WorldWideScience

Sample records for chiral supramolecular assembly

  1. Supramolecular chirality in self-assembled peptide amphiphile nanostructures.

    Science.gov (United States)

    Garifullin, Ruslan; Guler, Mustafa O

    2015-08-11

    Induced supramolecular chirality was investigated in the self-assembled peptide amphiphile (PA) nanosystems. Having shown that peptide chirality can be transferred to the covalently-attached achiral pyrene moiety upon PA self-assembly, the chiral information is transferred to molecular pyrene via weak noncovalent interactions. In the first design of a supramolecular chiral system, the chromophore was covalently attached to a peptide sequence (VVAGH) via an ε-aminohexanoic acid spacer. Covalent attachment yielded a PA molecule self-assembling into nanofibers. In the second design, the chromophore was encapsulated within the hydrophobic core of self-assembled nanofibers of another PA consisting of the same peptide sequence attached to lauric acid. We observed that supramolecular chirality was induced in the chromophore by PA assembly into chiral nanostructures, whether it was covalently attached, or noncovalently bound. PMID:26146021

  2. Generation of Supramolecular Chirality around Twofold Rotational or Helical Axes in Crystalline Assemblies of Achiral Components

    Directory of Open Access Journals (Sweden)

    Mikiji Miyata

    2015-10-01

    Full Text Available A multi-point approximation method clarifies supramolecular chirality of twofold rotational or helical assemblies as well as bundles of the one-dimensional (1D assemblies. While one-point approximation of materials claims no chirality generation of such assemblies, multi-point approximations do claim possible generation in the 1D assemblies of bars and plates. Such chirality derives from deformations toward three-axial directions around the helical axes. The chiral columns are bundled in chiral ways through symmetry operations. The preferable right- or left-handed columns are bundled together to yield chiral crystals with right- or left-handedness, respectively, indicating that twofold helix symmetry operations cause chiral crystals composed of achiral components via a three-stepwise and three-directional process.

  3. Supramolecular chiral host-guest nanoarchitecture induced by the selective assembly of barbituric acid derivative enantiomers

    Science.gov (United States)

    Sun, Xiaonan; Silly, Fabien; Maurel, Francois; Dong, Changzhi

    2016-10-01

    Barbituric acid derivatives are prochiral molecules, i.e. they are chiral upon adsorption on surfaces. Scanning tunneling microscopy reveals that barbituric acid derivatives self-assemble into a chiral guest-host supramolecular architecture at the solid-liquid interface on graphite. The host nanoarchitecture has a sophisticated wavy shape pattern and paired guest molecules are nested insides the cavities of the host structure. Each unit cell of the host structure is composed of both enantiomers with a ratio of 1:1. Furthermore, the wavy patterns of the nanoarchitecture are formed from alternative appearance of left- and right-handed chiral building blocks, which makes the network heterochiral. The functional guest-host nanoarchitecture is the result of two-dimensional chiral amplification from single enantiomers to organizational heterochiral supramolecular self-assembly.

  4. Self-assembled fibrillar networks of a multifaceted chiral squaramide: supramolecular multistimuli-responsive alcogels.

    Science.gov (United States)

    Schiller, Jana; Alegre-Requena, Juan V; Marqués-López, Eugenia; Herrera, Raquel P; Casanovas, Jordi; Alemán, Carlos; Díaz Díaz, David

    2016-05-11

    Chiral N,N'-disubstituted squaramide has been found to undergo self-assembly in a variety of alcoholic solvents at low concentrations leading to the formation of novel nanostructured supramolecular alcogels. The gels responded to thermal, mechanical, optical and chemical stimuli. Solubility studies, gelation ability tests and computer modeling of a series of structurally related squaramides proved the existence of a unique combination of non-covalent molecular interactions and favorable hydrophobic/hydrophilic balance in that drive the anisotropic growth of alcogel networks. The results have also revealed a remarkable effect of ultrasound on both the gelation kinetics and the properties of the alcogels. PMID:27087352

  5. Solvent-polarity-tuned morphology and inversion of supramolecular chirality in a self-assembled pyridylpyrazole-linked glutamide derivative: nanofibers, nanotwists, nanotubes, and microtubes.

    Science.gov (United States)

    Jin, Qingxian; Zhang, Li; Liu, Minghua

    2013-07-01

    The self-assembly of a low-molecular-weight organogelator into various hierarchical structures has been achieved for a pyridylpyrazole linked L-glutamide amphiphile in different solvents. Upon gel formation, supramolecular chirality was observed, which exhibited an obvious dependence on the polarity of the solvent. Positive supramolecular chirality was obtained in nonpolar solvents, whereas it was inverted into negative supramolecular chirality in polar solvents. Moreover, the gelator molecules self-assembled into a diverse array of nanostructures over a wide scale range, from nanofibers to nanotubes and microtubes, depending on the solvent polarity. Such morphological changes could even occur for the xerogels in the solvent vapors. We found that the interactions between the pyridylpyrazole headgroups and the solvents could subtly change the stacking of the molecules and, hence, their self-assembled nanostructures. This work exemplifies that organic solvents can significantly involve the gelation, as well as tune the structure and properties, of a gel.

  6. A chiral Mn(IV) complex and its supramolecular assembly: Synthesis, characterization and properties

    Indian Academy of Sciences (India)

    Chullikkattil P Pradeep; Panthapally S Zacharias; Samar K Das

    2006-07-01

    The open air reaction of the chiral Schiff base ligand H2L, prepared by the condensation of L-phenylalaninol and 5-bromosalicylaldehyde, with MnII(CH3COO)2$\\cdot$4H2O yielded dark brown complex [MnIVL2]$\\cdot$0.5 DMF (1). Compound 1 was characterized by elemental analysis, IR, UV-visible, CD and EPR spectroscopy, cyclic voltammetry and room temperature magnetic moment determination. Singlecrystal X-ray analysis revealed that compound 1 crystallises in the monoclinic 21 space group with six mononuclear [MnIVL2] units in the asymmetric unit along with three solvent DMF molecules. In the crystal structure, each Mn(IV) complex, acting as the building unit, undergoes supramolecular linking through C-H$\\cdots$O bonds leading to an intricate hydrogen bonding network.

  7. Chapter 8: Selective Stoichiometric and Catalytic Reactivity in the Confines of a Chiral Supramolecular Assembly

    Energy Technology Data Exchange (ETDEWEB)

    University of California, Berkeley; Lawrence Berkeley National Laboratory; Raymond, Kenneth; Pluth, Michael D.; Bergman, Robert G.; Raymond, Kenneth N.

    2007-09-27

    increased complexity of synthetic host molecules, most assembly conditions utilize self-assembly to form complex highly-symmetric structures from relatively simple subunits. For supramolecular assemblies able to encapsulate guest molecules, the chemical environment in each assembly--defined by the size, shape, charge, and functional group availability--greatly influences the guest-binding characteristics.[6, 13-17

  8. Inversion of Supramolecular Chirality by Sonication-Induced Organogelation

    Science.gov (United States)

    Maity, Sibaprasad; Das, Priyadip; Reches, Meital

    2015-11-01

    Natural helical structures have inspired the formation of well-ordered peptide-based chiral nanostructures in vitro. These structures have drawn much attention owing to their diverse applications in the area of asymmetric catalysts, chiral photonic materials, and nanoplasmonics. The self-assembly of two enantiomeric fluorinated aromatic dipeptides into ordered chiral fibrillar nanostructures upon sonication is described. These fibrils form organogels. Our results clearly indicate that fluorine-fluorine interactions play an important role in self-assembly. Circular dichroism analysis revealed that both peptides (peptides 1 and 2), containing two fluorines, depicted opposite cotton effects in their monomeric form compared with their aggregated form. This shows that supramolecular chirality inversion took place during the stimuli-responsive self-aggregation process. Conversely, peptide 3, containing one fluorine, did not exhibit chirality inversion in sonication-induced organogelation. Therefore, our results clearly indicate that fluorination plays an important role in the organogelation process of these aromatic dipeptides. Our findings may have broad implications regarding the design of chiral nanostructures for possible applications such as chiroptical switches, asymmetric catalysis, and chiral recognitions.

  9. Self-assembly mechanism of 1,3:2,4-di(3,4-dichlorobenzylidene)-D-sorbitol and control of the supramolecular chirality.

    Science.gov (United States)

    Li, Jingjing; Fan, Kaiqi; Guan, Xidong; Yu, Yingzhe; Song, Jian

    2014-11-11

    effective means of realizing in situ tuning of nanostructures and control of the expression of chirality at supramolecular levels.

  10. Intelligent Chiral Sensing Based on Supramolecular and Interfacial Concepts

    Directory of Open Access Journals (Sweden)

    Hironori Izawa

    2010-07-01

    Full Text Available Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized.

  11. Chiromers: conformation-driven mirror-image supramolecular chirality isomerism identified in a new class of helical rosette nanotubes

    Science.gov (United States)

    Hemraz, Usha D.; El-Bakkari, Mounir; Yamazaki, Takeshi; Cho, Jae-Young; Beingessner, Rachel L.; Fenniri, Hicham

    2014-07-01

    Rosette nanotubes are biologically inspired nanostructures, formed through the hierarchical organization of a hybrid DNA base analogue (G∧C), which features hydrogen-bonding arrays of guanine and cytosine. Several twin-G∧C motifs functionalized with chiral moieties, which undergo a self-assembly process under methanolic and aqueous conditions to produce helical rosette nanotubes (RNTs), were synthesized and characterized. The built-in molecular chirality in the twin-G∧C building blocks led to the supramolecular chirality exhibited by the RNTs, as evidenced by the CD activity. Depending on the motifs and environmental conditions, mirror-image supramolecular chirality due to absolute molecular chirality, solvent-induced and structure-dependent supramolecular chirality inversion, and pH-controlled chiroptical switching were observed.Rosette nanotubes are biologically inspired nanostructures, formed through the hierarchical organization of a hybrid DNA base analogue (G∧C), which features hydrogen-bonding arrays of guanine and cytosine. Several twin-G∧C motifs functionalized with chiral moieties, which undergo a self-assembly process under methanolic and aqueous conditions to produce helical rosette nanotubes (RNTs), were synthesized and characterized. The built-in molecular chirality in the twin-G∧C building blocks led to the supramolecular chirality exhibited by the RNTs, as evidenced by the CD activity. Depending on the motifs and environmental conditions, mirror-image supramolecular chirality due to absolute molecular chirality, solvent-induced and structure-dependent supramolecular chirality inversion, and pH-controlled chiroptical switching were observed. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr00340c

  12. Radiolytic syntheses of nanoparticles in supramolecular assemblies.

    Science.gov (United States)

    Chen, Qingde; Shen, Xinghai; Gao, Hongcheng

    2010-08-11

    Ionizing radiation is a powerful method in the syntheses of nanoparticles (NPs). The application of ionizing radiation in supramolecular assemblies can afford us more unique conditions to control the composition and morphology of the NPs. So far, most work focused on water-in-oil (W/O) microemulsions or reversed micelles. In this supramolecular organization, it has been proved that the effects of many conditions on the yield of e(aq)(-) play a key role, remarkably different from the mechanism in routine chemical method. Besides, some supramolecular assemblies of cyclodextrins and ionic liquids have been used in the syntheses of NPs by ionizing radiation, and many novel and interesting phenomena appeared. This review is intended to underline the three significant aspects of the radiolytic syntheses of NPs in supramolecular assemblies. PMID:20653087

  13. Controlled chiral electrochromism of polyoxometalates incorporated in supramolecular complexes.

    Science.gov (United States)

    Zhang, Bin; Guan, Weiming; Zhang, Simin; Li, Bao; Wu, Lixin

    2016-04-01

    A three-component supramolecular system was constructed by combining host-guest recognition and electrostatic interaction for realization of induced circular dichroism of achiral polyanionic clusters in aqueous solution, while the induced chiral heteropoly blue was built and switched off by controlling the redox of the inorganic component via electrochemistry. PMID:27002653

  14. Synergy in supramolecular chemistry

    CERN Document Server

    Nabeshima, Tatsuya

    2014-01-01

    Synergy and Cooperativity in Multi-metal Supramolecular Systems, T. NabeshimaHierarchically Assembled Titanium Helicates, Markus AlbrechtSupramolecular Hosts and Catalysts Formed by Self-assembly of Multinuclear Zinc Complexes in Aqueous Solution, Shin AokiSupramolecular Assemblies Based on Interionic Interactions, H. MaedaSupramolecular Synergy in the Formation and Function of Guanosine Quadruplexes, Jeffery T. DavisOn-Surface Chirality in Porous Self-Assembled Monolayers at Liquid-Solid Interface, Kazukuni Tahar

  15. Supramolecular Sheet Co(Ⅱ) Complex Assembled by Hydrogen Bond

    Institute of Scientific and Technical Information of China (English)

    LIU Gui-lei; LI Hui; SONG Fang; QIN Yong-jie

    2009-01-01

    etwork, and then assembled into a three-dimensional supramolecular architecture through electrostatic and hydrophobic interaction. In the structure, supramolecular sheet was observed, which contains alternative organic and inorganic layers.

  16. TPPS和Gemini表面活性剂的复合膜及其手性的研究%Supramolecular Assembly and Chirality of a Complex Film between Achiral TPPS and a Gemini Surfactant at the Air/water Interface

    Institute of Scientific and Technical Information of China (English)

    张莉; 王金本; 刘鸣华

    2004-01-01

    研究了一种新的gemini表面活性剂(C 12H24-α,ω-(C12H25N+(CH3)2Br-)2,(简写为C12-C12-C12)和TPPS在气液界面上形成的复合膜及其手性.实验发现,单独C12-C12-C12不能在纯水表面形成稳定的单分子膜,但当亚相中存在TPPS时,可形成稳定的单分子膜.通过水平提拉法将复合膜转移到固体基板上,发现在适当的pH值条件下,TPPS可在复合膜中形成J-聚集体,并且发现,尽管Gemini表面活性剂和TPPS都是非手性的,TPPS的J-聚集体表现出强烈的Cotton效应.另外,gemini表面活性剂的两个正电荷中心对TPPS的J-聚集体的手性并不能表现出协同效应.%Supramolecular assembly and chirality between a novel gemini surfactant (C12H24-α, ω-(C12H25N + (CH3)2Br-)2,(abbreviated as C12-C12-C12) and TPPS (tetrakis(4-sulfonatophenyl) porphine) at the air/water interface were investigated. It was found that although the gemini surfactant itself could not form a stable monolayer at the air/water interface, when there existed TPPS in the subphase, a stable complex monolayer could be formed. The complex monolayer could be transferred onto solid substrate by a horizontal lifting method. At a certain pH value of the subphase, TPPS could form a J-aggregate. It was further found that the J-aggregate of TPPS showed a strong split Cotton effect in the transferred film although both the gemini surfactant and TPPS are achiral. Further investigation through AFM measurements revealed that the nanothread formed in the transferred film was responsible for the chirality of the multilayer film. In addition, the two positive charge center of the gemini surfactant did not necessarily play the cooperative role in inducing the chirality of TPPS J-aggregate.

  17. Solvent-induced helical assembly and reversible chiroptical switching of chiral cyclic-dipeptide-functionalized naphthalenediimides.

    Science.gov (United States)

    Manchineella, Shivaprasad; Prathyusha, V; Priyakumar, U Deva; Govindaraju, T

    2013-12-01

    Understanding the roles of various parameters in orchestrating the preferential chiral molecular organization in supramolecular self-assembly processes is of great significance in designing novel molecular functional systems. Cyclic dipeptide (CDP) chiral auxiliary-functionalized naphthalenediimides (NCDPs 1-6) have been prepared and their chiral self-assembly properties have been investigated. Detailed photophysical and circular dichroism (CD) studies have unveiled the crucial role of the solvent in the chiral aggregation of these NCDPs. NCDPs 1-3 form supramolecular helical assemblies and exhibit remarkable chiroptical switching behaviour (M- to P-type) depending on the solvent composition of HFIP and DMSO. The strong influence of solvent composition on the supramolecular chirality of NCDPs has been further corroborated by concentration and solid-state thin-film CD studies. The chiroptical switching between supramolecular aggregates of opposite helicity (M and P) has been found to be reversible, and can be achieved through cycles of solvent removal and redissolution in solvent mixtures of specific composition. The control molecular systems (NCDPs 4-6), with an achiral or D-isomer second amino acid in the CDP auxiliary, did not show chiral aggregation properties. The substantial roles of hydrogen bonding and π-π interactions in the assembly of the NCDPs have been validated through nuclear magnetic resonance (NMR), photophysical, and computational studies. Quantum chemical calculations at the ab initio, semiempirical, and density functional theory levels have been performed on model systems to understand the stabilities of the right (P-) and left (M-) handed helical supramolecular assemblies and the nature of the intermolecular interactions. This study emphasizes the role of CDP chiral auxiliaries on the solvent-induced helical assembly and reversible chiroptical switching of naphthalenediimides. PMID:24281809

  18. Intrinsic nanoscale phase separation in miscible mixtures and supramolecular assemblies

    OpenAIRE

    Lei Zhang

    2011-01-01

    A model is used to describe the intrinsic nanoscale phase separation in miscible mixtures and supramolecular assemblies. Phase-separated nanostructures related to size-dependent surface tension, molecular structural factors and strong interphase interactions exist in miscible mixtures and supramolecular assemblies. The intrinsic nanoscale phase separation may exist universally in miscible mixtures.

