage and then the hydroxyethyl acrylate (HEA) as hydrophilic functional monomer was introduced subsequently. The effect of functional monomer concentration and UV irradiation time on grafting ratio was studied and discussed. The novel amphiphilic structure was designed and constructed based on adsorption capacity for the target micropollutants. The structure and composition of the amphiphilic adsorption materials were characterized by Fourier transform infrared spectrometer (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and contact angle (CA). The adsorption behaviors for EDCs of the amphiphilic adsorption materials were studied and the results indicated that the adsorption capacity and adsorption rate were superior to single SA grafted PP nonwoven (PP-g-SA) and single HEA grafted PP nonwoven (PP-g-HEA). The novel amphiphilic adsorption material was efficient for the removal of EDCs with different polarity and could be utilized as a potential adsorption material for removing EDCs from aqueous solution.

  9. Environment-sensitive amphiphilic fluorophore for selective sensing of protein. (United States)

    Ojha, Bimlesh; Das, Gopal


    Here we report the selective sensing of BSA (bovine serum albumin) by 8-(alkoxy)quinoline-based fluorescent probes, via non-covalent interactions. The weak fluorescence of these probes in aqueous solution showed a dramatic increase in quantum yield and lifetime upon binding with BSA, while the responses to various other proteins/enzymes used were negligible under similar experimental conditions. The emission of the probe is affected by the interplay with BSA but not with tryptophan amino acid suggesting that the microenvironment created by the macromolecule induces some change in their excited-state properties. Binding site assignment by a known site-selective binding ligand enabled us to conclude that the compounds predominantly bind at site I of BSA. The changes in fluorescence intensity and the position of emission maxima of compounds in presence of BSA along with the increase in steady state anisotropy values well reflect the nature of binding and location of the probe inside the protein environment. Compounds interact with BSA efficiently and exhibit site selectivity and thus have the potentiality to serve as an efficient and selective sensor of protein.

  10. Synthesis of Thermoresponsive Amphiphilic Polyurethane Gel as a New Cell Printing Material near Body Temperature. (United States)

    Tsai, Yi-Chun; Li, Suming; Hu, Shiaw-Guang; Chang, Wen-Chi; Jeng, U-Ser; Hsu, Shan-hui


    Waterborne polyurethane (PU) based on poly(ε-caprolactone) (PCL) diol and a second oligodiol containing amphiphilic blocks was synthesized in this study. The microstructure was characterized by dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and rheological measurement of the PU dispersion. The surface hydrophilicity measurement, infrared spectroscopy, wide-angle X-ray diffraction, mechanical and thermal analyses were conducted in solid state. It was observed that the presence of a small amount of amphiphilic blocks in the soft segment resulted in significant changes in microstructure. When 90 mol % PCL diol and 10 mol % amphiphilic blocks of poly(l-lactide)-poly(ethylene oxide) (PLLA-PEO) diol were used as the soft segment, the synthesized PU had a water contact angle of ∼24° and degree of crystallinity of ∼14%. The dispersion had a low viscosity below room temperature. As the temperature was raised to body temperature (37 °C), the dispersion rapidly (∼170 s) underwent sol-gel transition with excellent gel modulus (G' ≈ 6.5 kPa) in 20 min. PU dispersions with a solid content of 25-30% could be easily mixed with cells in sol state, extruded by a 3D printer, and deposited layer by layer as a gel. Cells remained alive and proliferating in the printed hydrogel scaffold. We expect that the development of novel thermoresponsive PU system can be used as smart injectable hydrogel and applied as a new type of bio-3D printing ink.

  11. Nonionic amphiphile nanoarchitectonics: self-assembly into micelles and lyotropic liquid crystals (United States)

    Shrestha, Lok Kumar; Strzelczyk, Karolina Maria; Goswami Shrestha, Rekha; Ichikawa, Kotoko; Aramaki, Kenji; Hill, Jonathan P.; Ariga, Katsuhiko


    Amphiphiles, molecules that possess both hydrophilic and hydrophobic moieties, are architecturally simple molecules that can spontaneously self-assemble into complex hierarchical structures from lower to higher dimensions either in the bulk phase or at an interface. Recent developments in multifunctional nanostructure design using the advanced concept of nanoarchitectonics utilize this simple process of assembly. Amphiphilic self-assemblies involving lipids or proteins mimic the structure of biological systems, thus highlighting the necessity of a fundamental physical understanding of amphiphilic self-assembly towards a realization of the complex mechanisms operating in nature. Herein, we describe self-assembled microstructures of biocompatible and biodegradable tetraglycerol lauryl ether (C12G4) nonionic surfactant in an aqueous solvent system. Temperature-composition analyses of equilibrium phases identified by using small-angle x-ray scattering (SAXS) provide strong evidence of various spontaneously self-assembled mesostructures, such as normal micelles (Wm), hexagonal liquid crystal (H1), and reverse micelles (Om). In contrast to conventional poly(oxyethylene) nonionic surfactants, C12G4 did not exhibit the clouding phenomenon at higher temperatures (phase separation was not observed up to 100 °C), demonstrating the greater thermal stability of the self-assembled mesophases. Generalized indirect Fourier transformation (GIFT) evaluation of the SAXS data confirmed the formation of core-shell-type spherical micelles with a maximum dimension ca. 8.7 nm. The shape and size of the C12G4 micelles remained apparently unchanged over a wide range of concentrations (up to 20%), but intermicellar interactions increased and could be described by the Percus-Yevick (PY) theory (after Carnahan and Starling), which provides a very accurate analytical expression for the osmotic pressure of a monodisperse hard sphere.

  12. Amphiphilic block copolymers bearing six-membered ortho ester ring in side chains as potential drug carriers: synthesis, characterization, and in vivo toxicity evaluation. (United States)

    Luo, Shi; Tao, Yangyang; Tang, Rupei; Wang, Rui; Ji, Weihang; Wang, Chun; Zhao, Youliang


    A new type of amphiphilic block copolymers, poly(ethylene glycol)-block-poly(2-methyl-acrylicacid 2-methoxy-5-methyl-[1,3]dioxin-5-ylmethyl ester) (PEG-b-PMME), bearing acid-labile six-membered ortho ester rings in side chains was synthesized by reversible addition-fragmentation chain-transfer polymerization, and the influence of chain length of the hydrophobic PMME block on micelle properties was investigated. The PEG-b-PMME micelles were stable in aqueous buffer at physiological pH with a low critical micelle concentration. Nile Red as a model drug was encapsulated into the micelles to explore the release profiles. The Nile Red-loaded polymeric micelles showed rapid release of Nile Red in weakly acidic environments (pH 5) but slow release under physiological condition (pH 7.4), due to different hydrolysis rate of ortho ester side chains of PEG-b-PMME. The Paclitaxel (PTX)-loaded micelles retained potency in killing lung cancer cells (A549), compared with the free PTX. No obvious toxicity was found in vitro and in vivo after intraperitoneal injection of the micelles, which confirms that the PEG-b-PMME micelles with unique acid-labile characteristic have great potential as nano-scaled carriers for drug delivery.

  13. Micelle and bilayer formation of amphiphilic janus particles in a slit-pore. (United States)

    Rosenthal, Gerald; Klapp, Sabine H L


    We employ molecular dynamics simulations to investigate the self-assembly of amphiphilic Janus particles in a slit-pore consisting of two plane-parallel, soft walls. The Janus particles are modeled as soft spheres with an embedded unit vector pointing from the hydrophobic to the hydrophilic hemisphere. The structure formation is analyzed via cluster size distributions, density and polarization profiles, and in-plane correlation functions. At low temperatures and densities, the dominating structures are spherical micelles, whereas at higher densities we also observe wall-induced bilayer formation. Finally, we compare the MD results with those from a previous density functional study.

  14. Micelle and Bilayer Formation of Amphiphilic Janus Particles in a Slit-Pore

    Directory of Open Access Journals (Sweden)

    Sabine H. L. Klapp


    Full Text Available We employ molecular dynamics simulations to investigate the self-assembly of amphiphilic Janus particles in a slit-pore consisting of two plane-parallel, soft walls. The Janus particles are modeled as soft spheres with an embedded unit vector pointing from the hydrophobic to the hydrophilic hemisphere. The structure formation is analyzed via cluster size distributions, density and polarization profiles, and in-plane correlation functions. At low temperatures and densities, the dominating structures are spherical micelles, whereas at higher densities we also observe wall-induced bilayer formation. Finally, we compare the MD results with those from a previous density functional study.

  15. Amphiphilic Polyphosphazene with Poly(ethylene oxide) Side Chains Prepared through the Decker-Forster Reaction

    Institute of Scientific and Technical Information of China (English)

    LIU Chengmei; HU Fuzhen; QIU Jinjun; LEI Guofu; BAO Rui


    Poly(4-methylphenoxyphosphazene)-graft-poly(ethylene oxide) (PPZ-g-PEO), a novel amphiphilic grafting polymer was prepared via the Decker-Forster reaction. It is found that the graft efficiency increased with extension of reaction time. Low molecular weight of poly(ethylene oxide) favored the grafting reaction. The grafted polymer has two different glass transition temperatures(Tg) with those of pure poly(4-methylphenoxy-phopsphazene) and PEO. The emulsifying ability of grafted polymer was studied with benzene-water mixture. The emulsifying volumes increased with the decreasing of PEO's molecular weight. The contact angle of film forming from grafted polymer decreased after introduction of PEO grafting chain.

  16. Plasmonic Vesicles of Amphiphilic Nanocrystals: Optically Active Multifunctional Platform for Cancer Diagnosis and Therapy. (United States)

    Song, Jibin; Huang, Peng; Duan, Hongwei; Chen, Xiaoyuan


    Vesicular structures with compartmentalized, water-filled cavities, such as liposomes of natural and synthetic amphiphiles, have tremendous potential applications in nanomedicine. When block copolymers self-assemble, the result is polymersomes with tailored structural properties and built-in releasing mechanisms, controlled by stimuli-responsive polymer building blocks. More recently, chemists are becoming interested in multifunctional hybrid vesicles containing inorganic nanocrystals with unique optical, electronic, and magnetic properties. In this Account, we review our recent progress in assembling amphiphilic plasmonic nanostructures to create a new class of multifunctional hybrid vesicles and applying them towards cancer diagnosis and therapy. Localized surface plasmon resonance (LSPR) gives plasmonic nanomaterials a unique set of optical properties that are potentially useful for both biosensing and nanomedicine. For instance, the strong light scattering at their LSPR wavelength opens up the applications of plasmonic nanostructures in single particle plasmonic imaging. Their superior photothermal conversion properties, on the other hand, make them excellent transducers for photothermal ablation and contrast agents for photoacoustic imaging. Of particular note for ultrasensitive detection is that the confined electromagnetic field resulting from excitation of LSPR can give rise to highly efficient surface enhanced Raman scattering (SERS) for molecules in close proximity. We have explored several ways to combine well-defined plasmonic nanocrystals with amphiphilic polymer brushes of diverse chemical functionalities. In multiple systems, we have shown that the polymer grafts impart amphiphilicity-driven self-assembly to the hybrid nanoparticles. This has allowed us to synthesize well-defined vesicles in which we have embedded plasmonic nanocrystals in the shell of collapsed hydrophobic polymers. The hydrophilic brushes extend into external and interior aqueous

  17. Synthesis and Characterization of Amphiphilic Block Copolymer Containing PVP and Poly(5-benzyloxytrimethylene carbonate)

    Institute of Scientific and Technical Information of China (English)

    Ying Xia WANG; Feng HE; Ren Xi ZHUO


    Amphiphilic copolymer of 5-benzyloxytrimethylene carbonate (BTMC) with poly (vinyl pyrrolidone) (PVP) was successfully synthesized using immobilized porcine pancreas lipase (IPPL) or SnOct2 as catalyst. Hydroxyl terminated PVP, synthesized with 2-mercaptoethanol as a chain transfer reagent, was employed as a macroinitiator. The resulting copolymers were characterized by GPC, 1H NMR and IR. Increasing the BTMC/PVP-OH feed ratio ([B]/[P])resulted in the increase of Mn of corresponding copolymers and the decrease of Mw/Mn.Immobilized enzyme has comparable catalytic activity to SnOct2 for the copolymerization.

  18. Mobilization and biodegradation of 2-methylnaphthalene by amphiphilic polyurethane nano-particle. (United States)

    Kim, Young-Bum; Kim, Ju-Young; Kim, Eun-ki


    Amphiphilic polyurethane (APU) nano-particle enhanced the mobilization of 2-methylnaphthalene (2-MNPT) in soil. Significant increase in the solubility of 2-MNPT was achieved. The molar solubilization ratio was 0.4 (mole 2-MNPT/mole APU). Simple precipitation of APU particle by 2 N CaCl(2) recovered 95% of APU particle and 92% of 2-MNPT simultaneously. Also, 2-MNPT, which was entrapped inside the APU particle, was directly degraded by Acinetobacter sp. as same efficiency as without APU particle. These results showed the potentials of APU particle in the mobilization and biodegradation of hydrophobic compounds from soil.

  19. Aggregation behavior of cholic acid derivatives in organic solvents and in water

    NARCIS (Netherlands)

    Willemen, H.M.


    In this thesis various cholic acid derivatives are reported that display aggregation in water or in organic solvents. Spontaneous aggregation of single molecules into larger, ordered structures occurs at the borderline of solubility. Amphiphilic compounds, or surfactants, which possess a hydrophobic

  20. Hydrogen-Abstraction, Energy Transfer and Exciplex Formation in Photoactive Systems Based on Bile Acids


    Miró Richart, Paula


    [EN] Bile acids are a family of amphiphilic steroids that play a pivotal role in physiological functions such as elimination of cholesterol or solubilization of lipids. Chemically, they share a steroidal skeleton with an unusual cis fusion between rings A and B, a short lateral chain ending in a carboxylic acid moiety and different number of hydroxyl groups on the alpha-face. Hence, bile acids offer a versatile architecture that can be used to investigate photophysical processes of interest ...

  1. Removal of volatile organic compounds using amphiphilic cyclodextrin-coated polypropylene

    Directory of Open Access Journals (Sweden)

    Ludmilla Lumholdt


    Full Text Available Polypropylene nonwovens were functionalised using a self-assembled, amphiphilic cyclodextrin coating and the potential for water purification by removal of pollutants was studied. As benzene is one of the problematic compounds in the Water Framework Directive, six volatile organic compounds (benzene and five benzene-based substances were chosen as model compounds. The compounds were tested as a mixture in order to provide a more realistic situation since the wastewater will be a complex mixture containing multiple pollutants. The volatile organic compounds are known to form stable inclusion complexes with cyclodextrins. Six different amphiphilic cyclodextrin derivatives were synthesised in order to elucidate whether or not the uptake abilities of the coating depend on the structure of the derivative. Headspace gas chromatography was used for quantification of the uptake exploiting the volatile nature of benzene and its derivatives. The capacity was shown to increase beyond the expected stoichiometries of guest–host complexes with ratios of up to 16:1.

  2. Rapidly recovering hydrogel scaffolds from self-assembling diblock copolypeptide amphiphiles (United States)

    Nowak, Andrew P.; Breedveld, Victor; Pakstis, Lisa; Ozbas, Bulent; Pine, David J.; Pochan, Darrin; Deming, Timothy J.


    Protein-based hydrogels are used for many applications, ranging from food and cosmetic thickeners to support matrices for drug delivery and tissue replacement. These materials are usually prepared using proteins extracted from natural sources, which can give rise to inconsistent properties unsuitable for medical applications. Recent developments have utilized recombinant DNA methods to prepare artificial protein hydrogels with specific association mechanisms and responsiveness to various stimuli. Here we synthesize diblock copolypeptide amphiphiles containing charged and hydrophobic segments. Dilute solutions of these copolypeptides would be expected to form micelles; instead, they form hydrogels that retain their mechanical strength up to temperatures of about 90°C and recover rapidly after stress. The use of synthetic materials permits adjustment of copolymer chain length and composition, which we varied to study their effect on hydrogel formation and properties. We find that gelation depends not only on the amphiphilic nature of the polypeptides, but also on chain conformations-α-helix, β-strand or random coil. Indeed, shape-specific supramolecular assembly is integral to the gelation process, and provides a new class of peptide-based hydrogels with potential for applications in biotechnology.

  3. Benzothiazole Amphiphiles Ameliorate Amyloid β-Related Cell Toxicity and Oxidative Stress. (United States)

    Cifelli, Jessica L; Chung, Tim S; Liu, Haiyan; Prangkio, Panchika; Mayer, Michael; Yang, Jerry


    Oxidative stress from the increase of reactive oxygen species in cells is a common part of the normal aging process and is accelerated in patients with Alzheimer's disease (AD). Herein, we report the evaluation of three benzothiazole amphiphiles (BAMs) that exhibit improved biocompatibility without loss of biological activity against amyloid-β induced cell damage compared to a previously reported hexa(ethylene glycol) derivative of benzothiazole aniline (BTA-EG6). The reduced toxicity of these BAM agents compared to BTA-EG6 corresponded with their reduced propensity to induce membrane lysis. In addition, all of the new BAMs were capable of protecting differentiated SH-SY5Y neuroblastoma cells from toxicity and concomitant oxidative stress induced by AD-related aggregated Aβ (1-42) peptides. Binding and microscopy studies support that these BAM agents target Aβ and inhibit the interactions of catalase with Aβ in cells, which, in turn, can account for an observed inhibition of Aβ-induced increases in hydrogen peroxide in cells treated with these compounds. These results support that this family of benzothiazole amphiphiles may have therapeutic potential for treating cellular damage associated with AD and other Aβ-related neurologic diseases.

  4. A synthetic strategy for novel nonsymmetrical bola amphiphiles based on carbohydrates. (United States)

    Schuur, Boelo; Wagenaar, Anno; Heeres, André; Heeres, Erik H J


    A number of novel nonionic bolaform amphiphiles with nonidentical aldityl head groups, 1-(1-deoxy-D-galactitol-1-ylamino)-6-(1-deoxy-D-glucitol-1-ylamino)hexane, 1-(1-deoxy-D-mannitol-1-ylamino)-6-(1-deoxy-D-glucitol-1-ylamino)hexane, and 1-(1-deoxy-D-galactitol-1-ylamino)-6-(1-deoxy-D-mannitol-1-ylamino)hexane were synthesized by two successive reductive aminations involving 1,6-diaminohexane (1) and the appropriate D-aldohexoses (D-glucose, D-mannose, and D-galactose) using 5% Pd on carbon as the catalyst. Typical reaction conditions were 40 degrees C, 4MPa hydrogen and a reaction time of 4.5 h. The compounds were isolated as white solids in yields ranging from 39% to 72%. The intermediate aminoalditols, 1-(1-deoxy-D-glucitol-1-ylamino)-6-aminohexane and 1-(1-deoxy-D-galactitol-1-ylamino)-6-aminohexane were obtained as off-white solids in 80-85% yield. The bolaform amphiphiles containing 1-deoxy-D-glucitol head group(s) showed markedly lower melting points than the compounds with the 1-deoxy-D-mannitol and 1-deoxy-D-galactitol head groups, due to the presence of 1,3-syn interactions within the carbohydrate moiety. The novel bolaform compounds are potential starting materials for the synthesis of a broad range of gemini surfactants with nonidentical, carbohydrate-based head groups.

  5. Using amphiphilic nanostructures to enable long-range ensemble coalescence and surface rejuvenation in dropwise condensation. (United States)

    Anderson, David M; Gupta, Maneesh K; Voevodin, Andrey A; Hunter, Chad N; Putnam, Shawn A; Tsukruk, Vladimir V; Fedorov, Andrei G


    Controlling coalescence events in a heterogeneous ensemble of condensing droplets on a surface is an outstanding fundamental challenge in surface and interfacial sciences, with a broad practical importance in applications ranging from thermal management of high-performance electronic devices to moisture management in high-humidity environments. Nature-inspired superhydrophobic surfaces have been actively explored to enhance heat and mass transfer rates by achieving favorable dynamics during dropwise condensation; however, the effectiveness of such chemically homogeneous surfaces has been limited because condensing droplets tend to form as pinned Wenzel drops rather than mobile Cassie ones. Here, we introduce an amphiphilic nanostructured surface, consisting of a hydrophilic base with hydrophobic tips, which promotes the periodic regeneration of nucleation sites for small droplets, thus rendering the surface self-rejuvenating. This unique amphiphilic nanointerface generates an arrangement of condensed Wenzel droplets that are fluidically linked by a wetted sublayer, promoting previously unobserved coalescence events where numerous droplets simultaneously merge, without direct contact. Such ensemble coalescences rapidly create fresh nucleation sites, thereby shifting the overall population toward smaller droplets and enhancing the rates of mass and heat transfer during condensation.

  6. Thymine-functionalized amphiphilic biodegradable copolymers for high-efficiency loading and controlled release of methotrexate. (United States)

    Cheng, Dong-Bing; Li, You-Mei; Cheng, Yin-Jia; Wu, Yan; Chang, Xiu-Peng; He, Feng; Zhuo, Ren-Xi


    In this study, a novel thymine-functionalized six-membered cyclic carbonate monomer (TAC) was synthesized by the Michael-addition reaction between thymine and acryloyl carbonate (AC). The corresponding functional amphiphilic block copolymer mPEG-b-PTAC was further successfully synthesized by ring-opening polymerization using immobilized porcine pancreas lipase (IPPL) as the catalyst and mPEG as the macroinitiator. Meanwhile, mPEG-b-P(TAC-co-DTC) and mPEG-b-PDTC were also synthesized by the same enzymatic methods for comparison on different TAC contents. The structures of monomer and copolymers were characterized by (1)H-NMR, (13)C-NMR and FTIR. All the amphiphilic block copolymers could self-assemble to form nano-sized micelles in aqueous solution. Transmission electron microscopy (TEM) observation showed that the micelles dispersed in spherical shape with nano-size before and after MTX loading. (1)H-NMR and FTIR results confirmed the successful formation of multiple hydrogen-bonding interactions between exposed thymine groups of hydrophobic PTAC segments and 2,6-diaminopyridine (DAP) groups of MTX molecules, which resulting in the higher drug loading capacity and the pH-sensitive drug release behavior. MTT assays also indicated lower toxicity of copolymer but higher potent cytotoxic activity of MTX-loaded copolymer against HeLa cells.

  7. Amphiphilic nanosheet self-assembly at the water/oil interface: computer simulations. (United States)

    Xiang, Wenjun; Zhao, Shuangliang; Song, Xianyu; Fang, Shenwen; Wang, Fen; Zhong, Cheng; Luo, Zhaoyang


    In this paper, dissipative particle dynamics simulations are performed to study the interfacial and emulsion stabilizing properties of various systems of amphiphilic nanosheets (ANs) self-assembled at the oil/water (O/W) interface. The ANs have a dimensional symmetry structure that encompasses a triangular-plate at the center and two soft comb-like shells constructed with hydrophilic and hydrophobic polymers. As the simulation results show, the AN molecules are highly oriented in interfacial films with their triangular nanosheets parallel to the O/W interface, while their hydrophobic and hydrophilic segments attempt to immerse into the oil phase and aqueous phase, respectively. These results reveal that the rotation of ANs at oil/water interfaces is greatly restricted, meanwhile, their nanosheet (or planar) configuration facilitates their favorable orientation thereby, thus making the emulsion more stable. At higher concentrations, a wrapped-like or micelle morphology is observed. The O/W emulsions stabilized by ANs were also simulated, and it is interesting to find AN 'patches' at the O/W interface which resembles the leather patches on a football. By introducing the "amphiphilic nanosheet balance" concept, the hydrophilic-lipophilic balance (HLB) values of ANs were calculated. Due to their properties of two-dimensional symmetry, the HLB values of ANs tend to approximately 1 which reveals a stronger stability for emulsions.

  8. Hydration-Induced Phase Separation in Amphiphilic Polymer Matrices and its Influence on Voclosporin Release

    Energy Technology Data Exchange (ETDEWEB)

    Khan, I. John [The State Univ. of New Jersey, Piscataway, NJ (United States); Murthy, N. Sanjeeva [The State Univ. of New Jersey, Piscataway, NJ (United States); Kohn, Joachim [The State Univ. of New Jersey, Piscataway, NJ (United States)


    Voclosporin is a highly potent, new cyclosporine -- a derivative that is currently in Phase 3 clinical trials in the USA as a potential treatment for inflammatory diseases of the eye. Voclosporin represents a number of very sparingly soluble drugs that are difficult to administer. It was selected as a model drug that is dispersed within amphiphilic polymer matrices, and investigated the changing morphology of the matrices using neutron and x-ray scattering during voclosporin release and polymer resorption. The hydrophobic segments of the amphiphilic polymer chain are comprised of desaminotyrosyl-tyrosine ethyl ester (DTE) and desaminotyrosyl-tyrosine (DT), and the hydrophilic component is poly(ethylene glycol) (PEG). Water uptake in these matrices resulted in the phase separation of hydrophobic and hydrophilic domains that are a few hundred Angstroms apart. These water-driven morphological changes influenced the release profile of voclosporin and facilitated a burst-free release from the polymer. No such morphological reorganization was observed in poly(lactide-co-glycolide) (PLGA), which exhibits an extended lag period, followed by a burst-like release of voclosporin when the polymer was degraded. An understanding of the effect of polymer composition on the hydration behavior is central to understanding and controlling the phase behavior and resorption characteristics of the matrix for achieving long-term controlled release of hydrophobic drugs such as voclosporin.

  9. Discriminating binding and positioning of amphiphiles to lipid bilayers by {sup 1}H NMR

    Energy Technology Data Exchange (ETDEWEB)

    Evanics, F. [Department of Chemistry, University of Toronto, UTM, 3359 Mississauga Rd. North Mississauga, Ont., L5L 1C6 (Canada); Prosser, R.S. [Department of Chemistry, University of Toronto, UTM, 3359 Mississauga Rd. North Mississauga, Ont., L5L 1C6 (Canada)]. E-mail:


    The binding and positioning in lipid bilayers of three well-known drugs--imipramine, nicotine, and caffeine--have been studied using {sup 1}H NMR. The membrane model system consisted of 'fast-tumbling' lipid bicelles, in which a bilayered lipid domain, composed of the unsaturated lipid, 1,2-dimyristelaidoyl-sn-glycero-3-phosphocholine (DMLPC) was surrounded by a rim of deuterated detergent-like lipids, consisting of 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC-d22). Binding and immersion depth information was obtained by three experiments. (1) {sup 1}H chemical shift perturbations, upon transfer of the amphiphiles from water to a bicelle mixture, were used to estimate regions of the amphiphiles that interact with the membrane. (2) Water contact to resolvable protons was measured through a Nuclear Overhauser Effect (NOE) between water and resolvable drug and lipid resonances. In the case of both lipids and membrane bound drugs, positive NOEs with large cross-relaxation rates were measured for most resonances originating from the membrane hydrophilic region, while negative NOEs were observed predominantly to resonances in the hydrophobic region of the membrane. (3) {sup 1}H NMR measurements of oxygen-induced (paramagnetic) spin-lattice relaxation rates, which are known to increase with membrane immersion depth, were used to corroborate conclusions based on chemical shift perturbations and water-ligand NOEs.

  10. Biodegradable amphiphilic block copolymers containing functionalized PEO blocks:Controlled synthesis and biomedical potentials

    Institute of Scientific and Technical Information of China (English)


    A series of controllable amphiphilic block copolymers composed of poly(ethylene oxide)(PEO) as the hydrophilic block and poly(ε-caprolactone)(PCL) as the hydrophobic block with the amino terminal group at the end of the PEO chain(PCL-b-PEO-NH2) were synthesized.Based on the further reaction of reactive amino groups,diblock copolymers with functional carboxyl groups(PCL-b-PEO-COOH) and functional compounds RGD(PCL-b-PEO-RGD) as well as the triblock copolymers with thermosensitive PNIPAAm blocks(PCL-b-PEO-b-PNIPAAM) were synthesized.The well-controlled structures of these copolymers with functional groups and blocks were characterized by gel permeation chromatography(GPC) and 1H NMR spectroscopy.These copolymers with functionalized hydrophilic blocks were fabricated into microspheres for the examination of biofunctions via cell culture experiments and in vitro drug release.The results indicated the significance of introducing functional groups(e.g.,NH2,COOH and RGD) into the end of the hydrophilic block of amphiphilic block copolymers for biomedical potentials in tissue engineering and controlled drug release.

  11. A designed amphiphilic peptide containing the silk fibroin motif as a potential carrier of hydrophobic drugs

    Institute of Scientific and Technical Information of China (English)

    Qinghan Zhou; Juan Lin; Jing Wang; Feng Li; Fushan Tang; Xiaojun Zhao


    The amphiphilic peptide is becoming attractive as a potential drug carder to improve the dissolvability of hydrophobic drugs in an aqueous system; thus, facilitating drug uptake by target cells. Here, we report a novel designed amphiphilic peptide, Ac-RADAGAGA-RADAGAGA-NH_2, which was able to stabilize pyrene, a hydrophobic model drug we chose to study in aqueous solution. This designed peptide formed a colloidal suspension by encapsulating pyrene inside the peptide-pyrene complex. Egg phosphatidylcholine (EPC) ves-icles were used to mimic cell bilayer membranes. We found that pyrene was released from the peptide coating into the EPC vesicles by mixing the colloidal suspension with EPC vesicles, which was followed by steady fluorescence spectra as a function of time. A calibration curve for the amount of pyrene released into the EPC vesicles at a given time was used to determine the final concentration of pyrene released into the lipid vesicles from the peptide-pyrene complex. The release rate of the peptide pyrene complex was calculated to quan-tify the transfer of pyrene into EPC vesicles.


    Institute of Scientific and Technical Information of China (English)

    Zhao-qiang Wu; Shu Yang; Wen-yan Liao; Ling-zhi Meng


    Novel amphiphilic fluorescent graft copolymer (PVP-PyAHy) was successfully synthesized by the free radical copolymerization of hydrophobic monomer N-(1-pyrenebutyryl)-N'-acryloyl hydrazide (PyAHy) with hydrophilic precursor polymers of vinyl-functionalized poly(N-vinylpyrrolidone) (PVP) in DMF. The copolymer is amphiphilic and has intrinsic fluorescence. FT-IR, 1H-NMR, TEM, gel permeation chromatography-multi-angle laser light scattering, UV-Vis spectroscopy and fluorescence spectroscopy were used to characterize this copolymer. The TEM observation shows that the copolymer PVP-PyAHy forms micelles in aqueous solution. Results of fluorometric measurements illustrate that the critical micelle concentration (CMC) value of PVP-PyAHy in aqueous solution is about 0.90 mg/mL. To examine the encapsulation ability of the copolymer in aqueous media, methyl yellow was employed as a model hydrophobic agent. The loading level of the polymer to methyl yellow is 8.8 mg/g. The cytotoxicity assays for Madin Darby Canine Kidney (MDCK) cells shows good biocompatibility of PVP-PyAHy in vitro. These results suggest the potential of this copolymer PVP-PyAHy as drugs delivery carrier and fluorescent tracer.

  13. Highly parallel computational study of amphiphilic molecules using the Wang--Landau method (United States)

    Vogel, Thomas; Landau, David


    The self-assembly process in amphiphilic solutions is a phenomenon of broad interest. Molecular dynamics simulations generally used to study micelle formation or lipid layer assembly in an explicit solvent are limited in time scale. Vast studies of structure formation processes via standard Markov-chain based Monte Carlo simulations are challenging, but the Wang--Landau method [1] provides a way to efficiently study such systems in a generalized thermodynamic ensemble. This makes it possible, for example, to get results over a broad temperature range from a single simulation. In an attempt to develop highly parallel applications using this method, we study the thermodynamic behavior of a generic coarse-grained model for amphiphilic molecules [2] as well as of a new coarse-grained lipid model specifically designed for dimyristoyl phosphatidylcholine (DMPC) [3]. Here, we focus on the design and the performance of our parallel Wang--Landau simulation on multi-CPU and GPU systems.[4pt] [1] F. Wang and D.P. Landau, Phys. Rev. Lett. 86, 2050 (2001)[0pt] [2] S. Fujiwara et al., J. Chem. Phys. 130, 144901 (2009)[0pt] [3] W. Shinoda et al., J. Phys. Chem. B 114, 6836 (2010)

  14. Interaction of a patterned amphiphilic polyphenylene dendrimer with a lipid monolayer: electrostatic interactions dominate. (United States)

    Okuno, Masanari; Mezger, Markus; Stangenberg, René; Baumgarten, Martin; Müllen, Klaus; Bonn, Mischa; Backus, Ellen H G


    Dendrimeric macromolecules with defined shape and size are promising candidates for delivering drug or DNA molecules into cells. In this work we study the influence of an amphiphilic polyphenylene dendrimer on a model cell membrane consisting of a condensed 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid monolayer. A small surface pressure decrease is observed when the dendrimer solution is injected into the aqueous phase below the monolayer. X-ray reflectivity measurements show that the surface monolayer remains intact. The molecular-scale picture is obtained with sum-frequency generation spectroscopy. With this technique, we observe that the tails of the surfactant molecules become less ordered upon interaction with the amphiphilic polyphenylene dendrimer. In contrast, the water molecules below the DPPC layer become more ordered. Our observations suggest that electrostatic interactions between the negative charge of the dendrimer and the positively charged part of the DPPC headgroup keep the dendrimer located below the headgroup. No evidence of dendrimer insertion into the membrane has been observed. Apparently before entering the cell membrane the dendrimer can stick at the hydrophilic part of the lipids.

  15. The non-peptidic part determines the internalization mechanism and intracellular trafficking of peptide amphiphiles.

    Directory of Open Access Journals (Sweden)

    Dimitris Missirlis

    Full Text Available BACKGROUND: Peptide amphiphiles (PAs are a class of amphiphilic molecules able to self-assemble into nanomaterials that have shown efficient in vivo targeted delivery. Understanding the interactions of PAs with cells and the mechanisms of their internalization and intracellular trafficking is critical in their further development for therapeutic delivery applications. METHODOLOGY/PRINCIPAL FINDINGS: PAs of a novel, cell- and tissue-penetrating peptide were synthesized possessing two different lipophilic tail architectures and their interactions with prostate cancer cells were studied in vitro. Cell uptake of peptides was greatly enhanced post-modification. Internalization occurred via lipid-raft mediated endocytosis and was common for the two analogs studied. On the contrary, we identified the non-peptidic part as the determining factor of differences between intracellular trafficking and retention of PAs. PAs composed of di-stearyl lipid tails linked through poly(ethylene glycol to the peptide exhibited higher exocytosis rates and employed different recycling pathways compared to ones consisting of di-palmitic-coupled peptides. As a result, cell association of the former PAs decreased with time. CONCLUSIONS/SIGNIFICANCE: Control over peptide intracellular localization and retention is possible by appropriate modification with synthetic hydrophobic tails. We propose this as a strategy to design improved peptide-based delivery systems.

  16. Synthesis of an amphiphilic rhodamine derivative and characterization of its solution and thin film properties

    Energy Technology Data Exchange (ETDEWEB)

    Aviv, Hagit [Department of Chemistry, Bar-Ilan University, Ramat-Gan (Israel); Bar-Ilan University Institute for Nanotechnology and Advanced Materials, Ramat-Gan (Israel); Harazi, Sivan [Department of Chemistry, Bar-Ilan University, Ramat-Gan (Israel); Department of Physics, Bar-Ilan University, Ramat-Gan (Israel); Bar-Ilan University Institute for Nanotechnology and Advanced Materials, Ramat-Gan (Israel); Schiff, Dillon [Department of Chemistry, Bar-Ilan University, Ramat-Gan (Israel); Bar-Ilan University Institute for Nanotechnology and Advanced Materials, Ramat-Gan (Israel); Ramon, Yoni [Department of Chemistry, Bar-Ilan University, Ramat-Gan (Israel); Department of Physics, Bar-Ilan University, Ramat-Gan (Israel); Bar-Ilan University Institute for Nanotechnology and Advanced Materials, Ramat-Gan (Israel); Tischler, Yaakov R., E-mail: [Department of Chemistry, Bar-Ilan University, Ramat-Gan (Israel); Bar-Ilan University Institute for Nanotechnology and Advanced Materials, Ramat-Gan (Israel)


    Here we present characterization of solution and thin film properties of Lissamine rhodamine B sulfonyl didodecyl amine (LRSD), an amphiphilic derivative of rhodamine. LRSD was synthesized by functionalizing Lissamine rhodamine B sulfonyl chloride (LRSC) with didodecylamine via a straightforward sulfonylation reaction. LRSD's long alkane chains make it highly soluble in chloroform, with a marked increase in brightness compared to the starting material. LRSD is shown to form well-defined robust micelles in water, without the addition of a co-surfactant and stable monolayers at the air–water interface. The greater lipophilicity of LRSD also enables doping into non-polar polymeric host matrices such as polystyrene with less aggregation and hence higher fluorescence quantum yield than LRSC or even rhodamine B. The monolayers of LRSD were prepared via Langmuir–Blodgett deposition and showed shifts in the photoluminescence peak from 575 nm to 595 nm, as the surface pressure is varied from 3 mN/m to 11 mN/m. - Highlights: • Lissamine rhodamine B sulfonyl didodecyl amine (LRSD) is soluble in chloroform. • LRSD shows robust quantum yield in solution and as a dopant in thin film. • LRSD is an amphiphilic rhodamine dye that forms compact fluorescent micelles. • LRSD forms a stable isotherm when spread at the air–water interface.