  19. Supramolecular Chirality: Solvent Chirality Transfer in Molecular Chemistry and Polymer Chemistry

    Directory of Open Access Journals (Sweden)

    Michiya Fujiki

    2014-08-01

    Full Text Available Controlled mirror symmetry breaking arising from chemical and physical origin is currently one of the hottest issues in the field of supramolecular chirality. The dynamic twisting abilities of solvent molecules are often ignored and unknown, although the targeted molecules and polymers in a fluid solution are surrounded by solvent molecules. We should pay more attention to the facts that mostly all of the chemical and physical properties of these molecules and polymers in the ground and photoexcited states are significantly influenced by the surrounding solvent molecules with much conformational freedom through non-covalent supramolecular interactions between these substances and solvent molecules. This review highlights a series of studies that include: (i historical background, covering chiral NaClO3 crystallization in the presence of d-sugars in the late 19th century; (ii early solvent chirality effects for optically inactive chromophores/fluorophores in the 1960s–1980s; and (iii the recent development of mirror symmetry breaking from the corresponding achiral or optically inactive molecules and polymers with the help of molecular chirality as the solvent use quantity.

  20. Water tuned the helical nanostructures and supramolecular chirality in organogels.

    Science.gov (United States)

    Liu, Changxia; Jin, Qingxian; Lv, Kai; Zhang, Li; Liu, Minghua

    2014-04-11

    Water was found to tune the self-assembled nanostructures of a cationic amphiphile in organic solvents from nanofibers to helical tapes, helical tubes and chiral nanotwists with various pitch lengths depending on water content. Inversion of CD spectra was observed in the water-triggered polar and non-polar solvent gels.

  1. Preparation for Supramolecular Complexes of Chiral Diols BDPDD, DMBDPD and BINOL with Some Prochiral Compounds

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Interaction between chiral diols BDPDD, DMBDPD and BINOL with prochiral compounds was examined and some new supramolecular complexes were prepared. It was found that these chiral hosts could include prochiral guests,α,β-unsaturated compounds or piper- azinedione derivatives to give inclusion crystals in different molar ratio. Formations of these supramolecular complexes were characterized by the data of IR and 1H NMR spectra.

  2. Two-dimensional pentacene:3,4,9,10-perylenetetracarboxylic dianhydride supramolecular chiral networks on Ag(111).

    Science.gov (United States)

    Chen, Wei; Li, Hui; Huang, Han; Fu, Yuanxi; Zhang, Hong Liang; Ma, Jing; Wee, Andrew Thye Shen

    2008-09-17

    Self-assembly of the binary molecular system of pentacene and 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) on Ag(111) has been investigated by low-temperature scanning tunneling microscopy, molecular dynamics (MD), and density functional theory (DFT) calculations. Well-ordered two-dimensional (2D) pentacene:PTCDA supramolecular chiral networks are observed to form on Ag(111). The 2D chiral network formation is controlled by the strong interfacial interaction between adsorbed molecules and the underlying Ag(111), as revealed by MD and DFT calculations. The registry effect locks the adsorbed pentacene and PTCDA molecules into specific adsorption sites due to the corrugation of the potential energy surface. The 2D supramolecular networks are further constrained through the directional CO...H-C multiple intermolecular hydrogen bonding between the anhydride groups of PTCDA and the peripheral aromatic hydrogen atoms of the neighboring pentacene molecules. PMID:18722423

  3. Supramolecular self-assemblies as functional nanomaterials

    Science.gov (United States)

    Busseron, Eric; Ruff, Yves; Moulin, Emilie; Giuseppone, Nicolas

    2013-07-01

    In this review, we survey the diversity of structures and functions which are encountered in advanced self-assembled nanomaterials. We highlight their flourishing implementations in three active domains of applications: biomedical sciences, information technologies, and environmental sciences. Our main objective is to provide the reader with a concise and straightforward entry to this broad field by selecting the most recent and important research articles, supported by some more comprehensive reviews to introduce each topic. Overall, this compilation illustrates how, based on the rules of supramolecular chemistry, the bottom-up approach to design functional objects at the nanoscale is currently producing highly sophisticated materials oriented towards a growing number of applications with high societal impact.

  4. Attomolar DNA detection with chiral nanorod assemblies

    OpenAIRE

    Ma, Wei; Kuang, Hua; Xu, Liguang; Ding, Li; Xu, Chuanlai; Wang, Libing; Kotov, Nicholas A.

    2013-01-01

    Nanoscale plasmonic assemblies display exceptionally strong chiral optical activity. So far, their structural design was primarily driven by challenges related to metamaterials whose practical applications are remote. Here we demonstrate that gold nanorods assembled by the polymerase chain reaction into DNA-bridged chiral systems have promising analytical applications. The chiroplasmonic activity of side-by-side assembled patterns is attributed to a 7–9 degree twist between the nanorod axes. ...

  5. Construction of Supramolecular Architectures via Self-assembly

    Institute of Scientific and Technical Information of China (English)

    Takeharu; Haino

    2007-01-01

    1 Results In this paper we report supramolecular polymeric nano networks formed by the molecular-recognition-directed self-assembly between a calix[5]arene and C60[1]. Covalently-linked double-calix[5]arenes take up C60 into their cavities[2]. This complementary interaction creates a strong non-covalent bonding; thus,the iterative self-assembly between dumbbell fullerene 1 and ditopic host 2 can produce the supramolecular polymer networks (See Fig.1).

  6. Chiral assembly of achiral pseudoisocyanine with D-and L-phenylalanine

    Institute of Scientific and Technical Information of China (English)

    ZENG LiXi; HE Yujian; DAI ZhiFeng; WANG Jian; WANG CaiQi; YANG YongGang

    2009-01-01

    Supramolecular chirality and molecular self-assembly are important and interesting phenomena in living and non-living systems.In this work,supramolecular chirality of achiral pseudoisocyanine (PIC) J-aggregates was successfully induced by D-,L-phenylalanine (Phe) and other amino acids in NaCI solution.The chiral J-aggregates showed a characteristic,induced circular dichroism (ICD) in the visible region of J-band chromophore which depends on the absolute configuration,concentration and side groups of a-amino acids,as well as temperature.The atomic force microscopy images indicated that the J-aggregates exist in large bundles of entangled nanof ibers,and the observed ICD might result from the macroscopic helical arrangement of the assemblies.

  7. Chiral assembly of achiral pseudoisocyanine with D-and L-phenylalanine

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Supramolecular chirality and molecular self-assembly are important and interesting phenomena in living and non-living systems.In this work,supramolecular chirality of achiral pseudoisocyanine(PIC) J-aggregates was successfully induced by D-,L-phenylalanine(Phe) and other amino acids in NaCl solution.The chiral J-aggregates showed a characteristic,induced circular dichroism(ICD) in the visible region of J-band chromophore which depends on the absolute configuration,concentration and side groups of α-amino acids,as well as temperature.The atomic force microscopy images indicated that the J-aggregates exist in large bundles of entangled nanofibers,and the observed ICD might result from the macroscopic helical arrangement of the assemblies.

  8. Self-Assembly of Hierarchical Chiral Nanostructures Based on Metal-Benzimidazole Interactions: Chiral Nanofibers, Nanotubes, and Microtubular Flowers.

    Science.gov (United States)

    Zhou, Xiaoqin; Jin, Qingxian; Zhang, Li; Shen, Zhaocun; Jiang, Long; Liu, Minghua

    2016-09-01

    Controlled hierarchical self-assembly of synthetic molecules into chiral nanoarchitectures to mimic those biological chiral structures is of great importance. Here, a low-molecular-weight organogelator containing a benzimidazole moiety conjugated with an amphiphilic l-glutamic amide has been designed and its self-assembly into various hierarchical chiral nanostructures is investigated. Upon gel formation in organic solvents, 1D chiral nanostructure such as nanofiber and nanotube are obtained depending on the solvents. In the presence of transition and rare earth metal ions, hierarchical chiral nanostructures are formed. Specifically, the addition of TbCl3 , EuCl3 , and AgNO3 leads to nanofiber structures, while the addition of Cu(NO3 )2 , Tb(NO3 )3 , or Eu(NO3 )3 provides the microflower structures and microtubular flower structures, respectively. While Eu(III) and Tb(III)-containing microtubular flowers keep the chirality, the Cu(II)-coordinated microflowers lose chirality. More interestingly, the nanofibers formed by the gelator coordinated with Eu(III) or Tb(III) ions show not only the supramolecular chirality but also the circularly polarized luminescence. PMID:27248367

  9. Interfacial organization of achiral porphyrins via unidirectional compression: a general method for chiroptical porphyrin assemblies of selected chirality.

    Science.gov (United States)

    Zhang, Xiao; Wang, Yanping; Chen, Penglei; Rong, Yunlong; Liu, Minghua

    2016-05-18

    Porphyrins are considered to be important scaffolds bridging supramolecular chemistry and chiral chemistry, where chirality selection via physical effects such as directional stirring and spin-coating has aroused particular interest. Nevertheless, these protocols could only work on a limited number of achiral porphyrins. It still remains a formidable challenge to pave a general avenue for the construction of chiral assemblies using achiral porphyrins. By means of a unique Langmuir-Schaefer (LS) technique of a unidirectional compression configuration, we herein have demonstrated that a series of achiral porphyrins could be facilely organized to form chiral interfacial assemblies of controlled supramolecular chirality. It has been disclosed that such a fascinating chirality selection scenario is intimately related to the direction of the compression-generated vortex-like flow, while the compression speed, one of the most significant parameters of the Langmuir technique, contributes less to this issue. With regard to a surface-pressure-dependent chirality selection phenomenon, it is suggested that the directional vortex-like flow generated by lateral compression might play a role in promoting the preferential growth of chiral assemblies showing an enhanced yet controlled CD signal. Our protocol might be, to some extent, a general method for achieving chiral porphyrin assemblies of controlled chirality.

  10. Reversible Guest Exchange Mechanisms in Supramolecular Host-GuestAssemblies

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael D.; Raymond, Kenneth N.

    2006-09-01

    Synthetic chemists have provided a wide array of supramolecular assemblies able to encapsulate guest molecules. The scope of this tutorial review focuses on supramolecular host molecules capable of reversibly encapsulating polyatomic guests. Much work has been done to determine the mechanism of guest encapsulation and guest release. This review covers common methods of monitoring and characterizing guest exchange such as NMR, UV-VIS, mass spectroscopy, electrochemistry, and calorimetry and also presents representative examples of guest exchange mechanisms. The guest exchange mechanisms of hemicarcerands, cucurbiturils, hydrogen-bonded assemblies, and metal-ligand assemblies are discussed. Special attention is given to systems which exhibit constrictive binding, a motif common in supramolecular guest exchange systems.

  11. Preparation of optical active polydiacetylene through gelating and the control of supramolecular chirality

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Achiral diacetylene 10,12-pentacosadinoic acid (PCDA) and a chiral low-molecular-weight organogelator could form co-gel in organic solvent and it could be polymerized in the presence of Zn(II) ion or in the corresponding xerogel under UV-irradiation. Optically active polydiacetylene (PDA) were subsequently obtained. Supramolecular chirality of PDA could be controlled by the chirality of gelators. Left-handed and right-handed helical fibers were obtained by using Land D-gelators in xerogels respectively, and CD spectra exhibited mirror-image circular dichroism. The PDA in xerogel exhibited typical blue-to-red transition responsive to the temperature and pH, while the supramolecular chirality of PDA showed a corresponding change.

  12. Enabling Light Work in Helical Self-Assembly for Dynamic Amplification of Chirality with Photoreversibility.

    Science.gov (United States)

    Cai, Yunsong; Guo, Zhiqian; Chen, Jianmei; Li, Wenlong; Zhong, Liubiao; Gao, Ya; Jiang, Lin; Chi, Lifeng; Tian, He; Zhu, Wei-Hong

    2016-02-24

    Light-driven transcription and replication are always subordinate to a delicate chirality transfer. Enabling light work in construction of the helical self-assembly with reversible chiral transformation becomes attractive. Herein we demonstrate that a helical hydrogen-bonded self-assembly is reversibly photoswitched between photochromic open and closed forms upon irradiation with alternative UV and visible light, in which molecular chirality is amplified with the formation of helixes at supramolecular level. The characteristics in these superhelixes such as left-handed or right-handed twist and helical length, height, and pitch are revealed by SEM and AFM. The helical photoswitchable nanostructure provides an easily accessible route to an unprecedented photoreversible modulation in morphology, fluorescence, and helicity, with precise assembly/disassembly architectures similar to biological systems such as protein and DNA. PMID:26709946

  13. Design and assembly of supramolecular dual-modality nanoprobes

    Science.gov (United States)

    Liu, Shuang; Zhang, Pengcheng; Ray Banerjee, Sangeeta; Xu, Jiadi; Pomper, Martin G.; Cui, Honggang

    2015-05-01

    We report the design and synthesis of self-assembling dual-modality molecular probes containing both a fluorophore for optical imaging and a metal ion chelator for imaging with MRI or radionuclide methods. These molecular probes can spontaneously associate into spherical nanoparticles under physiological conditions. We demonstrate the use of these supramolecular nanoprobes for live-cell optical imaging, as well as their potential use as MRI contrast agents after complexation with gadolinium. Our results suggest that self-assembly into supramolecular nanoprobes presents an effective means to enhance and tune the relaxivities of molecular probes.We report the design and synthesis of self-assembling dual-modality molecular probes containing both a fluorophore for optical imaging and a metal ion chelator for imaging with MRI or radionuclide methods. These molecular probes can spontaneously associate into spherical nanoparticles under physiological conditions. We demonstrate the use of these supramolecular nanoprobes for live-cell optical imaging, as well as their potential use as MRI contrast agents after complexation with gadolinium. Our results suggest that self-assembly into supramolecular nanoprobes presents an effective means to enhance and tune the relaxivities of molecular probes. Electronic supplementary information (ESI) available: Experimental methods, materials, synthesis schemes, sample characterization, fluorescence measurements, cellular uptake and MRI experimental details. See DOI: 10.1039/c5nr01518a

  14. Right handed chiral superstructures from achiral molecules: self-assembly with a twist.

    Science.gov (United States)

    Anuradha; La, Duong Duc; Al Kobaisi, Mohammad; Bhosale, Sheshanath V

    2015-01-01

    The induction and development of chiral supramolecular structures from hierarchical self-assembly of achiral compounds is closely related to the evolution of life and the chiral amplification found in nature. Here we show that the combination of achiral tetraphenylethene (TPE) an AIE-active luminophore bearing four long alkyl chains via amide linkage allows the entire process of induction and control of supramolecular chirality into well-defined uniform right-handed twisted superstructures via solvent composition and polarity, i.e. solvophobic effect. We showed that the degree of twist and the pitch of the ribbons can be controlled to one-handed helical structure via solvophobic effects. The twisted superstructure assembly was visualised by scanning electron microscope (SEM) and transmission electron microscopy (TEM), furthermore, circular dichroism (CD) confirms used to determine controlled right-handed assembly. This controlled assembly of an AIE-active molecule can be of practical value; for example, as templates for helical crystallisation, catalysis and a chiral mechanochromic luminescent superstructure formation. PMID:26493294

  15. Attomolar DNA detection with chiral nanorod assemblies

    Science.gov (United States)

    Ma, Wei; Kuang, Hua; Xu, Liguang; Ding, Li; Xu, Chuanlai; Wang, Libing; Kotov, Nicholas A.

    2013-10-01

    Nanoscale plasmonic assemblies display exceptionally strong chiral optical activity. So far, their structural design was primarily driven by challenges related to metamaterials whose practical applications are remote. Here we demonstrate that gold nanorods assembled by the polymerase chain reaction into DNA-bridged chiral systems have promising analytical applications. The chiroplasmonic activity of side-by-side assembled patterns is attributed to a 7-9 degree twist between the nanorod axes. This results in a strong polarization rotation that matches theoretical expectations. The amplitude of the bisignate ‘wave’ in the circular dichroism spectra of side-by-side assemblies demonstrates excellent linearity with the amount of target DNA. The limit of detection for DNA using side-by-side assemblies is as low as 3.7 aM. This chiroplasmonic method may be particularly useful for biological analytes larger than 2-5 nm which are difficult to detect by methods based on plasmon coupling and ‘hot spots’. Circular polarization increases for inter-nanorod gaps between 2 and 20 nm when plasmonic coupling rapidly decreases. Reaching the attomolar limit of detection for simple and reliable bioanalysis of oligonucleotides may have a crucial role in DNA biomarker detection for early diagnostics of different diseases, forensics and environmental monitoring.

  16. Chiral Supramolecular Chemistry of Basket Resorc[4]arenes

    OpenAIRE

    Calcaterra, Andrea

    2013-01-01

    Chiral Basket Resorc[4]arenes are well known chiral solvating agents that can induce enantiodiscrimination towards aminoacids, peptides and nucleosides. We synthesized both enantiomer of some basket resorc[4]arenes capable of forming stable diasteromeric host-guest complexes with some nucleosides like cytidine and cytarabine. The reactivity and the structures of the complexes were investigated in gas-phase (ESI-IRMPD, ESI-FT-ICR) and in solution (DOSY, ROESY). Different "in" and "out" struct...