  17. Amphiphilic comblike polymers enhance the colloidal stability of Fe(3)O(4) nanoparticles. (United States)

    Kim, Myeongjin; Jung, Jaeyeon; Lee, Jonghwan; Na, Kyunga; Park, Subeom; Hyun, Jinho


    Stable colloidal dispersions of magnetite (Fe(3)O(4)) nanoparticles (MNPs) were obtained with the inclusion of an amphiphilic comblike polyethylene glycol derivative (CL-PEG) as an amphiphilic polymeric surfactant. Both the size and morphology of the resulting CL-PEG-modified MNPs could be controlled and were characterized by transmission electron microscopy (TEM). The interaction between MNPs and CL-PEG was confirmed by the presence of characteristic infrared absorption peaks, and the colloidal stability of the nanoparticle dispersion in water was evaluated by long-term observation of the dispersion using UV-visible spectroscopy. SQUID measurements confirmed the magnetization of CL-PEG-modified MNPs. The zeta potential of the CL-PEG-modified MNPs showed a dramatic conversion from positive to negative in response to the pH of the surrounding aqueous medium due to the presence of carboxyl groups at the surface. These carboxyl groups can be used to functionalize the MNPs with biomolecules for biotechnological applications. However, regardless of surface electrostatics, the flexible, hydrophilic side chains of CL-PEG-modified MNPs prevented the approach of adjacent nanoparticles, thereby resisting aggregation and resulting in a stable aqueous colloid. The cytotoxicity of MNPs and CL-PEG-modified MNPs was evaluated by a MTT assay.

  18. Amphiphilic copolymers reduce aggregation of unfolded lysozyme more effectively than polyethylene glycol (United States)

    Chin, Jaemin; Mustafi, Devkumar; Poellmann, Michael J.; Lee, Raphael C.


    Certain amphiphilic block copolymers are known to prevent aggregation of unfolded proteins. To better understand the mechanism of this effect, the optical properties of heat-denatured and dithiothreitol reduced lysozyme were evaluated with respect to controls using UV–Vis spectroscopy, transmission electron microscopy (TEM) and circular dichroism (CD) measurements. Then, the effects of adding Polyethylene Glycol (8000 Da), the triblock surfactant Poloxamer 188 (P188), and the tetrablock copolymer Tetronic 1107 (T1107) to the lysozyme solution were compared. Overall, T1107 was found to be more effective than P188 in inhibiting aggregation, while PEG exhibited no efficacy. TEM imaging of heat-denatured and reduced lysozymes revealed spherical aggregates with on average 250–450 nm diameter. Using CD, more soluble lysozyme was recovered with T1107 than P188 with β-sheet secondary structure. The greater effectiveness of the larger T1107 in preventing aggregation of unfolded lysozyme than the smaller P188 and PEG points to steric hindrance at play; signifying the importance of size match between the hydrophobic region of denatured protein and that of amphiphilic copolymers. Thus, our results corroborate that certain multi-block copolymers are effective in preventing heat-induced aggregation of reduced lysozymes and future studies warrant more detailed focus on specific applications of these copolymers.

  19. Polydispersity-Driven Block Copolymer Amphiphile Self-Assembly into Prolate-Spheroid Micelles

    Energy Technology Data Exchange (ETDEWEB)

    Schmitt, Andrew L.; Repollet-Pedrosa, Milton H.; Mahanthappa, Mahesh K. (UW)


    The aqueous self-assembly behavior of polydisperse poly(ethylene oxide-b-1,4-butadiene-b-ethylene oxide) (OBO) macromolecular triblock amphiphiles is examined to discern the implications of continuous polydispersity in the hydrophobic block on the resulting aqueous micellar morphologies of otherwise monodisperse polymer surfactants. The chain length polydispersity and implicit composition polydispersity of these samples furnishes a distribution of preferred interfacial curvatures, resulting in dilute aqueous block copolymer dispersions exhibiting coexisting spherical and rod-like micelles with vesicles in a single sample with a O weight fraction, w{sub O}, of 0.18. At higher w{sub O} = 0.51-0.68, the peak in the interfacial curvature distribution shifts and we observe the formation of only American football-shaped micelles. We rationalize the formation of these anisotropically shaped aggregates based on the intrinsic distribution of preferred curvatures adopted by the polydisperse copolymer amphiphiles and on the relief of core block chain stretching by chain-length-dependent intramicellar segregation.

  20. Amphiphilic Beads as Depots for Sustained Drug Release Integrated into Fibrillar Scaffolds (United States)

    Gaharwar, Akhilesh K.; Mihaila, Silvia M.; Kulkarni, Ashish A.; Patel, Alpesh; Di Luca, Andrea; Reis, Rui L.; Gomes, Manuela E.; van Blitterswijk, Clemens; Moroni, Lorenzo; Khademhosseini, Ali


    Native extracellular matrix (ECM) is a complex fibrous structure loaded with bioactive cues that affects the surrounding cells. A promising strategy to mimicking native tissue architecture for tissue engineering applications is to engineer fibrous scaffolds using electrospinning. By loading appropriate bioactive cues within these fibrous scaffolds, various cellular functions such as cell adhesion, proliferation and differentiation can be regulated. Here, we report on the encapsulation and sustained release of model hydrophobic drug (dexamethasone (Dex)) within beaded fibrillar scaffold of poly(ethylene oxide terephthalate)-poly(butylene terephthalate) (PEOT/PBT), a polyether-ester multiblock copolymer to direct differentiation of human mesenchymal stem cells (hMSCs). The amphiphilic beads act as depots for sustained drug release that is integrated into the fibrillar scaffolds. The entrapment of Dex within the beaded structure results in sustained release of drug over the period of 28 days. This is mainly attributed to the diffusion driven release of Dex from the amphiphilic electrospun scaffolds. In vitro results indicate that hMSCs cultured on Dex containing beaded fibrillar scaffolds exhibit an increase in osteogenic differentiation potential, as evidenced by increased alkaline phosphatase (ALP) activity, compared to the direct infusion of Dex in culture medium. The formation of mineralized matrix is also significantly enhanced due to the controlled Dex release from the fibrous scaffolds. This approach can be used to engineer scaffolds with appropriate chemical cues to direct tissue regeneration. PMID:24794894

  1. Surface behavior of amphiphiles in aqueous solution: a comparison between different pentanol isomers. (United States)

    Walz, M-M; Caleman, C; Werner, J; Ekholm, V; Lundberg, D; Prisle, N L; Öhrwall, G; Björneholm, O


    Position isomerism is ubiquitous in atmospheric oxidation reactions. Therefore, we have compared surface-active oxygenated amphiphilic isomers (1- and 3-pentanol) at the aqueous surface with surface- and chemically sensitive X-ray photoelectron spectroscopy (XPS), which reveals information about the surface structure on a molecular level. The experimental data are complemented with molecular dynamics (MD) simulations. A concentration-dependent orientation and solvation of the amphiphiles at the aqueous surface is observed. At bulk concentrations as low as around 100 mM, a monolayer starts to form for both isomers, with the hydroxyl groups pointing towards the bulk water and the alkyl chains pointing towards the vacuum. The monolayer (ML) packing density of 3-pentanol is approx. 70% of the one observed for 1-pentanol, with a molar surface concentration that is approx. 90 times higher than the bulk concentration for both molecules. The molecular area at ML coverage (≈100 mM) was calculated to be around 32 ± 2 Å(2) per molecule for 1-pentanol and around 46 ± 2 Å(2) per molecule for 3-pentanol, which results in a higher surface concentration (molecules per cm(2)) for the linear isomer. In general we conclude therefore that isomers - with comparable surface activities - that have smaller molecular areas will be more abundant at the interface in comparison to isomers with larger molecular areas, which might be of crucial importance for the understanding of key properties of aerosols, such as evaporation and uptake capabilities as well as their reactivity.

  2. Bionanoparticles of amphiphilic copolymers polyacrylate bearing cholesterol and ascorbate for drug delivery. (United States)

    Liu, Yijiang; Wang, Yanzhai; Zhuang, Dequan; Yang, Junjiao; Yang, Jing


    In this study, a series of amphiphilic polymers with poly(ascorbyl acrylate) (PAAA) as hydrophilic blocks and polyacrylate bearing side-chain cholesteryl mesogens (PCholDEGA) as hydrophobic blocks were prepared using a combination of four-step reactions consisting of two consecutive reversible addition-fragmentation chain transfer (RAFT), desulfurization, and hydrogenolysis under normal pressure. The thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) as well as wide-angle X-ray diffraction (WAXD) studies showed that the copolymers with PCholDEGA as major block had relatively high stability and clear isotropization temperature (T(i)). Small-angle X-ray diffraction (SAXD) investigation exhibited that the copolymers had bilayer smectic A structure. Their self-assembly behavior was monitored by turbidity change using UV-vis spectrometer, and the morphology and size of the nanoparticles via self-assembly were detected using transmission electron microscopy (TEM) and dynamic light scattering (DLS). The entrapment efficiency and loading capacity of these amphiphilic copolymers were investigated using nile red and drug molecule Ibuprofen. These polymeric micelles with PAAA shell extending into the aqueous solution and strong hydrophobic PCholDEGA core have potential abilities to act as promising nanovehicles with high loading and targeting delivery.

  3. First-order phase transition during displacement of amphiphilic biomacromolecules from interfaces by surfactant molecules. (United States)

    Ettelaie, Rammile; Dickinson, Eric; Pugnaloni, Luis


    The adsorption of surfactants onto a hydrophobic interface, already laden with a fixed number of amphiphilic macromolecules, is studied using the self consistent field calculation method of Scheutjens and Fleer. For biopolymers having unfavourable interactions with the surfactant molecules, the adsorption isotherms show an abrupt jump at a certain value of surfactant bulk concentration. Alternatively, the same behaviour is exhibited when the number of amphiphilic chains on the interface is decreased. We show that this sudden jump is associated with a first-order phase transition, by calculating the free energy values for the stable and the metastable states at both sides of the transition point. We also observe that the transition can occur for two approaching surfaces, from a high surfactant coverage phase to a low surfactant coverage one, at sufficiently close separation distances. The consequence of this finding for the steric colloidal interactions, induced by the overlap of two biopolymer + surfactant films, is explored. In particular, a significantly different interaction, in terms of its magnitude and range, is predicted for these two phases. We also consider the relevance of the current study to problems involving the competitive displacement of proteins by surfactants in food colloid systems.

  4. Amphiphile grafted membranes for the separation of oil-in-water dispersions. (United States)

    Howarter, John A; Youngblood, Jeffrey P


    Perfluorinated end-capped polyethylene glycol surfactants were covalently attached to fritted glass membranes as a means to improve the separation of oil-in-water emulsions. Hexadecane was used as representative oil for the oil-in-water emulsions; membrane pore size was varied between 10 and 174 microm. Membranes were characterized with respect to contact angle, permeability of bulk fluids, and separation efficiency. Performance was compared to similar metrics applied to unmodified membranes. Modified membranes demonstrated static hexadecane contact angles which were higher than static water contact angles converse to their unmodified counterparts. The relative hydrophilicity and corresponding oleophobicity of the modified membranes resulted in greater water permeability as compared to hexadecane permeability. The presence of the perfluorinated constituent of the amphiphile retarded the flow of hexadecane. For modified membranes, suspended hexadecane coalesced at the membrane surface, was undercut by water, and floated to the surface such that only trace amounts of oil were present in the permeate. Therefore, modified membranes resisted fouling from oil due to the self-cleaning properties of the attached amphiphile.

  5. Carbon nanotube/biocompatible bola-amphiphile supramolecular biohybrid materials: preparation and their application in bacterial cell agglutination. (United States)

    Yu, Guocan; Li, Jinying; Yu, Wei; Han, Chengyou; Mao, Zhengwei; Gao, Changyou; Huang, Feihe


    Supramolecular biohybrid materials were successfully constructed driven by non-covalent interactions between three biocompatible bolaform amphiphiles and single walled carbon nanotubes (SWNTs). The existence of galactoses in these supramolecular systems endowed the hybrid materials with interesting bio-function. By introducing the SWNTs as semi-flexible platforms, these supramolecular biohybrid materials display excellent agglutination ability for E. coli.

  6. Polymorphism of pyridinium amphiphiles for gene delivery : Influence of ionic strength, helper lipid content, and plasmid DNA complexation

    NARCIS (Netherlands)

    Scarzello, M; Chupin, [No Value; Wagenaar, A; Stuart, MCA; Engberts, JBFN; Hulst, R; Chupin, Vladimir


    Two double-tailed pyridinium cationic amphiphiles, differing only in the degree of unsaturation of the alkyl chains, have been selected for a detailed study of their aggregation behavior, under conditions employed for transfection experiments. The transfection efficiencies of the two molecules are r

  7. Light-controlled formation of vesicles and supramolecular organogels by a cholesterol-bearing amphiphilic molecular switch

    NARCIS (Netherlands)

    van Herpt, Jochem T.; Areephong, Jetsuda; Stuart, Marc C. A.; Browne, Wesley R.; Feringa, Ben L.


    A new responsive material composed of an amphiphilic light-switchable dithienylethene unit functionalized with a hydrophobic cholesterol unit and a hydrophilic poly(ethylene glycol)-modified pyridinium group has been designed. This unique single-molecule system shows responsive light-switchable self

  8. Amphiphilic hollow porous shell encapsulated Au@Pd bimetal nanoparticles for aerobic oxidation of alcohols in water

    KAUST Repository

    Zou, Houbing


    © The Royal Society of Chemistry 2015. This work describes the design, synthesis and analysis of an amphiphilic hollow mesoporous shell encapsulating catalytically active Au@Pd bimetal nanoparticles. The particles exhibited excellent catalytic activity and stability in the aerobic oxidation of primary and secondary alcohols to their corresponding aldehydes or ketones in water when using air as an oxidizing agent under atmospheric pressure.

  9. Drying increases intracellular partitioning of amphiphilic substances into the lipid phase. Impact On membrane permeability and significance for desiccation tolerance (United States)

    Golovina; Hoekstra; Hemminga


    Previously we proposed that endogenous amphiphilic substances may partition from the aqueous cytoplasm into the lipid phase during dehydration of desiccation-tolerant organ(ism)s and vice versa during rehydration. Their perturbing presence in membranes could thus explain the transient leakage from imbibing organisms. To study the mechanism of this phenomenon, amphiphilic nitroxide spin probes were introduced into the pollen of a model organism, Typha latifolia, and their partitioning behavior during dehydration and rehydration was analyzed by electron paramagnetic resonance spectroscopy. In hydrated pollen the spin probes mainly occurred in the aqueous phase; during dehydration, however, the amphiphilic spin probes partitioned into the lipid phase and had disappeared from the aqueous phase below 0.4 g water g-1 dry weight. During rehydration the probes reappeared in the aqueous phase above 0.4 g water g-1 dry weight. The partitioning back into the cytoplasm coincided with the decrease of the initially high plasma membrane permeability. A charged polar spin probe was trapped in the cytoplasm during drying. Liposome experiments showed that partitioning of an amphiphilic spin probe into the bilayer during dehydration caused transient leakage during rehydration. This was also observed with endogenous amphipaths that were extracted from pollen, implying similar partitioning behavior. In view of the fluidizing effect on membranes and the antioxidant properties of many endogenous amphipaths, we suggest that partitioning with drying may be pivotal to desiccation tolerance, despite the risk of imbibitional leakage.

  10. Amphiphilic drugs as surfactants to fabricate excipient-free stable nanodispersions of hydrophobic drugs for cancer chemotherapy. (United States)

    Hu, Shiqi; Lee, Eunhye; Wang, Chi; Wang, Jinqiang; Zhou, Zhuxian; Li, Yixian; Li, Xiaoyi; Tang, Jianbin; Lee, Don Haeng; Liu, Xiangrui; Shen, Youqing


    Nanoformulations have been extensively explored to deliver water-insoluble drugs, but they generally use exotic new materials, for instance, amphiphilic block copolymers, which must first go through extensively clinical trials and be approved as drug excipients before any clinical uses. We hypothesize that using clinical amphiphilic drugs as surfactants to self-assemble with and thus solubilize hydrophobic drugs will lead to readily translational nanoformulations as they contain no new excipients. Herein, we show the first example of such excipient-free nanodispersions using an amphiphilic anti-tumor drug, irinotecan hydrochloride (CPT11). CPT11 self-assembles with its insoluble active parent drug, 7-ethyl-10-hydroxy camptothecin (SN38), into stable and water-dispersible nanoparticles, increasing SN38's water solubility by thousands of times up to 25 mg/mL with a loading efficiency close to 100%. The versatility of this approach is also demonstrated by fabricating nanodispersions of CPT11 with other water-insoluble drugs including paclitaxel (PTX) and camptothecin (CPT). These nanodispersions have much increased bioavailability and thereby improved anti-cancer activities. Thus, this strategy, using clinically proven amphiphilic drugs as excipients to fabricate nanodispersions, avoids new materials and makes readily translational nanoformulations of hydrophobic drugs.

  11. Triblock Copolymers with Grafted Fluorine-Free Amphiphilic Non-Ionic Side Chains for Antifouling and Fouling-Release Applications

    Energy Technology Data Exchange (ETDEWEB)

    Y Cho; H Sundaram; C Weinman; M Paik; M Dimitriou; J Finlay; M Callow; J Callow; E Kramer; C Ober


    Fluorine-free, amphiphilic, nonionic surface active block copolymers (SABCs) were synthesized through chemical modification of a polystyrene-block-poly(ethylene-ran-butylene)-block-polyisoprene triblock copolymer precursor with selected amphiphilic nonionic Brij and other surfactants. Amphiphilicity was imparted by a hydrophobic aliphatic group combined with a hydrophilic poly(ethylene glycol) (PEG) group-containing moiety. The surfaces were characterized by dynamic water contact angle, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and near edge X-ray absorption fine structure (NEXAFS) analysis. In biofouling assays, settlement (attachment) of both spores of the green alga Ulva and cells of the diatom Navicula on SABCs modified with Brij nonionic side chains was significantly reduced relative to a PDMS standard, with a nonionic surfactant combining a PEG group and an aliphatic moiety demonstrating the best performance. Additionally, a fouling-release assay using sporelings (young plants) of Ulva and Navicula suggested that the SABC derived from nonionic Brij side chains also out-performed PDMS as a fouling-release material. Good antifouling and fouling-release properties were not demonstrated for the other two amphiphilic surfaces derived from silicone and aromatic group containing nonionic surfactants included in this study. The results suggest that small differences in chemical surface functionality impart more significant changes with respect to the antifouling settlement and fouling-release performance of materials than overall wettability behavior.

  12. Monodisperse nanoparticles from self-assembling amphiphilic cyclodextrins: modulable tools for the encapsulation and controlled release of pharmaceuticals. (United States)

    Mendez-Ardoy, Alejandro; Gómez-García, Marta; Gèze, Annabelle; Putaux, Jean-Luc; Wouessidjewe, Denis; Ortiz Mellet, Carmen; Defaye, Jacques; García Fernández, José M; Benito, Juan M


    Selective chemical functionalization of cyclodextrins (CDs) is a readily amenable methodology to produce amphiphilic macromolecules endowed with modulable self-organizing capabilities. Herein, the synthesis of well-defined amphiphilic CD derivatives, with a "skirt-type" architecture, that incorporate long-chain fatty esters at the secondary hydroxyl rim and a variety of chemical functionalities (e. g. iodo, bromo, azido, cysteaminyl or isothiocyanato) at the primary hydroxyls rim is reported. Nanoprecipitation of the new CD facial amphiphiles, or binary mixtures of them, resulted in nanoparticles with average hydrodynamic diameters ranging from 100 to 240 nm that were stable in suspension for several months. The precise size, zeta potential and topology of the nanoparticles are intimately dependent on the functionalization pattern at the CD scaffold. Highly efficient molecular encapsulation capabilities of poorly bioavailable drugs such as diazepam (DZ) were demonstrated for certain derivatives, the drug release profile being dependent on the type of formulation (nanospheres or nanocapsules). The efficiency and versatility of the synthetic strategy, together with the possibility of exploiting the reactivity of the functional groups at the nanoparticle surface, offer excellent opportunities to further manipulate the carrier capabilities of this series of amphiphilic CDs from a bottom-up approach.

  13. Self-assembly of amphiphilic anionic calix[4]arenes and encapsulation of poorly soluble naproxen and flurbiprofen. (United States)

    Barbera, Lucia; Gattuso, Giuseppe; Kohnke, Franz H; Notti, Anna; Pappalardo, Sebastiano; Parisi, Melchiorre F; Pisagatti, Ilenia; Patanè, Salvatore; Micali, Norberto; Villari, Valentina


    Supramolecular aggregates formed through the association of an amphiphilic tetra-O-butylsulfonate calix[4]arene 1 were investigated in aqueous solution by a combination of different techniques (NMR, DLS and AFM). The ability of the micellar aggregates of calixarene 1 to increase the solubility of poorly water-soluble drugs was studied.

  14. Staphylococcal α -toxin: Oligomerization of Hydrophilic Monomers to Form Amphiphilic Hexamers Induced through Contact with Deoxycholate Detergent Micelles (United States)

    Bhakdi, Sucharit; Fussle, Roswitha; Tranum-Jensen, Jorgen


    Native staphylococcus aureus α -toxin is secreted as a hydrophilic polypeptide chain of Mr 34,000. The presence of deoxycholate above the critical micellar concentration induced the toxin monomers to self-associate, forming ring or cylindrical oligomers. The oligomers were amphiphilic and bound detergent. In deoxycholate solution, the protein-detergent complexes exhibited a sedimentation coefficient of 10.4 S. A Mr of 238,700 was determined by ultracentrifugation analyses at sedimentation equilibrium. Because quantitative detergent-binding studies indicated a protein/detergent ratio of approximately 5:1 (wt/wt), the protein moiety in each protein-detergent complex was determined to be approximately Mr 200 000, corresponding to a hexamer of the native molecule. The amphiphilic toxin hexamers were ultrastructurally indistinguishable from the cytolytic, annular toxin complexes that form on and in biological target membranes. They bound lipid and could be incorporated into artificial lecithin lipid vesicles. The transition of toxin protein molecules from a hydrophilic monomer to an amphiphilic oligomer through self-association has thus been shown to be inducible solely through contact of the native protein molecules with an appropriate amphiphilic substrate.

  15. Deconvoluting the Effect of the Hydrophobic and Hydrophilic Domains of an Amphiphilic Integral Membrane Protein in Lipid Bicontinuous Cubic Mesophases. (United States)

    van 't Hag, Leonie; Shen, Hsin-Hui; Lu, Jingxiong; Hawley, Adrian M; Gras, Sally L; Drummond, Calum J; Conn, Charlotte E


    Lipidic bicontinuous cubic mesophases with encapsulated amphiphilic proteins are widely used in a range of biological and biomedical applications, including in meso crystallization, as drug delivery vehicles for therapeutic proteins, and as biosensors and biofuel cells. However, the effect of amphiphilic protein encapsulation on the cubic phase nanostructure is not well-understood. In this study, we illustrate the effect of incorporating the bacterial amphiphilic membrane protein Ag43, and its individual hydrophobic β(43) and hydrophilic α(43) domains, in bicontinuous cubic mesophases. For the monoolein, monoalmitolein, and phytantriol cubic phases with and without 8% w/w cholesterol, the effect of the full length amphiphilic protein Ag43 on the cubic phase nanostructure was more significant than the sum of the individual hydrophobic β(43) and hydrophilic α(43) domains. Several factors were found to potentially influence the impact of the hydrophobic β(43) domain on the cubic phase internal nanostructure. These include the size of the hydrophobic β(43) domain relative to the thickness of the lipid bilayer, as well as its charge and diameter. The size of the hydrophilic α(43) domain relative to the water channel radius of the cubic mesophase was also found to be important. The secondary structure of the Ag43 proteins was affected by the hydrophobic thickness and physicochemical properties of the lipid bilayer and the water channel diameter of the cubic phase. Such structural changes may be small but could potentially affect membrane protein function.

  16. Effects of mutations in de novo designed synthetic amphiphilic β-sheet peptides on self-assembly of fibrils. (United States)

    Raz, Yoav; Rubinov, Boris; Matmor, Maayan; Rapaport, Hanna; Ashkenasy, Gonen; Miller, Yifat


    The self-assembly of two similar amphiphilic peptides into fibril structures is described. Molecular dynamic simulations show that both can organize similarly in a monolayer, but in the fibril bilayer, one prefers a single organization while the other forms two conformational variants. This assembly difference correlates well with our experimental results.

  17. Mixtures of achiral amphiphilic cyanine dyes form helical tubular J-aggregates

    Energy Technology Data Exchange (ETDEWEB)

    Berlepsch, Hans v., E-mail: [Forschungszentrum fuer Elektronenmikroskopie, Institut fuer Chemie und Biochemie, Freie Universitaet Berlin, Fabeckstrasse 36a, D-14195 Berlin (Germany); Ludwig, Kai [Forschungszentrum fuer Elektronenmikroskopie, Institut fuer Chemie und Biochemie, Freie Universitaet Berlin, Fabeckstrasse 36a, D-14195 Berlin (Germany); Kirstein, Stefan [Institut fuer Physik, Humboldt Universitaet zu Berlin, Newtonstrasse 15, D-12489 Berlin (Germany); Boettcher, Christoph, E-mail: [Forschungszentrum fuer Elektronenmikroskopie, Institut fuer Chemie und Biochemie, Freie Universitaet Berlin, Fabeckstrasse 36a, D-14195 Berlin (Germany)


    Graphical abstract: Two amphiphilic carbocyanine dye molecules that have very similar molecular structure and form J-aggregates of different morphology are mixed in an aqueous solution. The aggregates of the mixture are of the same morphology as the aggregates of one of the dyes but exhibit a different absorption spectrum. The details of the morphology are analysed by using 3D-reconstruction techniques of cryo-TEM images and are discussed in the context of their optical behaviour. Highlights: {yields} Two sulfonate-substituted amphiphilic cyanines form mixed J-aggregates in water. {yields} Absorption spectrum is not a superposition of pure component spectra. {yields} Cryo-TEM reveals 13 nm thin bilayered nanotubes with helical ultrastructure. {yields} The spatial structure of aggregates is determined by 3D-reconstruction techniques. - Abstract: The amphiphilic 3,3'-bis(2-sulfoethyl) and 3,3'-bis(2-sulfopropyl) substituted 5,5',6,6'-tetrachlorobenzimidacarbocyanine dyes (C8S2 and C8S3) self-aggregate in aqueous solution to form mixed J-aggregates. The individual dyes form planar (C8S2) or tubular (C8S3) aggregates, while the mixed solution forms tubular aggregates that are morphologically identical to those obtained from the pure C8S3. The optical spectra however differ significantly indicating a different structure on the molecular length scale. The structure and morphology is independent of the mixing ratio if the content of C8S2 is above 10%. The structure of the mixed C8S3/C8S2 aggregates is investigated in detail by means of cryogenic transmission electron microscopy (cryo-TEM) in combination with a 3D-image reconstruction technique, which yields a structure with a spatial resolution of {approx}2 nm. A comparison with the 3D structure of the tubular aggregates of C8S3 could not resolve any differences. Any structural difference that could describe the spectroscopic difference of the two types of tubular aggregates must be below this

  18. Synthesis of amphiphilic diblock copolymer for surface modification of Ethylene-Norbornene copolymers

    DEFF Research Database (Denmark)

    Levinsen, Simon; Svendsen, Winnie Edith; Horsewell, Andy


    The aim of this work is to produce polymer modifiers in order to develop hydrophilic polymeric surfaces for use in microfluidics. The use of hydrophilic polymers in microfluidics will have many advantages e.g. preventing protein absorbance. Here we present an amphiphilic diblock copolymer......-norbornene copolymer TOPAS. Through matching of the radius of gyration for the model polymer and TOPAS the miscibility was achieved. The poly(ethylene-1-butene) polymer was synthesized from a hydrogenated anionic polymerized polybutadiene polymer. As hydrophilic block poly(ethylene oxide) was subsequently added also...... with anionic polymerization. Recent miscibility results between the model polymer and TOPAS will be presented, as well ongoing efforts to study the hydrophilic surface....

  19. Synthesis and characterization of biodegradable amphiphilic PEG-grafted poly(DTC-co-CL)

    Institute of Scientific and Technical Information of China (English)

    Qiu Jin Zhang; Wei Pu Zhu; Zhi Quan Shen


    A novel biodegradable copolymer,poly(5,5-dibromomethyltrimethylene carbonate-co-ε-caprolactone)(poly(DBTC-co-CL))with pendant bromine groups,was synthesized via ring-opening polymerization(ROP)of ε-caprolactone(CL)and 5,5-dibromomethyltrimethylene carbonate(DBTC)using stannous octoate(Sn(Oct)2)as catalyst.Then the pendant bromine groups were completely converted into azide form,which permitted"click"reaction with alkyne-terminated polyethylene(A-PEG)by Huisgen 1,3-dipolar cycloadditions preparing biodegradable amphiphilic poly(DTC-co-CL)-g-PEG graft copolymer.The graft copolymer was characterized by nuclear magnetic resonance(NMR)and size-exclusion chromatography(SEC).

  20. Ordering of amphiphilic Janus particles at planar walls: a density functional study. (United States)

    Rosenthal, Gerald; Klapp, Sabine H L


    We investigate the structure formation of amphiphilic molecules at planar walls using density functional theory. The molecules are modeled as (hard) spheres composed of a hydrophilic and hydrophobic part. The orientation of the resulting Janus particles is described as a vector representing an internal degree of freedom. Our density functional approach involves fundamental measure theory combined with a mean-field approximation for the anisotropic interaction. Considering neutral, hydrophilic, and hydrophobic walls, we study the adsorption of the particles, focusing on the competition between the surface field and the interaction-induced ordering phenomena. Finally, we consider systems confined between two planar walls. It is shown that the anisotropic Janus interaction yields pronounced frustration effects at low temperatures.

  1. Sol-gel transition of charged fibrils composed of a model amphiphilic peptide. (United States)

    Owczarz, Marta; Bolisetty, Sreenath; Mezzenga, Raffaele; Arosio, Paolo


    We characterized the sol-gel transition of positively charged fibrils composed of the model amphiphilic peptide RADARADARADARADA (RADA 16-I) using a combination of microscopy, light scattering, microrheology and rheology techniques, and we investigated the dependence of the hydrogel formation on fibril concentration and ionic strength. The peptide is initially present as a dispersion of short rigid fibrils with average length of about 100 nm. During incubation, the fibrils aggregate irreversibly into longer fibrils and fibrillar aggregates. At peptide concentrations in the range 3-6.5 g/L, the fibrillar aggregates form a weak gel network which can be destroyed upon dilution. Percolation occurs without the formation of a nematic phase at a critical peptide concentration which decreases with increasing ionic strength. The gel structure can be well described in the frame of the fractal gel theory considering the network as a collection of fibrillar aggregates characterized by self-similar structure with a fractal dimension of 1.34.

  2. Novel fluorescent amphiphilic block copolymers: photophysics behavior and interactions with DNA

    Directory of Open Access Journals (Sweden)


    Full Text Available In this study, novel amphiphilic fluorescent copolymers poly(N-vinylpyrrolidone-b-poly(N-methacryloyl-N'-(α-naphthylthiourea (PVP-b-PNT were synthesized via ATRP with poly(N-vinylpyrrolidone-Cl as macroinitiator and N-methacryloyl-N'-α-naphthylthiourea (NT as hydrophobic segment. PVP-b-PNT copolymers were characterized by 1H NMR, GPC-MALLS and fluorescence measurements. The aggregation behavior of PVP-b-PNT in water was investigated by transmission electron microscope (TEM and dynamic light scattering (DLS measurement. The photophysics behavior of PVP-b-PNT showed that block copolymer formed strong excimer. The interaction of DNA with the block copolymer made the excimer of block copolymer quench. The cytotoxicity result of PVP-b-PNT in cell culture in vitro indicated that this copolymer PVP-b-PNT had good biocompatibility.

  3. New insight into surface properties of LB film of an amphiphilic terpolymer

    Institute of Scientific and Technical Information of China (English)

    Xiu Li Yue; Fang Ma; Zhi Fei Dai; Meng Liu; Lei Xing; Hai Yan Fan; Zhan Wen Xing; Shao Qin Liu


    Amphiphilic terpolymer (TPR) exhibits good film-forming behavior on pure water observed by means of n-A isotherms. To gain insight into physical properties of TPR, the films have been deposited on silicon substrates at different surface pressure by Langmuir-Blodgett (LB) technique. It was found that the increase in peak intensities of stretching mode was due to orderly packing of the films. The contact angles increased with increasing surface pressure, indicating an increase in hydrophobicity due to dense packing of chains of TPR. The cyclic voltammetric measurements indicated that TPR showed good current shielding effect for electron-transfer. In a word, LB films of TPR can produce a variety of structures with varied topography, enabling us to control not only the functionality of the surface, but also the interfacial transport characteristics.

  4. High-performance Polymer Membranes with Multi-functional Amphiphilic Micelles for CO2 Capture. (United States)

    Kim, Sang Jin; Jeon, Harim; Kim, Dong Jun; Kim, Jong Hak


    Herein, we report a high performance polymer membrane with simultaneously large improvements in the CO2 permeability and CO2/N2 selectivity. These improvements are obtained by incorporation of a multi-functional amphiphilic comb copolymer micelle, that is, poly(dimethylsiloxane)-g-poly(oxyethylene methacrylate) (PDMS-g-POEM), into a poly(amide-b-ethylene oxide) (Pebax) matrix. Both CO2 and N2 permeabilities continuously increased with PDMS-g-POEM content, whereas the CO2/N2 selectivity increased up to 40 wt % of PDMS-g-POEM, which enabled the maximum performance to approach the upper bound limit (2008). The membranes with PDMS-g-POEM exhibited greater CO2 permeability and CO2/N2 selectivity than those with a zeolitic imidazolate framework (ZIF-8), a well-known expensive inorganic filler, indicating the effectiveness of PDMS-g-POEM micelles for CO2 capture.

  5. Cytocompatibility of Self-assembled Hydrogel from IKVAV-containing Peptide Amphiphile with Neural Stem Cells

    Institute of Scientific and Technical Information of China (English)

    SONG Yulin; ZHENG Qixin; GUO Xiaodong; ZHENG Jianfeng


    Neural Stem Cells(NSCs)were incubated with self-assembled hydrogel from IKVAV-containing peptide amphiphile(IKVAV-PA)for one week.The cytocompatibility of hydrogel was evaluated.NSCs were seeded in three-dimensional(3D)hydrogels(Experimental Group,EG)or surface of coverslips(Control Group,CG),double-labeled with Calcein-AM and PI.A growth curve of cells was obtained according to CCK-8.TEM study of hydrogel revealed a network of nanofibers. NSCs began to proliferate after 24 h of incubation,and formed bigger neurospheres at 48 h in EG than in CG.Cell proliferation activity was higher in EG than in CG(P<0.05).The self-assembled Hydrogel had good cytocompatibility and promoted the proliferation of NSCs.

  6. Structure-property relationship in cytotoxicity and cell uptake of poly(2-oxazoline) amphiphiles

    KAUST Repository

    Luxenhofer, Robert


    The family of poly(2-oxazoline)s (POx) is being increasingly investigated in the context of biomedical applications. We tested the relative cytotoxicity of POx and were able to confirm that these polymers are typically not cytotoxic even at high concentrations. Furthermore, we report structure-uptake relationships of a series of amphiphilic POx block copolymers that have different architectures, molar mass and chain termini. The rate of endocytosis can be fine-tuned over a broad range by changing the polymer structure. The cellular uptake increases with the hydrophobic character of the polymers and is observed even at nanomolar concentrations. Considering the structural versatility of this class of polymers, the relative ease of preparation and their stability underlines the potential of POx as a promising platform candidate for the preparation of next-generation polymer therapeutics.

  7. Biphasic catalysis using amphiphilic polyphenols-chelated noble metals as highly active and selective catalysts (United States)

    Mao, Hui; Yu, Hong; Chen, Jing; Liao, Xuepin


    In the field of catalysis, it is highly desired to develop novel catalysts that combine the advantages of both homogeneous and heterogeneous catalysts. Here we disclose that the use of plant pholyphenol as amphiphilic large molecule ligand/stabilizer allows for the preparation of noble metal complex and noble metal nanoparticle catalysts. These catalysts are found to be highly selective and active in aqueous-organic biphasic catalysis of cinnamaldehyde and quinoline, and can be reused at least 3 times without significant loss of activity. Moreover, the catalytic activity and reusability of the catalysts can be rationally controlled by simply adjusting the content of polyphenols in the catalysts. Our strategy may be extended to design a wide range of aqueous-organic biphasic catalysis system.

  8. Linear-g-hyperbranched and cyclodextrin-based amphiphilic block copolymer as a multifunctional nanocarrier

    Directory of Open Access Journals (Sweden)

    Yamei Zhao


    Full Text Available In this paper, a novel, multifunctional polymer nanocarrier was designed to provide adequate volume for high drug loading, to afford a multiregion encapsulation ability, and to achieve controlled drug release. An amphiphilic, triblock polymer (ABC with hyperbranched polycarbonsilane (HBPCSi and β-cyclodextrin (β-CD moieties were first synthesized by the combination of a two-step reversible addition-fragmentation transfer polymerization into a pseudo-one-step hydrosilylation and quaternization reaction. The ABC then self-assembled into stable micelles with a core–shell structure in aqueous solution. These resulting micelles are multifunctional nanocarriers which possess higher drug loading capability due to the introduction of HBPCSi segments and β-CD moieties, and exhibit controlled drug release based on the diffusion release mechanism. The novel multifunctional nanocarrier may be applicable to produce highly efficient and specialized delivery systems for drugs, genes, and diagnostic agents.

  9. Salt Effect on the Cloud Point Phenomenon of Amphiphilic Drug-Hydroxypropylmethyl Cellulose System

    Directory of Open Access Journals (Sweden)

    Mohd. Sajid Ali


    Full Text Available Effect of two amphiphilic drugs (tricyclic antidepressant, nortriptyline hydrochloride (NORT, and nonsteroidal anti-inflammatory drug, sodium salt of ibuprofen (IBF on the cloud point of biopolymer hydroxypropylmethyl cellulose (HPMC was studied. Effect of NaCl was also seen on the CP of HPMC-drug system. CP of HPMC increases uniformly on increasing the (drug. Both drugs, though one being anionic (IBF and other cationic (NORT, affect the CP in almost the same manner but with different extent implying the role of hydrophobicity in the interaction between drug and polymer. Salt affects the CP of the drug in a dramatic way as low concentration of salt was only able to increase the value of the CP, though not affecting the pattern. However, in presence of high concentration of salts, minimum was observed on CP versus (drug plots. Various thermodynamic parameters were evaluated and discussed on the basis of the observed results.


    Institute of Scientific and Technical Information of China (English)

    Jing Li; Fei-peng Wu; Er-jian Wang


    A novel associating polymer P(AEBA) was synthesized by radical polymerization of the cationic amphiphilic monomer, 4-(2-(acryloyloxy)ethoxy)benzyl tri-ethyl ammonium bromide (AEBA), in aqueous solutions. P(AEBA) displays a strong tendency for self-association in aqueous solutions and is sensitive to the external stimulation such as added salt. The associative properties and morphologies of P(AEBA) were studied by fluorescnece probe technique, viscometry and TEM. In dilute salt-free solutions P(AEBA) behaves as polyelectrolyte, while its behavior is similar to that of the polysoap as salt added. Accompanying increasing polymer concentration, polymer aggregation conformation changes from an extended necklace-like structure to a compact globular aggregate corresponding to the viscosity reduction.

  11. Recent advances in amphiphilic polymers for simultaneous delivery of hydrophobic and hydrophilic drugs. (United States)

    Martin, Chloe; Aibani, Noorjahan; Callan, John F; Callan, Bridgeen


    Nanomedicine has evolved with the use of biological compounds such as proteins, peptides and DNA. These hydrophilic and often highly charged compounds require a delivery system to allow effective transport and release at the site of action. These new biological therapeutics have not replaced the more traditional smaller molecule, but instead are working synergistically to the benefit of the end user. To that end, drug delivery systems are now required to encapsulate both larger hydrophilic compounds as well as the smaller and generally more hydrophobic compound. This review highlights the emerging role in drug delivery of amphiphilic polymers that by their very nature can associate with compounds of differing physicochemical properties, in particular the role of micelles, polymersomes and nanocapsules.

  12. Langmuir and langmuir-blodgett films of metallosupramolecular polyelectrolyte-amphiphile complexes. (United States)

    Lehmann, Pit; Symietz, Christian; Brezesinski, Gerald; Krass, Henning; Kurth, Dirk G


    A detailed analysis of a metallosupramolecular polyelectrolyte-amphiphile complex (PAC) at the air-water interface is presented. Langmuir isotherms, Brewster angle microscopy, and X-ray reflectance and diffraction methods are employed to investigate the structure of the Langmuir monolayers. The PAC is self-assembled from 1,3-bis[4'-oxa-(2,2':6',2' '-terpyridinyl)]propane, iron acetate, and dihexadecyl phosphate (DHP). Spreading the PAC at the air-water interface results in a monolayer that consists of two strata. DHP forms a monolayer at the top of the interface, while the metallosupramolecular polyelectrolyte is immersed in the aqueous subphase. Both strata are coupled to each other through electrostatic interactions. The monolayers can be transferred onto solid substrates, resulting in well-ordered multilayers. Such multilayers are model systems for well-ordered metal ions in two dimensions.

  13. An effective dispersant for oil spills based on food-grade amphiphiles. (United States)

    Athas, Jasmin C; Jun, Kelly; McCafferty, Caitlyn; Owoseni, Olasehinde; John, Vijay T; Raghavan, Srinivasa R


    Synthetic dispersants such as Corexit 9500A were used in large quantities (∼2 million gallons) to disperse the oil spilled in the ocean during the recent Deepwater Horizon event. These dispersant formulations contain a blend of surfactants in a base of organic solvent. Some concerns have been raised regarding the aquatic toxicity and environmental impact of these formulations. In an effort to create a safer dispersant, we have examined the ability of food-grade amphiphiles to disperse (emulsify) crude oil in seawater. Our studies show that an effective emulsifier is obtained by combining two such amphiphiles: lecithin (L), a phospholipid extracted from soybeans, and Tween 80 (T), a surfactant used in many food products including ice cream. Interestingly, we find that L/T blends show a synergistic effect, i.e., their combination is an effective emulsifier, but neither L or T is effective on its own. This synergy is maximized at a 60/40 weight ratio of L/T and is attributed to the following reasons: (i) L and T pack closely at the oil-water interface; (ii) L has a low tendency to desorb, which fortifies the interfacial film; and (iii) the large headgroup of T provides steric repulsions between the oil droplets and prevents their coalescence. A comparison of L/T with Corexit 9500A shows that the former leads to smaller oil droplets that remain stable to coalescence for a much longer time. The smaller size and stability of crude oil droplets are believed to be important to their dispersion and eventual microbial degradation in the ocean. Our findings suggest that L/T blends could potentially be a viable alternative for the dispersion of oil spills.

  14. Bilayer vesicles of amphiphilic cyclodextrins: host membranes that recognize guest molecules. (United States)

    Falvey, Patrick; Lim, Choon Woo; Darcy, Raphael; Revermann, Tobias; Karst, Uwe; Giesbers, Marcel; Marcelis, Antonius T M; Lazar, Adina; Coleman, Anthony W; Reinhoudt, David N; Ravoo, Bart Jan


    A family of amphiphilic cyclodextrins (6, 7) has been prepared through 6-S-alkylation (alkyl=n-dodecyl and n-hexadecyl) of the primary side and 2-O-PEGylation of the secondary side of alpha-, beta-, and gamma-cyclodextrins (PEG=poly(ethylene glycol)). These cyclodextrins form nonionic bilayer vesicles in aqueous solution. The bilayer vesicles were characterized by transmission electron microscopy, dynamic light scattering, dye encapsulation, and capillary electrophoresis. The molecular packing of the amphiphilic cyclodextrins was investigated by using small-angle X-ray diffraction of bilayers deposited on glass and pressure-area isotherms obtained from Langmuir monolayers on the air-water interface. The bilayer thickness is dependent on the chain length, whereas the average molecular surface area scales with the cyclodextrin ring size. The alkyl chains of the cyclodextrins in the bilayer are deeply interdigitated. Molecular recognition of a hydrophobic anion (adamantane carboxylate) by the cyclodextrin vesicles was investigated by using capillary electrophoresis, thereby exploiting the increase in electrophoretic mobility that occurs when the hydrophobic anions bind to the nonionic cyclodextrin vesicles. It was found that in spite of the presence of oligo(ethylene glycol) substituents, the beta-cyclodextrin vesicles retain their characteristic affinity for adamantane carboxylate (association constant K(a)=7.1 x 10(3) M(-1)), whereas gamma-cyclodextrin vesicles have less affinity (K(a)=3.2 x 10(3) M(-1)), and alpha-cyclodextrin or non-cyclodextrin, nonionic vesicles have very little affinity (K(a) approximately 100 M(-1)). Specific binding of the adamantane carboxylate to beta-cyclodextrin vesicles was also evident in competition experiments with beta-cyclodextrin in solution. Hence, the cyclodextrin vesicles can function as host bilayer membranes that recognize small guest molecules by specific noncovalent interaction.

  15. Electrical release of dopamine and levodopa mediated by amphiphilic β-cyclodextrins immobilized on polycrystalline gold (United States)

    Foschi, Giulia; Leonardi, Francesca; Scala, Angela; Biscarini, Fabio; Kovtun, Alessandro; Liscio, Andrea; Mazzaglia, Antonino; Casalini, Stefano


    Vesicles of cationic amphiphilic β-cyclodextrins have been immobilized on polycrystalline gold by exploiting the chemical affinity between their amino groups and Au atoms. The presence of cyclodextrins has been widely investigated by means of AFM, XPS, kelvin probe and electrochemical measurements. This multi-functional coating confers distinct electrochemical features such as pH-dependent behavior and partial/total blocking properties towards electro-active species. The host-guest properties of β-cyclodextrins have been successfully exploited in order to trap drugs, like dopamine and levodopa. The further release of these drugs was successfully achieved by providing specific electrical stimuli. This proof-of-concept led us to fabricate an electronic device (i.e. an organic transistor) capable of dispensing both dopamine and levodopa in aqueous solution.Vesicles of cationic amphiphilic β-cyclodextrins have been immobilized on polycrystalline gold by exploiting the chemical affinity between their amino groups and Au atoms. The presence of cyclodextrins has been widely investigated by means of AFM, XPS, kelvin probe and electrochemical measurements. This multi-functional coating confers distinct electrochemical features such as pH-dependent behavior and partial/total blocking properties towards electro-active species. The host-guest properties of β-cyclodextrins have been successfully exploited in order to trap drugs, like dopamine and levodopa. The further release of these drugs was successfully achieved by providing specific electrical stimuli. This proof-of-concept led us to fabricate an electronic device (i.e. an organic transistor) capable of dispensing both dopamine and levodopa in aqueous solution. Electronic supplementary information (ESI) available: Kelvin probe, AFM and electrochemical data are reported. Furthermore, the chemical backbone of both types of cyclodextrins are shown. See DOI: 10.1039/c5nr05405b

  16. Facile synthesis and characterization of novel biodegradable amphiphilic block copolymers bearing pendant hydroxyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Gaicen; Fan, Xiaoshan; Xu, Bingcan; Zhang, Delong; Hu, Zhiguo, E-mail:


    Novel amphiphilic block copolymers bearing pendant hydroxyl groups polylactide-b–poly(3,3-bis(Hydroxymethyl–triazolylmethyl) oxetane)-b–polylactide (PLA-b–PHMTYO-b–PLA) were synthesized via a facile and efficient method. First, the block copolymer intermediates polylactide-b–poly(3,3-Diazidomethyloxetane)-b–polylactide (PLA-b–PBAMO-b–PLA) were synthesized through ring-opening polymerization of lactide using PBAMO as a macroinitiator. Following “Click” reaction of PLA-b–PBAMO-b–PLA with propargyl alcohol provided the targeted amphiphilic block copolymers PLA-b–PHMTYO-b–PLA with pendant hydroxyl groups. The composition and structure of prepared copolymers were characterized by {sup 1}H nuclear magnetic resonance ({sup 1}H NMR) spectroscopy, Fourier transform infrared (FT-IR) and gel permeation chromatography (GPC). The self-assembly behavior of the copolymers in water was investigated by transmission electron microscope (TEM), dynamic light scattering (DLS) and static light scattering (SLS). The results showed that the novel copolymers PLA-b–PHMTYO-b–PLA self-assembled into spherical micelles with diameters ranging from 100 nm to 200 nm in aqueous solution. These copolymers also exhibited low critical micellar concentrations (CMC: 6.9 × 10{sup −4} mg/mL and 3.9 × 10{sup −5} mg/mL, respectively). In addition, the in vitro cytotoxicity of these copolymers was determined in the presence of L929 cells. The results showed that the block copolymers PLA-b–PHMTYO-b–PLA exhibited better biocompatibility. Therefore, these well-defined copolymers are expected to find some applications in drug delivery or tissue engineering. - Highlights: • The method to synthesize PLA-b–PHMTYO-b–PLA is relatively facile and efficient. • PLA-b–PHMTYO-b–PLA self-assembles into spherical micelles with low CMC in water. • PLA-b–PHMTYO-b–PLA exhibits better biocompatibility and biodegradability.

  17. Terminal groups control self-assembly of amphiphilic block copolymers in solution (United States)

    Grzelakowski, M.; Kita-Tokarczyk, K.


    The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability.The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability. Electronic supplementary information (ESI) available: Fig. S1: Particle diameters for hydrated NH2-ABA-NH2 polymers with different degrees of functionalization; Fig. S2: TEM characterization of compound micelles from BA-OH polymer after extrusion; Fig. S3: Cryo-TEM and stopped flow characterization of lipid vesicles; Fig. S4 and S5: NMR spectra for ABA and BA polymers

  18. In vitro evaluation of anticancer nanomedicines based on doxorubicin and amphiphilic Y-shaped copolymers

    Directory of Open Access Journals (Sweden)

    Li D


    Full Text Available Di Li,1,2,* Jian Xun Ding,1,3,* Zhao Hui Tang,1 Hai Sun,1 Xiu Li Zhuang,1 Jing Zhe Xu,2 Xue Si Chen1 1Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 2Department of Chemistry, Yanbian University, Yanji, 3Graduate University of Chinese Academy of Sciences, Beijing, China *These authors contributed equally to this workAbstract: Four monomethoxy poly(ethylene glycol-poly(L-lactide-co-glycolide2 (mPEG-P(LA-co-GA2 copolymers were synthesized by ring-opening polymerization of L-lactide and glycolide with double hydroxyl functionalized mPEG (mPEG-(OH2 as macroinitiator and stannous octoate as catalyst. The copolymers self-assembled into nanoscale micellar/vesicular aggregations in phosphate buffer at pH 7.4. Doxorubicin (DOX, an anthracycline anticancer drug, was loaded into the micellar/vesicular nanoparticles, yielding micellar/vesicular nanomedicines. The in vitro release behaviors could be adjusted by content of hydrophobic polyester and pH of the release medium. In vitro cell experiments showed that the intracellular DOX release could be adjusted by content of P(LA-co-GA, and the nanomedicines displayed effective proliferation inhibition against Henrietta Lacks’s cells with different culture times. Hemolysis tests indicated that the copolymers were hemocompatible, and the presence of copolymers could reduce the hemolysis ratio of DOX significantly. These results suggested that the novel anticancer nanomedicines based on DOX and amphiphilic Y-shaped copolymers were attractive candidates as tumor tissular and intracellular targeting drug delivery systems in vivo, with enhanced stability during circulation and accelerated drug release at the target sites.Keywords: amphiphilic Y-shaped copolymer, anticancer nanomedicine, cellular proliferation inhibition, doxorubicin

  19. Structures of self-assembled amphiphilic peptide-heterodimers: effects of concentration, pH, temperature and ionic strength

    KAUST Repository

    Luo, Zhongli


    The amphiphilic double-tail peptides AXG were studied regarding secondary structure and self-assembly in aqueous solution. The two tails A = Ala 6 and G = Gly6 are connected by a central pair X of hydrophilic residues, X being two aspartic acids in ADG, two lysines in AKG and two arginines in ARG. The peptide AD (Ala6Asp) served as a single-tail reference. The secondary structure of the four peptides was characterized by circular dichroism spectroscopy under a wide range of peptide concentrations (0.01-0.8 mM), temperatures (20-98 °C), pHs (4-9.5) and ionic strengths. In salt-free water both ADG and AD form a β-sheet type of structure at high concentration, low pH and low temperature, in a peptide-peptide driven assembly of individual peptides. The transition has a two-state character for ADG but not for AD, which indicates that the added tail in ADG makes the assembly more cooperative. By comparison the secondary structures of AKG and ARG are comparatively stable over the large range of conditions covered. According to dynamic light scattering the two-tail peptides form supra-molecular aggregates in water, but high-resolution AFM-imaging indicate that ordered (self-assembled) structures are only formed when salt (0.1 M NaCl) is added. Since the CD-studies indicate that the NaCl has only a minor effect on the peptide secondary structure we propose that the main role of the added salt is to screen the electrostatic repulsion between the peptide building blocks. According to the AFM images ADG and AKG support a correlation between nanofibers and a β-sheet or unordered secondary structure, whereas ARG forms fibers in spite of lacking β-sheet structure. Since the AKG and ARG double-tail peptides self-assemble into distinct nanostructures while their secondary structures are resistant to environment factors, these new peptides show potential as robust building blocks for nano-materials in various medical and nanobiotechnical applications. © 2010 The Royal Society

  20. Spectroscopic characterizations of non-amphiphilic 2-(4-biphenylyl)-6-phenyl benzoxazole molecules at the air-water interface and in Langmuir-Blodgett films

    Energy Technology Data Exchange (ETDEWEB)

    Hussain, S.A. [Department of Physics, Tripura University, Suryamaninagar, Agartala: 799130 Tripura (India); Deb, S. [Department of Physics, Tripura University, Suryamaninagar, Agartala: 799130 Tripura (India); Bhattacharjee, D. [Department of Physics, Tripura University, Suryamaninagar, Agartala: 799130 Tripura (India)]. E-mail:


    This communication reports about the successful incorporation of a well-known non-amphiphilic derivative of oxazole chromophore 2-(4-biphenylyl)-6-phenyl benzoxazole abbreviated as PBBO, in Langmuir-Blodgett films when mixed with stearic acid (SA) as well as also an inert polymer matrix polymethylmethacrylate (PMMA). The surface pressure versus area per molecule isotherms of the Langmuir films of PBBO mixed with PMMA or SA at different mole fractions reveal that the area per molecule decreases consistently with increasing mole fractions of PBBO. Area per molecule versus mole fraction curve shows that the experimental data points coincide with the ideality curve predicted by the additivity rule, which leads to the conclusion of either ideal mixing or complete demixing of the binary components. The UV-vis absorption and fluorescence spectroscopic studies of mixed LB films of PBBO reveal the nature of complete demixing of the binary components of the sample molecules (PBBO) and PMMA or SA molecules. This complete demixing leads to the formation of clusters and aggregates of PBBO molecules in Langmuir and Langmuir-Blodgett films. J-type aggregates of PBBO molecules in LB films have been confirmed by UV-vis absorption spectroscopic study. Aggregation of PBBO molecules in LB films giving rise to excimeric emission has been demonstrated by fluorescence spectroscopic study. Excitation spectroscopic study clearly confirmed the presence of excimeric sites.

  1. Colloidal and antibacterial properties of novel triple-headed, double-tailed amphiphiles: exploring structure-activity relationships and synergistic mixtures. (United States)

    Marafino, John N; Gallagher, Tara M; Barragan, Jhosdyn; Volkers, Brandi L; LaDow, Jade E; Bonifer, Kyle; Fitzgerald, Gabriel; Floyd, Jason L; McKenna, Kristin; Minahan, Nicholas T; Walsh, Brenna; Seifert, Kyle; Caran, Kevin L


    Two novel series of tris-cationic, tripled-headed, double-tailed amphiphiles were synthesized and the effects of tail length and head group composition on the critical aggregation concentration (CAC), thermodynamic parameters, and minimum inhibitory concentration (MIC) against six bacterial strains were investigated. Synergistic antibacterial combinations of these amphiphiles were also identified. Amphiphiles in this study are composed of a benzene core with three benzylic ammonium bromide groups, two of which have alkyl chains, each 8-16 carbons in length. The third head group is a trimethylammonium or pyridinium. Log of critical aggregation concentration (log[CAC]) and heat of aggregation (ΔHagg) were both inversely proportional to the length of the linear hydrocarbon chains. Antibacterial activity increases with tail length until an optimal tail length of 12 carbons per chain, above which, activity decreased. The derivatives with two 12 carbon chains had the best antibacterial activity, killing all tested strains at concentrations of 1-2μM for Gram-positive and 4-16μM for Gram-negative bacteria. The identity of the third head group (trimethylammonium or pyridinium) had minimal effect on colloidal and antibacterial activity. The antibacterial activity of several binary combinations of amphiphiles from this study was higher than activity of individual amphiphiles, indicating that these combinations are synergistic. These amphiphiles show promise as novel antibacterial agents that could be used in a variety of applications.

  2. One-Pot Synthesis of (+-Nootkatone via Dark Singlet Oxygenation of Valencene: The Triple Role of the Amphiphilic Molybdate Catalyst

    Directory of Open Access Journals (Sweden)

    Bing Hong


    Full Text Available Efficient one-pot catalytic synthesis of (+-nootkatone was performed from (+-valencene using only hydrogen peroxide and amphiphilic molybdate ions. The process required no solvent and proceeded in three cascade reactions: (i singlet oxygenation of valencene according to the ene reaction; (ii Schenck rearrangement of one hydroperoxide into the secondary β-hydroperoxide; and (iii dehydration of the hydroperoxide into the desired (+-nootkatone. The solvent effect on the hydroperoxide rearrangement is herein discussed. The amphiphilic dimethyldioctyl ammonium molybdate, which is also a balanced surfactant, played a triple role in this process, as molybdate ions catalyzed at both Step 1 and Step 3 and it allowed the rapid formation of a three-phase microemulsion system that highly facilitates product recovery. Preparative synthesis of the high added value (+-nootkatone was thus performed at room temperature with an isolated yield of 46.5%. This is also the first example of a conversion of allylic hydroperoxides into ketones catalyzed by molybdate ions.


    Institute of Scientific and Technical Information of China (English)

    QIU Yongxing; YU Xiaojie; FENG Linxian; YANG Shilin


    Acryloyl terminated Poly (ethyleneoxide)macromonomers(PEO-A) with different PEO chain lengths have been prepared by deactivation of PEO alkoxide with acryloyl chloride. A new kind of amphiphilic polystyrene-g-poly (ethylene oxide)graft copolymer containing both microphase separated and PEO side chain structures has been synthesized from radical copolymerization of PEO-A macromonomer with styrene. After careful purification by a newly-developed method called "selective dissolution", the well-defined structure of the purified copolymers was confirmed by IR, 1H-NMR and GPC. Various experimental parameters controlling the copolymerization were studied in detail. The results indicated that the feed ratio of styrene to macromonomer(S/M) was the most important determining factor for the composition of the copolymers. A detailed "comb-model" was proposed to describe the molecular structure of the graft copolymers. Finally, this amphiphilic graft copolymers may readily form microphase separated structures as clearly indicated by transmission electron microscopy.

  4. Hybrid magnetic amphiphilic composites based on carbon nanotube/nanofibers and layered silicates fragments as efficient adsorbent for ethynilestradiol. (United States)

    Purceno, Aluir D; Teixeira, Ana Paula C; de Souza, Nubia Janaína; Fernandez-Outon, Luis E; Ardisson, José D; Lago, Rochel M


    In this work, hybrid magnetic amphiphilic composites were prepared by the catalytic growth of carbon nanotubes (CNTs) and nanofibers CNF on layered silicates fragments. SEM, TEM, Raman, XRD, Mössbauer, TG/DTA showed that CVD with CH(4) at 800°C produced CNF and magnetic Fe cores fixed on the surface of microfragments of silicates layers. Due to the amphiphilic character, the composites can be easily dispersed in water and efficiently adsorb hydrophobic contaminant molecules. For example, the composites showed remarkable adsorption capacities for the hormone ethinylestradiol, e.g. 2-4 mg m(-2), compared to ca. 0.1 mg m(-2) obtained for high surface area activated carbon and multiwall CNT. These results are discussed in terms of a high hydrophobic exposed surface area of the CNT and CNF fixed on the layered silicates fragments surface. Moreover, the composites can be easily removed from water by a simple magnetic separation process.

  5. Graphene oxide-enhanced sol-gel transition sensitivity and drug release performance of an amphiphilic copolymer-based nanocomposite (United States)

    Hu, Huawen; Wang, Xiaowen; Lee, Ka I.; Ma, Kaikai; Hu, Hong; Xin, John H.


    We report the fabrication of a highly sensitive amphiphilic copolymer-based nanocomposite incorporating with graphene oxide (GO), which exhibited a low-intensity UV light-triggered sol-gel transition. Non-cytotoxicity was observed for the composite gels after the GO incorporation. Of particular interest were the microchannels that were formed spontaneously within the GO-incorporated UV-gel, which expedited sustained drug release. Therefore, the present highly UV-sensitive, non-cytotoxic amphiphilic copolymer-based composites is expected to provide enhanced photothermal therapy and chemotherapy by means of GO’s unique photothermal properties, as well as through efficient passive targeting resulting from the sol-gel transition characteristic of the copolymer-based system with improved sensitivity, which thus promises the enhanced treatment of patients with cancer and other diseases.

  6. Graphene oxide-enhanced sol-gel transition sensitivity and drug release performance of an amphiphilic copolymer-based nanocomposite. (United States)

    Hu, Huawen; Wang, Xiaowen; Lee, Ka I; Ma, Kaikai; Hu, Hong; Xin, John H


    We report the fabrication of a highly sensitive amphiphilic copolymer-based nanocomposite incorporating with graphene oxide (GO), which exhibited a low-intensity UV light-triggered sol-gel transition. Non-cytotoxicity was observed for the composite gels after the GO incorporation. Of particular interest were the microchannels that were formed spontaneously within the GO-incorporated UV-gel, which expedited sustained drug release. Therefore, the present highly UV-sensitive, non-cytotoxic amphiphilic copolymer-based composites is expected to provide enhanced photothermal therapy and chemotherapy by means of GO's unique photothermal properties, as well as through efficient passive targeting resulting from the sol-gel transition characteristic of the copolymer-based system with improved sensitivity, which thus promises the enhanced treatment of patients with cancer and other diseases.

  7. Investigation of thermo-sensitive amphiphilic micelles as drug carriers for chemotherapy in cholangiocarcinoma in vitro and in vivo. (United States)

    Wang, Xuefeng; Li, Songgang; Wan, Ziwei; Quan, Zhiwei; Tan, Qinggang


    Cholangiocarcinoma is an epithelial cancer of the bile ducts with poor prognosis and, in recent years, a rapidly increasing incidence. In this study, nano-sized thermo-sensitive micelles were investigated as drug carriers to improve chemotherapy in cholangiocarcinoma. Thermo-sensitive amphiphilic block copolymer, P-(N,N-isopropylacrylamide-co-N-hydroxymethylacrylamide)-b-caprolactone [P-(NIPAAm-co-NHMAAm)-b-PCL] with lower critical solution temperature (LCST) at about 38°C was synthesized. Doxorubicin (DOX)-loaded micelles were prepared by dialysis method. The micelles exhibited a sustained and temperature-dependent DOX release. Toxicity of the blank micelles for human cholangiocarcinoma (QBC939) cells was minimal both in vitro and in vivo. In contrast, the DOX-loaded micelles effectively inhibited proliferation and induced apoptosis of QBC939 cells in vitro (pthermo-sensitive amphiphilic micelles are a promising and effective drug carrier, and show potential for improving chemotherapy for cholangiocarcinoma.

  8. Multiple cationic amphiphiles induce a Niemann-Pick C phenotype and inhibit Ebola virus entry and infection.

    Directory of Open Access Journals (Sweden)

    Charles J Shoemaker

    Full Text Available Ebola virus (EBOV is an enveloped RNA virus that causes hemorrhagic fever in humans and non-human primates. Infection requires internalization from the cell surface and trafficking to a late endocytic compartment, where viral fusion occurs, providing a conduit for the viral genome to enter the cytoplasm and initiate replication. In a concurrent study, we identified clomiphene as a potent inhibitor of EBOV entry. Here, we screened eleven inhibitors that target the same biosynthetic pathway as clomiphene. From this screen we identified six compounds, including U18666A, that block EBOV infection (IC(50 1.6 to 8.0 µM at a late stage of entry. Intriguingly, all six are cationic amphiphiles that share additional chemical features. U18666A induces phenotypes, including cholesterol accumulation in endosomes, associated with defects in Niemann-Pick C1 protein (NPC1, a late endosomal and lysosomal protein required for EBOV entry. We tested and found that all six EBOV entry inhibitors from our screen induced cholesterol accumulation. We further showed that higher concentrations of cationic amphiphiles are required to inhibit EBOV entry into cells that overexpress NPC1 than parental cells, supporting the contention that they inhibit EBOV entry in an NPC1-dependent manner. A previously reported inhibitor, compound 3.47, inhibits EBOV entry by blocking binding of the EBOV glycoprotein to NPC1. None of the cationic amphiphiles tested had this effect. Hence, multiple cationic amphiphiles (including several FDA approved agents inhibit EBOV entry in an NPC1-dependent fashion, but by a mechanism distinct from that of compound 3.47. Our findings suggest that there are minimally two ways of perturbing NPC1-dependent pathways that can block EBOV entry, increasing the attractiveness of NPC1 as an anti-filoviral therapeutic target.

  9. Multiple cationic amphiphiles induce a Niemann-Pick C phenotype and inhibit Ebola virus entry and infection. (United States)

    Shoemaker, Charles J; Schornberg, Kathryn L; Delos, Sue E; Scully, Corinne; Pajouhesh, Hassan; Olinger, Gene G; Johansen, Lisa M; White, Judith M


    Ebola virus (EBOV) is an enveloped RNA virus that causes hemorrhagic fever in humans and non-human primates. Infection requires internalization from the cell surface and trafficking to a late endocytic compartment, where viral fusion occurs, providing a conduit for the viral genome to enter the cytoplasm and initiate replication. In a concurrent study, we identified clomiphene as a potent inhibitor of EBOV entry. Here, we screened eleven inhibitors that target the same biosynthetic pathway as clomiphene. From this screen we identified six compounds, including U18666A, that block EBOV infection (IC(50) 1.6 to 8.0 µM) at a late stage of entry. Intriguingly, all six are cationic amphiphiles that share additional chemical features. U18666A induces phenotypes, including cholesterol accumulation in endosomes, associated with defects in Niemann-Pick C1 protein (NPC1), a late endosomal and lysosomal protein required for EBOV entry. We tested and found that all six EBOV entry inhibitors from our screen induced cholesterol accumulation. We further showed that higher concentrations of cationic amphiphiles are required to inhibit EBOV entry into cells that overexpress NPC1 than parental cells, supporting the contention that they inhibit EBOV entry in an NPC1-dependent manner. A previously reported inhibitor, compound 3.47, inhibits EBOV entry by blocking binding of the EBOV glycoprotein to NPC1. None of the cationic amphiphiles tested had this effect. Hence, multiple cationic amphiphiles (including several FDA approved agents) inhibit EBOV entry in an NPC1-dependent fashion, but by a mechanism distinct from that of compound 3.47. Our findings suggest that there are minimally two ways of perturbing NPC1-dependent pathways that can block EBOV entry, increasing the attractiveness of NPC1 as an anti-filoviral therapeutic target.

  10. New amphiphilic glycopolypeptide conjugate capable of self-assembly in water into reduction-sensitive micelles for triggered drug release

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Hui-Kang [DSAPM Lab and PCFM Lab, Department of Polymer and Materials Science, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275 (China); Zhang, Li-Ming, E-mail: [DSAPM Lab and PCFM Lab, Department of Polymer and Materials Science, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275 (China); Guangdong Provincial Key Laboratory of New Drug Design and Evaluation, School of Pharmaceutical Science, Sun Yat-sen University, Guangzhou 510006 (China)


    For the development of biomimetic carriers for stimuli-sensitive delivery of anticancer drugs, a novel amphiphilic glycopolypeptide conjugate containing the disulfide bond was prepared for the first time by the ring-opening polymerization of benzyl glutamate N-carboxy anhydride in the presence of (propargyl carbamate)ethyl dithio ethylamine and then click conjugation with α-azido dextran. Its structure was characterized by Fourier-transform infrared spectroscopy and nuclear magnetic resonance analyses. Owing to its amphiphilic nature, such a conjugate could self assemble into nanosize micelles in aqueous medium, as confirmed by fluorometry, transmission electron microscopy and dynamic light scattering. For the resultant micelles, it was found to encapsulate poorly water-soluble anticancer drug (methotrexate, MTX) with the loading efficiency of 45.2%. By the in vitro drug release tests, the release rate of encapsulated MTX was observed to be accelerated significantly in the presence of 10 mM 1,4-dithio-DL-threitol (DTT), analogous to the intracellular redox potential. - Graphical abstract: New amphiphilic glycopolypeptide conjugate containing the disulfide bond could self-assemble in aqueous solution into reduction-sensitive micelles for triggered release of an anticancer drug (methotrexate, MTX) in the presence of 10 mM 1,4-dithio-DL-threitol (DTT). - Highlights: • Amphiphilic glycopolypeptide conjugate containing disulfide bond was prepared. • Such a conjugate self assembled in aqueous solution into nanosize micelles. • The resultant micelles could encapsulate effectively methotrexate drug. • The drug-loaded micelles showed a reduction-sensitive drug release behavior.

  11. Understanding Peptide Oligomeric State in Langmuir Monolayers of Amphiphilic 3-Helix Bundle-Forming Peptide-PEG Conjugates (United States)

    Shu, Jessica Y.; Xu, Ting


    Coiled-coil peptide–polymer conjugates are an emerging class of biomaterials. Fundamental understanding of the coiled-coil oligomeric state and assembly process of these hybrid building blocks is necessary to exert control over their assembly into well-defined structures. Here, we studied the effect of peptide structure and PEGylation on the self-assembly process and oligomeric state of a Langmuir monolayer of amphiphilic coiled-coil peptide–polymer conjugates using X-ray reflectivity (XR) and grazing-incidence X-ray diffraction (GIXD). Our results show that the oligomeric state of PEGylated amphiphiles based on 3-helix bundle-forming peptide is surface pressure dependent, a mixture of dimers and trimers was formed at intermediate surface pressure but transitions into trimers completely upon increasing surface pressure. Moreover, the interhelical distance within the coiled-coil bundle of 3-helix peptide-PEG conjugate amphiphiles was not perturbed under high surface pressure. Present studies provide valuable insights into the self-assembly process of hybrid peptide–polymer conjugates and guidance to develop biomaterials with controlled multivalency of ligand presentation. PMID:27784156

  12. Exploring the structure-solubility relationship of asphaltene models in toluene, heptane, and amphiphiles using a molecular dynamic atomistic methodology. (United States)

    Aray, Yosslen; Hernández-Bravo, Raiza; Parra, José G; Rodríguez, Jesús; Coll, David S


    The solubility parameters, δ, of several asphaltene models were calculated by mean of an atomistic NPT ensemble. Continental and archipelago models were explored. A relationship between the solubility parameter and the molecule structure was determined. In general, increase of the fused-rings number forming the aromatic core and the numbers of heteroatoms such as oxygen, nitrogen, and sulfur produces an increase of the solubility parameter, while increases of the numbers and length of the aliphatic chains yield a systematic decrease of this parameter. Molecules with large total carbon atom number at the tails, n(c), and small aromatic ring number, n(r), exhibit the biggest values of δ, while molecules with small n(c) and large n(r) show the smallest δ values. A good polynomial correlation δ = 5.967(n(r)/n(c)) - 3.062(n(r)/n(c))(2) + 0.507(n(r)/n(c))(3) + 16.593 with R(2) = 0.965 was found. The solubilities of the asphaltene models in toluene, heptane, and amphiphiles were studied using the Scatchard-Hildebrand and the Hansen sphere methodologies. Generally, there is a large affinity between the archipelago model and amphiphiles containing large aliphatic tails and no aromatic rings, while continental models show high affinity for amphiphiles containing an aromatic ring and small aliphatic chains.