  17. From supramolecular chemistry to nanotechnology : assembly of 3D nanostructures

    OpenAIRE

    Ling, Xing Yi

    2008-01-01

    Fabricating well-defined and stable nanoparticle arrays and crystals in a controlled fashion receives growing attention in nanotechnology owing to the potential application in optoelectronic devices, biological sensors, and photonic structures. The research described in this thesis aims to construct stable, ordered and functional 2D and 3D nanoparticle structures. Molecular recognition abilities have been exploited by using a combination of supramolecularly directed self-assembly of receptor-...

  18. Assembly and characterization of supramolecular architectures for biosensor applications

    OpenAIRE

    Xu, Fei

    2005-01-01

    The research has included the efforts in designing, assembling and structurally and functionally characterizing supramolecular biofunctional architectures for optical biosensing applications. In the first part of the study, a class of interfaces based on the biotin-NeutrAvidin binding matrix for the quantitative control of enzyme surface coverage and activity was developed. Genetically modified ß-lactamase was chosen as a model enzyme and attached to five different types of NeutrAvidi...

  19. Electrostatically Directed Self-Assembly of Ultrathin Supramolecular Polymer Microcapsules

    OpenAIRE

    Parker, Richard M.; Zhang, Jing; Zheng, Yu; Coulston, Roger J.; Smith, Clive A; Salmon, Andrew R; Yu, Ziyi; Oren A. Scherman; Abell, Chris

    2015-01-01

    Supramolecular self-assembly offers routes to challenging architectures on the molecular and macroscopic scale. Coupled with microfluidics it has been used to make microcapsules—where a 2D sheet is shaped in 3D, encapsulating the volume within. In this paper, a versatile methodology to direct the accumulation of capsule-forming components to the droplet interface using electrostatic interactions is described. In this approach, charged copolymers are selectively partitioned to the microdroplet...

  20. Novel biosensing platform based on self-assembled supramolecular hydrogel.

    Science.gov (United States)

    Ma, Dong; Zhang, Li-Ming

    2013-07-01

    The supramolecular hydrogel self-assembled from α-cyclodextrin (α-CD) and an amphiphilic triblock copolymer was used for the first time as a biosensing platform by the in-situ incorporation of horseradish peroxidase and polyaniline (PANI) nanoparticles. It was found that the used triblock copolymer could disperse well PANI nanoparticles in aqueous system and then interact with α-CD in the presence of horseradish peroxidase for the formation of supramolecular hydrogel composite. The content of PANI nanoparticles was found to affect the gelation time and gel strength. The circular dichroism analyses showed that the entrapped horseradish peroxidase could retain its native conformation. By electrochemical experiments, the incorporated PANI nanoparticles were confirmed to improve the current response and enzymatic activity, and the fabricated biosensor was found to provide a fast amperometric response to hydrogen peroxide. PMID:23623078

  1. Intermolecular chiral assemblies in R(-) and S(+) 2-butanol detected by microcalorimetry measurements.

    Science.gov (United States)

    Cogan, Uri; Shpigelman, Avi; Portnaya, Irina; Rutenberg, Abraham; Scolnik, Yosef; Shinitzky, Meir

    2012-07-01

    Supramolecular chiral assemblies of R(-) and S(+) 2-butanol, in their neat form or when dissolved in their nonchiral isomer isobutanol, were evaluated by isothermal titration calorimetry (ITC) ensuing mixing. Dilution of 0.5 M solution of R(-) 2-butanol in isobutanol into the latter liberated heat of several calories per mole, which was approximately double than that obtained in parallel dilutions of S(+) 2-butanol in isobutanol. The ITC dilution profiles indicated an estimate of about 100 isobutanol solvent molecules surrounding each of the 2-butanol enantiomers, presumably arranged in chiral configurations, with different adopted order between the isomers. Mixings of neat R and S 2-butanol were followed by endothermic ITC profiles, indicating that, in racemic 2-butanol, both the supramolecular order and the intermolecular binding energies are lower than in each of the neat chiral isomers. The diversion from symmetrical ITC patterns in these mixings indicated again a subtle difference in molecular organization between the neat enantiomers. It should be noted that the presence of impurities, α-pinene and teterhydrofuran, at a level totaling 0.5%, did not influence the ITC heat flow profiles. The findings of this study demonstrate for the first time that chiral solutes in organic solvents are expected to acquire asymmetric solvent envelopes that may be different between the enantiomers, thus broadening this phenomenon beyond the previously demonstrated cases in aqueous solutions.

  2. Cyclodextrin Derivatives as Chiral Supramolecular Receptors for Enantioselective Sensing

    Directory of Open Access Journals (Sweden)

    Uwe Pieles

    2006-06-01

    Full Text Available In view of the chiral nature of many bio-molecules (and all bio-macromolecules,most of therapeutically active compounds which target these molecules need to be chiraland “good handed” to be effective. In addition to asymmetric synthetic and separationmethodologies, enantioselective chemical sensors, able to distinguish between twoenantiomers of the same molecule, are of relevance. In order to design these sensing tools,two major classes of enantioselective layers have been developed. The first is based onmolecularly imprinted polymers which are produced (polymerized in the presence of theirtarget, thus the polymeric material keep in “memory” the size and the shape of this moleculeand the system could be used for sensing (not reviewed here. The second approach makesuse of sensitive layers containing chiral macrocyclic receptors able of stereoselectivemolecular recognition; these receptors are mainly based on cyclodextrins. In thiscontribution, are reviewed achievements in the use of native or chemically modifiedcyclodextrins for chiral sensing purposes (at interfaces. Potentialities of other chiralmacrocycles based on calixarenes, calix-resorcinarenes or crown-ethers as supramolecularreceptors for enantioselective sensing are discussed.

  3. Colloidal chirality in wormlike micellar systems exclusively originated from achiral species: Role of secondary assembly and stimulus responsivity.

    Science.gov (United States)

    Zhao, Wenrong; Hao, Jingcheng

    2016-09-15

    Colloidal chirality in wormlike micellar systems exclusively originated from achiral species and discussion of the role of secondary assembly of fiber-like aggregates in chirality generation were presented in this paper. Herein, formation of colloidal wormlike micelles for the first time incorporated chirality and redox-responsiveness into one design via noncovalent interaction. A dual-stimuli-responsive gel of wormlike micelles which were designed by employing a dual-responsive cationic surfactant (FTMA) and a strong gelator (AzoNa4) and regulated by redox reaction and host-guest inclusion is presented. Both the redox and host-guest interaction play an important role in regulating the viscosity and supramolecular chirality of gels of the wormlike micelles. The supramolecular chirality and viscosity of the wormlike micelle gels were switched reversibly by exerting chemical redox onto the ferrocenyl groups. For the amphiphile FTMA containing redox-active ferrocenyl group, reversible control of the oxidation state of ferrocenyl groups leads to the charge and hydrophobicity changes of FTMA, therefore change its self-assembly behavior. Of equal interest, β-CD successfully detached the wormlike micelles via the recognition-inclusion behavior with FTMA and invalidate the H-bond and hydrophobic interaction between FTMA and AzoH4. This designed system provides a new strategy to tune the supramolecular chirality of colloidal aggregates and explore the specific packing mode detail within the micelles or the secondary assembly of the inter-micelles. We anticipate this dual-responsive H-bond-directed chiral gel switch could propose a new strategy when researchers designing new, multi-responsive functional gel materials. PMID:27314643

  4. Assembly of supramolecular nanotubes from molecular triangles and 1,2-dihalohydrocarbons.

    Science.gov (United States)

    Liu, Zhichang; Liu, Guoliang; Wu, Yilei; Cao, Dennis; Sun, Junling; Schneebeli, Severin T; Nassar, Majed S; Mirkin, Chad A; Stoddart, J Fraser

    2014-11-26

    Precise control of molecular assembly is a challenging goal facing supramolecular chemists. Herein, we report the highly specific assembly of a range of supramolecular nanotubes from the enantiomeric triangular naphthalenediimide-based macrocycles (RRRRRR)- and (SSSSSS)-NDI-Δ and a class of similar solvents, namely, the 1,2-dihalo-ethanes and -ethenes (DXEs). Three kinds of supramolecular nanotubes are formed from the columnar stacking of NDI-Δ units with a 60° mutual rotation angle as a result of cooperative [C-H···O] interactions, directing interactions of the [X···X]-bonded DXE chains inside the nanotubes and lateral [X···π] or [π···π] interactions. They include (i) semiflexible infinite nanotubes formed in the gel state from NDI-Δ and (E)-1,2-dichloroethene, (ii) rigid infinite nonhelical nanotubes produced in the solid state from NDI-Δ and BrCH2CH2Br, ClCH2CH2Br, and ClCH2CH2I, and (iii) a pair of rigid tetrameric, enantiomeric single-handed (P)- and (M)-helical nanotubes formed in the solid state from the corresponding (RRRRRR)- and (SSSSSS)-NDI-Δ with ClCH2CH2Cl. In case (i), only the electron-rich C═C double bond of (E)-1,2-dichloroethene facilitates the gelation of NDI-Δ. In cases (ii) and (iii), the lengths of anti-DXEs determine the translation of the chirality of NDI-Δ into the helicity of nanotubes. Only ClCH2CH2Cl induces single-handed helicity into the nanotubes. The subtle interplay of noncovalent bonding interactions, resulting from the tiny structural variations involving the DXE guests, is responsible for the diverse and highly specific assembly of NDI-Δ. This research highlights the critical role that guests play in constructing assembled superstructures of hosts and offers a novel approach to creating supramolecular nanotubes. PMID:25357152

  5. Small molecule-guided thermoresponsive supramolecular assemblies

    KAUST Repository

    Rancatore, Benjamin J.

    2012-10-23

    Small organic molecules with strong intermolecular interactions have a wide range of desirable optical and electronic properties and rich phase behaviors. Incorporating them into block copolymer (BCP)-based supramolecules opens new routes to generate functional responsive materials. Using oligothiophene- containing supramolecules, we present systematic studies of critical thermodynamic parameters and kinetic pathway that govern the coassemblies of BCP and strongly interacting small molecules. A number of potentially useful morphologies for optoelectronic materials, including a nanoscopic network of oligothiophene and nanoscopic crystalline lamellae, were obtained by varying the assembly pathway. Hierarchical coassemblies of oligothiophene and BCP, rather than macrophase separation, can be obtained. Crystallization of the oligothiophene not only induces chain stretching of the BCP block the oligothiophene is hydrogen bonded to but also changes the conformation of the other BCP coil block. This leads to an over 70% change in the BCP periodicity (e.g., from 31 to 53 nm) as the oligothiophene changes from a melt to a crystalline state, which provides access to a large BCP periodicity using fairly low molecular weight BCP. The present studies have demonstrated the experimental feasibility of generating thermoresponsive materials that convert heat into mechanical energy. Incorporating strongly interacting small molecules into BCP supramolecules effectively increases the BCP periodicity and may also open new opportunities to tailor their optical properties without the need for high molecular weight BCP. © 2012 American Chemical Society.

  6. Preface: Special Topic on Supramolecular Self-Assembly at Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Bartels, Ludwig [Department of Chemistry and the Materials Science and Engineering Program, University of California - Riverside, Riverside, California 92521 (United States); Ernst, Karl-Heinz [EMPA, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, CH-8600 Dubendorf (Switzerland); Gao, Hong-Jun [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics,Chinese Academy of Sciences, Beijing 100190 (China); Thiel, Patricia A. [Department of Chemistry, Department of Materials Science and Engineering, Ames Laboratory,Iowa State University, Ames, Iowa 50011 (United States)

    2015-03-14

    Supramolecular self-assembly at surfaces is one of the most exciting and active fields in Surface Science today. Applications can take advantage of two key properties: (i) versatile pattern formation over a broad length scale and (ii) tunability of electronic structure and transport properties, as well as frontier orbital alignment. It provides a new frontier for Chemical Physics as it uniquely combines the versatility of Organic Synthesis and the Physics of Interfaces. The Journal of Chemical Physics is pleased to publish this Special Topic Issue, showcasing recent advances and new directions.

  7. Self-Assembled Supramolecular Architectures Lyotropic Liquid Crystals

    CERN Document Server

    Garti, Nissim

    2012-01-01

    This book will describe fundamentals and recent developments in the area of Self-Assembled Supramolecular Architecture and their relevance to the  understanding of the functionality of  membranes  as delivery systems for active ingredients. As the heirarchial architectures determine their performance capabilities, attention will be paid to theoretical and design aspects related to the construction of lyotropic liquid crystals: mesophases such as lamellar, hexagonal, cubic, sponge phase micellosomes. The book will bring to the reader mechanistic aspects, compositional c

  8. Metal-Directed Design of Supramolecular Protein Assemblies.

    Science.gov (United States)

    Bailey, J B; Subramanian, R H; Churchfield, L A; Tezcan, F A

    2016-01-01

    Owing to their central roles in cellular signaling, construction, and biochemistry, protein-protein interactions (PPIs) and protein self-assembly have become a major focus of molecular design and synthetic biology. In order to circumvent the complexity of constructing extensive noncovalent interfaces, which are typically involved in natural PPIs and protein self-assembly, we have developed two design strategies, metal-directed protein self-assembly (MDPSA) and metal-templated interface redesign (MeTIR). These strategies, inspired by both the proposed evolutionary roles of metals and their prevalence in natural PPIs, take advantage of the favorable properties of metal coordination (bonding strength, directionality, and reversibility) to guide protein self-assembly with minimal design and engineering. Using a small, monomeric protein (cytochrome cb562) as a model building block, we employed MDPSA and MeTIR to create a diverse array of functional supramolecular architectures which range from structurally tunable oligomers to metalloprotein complexes that can properly self-assemble in living cells into novel metalloenzymes. The design principles and strategies outlined herein should be readily applicable to other protein systems with the goal of creating new PPIs and protein assemblies with structures and functions not yet produced by natural evolution. PMID:27586336

  9. Unzipping the role of chirality in nanoscale self-assembly of tripeptide hydrogels.

    Science.gov (United States)

    Marchesan, Silvia; Waddington, Lynne; Easton, Christopher D; Winkler, David A; Goodall, Liz; Forsythe, John; Hartley, Patrick G

    2012-11-01

    Change of chirality is a useful tool to manipulate the aqueous self-assembly behaviour of uncapped, hydrophobic tripeptides. In contrast with other short peptides, these tripeptides form hydrogels at a physiological pH without the aid of organic solvents or end-capping groups (e.g. Fmoc). The novel hydrogel forming peptide (D)Leu-Phe-Phe ((D)LFF) and its epimer Leu-Phe-Phe (LFF) exemplify dramatic supramolecular effects induced by subtle changes to stereochemistry. Only the d-amino acid-containing peptide instantly forms a hydrogel in aqueous solution following a pH switch, generating long fibres (>100 μm) that entangle into a 3D network. However, unexpected nanostructures are observed for both peptides and they are particularly heterogeneous for LFF. Structural analyses using CD, FT-IR and fluorescent amyloid staining reveal anti-parallel beta-sheets for both peptides. XRD analysis also identifies key distances consistent with beta-sheet formation in both peptides, but suggests additional high molecular order and extended molecular length for (D)LFF only. Molecular modelling of the two peptides highlights the key interactions responsible for self-assembly; in particular, rapid self-assembly of (D)LFF is promoted by a phenylalanine zipper, which is not possible because of steric factors for LFF. In conclusion, this study elucidates for the first time the molecular basis for how chirality can dramatically influence supramolecular organisation in very short peptide sequences. PMID:22955637

  10. Self-assembly of supramolecularly engineered polymers and their biomedical applications.

    Science.gov (United States)

    Wang, Dali; Tong, Gangsheng; Dong, Ruijiao; Zhou, Yongfeng; Shen, Jian; Zhu, Xinyuan

    2014-10-18

    Noncovalent interactions provide a flexible method of engineering various chemical entities with tailored properties. Specific noncovalent interactions between functionalized small molecules, macromolecules or both of them bearing complementary binding sites can be used to engineer supramolecular complexes that display unique structure and properties of polymers, which can be defined as supramolecularly engineered polymers. Due to their dynamic tunable structures and interesting physical/chemical properties, supramolecularly engineered polymers have recently received more and more attention from both academia and industry. In this feature article, we summarize the recent progress in the self-assembly of supramolecularly engineered polymers as well as their biomedical applications. In view of different molecular building units, the supramolecularly engineered polymers can be classified into the following three major types: supramolecularly engineered polymers built by small molecules, supramolecularly engineered polymers built by small molecules and macromolecules, and supramolecularly engineered polymers built by macromolecules, which possess distinct morphologies, definite architectures and specific functions. Owing to the reversible nature of the noncovalent interactions, the supramolecularly engineered polymers have exhibited unique features or advantages in molecular self-assembly, for example, facile preparation and functionalization, controllable morphologies and structures, dynamic self-assembly processes, adjustable performance, and so on. Furthermore, the self-assembled supramolecular structures hold great potential as promising candidates in various biomedical fields, including bioimaging, drug delivery, gene transfection, protein delivery, regenerative medicine and tissue engineering. Such developments in the self-assembly of supramolecularly engineered polymers and their biomedical applications greatly promote the interdiscipline research among

  11. Controlling the amplification of chirality in hydrogen-bonded assemblies

    NARCIS (Netherlands)

    Mateos-Timoneda, Miguel A.; Crego-Calama, Mercedes; Reinhoudt, David N.