  13. Dehydration-induced redistribution of amphiphilic molecules between cytoplasm and lipids is associated with desiccation tolerance in seeds. (United States)

    Buitink, J; Leprince, O; Hoekstra, F A


    This study establishes a relationship between desiccation tolerance and the transfer of amphiphilic molecules from the cytoplasm into lipids during drying, using electron paramagnetic resonance spectroscopy of amphiphilic spin probes introduced into imbibed radicles of pea (Pisum sativum) and cucumber (Cucumis sativa) seeds. Survival following drying and a membrane integrity assay indicated that desiccation tolerance was present during early imbibition and lost in germinated radicles. In germinated cucumber radicles, desiccation tolerance could be re-induced by an incubation in polyethylene glycol (PEG) before drying. In desiccation-intolerant radicles, partitioning of spin probes into lipids during dehydration occurred at higher water contents compared with tolerant and PEG-induced tolerant radicles. The difference in partitioning behavior between desiccation-tolerant and -intolerant tissues could not be explained by the loss of water. Consequently, using a two-phase model system composed of sunflower or cucumber oil and water, physical properties of the aqueous solvent that may affect the partitioning of amphiphilic spin probes were investigated. A significant relationship was found between the partitioning of spin probes and the viscosity of the aqueous solvent. Moreover, in desiccation-sensitive radicles, the rise in cellular microviscosity during drying commenced at higher water contents compared with tolerant or PEG-induced tolerant radicles, suggesting that the microviscosity of the cytoplasm may control the partitioning behavior in dehydrating seeds.

  14. A minimal hydrophobicity is needed to employ amphiphilic p(HPMA)-co-p(LMA) random copolymers in membrane research. (United States)

    Stangl, Michael; Hemmelmann, Mirjam; Allmeroth, Mareli; Zentel, Rudolf; Schneider, Dirk


    Because a polymer environment might be milder than a detergent micelle, amphiphilic polymers have attracted attention as alternatives to detergents in membrane biochemistry. The polymer poly[N-(2-hydroxypropyl)-methacrylamid] [p(HPMA)] has recently been modified with hydrophobic lauryl methacrylate (LMA) moieties, resulting in the synthesis of amphiphilic p(HPMA)-co-p(LMA) polymers. p(HPMA)-co-p(LMA) polymers with a LMA content of 5 or 15% have unstable hydrophobic cores. This, on one hand, promotes interactions of the hydrophobic LMA moieties with membranes, resulting in membrane rupture, but at the same time prevents formation of a hydrophobic, membrane mimetic environment that is sufficiently stable for the incorporation of transmembrane proteins. On the other hand, the p(HPMA)-co-p(LMA) polymer with a LMA content of 25% forms a stable hydrophobic core structure, which prevents hydrophobic interactions with membrane lipids but allows stable incorporation of membrane proteins. On the basis of our data, it becomes obvious that amphiphilic polymers have to have threshold hydrophobicities should an application in membrane protein research be anticipated.

  15. Nano-Assemblies of Modified Cyclodextrins and Their Complexes with Guest Molecules: Incorporation in Nanostructured Membranes and Amphiphile Nanoarchitectonics Design

    Directory of Open Access Journals (Sweden)

    Leïla Zerkoune


    Full Text Available A variety of cyclodextrin-based molecular structures, with substitutions of either primary or secondary faces of the natural oligosaccharide macrocycles of α-, β-, or γ-cyclodextrins, have been designed towards innovative applications of self-assembled cyclodextrin nanomaterials. Amphiphilic cyclodextrins have been obtained by chemical or enzymatic modifications of their macrocycles using phospholipidyl, peptidolipidyl, cholesteryl, and oligo(ethylene oxide anchors as well as variable numbers of grafted hydrophobic hydrocarbon or fluorinated chains. These novel compounds may self-assemble in an aqueous medium into different types of supramolecular nanoassemblies (vesicles, micelles, nanorods, nanospheres, and other kinds of nanoparticles and liquid crystalline structures. This review discusses the supramolecular nanoarchitectures, which can be formed by amphiphilic cyclodextrin derivatives in mixtures with other molecules (phospholipids, surfactants, and olygonucleotides. Biomedical applications are foreseen for nanoencapsulation of drug molecules in the hydrophobic interchain volumes and nanocavities of the amphiphilic cyclodextrins (serving as drug carriers or pharmaceutical excipients, anticancer phototherapy, gene delivery, as well as for protection of instable active ingredients through inclusion complexation in nanostructured media.

  16. Self-Assembly of Amphiphilic Block Copolypeptoids with C 2 -C 5 Side Chains in Aqueous Solution

    KAUST Repository

    Fetsch, Corinna


    © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Nowadays, amphiphilic molecules play an important role in our life. In medical applications, amphiphilic block copolymers have attracted much attention as excipients in drug delivery systems. Here, the polymers are used as emulsifiers, micelles, or polymersomes with a hydrophilic corona block and a hydrophobic core or membrane. The aggregation behavior in aqueous solutions of a series of different amphiphilic block copolypeptoids comprising polysarcosine as a hydrophilic part is here reported. The formation of aggregates is investigated with 1H NMR spectroscopy and dynamic light scattering, and the determination of the critical micelle concentration (cmc) is performed using pyrene fluorescence spectroscopy. For the different block copolypeptoids cmc values ranging from 0.6 × 10-6 M to 0.1 × 10-3 M are found. The tendency to form micelles increases with increasing hydrophobicity at the nitrogen side chain in the hydrophobic moiety. Furthermore, in the case of the same hydrophobic side chain, a decreasing hydrophilic/lipophilic balance leads to the formation of larger aggregates. The aggregates formed in the buffer are able to solubilize the hydrophobic model compounds Reichardt\\'s dye and pyrene, and exhibit versatile microenvironments. Final investigations about the cytotoxicity reveal that the block copolypeptoids are well tolerated by mammalian cells up to high concentrations.

  17. Hydrophobic Effect of Amphiphilic Derivatives of Chitosan on the Antifungal Activity against Aspergillus flavus and Aspergillus parasiticus

    Directory of Open Access Journals (Sweden)

    Vera Ap. de Oliveira Tiera


    Full Text Available Low molecular weight amphiphilic derivatives of chitosan were synthesized, characterized and their antifungal activities against Aspergillus flavus and Aspergillus parasiticus were tested. The derivatives were synthesized using as starting material a deacetylated chitosan sample in a two step process: the reaction with propyltrimethyl-ammonium bromide (Pr, followed by reductive amination with dodecyl aldehyde. Aiming to evaluate the effect of the hydrophobic modification of the derivatives on the antifungal activity against the pathogens, the degree of substitution (DS1 by Pr groups was kept constant and the proportion of dodecyl (Dod groups was varied from 7 to 29% (DS2. The derivatives were characterized by 1H-NMR and FTIR and their antifungal activities against the pathogens were tested by the radial growth of the colony and minimum inhibitory concentration (MIC methods. The derivatives substituted with only Pr groups exhibited modest inhibition against A. flavus and A. parasiticus, like that obtained with deacetylated chitosan. Results revealed that the amphiphilic derivatives grafted with Dod groups exhibited increasing inhibition indexes, depending on polymer concentration and hydrophobic content. At 0.6 g/L, all amphiphilic derivatives having from 7.0 to 29% of Dod groups completely inhibited fungal growth and the MIC values were found to decrease from 4.0 g/L for deacetylated chitosan to 0.25–0.50 g/L for the derivatives. These new derivatives open up the possibility of new applications and avenues to develop effective biofungicides based on chitosan.

  18. From superamphiphobic to amphiphilic polymeric surfaces with ordered hierarchical roughness fabricated with colloidal lithography and plasma nanotexturing. (United States)

    Ellinas, K; Tserepi, A; Gogolides, E


    Ordered, hierarchical (triple-scale), superhydrophobic, oleophobic, superoleophobic, and amphiphilic surfaces on poly(methyl methacrylate) PMMA polymer substrates are fabricated using polystyrene (PS) microparticle colloidal lithography, followed by oxygen plasma etching-nanotexturing (for amphiphilic surfaces) and optional subsequent fluorocarbon plasma deposition (for amphiphobic surfaces). The PS colloidal microparticles were assembled by spin-coating. After etching/nanotexturing, the PMMA plates are amphiphilic and exhibit hierarchical (triple-scale) roughness with microscale ordered columns, and dual-scale (hundred nano/ten nano meter) nanoscale texture on the particles (top of the column) and on the etched PMMA surface. The spacing, diameter, height, and reentrant profile of the microcolumns are controlled with the etching process. Following the design requirements for superamphiphobic surfaces, we demonstrate enhancement of both hydrophobicity and oleophobicity as a result of hierarchical (triple-scale) and re-entrant topography. After fluorocarbon film deposition, we demonstrate superhydrophobic surfaces (contact angle for water 168°, compared to 110° for a flat surface), as well as superoleophobic surfaces (153° for diiodomethane, compared to 80° for a flat surface).

  19. Novel functional materials from renewable lipids: Amphiphilic antimicrobial polymers and latent heat thermal energy storage (United States)

    Floros, Michael Christopher

    Vegetable oils represent an ideal and renewable feedstock for the synthesis of a variety of functional materials. However, without financial incentive or unique applications motivating a switch, commercial products continue to be manufactured from petrochemical resources. Two different families of high value, functional materials synthesized from vegetable oils were studied. These materials demonstrate superior and unique performance to comparable petrochemical analogues currently on the market. In the first approach, 3 amphiphilic thermoplastic polytriazoles with differing lipophilic segment lengths were synthesized in a polymerization process without solvents or catalysts. Investigation of monomer structure influence on the resultant functional behaviour of these polymers found distinctive odd/even behaviour reliant on the number of carbon atoms in the monomers. Higher concentrations of triazole groups, due to shorter CH2 chains in the monomeric dialkynes, resulted in more brittle polymers, displaying higher tensile strengths but reduced elongation to break characteristics. These polymers had similar properties to commercial petroleum derived thermoplastics. One polymer demonstrated self-assembled surface microstructuring, and displayed hydrophobic properties. Antimicrobial efficacy of the polymers were tested by applying concentrated bacterial solutions to the surfaces, and near complete inhibition was demonstrated after 4 hours. Scanning electron microscope images of killed bacteria showed extensive membrane damage, consistent with the observed impact of other amphiphilic compounds in literature. These polytriazoles are suited for applications in medical devices and implants, where major concerns over antibiotic resistance are prevalent. In the second approach, a series of symmetric, saturated diester phase change materials (PCMs) were also synthesized with superior latent heat values compared to commercial petrochemical analogues. These diesters exhibit

  20. Synthesis and self-assembly of amphiphilic poly(acrylicacid)-poly(ɛ-caprolactone)-poly(acrylicacid) block copolymer as novel carrier for 7-ethyl-10-hydroxy camptothecin. (United States)

    Djurdjic, Beti; Dimchevska, Simona; Geskovski, Nikola; Petrusevska, Marija; Gancheva, Valerya; Georgiev, Georgi; Petrov, Petar; Goracinova, Katerina


    The process of molecular self-assembly plays a crucial role in formulation of polymeric nanoparticulated drug delivery carriers as it creates the possibility for enhanced drug encapsulation and carrier surface engineering. This study aimed to develop a novel self-assembled polymeric micelles for targeted delivery in tumor cells in order to overcome not only various drawbacks of 7-ethyl-10-hydroxy camptothecin (SN-38) but also various reported limitations of other drug delivery systems, especially low drug loading and premature release. Custom synthesized amphiphilic triblock copolymer poly(acrylic acid)-poly(ɛ-caprolactone)-poly(acrylic acid) (PAA(13)-PCL(35)-PAA(13)) was used to prepare kinetically stable micelles by nanoprecipitation and modified nanoprecipitation procedure. Core-shell micelles with diameter of 120-140 nm, negative zeta potential and satisfactory drug loading were produced. The prepared formulations were stable in pH range of 3-12 and in media with NaCl concentration <1 mol/l. Screening mixed level factorial 3 × 2(2) design identified that the process temperature as well as the type of organic solvent has influence upon the efficacy of encapsulation, particle size, dissolution rate and burst release. Fourier transform infrared and differential scanning calorimetry analyses confirmed the entrapment of the active substance into the micelles. The kinetic analysis of dissolution studies revealed that the main mechanism of drug release from the prepared formulations is Fickian diffusion. Growth inhibition studies as well as DNA fragmentation assay performed on SW-480 cell lines clearly demonstrated increased growth inhibition effect and presence of fragmented DNA in cells treated with loaded micelles compared to SN-38 solution. Altogether, these results point out to potential biomedical and clinical application of PAA-PCL-PAA systems in the future.

  1. Formation and Mechanism of Superhydrophobic/Hydrophobic Surfaces Made from Amphiphiles through Droplet-Mediated Evaporation-Induced Self-Assembly. (United States)

    Dong, Fangyuan; Zhang, Mi; Tang, Wai-Wa; Wang, Yi


    Superhydrophobic/hydrophobic surfaces have attracted wide attention because of their broad applications in various regions, including coating, textile, packaging, electronic devices, and bioengineering. Many studies have been focused on the fabrication of superhydrophobic/hydrophobic surfaces using natural materials. In this paper, superhydrophobic/hydrophobic surfaces were formed by an amphiphilic natural protein, zein, using electrospinning. Water contact angle (WCA) and scanning electron microscopy (SEM) were used to characterize the hydrophobicity and surface morphology of the electrospun structures. The highest WCA of the zein electrospun surfaces could reach 155.5 ± 1.4°. To further understand the mechanism of superhydrophobic surface formation from amphiphiles using electrospinning, a synthetic amphiphilic polymer was selected, and also, a method similar to electrospinning, spray drying, was tried. The electrospun amphiphilic polymer surface showed a high hydrophobicity with a WCA of 141.4 ± 0.7°. WCA of the spray-dried zein surface could reach 125.3 ± 2.1°. The secondary structures of the zein in the electrospun film and cast-dried film were studied using ATR-FTIR, showing that α-helix to β-sheet transformation happened during the solvent evaporation in the cast drying process but not in the electrospinning process. A formation mechanism was proposed on the basis of the orientation of the amphiphiles during the solvent evaporation of different fabrication methods. The droplet-based or jet-based evaporation during electrospinning and spray drying led to the formation of the superhydrophobic/hydrophobic surface by the accumulation of the hydrophobic groups of the amphiphiles on the surface, while the surface-based evaporation during cast drying led to the formation of the hydrophilic surface by the accumulation of the hydrophilic groups of the amphiphiles on the surface.

  2. New insights into the intracellular distribution pattern of cationic amphiphilic drugs (United States)

    Vater, Magdalena; Möckl, Leonhard; Gormanns, Vanessa; Schultz Fademrecht, Carsten; Mallmann, Anna M.; Ziegart-Sadowska, Karolina; Zaba, Monika; Frevert, Marie L.; Bräuchle, Christoph; Holsboer, Florian; Rein, Theo; Schmidt, Ulrike; Kirmeier, Thomas


    Cationic amphiphilic drugs (CADs) comprise a wide variety of different substance classes such as antidepressants, antipsychotics, and antiarrhythmics. It is well recognized that CADs accumulate in certain intracellular compartments leading to specific morphological changes of cells. So far, no adequate technique exists allowing for ultrastructural analysis of CAD in intact cells. Azidobupramine, a recently described multifunctional antidepressant analogue, allows for the first time to perform high-resolution studies of CADs on distribution pattern and morphological changes in intact cells. We showed here that the intracellular distribution pattern of azidobupramine strongly depends on drug concentration and exposure time. The mitochondrial compartment (mDsRed) and the late endo-lysosomal compartment (CD63-GFP) were the preferred localization sites at low to intermediate concentrations (i.e. 1 μM, 5 μM). In contrast, the autophagosomal compartment (LC3-GFP) can only be reached at high concentrations (10 μM) and long exposure times (72 hrs). At the morphological level, LC3-clustering became only prominent at high concentrations (10 μM), while changes in CD63 pattern already occurred at intermediate concentrations (5 μM). To our knowledge, this is the first study that establishes a link between intracellular CAD distribution pattern and morphological changes. Therewith, our results allow for gaining deeper understanding of intracellular effects of CADs. PMID:28281674

  3. Glycoconjugated amphiphilic polymers via click-chemistry for the encapsulation of quantum dots. (United States)

    Schmidtke, Christian; Kreuziger, Anna-Marlena; Alpers, Dirk; Jacobsen, Anna; Leshch, Yevgeniy; Eggers, Robin; Kloust, Hauke; Tran, Huong; Ostermann, Johannes; Schotten, Theo; Thiem, Joachim; Thimm, Julian; Weller, Horst


    Herein, we present a strategy for the glycoconjugation of nanoparticles (NPs), with a special focus on fluorescent quantum dots (QDs), recently described by us as "preassembly" approach. Therein, prior to the encapsulation of diverse nanoparticles by an amphiphilic poly(isoprene)-b-poly(ethylene glycol) diblock copolymer (PI-b-PEG), the terminal PEG appendage was modified by covalently attaching a carbohydrate moiety using Huisgen-type click-chemistry. Successful functionalization was proven by NMR spectroscopy. The terminally glycoconjugated polymers were subsequently used for the encapsulation of QDs in a phase transfer process, which fully preserved fluorescence properties. Binding of these nanoconstructs to the lectin Concanavalin A (Con A) was studied via surface plasmon resonance (SPR). Depending on the carbohydrate moiety, namely, D-manno-heptulose, D-glucose, D-galactose, 2-deoxy-2-{[methylamino)carbonyl]amino}-D-glucopyranose ("des(nitroso)-streptozotocin"), or D-maltose, the glycoconjugated QDs showed enhanced affinity constants due to multivalent binding effects. None of the constructs showed toxicity from 0.001 to 1 μM (particle concentration) using standard WST and LDH assays on A549 cells.

  4. New amphiphilic PEG-b-P(ester-ether) micelles as potential drug nanocarriers

    Energy Technology Data Exchange (ETDEWEB)

    Jeetah, Roubeena; Bhaw-Luximon, Archana; Jhurry, Dhanjay, E-mail: [University of Mauritius, ANDI Centre of Excellence for Biomedical and Biomaterials Research, MSIRI Building (Mauritius)


    A range of diblock and triblock copolymers of dioxanone and methyl dioxanone (MeDX) were synthesized by ring-opening polymerization of dioxanone and MeDX initiated by hydroxyl-terminated PEG (MPEG) or di-amino-terminated PEG (Jeffamine{sup Registered-Sign }) as macroinitiator in the presence of Sn(Oct){sub 2}. The copolymers exhibit amphiphilic behavior in water forming core-shell micelles in the size range 120-300 nm as measured by DLS. DSC measurements exhibit only one melting transition for all copolymers and confirm that increasing MeDX content of the copolymers lead to decreasing crystalline character and hydrophobic-hydrophilic chain entanglement. Anti-inflammatory drug ketoprofen was successfully loaded into the hydrophobic core of the micelles. Various key parameters such as micelle size, drug entrapment efficiency and drug release, which are dependent on crystalline structure and biodegradability characteristics of the hydrophobic core, could effectively be controlled by varying the dioxanone/MeDX ratio of the (ester-ether) copolymer.

  5. Synthesis and characterization of an elastin-mimetic amphiphilic block copolymer protein (United States)

    Lee, Terrence Anita-Talley


    The overall goal in material science is to be able to control the molecular architecture of a material and thus its end properties. There is no method that offers greater control than the biological synthesis of proteins. From the DNA sequence to the final synthesized protein, the entire process is finitely controlled. This present work describes methods developed and used to synthesize protein polymers by manipulating this process. From the initial DNA sequence chosen, the end properties that the protein polymer will have are dictated. An amphiphilic diblock copolymer was designed based on environmentally responsive elastin-mimetic peptide sequences [(Val/Ile)-Pro-Gly-Xaa-Gly] (Xaa = Ala or Glu for the hydrophilic block, Val or Phe for the hydrophobic block) and synthesized using a genetic engineering approach. Differential scanning calorimetry measurements in aqueous solution revealed that reversible hydrophobic folding and assembly of the copolymer occurs above the inverse temperature transition, Tt, of the hydrophobic block. This process results in the formation of 50 nm protein-based micellar aggregates, which were characterized by electron microscopy and temperature-dependent dynamic light scattering techniques. The distribution of micellar aggregates can be altered reproducibly through variation of environmental conditions including pH and temperature. The uniform and defined macromolecular architecture of this protein copolymer permits greater control over the physical properties of the micelles, which therefore may facilitate applications in controlled release of small molecules.

  6. Thermodynamic stability and structural properties of cluster crystals formed by amphiphilic dendrimers (United States)

    Lenz, Dominic A.; Mladek, Bianca M.; Likos, Christos N.; Blaak, Ronald


    We pursue the goal of finding real-world examples of macromolecular aggregates that form cluster crystals, which have been predicted on the basis of coarse-grained, ultrasoft pair potentials belonging to a particular mathematical class [B. M. Mladek et al., Phys. Rev. Lett. 46, 045701 (2006)]. For this purpose, we examine in detail the phase behavior and structural properties of model amphiphilic dendrimers of the second generation by means of monomer-resolved computer simulations. On augmenting the density of these systems, a fluid comprised of clusters that contain several overlapping and penetrating macromolecules is spontaneously formed. Upon further compression of the system, a transition to multi-occupancy crystals takes place, the thermodynamic stability of which is demonstrated by means of free-energy calculations, and where the FCC is preferred over the BCC-phase. Contrary to predictions for coarse-grained theoretical models in which the particles interact exclusively by effective pair potentials, the internal degrees of freedom of these molecules cause the lattice constant to be density-dependent. Furthermore, the mechanical stability of monodisperse BCC and FCC cluster crystals is restricted to a bounded region in the plane of cluster occupation number versus density. The structural properties of the dendrimers in the dense crystals, including their overall sizes and the distribution of monomers are also thoroughly analyzed.

  7. Synthesis and Self-Assembly Behaviors of Polyhedral Oligomeric Silsesquioxane Based Giant Molecular Shape Amphiphiles (United States)

    Yue, Kan; Yu, Xinfei; Liu, Chang; Zhang, Wen-Bin; Cheng, Stephen


    Recently, our group has focus on the synthesis and characterization of novel giant molecular shape amphiphiles (GMSAs) based on functionalized molecular nanoparticles (MNPs), such as polyhedral oligomeric silsesquioxane (POSS), tethered with polymeric tails. A general synthetic method via the combination of sequential ?click? reactions has been developed and several model GMSAs with various tail lengths and distinct molecular topologies, which can be referred as the ?giant surfactants?, ?giant lipids?, ?giant gemini surfactants?, and ?giant bolaform surfactants? etc., have been demonstrated. Studies on their self-assembly behaviors in the bulk have revealed the formation of different ordered mesophase structures with feature sizes around 10 nanometers, which have been investigated in detail by small angle X-ray scattering (SAXS) technique and transmission electron microscopy (TEM). These findings have general implications on understanding the underlying principles of self-assembly behaviors of GMSAs, and might have potential applications in nano-patterning technology. This work is supported by NSF (DMR-0906898) and the Joint-Hope Foundation.

  8. Interplay between alkyl chain asymmetry and cholesterol addition in the rigid ion pair amphiphile bilayer systems (United States)

    Huang, Fong-yin; Chiu, Chi-cheng


    Ion pair amphiphile (IPA), a molecular complex composed of a pair of cationic and anionic surfactants, has been proposed as a novel phospholipid substitute. Controlling the physical stability of IPA vesicles is important for its application developments such as cosmetic and drug deliveries. To investigate the effects of IPA alkyl chain combinations and the cholesterol additive on the structural and mechanical properties of IPA vesicular bilayers, we conducted a series of molecular dynamics studies on the hexadecyltrimethylammonium-dodecylsulfate (HTMA-DS) and dodecyltrimethylammonium-hexadecylsulfate (DTMA-HS) IPA bilayers with cholesterol. We found that both IPA bilayers are in the gel phase at 298 K, consistent with experimental observations. Compared with the HTMA-DS system, the DTMA-HS bilayer has more disordered alkyl chains in the hydrophobic region. When adding cholesterol, it induces alkyl chain ordering around its rigid sterol ring. Yet, cholesterol increases the molecular areas for all species and disturbs the molecular packing near the hydrophilic region and the bilayer core. Cholesterol also promotes the alkyl chain mismatch between the IPA moieties, especially for the DTMA-HS bilayer. The combined effects lead to non-monotonically enhancement of the membrane mechanical moduli for both IPA-cholesterol systems. Furthermore, cholesterol can form H-bonds with the alkylsulfate and thus enhance the contribution of alkylsulfate to the overall mechanical moduli. Combined results provide valuable molecular insights into the roles of each IPA component and the cholesterol on modulating the IPA bilayer properties.

  9. Self-Assembly of Amphiphilic Block Copolypeptoids – Micelles, Worms and Polymersomes (United States)

    Fetsch, Corinna; Gaitzsch, Jens; Messager, Lea; Battaglia, Giuseppe; Luxenhofer, Robert


    Polypeptoids are an old but recently rediscovered polymer class with interesting synthetic, physico-chemical and biological characteristics. Here, we introduce new aromatic monomers, N-benzyl glycine N-carboxyanhydride and N-phenethyl glycine N-carboxyanhydride and their block copolymers with the hydrophilic polysarcosine. We compare their self-assembly in water and aqueous buffer with the self-assembly of amphiphilic block copolypeptoids with aliphatic side chains. The aggregates in water were investigated by dynamic light scattering and electron microscopy. We found a variety of morphologies, which were influenced by the polymer structure as well as by the preparation method. Overall, we found polymersomes, worm-like micelles and oligo-lamellar morphologies as well as some less defined aggregates of interconnected worms and vesicles. Such, this contribution may serve as a starting point for a more detailed investigation of the self-assembly behavior of the rich class of polypeptoids and for a better understanding between the differences in the aggregation behavior of non-uniform polypeptoids and uniform peptoids. PMID:27666081

  10. Amphiphilic diblock copolymer and polycaprolactone blends to produce new vesicular nanocarriers. (United States)

    Penott-Chang, Evis; Walther, Andreas; Millard, Pierre; Jäger, Alessandro; Jäger, Eliezer; Müller, Axel H E; Guterres, Sílvia S; Pohlmann, Adriana R


    New Melatonin-loaded vesicular nanocarriers were prepared by interfacial deposition using a blend of an amphiphilic diblock copolymer, poly(methyl methacrylate)-block-poly(2-(dimethylamino)ethyl methacrylate), PMMA-b-PDMAEMA, with poly(epsilon-caprolactone), PCL. Particle size and morphology of the nanocarriers was evaluated. Dynamic light scattering shows that the nanocarriers have hydrodynamic radii between 100 and 180 nm, with unimodal particle size distribution for each formulation. Shape and structure were visualized by transmission electron microscopy (TEM), cryogenic TEM and scanning electron microscopy. Standard TEM for nanocapsules showed an oily core surrounded by a thin layer composed by PCL/PMMA-b-PDMAEMA. Cryo-TEM also indicated the presence of spherical nano-objects with a diffuse polymer corona. Encapsulation efficiencies were determined assaying the nanoparticles by HPLC and higher values of ca. 25% are shown by the nanocapsules. We could successfully incorporate platinum nanoparticles into the nanocarrier as evidenced by TEM, which opens up the possibility for promising applications like monitoring the encapsulated drug in the body.

  11. Micellar and structural stability of nanoscale amphiphilic polymers: Implications for anti-atherosclerotic bioactivity. (United States)

    Zhang, Yingyue; Li, Qi; Welsh, William J; Moghe, Prabhas V; Uhrich, Kathryn E


    Atherosclerosis, a leading cause of mortality in developed countries, is characterized by the buildup of oxidized low-density lipoprotein (oxLDL) within the vascular intima, unregulated oxLDL uptake by macrophages, and ensuing formation of arterial plaque. Amphiphilic polymers (AMPs) comprised of a branched hydrophobic domain and a hydrophilic poly(ethylene glycol) (PEG) tail have shown promising anti-atherogenic effects through direct inhibition of oxLDL uptake by macrophages. In this study, five AMPs with controlled variations were evaluated for their micellar and structural stability in the presence of serum and lipase, respectively, to develop underlying structure-atheroprotective activity relations. In parallel, molecular dynamics simulations were performed to explore the AMP conformational preferences within an aqueous environment. Notably, AMPs with ether linkages between the hydrophobic arms and sugar backbones demonstrated enhanced degradation stability and storage stability, and also elicited enhanced anti-atherogenic bioactivity. Additionally, AMPs with increased hydrophobicity elicited increased atheroprotective bioactivity in the presence of serum. These studies provide key insights for designing more serum-stable polymeric micelles as prospective cardiovascular nanotherapies.

  12. Augmentation of sarcolemmal Ca by anionic amphiphile: contractile response of three ventricular tissues. (United States)

    Langer, G A; Rich, T L


    The anionic amphiphile dodecyl sulfate was used at the concentration of 100 microM, below the concentration at which membrane permeability is compromised. In rat myocardial tissue culture dodecyl sulfate induced a large increase in Ca uptake in the intact cells, of which 84% was distributed in a rapidly exchangeable (t1/2 less than 18 s) and 16% in a slowly exchangeable (t1/2 = 17 min) compartment. Dodecyl sulfate induced a large increase in Ca bound to isolated sarcolemmal membrane of these cells. This increase in membrane binding and the distribution in whole cells is consistent with insertion of dodecyl sulfate in the sarcolemma (SL) with subsequent Ca binding to its anionic head group. With perfusate extracellular calcium concentration ([Ca]o) equal to 1 mM, dodecyl sulfate produced greater than 60% increase in active force in ventricular tissue from adult rabbit and neonatal rat but virtually no increase in adult rat ventricle. Preperfusion with 0.1 mM [Ca]o or 10(-6) M ryanodine markedly increased the relative response of adult rat ventricle to dodecyl sulfate. After a quiescent period in rabbit ventricle, dodecyl sulfate caused a progressive increase of force of each beat compared with control; i.e., the treppe response was increased at each successive beat. This did not occur in adult rat ventricle. These results further clarify the different quantitative role of SL-bound versus sarcotubular Ca in the hearts of different species.

  13. Activity and Mechanism of Antimicrobial Peptide-Mimetic Amphiphilic Polymethacrylate Derivatives

    Directory of Open Access Journals (Sweden)

    Kenichi Kuroda


    Full Text Available Cationic amphiphilic polymethacrylate derivatives (PMAs have shown potential as a novel class of synthetic antimicrobials. A panel of PMAs with varied ratios of hydrophobic and cationic side chains were synthesized and tested for antimicrobial activity and mechanism of action. The PMAs are shown to be active against a panel of pathogenic bacteria, including a drug-resistant Staphylococcus aureus, compared to the natural antimicrobial peptide magainin which did not display any activity against the same strain. The selected PMAs with 47–63% of methyl groups in the side chains showed minimum inhibitory concentrations of ≤2–31 µg/mL, but cause only minimal harm to human red blood cells. The PMAs also exhibit rapid bactericidal kinetics. Culturing Escherichia coli in the presence of the PMAs did not exhibit any potential to develop resistance against the PMAs. The antibacterial activities of PMAs against E. coli and S. aureus were slightly reduced in the presence of physiological salts. The activity of PMAs showed bactericidal effects against E. coli and S. aureus in both exponential and stationary growth phases. These results demonstrate that PMAs are a new antimicrobial platform with no observed development of resistance in bacteria. In addition, the PMAs permeabilized the E. coli outer membrane at polymer concentrations lower than their MIC values, but they did not show any effect on the bacterial inner membrane. This indicates that mechanisms other than membrane permeabilization may be the primary factors determining their antimicrobial activity.

  14. Polypeptoids from N -Substituted Glycine N -Carboxyanhydrides: Hydrophilic, Hydrophobic, and Amphiphilic Polymers with Poisson Distribution

    KAUST Repository

    Fetsch, Corinna


    Preparation of defined and functional polymers has been one of the hottest topics in polymer science and drug delivery in the recent decade. Also, research on (bio)degradable polymers gains more and more interest, in particular at the interface of these two disciplines. However, in the majority of cases, combination of definition, functionality and degradability, is problematic. Here we present the preparation and characterization (MALDI-ToF MS, NMR, GPC) of nonionic hydrophilic, hydrophobic, and amphiphilic N-substituted polyglycines (polypeptoids), which are expected to be main-chain degradable and are able to disperse a hydrophobic model compound in aqueous media. Polymerization kinetics suggest that the polymerization is well controlled with strictly linear pseudo first-order kinetic plots to high monomer consumption. Moreover, molar mass distributions of products are Poisson-type and molar mass can be controlled by the monomer to initiator ratio. The presented polymer platform is nonionic, backbone degradable, and synthetically highly flexible and may therefore be valuable for a broad range of applications, in particular as a biomaterial. © 2011 American Chemical Society.

  15. Nanospheres and nanocapsules of amphiphilic copolymers constituted by methoxypolyethylene glycol cyanoacrylate and hexadecyl cyanoacrylate units

    Directory of Open Access Journals (Sweden)

    J. Puiggali


    Full Text Available Nanospheres and nanocapsules of an amphiphilic copolymer having methylated polyethylene glycol and hexadecyl lateral groups were prepared by the solvent displacement method and using confined impinging jet mixers. Degradation, thermal properties and crystalline structure were investigated. Interestingly, pegylated chains hydrolyzed through ester bond cleavage, whereas the more hydrophobic hexadecyl ester groups were resistant to degradation in aqueous media. The copolymer crystallized from the melt, giving rise to spherulites with a negative birefringence and domains corresponding to crystallization of the different lateral groups. Size distribution and morphology of nanoparticles were mainly evaluated by electron microscopy. Nanocapsules were characterized by a stable membrane with a thickness close to 5 nm that allowed efficient encapsulation of a triglyceride oil. Triclosan was selected as an example of a hydrophobic drug to be loaded in both nanospheres and nanocapsules. The release behavior of these dosage forms was clearly different. Thus, the Burst effect was practically suppressed when using nanocapsules; in addition, these showed a sustained, controlled release over a greater time period. Antimicrobial activity of triclosan loaded nanospheres and nanocapsules was evaluated using Gram-negative and Gram-positive bacteria. The former were highly sensitive to the released triclosan whereas the latter strongly depended on the number of particles in the culture medium.

  16. Investigations on diffusion limitations of biocatalyzed reactions in amphiphilic polymer conetworks in organic solvents. (United States)

    Schoenfeld, Ina; Dech, Stephan; Ryabenky, Benjamin; Daniel, Bastian; Glowacki, Britta; Ladisch, Reinhild; Tiller, Joerg C


    The use of enzymes as biocatalysts in organic media is an important issue in modern white biotechnology. However, their low activity and stability in those media often limits their full-scale application. Amphiphilic polymer conetworks (APCNs) have been shown to greatly activate entrapped enzymes in organic solvents. Since these nanostructured materials are not porous, the bioactivity of the conetworks is strongly limited by diffusion of substrate and product. The present manuscript describes two different APCNs as nanostructured microparticles, which showed greatly increased activities of entrapped enzymes compared to those of the already activating membranes and larger particles. We demonstrated this on the example of APCN particles based on PHEA-l-PDMS loaded with α-Chymotrypsin, which resulted in an up to 28,000-fold higher activity of the enzyme compared to the enzyme powder. Furthermore, lipase from Rhizomucor miehei entrapped in particles based on PHEA-l-PEtOx was tested in n-heptane, chloroform, and substrate. Specific activities in smaller particles were 10- to 100-fold higher in comparison to the native enzyme. The carrier activity of PHEA-l-PEtOx microparticles was tenfold higher with some 25-50-fold lower enzyme content compared to a commercial product.

  17. Preparation of Chiral 1,4-Phenylene-silicas via Chiral Low-molecular-weight Amphiphiles

    Institute of Scientific and Technical Information of China (English)

    XIAO Min; LIU Xiao-juan; HU Kai; WU Li-min; LI Yi; LI Bao-zong; YANG Yong-gang


    Chiral organic-inorganic hybrid silicas can be prepared via the self-assemblies of chiral surfactants and gelators as templates.However,the relationship between the chirality of the hybrid silica and the structure of the surfactant/gelator has not been systemically studied.Herein,a series of chiral low-molecular-weight amphiphiles(LMWAs) derived from L-valine was synthesized.Their alkyl chains were n-butadecyl,n-hexadecyl and n-octadecyl,respectively.They can form viscous liquids in pure water,and physical gels in tetrahydrofuran,cyclohexanone,acetonitrile,acetone,chlorobenzene and nitrobenzenc.Chiral 1,4-phenylene-silicas were prepared via the self-assemblies of these LMWAs as templates.With increasing the alkyl chain length,the 1,4-phenylene-silicas changed from short mesoporous nanorods to long nanotubcs. The circular dichroism spectra of the 1,4-phenylene-silicas indicated that the long nanotubes exhibit the strongest chirality.

  18. Adsorption of an amphiphilic penicillin onto human serum albumin: characterisation of the complex. (United States)

    Ruso, J M; Taboada, P; Varela, L M; Attwood, D; Mosquera, V


    The complex formed by the interaction of the amphiphilic penicillin drug nafcillin and human serum albumin (HSA) in water at 25 degrees C has been characterised using a range of physicochemical techniques. Measurements of the solution conductivity and the electrophoretic mobility of the complexes have shown an ionic adsorption of the drug on the protein surface leading to a surface saturation at a nafcillin concentration of 0.012 mmol kg(-1) and subsequent formation of drug micelles in solutions of higher nafcillin concentration. Measurements of the size of the complex and the thickness of the adsorbed layer by static and dynamic light scattering have shown a gradual change in hydrodynamic radius of the complex with increasing drug concentration typical of a saturation rather than a denaturation process, the magnitude of the change being insufficient to account for any appreciable extension or unfolding of the HSA molecule. The interaction potential between the HSA/nafcillin complexes, and the stability of the complexes were determined from the dependence of diffusion coefficients on protein concentration by application of the DLVO colloidal stability theory. The results indicate decreasing stability of the colloidal dispersion of the drug/protein complexes with an increase in the concentration of added drug.

  19. Photophysical studies of six amphiphilic 2:1 cyclodextrin:[60]fullerene derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Quaranta, Annamaria [Laboratoire de Chimie et Biochimie des Substances Naturelles, MNHN, UMR CNRS 5154, 63 rue Buffon, 75005 Paris (France)], E-mail:; Zhang, Yongmin [Ecole Normale Superieure, Departement de Chimie, UMR 8642: CNRS-ENS-Universite Pierre-et-Marie-Curie, 24 rue Lhomond, 75231 Paris Cedex 05 (France)], E-mail:; Filippone, Salvatore [Laboratoire de Chimie et Biochimie des Substances Naturelles, MNHN, UMR CNRS 5154, 63 rue Buffon, 75005 Paris (France)]|[Ecole Normale Superieure, Departement de Chimie, UMR 8640: CNRS-ENS-Universite Pierre-et-Marie-Curie, 24 rue Lhomond, 75231 Paris Cedex 05 (France)], E-mail:; Yang, Juan; Sinay, Pierre; Rassat, Andre [Ecole Normale Superieure, Dept. de Chimie, UMR 8640: CNRS-ENS-Univ. Pierre-et-Marie-Curie, 24 rue Lhomond, 75231 Paris Cedex 05 (France); Edge, Ruth [Free Radical Research Facility, CLRC Daresbury Lab., Warrington, WA4 4AD, UK, and School of Physical and Geographical Sciences, Lennard-Jones Labs., Keele Univ., Keele, Staffordshire, ST5 5BG (United Kingdom); Navaratnam, Suppiah [Free Radical Research Facility, CLRC Daresbury Lab., Warrington, WA4 4AD (United Kingdom)]|[BioSciences Research Inst., Univ. of Salford, M5 4WT (United Kingdom); McGarvey, David J. [School of Physical and Geographical Sciences, Lennard-Jones Labs., Keele Univ., Keele, Staffordshire, ST5 5BG (United Kingdom); Land, Edward J. [School of Physical and Geographical Sciences, Lennard-Jones Labs., Keele Univ., Keele, Staffordshire, ST5 5BG (United Kingdom); Brettreich, Michael [Inst. fuer Organische Chemie der Univ. Erlangen-Nuernberg, Henkestrasse 42, 91054 Erlangen (Germany); Hirsch, Andreas [Inst. fuer Organische Chemie der Univ. Erlangen-Nuernberg, Henkestrasse 42, 91054 Erlangen (Germany); Bensasson, Rene V. [Lab. de Chimie et Biochimie des Substances Naturelles, MNHN, UMR CNRS 5154, 63 rue Buffon, 75005 Paris (France)


    In search of a simple internal complexation of C{sub 60} in cyclodextrins, six 2:1 cyclodextrin:[60]fullerene conjugates involving different types of linkers have been synthesised. Using spectrophotometry, laser flash photolysis and pulse radiolysis, we have investigated spectroscopic and photophysical properties of these 2:1 cyclodextrin [60]fullerene monoadduct conjugates (CDF), including ground and triplet state absorption spectra, triplet molar absorption coefficients ({epsilon} {sub T}), quantum yields of triplet ({phi} {sub T}) and singlet oxygen formation ({phi} {sub {delta}}) in water and toluene, in order to probe the possibility of 2:1 inclusion complexes of C{sub 60} between two cyclodextrins. In water, the CDF spectroscopic and photophysical properties indicate hydrophobically driven self-assemblies of the amphiphilic conjugates into spherical micelles with no evidence for the presence of a 2:1 inclusion complex, while in toluene they show no sign of aggregation. It is observed that formation of aggregates in water does not prevent scavenging of HO {sup {center_dot}} radical by the C{sub 60} moiety of the CD-C{sub 60} conjugates.

  20. Self-assembly of metal--polymer analogues of amphiphilic triblock copolymers (United States)

    Nie, Zhihong; Fava, Daniele; Kumacheva, Eugenia; Zou, Shan; Walker, Gilbert; Rubinstein, Michael


    We proposed a block copolymer approach to the self-assembly of inorganic nanrods terminated with polymer molecules at both ends. We organized metal nanorods in structures with varying geometries by using a striking analogy between amphiphilic ABA triblock copolymers and the hydrophilic nanorods tetheredwith hydrophobic polymer chains at both ends. The self-assembly was tunable and reversible and it was achieved solely by changing the solvent quality for the constituent blocks. The distance between adjacent nanorods along chains can be tuned by varying the composition of mixture solvents or the molecular weight of polymer blocks, which allows us precisely control the plasmonic band of self-assembled structures. A systematic study of the self-assembly as a function of solvent composition and the molecular weight of the polymer blocks allowed us to construct a diagram that maps the assembled structures. This approach provides a new route to the organization of anisotropic nanoparticles by using the strategies that are established for the self-assembly of block copolymers.

  1. Amphiphilic comb-like polymer for harvest of conductive nano-cellulose. (United States)

    Choi, Jaeyoo; Park, Subeom; Cheng, Jie; Park, Minsung; Hyun, Jinho


    In this study, electrically conductive bacterial cellulose (BC) was prepared by culturing Gluconacetobacter xylinus in a carbon nanotube (CNT)-dispersed medium. The CNTs were dispersed by adopting a non-covalent approach in the presence of non-ionic amphiphilic comb-like polymer (CLP). Specifically, the hydrophobic backbone of CLP was chemophysically attached to the surface of the CNTs and the hydrophilic side chains were released freely toward the medium in an aqueous environment. CLP-modified CNTs were stable and did not show any noticeable sediment, even after centrifugation at 15,000 rpm for 30 min. Notably, the dispersion solution of CLP-modified CNTs was stable at room temperature for several months because the long-range entropic repulsion among polymer-decorated tubes acted as a barrier to aggregation. The morphology of the BC membrane was studied by field-emission scanning electron microscopy. The presence of CLP bound to the CNT surface was characterized by Fourier transform infrared spectroscopy and the conductivity of the CNT-incorporated BC membrane was measured by four-probe measurements.

  2. Nonionic diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains: thermotropic and lyotropic liquid crystalline phase behaviour

    Energy Technology Data Exchange (ETDEWEB)

    Sagnella, Sharon M.; Conn, Charlotte E.; Krodkiewska, Irena; Drummond, Calum J. (CSIRO/MSE)


    The thermotropic and lyotropic liquid crystalline phase behaviour of a series of diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains (geranoyl, H-farnesoyl, and phytanoyl) has been investigated. When neat, both H-farnesoyl and phytanoyl diethanolamide form a smectic liquid crystalline structure at sub-zero temperatures. In addition, all three diethanolamides exhibit a glass transition temperature at around -73 C. Geranoyl diethanolamide forms a lamellar crystalline phase with a lattice parameter of 17.4 {angstrom} following long term storage accompanied by the loss of the glass transition. In the presence of water, H-farnesoyl and phytanoyl diethanolamide form lyotropic liquid crystalline phases, whilst geranoyl diethanolamide forms an L{sub 2} phase. H-farnesoyl diethanolamide forms a fluid lamellar phase (L{sub {alpha}}) at room temperature and up to {approx} 40 C. Phytanoyl diethanolamide displays a rich mesomorphism forming the inverse diamond (Q{sub II}{sup D}) and gyroid (Q{sub II}{sup G}) bicontinuous cubic phases in addition to an L{sub {alpha}} phase.

  3. Amphiphilic conetworks as activating carriers for the enhancement of enzymatic activity in supercritical CO2. (United States)

    Bruns, Nico; Bannwarth, Willi; Tiller, Joerg C


    Enzymatic reactions in supercritical carbon dioxide (scCO2) represent a way of combining the advantages of biocatalysis with the environmental benign nature of scCO2 as a solvent. Here we demonstrate that activities of enzymes in scCO2 can be greatly enhanced by incorporating them into amphiphilic conetworks (APCNs), a novel type of enzyme support. Two sets of hydrophilic/scCO2-philic APCNs, poly(2-hydroxyethyl acrylate)-linked by-poly(dimethylsiloxane) (PHEA-l-PDMS) and poly(2-hydroxyethyl acrylate)-linked by-perfluoropolyether (PHEA-l-PFPE), were prepared and loaded with the synthetically relevant lipase from Rhizomucor miehei. The effect of the APCNs' composition on the amount of the absorbed lipase was studied. It is observed that both sets of lipase-loaded APCNs enhance the catalytic activity of the enzyme in scCO2. The chemical nature of the scCO2-philic phase as well as the conetworkscomposition greatly influences the activity of the lipase in the conetworks. Activities obtained with PFPE-basedAPCNS were up to 10-fold higher than those obtained with PDMS-based conetworks. The highest specific activity measured corresponds to a 2,000-fold activation compared to the lyophilized enzyme powder. This activity is 10 times higher than the specific activity of the lipase immobilized on an optimized commercial carrier.

  4. Controlling Phase Separation of Tough Interpenetrating Polymer Networks via Addition of Amphiphilic Block Copolymers (United States)

    Rohde, Brian; Krishnamoorti, Ramanan; Robertson, Megan

    Interpenetrating polymer networks (IPNs) offer a unique way to combine the mechanical properties of two thermoset systems. Often used to create a material that possesses both high toughness and tensile properties, here we use polydicyclopentadiene, cured via ring opening metathesis polymerization, to contribute high toughness and diglycidyl ether of bisphenol A cured via anhydride chemistry to contribute high tensile strength and modulus. As the uncompatibilized system reacts in the presence of one another, mesoscopic phase separation occurs and dictates the overall efficacy of combining mechanical properties. To control phase separation and drive the system towards more mechanically robust nanostructed IPNs, amphiphilic block copolymers of polybutadiene- b-polyethylene oxide, where one block possesses strong affinity to polyDCPD and the other the DGEBA, were added to the system. Here we present a systematic study of the influence of block copolymer composition in the overall blend on degree of phase separation and morphology using a combination of small-angle x-ray scattering (SAXS) and scanning electron microscopy (SEM) techniques. The resultant mechanical properties are then explored in an effort to link mechanical properties to blend morphology.

  5. Application of Super-Amphiphilic Silica-Nanogel Composites for Fast Removal of Water Pollutants. (United States)

    Atta, Ayman M; Al-Lohedan, Hamad A; Tawfik, Ahmed M; Ezzat, Abdelrahman O


    This work first reports the preparation of super-amphiphilic silica-nanogel composites to reduce the contact angle of water to increase the diffusion of pollutant into adsorbents. In this respect, the silica nanoparticles were encapsulated into nanogels based on ionic and nonionic polyacrylamides by dispersion polymerization technique. The morphologies and the dispersion stability of nanogel composites were investigated to clarify the ability of silica-nanogel composites to adsorb at different interfaces. The feasibility of silica polyacrylamide nanogel composites to act as a high-performance adsorbent for removal of methylene blue (MB) dye and heavy metals (Co(2+) and Ni(2+)) from aqueous solution was investigated. The surface tension, contact angle, average pore size, and zeta potential of the silica-nanogel composites have been evaluated. The MB dye and heavy metal adsorption capacity achieved Qmax = 438-387 mg/g which is considerably high. The adsorption capacity results are explained from the changes in the morphology of the silica surfaces as recorded from scanning electron microscopy (SEM).

  6. Preparation of amorphous aluminum oxide-hydroxide nanoparticles in amphiphilic silicone-based copolymer microemulsions. (United States)

    Berkovich, Yana; Aserin, Abraham; Wachtel, Ellen; Garti, Nissim


    Organo-inorgano nanocomposites with colloidal dimensions have interesting optical, catalytic, and mechanical properties, particularly when such hybrids are reinforced with transition metal oxide nanoparticles. Nanoparticles with a mean size of 1.0-2.4 nm are obtained through hydrolysis of aluminum isopropoxide in the L(2) phase of amphiphilic (PDMS-POE) polydimethylsiloxane-polyoxyethylene Silwet L-7607-octanol/acetylacetone-water mixtures. The particle sizes are related weakly to the microemulsion composition: 0.8-1.2 nm for 20 wt% Silwet L-7607 and 2.0-2.4 nm for 50 wt% Silwet L-7607. Protection of the particles against aggregation is ensured through their confinement in the intraaggregate colloidal domains. Factors affecting the hydrolysis-condensation process of acetylacetone-complexed aluminum isopropoxide in copolymer-poor and copolymer-rich regions of PDMS-POE W/O microemulsions are studied by Fourier transform infrared spectroscopy, small angle X-ray scattering, and transmission electron microscopy. Prepared nanoparticulate dispersions possess long-term stability and form clear mixtures in different organic polar and nonpolar solvents.

  7. Synthesis, Micellization and Characterization of Novel Amphiphilic β-Cyclodextrin/Poly(L-aspartate) Copolymer

    Institute of Scientific and Technical Information of China (English)

    GUO Yan-ling; CUI Zhao-shan; HAN Min


    A novel amphiphilic β-cyclodextrin/poly(L-aspartate)(β-CD-PASP) copolymer was prepared by ringopening polymerization of polysuccinimide(PSI).This copolymer bears β-CD units along the macromolecular chain and the structure was characterized by infrared(IR) and proton nuclear magnetic resonance(1H NMR).The molecular weight of the copolymer was determined by gel permeation chromatography(GPC).The copolymer micelle were prepared by direct dissolution method.The critical micelle concentration(CMC) of the copolymer micelle was measured by flourescence technique with pyrene as probe.The size distribution of micelle was characterized on a dynamic laser light scattering particle size analyzer and its shape was observed by transmission electron microscopy(TEM).The results show that the copolymer could self-assemble into micelle with a low CMC,and the effective diameter of the micelle was 116.3 nm.The methotrexate(MTX)-loaded micelle were prepared and the drug loading content(DLC) was 22.86%.The MTX-loaded copolymer exhibited a better water-solubility than the free drug.

  8. Application of Super-Amphiphilic Silica-Nanogel Composites for Fast Removal of Water Pollutants

    Directory of Open Access Journals (Sweden)

    Ayman M. Atta


    Full Text Available This work first reports the preparation of super-amphiphilic silica-nanogel composites to reduce the contact angle of water to increase the diffusion of pollutant into adsorbents. In this respect, the silica nanoparticles were encapsulated into nanogels based on ionic and nonionic polyacrylamides by dispersion polymerization technique. The morphologies and the dispersion stability of nanogel composites were investigated to clarify the ability of silica-nanogel composites to adsorb at different interfaces. The feasibility of silica polyacrylamide nanogel composites to act as a high-performance adsorbent for removal of methylene blue (MB dye and heavy metals (Co2+ and Ni2+ from aqueous solution was investigated. The surface tension, contact angle, average pore size, and zeta potential of the silica-nanogel composites have been evaluated. The MB dye and heavy metal adsorption capacity achieved Qmax = 438–387 mg/g which is considerably high. The adsorption capacity results are explained from the changes in the morphology of the silica surfaces as recorded from scanning electron microscopy (SEM.

  9. Development of broad-spectrum antimicrobial latex paint surfaces employing active amphiphilic compounds. (United States)

    Fulmer, Preston A; Wynne, James H


    With the increase in antibiotic-resistant microbes, the production of self-decontaminating surfaces has become an area of research that has seen a surge of interest in recent years. Such surfaces, when incorporated into commercial products such as children's toys, medical devices and hospital surfaces could reduce the number of infections caused by pathogenic microorganisms. A number of active components for self-decontaminating surfaces have been investigated, including common antibiotics, metal ions, quaternary ammonium salts (QAS), and antimicrobial peptides (AMP). A recent research focus has been development of a wide range of amphiphilic antimicrobial additives that when combined with modern low volatile organic compound (VOC), water-based paints leads to a surface concentration of the active compounds as the coating cures. Herein we report the development of antimicrobial coatings containing a variety of additives, both QAS and AMP that are active against a broad-spectrum of potentially pathogenic bacteria (1-7 log kill), as well as enveloped viruses (2-7 log kill) and fungi (1-2 log kill). Additionally, these additives were compatible with water-dispersed acrylate coatings (latex paint) which have a broad range of real world applicability, and remained active for multiple challenges and when exposed to various cleaning scenarios in which they might encounter in real world situations.

  10. Synthesis and Characterization of Cross-linked Poly (β-Cyclodextin) Graft Poly(lactic acid) through Direct Polycondensation

    Institute of Scientific and Technical Information of China (English)

    Z.L.Ren; D.D.Lu; Z.Q.Lei


    1 Results Polylactide or polylactic acid (PLA) and poly(lactic-co-glycolic acid) (PLGA) have been utilized as bioabsorbable materials in the medical and pharmaceutical fields due to their biodegradable and biocompatible properties[1].However,due to its hydrophobicity and free carboxylic group,PLA or PLGA was not suitable for use to encapsulate the protein.Recently,poly (ε-caprolactone) and poly (D,L-lactide) were respectively grafted onto hydrophilic dextrin and gelatin to obtain the amphiphilic biodeg...

  11. The solubilization of fatty acids in systems based on block copolymers and nonionic surfactants (United States)

    Mirgorodskaya, A. B.; Yatskevich, E. I.; Zakharova, L. Ya.


    The solubilizing action of micellar, microemulsion, and polymer-colloid systems formed on the basis of biologically compatible amphiphilic polymers and nonionic surfactants on capric, lauric, palmitic, and stearic acids was characterized quantitatively. Systems based on micelle forming oxyethyl compounds increased the solubility of fatty acids by more than an order of magnitude. Acid molecules incorporated into micelles increased their size and caused structural changes. Solubilization was accompanied by complete or partial destruction of intrinsic acid associates and an increase in their p K a by 1.5-2 units compared with water.

  12. Self-assembled Monolayers of n-Hexadecanoic Acid and α-Hydroxyl n-Hexadecanoic Acid on Titanium Surfaces

    Institute of Scientific and Technical Information of China (English)

    CHEN,Hai-Gang(陈海刚); WU,Xue-Dong(乌学东); YU,Qin-Qin(虞勤琴); YANG,Sheng-Rong(杨生荣); WANG,Da-Pu(王大璞); SHEN,Wen-Zhong(沈文忠)


    n-Hexadecanoic acid (HA) and a.hydroxyl n-hexadecanoic acid ( HHA ) are shown to spontaneously assemble on Si-supported titanium surfaces. Contact angle measurements, reflection absorbance IR, AFM and XPS characterizatiions are performed to examine the physical and chenical states of attached monolayers. The results show that the two amphiphiles tend to form disordered monolayers on titanium surfaces. The HHA headgroups are believed to form polydentate coordination with Ti, which is more chemically stable than the bidentate coordination of HA. All the facts of characterization indicate that HHA monolayer has more surface coverage than HA monolayer.

  13. Amphiphilic, cross-linkable diblock copolymers for multifunctionalized nanoparticles as biological probes (United States)

    Schmidtke, Christian; Pöselt, Elmar; Ostermann, Johannes; Pietsch, Andrea; Kloust, Hauke; Tran, Huong; Schotten, Theo; Bastús, Neus G.; Eggers, Robin; Weller, Horst


    Nanoparticles (NPs) play an increasingly important role in biological labeling and imaging applications. However, preserving their useful properties in an aqueous biological environment remains challenging, even more as NPs therein have to be long-time stable, biocompatible and nontoxic. For in vivo applications, size control is crucial in order to route excretion pathways, e.g. renal clearance vs. hepato-biliary accumulation. Equally necessary, cellular and tissue specific targeting demands suitable linker chemistry for surface functionalization with affinity molecules, like peptides, proteins, carbohydrates and nucleotides. Herein, we report a three stage encapsulation process for NPs comprised of (1) a partial ligand exchange by a multidentate polyolefinic amine ligand, PI-N3, (2) micellar encapsulation with a precisely tuned amphiphilic diblock PI-b-PEG copolymer, in which the PI chains intercalate to the PI-N3 prepolymer and (3) radical cross-linking of the adjacent alkenyl bonds. As a result, water-soluble NPs were obtained, which virtually maintained their primal physical properties and were exceptionally stable in biological media. PEG-terminal functionalization of the diblock PI-b-PEG copolymer with numerous functional groups was mostly straightforward by chain termination of the living anionic polymerization (LAP) with the respective reagents. More complex affinity ligands, e.g. carbohydrates or biotin, were introduced in a two-step process, prior to micellar encapsulation. Advantageously, this pre-assembly approach opens up rapid access to precisely tuned multifunctional NPs, just by using mixtures of diverse functional PI-b-PEG polymers in a combinatorial manner. All constructs showed no toxicity from 0.001 to 1 μM (particle concentration) in standard WST and LDH assays on A549 cells, as well as only marginal unspecific cellular uptake, even in serum-free medium.Nanoparticles (NPs) play an increasingly important role in biological labeling and imaging

  14. Formation of nanoscale networks: selectively swelling amphiphilic block copolymers with CO2-expanded liquids (United States)

    Gong, Jianliang; Zhang, Aijuan; Bai, Hua; Zhang, Qingkun; Du, Can; Li, Lei; Hong, Yanzhen; Li, Jun


    Polymeric films with nanoscale networks were prepared by selectively swelling an amphiphilic diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), with the CO2-expanded liquid (CXL), CO2-methanol. The phase behavior of the CO2-methanol system was investigated by both theoretical calculation and experiments, revealing that methanol can be expanded by CO2, forming homogeneous CXL under the experimental conditions. When treated with the CO2-methanol system, the spin cast compact PS-b-P4VP film was transformed into a network with interconnected pores, in a pressure range of 12-20 MPa and a temperature range of 45-60 °C. The formation mechanism of the network, involving plasticization of PS and selective swelling of P4VP, was proposed. Because the diblock copolymer diffusion process is controlled by the activated hopping of individual block copolymer chains with the thermodynamic barrier for moving PVP segments from one to another, the formation of the network structures is achieved in a short time scale and shows ``thermodynamically restricted'' character. Furthermore, the resulting polymer networks were employed as templates, for the preparation of polypyrrole networks, by an electrochemical polymerization process. The prepared porous polypyrrole film was used to fabricate a chemoresistor-type gas sensor which showed high sensitivity towards ammonia.Polymeric films with nanoscale networks were prepared by selectively swelling an amphiphilic diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), with the CO2-expanded liquid (CXL), CO2-methanol. The phase behavior of the CO2-methanol system was investigated by both theoretical calculation and experiments, revealing that methanol can be expanded by CO2, forming homogeneous CXL under the experimental conditions. When treated with the CO2-methanol system, the spin cast compact PS-b-P4VP film was transformed into a network with interconnected pores, in a pressure range of 12-20 MPa and a

  15. J-aggregates of amphiphilic cyanine dyes: Self-organization of artificial light harvesting complexes

    Directory of Open Access Journals (Sweden)

    Stefan Kirstein


    Full Text Available The simultaneous chemical linkage of cyanine dye chromophores with both hydrophobic and hydrophilic substituents leads to a new type of amphiphilic molecules with the ability of spontaneous self-organization into highly ordered aggregates of various structures and morphologies. These aggregates carry the outstanding optical properties of J-aggregates, namely, efficient exciton coupling and fast exciton energy migration, which are essential for the build up of artificial light harvesting systems. The morphology of the aggregates depends sensitively on the molecular structure of the chemical substituents of the dye chromophore. Accordingly, lamellar ribbon-like structures, vesicles , tubes, and bundles of tubes are found depending on the dyes and the structure can further be altered by addition of surfactants, alcohols, or other additives. Altogether the tubular structure is the most noticeable structural motif of these types of J-aggregates. The optical spectra are characterized in general by a complex exciton spectrum which is composed of several electronic transitions. The spectrum is red-shifted as a total with respect to the monomer absorption and exhibits resonance fluorescence from the lowest energy transition. For the tubular structures, the optical spectra can be related to a structural model. Although the molecules itself are strictly achiral, a pronounced circular dichroism (CD is observed for the tubular aggregates and explained by unequal distribution of left- and right-handed helicity of the tubes. Photo-induced electron transfer (PET reactions from the dye aggregates to electron acceptor molecules lead to superquenching which proves the delocalization of the excitation. This property is used to synthesize metal nanoparticles on the aggregate surface by photo-induced reduction of metal ions.

  16. Amphiphilic macromolecule nanoassemblies suppress smooth muscle cell proliferation and platelet adhesion. (United States)

    Chan, Jennifer W; Lewis, Daniel R; Petersen, Latrisha K; Moghe, Prabhas V; Uhrich, Kathryn E


    While the development of second- and third-generation drug-eluting stents (DES) have significantly improved patient outcomes by reducing smooth muscle cell (SMC) proliferation, DES have also been associated with an increased risk of late-stent thrombosis due to delayed re-endothelialization and hypersensitivity reactions from the drug-polymer coating. Furthermore, DES anti-proliferative agents do not counteract the upstream oxidative stress that triggers the SMC proliferation cascade. In this study, we investigate biocompatible amphiphilic macromolecules (AMs) that address high oxidative lipoprotein microenvironments by competitively binding oxidized lipid receptors and suppressing SMC proliferation with minimal cytotoxicity. To determine the influence of nanoscale assembly on proliferation, micelles and nanoparticles were fabricated from AM unimers containing a phosphonate or carboxylate end-group, a sugar-based hydrophobic domain, and a hydrophilic poly(ethylene glycol) domain. The results indicate that when SMCs are exposed to high levels of oxidized lipid stimuli, nanotherapeutics inhibit lipid uptake, downregulate scavenger receptor expression, and attenuate scavenger receptor gene transcription in SMCs, and thus significantly suppress proliferation. Although both functional end-groups were similarly efficacious, nanoparticles suppressed oxidized lipid uptake and scavenger receptor expression more effectively compared to micelles, indicating the relative importance of formulation characteristics (e.g., higher localized AM concentrations and nanotherapeutic stability) in scavenger receptor binding as compared to AM end-group functionality. Furthermore, AM coatings significantly prevented platelet adhesion to metal, demonstrating its potential as an anti-platelet therapy to treat thrombosis. Thus, AM micelles and NPs can effectively repress early stage SMC proliferation and thrombosis through non-cytotoxic mechanisms, highlighting the promise of nanomedicine for

  17. Study on the interaction between amphiphilic drug and bovine serum albumin: A thermodynamic and spectroscopic description

    Energy Technology Data Exchange (ETDEWEB)

    Rub, Malik Abdul, E-mail: [Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah-21589 (Saudi Arabia); Khan, Javed Masood [Interdisciplinary Biotechnology Unit, Aligarh Muslim University, Aligarh 202002 (India); Asiri, Abdullah M. [Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah-21589 (Saudi Arabia); Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah-21589 (Saudi Arabia); Khan, Rizwan Hasan, E-mail: [Interdisciplinary Biotechnology Unit, Aligarh Muslim University, Aligarh 202002 (India); Kabir-ud-Din [Department of Applied Chemistry, Aligarh Muslim University, Aligarh-202002 (India)


    Herein we report the interaction of amphiphilic drug clomipramine hydrochloride (CLP—a tricyclic antidepressant) with bovine serum albumin (BSA) studied by fluorescence, UV–vis, and circular dichroism (CD) spectroscopic techniques. Clomipramine hydrochloride is used to treat a variety of mental health problems. The quenching rate constant (k{sub q}) values, calculated according to the fluorescence data, decrease with increase in temperature indicating the static quenching procedure for the CLP–BSA interaction. The association binding constants (K{sub A}), evaluated at different conditions, and the thermodynamic parameters (free energy, enthalpy and entropy changes) indicate that the hydrophobic forces play a major role in the binding interaction of drug. The interaction of BSA with CLP was further confirmed by UV absorption spectra. Blue shift of position was detected due to the complex formation between the BSA–CLP. The molecular distance, r{sub 0}, between donor (BSA) and acceptor (CLP) was estimated by fluorescence resonance energy transfer (FRET) whose value (4.47 nm) suggests high probability of static quenching interaction. The CD results prove the conformational changes in the BSA on binding with the drug. Thus, the results supply qualitative and quantitative understanding of the binding of BSA to CLP, which is important in understanding their effect as therapeutic agents. - Highlights: • BSA can be considered as a good carrier for transportation of CLP in vivo. • The fluorescence results indicated the presence of static quenching mechanism in the binding process. • CD spectra showed the change in molecular conformation of BSA in the presence of CLP. • The results have applicability in model drug delivery.

  18. Inhibition of the ATPase activity of the catalytic portion of ATP synthases by cationic amphiphiles. (United States)

    Datiles, Manuel J; Johnson, Eric A; McCarty, Richard E


    Melittin, a cationic, amphiphilic polypeptide, has been reported to inhibit the ATPase activity of the catalytic portions of the mitochondrial (MF1) and chloroplast (CF1) ATP synthases. Gledhill and Walker [J.R. Gledhill, J.E. Walker. Inhibition sites in F1-ATPase from bovine heart mitochondria, Biochem. J. 386 (2005) 591-598.] suggested that melittin bound to the same site on MF1 as IF1, the endogenous inhibitor polypeptide. We have studied the inhibition of the ATPase activity of CF1 and of F1 from Escherichia coli (ECF1) by melittin and the cationic detergent, cetyltrimethylammonium bromide (CTAB). The Ca2+- and Mg2+-ATPase activities of CF1 deficient in its inhibitory epsilon subunit (CF1-epsilon) are sensitive to inhibition by melittin and by CTAB. The inhibition of Ca2+-ATPase activity by CTAB is irreversible. The Ca2+-ATPase activity of F1 from E. coli (ECF1) is inhibited by melittin and the detergent, but Mg2+-ATPase activity is much less sensitive to both reagents. The addition of CTAB or melittin to a solution of CF1-epsilon or ECF1 caused a large increase in the fluorescence of the hydrophobic probe, N-phenyl-1-naphthylamine, indicating that the detergent and melittin cause at least partial dissociation of the enzymes. ATP partially protects CF1-epsilon from inhibition by CTAB. We also show that ATP can cause the aggregation of melittin. This result complicates the interpretation of experiments in which ATP is shown to protect enzyme activity from inhibition by melittin. It is concluded that melittin and CTAB cause at least partial dissociation of the alpha/beta heterohexamer.

  19. Bioreducible unimolecular micelles based on amphiphilic multiarm hyperbranched copolymers for triggered drug release

    Institute of Scientific and Technical Information of China (English)


    A novel type of bioreducible amphiphilic multiarm hyperbranched copolymer (H40-star-PLA-SS-PEG) based on Boltorn H40 core,poly(L-lactide) (PLA) inner-shell,and poly(ethylene glycol) (PEG) outer-shell with disulfide-linkages between the hydrophobic and hydrophilic moieties was developed as unimolecular micelles for controlled drug release triggered by reduction.The obtained H40-star-PLA-SS-PEG was characterized in detail by nuclear magnetic resonance (NMR),Fourier transform infrared (FTIR),gel permeation chromatography (GPC),differential scanning calorimeter (DSC),and thermal gravimetric analysis (TGA).Transmission electron microscopy (TEM) and dynamic light scattering (DLS) analyses suggested that H40-star-PLA-SS-PEG formed stable unimolecular micelles in aqueous solution with an average diameter of 19 nm.Interestingly,these micelles aggregated into large particles rapidly in response to 10 mM dithiothreitol (DTT),most likely due to shedding of the hydrophilic PEG outer-shell through reductive cleavage of the disulfide bonds.As a hydrophobic anticancer model drug,doxorubicin (DOX) was encapsulated into these reductive unimolecular micelles.In vitro release studies revealed that under the reduction-stimulus,the detachment of PEG outer-shell in DOX-loaded micelles resulted in a rapid drug release.Flow cytometry and confocal laser scanning microscopy (CLSM) measurements indicated that these DOX-loaded micelles were easily internalized by living cells.Methyl tetrazolium (MTT) assay demonstrated a markedly enhanced drug efficacy of DOX-loaded H40-star-PLA-SS-PEG micelles as compared to free DOX.All of these results show that these bioreducible unimolecular micelles are promising carriers for the triggered intracellular delivery of hydrophobic anticancer drugs.

  20. A hybrid biomimetic scaffold composed of electrospun polycaprolactone nanofibers and self-assembled peptide amphiphile nanofibers

    Energy Technology Data Exchange (ETDEWEB)

    Tambralli, Ajay; Blakeney, Bryan; Anderson, Joel; Kushwaha, Meenakshi; Andukuri, Adinarayana; Jun, Ho-Wook [Department of Biomedical Engineering, University of Alabama at Birmingham, 801 Shelby Building, 1825 University Boulevard, Birmingham, AL 35294 (United States); Dean, Derrick [Department of Materials Science and Engineering, University of Alabama at Birmingham, BEC 254, 1150 10th Ave South, Birmingham, AL 35294 (United States)], E-mail:


    Nanofibrous electrospun poly ({epsilon}-caprolactone) (ePCL) scaffolds have inherent structural advantages, but lack of bioactivity has limited their usefulness in biomedical applications. Thus, here we report the development of a hybrid, nanostructured, extracellular matrix (ECM) mimicking scaffold by a combination of ePCL nanofibers and self-assembled peptide amphiphile (PA) nanofibers. The PAs have ECM mimicking characteristics including a cell adhesive ligand (RGDS) and matrix metalloproteinase-2 (MMP-2) mediated degradable sites. Transmission electron microscope imaging verified successful PA self-assembly into nanofibers (diameters of 8-10 nm) using a solvent evaporation method. This evaporation method was then used to successfully coat PAs onto ePCL nanofibers (diameters of 300-400 nm), to develop hybrid, bioactive scaffolds. Scanning electron microscope characterization showed that the PA coatings did not interfere with the porous ePCL nanofiber network. Human mesenchymal stem cells (hMSCs) were seeded onto the hybrid scaffolds to evaluate their bioactivity. Significantly greater attachment and spreading of hMSCs were observed on ePCL nanofibers coated with PA-RGDS as compared to ePCL nanofibers coated with PA-S (no cell adhesive ligand) and uncoated ePCL nanofibers. Overall, this novel strategy presents a new solution to overcome the current bioactivity challenges of electrospun scaffolds and combines the unique characteristics of ePCL nanofibers and self-assembled PA nanofibers to provide an ECM mimicking environment. This has great potential to be applied to many different electrospun scaffolds for various biomedical applications.