    2005-01-01

    The amplification of chirality (a high enantiomeric or diastereomeric excess induced by a small initial amount of chiral bias) on hydrogen-bonded assemblies has been studied using “sergeants-and-soldiers” experiments under thermodynamically controlled conditions. Here it is shown that different subs

  12. Salan ligands assembled around chiral bipyrrolidine: predetermination of chirality around octahedral Ti and Zr centres.

    Science.gov (United States)

    Sergeeva, Ekaterina; Kopilov, Jacob; Goldberg, Israel; Kol, Moshe

    2009-06-01

    The first synthesis of Salan ligands assembled around the chiral 2,2'-bipyrrolidine backbone is described; as chelation to a metal can only occur via specific faces of the two pyrrolidine nitrogens, these ligands lead to predetermined chirality at metal centres of octahedral titanium and zirconium complexes. PMID:19462084

  13. From micelle supramolecular assemblies in selective solvents to isoporous membranes

    KAUST Repository

    Nunes, Suzana Pereira

    2011-08-16

    The supramolecular assembly of PS-b-P4VP copolymer micelles induced by selective solvent mixtures was used to manufacture isoporous membranes. Micelle order in solution was confirmed by cryo-scanning electron microscopy in casting solutions, leading to ordered pore morphology. When dioxane, a solvent that interacts poorly with the micelle corona, was added to the solution, polymer-polymer segment contact was preferential, increasing the intermicelle contact. Immersion in water gave rise to asymmetric porous membranes with exceptional pore uniformity and high porosity. The introduction of a small number of carbon nanotubes to the casting solution improved the membrane stability and the reversibility of the gate response in the presence of different pH values. © 2011 American Chemical Society.

  14. Solvent-induced chirality inversion involving supramolecular helix transformation and color-tunable fluorescence of a C(6)-symmetric hexakis(phenylethynyl)benzene derivative.

    Science.gov (United States)

    Sakajiri, Koichi; Sugisaki, Takeshi; Moriya, Keiichi; Kutsumizu, Shoichi

    2009-09-21

    A C(6)-symmetric disk-like molecule, a hexakis(phenylethynyl)benzene derivative bearing chiral alanine parts, L-1, exhibited a solvent-induced supramolecular helix-sense inversion involving conformational changes followed by destruction of the supramolecular helical column. This phenomenon has been found by investigating the supramolecular assembly state of L-1 in mixed solvents of various chloroform (CHCl(3))/n-hexane (Hx) ratios. L-1 forms a stable helical columnar assembly via multiple noncovalent bonding interactions in nonpolar Hx, while the molecules in relatively polar CHCl(3) are in a molecularly dispersed state. Although one would expect disruption of the helical column with the addition of nonhelicogenic CHCl(3), an opposite-handed helical columnar structure was formed at 8-15 vol% of CHCl(3), and subsequently the inverted helical column was disassembled by a further increase of CHCl(3). In addition, this morphological transformation was accompanied by a significant change in fluorescent color, which varies over a wide visible range from orange in an original helical columnar state to light blue in a molecularly dispersed state through yellow in an inverted helical columnar state. These unprecedented behaviors are shown by the spectroscopic results, and the molecular conformations of L-1 and the driving force for the helical sense inversion are discussed.

  15. Cucurbit[7]uriI-Based Vesicles Formed by Self-assembly of Supramolecular Amphiphiles

    Institute of Scientific and Technical Information of China (English)

    李佳锡; 周黎鹏; 罗全; 王永国; 张春秋; 卢伟; 徐家云; 刘俊秋

    2012-01-01

    Cucurbituril (CB), a well-known macrocyclic cavitand, has been used extensively to construct supramolecular aggregates. Based on host-guest intertactions, an adamantanyl derivative guest molecule was designed and syn- thesized to prepare a supramolecular amphiphile with cucurbit[7]uril. In aqueous solution, the cucurbit[7]uril based supramolecular amphiphiles self-assemble into well-defined vesicles, and their disassembly can be achieved by addition of excess competitive agent 1-adamantanamine hydrochloride. This vesicle functions as a new nanocapsule to encapsulate molecules within its hollow cavity. Through competitive disassembly of supramolecular amphiphiles, the vesicles behave as a novel drug delivery carrier.

  16. Chiral and fractal: from simple design rules to complex supramolecular constructs.

    Science.gov (United States)

    Nieckarz, D; Szabelski, P

    2016-10-01

    Using theoretical modeling, we demonstrate the self-assembly of functional organic molecules into 2D fractal aggregates resembling the Sierpiński triangle (ST). It is shown for the first time that the fractal self-assembly can be realized in one-component systems comprising K- and A-shaped tectons whose arms meet to form chiral nodes with directional intermolecular bonds. PMID:27545303

  17. Incorporating bacteria as a living component in supramolecular self-assembled monolayers through dynamic nanoscale interactions

    NARCIS (Netherlands)

    Sankaran, Shrikrishnan; Kiren, Mustafa Can; Jonkheijm, Pascal

    2015-01-01

    Supramolecular assemblies, formed through noncovalent interactions, has become particularly attractive to develop dynamic and responsive architectures to address living systems at the nanoscale. Cucurbit[8]uril (CB[8]), a pumpkin shaped macrocylic host molecule, has been successfully used to constru

  18. Self-Assembled PDINH Supramolecular System for Photocatalysis under Visible Light.

    Science.gov (United States)

    Liu, Di; Wang, Jun; Bai, Xiaojuan; Zong, Ruilong; Zhu, Yongfa

    2016-09-01

    A self-assembled perylene-3,4,9,10-tetracarboxylic diimide(PDINH) supramolecular system consisting of all-organic PDINH molecule building blocks through non-covalent interactions works as a visible light photocatalyst with high activity.

  19. Progress in non-viral gene delivery systems fabricated via supramolecular assembly

    Institute of Scientific and Technical Information of China (English)

    WANG Youxiang; SHEN Jiacong

    2005-01-01

    Gene delivery systems are one of key issues that limit the development of gene therapy. The novel non-viral gene delivery systems fabricated via supramolecular assembly have begun to show increasing promising and applications in gene therapy due to its suitable nanometric size, controllable structure and excellent biocompatibility. In this review, the fundamental and recent progress of non-viral gene supramolecular assembly is reviewed. Artificial viruses--the future direction of non-viral gene delivery systems are also described.

  20. Self-assembly of dendritic dipeptides as a model of chiral selection in primitive biological systems.

    Science.gov (United States)

    Rosen, Brad M; Roche, Cécile; Percec, Virgil

    2013-01-01

    Biological macromolecules are homochiral, composed of sequences of stereocenters possessing the same repeated absolute configuration. This chapter addresses the mechanism of homochiral selection in polypeptides. In particular, the relationship between the stereochemistry (L or D) of structurally distinct α-amino acids is explored. Through functionalization of Tyr-Xaa dipeptides with self-assembling dendrons, the effect of stereochemical sequence of the dipeptide on the thermodynamics of self-assembly and the resulting structural features can be quantified. The dendritic dipeptide approach effectively isolates the stereochemical information of the shortest sequence of stereochemical information possible in polypeptide, while simultaneously allowing for dendron driven tertiary and quaternary structure formation and subsequent transfer of chiral information from the dipeptide to the dendritic sheath. This approach elucidates a mechanism of selecting a homochiral relationship between dissimilar but neighboring α-amino acids through thermodynamic preference for homochirality in solution-phase and bulk supramolecular helical polymerization. PMID:23306867

  1. Construction of Chiral Metamaterial with U-Shaped Resonator Assembly

    CERN Document Server

    Xiong, Xiang; Bao, Yong-Jun; Peng, Ru-Wen; Wang, Mu; Sun, Cheng; Lu, Xiang; Shao, Jun; Li, Zhi-Feng; Ming, Nai-Ben

    2009-01-01

    Chiral structure can be applied to construct metamaterial with negative refractive index (NRI). In an assembly of double-layered metallic U-shaped resonators with two resonant frequencies wH and wL, the effective induced electric and magnetic dipoles, which are contributed by the specific surface current distributions, are collinear at the same frequency. Consequently, for left circularly polarized light, NRI occurs at wH, whereas for right circularly polarized light it occurs at wL. Our design provides a new example to apply chiral structures to tune electromagnetic properties, and could be enlightening in exploring chiral metamaterials.

  2. Memorized chiral arrangement of gemini surfactant assemblies in nanometric hybrid organic-silica helices.

    Science.gov (United States)

    Ryu, Naoya; Okazaki, Yutaka; Hirai, Kana; Takafuji, Makoto; Nagaoka, Shoji; Pouget, Emilie; Ihara, Hirotaka; Oda, Reiko

    2016-04-30

    Hybrid nanohelices were obtained from silicification of self-assemblies of gemini surfactants with tartrate counterions. The chiral arrangement of these non-chiral gemini surfactants was preserved in the silica matrix even after the counterion exchange for a non-chiral bromide, and was capable of inducing the chiral organisation of a non-chiral dye, methyl orange. PMID:26961377

  3. Supramolecular design of self-assembling nanofibers for cartilage regeneration.

    Science.gov (United States)

    Shah, Ramille N; Shah, Nirav A; Del Rosario Lim, Marc M; Hsieh, Caleb; Nuber, Gordon; Stupp, Samuel I

    2010-02-23

    Molecular and supramolecular design of bioactive biomaterials could have a significant impact on regenerative medicine. Ideal regenerative therapies should be minimally invasive, and thus the notion of self-assembling biomaterials programmed to transform from injectable liquids to solid bioactive structures in tissue is highly attractive for clinical translation. We report here on a coassembly system of peptide amphiphile (PA) molecules designed to form nanofibers for cartilage regeneration by displaying a high density of binding epitopes to transforming growth factor beta-1 (TGFbeta-1). Growth factor release studies showed that passive release of TGFbeta-1 was slower from PA gels containing the growth factor binding sites. In vitro experiments indicate these materials support the survival and promote the chondrogenic differentiation of human mesenchymal stem cells. We also show that these materials can promote regeneration of articular cartilage in a full thickness chondral defect treated with microfracture in a rabbit model with or even without the addition of exogenous growth factor. These results demonstrate the potential of a completely synthetic bioactive biomaterial as a therapy to promote cartilage regeneration. PMID:20133666

  4. Energy Landscapes for the Self-Assembly of Supramolecular Polyhedra

    Science.gov (United States)

    Russell, Emily R.; Menon, Govind

    2016-06-01

    We develop a mathematical model for the energy landscape of polyhedral supramolecular cages recently synthesized by self-assembly (Sun et al. in Science 328:1144-1147, 2010). Our model includes two essential features of the experiment: (1) geometry of the organic ligands and metallic ions; and (2) combinatorics. The molecular geometry is used to introduce an energy that favors square-planar vertices (modeling {Pd}^{2+} ions) and bent edges with one of two preferred opening angles (modeling boomerang-shaped ligands of two types). The combinatorics of the model involve two-colorings of edges of polyhedra with four-valent vertices. The set of such two-colorings, quotiented by the octahedral symmetry group, has a natural graph structure and is called the combinatorial configuration space. The energy landscape of our model is the energy of each state in the combinatorial configuration space. The challenge in the computation of the energy landscape is a combinatorial explosion in the number of two-colorings of edges. We describe sampling methods based on the symmetries of the configurations and connectivity of the configuration graph. When the two preferred opening angles encompass the geometrically ideal angle, the energy landscape exhibits a very low-energy minimum for the most symmetric configuration at equal mixing of the two angles, even when the average opening angle does not match the ideal angle.

  5. Unzipping the role of chirality in nanoscale self-assembly of tripeptide hydrogels

    Science.gov (United States)

    Marchesan, Silvia; Waddington, Lynne; Easton, Christopher D.; Winkler, David A.; Goodall, Liz; Forsythe, John; Hartley, Patrick G.

    2012-10-01

    Change of chirality is a useful tool to manipulate the aqueous self-assembly behaviour of uncapped, hydrophobic tripeptides. In contrast with other short peptides, these tripeptides form hydrogels at a physiological pH without the aid of organic solvents or end-capping groups (e.g. Fmoc). The novel hydrogel forming peptide DLeu-Phe-Phe (DLFF) and its epimer Leu-Phe-Phe (LFF) exemplify dramatic supramolecular effects induced by subtle changes to stereochemistry. Only the d-amino acid-containing peptide instantly forms a hydrogel in aqueous solution following a pH switch, generating long fibres (>100 μm) that entangle into a 3D network. However, unexpected nanostructures are observed for both peptides and they are particularly heterogeneous for LFF. Structural analyses using CD, FT-IR and fluorescent amyloid staining reveal anti-parallel beta-sheets for both peptides. XRD analysis also identifies key distances consistent with beta-sheet formation in both peptides, but suggests additional high molecular order and extended molecular length for DLFF only. Molecular modelling of the two peptides highlights the key interactions responsible for self-assembly; in particular, rapid self-assembly of DLFF is promoted by a phenylalanine zipper, which is not possible because of steric factors for LFF. In conclusion, this study elucidates for the first time the molecular basis for how chirality can dramatically influence supramolecular organisation in very short peptide sequences.Change of chirality is a useful tool to manipulate the aqueous self-assembly behaviour of uncapped, hydrophobic tripeptides. In contrast with other short peptides, these tripeptides form hydrogels at a physiological pH without the aid of organic solvents or end-capping groups (e.g. Fmoc). The novel hydrogel forming peptide DLeu-Phe-Phe (DLFF) and its epimer Leu-Phe-Phe (LFF) exemplify dramatic supramolecular effects induced by subtle changes to stereochemistry. Only the d-amino acid-containing peptide

  6. Hollow spherical supramolecular dendrimers.

    Science.gov (United States)

    Percec, Virgil; Peterca, Mihai; Dulcey, Andrés E; Imam, Mohammad R; Hudson, Steven D; Nummelin, Sami; Adelman, Peter; Heiney, Paul A

    2008-10-01

    The synthesis of a library containing 12 conical dendrons that self-assemble into hollow spherical supramolecular dendrimers is reported. The design principles for this library were accessed by development of a method that allows the identification of hollow spheres, followed by structural and retrostructural analysis of their Pm3n cubic lattice. The first hollow spherical supramolecular dendrimer was made by replacing the tapered dendron, from the previously reported tapered dendritic dipeptide that self-assembled into helical pores, with its constitutional isomeric conical dendron. This strategy generated a conical dendritic dipeptide that self-assembled into a hollow spherical supramolecular dendrimer that self-organizes in a Pm3n cubic lattice. Other examples of hollow spheres were assembled from conical dendrons without a dipeptide at their apex. These are conical dendrons originated from tapered dendrons containing additional benzyl ether groups at their apex. The inner part of the hollow sphere assembled from the dipeptide resembles the path of a spherical helix or loxodrome and, therefore, is chiral. The spheres assembled from other conical dendrons are nonhelical, even when they contain stereocenters on the alkyl groups from their periphery. Functionalization of the apex of the conical dendrons with diethylene glycol allowed the encapsulation of LiOTf and RbOTf in the center of the hollow sphere. These experiments showed that hollow spheres function as supramolecular dendritic capsules and therefore are expected to display functions complementary to those of other related molecular and supramolecular structures. PMID:18771261

  7. From metal-organic squares to porous zeolite-like supramolecular assemblies

    KAUST Repository

    Wang, Shuang

    2010-12-29

    We report the synthesis, structure, and characterization of two novel porous zeolite-like supramolecular assemblies, ZSA-1 and ZSA-2, having zeolite gis and rho topologies, respectively. The two compounds were assembled from functional metal-organic squares (MOSs) via directional hydrogen-bonding interactions and exhibited permanent microporosity and thermal stability up to 300 °C. © 2010 American Chemical Society.

  8. Fabrication of a Complex Two-Dimensional Adenine-Perylene-3,4,9, 10-tetracarboxylic Dianhydride Chiral Nanoarchitecture through Molecular Self-Assembly

    OpenAIRE

    Sun, Xiaonan; Mura, Manuela; Jonkman, Harry T.; Kantorovich, Lev N.; Silly, Fabien

    2012-01-01

    The two-dimensional self-assembly of a nonsyrnmetric adenine DNA base mixed with symmetric perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules is investigated using scanning tunneling microscopy (STM). We experimentally observe that these two building blocks form a complex close-packed chiral supramolecular network on Au(111). The unit cell of the adenine PTCDA nanoarchitecture is composed of 14 molecules. The high stability of this structure relies on PTCDA-PTCDA and PTCDA-adenin...

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

    Directory of Open Access Journals (Sweden)

    Domenico Lombardo

    2015-01-01

    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.

  10. Green fluorescent protein nanopolygons as monodisperse supramolecular assemblies of functional proteins with defined valency

    Science.gov (United States)

    Kim, Young Eun; Kim, Yu-Na; Kim, Jung A.; Kim, Ho Min; Jung, Yongwon

    2015-05-01

    Supramolecular protein assemblies offer novel nanoscale architectures with molecular precision and unparalleled functional diversity. A key challenge, however, is to create precise nano-assemblies of functional proteins with both defined structures and a controlled number of protein-building blocks. Here we report a series of supramolecular green fluorescent protein oligomers that are assembled in precise polygonal geometries and prepared in a monodisperse population. Green fluorescent protein is engineered to be self-assembled in cells into oligomeric assemblies that are natively separated in a single-protein resolution by surface charge manipulation, affording monodisperse protein (nano)polygons from dimer to decamer. Several functional proteins are multivalently displayed on the oligomers with controlled orientations. Spatial arrangements of protein oligomers and displayed functional proteins are directly visualized by a transmission electron microscope. By employing our functional protein assemblies, we provide experimental insight into multivalent protein-protein interactions and tools to manipulate receptor clustering on live cell surfaces.

  11. Chiral bis(amino alcohol)oxalamide gelators-gelation properties and supramolecular organization: racemate versus pure enantiomer gelation.

    Science.gov (United States)

    Makarević, Janja; Jokić, Milan; Raza, Zlata; Stefanić, Zoran; Kojić-Prodić, Biserka; Zinić, Mladen

    2003-11-21

    Four new chiral bis(amino alcohol)oxalamides (1-4: amino alcohol=leucinol, valinol, phenylglycinol, and phenylalaninol, respectively) have been prepared as low-molecular-weight organic gelators. Their gelation properties towards various organic solvents and mixtures were determined and these were then compared to related bis(amino acid) oxalamide gelators. Spectroscopic (FTIR, (1)H NMR) and X-ray diffraction studies revealed that the primary organization motif of (S,S)-1 and racemate 1 (rac-1) in lipophilic solvents involved the formation of inverse bilayers. The X-ray crystal structure of (S,S)-1 also shows this type of bilayer organization. The crystal structure of rac-2 reveals meso bilayers of hydrogen-bonded aggregates. Within the bilayers formed, the gelator molecules are connected by cooperative hydrogen bonding between oxalamide units and OH groups, while the interbilayer interactions are realized through lipophilic interactions between the iBu groups of leucinol. Oxalamide meso-1 lacks any gelation ability and crystallizes in monolayers. In dichloromethane rac-1 forms an unstable gel; this is prone to crystallization as a result of the formation of symmetrical meso bilayers. In contrast, in aromatic solvents rac-1 forms stable gels; this indicates that enantiomeric bilayers are formed. Oxalamide rac-1 is capable of gelling a volume of toluene three times larger than (S,S)-1. A tranmission electron microscopy investigation of rac-1 and (S,S)-1 toluene gels reveals the presence of thinner fibers in the former gel, and, hence, a more compact network that is capable of immobilizing a larger volume of the solvent. The self-assembly of these types of gelator molecules into bilayers and subsequent formation of fibrous aggregates can be explained by considering the strength and direction of aggregate forces (supramolecular vectors) in three-dimensional space. PMID:14639640

  12. Self-assembly of cationic multidomain peptide hydrogels: supramolecular nanostructure and rheological properties dictate antimicrobial activity.

    Science.gov (United States)

    Jiang, Linhai; Xu, Dawei; Sellati, Timothy J; Dong, He

    2015-12-01

    Hydrogels are an important class of biomaterials that have been widely utilized for a variety of biomedical/medical applications. The biological performance of hydrogels, particularly those used as wound dressing could be greatly advanced if imbued with inherent antimicrobial activity capable of staving off colonization of the wound site by opportunistic bacterial pathogens. Possessing such antimicrobial properties would also protect the hydrogel itself from being adversely affected by microbial attachment to its surface. We have previously demonstrated the broad-spectrum antimicrobial activity of supramolecular assemblies of cationic multi-domain peptides (MDPs) in solution. Here, we extend the 1-D soluble supramolecular assembly to 3-D hydrogels to investigate the effect of the supramolecular nanostructure and its rheological properties on the antimicrobial activity of self-assembled hydrogels. Among designed MDPs, the bactericidal activity of peptide hydrogels was found to follow an opposite trend to that in solution. Improved antimicrobial activity of self-assembled peptide hydrogels is dictated by the combined effect of supramolecular surface chemistry and storage modulus of the bulk materials, rather than the ability of individual peptides/peptide assemblies to penetrate bacterial cell membrane as observed in solution. The structure-property-activity relationship developed through this study will provide important guidelines for designing biocompatible peptide hydrogels with built-in antimicrobial activity for various biomedical applications.

  13. Chiral assembly of weakly curled hard rods: Effect of steric chirality and polarity

    Energy Technology Data Exchange (ETDEWEB)

    Wensink, H. H., E-mail: wensink@lps.u-psud.fr; Morales-Anda, L. [Laboratoire de Physique des Solides–UMR 8502, Université Paris-Sud & CNRS, 91405 Orsay (France)

    2015-10-14

    We theoretically investigate the pitch of lyotropic cholesteric phases composed of slender rods with steric chirality transmitted via a weak helical deformation of the backbone. In this limit, the model is amenable to analytical treatment within Onsager theory and a closed expression for the pitch versus concentration and helical shape can be derived. Within the same framework, we also briefly review the possibility of alternative types of chiral order, such as twist-bend or screw-like nematic phases, finding that cholesteric order dominates for weakly helical distortions. While long-ranged or “soft” chiral forces usually lead to a pitch decreasing linearly with concentration, steric chirality leads to a much steeper decrease of quadratic nature. This reveals a subtle link between the range of chiral intermolecular interaction and the pitch sensitivity with concentration. A much richer dependence on the thermodynamic state is revealed for polar helices where parallel and anti-parallel pair alignments along the local director are no longer equivalent. It is found that weak temperature variations may lead to dramatic changes in the pitch, despite the lyotropic nature of the assembly.

  14. Controlling Electronic Transitions in Fullerene van der Waals Aggregates via Supramolecular Assembly.

    Science.gov (United States)

    Das, Saunak; Herrmann-Westendorf, Felix; Schacher, Felix H; Täuscher, Eric; Ritter, Uwe; Dietzek, Benjamin; Presselt, Martin

    2016-08-24

    Morphologies crucially determine the optoelectronic properties of organic semiconductors. Therefore, hierarchical and supramolecular approaches have been developed for targeted design of supramolecular ensembles of organic semiconducting molecules and performance improvement of, e.g., organic solar cells (OSCs), organic light emitting diodes (OLEDs), and organic field-effect transistors (OFETs). We demonstrate how the photonic properties of fullerenes change with the formation of van der Waals aggregates. We identified supramolecular structures with broadly tunable absorption in the visible spectral range and demonstrated how to form aggregates with targeted visible (vis) absorption. To control supramolecular structure formation, we functionalized the C60-backbone with polar (bis-polyethylene glycol malonate-MPEG) tails, thus yielding an amphiphilic fullerene derivative that self-assembles at interfaces. Aggregates of systematically tuned size were obtained from concentrating MPEGC60 in stearic acid matrices, while different supramolecular geometries were provoked via different thin film preparation methods, namely spin-casting and Langmuir-Blodgett (LB) deposition from an air-water interface. We demonstrated that differences in molecular orientation in LB films (C2v type point group aggregates) and spin-casting (stochastic aggregates) lead to huge changes in electronic absorption spectra due to symmetry and orientation reasons. These differences in the supramolecular structures, causing the different photonic properties of spin-cast and LB films, could be identified by means of quantum chemical calculations. Employing supramolecular assembly, we propounded that molecular symmetry in fullerene aggregates is extremely important in controlling vis absorption to harvest photons efficiently, when mixed with a donor molecule, thus improving active layer design and performance of OSCs. PMID:27482718

  15. Self-assembled and responsive supramolecular nanoparticles mediated by cucurbit[8]uril host-guest interactions

    NARCIS (Netherlands)

    Stoffelen, Carmen

    2015-01-01

    Supramolecular nanoparticles (SNPs) have gained large interest in nanoscience because stable, but reversible three-dimensional assemblies can be used for a variety of applications, ranging from stimuli-responsive and self-healing materials to biomedical applications. In particular soft SNPs are prom

  16. Supramolecular Assembly of Complementary Cyanine Salt J-Aggregates

    KAUST Repository

    Li, Zhong’an

    2015-09-09

    An understanding of structure–property relationships in cyanine dyes is critical for their design and application. Anionic and cationic cyanines can be organized into complementary cyanine salts, offering potential building blocks to modulate their intra/intermolecular interactions in the solid state. Here, we demonstrate how the structures of these complementary salts can be tuned to achieve highly ordered J-type supramolecular aggregate structures of heptamethine dyes in crystalline solids.

  17. Macromolecularly crowded in vitro microenvironments accelerate the production of extracellular matrix-rich supramolecular assemblies

    OpenAIRE

    Kumar, Pramod; Satyam, Abhigyan; Fan, Xingliang; Rodriguez, Brian J.; et al

    2015-01-01

    Therapeutic strategies based on the principles of tissue engineering by self-assembly put forward the notion that functional regeneration can be achieved by utilising the inherent capacity of cells to create highly sophisticated supramolecular assemblies. However, in dilute ex vivo microenvironments, prolonged culture time is required to develop an extracellular matrix-rich implantable device. Herein, we assessed the influence of macromolecular crowding, a biophysical phenomenon that regulate...

  18. Chiral recognition and selection during the self-assembly process of protein-mimic macroanions

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Panchao; Zhang, Zhi-Ming; Lv, Hongjin; Li, Tao; Haso, Fadi; Hu, Lang; Zhang, Baofang; Basca, John; Wei, Yongge; Gao, Yanqing; Hou, Yu; Li, Yang-Guang; Hill, Craig L.; Wang, En-Bo; Liu, Tianbo

    2015-03-01

    The research on chiral recognition and chiral selection is not only fundamental in resolving the puzzle of homochirality, but also instructive in chiral separation and stereoselective catalysis. Here we report the chiral recognition and chiral selection during the self-assembly process of two enantiomeric wheel-shaped macroanions, [Fe28(μ3-O)8(Tart)16(HCOO)24]20- (Tart=D- or L-tartaric acid tetra-anion). The enantiomers are observed to remain self-sorted and self-assemble into their individual assemblies in their racemic mixture solution. The addition of chiral co-anions can selectively suppress the self-assembly process of the enantiomeric macroanions, which is further used to separate the two enantiomers from their mixtures on the basis of the size difference between the monomers and the assemblies. We believe that delicate long-range electrostatic interactions could be responsible for such high-level chiral recognition and selection.

  19. Chiral recognition and selection during the self-assembly process of protein-mimic macroanions.

    Science.gov (United States)

    Yin, Panchao; Zhang, Zhi-Ming; Lv, Hongjin; Li, Tao; Haso, Fadi; Hu, Lang; Zhang, Baofang; Bacsa, John; Wei, Yongge; Gao, Yanqing; Hou, Yu; Li, Yang-Guang; Hill, Craig L; Wang, En-Bo; Liu, Tianbo

    2015-01-01

    The research on chiral recognition and chiral selection is not only fundamental in resolving the puzzle of homochirality, but also instructive in chiral separation and stereoselective catalysis. Here we report the chiral recognition and chiral selection during the self-assembly process of two enantiomeric wheel-shaped macroanions, [Fe28(μ3-O)8(Tart)16(HCOO)24](20-) (Tart=D- or L-tartaric acid tetra-anion). The enantiomers are observed to remain self-sorted and self-assemble into their individual assemblies in their racemic mixture solution. The addition of chiral co-anions can selectively suppress the self-assembly process of the enantiomeric macroanions, which is further used to separate the two enantiomers from their mixtures on the basis of the size difference between the monomers and the assemblies. We believe that delicate long-range electrostatic interactions could be responsible for such high-level chiral recognition and selection. PMID:25756393

  20. Supramolecular Electrochemistry

    Science.gov (United States)

    Kaifer, Angel E.; Gomez-Kaifer, Marielle

    1999-12-01

    This book describes the electrochemical behavior of supramolecular systems. Special emphasis will be given to the electrochemistry of host-guest complexes, monolayer and multilayer assemblies, dendrimers, and other supramolecular assemblies. A fundamental theme throughout the book is to explore the effects that supramolecular structure exerts on the thermodynamics and kinetics of electrochemical reactions. Conversely, attention will be placed to the various ways in which electrochemical or redox conversions can be utilized to control or affect the structure or properties of supramolecular systems. This first book on this topic will be of value for graduate students and advanced researchers in both electrochemistry and supramolecular chemistry.

  1. Enantiomeric Excess-Tuned 2D Structural Transition: From Heterochiral to Homochiral Supramolecular Assemblies.

    Science.gov (United States)

    Li, Shu-Ying; Chen, Ting; Wang, Lin; Sun, Bing; Wang, Dong; Wan, Li-Jun

    2016-07-12

    Spontaneous resolution of enantiomers is an intriguing and important phenomenon in surface chirality studies. Herein, we report on a two-dimensional (2D) structural transition from the heterochiral to homochiral assembly tuned by changing the enantiomeric excess (ee) of enantiomers in the solution phase. Enantiomers cocrystallize as racemates on the surface when the ee of the R-enantiomer (or S-enantiomer) remains below a critical value, whereas chiral segregation is achieved, and globally homochiral surfaces composed of exclusively one enantiomer are obtained as the critical ee is exceeded. The heterochiral-homochiral transition is ascribed to the formation of energetically unfavored homochiral molecular dimers under the control of the majority-rules principle at high ee values. Such results present an intriguing phenomenon in chiral ordering at surfaces, promising a new enlightenment toward understanding chiral resolution and the evolution of chirality. PMID:27287273

  2. Protein-responsive assemblies from catechol-metal ion supramolecular coordination.

    Science.gov (United States)

    Yuan, C; Chen, J; Yu, S; Chang, Y; Mao, J; Xu, Y; Luo, W; Zeng, B; Dai, L

    2015-03-21

    Supramolecular self-assembly driven by catechol-metal ion coordination has gained great success in the fabrication of functional materials including adhesives, capsules, coatings and hydrogels. However, this route has encountered a great challenge in the construction of nanoarchitectures in the absence of removable templates, because of the uncontrollable crosslinking of catechol-metal ion coordination. Herein, we show that a supramolecular approach, combining both catechol-metal ion coordination and polymer self-assembly together, can organize polymers into hybrid nanoassemblies ranging from solid particles, homogeneous vesicles to Janus vesicles. Without the introduction of a specific binding ligand or complicated molecular design, these assemblies can totally disassemble in response to proteins. UV/vis absorption, fluorescence quenching and recovery investigations have confirmed that proteins can seize metal ions from the hybrid nanoassemblies, thus causing the degradation of catechol-metal ion coordination networks.

  3. Thermally assisted photonic inversion of supramolecular handedness.

    Science.gov (United States)

    Gopal, Anesh; Hifsudheen, Mohamed; Furumi, Seiichi; Takeuchi, Masayuki; Ajayaghosh, Ayyappanpillai

    2012-10-15

    Spiraling into control: A photoresponsive supramolecular assembly demonstrates that light, along with heating (Δ) and cooling (), can cause chiral communication between molecules. This effect leads to bias in the helicity of the complex, causing a reversible switching of macroscopic handedness, as shown by a reversal of sign of the circularly polarized luminescence (CPL) that is emitted.

  4. Self-assembly of cationic multidomain peptide hydrogels: supramolecular nanostructure and rheological properties dictate antimicrobial activity

    Science.gov (United States)

    Jiang, Linhai; Xu, Dawei; Sellati, Timothy J.; Dong, He

    2015-11-01

    Hydrogels are an important class of biomaterials that have been widely utilized for a variety of biomedical/medical applications. The biological performance of hydrogels, particularly those used as wound dressing could be greatly advanced if imbued with inherent antimicrobial activity capable of staving off colonization of the wound site by opportunistic bacterial pathogens. Possessing such antimicrobial properties would also protect the hydrogel itself from being adversely affected by microbial attachment to its surface. We have previously demonstrated the broad-spectrum antimicrobial activity of supramolecular assemblies of cationic multi-domain peptides (MDPs) in solution. Here, we extend the 1-D soluble supramolecular assembly to 3-D hydrogels to investigate the effect of the supramolecular nanostructure and its rheological properties on the antimicrobial activity of self-assembled hydrogels. Among designed MDPs, the bactericidal activity of peptide hydrogels was found to follow an opposite trend to that in solution. Improved antimicrobial activity of self-assembled peptide hydrogels is dictated by the combined effect of supramolecular surface chemistry and storage modulus of the bulk materials, rather than the ability of individual peptides/peptide assemblies to penetrate bacterial cell membrane as observed in solution. The structure-property-activity relationship developed through this study will provide important guidelines for designing biocompatible peptide hydrogels with built-in antimicrobial activity for various biomedical applications.Hydrogels are an important class of biomaterials that have been widely utilized for a variety of biomedical/medical applications. The biological performance of hydrogels, particularly those used as wound dressing could be greatly advanced if imbued with inherent antimicrobial activity capable of staving off colonization of the wound site by opportunistic bacterial pathogens. Possessing such antimicrobial properties would

  5. A novel nanostructured supramolecular hydrogel self-assembled from tetraphenylethylene-capped dipeptides.

    Science.gov (United States)

    Yeh, Mei-Yu; Huang, Chen-Wei; Chang, Jui-Wen; Huang, Yu-Tang; Lin, Jhong-Hua; Hsu, Shu-Min; Hung, Shih-Chieh; Lin, Hsin-Chieh

    2016-08-14

    Herein, we report a tetraphenylethylene-diglycine (TPE-GG) hydrogelator from a systematic study of TPE-capped dipeptides with various amphiphilic properties. From a chemical design, we found that the hydrogelation of TPE-GG molecules can be utilized to generate supramolecular nanostructures with a large TPE-based nanobelt width (∼300 nm) and lateral dimension ratio (>30 fold). In addition, TPE-GG has the lowest molecular weight and minimum number of atoms compared to any TPE-capped peptide hydrogelator reported to date. This minimal self-assembled hydrogelator can fundamentally achieve the gel features compared with other TPE-capped peptides. A combined experimental and computational study indicates the π-π interactions, electrostatic interactions and hydrogen-bonding interactions are the major driving forces behind the formation of self-assembled nanobelts. This study demonstrates the importance of structure-property relationships and provides new insights into the design of supramolecular nanomaterials. PMID:27381445

  6. Interaction of chiral rafts in self-assembled colloidal membranes

    Science.gov (United States)

    Xie, Sheng; Hagan, Michael F.; Pelcovits, Robert A.