  1. The Effect of Hydrophilic and Hydrophobic Structure of Amphiphilic Polymeric Micelles on Their Transportation in Rats. (United States)

    Deng, Feiyang; Yu, Chao; Zhang, Hua; Dai, Wenbing; He, Bing; Zheng, Ying; Wang, Xueqing; Zhang, Qiang


    In the previous study, we have clarified how the hydrophilic and hydrophobic structures of amphiphilic polymers impact the transport of their micelles (PEEP-PCL, PEG-PCL and PEG-DSPE micelles) in epithelial MDCK cells (Biomaterials 2013, 34: 6284-6298). In this study, we attempt to clarify the behavior of the three micelles in rats. Coumarin-6 loaded micelles were injected into different sections of intestine of rats and observed by confocal laser scanning microscope (CLSM) or orally administrated and conducted pharmacokinetic study. All of the three kinds of micelles were able to cross the intestinal epithelial cells and enter blood circulation. The PEEP-PCL micelles demonstrated the fastest distribution mainly in duodenum, while the PEGDSPE micelles showed the longest distribution with the highest proportion in ileum of the three. No significant difference was observed among the pharmacokinetic parameters of the three micelles. The results were consistent in the two analysis methods mentioned above, yet there were some differences between in vivo and in vitro results reported previously. It might be the distinction between the environments in MDCK model and intestine that led to the discrepancy. The hydrophobicity of nanoparticles could both enhance uptake and hinder the transport across the mucus. However, there was no intact mucus in MDCK model, which preferred hydrophobic nanoparticles. PEEP was the most hydrophilic material constructing the micelles in the study and its uptake would be increased in rats compared to that in MDCK model, while DSPE was more hydrophobic than the others and MDCK model would be more ideal for its uptake. Considering the inconsistency of the results in the two models, whether the methods researchers were generally using at present were reasonable needs further investigation.

  2. The Effect of Nano-Morphology Modification Using an Amphiphilic Polymer on the Proton Conductivity of Composite Membrane for a Polymer Membrane-Based Fuel Cell. (United States)

    Roh, Sung-Hee; Rho, Seon-Gyun; Kim, Sang-Chai; Kim, Ju-Young; Jung, Ho-Young


    The effect of morphology modification using an amphiphilic polymer on the proton conductivity of composite membrane for a polymer membrane-based fuel cell was investigated. The proton conductivity of each composite membrane was analyzed by the electrochemical impedance spectroscopy (EIS). The morphological change was confirmed by scanning electron microscope (SEM). In the composite membrane, the proton conductive component was sulfonated poly(ether ether ketone) (sPEEK), while the nonconductive component was poly(vinylidenedifluoride) and the amphiphilic polymer as a compatibilizer was urethane acrylate non-ionomer (UAN). UAN as a compatibilizer improved the interfacial stability between sPEEK and PVdF polymers, even though two polymers were apparently immiscible. The homogeneous distribution of sPEEK and PVdF domains in the composite membrane was obtained with the introduction of UAN due to the amphiphilicity. Therefore, it was found that the proton conductivity of the composite membrane increased with the incorporation of UAN as a compatibilizer.

  3. Membrane behavior as influenced by partitioning of amphiphiles during drying: a comparative study in anhydrobiotic plant systems. (United States)

    Golovina, Elena A; Hoekstra, Folkert A


    During cellular desiccation, reduction in volume can in principle cause amphiphilic compounds to partition from the cytoplasm into membranes, with structural perturbance as the result. Here, we studied the effect of partitioning of endogenous amphiphiles on membrane surface dynamics in desiccation-tolerant and -intolerant, higher and lower plant systems, using electron paramagnetic resonance (EPR) spin probe techniques. Labeling cells with the amphiphilic spin probe perdeuterated TEMPONE (PDT) enabled partitioning into the various phases to be followed. During drying, PDT molecules preferentially partitioned from the aqueous cytoplasm into the membrane surface and, at advanced stages of water loss, also into oil bodies. There was no specific partition behavior that could be correlated with lower/higher plants or with desiccation-tolerance. In vivo labeling with 5-doxylstearate (5-DS) enabled membrane surface fluidity to be characterized. In hydrated plants, the 5-DS spectra contained an immobile and a fluid component. The characteristics of the immobile component could not be specifically correlated with either lower or higher plants, or with desiccation tolerance. The relative contribution of the fluid component to the 5-DS spectra was higher in lower plants than in higher plants, but considerably decreased with drying in all desiccation-tolerant organisms. In contrast, the proportion of the fluid component in desiccation-sensitive wheat seedling root was higher than that in desiccation-tolerant wheat axis and considerably increased at the onset of water loss. We suggest that partitioning of amphipaths fluidize the membrane surface, but that in desiccation-tolerant systems the membranes are protected from excessive fluidization.

  4. Amphiphilic surface active triblock copolymers with mixed hydrophobic and hydrophilic side chains for tuned marine fouling-release properties. (United States)

    Park, Daewon; Weinman, Craig J; Finlay, John A; Fletcher, Benjamin R; Paik, Marvin Y; Sundaram, Harihara S; Dimitriou, Michael D; Sohn, Karen E; Callow, Maureen E; Callow, James A; Handlin, Dale L; Willis, Carl L; Fischer, Daniel A; Kramer, Edward J; Ober, Christopher K


    Two series of amphiphilic triblock surface active block copolymers (SABCs) were prepared through chemical modification of two polystyrene-block-poly(ethylene-ran-butylene)-block-polyisoprene ABC triblock copolymer precursors. The methyl ether of poly(ethylene glycol) [M(n) approximately 550 g/mol (PEG550)] and a semifluorinated alcohol (CF(3)(CF(2))(9)(CH(2))(10)OH) [F10H10] were attached at different molar ratios to impart both hydrophobic and hydrophilic groups to the isoprene segment. Coatings on glass slides consisting of a thin layer of the amphiphilic SABC deposited on a thicker layer of an ABA polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene thermoplastic elastomer were prepared for biofouling assays with algae. Dynamic water contact angle analysis, X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) measurements were utilized to characterize the surfaces. Clear differences in surface structure were realized as the composition of attached side chains was varied. In biofouling assays, the settlement (attachment) of zoospores of the green alga Ulva was higher for surfaces incorporating a large proportion of the hydrophobic F10H10 side chains, while surfaces with a large proportion of the PEG550 side chains inhibited settlement. The trend in attachment strength of sporelings (young plants) of Ulva did not show such an obvious pattern. However, amphiphilic SABCs incorporating a mixture of PEG550 and F10H10 side chains performed the best. The number of cells of the diatom Navicula attached after exposure to flow decreased as the content of PEG550 to F10H10 side chains increased.

  5. Self-assembly behaviour of amphiphilic diblock copolymer in selective solvents studied by synchrotron small-angle x-ray scattering

    Institute of Scientific and Technical Information of China (English)

    荣利霞; 魏柳禾; 董宝中; 洪新国; 李福绵; 李子臣


    The aggregation behaviour of styrene-vinyl benzoic acid (PSm-b-PVBAn) amphiphilic diblock copolymers inselective solvents with different m and n was investigated by synchrotron small-angle x-ray scattering (SAXS). We havecarried out a detailed analysis of scattering intensity, dimension, shape and microstructure of the diblock copolymersof narrow distribution in water, methanol, ethanol and isopropanol selective solvents, respectively. We have found thatthe aggregation behaviour of the copolymer depends on the nature of the solvent and the micelle forms flat disc objectswith the ratio of radius w=0.4. The average radius gyration Rg of the copolymer decreases as solvents change fromisopropanol to ethanol and to methanol, and increases with increasing pH in aqueous solution, but decreases with theaddition of CoCl2 in ethanol solvent. The scattering intensity of diblock copolymer micelle follows I(h) ∞ h-α indifferont selective solutions, suggesting that the PSm-b-PVBAn coils have self-similar structure behaviour or a fractalstructure in the selective solvents. All of these revealed that the aggregation behaviour of the diblock copolymer changesdramatically with experimental condition in the selective solvent. The increase of mass fractal dimension (Dm) from2.12 to 2.47 indicates that the copolymer chain changes from a swollen coil to a rather compact disc in the course ofchanging solvents, decreasing surface fractal dimension (Ds) from 2.98 to 2.58 indicates that the copolymer micellechange from a rather rough surface to a smooth form in the course of increasing pH in aqueous solutions, and increasingDm and Ds from 2.29 to 2.35 and 2.70 to 2.90, respectively, indicates the shrinkage of copolymer micelle to a rathercompact and rough disc form by adding CoCl2 in ethanol solvents.


    Institute of Scientific and Technical Information of China (English)

    Huai-chao Wang; Ming-zu Zhang; Pei-hong Ni; Jin-lin He; Ying Hao; Yi-xian Wu


    Two pH-responsive amphiphilic diblock copolymers,namely polyisobutylene-block-poly[2-(N,N-dimethylamino)ethyl methacrylate] (PIB-b-PDMAEMA) and polyisobutylene-block-poly(metharylic acid) (PIB-b-PMAA),were synthesized via oxyanion-initiated polymerization,and their multiple self-assembly behaviors have been studied.An exo-o1efin-terminated highly reactive polyisobutylene (HRPIB) was first changed to hydroxyl-terminated PIB (PIB-OH) via hydroboration-oxidation of C=C double bond in the chain end,and then reacted with KH to yield a potassium alcoholate of PIB (PIB-O-K+).PIB-O-K+ was immediately used as a macroinitiator to polymerize DMAEMA monomer,resulting in a cationic diblock copolymer PIB-b-PDMAEMA.With the similar synthesis procedure,the anionic diblock copolymer PIB-b-PMAA could be prepared via a combination of oxyanion-initiated polymerization of tert-butyl methacrylate (tBMA) and subsequent hydrolysis of tert-butyl ester groups in PtBMA block.The functional PIB and block copolymers have been fully characterized by 1H-NMR,FT-IR spectroscopy,and gel permeation chromatography (GPC).These samples allowed us to systematically investigate the effects of block composition on the pH responsivity and various self-assembled morphologies of the copolymers in THF/water mixed solvent.Transmission electron microscopy (TEM) images revealed that these diblock copolymers containing small amount of original PIB without exo-olefin-terminated group are able to self-assemble into micelles,vesicles with different particle sizes and cylindrical aggregates,depending on various factors including block copolymer composition,solvent polarity and pH value.

  7. Self-assembly behaviour of amphiphilic diblock copolymer in selective solvents studied by synchrotron small-angle x-ray scattering

    Institute of Scientific and Technical Information of China (English)

    李福绵; 李子臣; 荣利霞; 魏柳禾; 董宝中; 洪新国


    The aggregation behaviour of styrene-vinyl benzoic acid (PSm-b-PVBAn) amphiphilic diblock copolymers in selective solvents with different m and n was investigated by synchrotron small-angle x-ray scattering (SAXS). We have carried out a detailed analysis of scattering intensity, dimension, shape and microstructure of the diblock copolymers of narrow distribution in water, methanol, ethanol and isopropanol selective solvents, respectively. We have found that the aggregation behaviour of the copolymer depends on the nature of the solvent and the micelle forms fiat disc objects with the ratio of radius ω=0.4. The average radius gyration Rg of the copolymer decreases as solvents change from isopropanol to ethanol and to methanol, and increases with increasing pH in aqueous solution, but decreases with the addition of COCl2 in ethanol solvent. The scattering intensity of diblock copolymer micelle follows I(h) ∝ h-α in different selective solutions, suggesting that the PSm-b-PVBAn coils have self-similar structure behaviour or a fractal structure in the selective solvents. All of these revealed that the aggregation behaviour of the diblock copolymer changes dramatically with experimental condition in the selective solvent. The increase of mass fractal dimension (Dm) from 2.12 to 2.47 indicates that the copolymer chain changes from a swollen coil to a rather compact disc in the course of changing solvents, decreasing surface fractal dimension (Ds) from 2.98 to 2.58 indicates that the copolymer micelle change from a rather rough surface to a smooth form in the course of increasing pH in aqueous solutions, and increasing Dm and Ds from 2.29 to 2.35 and 2.70 to 2.90, respectively, indicates the shrinkage of copolymer micelle to a rather compact and rough disc form by adding COCl2 in ethanol solvents.

  8. Novel 4-Arm Poly(Ethylene Glycol-Block-Poly(Anhydride-Esters Amphiphilic Copolymer Micelles Loading Curcumin: Preparation, Characterization, and In Vitro Evaluation

    Directory of Open Access Journals (Sweden)

    Li Lv


    Full Text Available A novel 4-arm poly(ethylene glycol-block-poly(anhydride-esters amphiphilic copolymer (4-arm PEG-b-PAE was synthesized by esterization of 4-arm poly(ethylene glycol and poly(anhydride-esters which was obtained by melt polycondensation of α-, ω-acetic anhydride terminated poly(L-lactic acid. The obtained 4-arm PEG-b-PAE was characterized by 1H-NMR and gel permeation chromatography. The critical micelle concentration of 4-arm PEG-b-PAE was 2.38 μg/mL. The curcumin-loaded 4-arm PEG-b-PAE micelles were prepared by a solid dispersion method and the drug loading content and encapsulation efficiency of the micelles were 7.0% and 85.2%, respectively. The curcumin-loaded micelles were spherical with a hydrodynamic diameter of 151.9 nm. Curcumin was encapsulated within 4-arm PEG-b-PAE micelles amorphously and released from the micelles, faster in pH 5.0 than pH 7.4, presenting one biphasic drug release pattern with rapid release at the initial stage and slow release later. The hemolysis rate of the curcumin-loaded 4-arm PEG-b-PAE micelles was 3.18%, which was below 5%. The IC50 value of the curcumin-loaded micelles against Hela cells was 10.21 μg/mL, lower than the one of free curcumin (25.90 μg/mL. The cellular uptake of the curcumin-loaded micelles in Hela cell increased in a time-dependent manner. The curcumin-loaded micelles could induce G2/M phase cell cycle arrest and apoptosis of Hela cells.

  9. Neomycin-phenolic conjugates: polycationic amphiphiles with broad-spectrum antibacterial activity, low hemolytic activity and weak serum protein binding. (United States)

    Findlay, Brandon; Zhanel, George G; Schweizer, Frank


    Here we present a proof-of-concept study, combining two known antimicrobial agents into a hybrid structure in order to develop an emergent cationic detergent-like interaction with the bacterial membrane. Six amphiphilic conjugates were prepared by copper (I)-catalyzed 1,3-dipolar cycloaddition between a neomycin B-derived azide and three alkyne-modified phenolic disinfectants. Three conjugates displayed good activity against a variety of clinically relevant Gram positive and Gram negative bacteria, including MRSA, without the high level of hemolysis or strong binding to serum proteins commonly observed with other cationic antimicrobial peptides and detergents.

  10. Multicompartment micellar aggregates of linear ABC amphiphiles in solvents selective for the C block: A Monte Carlo simulation

    KAUST Repository

    Zhu, Yutian


    In the current study, we applied the Monte Carlo method to study the self-assembly of linear ABC amphiphiles composed of two solvophobic A and B blocks and a solvophilic C block. A great number of multicompartment micelles are discovered from the simulations and the detailed phase diagrams for the ABC amphiphiles with different block lengths are obtained. The simulation results reveal that the micellar structure is largely controlled by block length, solvent quality, and incompatibility between the different block types. When the B block is longer than or as same as the terminal A block, a rich variety of micellar structures can be formed from ABC amphiphiles. By adjusting the solvent quality or incompatibility between the different block types, multiple morphological transitions are observed. These morphological sequences are well explained and consistent with all the previous experimental and theoretical studies. Despite the complexity of the micellar structures and morphological transitions observed for the self-assembly of ABC amphiphiles, two important common features of the phase behavior are obtained. In general, the micellar structures obtained in the current study can be divided into zero-dimensional (sphere-like structures, including bumpy-surfaced spheres and sphere-on-sphere structures), one-dimensional (cylinder-like structures, including rod and ring structures), two-dimensional (layer-like structures, including disk, lamella and worm-like and hamburger structures) and three-dimensional (vesicle) structures. It is found that the micellar structures transform from low- to high- dimensional structures when the solvent quality for the solvophobic blocks is decreased. In contrast, the micellar structures transform from high- to low-dimensional structures as the incompatibility between different block types increases. Furthermore, several novel micellar structures, such as the CBABC five-layer vesicle, hamburger, CBA three-layer ring, wormlike shape with

  11. Synthesis of Hydrophilic and Amphiphilic Acryl Sucrose Monomers and Their Copolymerisation with Styrene, Methylmethacrylate and α- and β-Pinenes

    Directory of Open Access Journals (Sweden)

    Maria Teresa Barros


    Full Text Available Herein, we report the synthesis of monomethacryloyl sucrose esters, and their successful free radical homo- and co-polymerisation with styrene, methylmethacrylate, α- and β-pinene. The chemical, physical, structural and surface chemical properties of these polymers, containing a hydrophobic olefin backbone and hydrophilic sugar moieties as side chains, have been investigated. Biodegradation tests of the copolymer samples by a microbial fungal culture (Aspergillus niger method showed good biodegradability. The chemical structure and surface chemistry of the synthesized homo- and co-polymers demonstrate their potential technological relevance as amphiphilic and biodegradable polymers.

  12. Synthesis of Novel Amphiphilic Poly (ester-amine) Dendrimers and Their Recognition of Hg2+ at the Air/Water Interface

    Institute of Scientific and Technical Information of China (English)

    申亮; 李富友; 沙耀武; 潘峥峥; 洪啸吟; 黄春辉


    Two novel amphiphilic poly(ester-amine)dendrimers were synthesized and characterized by 1H NMR,13C NMR and IR spectra.Their properties of Langmuir film were investigated at the air/water interface.The relationship between the surface pressure and area isotherms of the dendrimers was found to be dependent on the nature of subphases,Interaction between HgCl2 and the dendrimers was observed,indicating that the amphiphilic dendrimers could act as a sensor for Hg2+.

  13. Synthesis and Characterization of Biodegradable Amphiphilic Star and Y-Shaped Block Copolymers as Potential Carriers for Vinorelbine

    Directory of Open Access Journals (Sweden)

    Fatemeh Bahadori


    Full Text Available Two amphiphilic block copolymers using hydrophobic poly(ε-caprolactone (PCL and hydrophilic poly(ethylene glycol (PEG were successfully synthesized. One of them is an (A-b-B4 type star polymer [(PCL-b-PEG4] and the other one is a Y-shaped PEG–(PCL2. A star-shaped polymer (PCL-b-PEG4 was prepared by ring-opening polymerization (ROP of ε-caprolactone continued by click reaction of (PCL-azide4 and PEG-alkyne. The synthesis of Y-shaped PEG–(PCL2 block copolymer was carried out via Diels-Alder click reaction of a furan protected maleimide end-functionalized PEG (PEG-MI with an anthracene end-functionalized PCL following the ROP of ε-caprolactone. The characterization of micelles is carried out using both materials in aqueous media as drug delivery vehicles, which showed satisfying results and enhanced the cytotoxic effect of the anti-cancer drug vinorelbine (VLB. However, micelles consisted of Y-shaped unimers were found to be more convenient for delivery of hydrophobic drugs such as VLB because they formed in lower concentration, carrying a higher amount of drugs and owing a monomodal distribution. We concluded that the free tails of hydrophobic chains in Y-shaped block copolymer facilitate the assembly of amphiphilic material in water to form micelles.

  14. Versatile antifouling polyethersulfone filtration membranes modified via surface grafting of zwitterionic polymers from a reactive amphiphilic copolymer additive. (United States)

    Zhao, Yi-Fan; Zhang, Pei-Bin; Sun, Jian; Liu, Cui-Jing; Yi, Zhuan; Zhu, Li-Ping; Xu, You-Yi


    Here we describe the development of versatile antifouling polyethersulfone (PES) filtration membranes modified via surface grafting of zwitterionic polymers from a reactive amphiphilic copolymer additive. Amphiphilic polyethersulfone-block-poly(2-hydroxyethyl methacrylate) (PES-b-PHEMA) was beforehand designed and used as the blending additive of PES membranes prepared by phase inversion technique. The surface enriched PHEMA blocks on membrane surface acted as an anchor to immobilize the initiating site. Poly(sulfobetaine methacrylate) (PSBMA) were subsequently grafted onto the PES blend membranes by surface-initiated atom transfer radical polymerization (SI-ATRP). The analysis of surface chemistry confirmed the successful grafting of zwitterionic PSBMA brushes on PES membrane surface. The resulted PES-g-PSBMA membranes were capable of separating proteins from protein solution and oil from oil/water emulsion efficiently. Furthermore, the modified membranes showed high hydrophilicity and strongly antifouling properties due to the incorporation of well-defined PSBMA layer. In addition, the PES-g-PSBMA membranes exhibited excellent blood compatibility and durability during the washing process. The developed antifouling PES membranes are versatile and can find their applications in protein filtration, blood purification and oil/water separation, etc.

  15. Highly protein-resistant coatings and suspension cell culture thereon from amphiphilic block copolymers prepared by RAFT polymerization. (United States)

    Haraguchi, Kazutoshi; Kubota, Kazuomi; Takada, Tetsuo; Mahara, Saori


    Novel amphiphilic block copolymers composed of hydrophobic (poly(2-methoxyethyl acrylate): M) and hydrophilic (poly(N,N-dimethylacrylamide): D) segments were synthesized by living radical polymerization: a reversible addition-fragmentation chain-transfer polymerization. Two types of amphiphilic block copolymers, triblock (MDM) and 4-arm block ((MD)4) copolymers with specific compositions (D/M = (750-1500)/250), were prepared by a versatile one-pot synthesis. These copolymers show good adhesion to various types of substrates (e.g., polystyrene, polycarbonate, polypropylene, Ti, and glass), and the surface coating showed high protein repellency and a low contact angle for water, regardless of the substrate. The two opposing characteristics of high protein repellency and good substrate adhesion were achieved by the combined effects of the molecular architecture of the block copolymers, the high molecular weight, and the characteristics of each segment, that is, low protein adsorption capability of both segments and low glass transition temperature of the hydrophobic segment. Further, a polystyrene dish coated with the MDM block copolymer could be sterilized by γ-ray irradiation and used as a good substrate for a suspension cell culture that exhibits low cell adhesion and good cell growth.

  16. Efficient and versatile fibrous adsorbent based on magnetic amphiphilic composites of chrysotile/carbon nanostructures for the removal of ethynilestradiol. (United States)

    Teixeira, Ana Paula C; Purceno, Aluir D; de Paula, Camila C A; da Silva, Julio César C; Ardisson, José D; Lago, Rochel M


    In this work, chrysotile was used as support to grow carbon nanotubes and nanofibers to produce fibrous amphiphilic magnetic nanostructured composites. Iron impregnated on the chrysotile surface at 1, 5 and 15 wt% was used as catalyst to grow carbon nanostructures by CVD (chemical vapor deposition) with ethanol at 800°C. Raman, TG/DTA, Mössbauer, XRD, BET, SEM, TEM, elemental analyses and contact angle measurements suggested the formation of a complex amphiphilic material containing up to 21% of nanostructured hydrophobic carbon supported on hydrophilic Mg silicate fibers with magnetic Fe cores protected by carbon coating. Adsorption tests for the hormone ethynilestradiol (EE), a hazardous water contaminant, showed remarkable adsorption capacities even compared to high surface area activated carbon and multiwall carbon nanotubes. These results are discussed in terms of the hydrophobic surface of the carbon nanotubes and nanofibers completely exposed and accessible for the adsorption of the EE molecules combined with the hydrophilic Mg silicate surface which allows good dispersion in water. The composites are magnetic and after adsorption the dispersed particles can be removed by a simple magnetic process. Moreover, the fibrous composites can be conformed as threads, screens and pellets to produce different filtering media.

  17. Mucoadhesive Amphiphilic Methacrylic Copolymer-Functionalized Poly(ε-caprolactone) Nanocapsules for Nose-to-Brain Delivery of Olanzapine. (United States)

    Fonseca, Francisco N; Betti, Andresa H; Carvalho, Flávia C; Gremião, Maria P D; Dimer, Frantiescoli A; Guterres, Sílvia S; Tebaldi, Marli L; Rates, Stela M K; Pohlmann, Adriana R


    Nose-to-brain drug delivery has been proposed to overcome the low absorption of drugs in central nervous system due to the absence of brain-blood barrier in the olfactory nerve pathway. However, the presence of a mucus layer and quick clearance limit the use of this route. Herein, amphiphilic methacrylic copolymer-functionalized poly(ε-caprolactone) nanocapsules were proposed as a mucoadhesive system to deliver olanzapine after intranasal administration. In vitro evaluations showed that these nanocapsules were able to interact with mucin (up to 17% of increment in particle size and 30% of reduction of particle concentration) and nasal mucosa (2-fold higher force for detaching), as well as to increase the retention of olanzapine (about 40%) on the nasal mucosa after continuous wash. The olanzapine-loaded amphiphilic methacrylic copolymer-functionalized PCL nanocapsules enhanced the amount of drug in the brain of rats (1.5-fold higher compared to the drug solution). In accordance with this finding, this formulation improved the prepulse inhibition impairment induced by apomorphine, which is considered as an operational measure of pre-attentive sensorimotor gating impairment present in schizophrenia. Besides, nanoencapsulated olanzapine did not affect the nasal mucosa integrity after repeated doses. These data evidenced that the designed nanocapsules are a promising mucoadhesive system for nose-to-brain delivery of drugs.

  18. A Contact Angle Study of the Interaction between Embedded Amphiphilic Molecules and the PDMS Matrix in an Aqueous Environment

    Directory of Open Access Journals (Sweden)

    Wenjun Qiu


    Full Text Available Poly(dimethylsiloxane (PDMS surface modification via gradient-induced transport of embedded amphiphilic molecules is a novel, easy, flexible, and environmentally friendly approach for reducing protein adsorption on PDMS in microfluidic applications. To better understand the processing and the potential use in the viability-sensitive applications such as manipulation and culturing of primary neural cells, we systematically investigate how embedded molecules interact with a PDMS matrix and its surface in aqueous environments by studying the wetting angle over time under various processing conditions, including water exposure time, water exposure temperature, curing master materials, in addition to comparing different embedded amphiphilic molecules. The results indicate that the water exposure time clearly plays an important role in the surface properties. Our interpretation is that molecular rearrangement of the surface-embedded molecules improves surface coverage in the short term; while over a longer period, the transport of molecules embedded in the bulk enhance its coverage. However, this improvement finally terminates when molecules transported from the bulk to the surface are not sufficient to replace the molecules leaching into the water.

  19. Nanoassemblies Based on Supramolecular Complexes of Nonionic Amphiphilic Cyclodextrin and Sorafenib as Effective Weapons to Kill Human HCC Cells. (United States)

    Bondì, Maria Luisa; Scala, Angela; Sortino, Giuseppe; Amore, Erika; Botto, Chiara; Azzolina, Antonina; Balasus, Daniele; Cervello, Melchiorre; Mazzaglia, Antonino


    Sorafenib (Sor), an effective chemiotherapeutic drug utilized against hepatocellular carcinoma (HCC), robustly interacts with nonionic amphiphilic cyclodextrin (aCD, SC6OH), forming, in aqueous solution, supramolecular complexes that behave as building blocks of highly water-dispersible colloidal nanoassemblies. SC6OH/Sor complex has been characterized by complementary spectroscopic techniques, such as UV-vis, steady-state fluorescence and anisotropy, resonance light scattering and (1)H NMR. The spectroscopic evidences and experiments carried out in the presence of an adamantane derivative, which competes with drug for CD cavity, agree with the entrapment of Sor in aCD, pointing out the role of the aCD cavity in the interaction between drug and amphiphile. Nanoassemblies based on SC6OH/Sor display size of ∼200 nm, negative zeta-potential (ζ = -11 mV), and both maximum loading capacity (LC ∼ 17%) and entrapment efficiency (EE ∼ 100%). Kinetic release profiles show a slower release of Sor from nanoassemblies with respect to the free drug. SC6OH/Sor nanoassemblies have very low hemolytic activity and high efficiency in vitro in decreasing cell growth and viability of HCC cell lines, such as HepG2, Hep3B, and PLC/PRF/5, opening promising chances to their in vivo applications.

  20. Self-consistent field theoretic simulations of amphiphilic triblock copolymer solutions: Polymer concentration and chain length effects

    Directory of Open Access Journals (Sweden)

    X.-G. Han


    Full Text Available Using the self-consistent field lattice model, polymer concentration φP and chain length N (keeping the length ratio of hydrophobic to hydrophilic blocks constant the effects on temperature-dependent behavior of micelles are studied, in amphiphilic symmetric ABA triblock copolymer solutions. When chain length is increased, at fixed φP, micelles occur at higher temperature. The variations of average volume fraction of stickers φcos and the lattice site numbers Ncols at the micellar cores with temperature are dependent on N and φP, which demonstrates that the aggregation of micelles depends on N and φP. Moreover, when φP is increased, firstly a peak appears on the curve of specific heat CV for unimer-micelle transition, and then in addition a primary peak, the secondary peak, which results from the remicellization, is observed on the curve of CV. For a long chain, in intermediate and high concentration regimes, the shape of specific heat peak markedly changes, and the peak tends to be a more broad peak. Finally, the aggregation behavior of micelles is explained by the aggregation way of amphiphilic triblock copolymer. The obtained results are helpful in understanding the micellar aggregation process.

  1. Molecular fouling resistance of zwitterionic and amphiphilic initiated chemically vapor-deposited (iCVD) thin films

    Energy Technology Data Exchange (ETDEWEB)

    Yang, R; Goktekin, E; Wang, MH; Gleason, KK


    Biofouling is a universal problem in various applications ranging from water purification to implantable biomedical devices. Recent advances in surface modification have created a rich library of antifouling surface chemistries, many of which can be categorized into one of the two groups: hydrophilic surfaces or amphiphilic surfaces. We report the straightforward preparation of antifouling thin film coatings in both categories via initiated chemical vapor deposition. A molecular force spectroscopy-based method is demonstrated as a rapid and quantitative assessment tool for comparing the differences in antifouling characteristics. The fouling propensity of single molecules, as opposed to bulk protein solution or bacterial culture, is assessed. This method allows for the interrogation of molecular interaction without the complication resulted from protein conformational change or micro-organism group interactions. The molecular interaction follows the same trend as bacterial adhesion results obtained previously, demonstrating that molecular force probe is a valid method for the quantification and mechanistic examination of fouling. In addition, the molecular force spectroscopy-based method is able to distinguish differences in antifouling capability that is not resolvable by traditional static protein adsorption tests. To lend further insight into the intrinsic fouling resistance of zwitterionic and amphiphilic surface chemistries, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, advancing and receding water contact angles, and atomic force microscopy are used to elucidate the film properties that are relevant to their antifouling capabilities.

  2. Real-time monitoring of the penetration of amphiphilic acrylate copolymer in leather using a fluorescent copolymer as tracer. (United States)

    Du, Jin-Xia; Shi, Lu; Peng, Bi-Yu


    A fluorescent tracer, poly (acrylic-co-stearyl acrylate-co-3-acryloyl fluorescein) [poly (AA-co-SA-co-Ac-Flu)], used for real-time monitoring the penetration of amphiphilic acrylate copolymer, poly (acrylic-co-stearyl acrylate) [poly (AA-co-SA)], in leather was synthesized by radical polymerization of acrylic, stearyl acrylate and fluorescent monomer, 3-acryloyl fluorescein (Ac-Flu). The structure, molecular weight, introduced fluorescent group content and fluorescent characteristics of the fluorescent tracer and target copolymer, amphiphilic acrylate copolymer, were also characterized. The results show that the tracer presents the similar structural characteristics to the target and enough fluorescence intensity with 1.68 wt % of the fluorescent monomer introduced amount. The vertical section of the leather treated with the target copolymer mixing with 7% of the tracer exhibits evident fluorescence, and the change of fluorescence intensity along with the vertical section with treating time increasing can reflect the penetration depth of the target copolymer. The introduction of the fluorescent group in polymer structure through copolymerization with a limited amount of fluorescent monomer, Ac-Flu, is an effective way to make a tracer to monitor the penetration of the target in leather, which provides a new thought for the penetration research of syntans such as vinyl copolymer materials in leather manufacture.

  3. Self-Aggregation of Amphiphilic Dendrimer in Aqueous Solution: The Effect of Headgroup and Hydrocarbon Chain Length. (United States)

    Zhang, Pei; Xu, Xiaohui; Zhang, Minghui; Wang, Jinben; Bai, Guangyue; Yan, Haike


    The self-aggregation of amphiphilic dendrimers G1QPAMCm based on poly(amidoamine) PAMAM possessing the same hydrophilic group but differing in alkyl chain length in aqueous solution was investigated. Differences in the chemical structures lead to significant specificities in the aggregate building process. A variety of physicochemical parameters presented monotonous regularity with the increase in alkyl chain length in multibranched structure, as traditional amphiphilic molecules. A significant difference, however, existed in the morphology and the microenvironment of the microdomain of the aggregates, with G1QPAMCm with an alkyl chain length of 16 intending to form vesicles. To obtain supporting information about the aggregation mechanism, the thermodynamic parameters of micellization, the free Gibbs energy ΔGmic, and the entropy ΔSmic were derived subsequently, of which the relationship between the hydrophobic chain length and the thermodynamic properties indicated that the self-assembly process was jointly driven by enthalpy and entropy. Other than traditional surfactants, the contribution of enthalpy has not increased identically to the increase in hydrophobic interactions, which depends on the ratio of the alkyl chain length to the radius in the headgroup. Continuous increases in the hydrophobic chain length from 12 to 16 lead to the intracohesion of the alkyl chain involved in the process of self-assembly, weakening the hydrophobic interactions, and the increase in -ΔHmic, which offers an explanation of the formation of vesicular structures.

  4. Self-assembled nanoparticles based on amphiphilic chitosan derivative and arginine for oral curcumin delivery

    Directory of Open Access Journals (Sweden)

    Raja MA


    Full Text Available Mazhar Ali Raja, Shah Zeenat, Muhammad Arif, Chenguang Liu College of Marine Life Science, Ocean University of China, Qingdao, Shandong, People’s Republic of China Abstract: Curcumin (Cur is a striking anticancer agent, but its low aqueous solubility, poor absorption, hasty metabolism, and elimination limit its oral bioavailability and consequently hinder its development as a drug. To redress these limitations, amphiphilic chitosan (CS conjugate with improved mucoadhesion and solubility over a wider pH range was developed by modification with hydrophobic acrylonitrile (AN and hydrophilic arginine (Arg; the synthesized conjugate (AN–CS–Arg, which was well characterized by Fourier transform infrared and 1H nuclear magnetic resonance spectroscopy. Results of critical aggregation concentration revealed that the AN–CS–Arg conjugate had low critical aggregation concentration and was prone to form self-assembled nanoparticles (NPs in aqueous medium. Cur-encapsulated AN–CS–Arg NPs (AN–CS–Arg/Cur NPs were developed by a simple sonication method and characterized for the physicochemical parameters such as zeta potential, particle size, and drug encapsulation. The results showed that zeta potential of the prepared NPs was 40.1±2.81 mV and the average size was ~218 nm. A considerable improvement in the aqueous solubility of Cur was observed after encapsulation into AN–CS–Arg/Cur NPs. With the increase in Cur concentration, loading efficiency increased but encapsulation efficiency decreased. The in vitro release profile exhibited sustained release pattern from the AN–CS–Arg/Cur NPs in typical biological buffers. The ex vivo mucoadhesion study revealed that AN–CS–Arg/Cur NPs had greater mucoadhesion than the control CS NPs. Compared with free Cur solution, AN–CS–Arg/Cur NPs showed stronger dose-dependent cytotoxicity against HT-29 cells. In addition, it was observed that cell uptake of AN–CS–Arg/Cur NPs was much higher

  5. Synthesis of nonionic reduced-sugar based bola amphiphiles and gemini surfactants with an alpha,omega-diamino-(oxa)alkyl spacer

    NARCIS (Netherlands)

    Wagenaar, Anno; Engberts, Jan B. F. N.


    Reduced-sugar based gemini surfactants with an alpha,omega-diamino-(oxa) alkyl spacer exhibit a rich pH-dependent aggregation behavior and are efficient DNA carriers in gene transfection. Herein, we describe an improved synthetic procedure for these amphiphiles. First, a series of novel nonionic bol

  6. Hepatobiliary and intestinal clearance of amphiphilic cationic drugs in mice in which both mdr1a and mdr1b genes have been disrupted

    NARCIS (Netherlands)

    Smit, JW; Schinkel, AH; Weert, B; Meijer, DKF


    1 We have used mice with homozygously disrupted mdr1a and mdr1b genes (mdr1a/1b (-/-) mice) to study the role of the mdr1-type beta-glycoprotein (P-gp) in the elimination of cationic amphiphilic compounds from the body. These mice lack drug-transporting P-gps, but show no physiological abnormalities

  7. GdDOTAGA(C18)2: an efficient amphiphilic Gd(iii) chelate for the preparation of self-assembled high relaxivity MRI nanoprobes. (United States)

    Filippi, M; Remotti, D; Botta, M; Terreno, E; Tei, L


    A new amphiphilic GdDOTA-like complex functionalized with two octadecyl chains was synthesised and incorporated into the bilayer of liposomes and dendrimersomes. (1)H NMR relaxometric studies and in vivo MRI experiments on mice bearing a syngeneic melanoma tumour have shown a great improvement in performance.