    2016-03-01

    Colloidal membranes are monolayer assemblies of rodlike particles that capture the long-wavelength properties of lipid bilayer membranes on the colloidal scale. Recent experiments on colloidal membranes formed by chiral rodlike viruses showed that introducing a second species of virus with different length and opposite chirality leads to the formation of rafts—micron-sized domains of one virus species floating in a background of the other viruses [Sharma et al., Nature (London) 513, 77 (2014), 10.1038/nature13694]. In this article we study the interaction of such rafts using liquid crystal elasticity theory. By numerically minimizing the director elastic free energy, we predict the tilt angle profile for both a single raft and two rafts in a background membrane, and the interaction between two rafts as a function of their separation. We find that the chiral penetration depth in the background membrane sets the scale for the range of the interaction. We compare our results with the experimental data and find good agreement for the strength and range of the interaction. Unlike the experiments, however, we do not observe a complete collapse of the data when rescaled by the tilt angle at the raft edge.

  7. Supramolecular nanoparticles generated by the self-assembly of polyrotaxanes for antitumor drug delivery

    OpenAIRE

    Liu R; Lai YS; He B; Li Y; Wang G; Chang S; Gu Z

    2012-01-01

    Rong Liu,1,2,* Yusi Lai,1,* Bin He,1 Yuan Li,1 Gang Wang,1 Shuang Chang,1 Zhongwei Gu1 1National Engineering Research Center for Biomaterials, Sichuan University, Chengdu, China; 2Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China*These authors contributed equally to this paperAbstract: A new approach of fabricating supramolecular nanoparticles generated by self-assembly polyrotaxanes for antitumor drug delivery has been reported. Cinnamic-acid-modified poly(ethy...

  8. Supramolecular Crafting of Self-Assembling Camptothecin Prodrugs with Enhanced Efficacy against Primary Cancer Cells

    OpenAIRE

    Su, Hao; Zhang, Pengcheng; Cheetham, Andrew G.; Koo, Jin Mo; Lin, Ran; Masood, Asad; Schiapparelli, Paula; Quiñones-Hinojosa, Alfredo; Cui, Honggang

    2016-01-01

    Chemical modification of small molecule hydrophobic drugs is a clinically proven strategy to devise prodrugs with enhanced treatment efficacy. While this prodrug strategy improves the parent drug's water solubility and pharmacokinetic profile, it typically compromises the drug's potency against cancer cells due to the retarded drug release rate and reduced cellular uptake efficiency. Here we report on the supramolecular design of self-assembling prodrugs (SAPD) with much improved water solubi...

  9. Development of Self-Assembled Supramolecular Catalysts and Their Applications to Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    Shiro IKEGAMI

    2005-01-01

    @@ 1Introduction In modern synthetic organic chemistry, the development of efficient reagent or catalyst recycling systems is regarded as one of the most important topics. We have previously reported a self-assembled process between poly(N-isopropylacrylamide) (PNIPAAm) based polymer ligands and an inorganic species[1]. This process afforded a networked supramolecular complex where the polymers are cross-linked together by the inorganic species. Thus obtained complex was insoluble in water and worked as an efficient triphase catalyst.

  10. Tuning Cellular Uptake of Molecular Probes by Rational Design of Their Assembly into Supramolecular Nanoprobes.

    Science.gov (United States)

    Lock, Lye Lin; Reyes, Claudia D; Zhang, Pengcheng; Cui, Honggang

    2016-03-16

    Intracellular sensing of pathologically relevant biomolecules could provide essential information for accurate evaluation of disease staging and progression, yet the poor cellular uptake of water-soluble molecular probes limits their use as protease sensors. In other cases such as extracellular sensing, cellular uptake should be effectively inhibited. Self-assembly of molecular probes into supramolecular nanoprobes presents a potential strategy to alter their interaction mechanisms with cells to promote or reduce their cellular uptake. Here, we report on the design, synthesis, and assembly of peptide-based molecular beacons into supramolecular protease sensors of either spherical or filamentous shapes. We found that positively charged spherical nanobeacons demonstrate much higher cellular uptake efficiency than its monomeric form, thus making them most suitable for intracellular sensing of the lysosomal protease cathepsin B. Our results also suggest that assembly into filamentous nanobeacons significantly reduces their internalization by cancer cells, an important property that can be utilized for probing extracellular protease activities. These studies provide important guiding principles for rational design of supramolecular nanoprobes with tunable cellular uptake characteristics.

  11. Directed flexibility: self-assembly of a supramolecular tetrahedron.

    Science.gov (United States)

    Ludlow, James M; Xie, Tingzheng; Guo, Zaihong; Guo, Kai; Saunders, Mary Jane; Moorefield, Charles N; Wesdemiotis, Chrys; Newkome, George R

    2015-03-01

    Self-assembly of a tribenzo-27-crown-9 ether functionalized with six terpyridines generated (85%) an expanded tetrahedral structure comprised of four independent triangular surfaces interlinked by crown ether vertices.

  12. Expanding the structural diversity of self-assembling dendrons and supramolecular dendrimers via complex building blocks.

    Science.gov (United States)

    Percec, Virgil; Won, Betty C; Peterca, Mihai; Heiney, Paul A

    2007-09-12

    The design and synthesis of the first examples of AB4 and AB5 dendritic building blocks with complex architecture are reported. Structural and retrostructural analysis of supramolecular dendrimers self-assembled from hybrid dendrons based on different combinations of AB4 and AB5 building blocks with AB2 and AB3 benzyl ether dendrons demonstrated that none of these new hybrid dendrons exhibit the previously encountered conformations of libraries of benzyl ether dendrons. These hybrid dendrons enabled the discovery of some highly unusual tapered and conical dendrons generated by the intramolecular back-folding of their repeat units and of their apex. The new back-folded tapered dendrons have double thickness and self-assemble into pine-tree-like columns exhibiting a long-range 7/2 helical order. The back-folded conical dendrons self-assemble into spherical dendrimers. Non-back-folded truncated conical dendrons were also discovered. They self-assemble into spherical dendrimers with a less densely packed center. The discovery of dendrons displaying a novel crown-like conformation is also reported. Crown-like dendrons self-assemble into long-range 5/1 helical pyramidal columns. The long-range 7/2 and 5/1 helical structures were established by applying, for the first time, the helical diffraction theory to the analysis of X-ray patterns obtained from oriented fibers of supramolecular dendrimers. PMID:17705390

  13. Regulated assembly of a supramolecular centrosome scaffold in vitro

    DEFF Research Database (Denmark)

    Woodruff, J. B.; Wueseke, O.; Viscardi, V.;

    2015-01-01

    The centrosome organizes microtubule arrays within animal cells and comprises two centrioles surrounded by an amorphous protein mass called the pericentriolar material (PCM). Despite the importance of centrosomes as microtubule-organizing centers, the mechanism and regulation of PCM assembly are ...

  14. Supramolecular nanoparticles generated by the self-assembly of polyrotaxanes for antitumor drug delivery

    Science.gov (United States)

    Liu, Rong; Lai, Yusi; He, Bin; Li, Yuan; Wang, Gang; Chang, Shuang; Gu, Zhongwei

    2012-01-01

    A new approach of fabricating supramolecular nanoparticles generated by self-assembly polyrotaxanes for antitumor drug delivery has been reported. Cinnamic-acid-modified poly(ethylene glycol) chains were threaded in α-cyclodextrins to form polyrotaxanes. The polyrotaxanes self-assembled supramolecular nanoparticles. The morphology of the nanoparticles was changed from nanovesicle to micelle after the antitumor drug, doxorubicin, was loaded. The release profile of the drug-loaded nanoparticles was investigated, and it was found that the sustaining release time could last for 32 hours. The drug-loaded nanoparticles were co-cultured with mouse 4T1 breast cancer cells with a drug concentration of 10 μg/mL; the cell survival rate was 3.3% after a 72-hour incubation. In an in vivo study of breast cancer in a mouse model, the drug-loaded nanoparticles were injected in the tail veins of mice with a dose of 5 mg/kg body weight. The tumor inhibition rate of drug-loaded nanoparticles was 53%, which was better than that of doxorubicin hydrochloride. The cardiac toxicity of doxorubicin was decreased greatly after the encapsulation into supramolecular polyrotaxane nanoparticles. PMID:23055732

  15. Supramolecular Assemblies Using Piperazine with Dicarboxylic Acids and Hydroxy-carboxylic Acids

    Institute of Scientific and Technical Information of China (English)

    CHEN Zi-Yun; PENG Meng-Xia

    2008-01-01

    The molecular self-assembly of piperazine (pip) with 1,4-cyclohexanedicarboxylic acid (H2chda),m-phthalic acid (H2mpda),6-hydroxy-2-naphthalic acid (Hohna) and 1-hydroxy-2-naphthalic acid (Hshna) results in four new supramolecular networks formulated as H2pip·chda (1),H2pip·2Hmpda (2),HEpip·ohna·2H2O(3) and H2pip·shna (4),respectively.Single-crystal X-ray diffraction study reveals that compounds 1--3 are three-dimensional supramolecular networks,while 4 has a one-dimensional hydrogen-bonded chain-based structure,with CCDC:672051 (1),672052 (2),672053 (3) and 672054 (4).

  16. Enzyme-Regulated Supramolecular Assemblies of Cholesterol Conjugates against Drug-Resistant Ovarian Cancer Cells.

    Science.gov (United States)

    Wang, Huaimin; Feng, Zhaoqianqi; Wu, Dongdong; Fritzsching, Keith J; Rigney, Mike; Zhou, Jie; Jiang, Yujie; Schmidt-Rohr, Klaus; Xu, Bing

    2016-08-31

    We report that phosphotyrosine-cholesterol conjugates effectively and selectively kill cancer cells, including platinum-resistant ovarian cancer cells. The conjugate increases the degree of noncovalent oligomerization upon enzymatic dephosphorylation in aqueous buffer. This enzymatic conversion also results in the assembly of the cholesterol conjugates inside and outside cells and leads to cell death. Preliminary mechanistic studies suggest that the formed assemblies of the conjugates not only interact with actin filaments and microtubules but also affect lipid rafts. As the first report of multifaceted supramolecular assemblies of cholesterol conjugates against cancer cells, this work illustrates the integration of enzyme catalysis and self-assembly of essential biological small molecules on and inside cancer cells as a promising strategy for developing multifunctional therapeutics to treat drug-resistant cancers. PMID:27529637

  17. Cooperative Self-Assembly Transfer from Hierarchical Supramolecular Polymers to Gold Nanoparticles.

    Science.gov (United States)

    Coelho, João Paulo; Tardajos, Gloria; Stepanenko, Vladimir; Rödle, Alexander; Fernández, Gustavo; Guerrero-Martínez, Andrés

    2015-11-24

    The transfer of information encoded by molecular subcomponents is a key phenomenon that regulates the biological inheritance in living organisms, yet there is a lack of understanding of related transfer mechanisms at the supramolecular level in artificial multicomponent systems. Our contribution to tackle this challenge has focused on the design of a thiolated π-conjugated linking unit, whose hierarchical, cooperative self-assembly in nonpolar media can be efficiently transferred from the molecular to the nanoscopic level, thereby enabling the reversible self-assembly of gold nanoparticle (AuNP) clusters. The transfer of supramolecular information by the linking π-system can only take place when a specific cooperative nucleation-elongation mechanism is operative, whereas low-ordered noncooperative assemblies formed below a critical concentration do not suffice to extend the order to the AuNP level. To the best of our knowledge, our approach has allowed for the first time a deep analysis of the hierarchy levels and thermodynamics involved in the self-assembly of AuNPs.

  18. Hyaluronic Acid-Based Biocompatible Supramolecular Assembly for Sustained Release of Antiretroviral Drug.

    Science.gov (United States)

    Song, Byeongwoon; Puskás, István; Szente, Lajos; Hildreth, James E K

    2016-09-01

    Human immunodeficiency virus (HIV) infection and its associated diseases continue to increase despite the progress in our understanding of HIV biology and the availability of a number of antiretroviral drugs. Adherence is a significant factor in the success of HIV therapy and current HIV treatment regimens require a combination of antiviral drugs to be taken at least daily for the remainder of a patient's life. A drug delivery system that allows sustained drug delivery could reduce the medical burden and costs associated with medication nonadherence. Here, we describe a novel supramolecular assembly or matrix that contains an anionic polymer hyaluronic acid, cationic polymer poly-l-lysine, and anionic oligosaccharide sulfobutylether-beta-cyclodextrin. HIV reverse transcriptase inhibitors Zidovudine and Lamivudine were successfully encapsulated into the polymer assembly in a noncovalent manner. The physicochemical properties and antiviral activity of the polymer assemblies were studied. The results of this study suggest that the supramolecular assemblies loaded with HIV drugs exert potent antiviral activity and allow sustained drug release. A novel drug delivery formulation such as the one described here could facilitate our efforts to reduce the morbidity and mortality associated with HIV infections and could be utilized in the design of therapeutic approaches for other diseases. PMID:26975245

  19. Molecular self-assembly approaches for supramolecular electronic and organic electronic devices

    Science.gov (United States)

    Yip, Hin-Lap

    Molecular self-assembly represents an efficient bottom-up strategy to generate structurally well-defined aggregates of semiconducting pi-conjugated materials. The capability of tuning the chemical structures, intermolecular interactions and nanostructures through molecular engineering and novel materials processing renders it possible to tailor a large number of unprecedented properties such as charge transport, energy transfer and light harvesting. This approach does not only benefit traditional electronic devices based on bulk materials, but also generate a new research area so called "supramolecular electronics" in which electronic devices are built up with individual supramolecular nanostructures with size in the sub-hundred nanometers range. My work combined molecular self-assembly together with several novel materials processing techniques to control the nucleation and growth of organic semiconducting nanostructures from different type of pi-conjugated materials. By tailoring the interactions between the molecules using hydrogen bonds and pi-pi stacking, semiconducting nanoplatelets and nanowires with tunable sizes can be fabricated in solution. These supramolecular nanostructures were further patterned and aligned on solid substrates through printing and chemical templating methods. The capability to control the different hierarchies of organization on surface provides an important platform to study their structural-induced electronic properties. In addition to using molecular self-assembly to create different organic nanostructures, functional self-assembled monolayer (SAM) formed by spontaneous chemisorption on surfaces was used to tune the interfacial property in organic solar cells. Devices showed dramatically improved performance when appropriate SAMs were applied to optimize the contact property for efficiency charge collection.

  20. Structural Consequences of Anionic Host-Cationic Guest Interactions in a Supramolecular Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael D.; Johnson, Darren W.; Szigethy, Geza; Davis, Anna V.; Teat, Simon J.; Oliver, Allen G.; Bergman, Robert G.; Raymond, Kenneth N.

    2008-07-09

    The molecular structure of the self-assembled supramolecular assembly [M{sub 4}L{sub 6}]{sup 12-} has been explored with different metals (M = Ga{sup III}, Fe{sup III}, Ti{sup IV}) and different encapsulated guests (NEt{sub 4}{sup +}, BnNMe{sub 3}{sup +}, Cp{sub 2}Co{sup +}, Cp*{sub 2}Co{sup +}) by X-ray crystallography. While the identity of the metal ions at the vertices of the M{sub 4}L{sub 6} structure is found to have little effect on the assembly structure, encapsulated guests significantly distort the size and shape of the interior cavity of the assembly. Cations on the exterior of the assembly are found to interact with the assembly through either {pi}-{pi}, cation-{pi}, or CH-{pi} interactions. In some cases, the exterior guests interact with only one assembly, but cations with the ability to form multiple {pi}-{pi} interactions are able to interact with adjacent assemblies in the crystal lattice. The solvent accessible cavity of the assembly is modeled using the rolling probe method and found to range from 253-434 {angstrom}{sup 3}, depending on the encapsulated guest. Based on the volume of the guest and the volume of the cavity, the packing coefficient for each host-guest complex is found to range from 0.47-0.67.

  1. Supramolecular nanoparticles generated by the self-assembly of polyrotaxanes for antitumor drug delivery

    Directory of Open Access Journals (Sweden)

    Liu R

    2012-10-01

    Full Text Available Rong Liu,1,2,* Yusi Lai,1,* Bin He,1 Yuan Li,1 Gang Wang,1 Shuang Chang,1 Zhongwei Gu1 1National Engineering Research Center for Biomaterials, Sichuan University, Chengdu, China; 2Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China*These authors contributed equally to this paperAbstract: A new approach of fabricating supramolecular nanoparticles generated by self-assembly polyrotaxanes for antitumor drug delivery has been reported. Cinnamic-acid-modified poly(ethylene glycol chains were threaded in a-cyclodextrins to form polyrotaxanes. The polyrotaxanes self-assembled supramolecular nanoparticles. The morphology of the nanoparticles was changed from nanovesicle to micelle after the antitumor drug, doxorubicin, was loaded. The release profile of the drug-loaded nanoparticles was investigated, and it was found that the sustaining release time could last for 32 hours. The drug-loaded nanoparticles were co-cultured with mouse 4T1 breast cancer cells with a drug concentration of 10 µg/mL; the cell survival rate was 3.3% after a 72-hour incubation. In an in vivo study of breast cancer in a mouse model, the drug-loaded nanoparticles were injected in the tail veins of mice with a dose of 5 mg/kg body weight. The tumor inhibition rate of drug-loaded nanoparticles was 53%, which was better than that of doxorubicin hydrochloride. The cardiac toxicity of doxorubicin was decreased greatly after the encapsulation into supramolecular polyrotaxane nanoparticles.Keywords: polyrotaxane, self-assembly, nanoparticle, doxorubicin, supermolecular

  2. Mechanism of N-octadecyl-N'-maleoyl-L-phenylalanine self-assembled into supramolecular structures

    Institute of Scientific and Technical Information of China (English)

    Sheng Zu Zhang; Xin Jian Fu; Hong Wang; Ya Jiang Yang

    2008-01-01

    N-Octadecyl-N'-maleoyl-L-phenylalanine (ODMA-L-Phe) was synthesized through the condensation, deprotection and aeid-ylation reaction of BOC-L-phenylalanine, octadecylamine and maleic anhydride. ODMA-L-Phe can self-assemble in some organic solvents and turned them into thermally reversible physical supramolecular organogels. The morphology of ODMA-L-Phe aggregates was characterized by polarized optical microscopy (POM) and field emission scanning electron microscope (FE-SEM). The aggregates of ODMA-L-Phe were needle-like fibrils with diameters of approximately 100-200 nm. The mechanism of ODMA-L-Phe self-assembly in organic solvents was investigated using 1H NMR and circular dichroism (CD). The results indicated that hydrogen bonding was one of the main driving forces for the self-assembly of ODMA-L-Phe.

  3. The Acid Hydrolysis Mechanism of Acetals Catalyzed by a Supramolecular Assembly in Basic Solution

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael D.; Bergman, Robert G.; Raymond, Kenneth N.

    2008-09-24

    A self-assembled supramolecular host catalyzes the hydrolysis of acetals in basic aqueous solution. The mechanism of hydrolysis is consistent with the Michaelis-Menten kinetic model. Further investigation of the rate limiting step of the reaction revealed a negative entropy of activation ({Delta}S{double_dagger} = -9 cal mol{sup -1}K{sup -1}) and an inverse solvent isotope effect (k(H{sub 2}O)/k(D{sub 2}O) = 0.62). These data suggest that the mechanism of hydrolysis that takes place inside the assembly proceeds through an A-2 mechanism, in contrast to the A-1 mechanism operating in the uncatalyzed reaction. Comparison of the rates of acetal hydrolysis in the assembly with the rate of the reaction of unencapsulated substrates reveals rate accelerations of up to 980 over the background reaction for the substrate diethoxymethane.

  4. Dynamic Characterization of Crystalline Supramolecular Rotors Assembled through Halogen Bonding.

    Science.gov (United States)

    Catalano, Luca; Pérez-Estrada, Salvador; Terraneo, Giancarlo; Pilati, Tullio; Resnati, Giuseppe; Metrangolo, Pierangelo; Garcia-Garibay, Miguel A

    2015-12-16

    A modular molecular kit for the preparation of crystalline molecular rotors was devised from a set of stators and rotators to gain simple access to a large number of structures with different dynamic performance and physical properties. In this work, we have accomplished this with crystalline molecular rotors self-assembled by halogen bonding of diazabicyclo[2.2.2]octane, acting as a rotator, and a set of five fluorine-substituted iodobenzenes that take the role of the stator. Using variable-temperature (1)H T1 spin-lattice relaxation measurements, we have shown that all structures display ultrafast Brownian rotation with activation energies of 2.4-4.9 kcal/mol and pre-exponential factors of the order of (1-9) × 10(12) s(-1). Line shape analysis of quadrupolar echo (2)H NMR measurements in selected examples indicated rotational trajectories consistent with the 3-fold or 6-fold symmetric potential of the rotator. PMID:26583701

  5. Complexation-induced supramolecular assembly drives metal-ion extraction.

    Science.gov (United States)

    Ellis, Ross J; Meridiano, Yannick; Muller, Julie; Berthon, Laurence; Guilbaud, Philippe; Zorz, Nicole; Antonio, Mark R; Demars, Thomas; Zemb, Thomas

    2014-09-26

    Combining experiment with theory reveals the role of self-assembly and complexation in metal-ion transfer through the water-oil interface. The coordinating metal salt Eu(NO3)3 was extracted from water into oil by a lipophilic neutral amphiphile. Molecular dynamics simulations were coupled to experimental spectroscopic and X-ray scattering techniques to investigate how local coordination interactions between the metal ion and ligands in the organic phase combine with long-range interactions to produce spontaneous changes in the solvent microstructure. Extraction of the Eu(3+)-3(NO3(-)) ion pairs involves incorporation of the "hard" metal complex into the core of "soft" aggregates. This seeds the formation of reverse micelles that draw the water and "free" amphiphile into nanoscale hydrophilic domains. The reverse micelles interact through attractive van der Waals interactions and coalesce into rod-shaped polynuclear Eu(III) -containing aggregates with metal centers bridged by nitrate. These preorganized hydrophilic domains, containing high densities of O-donor ligands and anions, provide improved Eu(III) solvation environments that help drive interfacial transfer, as is reflected by the increasing Eu(III) partitioning ratios (oil/aqueous) despite the organic phase approaching saturation. For the first time, this multiscale approach links metal-ion coordination with nanoscale structure to reveal the free-energy balance that drives the phase transfer of neutral metal salts. PMID:25169678

  6. Self-assembly behavior of a linear-star supramolecular amphiphile based on host-guest complexation.

    Science.gov (United States)

    Wang, Juan; Wang, Xing; Yang, Fei; Shen, Hong; You, Yezi; Wu, Decheng

    2014-11-01

    A star polymer, β-cyclodextrin-poly(l-lactide) (β-CD-PLLA), and a linear polymer, azobenzene-poly(ethylene glycol) (Azo-PEG), could self-assemble into a supramolecular amphiphilic copolymer (β-CD-PLLA@Azo-PEG) based on the host-guest interaction between β-CD and azobenzene moieties. This linear-star supramolecular amphiphilic copolymer further self-assembled into a variety of morphologies, including sphere-like micelle, carambola-like micelle, naan-like micelle, shuttle-like lamellae, tube-like fiber, and random curled-up lamellae, by tuning the length of hydrophilic or hydrophobic chains. The variation of morphology was closely related to the topological structure and block ratio of the supramolecular amphiphiles. These self-assembly structures could disassemble upon an ultraviolet (UV) light irradiation. PMID:25310380

  7. A Dynamic Combinatorial Approach for Identifying Side Groups that Stabilize DNA-Templated Supramolecular Self-Assemblies

    Directory of Open Access Journals (Sweden)

    Delphine Paolantoni

    2015-02-01

    Full Text Available DNA-templated self-assembly is an emerging strategy for generating functional supramolecular systems, which requires the identification of potent multi-point binding ligands. In this line, we recently showed that bis-functionalized guanidinium compounds can interact with ssDNA and generate a supramolecular complex through the recognition of the phosphodiester backbone of DNA. In order to probe the importance of secondary interactions and to identify side groups that stabilize these DNA-templated self-assemblies, we report herein the implementation of a dynamic combinatorial approach. We used an in situ fragment assembly process based on reductive amination and tested various side groups, including amino acids. The results reveal that aromatic and cationic side groups participate in secondary supramolecular interactions that stabilize the complexes formed with ssDNA.

  8. Creating Prebiotic Sanctuary: Self-Assembling Supramolecular Peptide Structures Bind and Stabilize RNA

    Science.gov (United States)

    Carny, Ohad; Gazit, Ehud

    2011-04-01

    Any attempt to uncover the origins of life must tackle the known `blind watchmaker problem'. That is to demonstrate the likelihood of the emergence of a prebiotic system simple enough to be formed spontaneously and yet complex enough to allow natural selection that will lead to Darwinistic evolution. Studies of short aromatic peptides revealed their ability to self-assemble into ordered and stable structures. The unique physical and chemical characteristics of these peptide assemblies point out to their possible role in the origins of life. We have explored mechanisms by which self-assembling short peptides and RNA fragments could interact together and go through a molecular co-evolution, using diphenylalanine supramolecular assemblies as a model system. The spontaneous formation of these self-assembling peptides under prebiotic conditions, through the salt-induced peptide formation (SIPF) pathway was demonstrated. These peptide assemblies possess the ability to bind and stabilize ribonucleotides in a sequence-depended manner, thus increase their relative fitness. The formation of these peptide assemblies is dependent on the homochirality of the peptide monomers: while homochiral peptides (L-Phe-L-Phe and D-Phe-D-Phe) self-assemble rapidly in aqueous environment, heterochiral diastereoisomers (L-Phe-D-Phe and D-Phe-L-Phe) do not tend to self-assemble. This characteristic consists with the homochirality of all living matter. Finally, based on these findings, we propose a model for the role of short self-assembling peptides in the prebiotic molecular evolution and the origin of life.

  9. Supramolecular Assembly of an Evolved Miniprotein Host and Fluorogenic Guest Pair.

    Science.gov (United States)

    Xu, Bi; Zhou, Xinqi; Stains, Cliff I

    2015-11-18

    Small-molecule-induced assembly of defined protein structures could have broad implications for the fabrication of new materials as well as biological signaling pathways. However, the design of new host-guest pairs capable of small-molecule-induced assembly in a biologically relevant context remains a significant challenge. Herein, we report a series of miniprotein hosts, evolved from the tenth type III domain of fibronectin (Fn3), that display remarkable binding affinity toward a red-shifted environment-sensitive merocyanine derivative, termed sI-Pht. Importantly, the consensus binder isolated from directed evolution experiments (6.2.18) forms a higher order assembly in response to addition of sI-Pht, as assessed by analytical ultracentrifugation. sI-Pht-induced assembly of 6.2.18 results in a 570-fold increase in fluorescence compared to free dye. This property enables the direct visualization of host-guest assemblies by fluorescence microscopy. As a demonstration, we show that supramolecular assembly of the 6.2.18-sI-Pht system can be visualized on the surface of living yeast cells. This new host-guest pair provides a tool for the potential development of new materials as well as pathway engineering. In a broader context, this work details a new design paradigm for the discovery of host-guest systems that function in the context of living cells. PMID:26523606

  10. In situ clicking methylglyoxal for hierarchical self-assembly of nanotubes in supramolecular hydrogel.

    Science.gov (United States)

    Liu, Shuang; Luo, Yufeng; Liang, Gaolin

    2016-01-14

    Methylglyoxal (MGO) is a toxic, dicarbonyl metabolite in all living cells and its detoxification is regulated by glyoxalase I (GLOI). Herein, we rationally designed a precursor o-phenylenediamine-Phe-Phe-OH (1) which “click” reacts with MGO to yield amphiphilic methylquinoxaline-Phe-Phe-OH (2) to self-assemble into supramolecular hydrogel II (Gel II). Cryo-TEM images of Gel II suggested that there existed two orders of self-assembly to form the 32.8 nm width-nanotubes in the hydrogel. The hypothesis was validated with the analyses of the fluorescence, transmittance, and circular dichroism data of the serial dilutions of Gel II. Interference tests indicated that hydrogelation of 1 with MGO would not be affected by nitric oxide (NO). Our results suggest that 1 could be applied for specific hydrogelation with MGO, and potentially the removal of MGO in vitro. PMID:26660853

  11. Self-assembled sorbitol-derived supramolecular hydrogels for the controlled encapsulation and release of active pharmaceutical ingredients.

    Science.gov (United States)

    Howe, Edward J; Okesola, Babatunde O; Smith, David K

    2015-05-01

    A simple supramolecular hydrogel based on 1,3:2,4-di(4-acylhydrazide)benzylidene sorbitol (DBS-CONHNH2), is able to extract acid-functionalised anti-inflammatory drugs via directed interactions with the self-assembled gel nanofibres. Two-component hydrogel-drug hybrid materials can be easily formed by mixing and exhibit pH-controlled drug release.

  12. Giant, Hollow 2D Metalloarchitecture: Stepwise Self-Assembly of a Hexagonal Supramolecular Nut.

    Science.gov (United States)

    Li, Yiming; Jiang, Zhilong; Wang, Ming; Yuan, Jie; Liu, Die; Yang, Xiaoyu; Chen, Mingzhao; Yan, Jun; Li, Xiaopeng; Wang, Pingshan

    2016-08-10

    A polyterpyridinyl building block-based nutlike hexagonal bismetallo architecture with a central hollow Star of David was assembled by a stepwise strategy. This nanoarchitecture can be viewed as a recursive mathematical form that possesses a supramolecular corner-connected cyclic structure, i.e., a triangle or rhombus at various levels of scale or detail. The key metallo-organic ligand (MOL) with four uncomplexed free terpyridines was obtained by a final Suzuki cross-coupling reaction with a tetrabromoterpyridine Ru dimer. The molecular metallorhombus was prepared by reacting the MOL with a 60° bis-terpyridine and Fe(2+). The giant hollow hexagonal nut with a diameter of more than 11 nm and a molecular weight of ca. 33 kDa was obtained in near-quantitative yield by mixing the two types of multi-terpyridine ligands with Fe(2+). The supramolecular architecture was characterized by NMR ((1)H and (13)C), 2D NMR (COSY and ROESY), and DOSY spectroscopies, high-resolution electrospray ionization mass spectrometry, traveling-wave ion mobility mass spectrometry, and transmission electron microscopy. PMID:27447878

  13. Encapsulation and characterization of proton-bound amine homodimers in a water-soluble, self-assembled supramolecular host

    OpenAIRE

    Pluth, Michael D.; Fiedler, Dorothea; Mugridge, Jeffrey S.; Bergman, Robert G.; Raymond, Kenneth N.

    2009-01-01

    Cyclic amines can be encapsulated in a water-soluble self-assembled supramolecular host upon protonation. The hydrogen-bonding ability of the cyclic amines, as well as the reduced degrees of rotational freedom, allows for the formation of proton-bound homodimers inside of the assembly that are otherwise not observable in aqueous solution. The generality of homodimer formation was explored with small N-alkyl aziridines, azetidines, pyrrolidines, and piperidines. Proton-bound homodimer formatio...

  14. Control over Structure and Function of Peptide Amphiphile Supramolecular Assemblies through Molecular Design and Energy Landscapes

    Science.gov (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

  15. Acceleration of Amide Bond Rotation by Encapsulation in the Hydrophobic Interior of a Water-Soluble Supramolecular Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael D.; Bergman, Robert G.; Raymond, Kenneth N.

    2008-04-08

    The hydrophobic interior cavity of a self-assembled supramolecular assembly exploits the hydrophobic effect for the encapsulation of tertiary amides. Variable temperature 1H NMR experiments reveal that the free energy barrier for rotation around the C-N amide bond is lowered by up to 3.6 kcal/mol upon encapsulation. The hydrophobic cavity of the assembly is able to stabilize the less polar transition state of the amide rotation process. Carbon-13 labeling studies showed that the {sup 13}C NMR carbonyl resonance increases with temperature for the encapsulated amides which suggests that the assembly is able to favor a twisted for of the amide.