  8. Polystyrene-Poly(sodium methacrylate) Amphiphilic Block Copolymers by ATRP : Effect of Structure, pH, and Ionic Strength on Rheology of Aqueous Solutions

    NARCIS (Netherlands)

    Raffa, Patrizio; Brandenburg, Piter; Wever, Diego A. Z.; Broekhuis, Antonius A.; Picchioni, Francesco


    Three well-defined polystyrene-poly(sodium methacrylate) amphiphilic block copolymers characterized by different molecular architecture (diblock, triblock, and four-arm star) have been synthesized by ATRP. The rheology of their water solutions has been evaluated by measuring dynamic moduli and shear

  9. Butane-1,2,3,4-tetraol-based amphiphilic stereoisomers for membrane protein study: importance of chirality in the linker region

    DEFF Research Database (Denmark)

    Das, Manabendra; Du, Yang; Mortensen, Jonas S.;


    Amphiphile selection is a crucial step in membrane protein structural and functional study. As conventional detergents have limited scope and utility, novel agents with enhanced efficacy need to be developed. Although a large number of novel agents have been reported, so far there has been no sys...

  10. Studies on an ester-modified cationic amphiphile in aqueous systems: behavior of binary solutions and ternary mixtures with conventional surfactants. (United States)

    Lundberg, Dan; Unga, Johan; Galloway, Ashley L; Menger, Fredric M


    The aqueous behavior of an ester-modified cationic amphiphile with the molecular structure CH3CH2O(C=O)(CH2)6(C=O)O(CH2)8N+(CH3)3Br-, in the following referred to as A, has been investigated. Systems with A as the only solute, as well as different aqueous mixtures with conventional cationic surfactants, primarily dodecyltrimethylammonium bromide (DTAB), were included in the study. Isotropic solution samples were characterized using 1H NMR, 13C NMR, NMR diffusometry, and conductivity measurements, whereas liquid crystalline samples were investigated by optical polarization microscopy and small-angle X-ray diffraction. The results are compared to the behavior of the binary system of DTAB and water. A does not exhibit a typical surfactant behavior. When it is present as the only solute in a binary aqueous system, it forms neither conventional micelles nor liquid crystalline phases. However, there is clear evidence that it assembles with lower cooperativity into loose clusters at concentrations above 25-30 mM. When A is mixed with DTAB in solution, the two amphiphiles form mixed assemblies, the structure of which varies with the total amphiphile concentration. In concentrated mixtures with alkyltrimethylammonium surfactants, A can participate in hexagonal liquid crystalline phases even when it constitutes a significant fraction of the total amphiphile content.

  11. Evidence of interlipidic ion-pairing in anion-induced DNA release from cationic amphiphile-DNA complexes. Mechanistic implications in transfection. (United States)

    Bhattacharya, S; Mandal, S S


    Complex formation of DNA with a number of cationic amphiphiles has been examined using fluorescence, gel electrophoresis, and chemical nuclease digestion. Here we have addressed the status of both DNA and lipid upon complexation with each other. DNA upon binding with cationic amphiphiles changes its structure in such a way that it loses the ability to intercalate and becomes resistant to nuclease digestion. Fluorescence anisotropy measurements due to 1, 6-diphenylhexatriene (DPH) doped in cationic liposomes demonstrated that upon complexation with DNA, the resulting complexes still retain lamellar organizations with modest enhancement in thermal stabilities. The lipid-DNA complexation is most effective only when the complexation was carried out at or around the phase transition temperatures of the cationic lipid employed in the complexation with DNA. The release of DNA from cationic lipid-DNA complexes could be induced by several anionic additives. Determination of fluorescence anisotropies (due to DPH) as a function of temperature clearly demonstrates that the addition of equivalent amounts of anionic amphiphile into cationic lipid-DNA complexes leads to the ion-pairing of the amphiphiles, the melting profiles of which are virtually the same as those obtained in the absence of DNA. In this process DNA gets released from its complexes with cationic lipids and regains its natural intercalation ability, movement, and staining ability on agarose gel and also the sensitivities toward nuclease digestion. This clearly suggests that combination of ion-pairing and hydrophobic interactions between cationic and anionic amphiphiles is stronger than the electrostatic forces involved in the cationic lipid-DNA complexation. It is further revealed that the DNA release by anions is most efficient from the cationic lipid-DNA complexes at or around the Tm of the cationic lipid used in DNA complexation. This explains why more effective DNA delivery is achieved with cationic lipids

  12. Amphiphilic core shell nanoparticles containing dense polyethyleneimine shells for efficient delivery of microRNA to Kupffer cells

    Directory of Open Access Journals (Sweden)

    Liu Z


    Full Text Available Zuojin Liu,1,* Dechao Niu,2,3,* Junyong Zhang,1 Wenfeng Zhang,1 Yuan Yao,2 Pei Li,2 Jianping Gong1 1Department of Hepatobiliary Surgery, The Second Affiliated Hospital of Chongqing Medical University, Chongqing, 2Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, 3Lab of Low-Dimensional Materials Chemistry, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, People’s Republic of China *These authors contributed equally to this work Abstract: Efficient and targeted delivery approach to transfer exogenous genes into macrophages is still a great challenge. Current gene delivery methods often result in low cellular uptake efficiency in vivo in some types of cells, especially for the Kupffer cells (KCs. In this article, we demonstrate that amphiphilic core–shell nanoparticles (NPs consisting of well-defined hydrophobic poly(methyl methacrylate (PMMA cores and branched polyethyleneimine (PEI shells (denoted as PEI@PMMA NPs are efficient nanocarriers to deliver microRNA (miRNA-loaded plasmid to the KCs. Average hydrodynamic diameter of PEI@PMMA NPs was 279 nm with a narrow size distribution. The NPs also possessed positive surface charges up to +30 mV in water, thus enabling effective condensation of negatively charged plasmid DNA. Gel electrophoresis assay showed that the resultant PEI@PMMA NPs were able to completely condense miRNA plasmid at a weight ratio of 25:1 (N/P ratio equal to 45:1. The Cell Counting Kit-8 assay and flow cytometry results showed that the PEI@PMMA/miRNA NPs displayed low cytotoxicity and cell apoptosis activity against the KCs. The maximum cell transfection efficiency reached 34.7% after 48 hours, which is much higher than that obtained by using the commercial Lipofectamine™ 2000 (1.7%. Bio-transmission electron microscope observation revealed that the PEI@PMMA NPs were mainly distributed in

  13. Degradable copolymer based on amphiphilic N-octyl-N-quatenary chitosan and low-molecular weight polyethylenimine for gene delivery

    Directory of Open Access Journals (Sweden)

    Liu CC


    Full Text Available Chengchu Liu,1,2,* Qing Zhu,1,* Wenhui Wu,1 Xiaolin Xu,1 Xiaoyu Wang,3 Shen Gao,3 Kehai Liu11Department of Biopharmaceutics, College of Food Science and Technology, Shanghai Ocean University, Shanghai, China; 2Shanghai Engineering Research Center of Aquatic-Product Processing and Preservation, Shanghai, China; 3Department of Pharmaceutics, Changhai Hospital, Second Military Medical University, Shanghai China*The first two authors contributed equally to this workBackground: Chitosan shows particularly high biocompatibility and fairly low cytotoxicity. However, chitosan is insoluble at physiological pH. Moreover, it lacks charge, so shows poor transfection. In order to develop a new type of gene vector with high transfection efficiency and low cytotoxicity, amphiphilic chitosan was synthesized and linked with low-molecular weight polyethylenimine (PEI.Methods: We first synthesized amphiphilic chitosan – N-octyl-N-quatenary chitosan (OTMCS, then prepared degradable PEI derivates by cross-linking low-molecular weight PEI with amphiphilic chitosan to produce a new polymeric gene vector (OTMCS–PEI. The new gene vector was characterized by various physicochemical methods. We also determined its cytotoxicity and gene transfecton efficiency in vitro and in vivo.Results: The vector showed controlled degradation. It was very stable and showed excellent buffering capacity. The particle sizes of the OTMCS–PEI/DNA complexes were around 150–200 nm with proper zeta potentials from 10 mV to 30 mV. The polymer could protect plasmid DNA from being digested by DNase I at a concentration of 2.25 U DNase I/µg DNA. Furthermore, they were resistant to dissociation induced by 50% fetal bovine serum and 1100 µg/mL sodium heparin. OTMCS–PEI revealed lower cytotoxicity, even at higher doses. Compared with PEI 25 KDa, the OTMCS–PEI/DNA complexes also showed higher transfection efficiency in vitro and in vivo.Conclusion: OTMCS–PEI was a potential candidate as

  14. Self-Assembling Peptide Amphiphiles for Therapeutic Delivery of Proteins, Drugs, and Stem Cells (United States)

    Lee, Sungsoo Seth

    Biomaterials are used to help regenerate or replace the structure and function of damaged tissues. In order to elicit desired therapeutic responses in vivo, biomaterials are often functionalized with bioactive agents, such as growth factors, small molecule drugs, or even stem cells. Therefore, the strategies used to incorporate these bioactive agents in the microstructures and nanostructures of biomaterials can strongly influence the their therapeutic efficacy. Using self-assembling peptide amphiphiles (PAs), this work has investigated supramolecular nanostructures with improved interaction with three types of therapeutic agents: bone morphogenetic protein 2 (BMP-2) which promotes osteogenic differentiation and bone growth, anti-inflammatory drug naproxen which is used to treat osteo- and rheumatoid arthritis, and neural stem cells that could differentiate into neurons to treat neurodegenerative diseases. For BMP-2 delivery, two specific systems were investigated with affinity for BMP-2: 1) heparin-binding nanofibers that display the natural ligand of the osteogenic protein, and 2) nanofibers that display a synthetic peptide ligand discovered in our laboratory through phage display to directly bind BMP-2. Both systems promoted enhanced osteoblast differentiation of pluripotent C2C12 cells and augmented bone regeneration in two in vivo models, a rat critical-size femur defect model and spinal arthrodesis model. The thesis also describes the use of PA nanofibers to improve the delivery of the anti-inflammatory drug naproxen. To promote a controlled release, naproxen was chemically conjugated to the nanofiber surface via an ester bond that would only be cleaved by esterases, which are enzymes found naturally in the body. In the absence of esterases, the naproxen remained conjugated to the nanofibers and was non-bioactive. On the other hand, in the presence of esterases, naproxen was slowly released and inhibited cyclooxygenase-2 (COX-2) activity, an enzyme responsible

  15. Preparation of copper sulphide clusters in organic-inorganic composites of Langmuir-Blodgett films of amphiphilic Schiff bases

    Indian Academy of Sciences (India)

    G Hemakanthi; Aruna Dhathathreyan; T Ramasami; D Möbius


    Copper sulphide clusters were prepared in Langmuir-Blodgett films of copper complexes of amphiphilic Schiff bases-3,4-dimethoxy-N-benzylidene hexadeylamine (I) and 3,4-dimethoxy-N-benzylidene-4 -(hexadecylamino) benzylamine (II) The clusters obtained were analysed using UV-Vis spectroscopy and optical microscopy. Brewster angle microscopic studies on monolayers of I and II at air/water interface showed formation of needle-like domains which seem to cluster faster in I than in II. Atomic force microscopy (AFM) studies also showed fairly uniform sized clusters in II whereas in the case of I they seem to show varying sizes. From the results it is concluded that -elongation in the polar head groups leads to controlled cluster sizes in compound II as compared to those in compound I.

  16. An amphiphilic graft copolymer-based nanoparticle platform for reduction-responsive anticancer and antimalarial drug delivery (United States)

    Najer, Adrian; Wu, Dalin; Nussbaumer, Martin G.; Schwertz, Geoffrey; Schwab, Anatol; Witschel, Matthias C.; Schäfer, Anja; Diederich, François; Rottmann, Matthias; Palivan, Cornelia G.; Beck, Hans-Peter; Meier, Wolfgang


    Medical applications of anticancer and antimalarial drugs often suffer from low aqueous solubility, high systemic toxicity, and metabolic instability. Smart nanocarrier-based drug delivery systems provide means of solving these problems at once. Herein, we present such a smart nanoparticle platform based on self-assembled, reduction-responsive amphiphilic graft copolymers, which were successfully synthesized through thiol-disulfide exchange reaction between thiolated hydrophilic block and pyridyl disulfide functionalized hydrophobic block. These amphiphilic graft copolymers self-assembled into nanoparticles with mean diameters of about 30-50 nm and readily incorporated hydrophobic guest molecules. Fluorescence correlation spectroscopy (FCS) was used to study nanoparticle stability and triggered release of a model compound in detail. Long-term colloidal stability and model compound retention within the nanoparticles was found when analyzed in cell media at body temperature. In contrast, rapid, complete reduction-triggered disassembly and model compound release was achieved within a physiological reducing environment. The synthesized copolymers revealed no intrinsic cellular toxicity up to 1 mg mL-1. Drug-loaded reduction-sensitive nanoparticles delivered a hydrophobic model anticancer drug (doxorubicin, DOX) to cancer cells (HeLa cells) and an experimental, metabolically unstable antimalarial drug (the serine hydroxymethyltransferase (SHMT) inhibitor (+/-)-1) to Plasmodium falciparum-infected red blood cells (iRBCs), with higher efficacy compared to similar, non-sensitive drug-loaded nanoparticles. These responsive copolymer-based nanoparticles represent a promising candidate as smart nanocarrier platform for various drugs to be applied to different diseases, due to the biocompatibility and biodegradability of the hydrophobic block, and the protein-repellent hydrophilic block.Medical applications of anticancer and antimalarial drugs often suffer from low aqueous

  17. Optimum design of amphiphilic polymers bearing hydrophobic groups for both cell surface ligand presentation and intercellular cross-linking. (United States)

    Takeo, Masafumi; Li, Cuicui; Matsuda, Masayoshi; Nagai, Hiroko; Hatanaka, Wataru; Yamamoto, Tatsuhiro; Kishimura, Akihiro; Mori, Takeshi; Katayama, Yoshiki


    Amphiphilic polymers bearing hydrophobic alkyl groups are expected to be applicable for both ligand presentation on the cell surface and intercellular crosslinking. To explore the optimum design for each application, we synthesized eight different acyl-modified dextrans with varying molecular weight, alkyl length, and alkyl modification degree. We found that the behenate-modified polymers retained on the cell surface longer than the palmitate-modified ones. Since the polymers were also modified with biotin, streptavidin can be presented on the cell surface through biotin-streptavidin recognition. The duration of streptavidin on the cell surface is longer in the behenate-modified polymer than the palmitate-modified one. As for the intercellular crosslinking, the palmitate-modified polymers were more efficient than the behenate-modified polymers. The findings in this research will be helpful to design the acyl-modified polymers for the cell surface engineering.

  18. Behavior of the amphiphile CHAPS alone and in combination with the biopolymer inulin in water and isopropanol-water media. (United States)

    Naskar, Bappaditya; Ghosh, Soumen; Nagadome, Shigemi; Sugihara, Ghosuke; Moulik, Satya P


    Self-aggregation of the zwitterionic surfactant 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate (CHAPS) in water and isopropanol-water media, and interaction of the amphiphile with the biopolymer inulin in these media were investigated. The micellar properties of the zwitterionic surfactant and its associated interfacial and bulk properties along with the related energetic, and aggregation number were determined. The different stages of interaction of the CHAPS-inulin combines were identified and assessed. The complexes were formed and aggregated in solution at different stages of their molecular compositions. The aggregated sizes were determined by dynamic light scattering study and the morphology in the solvent removed states were examined using scanning electron microscope and transmission electron microscope techniques. The results witnessed formation of ensembles of varied and striking patterns.

  19. π-π interaction of aromatic groups in amphiphilic molecules directing for single-crystalline mesostructured zeolite nanosheets. (United States)

    Xu, Dongdong; Ma, Yanhang; Jing, Zhifeng; Han, Lu; Singh, Bhupendra; Feng, Ji; Shen, Xuefeng; Cao, Fenglei; Oleynikov, Peter; Sun, Huai; Terasaki, Osamu; Che, Shunai


    One of the challenges in material science has been to prepare macro- or mesoporous zeolite. Although examples of their synthesis exist, there is a need for a facile yet versatile approach to such hierarchical structures. Here we report a concept for designing a single quaternary ammonium head amphiphilic template with strong ordered self-assembling ability through π-π stacking in hydrophobic side, which stabilizes the mesostructure to form single-crystalline mesostructured zeolite nanosheets. The concept is demonstrated for the formation of a new type of MFI (zeolite framework code by International Zeolite Association) nanosheets joined with a 90° rotational boundary, which results in a mesoporous zeolite with highly specific surface area even after calcination. Low binding energies for this self-assembling system are supported by a theoretical analysis. A geometrical matching between the arrangement of aromatic groups and the zeolitic framework is speculated for the formation of single-crystalline MFI nanosheets.

  20. In vitro Plasmodium falciparum drug sensitivity assay: inhibition of parasite growth by incorporation of stomatocytogenic amphiphiles into the erythrocyte membrane

    DEFF Research Database (Denmark)

    Ziegler, Hanne L; Staerk, Dan; Christensen, Jette


    culture continued to grow well in untreated erythrocytes. Thus, the antiplasmodial activity of lupeol appears to be indirect, being due to stomatocytic transformation of the host cell membrane and not to toxic effects via action on a drug target within the parasite. A number of amphiphiles that cause...... stomatocyte formation, but not those causing echinocyte formation, were shown to inhibit growth of the parasites, apparently via a mechanism similar to that of lupeol. Since antiplasmodial agents that inhibit parasite growth through erythrocyte membrane modifications must be regarded as unsuitable as leads...... for development of new antimalarial drugs, care must be exercised in the interpretation of results of screening of plant extracts and natural product libraries by an in vitro Plasmodium toxicity assay....

  1. Mesitylene-Cored Glucoside Amphiphiles (MGAs) for Membrane Protein Studies: Importance of Alkyl Chain Density in Detergent Efficacy

    DEFF Research Database (Denmark)

    Cho, Kyung Ho; Ribeiro, Orquidea; Du, Yang


    Detergents serve as useful tools for membrane protein structural and functional studies. Their amphipathic nature allows detergents to associate with the hydrophobic regions of membrane proteins whilst maintaining the proteins in aqueous solution. However, widely used conventional detergents...... are limited in their ability to maintain the structural integrity of membrane proteins and thus there are major efforts underway to develop novel agents with improved properties. We prepared mesitylene-cored glucoside amphiphiles (MGAs) with three alkyl chains and compared these agents with previously...... developed xylene-linked maltoside agents (XMAs) with two alkyl chains and a conventional detergent (DDM). When these agents were evaluated for four membrane proteins including a G protein-coupled receptor (GPCR), some agents such as MGA-C13 and MGA-C14 resulted in markedly enhanced stability of membrane...

  2. Determination of the cationic amphiphilic drug-DNA binding mode and DNA-assisted fluorescence resonance energy transfer amplification. (United States)

    Yaseen, Zahid; Banday, Abdul Rouf; Hussain, Mohammed Aamir; Tabish, Mohammad; Kabir-ud-Din


    Understanding the mechanism of drug-DNA binding is crucial for predicting the potential genotoxicity of drugs. Agarose gel electrophoresis, absorption, steady state fluorescence, and circular dichroism have been used in exploring the interaction of cationic amphiphilic drugs (CADs) such as amitriptyline hydrochloride (AMT), imipramine hydrochloride (IMP), and promethazine hydrochloride (PMT) with calf thymus or pUC19 DNA. Agarose gel electrophoresis assay, along with absorption and steady state fluorescence studies, reveal interaction between the CADs and DNA. A comparative study of the drugs with respect to the effect of urea, iodide induced quenching, and ethidium bromide (EB) exclusion assay reflects binding of CADs to the DNA primarily in an intercalative fashion. Circular dichroism data also support the intercalative mode of binding. Besides quenching, there is fluorescence exchange energy transfer (FRET) in between CADs and EB using DNA as a template.

  3. Controlled Self-Assembly of Cyclophane Amphiphiles: From 1D Nanofibers to Ultrathin 2D Topological Structures

    Energy Technology Data Exchange (ETDEWEB)

    Cai, Zhengxu; Li, Lianwei; Lo, Wai-Yip; Zhao, Donglin; Wu, Qinghe; Zhang, Na; Su, Yu-An; Chen, Wei; Yu, Luping


    A novel series of amphiphilic TC-PEG molecules were designed and synthesized based on the orthogonal cyclophane unit. These molecules were able to self-assemble from 1D nanofibers and nanobelts to 2D ultrathin nanosheets (3 nm thick) in a controlled way by tuning the length of PEG side chains. The special structure of the cyclophane moiety allowed control in construction of nanostructures through programmed noncovalent interactions (hydrophobic hydrophilic interaction and pi-pi interaction). The self-assembled nanostructures were characterized by combining real space imaging (TEM, SEM, and AFM) and reciprocal space scattering (GIWAXS) techniques. This unique supramolecular system may provide a new strategy for the design of materials with tunable nanomorphology and functionality.

  4. Polymer micelles with hydrophobic core and ionic amphiphilic corona. 1. Statistical distribution of charged and nonpolar units in corona. (United States)

    Lysenko, Evgeny A; Kulebyakina, Alevtina I; Chelushkin, Pavel S; Rumyantsev, Artem M; Kramarenko, Elena Yu; Zezin, Alexander B


    Polymer micelles with hydrophobic polystyrene (PS) core and ionic amphiphilic corona from charged N-ethyl-4-vinylpyridinium bromide (EVP) and uncharged 4-vinylpyridine (4VP) units spontaneously self-assembled from PS-block-poly(4VP-stat-EVP) macromolecules in mixed dimethylformamide/methanol/water solvent. The fraction of statistically distributed EVP units in corona-forming block is β = [EVP]/([EVP]+[4VP]) = 0.3-1. Micelles were transferred into water via dialysis technique, and pH was adjusted to 9, where 4VP is insoluble. Structural characteristics of micelles were investigated both experimentally and theoretically as a function of corona composition β. Methods of dynamic and static light scattering, electrophoretic mobility measurements, sedimentation velocity, transmission electron microscopy, and UV spectrophotometry were applied. All micelles possessed spherical morphology. The aggregation number, structure, and electrophoretic mobility of micelles changed in a jumplike manner near β ~ 0.6-0.75. Below and above this region, micelle characteristics were constant or insignificantly changed upon β. Theoretical dependencies for micelle aggregation number, corona dimensions, and fraction of small counterions outside corona versus β were derived via minimization the micelle free energy, taking into account surface, volume, electrostatic, and elastic contributions of chain units and translational entropy of mobile counterions. Theoretical estimations also point onto a sharp structural transition at a certain corona composition. The abrupt reorganization of micelle structure at β ~ 0.6-0.75 entails dramatic changes in micelle dispersion stability in the presence of NaCl or in the presence of oppositely charged polymeric (sodium polymethacrylate) or amphiphilic (sodium dodecyl sulfate) complexing agents.

  5. Amphiphilic core-shell nanoparticles containing dense polyethyleneimine shells for efficient delivery of microRNA to Kupffer cells. (United States)

    Liu, Zuojin; Niu, Dechao; Zhang, Junyong; Zhang, Wenfeng; Yao, Yuan; Li, Pei; Gong, Jianping


    Efficient and targeted delivery approach to transfer exogenous genes into macrophages is still a great challenge. Current gene delivery methods often result in low cellular uptake efficiency in vivo in some types of cells, especially for the Kupffer cells (KCs). In this article, we demonstrate that amphiphilic core-shell nanoparticles (NPs) consisting of well-defined hydrophobic poly(methyl methacrylate) (PMMA) cores and branched polyethyleneimine (PEI) shells (denoted as PEI@PMMA NPs) are efficient nanocarriers to deliver microRNA (miRNA)-loaded plasmid to the KCs. Average hydrodynamic diameter of PEI@ PMMA NPs was 279 nm with a narrow size distribution. The NPs also possessed positive surface charges up to +30 mV in water, thus enabling effective condensation of negatively charged plasmid DNA. Gel electrophoresis assay showed that the resultant PEI@PMMA NPs were able to completely condense miRNA plasmid at a weight ratio of 25:1 (N/P ratio equal to 45:1). The Cell Counting Kit-8 assay and flow cytometry results showed that the PEI@PMMA/miRNA NPs displayed low cytotoxicity and cell apoptosis activity against the KCs. The maximum cell transfection efficiency reached 34.7% after 48 hours, which is much higher than that obtained by using the commercial Lipofectamine™ 2000 (1.7%). Bio-transmission electron microscope observation revealed that the PEI@PMMA NPs were mainly distributed in the cytoplasm of the KCs. Furthermore, when compared to the control groups, the protein expression of target nuclear factor κB P65 was considerably inhibited (P<0.05) both in vitro and in vivo. These results demonstrate that the PEI@PMMA NPs with a unique amphiphilic core-shell nanostructure are promising nanocarriers for delivering miRNA plasmid to KCs.

  6. Molecular Differentiated Initiator Reactivity in the Synthesis of Poly(caprolactone-Based Hydrophobic Homopolymer and Amphiphilic Core Corona Star Polymers

    Directory of Open Access Journals (Sweden)

    Eileen Deng


    Full Text Available Macromolecules that possess three-dimensional, branched molecular structures are of great interest because they exhibit significantly differentiated application performance compared to conventional linear (straight chain polymers. This paper reports the synthesis of 3- and 4-arm star branched polymers via ring opening polymerisation (ROP utilising multi-functional hydroxyl initiators and Sn(Oct2 as precatalyst. The structures produced include mono-functional hydrophobic and multi-functional amphiphilic core corona stars. The characteristics of the synthetic process were shown to be principally dependent upon the physical/dielectric properties of the initiators used. ROP’s using initiators that were more available to become directly involved with the Sn(Oct2 in the “in-situ” formation of the true catalytic species were observed to require shorter reaction times. Use of microwave heating (MWH in homopolymer star synthesis reduced reaction times compared to conventional heating (CH equivalents, this was attributed to an increased rate of “in-situ” catalyst formation. However, in amphiphilic core corona star formation, the MWH polymerisations exhibited slower propagation rates than CH equivalents. This was attributed to macro-structuring within the reaction medium, which reduced the potential for reaction. It was concluded that CH experiments were less affected by this macro-structuring because it was disrupted by the thermal currents/gradients caused by the conductive/convective heating mechanisms. These gradients are much reduced/absent with MWH because it selectively heats specific species simultaneously throughout the entire volume of the reaction medium. These partitioning problems were overcome by introducing additional quantities of the species that had been determined to selectively heat.

  7. Aspartic acid (United States)

    Aspartic acid is a nonessential amino acids . Amino acids are building blocks of proteins. "Nonessential" means that our ... this amino acid from the food we eat. Aspartic acid is also called asparaginic acid. Aspartic acid helps ...

  8. 用于肿瘤靶向性MRI对比剂双亲性超顺磁复合物的制备%Preparation of amphiphilic superparamagnetic composite particles with tumor targeted MRI contrast agent

    Institute of Scientific and Technical Information of China (English)

    顾隽珩; 张庆云; 张伟; 杨新林


    BACKGROUND:Superparamagnetic iron oxide nanoparticles (Fe3O4 NPs) have been widely used in MRI. It is vital to prepare the superparamagnetic MRI contrast agent with high stability, biocompatibility and tumor targeting in order to prevent the aggregation of Fe 3 O 4 NPs and realize the high-precision diagnose of tumor. OBJECTIVE:To prepare the amphiphilic superparamagnetic composite particles with tumor targeting mediated by folate receptor. METHODS:The stable amphiphilic superparamagnetic composite particles with tumor targeting function were prepared by coating the Fe3O4 NPs with a Pluronic F127-folic acid conjugate, which was synthesized via an esterification reaction between the carboxyl group of the tumor targeting molecule, folic acid and the hydroxyl group of an amphiphilic triblock copolymer, Pluronic F127. The resultant Pluronic F127-folic acid-Fe3O4 composite particles were characterized by transmission electron microscopy, Fourier transform infrared-spectra, UV-vis absorption spectra, thermal gravimetric analysis, vibrating sample magnetometer and T2-weighted imaging. WST assay was used to characterize their cytotoxicity preliminarily. RESULTS AND CONCLUSION:The Pluronic F127-folic acid conjugates were prepared via esterification reaction. Then Fe 3 O 4 NPs were wrapped with Pluronic F127-folic acid to result in the superparamagnetic composite particles with wel dispersion and biocompatibility. The size of most superparamagnetic composite particles was less than 200 nm and the size of Fe 3 O 4 core was 10-20 nm from the observation of transmission electron microscopy. The results from the Fourier transform infrared-spectra and UV-vis absorption spectroscop confirmed that folic acid molecules were modified on the surface of the superparamagnetic composite particles successful y. The mass ratio of Pluronic F127-folic acid conjugate was determined by thermal gravimetric analysis as 27.2 wt%in the resultant Pluronic F127-folic acid-Fe 3 O 4 composite

  9. A Comparative Study of Cellular Uptake and Subcellular Localization of Doxorubicin Loaded in Self-Assemblies of Amphiphilic Copolymers with Pendant Dendron by MDA-MB-231 Human Breast Cancer Cells. (United States)

    Viswanathan, Geetha; Hsu, Yu-Hsuan; Voon, Siew Hui; Imae, Toyoko; Siriviriyanun, Ampornphan; Lee, Hong Boon; Kiew, Lik Voon; Chung, Lip Yong; Yusa, Shin-Ichi


    Previously synthesized amphiphilic diblock copolymers with pendant dendron moieties have been investigated for their potential use as drug carriers to improve the delivery of an anticancer drug to human breast cancer cells. Diblock copolymer (P71 D3 )-based micelles effectively encapsulate the doxorubicin (DOX) with a high drug-loading capacity (≈95%, 104 DOX molecules per micelle), which is approximately double the amount of drug loaded into the diblock copolymer (P296 D1 ) vesicles. DOX released from the resultant P71 D3 /DOX micelles is approximately 1.3-fold more abundant, at a tumoral acidic pH of 5.5 compared with a pH of 7.4. The P71 D3 /DOX micelles also enhance drug potency in breast cancer MDA-MB-231 cells due to their higher intracellular uptake, by approximately twofold, compared with the vesicular nanocarrier, and free DOX. Micellar nanocarriers are taken up by lysosomes via energy-dependent processes, followed by the release of DOX into the cytoplasm and subsequent translocation into the nucleus, where it exert its cytotoxic effect.

  10. Control over Structure and Function of Peptide Amphiphile Supramolecular Assemblies through Molecular Design and Energy Landscapes (United States)

    Tantakitti, Faifan

    Supramolecular chemistry is a powerful tool to create a material of a defined structure with tunable properties. This strategy has led to catalytically active, bioactive, and environment-responsive materials, among others, that are valuable in applications ranging from sensor technology to energy and medicine. Supramolecular polymers formed by peptide amphiphiles (PAs) have been especially relevant in tissue regeneration due to their ability to form biocompatible structures and mimic many important signaling molecules in biology. These supramolecular polymers can form nanofibers that create networks which mimic natural extracellular matrices. PA materials have been shown to induce growth of blood vessels, bone, cartilage, and nervous tissue, among others. The work described in this thesis not only studied the relationship between molecular structure and functions of PA assemblies, but also uncovered a powerful link between the energy landscape of their supramolecular self-assembly and the ability of PA materials to interact with cells. In chapter 2, it is argued that fabricating fibrous nanostructures with defined mechanical properties and decoration with bioactive molecules is not sufficient to create a material that can effectively communicate with cells. By systemically placing the fibronectin-derived RGDS epitope at increasing distances from the surface of PA nanofibers through a linker of one to five glycine residues, integrin-mediated RGDS signaling was enhanced. The results suggested that the spatial presentation of an epitope on PA nanofibers strongly influences the bioactivity of the PA substrates. In further improving functionality of a PA-based scaffold to effectively direct cell growth and differentiation, chapter 3 explored the use of a cell microcarrier to compartmentalize and simultaneously tune insoluble and soluble signals in a single matrix. PA nanofibers were incorporated at the surface of the microcarrier in order to promote cell adhesion, while

  11. Surfactant-Amino Acid and Surfactant-Surfactant Interactions in Aqueous Medium: a Review. (United States)

    Malik, Nisar Ahmad


    An overview of surfactant-amino acid interactions mainly in aqueous medium has been discussed. Main emphasis has been on the solution thermodynamics and solute-solvent interactions. Almost all available data on the topic has been presented in a lucid and simple way. Conventional surfactants have been discussed as amphiphiles forming micelles and amino acids as additives and their effect on the various physicochemical properties of these conventional surfactants. Surfactant-surfactant interactions in aqueous medium, various mixed surfactant models, are also highlighted to assess their interactions in aqueous medium. Finally, their applied part has been taken into consideration to interpret their possible uses.

  12. How To Tackle the Issues in Free Energy Simulations of Long Amphiphiles Interacting with Lipid Membranes: Convergence and Local Membrane Deformations

    DEFF Research Database (Denmark)

    Filipe, H. A. L.; Moreno, M. J.; Rog, T.;


    One of the great challenges in membrane biophysics is to find a means to foster the transport of drugs across complex membrane structures. In this spirit, we elucidate methodological challenges associated with free energy computations of complex chainlike molecules across lipid membranes....... As an appropriate standard molecule to this end, we consider 7-nitrobenz-2-oxa-1,3-diazol-4-yl-labeled fatty amine, NBD-C-n, which is here dealt with as a homologous series with varying chain lengths. We found the membrane-water interface region to be highly sensitive to details in free energy computations. Despite...... of radius 1.7 nm from the amphiphile. Importantly, the free energy results given by PGC were found to be qualitatively consistent with experimental data, while the PGD results were not. We conclude that with long amphiphiles there is reason for concern with regard to computations of their free energy...

  13. Phase behavior of fluorocarbon and hydrocarbon double-chain hydroxylated and galactosylated amphiphiles and bolaamphiphiles. Long-term shelf-stability of their liposomes. (United States)

    Clary, L; Gadras, C; Greiner, J; Rolland, J P; Santaella, C; Vierling, P; Gulik, A


    This paper describes the morphological characterization, by freeze-fracture electron microscopy, and the thermotropic phase behavior, by differential scanning calorimetry and/or X-ray scattering, of aqueous dispersions of various hydroxylated and galactosylated double-chain amphiphiles and bolaamphiphiles, several of them containing one or two hydrophobic fluorocarbon chains. Colloidal systems are observed in water with the hydroxylated hydrocarbon or fluorocarbon bolaamphiphiles only when they are dispersed with a co-amphiphile such as rac-1,2-dimyristoylphosphatidylcholine (DMPC) or rac-1,2-distearoylphosphatidylcholine (DSPC). Liposomes are formed providing the relative content of bolaamphiphiles does not exceed 20% mol. Most of these liposomes can be thermally sterilized and stored at room temperature for several months without any significant modification of their size and size distribution. The hydrocarbon galactosylated bolaamphiphile HO[C24][C12]Gal forms in water a lamellar phase (the gel to liquid-crystal phase transition is complete at 45 degrees C) and a Im3m cubic phase above 47 degrees C. The fluorocarbon HO[C24][F6C5]Gal analog displays a more complex and metastable phase behavior. The fluorinated non-bolaform galactosylated [F8C7][C16]AEGal and SerGal amphiphiles form lamellar phases in water. Low amounts (10% molar ratio) of the HO[C24][F6C5]Gal or HO[C24][C12]Gal bolaamphiphiles or of the single-headed [F8C7][C16]AEGal improve substantially the shelf-stability of reference phospholipon/cholesterol 2/1 liposomes. These liposomes when co-formulated with a single-headed amphiphile from the SerGal series are by far less stable.

  14. Bimodal self-assembly of an amphiphilic gelator into a hydrogel-nanocatalyst and an organogel with different morphologies and photophysical properties. (United States)

    Sutar, Papri; Maji, Tapas Kumar


    We design a flexible, amphiphilic LMWG consisting of donor and acceptor π-chromophores which self-assembles into a hydrogel and an organogel with different nano-morphologies. Different mechanisms of self-assembly evolve charge transfer (CT) emission in the hydrogel and LMWG-based emission in the organogel. Moreover, the hydrogel-nanostructure with surface exposed amide groups is explored for catalyzing Knoevenagel condensation reaction.

  15. An organosilane-directed growth-induced etching strategy for preparing hollow/yolk–shell mesoporous organosilica nanospheres with perpendicular mesochannels and amphiphilic frameworks

    KAUST Repository

    Zou, Houbing


    We have developed an organosilane-directed growth-induced etching strategy to prepare hollow periodic mesoporous organosilica (PMO) nanospheres with perpendicular mesoporous channels and a clear hollow interior as well as an amphiphilic framework. This facile strategy is simple, efficient, and highly controllable. Silica nanospheres were utilized as hard templates to obtain hollow PMO nanospheres through a one-step route, with the structure parameter highly controlled by adjusting the synthesis conditions. Different organosilanes were used to obtain bridged hollow PMO nanospheres of different organic groups and showed different directed capacities. The integrity of the bridged organic group was confirmed by Fourier-transform infrared (FT-IR) spectroscopy and solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Transmission electron microscopy (TEM) observations showed that the growth of the PMO shell and the dissolution of the silica nanosphere core occurred simultaneously for each nanosphere, while 29Si NMR spectra revealed that the dissolved silica species from the silica nanospheres transformed into PMO shells by co-condensation with hydrolyzed organosilane oligomers. As a result, the obtained hollow nanospheres were amphiphilic, which can even be used as a particle emulsifier for O-W or W-O emulsion in various systems. These materials can also be served as an efficient sorbent for removal of hydrophobic contaminants in water. Using the proposed formation mechanism, this strategy can be extended to transform silica-coated composite materials into yolk-shell structures with a functional interior core and a perpendicular mesoporous amphiphilic shell. As a nanoreactor, the -Ph- bridged amphiphilic shell showed a faster diffusion rate for organic reactants in water than the hydrophilic silica shell, and thus better catalytic activity for reduction of 4-nitrophenol. This journal is © the Partner Organisations 2014.

  16. Amino acid-based surfactants – do they deserve more attention? (United States)

    Bordes, Romain; Holmberg, Krister


    The 20 standard amino acids (together with a few more that are not used in the biosynthesis of proteins) constitute a versatile tool box for synthesis of surfactants. Anionic, cationic and zwitterionic amphiphiles can be prepared and surfactants with several functional groups can be obtained by the proper choice of starting amino acid. This review gives examples of procedures used for preparation and discusses important physicochemical properties of the amphiphiles and how these can be taken advantage of for various applications. Micelles with a chiral surface can be obtained by self-assembly of enantiomerically pure surfactants and such supramolecular chirality can be utilized for asymmetric organic synthesis and for preparation of mesoporous materials with chiral pores. Surfactants based on amino acids with two carboxyl groups are effective chelating agents and can be used as collectors in mineral ore flotation. A surfactant based on cysteine readily oxidizes into the corresponding cystine compound, which can be regarded as a gemini surfactant. The facile and reversible cysteine-cystine transformation has been taken advantage of in the design of a switchable surfactant. A very attractive aspect of surfactants based on amino acids is that the polar head-group is entirely natural and that the linkage to the hydrophobic tail, which is often an ester or an amide bond, is easily cleaved. The rate of degradation can be tailored by the structure of the amphiphile. The ester linkage in betaine ester surfactants is particularly susceptible to alkaline hydrolysis and this surfactant type can be used as a biocide with short-lived action. This paper is not intended as a full review on the topic. Instead it highlights concepts that are unique to amino acid-based surfactants and that we believe can have practical implications.

  17. BRCAA1 antibody- and Her2 antibody-conjugated amphiphilic polymer engineered CdSe/ZnS quantum dots for targeted imaging of gastric cancer (United States)

    Li, Chao; Ji, Yang; Wang, Can; Liang, Shujing; Pan, Fei; Zhang, Chunlei; Chen, Feng; Fu, Hualin; Wang, Kan; Cui, Daxiang


    Successful development of safe and highly effective nanoprobes for targeted imaging of in vivo early gastric cancer is a great challenge. Herein, we choose the CdSe/ZnS (core-shell) quantum dots (QDs) as prototypical materials, synthesized one kind of a new amphiphilic polymer including dentate-like alkyl chains and multiple carboxyl groups, and then used the prepared amphiphilic polymer to modify QDs. The resultant amphiphilic polymer engineered QDs (PQDs) were conjugated with BRCAA1 and Her2 monoclonal antibody, and prepared BRCAA1 antibody- and Her2 antibody-conjugated QDs were used for in vitro MGC803 cell labeling and in vivo targeted imaging of gastric cancer cells. Results showed that the PQDs exhibited good water solubility, strong photoluminescence (PL) intensity, and good biocompatibility. BRCAA1 antibody- and Her2 antibody-conjugated QD nanoprobes successfully realized targeted imaging of in vivo gastric cancer MGC803 cells. In conclusion, BRCAA1 antibody- and Her2 antibody-conjugated PQDs have great potential in applications such as single cell labeling and in vivo tracking, and targeted imaging and therapeutic effects' evaluation of in vivo early gastric cancer cells in the near future.

  18. Use of hybrid composite particles prepared using alkoxysilane-functionalized amphiphilic polymer precursors for simultaneous removal of various pollutants from water. (United States)

    Cho, Seulki; Kim, Nahae; Lee, Soonjae; Lee, Hoseok; Lee, Sang-Hyup; Kim, Juyoung; Choi, Jae-Woo


    In this study, we present new inorganic-organic hybrid particles and their possible application as an adsorbent for simultaneous removal of hydrophobic and hydrophilic pollutants from water. These hybrid particles were prepared using tailor-made alkoxysilane-functionalized amphiphilic polymer precursors (M-APAS), which have amphiphilic polymers and reactive alkoxysilane groups attached to the same backbone. Through a single conventional sol-gel process, the polymerization of M-APAS and the chemical conjugation of M-APAS onto silica nanoparticles was simultaneous, resulting in the formation of hybrid particles (M-APAS-SiO2) comprised of hyperbranch-like amphiphilic polymers bonded onto silica nanoparticles with a relatively high grafting efficiency. A test for the adsorption of water-soluble dye (organe-16) and water insoluble dye (solvent blue-35) onto the hybrid particles was performed to evaluate the possibility of adsorbing hydrophilic and hydrophobic compound within the same particle. The hybrid particle was also evaluated as an adsorbent for the removal of contaminated water containing various pollutants by wastewater treatment test. The hybrid particle could remove phenolic compounds from wastewater and the azo dye reactive orange-16 from aqueous solutions, and it was easily separated from the treated wastewater because of the different densities involved. These results demonstrate that the hybrid particles are a promising sorbent for hydrophilic and/or hydrophobic pollutants in water.

  19. Effects of solubilization of short and medium-chain molecules in the self-assembly of two amphiphilic drugs in solution

    Energy Technology Data Exchange (ETDEWEB)

    Barbosa, Silvia [Grupo de Fisica de Coloides y Polimeros, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela (Spain)], E-mail:; Cheema, Mohammad Arif; Siddiq, Mohammad [Department of Chemistry, Quaid-i-Azam University of Islamabad, 45320 (Pakistan); Taboada, Pablo [Grupo de Fisica de Coloides y Polimeros, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela (Spain); Mosquera, Victor [Grupo de Fisica de Coloides y Polimeros, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela (Spain)], E-mail:


    The effect of short and medium chain length alcohols ethanol, propanol, and butanol on the thermodynamic properties of aqueous solutions of the ionic amphiphilic antidepressants imipramine and clomipramine hydrochlorides has been investigated at T = 293 K. Critical concentrations of the drugs were obtained from ultrasound velocity measurements. Experimental results have shown a strong dependence of the ultrasound velocity with the alcohol concentration and chain length. Differences in the aggregate properties of both amphiphiles arise from the presence of the extra Cl{sup -} substituent on the ring system of clomipramine. Density and ultrasound measurements have been used to obtain the apparent molar volumes, V{sub {phi}}, and isentropic apparent molar compressibilities, K{sub {phi}}{sub (S)}, for the aqueous drug/water-alcohol solutions. The distribution coefficient of the amount solubilized between water and the aggregates, K, has been determined using an indirect method based on the pseudo-phase model by using apparent molar volume values. This method allows the calculation of the distribution coefficients at concentrations below saturation. The standard molar Gibbs free energy change on transfer from the aqueous to the micellar, {delta}G{sup 0}, phase was calculated from the partition coefficient. The results have highlighted the structural differences between both amphiphiles.

  20. Micellar Surfactant Association in the Presence of a Glucoside-based Amphiphile Detected via High-Throughput Small Angle X-ray Scattering

    Energy Technology Data Exchange (ETDEWEB)

    Stanic, Vesna [Brazilian Synchrotron Light Source, Campinas (Brazil); Broadbent, Charlotte [Columbia Univ., New York, NY (United States). Engineering Dept.; DiMasi, Elaine [Brookhaven National Lab. (BNL), Upton, NY (United States). Photon Sciences Division; Galleguillos, Ramiro [Lubrizol Advanced Materials, Cleveland, OH (United States); Woodward, Valerie [Lubrizol Advanced Materials, Cleveland, OH (United States)


    The interactions of mixtures of anionic and amphoteric surfactants with sugar amphiphiles were studied via high throughput small angle x-ray scattering (SAXS). The sugar amphiphile was composed of Caprate, Caprylate, and Oleate mixed ester of methyl glucoside, MeGCCO. Optimal surfactant interactions are sought which have desirable physical properties, which must be identified in a cost effective manner that can access the large phase space of possible molecular combinations. X-ray scattering patterns obtained via high throughput SAXS can probe a combinatorial sample space and reveal the incorporation of MeGCCO into the micelles and the molecular associations between surfactant molecules. Such data make it possible to efficiently assess the effects of the new amphiphiles in the formulation. A specific finding of this study is that formulations containing comparatively monodisperse and homogeneous surfactant mixtures can be reliably tuned by addition of NaCl, which swells the surfactant micelles with a monotonic dependence on salt concentration. In contrast, the presence of multiple different surfactants destroys clear correlations with NaCl concentration, even in otherwise similar series of formulations.

  1. J-Aggregates of Amphiphilic Cyanine Dyes for Dye-Sensitized Solar Cells: A Combination between Computational Chemistry and Experimental Device Physics

    Directory of Open Access Journals (Sweden)

    M. S. A. Abdel-Mottaleb


    Full Text Available We report on the design and structure principles of 5,5′-6,6′-tetrachloro-1,1′-dioctyl-3,3′-bis-(3-carboxypropyl-benzimidacarbocyanine (Dye 1. Such metal-free amphiphilic cyanine dyes have many applications in dye-sensitized solar cells. AFM surface topographic investigation of amphiphilic molecules of Dye 1 adsorbed on TiO2 anode reveals the ability of spontaneous self-organization into highly ordered aggregates of fiber-like structure. These aggregates are known to exhibit outstanding optical properties of J-aggregates, namely, efficient exciton coupling and fast exciton energy migration, which are essential for building up artificial light harvesting to the photovoltaic device. A light-to-electricity conversion efficiency of DSSC based on the metal free amphiphilic Dye 1 is η=3.75, which is about 50% of that based on metal-based N719 Ru-dye (Di-tetrabutylammoniumcis-bis(isothiocyanatobis(2,2′-bipyridyl-4,4′-dicarboxylatoruthenium(II. DFT and TD-DFT studies show that large intramolecular charge transfer takes place from the HOMO to LUMO. HOMO is localized on a part of the molecule with almost no contribution from the carboxylic moiety. This clearly indicates that the anchoring carboxylic group plays a minor role.

  2. Biodegradation of flax fiber reinforced poly lactic acid

    Directory of Open Access Journals (Sweden)


    Full Text Available Woven and nonwoven flax fiber reinforced poly lactic acid (PLA biocomposites were prepared with amphiphilic additives as accelerator for biodegradation. The prepared composites were buried in farmland soil for biodegradability studies. Loss in weight of the biodegraded composite samples was determined at different time intervals. The surface morphology of the biodegraded composites was studied with scanning electron microscope (SEM. Results indicated that in presence of mandelic acid, the composites showed accelerated biodegradation with 20–25% loss in weight after 50–60 days. On the other hand, in presence of dicumyl peroxide (as additive, biodegradation of the composites was relatively slow as confirmed by only 5–10% loss in weight even after 80–90 days. This was further confirmed by surface morphology of the biodegraded composites. We have attempted to show that depending on the end uses, we can add different amphiphilic additives for delayed or accelerated biodegradability. This work gives us the idea of biodegradation of materials from natural fiber reinforced PLA composites when discarded carelessly in the environment instead of proper waste disposal site.

  3. Self-assembled micelles of amphiphilic poly(L-phenylalanine-b-poly(L-serine polypeptides for tumor-targeted delivery

    Directory of Open Access Journals (Sweden)

    Zhao ZM


    Full Text Available Ziming Zhao,1,2,* Yu Wang,1,2,* Jin Han,1,2 Keli Wang,1 Dan Yang,1,2 Yihua Yang,1,2 Qian Du,1,2 Yuanjian Song,3 Xiaoxing Yin1,2 1Department of Pharmacy, 2Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, 3Department of Basic Medical Sciences, Xuzhou Medical College, Xuzhou, People’s Republic of China *These authors contributed equally to this work Abstract: The aim of this work was to design, synthesize, and characterize self-assembled micelles based on polypeptides as a potential antitumor drug carrier. Amphiphilic poly(L-phenylalanine-b-poly(L-serine (PFS polypeptides were obtained through the polymerization of N-carboxyanhydride. As a novel hydrophilic segment, poly(L-serine was utilized to enhance tumor targeting due to a large demand of tumors for serine. PFS could self-assemble into micelles with an average diameter of 110–240 nm and a slightly negative charge. PFS polypeptides adopted random coil in pH 7.4 phosphate-buffered saline and could partly transform to a-helix induced by trifluoroethanol. PFS micelles with a low critical micelle concentration of 4.0 µg mL-1 were stable in pH 5–9 buffers and serum albumin solution. PFS micelles had a loading capacity of 3.8% for coumarin-6 and exhibited a sustained drug release. Coumarin-6 loaded rhodamine B isothiocyanate-labeled PFS micelles were incubated with Huh-7 tumor cells to study the correlation between drugs and carriers during endocytosis. The uptake of drugs was consistent with the micelles, illustrating that the intracellular transport of drugs highly depended on the micelles. PFS micelles diffused in whole cytoplasm while coumarin-6 assumed localized distribution, suggesting that the micelles could release the loaded drugs in particular areas. The internalization mechanism of PFS micelles was involved with clathrin-mediated endocytosis and macropinocytosis. Excess serine inhibited the uptake of PFS micelles, which demonstrated that serine receptors played

  4. Amphiphilic dendritic derivatives as nanocarriers for the targeted delivery of antimalarial drugs


    Movellan, Julie; Urbán, Patricia; Moles, Ernest; de la Fuente, Jesús M.; Sierra, Teresa; Serrano, José Luis; Fernàndez-Busquets, Xavier


    It can be foreseen that in a future scenario of malaria eradication, a varied armamentarium will be required, including strategies for the targeted administration of antimalarial compounds. The development of nanovectors capable of encapsulating drugs and of delivering them to Plasmodium-infected cells with high specificity and efficacy and at an affordable cost is of particular interest. With this objective, dendritic derivatives based on 2,2-bis(hydroxymethyl)propionic acid (bis-MPA) and Pl...

  5. Induced liquid-crystalline ordering in solutions of stiff and flexible amphiphilic macromolecules: Effect of mixture composition. (United States)

    Glagolev, Mikhail K; Vasilevskaya, Valentina V; Khokhlov, Alexei R


    Impact of mixture composition on self-organization in concentrated solutions of stiff helical and flexible macromolecules was studied by means of molecular dynamics simulation. The macromolecules were composed of identical amphiphilic monomer units but a fraction f of macromolecules had stiff helical backbones and the remaining chains were flexible. In poor solvents the compacted flexible macromolecules coexist with bundles or filament clusters from few intertwined stiff helical macromolecules. The increase of relative content f of helical macromolecules leads to increase of the length of helical clusters, to alignment of clusters with each other, and then to liquid-crystalline-like ordering along a single direction. The formation of filament clusters causes segregation of helical and flexible macromolecules and the alignment of the filaments induces effective liquid-like ordering of flexible macromolecules. A visual analysis and calculation of order parameter relaying the anisotropy of diffraction allow concluding that transition from disordered to liquid-crystalline state proceeds sharply at relatively low content of stiff components.

  6. Magnetic core–bilayer shell complex of magnetite nanoparticle stabilized with mPEG–polyester amphiphilic block copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Mekkapat, Supachai; Thong-On, Bandit; Rutnakornpituk, Boonjira; Wichai, Uthai; Rutnakornpituk, Metha, E-mail: [Naresuan University, Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science (Thailand)


    In this article, we report the synthesis of magnetite nanoparticles (Fe{sub 3}O{sub 4}) coated with methoxy poly(ethylene glycol) (mPEG)–polyester amphiphilic block copolymers. The coating polymer layer contains a hydrophobic inner layer of polyester and a hydrophilic corona of mPEG. The copolymers were first prepared via a direct condensation between diacid, diol compounds and mPEG oligomer to obtain a hydrophobic polyester block and hydrophilic mPEG block and then “grafted onto” a magnetite nanoparticle surface. The copolymer composition was varied by changing the structure of the diacid, diol, and the molecular weight ( M-bar {sub n} ) of the mPEG such that particles with good dispersibility and stability in water were obtained. It was found that the copolymer prepared from 1,6-hexanediol can effectively stabilize the particles in water regardless of the types of diacid and M-bar {sub n} of mPEG used. The particle size was approximately 10 nm in diameter, and the particle dispersibility in water was quite dependent on the type and concentration of the copolymer used. Thermogravimetric analysis revealed the presence of less than 37 % Fe{sub 3}O{sub 4} and about 48–53 % of the copolymer in the complexes. The percent entrapment efficiency and loading efficiency of indomethacin model drug in the copolymer-coated magnetite nanoparticles were 19 and 77 %, respectively.

  7. Amphiphilic graft copolymer based on poly(styrene-co-maleic anhydride with low molecular weight polyethylenimine for efficient gene delivery

    Directory of Open Access Journals (Sweden)

    Duan XP


    Full Text Available Xiaopin Duan,1,2 Jisheng Xiao,2 Qi Yin,2 Zhiwen Zhang,2 Shirui Mao,1 Yaping Li21School of Pharmacy, Shenyang Pharmaceutical University, Shenyang, 2Center of Pharmaceutics, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai, ChinaBackground and methods: A new amphiphilic comb-shaped copolymer (SP was synthesized by conjugating poly(styrene-co-maleic anhydride with low molecular weight polyethyleneimine for gene delivery. Fourier transform infrared spectrum, 1H nuclear magnetic resonance, and gel permeation chromatography were used to characterize the graft copolymer.Results: The buffering capability of SP was similar to that of polyethyleneimine within the endosomal pH range. The copolymer could condense DNA effectively to form complexes with a positive charge (13–30 mV and a small particle size (130–200 nm at N/P ratios between 5 and 20, and protect DNA from degradation by DNase I. In addition, SP showed much lower cytotoxicity than polyethyleneimine 25,000. Importantly, the gene transfection activity and cellular uptake of SP-DNA complexes were all markedly higher than that of complexes of polyethyleneimine 25,000 and DNA in MCF-7 and MCF-7/ADR cell lines.Conclusion: This work highlights the promise of SP as a safe and efficient synthetic vector for DNA delivery.Keywords: poly(styrene-co-maleic anhydride, polyethylenimine, DNA, gene delivery

  8. Controlling the thermodynamic stability of intermediate phases in a cationic-amphiphile-water system with strongly binding counterions. (United States)

    Gupta, Santosh Prasad; Raghunathan, V A


    We have studied the influence of two structurally isomeric organic salts, namely, 2-sodium-3-hydroxy naphthoate (SHN) and 1-sodium-2-hydroxy naphthoate (SHN1), on the phase behavior of concentrated aqueous solutions of the cationic surfactant cetylpyridinium chloride (CPC). Partial phase diagrams of the two systems have been constructed using polarizing optical microscopy and x-ray diffraction techniques. A variety of intermediate phases is seen in both systems for a range of salt concentrations. The CPC-SHN-water system exhibits the rhombohedral and tetragonal mesh phases in addition to the random mesh phase, whereas the CPC-SHN1-water system shows only the tetragonal and random mesh phases. The CPC-SHN-water system also exhibits two nematic phases consisting of cylindrical and disk-like micelles at relatively low and high salt concentrations, respectively. These results show that the concentration of the strongly bound counterion provided by the organic salt can be used as a control parameter to tune the stability of different intermediate phases in amphiphile-water systems.

  9. Tunable Nanocarrier Morphologies from Glycopolypeptide-based Amphiphilic Biocompatible Star Copolymers and Their Carbohydrate Specific Intracellular Delivery

    KAUST Repository

    Pati, Debasis


    Nano-carriers with carbohydrates on the surface represent a very interesting class of drug delivery vehicles since carbohydrates are involved in bio-molecular recognition events in vivo. We have synthesized biocompatible miktoarm star copolymers comprising glycopolypeptide and poly(ε-caprolactone) chains, using ring opening polymerization and ‘click chemistry’. The amphiphilic copolymers were self-assembled in water into morphologies such as nanorods, polymersomes and micelles with carbohydrates displayed on the surface. We demonstrate that, the formation of nanostructure could be tuned by chain length of the blocks and was not affected by the type of sugar residue. These nanostructures were characterized in detail using a variety of techniques such as TEM, AFM, cryogenic electron microscopy, spectrally resolved fluorescence imaging and dye encapsulation techniques. We show that it is possible to sequester both hydrophobic as well as hydrophilic dyes within the nanostructures. Finally, we show that these non-cytotoxic manno-sylated rods and polymersomes were selectively and efficiently taken up by MDA-MB-231 breast cancer cells demonstrating their potential as nanocarriers for drug delivery.

  10. Two-dimensional growth of crystalline nanofiber fabricated from Gemini-type amphiphilic diamide derivative inducing the thixotropic property. (United States)

    Iizuka, Manami; Nakagawa, Yuto; Ohmura, Kyohei; Satou, Eiichi; Fujimori, Atsuhiro


    The formation of a nanofiber morphology at the mesoscopic scale and the molecular-level packing of a gemini-type amphiphilic diamide derivative with two hydrocarbons were investigated from two perspectives. First, it was confirmed that a diamide derivative with two hydrocarbons forms crystalline nanofibers even in a monomolecular layer. The height, thickness, and lattice spacing of the two-dimensional orthorhombic system of this crystalline nanofiber in the monolayer of a diamide derivative with two hydrocarbons are 5, 30, and 0.4nm, respectively. Next, it was determined that the fibrous growth of the diamide derivative with two hydrocarbons, which contributes to the thixotropic ability, can be achieved by the addition of a quaternary ammonium cation with long chains, modified with montmorillonite. Here, the interlayer spacing was about 3.8nm for the organo-modified montmorillonite and was consistent with the layer spacing of the diamide derivative having two hydrocarbons. The surface pressure-area isotherms of the mixed monolayers suggest that there is miscibility between these materials. From "the affinity due to the van der Waals interaction between the terminal groups of the alkyl chains" and the "similarity of layer spacing," epitaxial growth is expected.

  11. Effect of inorganic salts on the clouding behavior of hydroxypropyl methyl cellulose in presence of amphiphilic drugs. (United States)

    Khan, Iqrar Ahmad; Anjum, Kahkashan; Koya, P Ajmal; Kabir-Ud-Din


    In this paper we report the effect of two cationic (imipramine hydrochloride (IMP) and promazine hydrochloride (PMZ)) and one anionic (sodium salt of ibuprofen (IBF)) drugs on the clouding behavior of a nonionic polymer hydroxypropyl methyl cellulose (HPMC). Though all the three drugs increase the cloud point (CP) of HPMC, the effect was found to be minimum in the case of IBF. Further, the effect of adding salts (NaF, NaCl, NaBr, NaNO(3), Na(2)SO(4), Na(3)PO(4), KCl, KBr, KNO(3)) in the presence of amphiphilic drugs (IMP and PMZ) on the CP of HPMC was seen. Almost linear decrease in the CP was observed with the [salt] at fixed concentrations of these drugs whereas in the absence of drugs the decrement in the CP was slight. The energetic parameters (ΔG(c)(0), ΔH(c)(0) and TΔS(c)(0)) were evaluated and it implies that the disruption of water structure becomes significantly prominent at lower concentrations of the drugs at fixed salt concentrations.

  12. DNA association-enhanced physical stability of catanionic vesicles composed of ion pair amphiphile with double-chain cationic surfactant. (United States)

    Lee, Jung; Chang, Chien-Hsiang


    Physical stability control of vesicle/DNA complexes is a key issue for the development of catanionic vesicles composed of ion pair amphiphile (IPA) as DNA carriers. In this work, physical stability characteristics of the complexes of DNA with positively charged catanionic vesicles composed of an IPA and a double-chain cationic surfactant, dihexadecyldimethylammonium bromide (DHDAB), were explored. It was found that in water, the mixed IPA/DHDAB catanionic vesicles became stable when the mole fraction of DHDAB (xDHDAB) was increased up to 0.5. The improved physical stability of the vesicles with a high xDHDAB could be related to the enhanced electrostatic interaction between the vesicles. When the catanionic vesicles interacted with DNA, excellent physical stability was detected for the vesicle/DNA complexes especially with a high xDHDAB. However, this could not be fully explained by the electrostatic interaction effect, and the role of molecular packing within the vesicular bilayers was apparently important. The corresponding Langmuir monolayer study demonstrated that the molecular packing of mixed IPA/DHDAB layers became ordered with DNA association due to inhibited desorption of the positively charged moiety of the IPA. Moreover, the DNA association-induced improvement in the molecular packing of the mixed IPA/DHDAB layers became pronounced with increased xDHDAB. The results imply that one can fabricate catanionic vesicle/DNA complexes with excellent physical stability through the improved molecular packing in the IPA vesicular bilayers with DHDAB addition and DNA association.

  13. Self-assembled nanostructures of amphiphilic zinc(II) salophen complexes: role of the solvent on their structure and morphology. (United States)

    Oliveri, Ivan Pietro; Malandrino, Graziella; Di Bella, Santo


    This contribution explores the effect of several solvent properties, such as volatility, polarity, and Lewis basicity on the formation of molecular self-assembled nanostructures in the solid state, obtained either by casting of related solutions or by complete solvent evaporation, using seven solvents representative of common classes of coordinating organic solvents, of an amphiphilic Zn(II) Schiff-base complex. In all cases, the existence of well-defined X-ray diffraction patterns, for both the cast and powder samples, indicates a strong tendency towards the molecular self-assembly of such complexes. While nanostructures formed in acetone, THF, pyridine, and DMF have a lamellar organization, those formed in ACN, ethanol, and DMSO exhibit a 2D columnar square structure. Field emission scanning electron microscopy analysis indicates that nanostructures formed in volatile acetone, THF, ACN, and ethanol solvents show a fibrous morphology, while those formed in less volatile pyridine, DMF, and DMSO have a ribbon appearance. Overall, the results indicate that while the formation of such nanostructures is independent of the Lewis basicity of the solvent, the solvent polarity affects their structure - more polar solvents favour higher symmetry structures - and the solvent volatility influences their morphology and ordering in the cast films - lower volatility of the solvent parallels the formation of much more ordered structures. Therefore, the appropriate choice of solvent allows control of the structure, morphology, and ordering of these molecular assemblies.

  14. Real-Time Monitoring of Chemical and Topological Rearrangements in Solidifying Amphiphilic Polymer Co-Networks: Understanding Surface Demixing. (United States)

    Guzman, Gustavo; Nugay, Turgut; Kennedy, Joseph P; Cakmak, Mukerrem


    Amphiphilic polymer co-networks provide a unique route to integrating contrasting attributes of otherwise immiscible components within a bicontinuous percolating morphology and are anticipated to be valuable for applications such as biocatalysis, sensing of metabolites, and dual dialysis membranes. These co-networks are in essence chemically forced blends and have been shown to selectively phase-separate at surfaces during film formation. Here, we demonstrate that surface demixing at the air-film interface in solidifying polymer co-networks is not a unidirectional process; instead, a combination of kinetic and thermodynamic interactions leads to dynamic molecular rearrangement during solidification. Time-resolved gravimetry, low contact angles, and negative out-of-plane birefringence provided strong experimental evidence of the transitory trapping of thermodynamically unfavorable hydrophilic moieties at the air-film interface due to fast asymmetric solvent depletion. We also find that slow-drying hydrophobic elements progressively substitute hydrophilic domains at the surface as the surface energy is minimized. These findings are broadly applicable to common-solvent bicontinuous systems and open the door for process-controlled performance improvements in diverse applications. Similar observations could potentially be coupled with controlled polymerization rates to maximize the intermingling of bicontinuous phases at surfaces, thus generating true three-dimensional, bicontinuous, and undisturbed percolation pathways throughout the material.

  15. Nucleation, growth, and dissolution of Ag nanostructures formed in nanotubular J-aggregates of amphiphilic cyanine dyes

    CERN Document Server

    Polzer, Egon Steeg Frank; Qiao, Yan; Rabe, Jürgen P; Kirstein, Stefan


    The nucleation, growth, and dissolution of silver nanowires within tubular aggregates of the dye C8S3 are investigated. The tubular aggregates are formed in aqueous solution from amphiphilic dyes and the silver wires are grown from silver salt. Samples were investigated systematically and in detail using cryo-TEM and TEM at different time steps after addition of silver salt (AgNO3) and short illumination with blue light (420 nm) for production of nuclei. The enhanced concentration of silver ions in proximity of the aggregates surface leads to favoured growth of seeds at or within the aggregates. The early stage of the seed growth is observable by cryo-TEM and shows to be well separated and isolated. There are no indications that nuclei are formed at preferred defect sites at the aggregates which is interpreted as homogeneous nucleation. The spatial position of the majority of initially formed seeds discriminates between growth of particles at the outer surface of the aggregate or wires at the inner space. The...

  16. Syntheses of amphiphilic biodegradable copolymers of poly(ethyl ethylene phosphate) and poly(3-hydroxybutyrate) for drug delivery

    Institute of Scientific and Technical Information of China (English)


    Biodegradable and amphiphilic triblock copolymers poly(ethyl ethylene phosphate)-poly(3-hydroxybutyrate)-poly(ethyl ethylene phosphate) (PEEP-b-PHB-b-PEEP) have been successfully synthesized through ring-opening polymerization. The structures are confirmed by gel permeation chromatography and NMR analyses. Crystallization investigated by X-ray diffraction reveals that the block copolymer with higher content of poly(ethyl ethylene phosphate) (PEEP) is more amorphous, showing decreased crystallizability. The obtained copolymers self-assemble into biodegradable nanoparticles with a coreshell micellar structure in aqueous solution, verified by the probe-based fluorescence measurements and transmission electronic microscopy (TEM) observation. The hydrophobic poly(3-hydroxybutyrate) (PHB) block serves as the core of the micelles and the micelles are stabilized by the hydrophilic PEEP block. The size and size distribution are related to the compositions of the copolymers. Paclitaxel (PTX) has been encapsulated into the micelles as a model drug and a sustained drug release from the micelles is observed. MTT assay also demonstrates that the block copolymers are biocompatible, rendering these copolymers attractive for drug delivery.

  17. Protein Modification with Amphiphilic Block Copoly(2-oxazoline)s as a New Platform for Enhanced Cellular Delivery

    KAUST Repository

    Tong, Jing


    Several homopolymers, random copolymers and block copolymers based on poly(2-oxazoline)s (POx) were synthesized and conjugated to horseradish peroxidase (HRP) using biodegradable and nonbiodegradable linkers. These conjugates were characterized by amino group titration, polyacrylamide gel electrophoresis (PAGE), isoelectric focusing, enzymatic activity assay and conformation analysis. The conjugates contained on average from about one to two polymer chains per enzyme. From 70% to 90% of enzymatic activity was retained in most cases. Circular dichroism (CD) analysis revealed that HRP modification affected the secondary structure of the apoprotein but did not affect the tertiary structure and heme environment. Enhanced cellular uptake was found in the conjugates of two block copolymers using both MDCK cells and Caco-2 cells, but not in the conjugates of random copolymer and homopolymer. Conjugation with a block copolymer of 2-methyl-2-oxazoline and 2-butyl-2-oxazoline led to the highest cellular uptake as compared to other conjugates. Our data indicates that modification with amphiphilic POx has the potential to modulate and enhance cellular delivery of proteins.

  18. Aggregation behavior of amphiphilic p(HPMA)-co-p(LMA) copolymers studied by FCS and EPR spectroscopy. (United States)

    Hemmelmann, Mirjam; Kurzbach, Dennis; Koynov, Kaloian; Hinderberger, Dariush; Zentel, Rudolf


    A combined study of fluorescence correlation spectroscopy and electron paramagnetic resonance spectroscopy gave a unique picture of p(HPMA)-co-p(LMA) copolymers in aqueous solutions, ranging from the size of micelles and aggregates to the composition of the interior of these self-assembled systems. P(HPMA)-co-p(LMA) copolymers have shown high potential as brain drug delivery systems, and a detailed study of their physicochemical properties can help to elucidate their mechanism of action. Applying two complementary techniques, we found that the self-assembly behavior as well as the strength of hydrophobic attraction of the amphiphilic copolymers can be tuned by the hydrophobic LMA content or the presence of hydrophobic molecules or domains. Studies on the dependence of the hydrophobic lauryl side chain content on the aggregation behavior revealed that above 5 mol % laury side-chain copolymers self-assemble into intrachain micelles and larger aggregates. Above this critical alkyl chain content, p(HPMA)-co-p(LMA) copolymers can solubilize the model drug domperidone and exhibit the tendency to interact with model cell membranes.

  19. Spatial location of indomethacin associated with unimeric amphiphilic carrier macromolecules as determined by nuclear magnetic resonance spectroscopy. (United States)

    Orban, David E; Moretti, Alysha; Uhrich, Kathryn E


    A combination of nuclear magnetic resonance (NMR) techniques including, proton NMR, relaxation analysis, two-dimensional nuclear Overhauser effect spectroscopy, and diffusion-ordered spectroscopy, has been used to demonstrate the spatial location of indomethacin within a unimolecular micelle. Understanding the location of drugs within carrier molecules using such NMR techniques can facilitate rational carrier design. In addition, this information provides insight to encapsulation efficiency of different drugs to determine the most efficient system for a particular bioactive. This study demonstrates that drugs loaded by the unimolecular amphiphile under investigation are not necessarily encapsulated but reside or localize to the periphery or interfacial region of the carrier molecule. The results have further implications as to the features of the unimolecular carrier that contribute to drug loading. In addition, evidence of drug retention associated with the unimolecular surfactant is possible in organic media, as well as in an aqueous environment. Such findings have implications for rational carrier design to correlate the carrier features to the drug of interest and indicate the strong retention capabilities of the unimolecular micelle for delivery applications. Copyright © 2016 John Wiley & Sons, Ltd.

  20. A 'Plug and Play' Method to Create Water-dispersible Nanoassemblies Containing an Amphiphilic Polymer, Organic Dyes and Upconverting Nanoparticles. (United States)

    Arafeh, Khaled M; Asadirad, Amir M; Li, Jason Woodson; Wilson, Danielle; Wu, Tuoqi; Branda, Neil R


    In this protocol, we first describe a procedure to synthesize lanthanide doped upconverting nanoparticles (UCNPs). We then demonstrate how to generate amphiphilic polymers in situ, and describe a protocol to encapsulate the prepared UCNPs and different organic dye molecules (porphyrins and diarylethenes) using polymer shells to form stable water-dispersible nanoassemblies. The nanoassembly samples containing both the UCNPs and the diarylethene organic dyes have interesting photochemical and photophysical properties. Upon 365 nm UV irradiation, the diarylethene group undergoes a visual color change. When the samples are irradiated with visible light of another specific wavelength, the color fades and the samples return to the initial colorless state. The samples also emit visible light from the UCNPs upon irradiation with 980 nm near-infrared light. The emission intensity of the samples can be tuned through alternate irradiation with UV and visible light. Modulation of fluorescence can be performed for many cycles without observable degradation of the samples. This versatile encapsulation procedure allows for the transfer of hydrophobic molecules and nanoparticles from an organic solvent to an aqueous medium. The polymer helps to maintain a lipid-like microenvironment for the organic molecules to aid in preservation of their photochemical behavior in water. Thus this method is ideal to prepare water-dispersible photoresponsive systems. The use of near-infrared light to activate upconverting nanoparticles allows for lower energy light to be used to activate photoreactions instead of more harmful ultraviolet light.