  16. Proton Mediated Chemistry and Catalysis in a Self-Assembled Supramolecular Host

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael; Bergman, Robert; Raymond, Kenneth

    2009-04-10

    Synthetic supramolecular host assemblies can impart unique reactivity to encapsulated guest molecules. Synthetic host molecules have been developed to carry out complex reactions within their cavities, despite the fact that they lack the type of specifically tailored functional groups normally located in the analogous active sites of enzymes. Over the past decade, the Raymond group has developed a series of self-assembled supramolecules and the Bergman group has developed and studied a number of catalytic transformations. In this Account, we detail recent collaborative work between these two groups, focusing on chemical catalysis stemming from the encapsulation of protonated guests and expanding to acid catalysis in basic solution. We initially investigated the ability of a water-soluble, self-assembled supramolecular host molecule to encapsulate protonated guests in its hydrophobic core. Our study of encapsulated protonated amines revealed rich host-guest chemistry. We established that self-exchange (that is, in-out guest movement) rates of protonated amines were dependent on the steric bulk of the amine rather than its basicity. The host molecule has purely rotational tetrahedral (T) symmetry, so guests with geminal N-methyl groups (and their attendant mirror plane) were effectively desymmetrized; this allowed for the observation and quantification of the barriers for nitrogen inversion followed by bond rotation. Furthermore, small nitrogen heterocycles, such as N-alkylaziridines, N-alkylazetidines, and N-alkylpyrrolidines, were found to be encapsulated as proton-bound homodimers or homotrimers. We further investigated the thermodynamic stabilization of protonated amines, showing that encapsulation makes the amines more basic in the cavity. Encapsulation raises the effective basicity of protonated amines by up to 4.5 pK{sub a} units, a difference almost as large as that between the moderate and strong bases carbonate and hydroxide. The thermodynamic stabilization

  17. Proton-Mediated Chemistry and Catalysis in a Self-Assembled Supramolecular Host

    International Nuclear Information System (INIS)

    Synthetic supramolecular host assemblies can impart unique reactivity to encapsulated guest molecules. Synthetic host molecules have been developed to carry out complex reactions within their cavities, despite the fact that they lack the type of specifically tailored functional groups normally located in the analogous active sites of enzymes. Over the past decade, the Raymond group has developed a series of self-assembled supramolecules and the Bergman group has developed and studied a number of catalytic transformations. In this Account, we detail recent collaborative work between these two groups, focusing on chemical catalysis stemming from the encapsulation of protonated guests and expanding to acid catalysis in basic solution. We initially investigated the ability of a water-soluble, self-assembled supramolecular host molecule to encapsulate protonated guests in its hydrophobic core. Our study of encapsulated protonated amines revealed rich host-guest chemistry. We established that self-exchange (that is, in-out guest movement) rates of protonated amines were dependent on the steric bulk of the amine rather than its basicity. The host molecule has purely rotational tetrahedral (T) symmetry, so guests with geminal N-methyl groups (and their attendant mirror plane) were effectively desymmetrized; this allowed for the observation and quantification of the barriers for nitrogen inversion followed by bond rotation. Furthermore, small nitrogen heterocycles, such as N-alkylaziridines, N-alkylazetidines, and N-alkylpyrrolidines, were found to be encapsulated as proton-bound homodimers or homotrimers. We further investigated the thermodynamic stabilization of protonated amines, showing that encapsulation makes the amines more basic in the cavity. Encapsulation raises the effective basicity of protonated amines by up to 4.5 pKa units, a difference almost as large as that between the moderate and strong bases carbonate and hydroxide. The thermodynamic stabilization of

  18. Competitive Self-Assembly Manifests Supramolecular Darwinism in Soft-Oxometalates

    Science.gov (United States)

    Das, Santu; Kumar, Saurabh; Mallick, Apabrita; Roy, Soumyajit

    2015-09-01

    Topological transformation manifested in inorganic materials shows manifold possibilities. In our present work, we show a clear topological transformation in a soft-oxometalate (SOM) system which was formed from its polyoxometalate (POM) precursor [PMo12@Mo72Fe30]. This topological transformation was observed due to time dependent competitive self-assembly of two different length scale soft-oxometalate moieties formed from this two-component host-guest reaction. We characterized different morphologies by scanning electron microscopy, electron dispersive scattering spectroscopy, dynamic light scattering, horizontal attenuated total reflection-infrared spectroscopy and Raman spectroscopy. The predominant structure is selected by its size in a sort of supramolecular Darwinian competition in this process and is described here.

  19. The assembly and structure of self-assembling peptides: molecular to supramolecular

    OpenAIRE

    Morris, Kyle

    2012-01-01

    Self-assembling molecules are central to a plethora of processes found in nature, biotechnology and even disease. The importance of the non-covalent interaction of monomers to the formation of fibrillar assemblies is evident in the repeated use of this mechanism throughout nature, from essential cellular processes such as the formation of the cytoskeleton to the production of silk. Further, it has been recognised in the last two decades that a self-assembly mechanism, that is t...

  20. Study on the α-cyclodextrin/poly(ethylene glycol) self-assembly supramolecular nanoparticles for drug delivery

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    This paper reports the synthesis and drug delivery properties of a novel supramolecular nanoparticle.α-Cyclodextrins(α-CD) were threaded on cinnamic acid modified poly(ethylene glycol) to form inclusion complex nanoparticles by supramolecular self-assemble.The anti-tumor drug doxorubicin was loaded in the nanoparticles and released in vitro to study the drug release behavior and the anti-tumor effects.The structure and morphology of the nanoparticles were characterized by nuclear magnetic resonance,X-ray diffraction,ultraviolet absorbance,dynamic laser scattering,scanning electronic microscopy,transmission electron microscopy and atom force microscopy.The distribution of the drug loaded nanoparticles in cells and the anti-tumor effects were studied by confocal laser microscopy.The results demonstrate that the supramolecular nanoparticle is biocompatible and it is a promising carrier for drug delivery systems.

  1. Sensitization effects of supramolecular assemblies on the luminescence of terbium-ion prulifloxacin complexes

    Energy Technology Data Exchange (ETDEWEB)

    Wang Hong; Yi Chongyue; Li Xue; Fang Fang [School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Yang Yajiang, E-mail: yjyang@mail.hust.edu.c [School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2011-04-15

    Luminescence enhancement of terbium-ion prulifloxacin complexes (Tb(III)-PUFX) in supramolecular hydrogels formed by assembly of 1,3:2,4-di-O-benzylidene-D-sorbitol (DBS) was investigated by steady-state fluorescence, varying temperature fluorescence and time-resolved fluorescence. The luminescence images show that Tb(III)-PUFX were dispersed in the DBS gels. The luminescence intensity of Tb(III)-PUFX in the DBS gels was significantly increased in comparison with that in corresponding aqueous solutions. The varying temperature fluorescent spectra show that the luminescence intensity of Tb(III)-PUFX decreased with an increase in the temperature. This implies that the luminescence enhancement of Tb(III)-PUFX is related to the dissociation and the formation of the DBS assemblies. Time-resolved fluorescence measurements show slower rotational motion in DBS gels in comparison with that in the corresponding aqueous solutions. This may be ascribed to a unique microstructure of three-dimensional network formed by DBC aggregates, resulting in deactivation of the nonradiative relaxation. The images of field emission scanning electron microscopy and polarized optical microscopy indicate that the morphology of the DBS assemblies was not influenced upon addition of Tb(III)-PUFX to the DBS gels.

  2. Exploration of supramolecular assemblies of rac-1,3-cyclohexanedicarboxylic acid

    Science.gov (United States)

    Giri, Lopamudra; Pedireddi, V. R.

    2015-11-01

    Supramolecular assemblies of rac-1,3-cyclohexanedicarboxylic acid (1) with melamine (a), 1,2-bis(4-pyridyl)ethene (b); 1, 2-bis(4pyridyl)ethane (c) in the presence of Co(II), and 1,10-phenanthroline (d) along with Cu(II) and Ni(II), respectively 1a - 1d and 1d', have been reported. All the assemblies were prepared by crystallization method, through slow-evaporation process, at ambient conditions. All the complexes yield sheet structures that are stacked in three-dimensional arrangement, however, each structure is unique within three-dimensional networks with varied arrangements of either organic entities or coordinated ensembles. For instance, while a host-guest type assembly was observed in 1a, only crinkled tapes are observed in 1b. Among coordination complexes, 1c has an interpenetrated cubic network, whereas 1d and 1d' form host-guest networks. A noteworthy feature to highlight is that the water molecules in the channels of 1d organize in the form of pentamers, which are further held together through tetrameric network, with the aid of hydrogen bonds. A further interesting feature is the presence of acid 1 in different conformations in the complexes as cis form in 1b, 1c and 1d and trans form in 1d'. However, in 1a both cis and trans conformers are observed.

  3. Supramolecular assemblies of 4,7-phenanthroline with various aromatic polycarboxylic acids

    Science.gov (United States)

    Biswas, Sharmita Nandy; Nandy, Purnendu

    2016-10-01

    Five molecular complexes 1a-1e, of 4,7-phenanthroline (1) with various aromatic polycarboxylic acids such as benzene-1,3-dicarboxylic acid (a), pyridine-2,6-dicarboxylic acid (b), pyridine-2,5-dicarboxylic acid (c), benzene-1,2,3,4,5-pentacarboxylic acid (d) and 1,2,3,4,5,6-benzenehexacarboxylic acid (e) have been prepared and characterized by single crystal X-ray diffraction and thermogravimetric analyses. The analysis shows that all the assemblies crystallized as hydrates, except complex, 1c, formed between 1 and pyridine-2,5-dicarboxylic acid. Single crystal X-ray data reveals that the packing patterns of all the molecular complexes have been directed by strong hydrogen bonding O-H⋯O/O-H⋯N/N+-H⋯O- and weak hydrogen bonding C-H⋯O interactions. All the hydrated assemblies aggregate through the formation of cyclic networks as basic recognition pattern. Further, we observed that water molecules play significant role for production of supramolecular assemblies.

  4. Supramolecular Self-Assembled Chaos: Polyphenolic Lignin’s Barrier to Cost-Effective Lignocellulosic Biofuels

    Directory of Open Access Journals (Sweden)

    Shawn Matthew Dirk

    2010-11-01

    Full Text Available Phenylpropanoid metabolism yields a mixture of monolignols that undergo chaotic, non-enzymatic reactions such as free radical polymerization and spontaneous self-assembly in order to form the polyphenolic lignin which is a barrier to cost-effective lignocellulosic biofuels. Post-synthesis lignin integration into the plant cell wall is unclear, including how the hydrophobic lignin incorporates into the wall in an initially hydrophilic milieu. Self-assembly, self-organization and aggregation give rise to a complex, 3D network of lignin that displays randomly branched topology and fractal properties. Attempts at isolating lignin, analogous to archaeology, are instantly destructive and non-representative of in planta. Lack of plant ligninases or enzymes that hydrolyze specific bonds in lignin-carbohydrate complexes (LCCs also frustrate a better grasp of lignin. Supramolecular self-assembly, nano-mechanical properties of lignin-lignin, lignin-polysaccharide interactions and association-dissociation kinetics affect biomass deconstruction and thereby cost-effective biofuels production.

  5. A novel self-assembly with zinc porphyrin coordination polymer for enhanced photocurrent conversion in supramolecular solar cells

    International Nuclear Information System (INIS)

    Graphical abstract: An innovative type of self-assembly based on acetohydrazide zinc porphyrin coordination polymer has been prepared in supramolecular solar cells. - Highlights: • A novel assembly with acetohydrazide porphyrin coordination polymer. • The assembly based on porphyrin is prepared as parallel sample. • Coordination polymer-based assembly shows enhanced photoelectronic behavior. • A series of different organic acid ligands as anchoring groups are prepared. - Abstract: In this work, a novel acetohydrazide zinc porphyrin-based coordination polymer (CP)-isonicotinic acid self-assembly by metal-ligand axial coordination to modify the nano-structured TiO2 electrode surface has been investigated in photoelectrochemical device. Compared to the assembly based on corresponding zinc porphyrin combined with isonicotinic acid by metal-ligand axial coordination, CP-isonicotinic acid assembly exhibits a significantly enhanced photoelectronic behavior. In addition, a series of different organic acid ligands were prepared to probe the impact of their structures on the photoelectronic performances of their corresponding assemblies-sensitized cells. This study affords a novel type of self-assembly to functionalize the nanostructured TiO2 electrode surface in supramolecular solar cells

  6. Rhodium-Catalyzed Asymmetric Reactions Using Self-Assembled Chiral Bidentate Ligands

    Institute of Scientific and Technical Information of China (English)

    Kittichai Chaiseeda; Shin A. Moteki; D. Sahadeva Reddy; Di Wu; Kusumlata Chandra; James M. Takacs

    2005-01-01

    @@ 1 Introduction We recently described a new combinatorial strategy for modular catalyst development, one using self-assembly in the ligand scaffold-generating step to produce libraries of chiral self-assembled ligands. Metal-directed self-assembly of bifunctional subunits around a structural metal (typically zinc) can be used to form a heteroleptic complex in which a second set of ligating groups are suitably disposed to form a heterobimetallic catalyst system[1]. See Fig. 1

  7. Responsive supramolecular polymer metallogel constructed by orthogonal coordination-driven self-assembly and host/guest interactions.

    Science.gov (United States)

    Yan, Xuzhou; Cook, Timothy R; Pollock, J Bryant; Wei, Peifa; Zhang, Yanyan; Yu, Yihua; Huang, Feihe; Stang, Peter J

    2014-03-26

    An emerging strategy for the fabrication of advanced supramolecular materials is the use of hierarchical self-assembly techniques wherein multiple orthogonal interactions between molecular precursors can produce new species with attractive properties. Herein, we unify the spontaneous formation of metal-ligand bonds with the host/guest chemistry of crown ethers to deliver a 3D supramolecular polymer network (SPN). Specifically, we have prepared a highly directional dipyridyl donor decorated with a benzo-21-crown-7 moiety that undergoes coordination-driven self-assembly with a complementary organoplatinum acceptor to furnish hexagonal metallacycles. These hexagons subsequently polymerize into a supramolecular network upon the addition of a bisammonium salt due to the formation of [2]pseudorotaxane linkages between the crown ether and ammonium moieties. At high concentrations, the resulting 3D SPN becomes a gel comprising many cross-linked metallohexagons. Notably, thermo- and cation-induced gel-sol transitions are found to be completely reversible, reflecting the dynamic and tunable nature of such supramolecular materials. As such, these results demonstrate the structural complexity that can be obtained when carefully controlling multiple interactions in a hierarchical fashion, in this case coordination and host/guest chemistry, and the interesting dynamic properties associated with the materials thus obtained.

  8. Graphene–cyclodextrin–cytochrome c layered assembly with improved electron transfer rate and high supramolecular recognition capability

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Cheng-Bin; Guo, Cong-Cong; Jiang, Dan; Tang, Qian, E-mail: qiantang@swu.edu.cn; Liu, Chang-Hua; Ma, Xue-Bing

    2014-06-01

    This study aimed to develop a new graphene-based layered assembly, named graphene–cyclodextrin–cytochrome c with improved electron transfer rate. This assembly has combined high conductivity of graphene nanosheets (GNs), selectively binding properties and electronegativity of cyclodextrins (CDs), as well as electropositivity of cytochrome c (Cyt c). This assembly can also mimic the confined environments of the intermembrane space of mitochondria. A β-cyclodextrin (β-CD) functionalized GN (GN–CD) assembly was initially prepared by a simple wet-chemical strategy, i.e., in situ thermal reduction of graphene oxide with hydrazine hydrate in the presence of β-CD. Cyt c was then intercalated to the GN–CD assembly to form a layered self-assembled structure, GN–CD–Cyt c, through electrostatic interaction. Compared with GNs and GN–CD, GN–CD–Cyt c assembly displayed improved electron transfer rate and high supramolecular recognition capability toward six probe molecules. - Highlights: • A new tertiary layered assembly named GN–CD–Cyt c was prepared. • Compared with GNs and GN–CD, GN–CD–Cyt c shows improved electron transfer rate. • GN–CD–Cyt c displays high supramolecular recognition capability.

  9. Reciprocal Self-Assembly of Peptide-DNA Conjugates into a Programmable Sub-10-nm Supramolecular Deoxyribonucleoprotein.

    Science.gov (United States)

    Kye, Mahnseok; Lim, Yong-Beom

    2016-09-19

    To overcome the limitations of molecular assemblies, the development of novel supramolecular building blocks and self-assembly modes is essential to create more sophisticated, complex, and controllable aggregates. The self-assembly of peptide-DNA conjugates (PDCs), in which two orthogonal self-assembly modes, that is, β-sheet formation and Watson-Crick base pairing, are covalently combined in one supramolecular system, is reported. Despite extensive research, most self-assembly studies have focused on using only one type of building block, which restricts structural and functional diversity compared to multicomponent systems. Multicomponent systems, however, suffer from poor control of self-assembly behaviors. Covalently conjugated PDC building blocks are shown to assemble into well-defined and controllable nanostructures. This controllability likely results from the decrease in entropy associated with the restriction of the molecular degrees of freedom by the covalent constraints. Using this strategy, the possibility to thermodynamically program nano-assemblies to exert gene regulation activity with low cytotoxicity is demonstrated. PMID:27553897

  10. Supramolecular Engineering of Hierarchically Self-Assembled, Bioinspired, Cholesteric Nanocomposites Formed by Cellulose Nanocrystals and Polymers.

    Science.gov (United States)

    Zhu, Baolei; Merindol, Remi; Benitez, Alejandro J; Wang, Baochun; Walther, Andreas

    2016-05-01

    Natural composites are hierarchically structured by combination of ordered colloidal and molecular length scales. They inspire future, biomimetic, and lightweight nanocomposites, in which extraordinary mechanical properties are in reach by understanding and mastering hierarchical structure formation as tools to engineer multiscale deformation mechanisms. Here we describe a hierarchically self-assembled, cholesteric nanocomposite with well-defined colloid-based helical structure and supramolecular hydrogen bonds engineered on the molecular level in the polymer matrix. We use reversible addition-fragmentation transfer polymerization to synthesize well-defined hydrophilic, nonionic polymers with a varying functionalization density of 4-fold hydrogen-bonding ureidopyrimidinone (UPy) motifs. We show that these copolymers can be coassembled with cellulose nanocrystals (CNC), a sustainable, stiff, rod-like reinforcement, to give ordered cholesteric phases with characteristic photonic stop bands. The dimensions of the helical pitch are controlled by the ratio of polymer/CNC, confirming a smooth integration into the colloidal structure. With respect to the effect of the supramolecular motifs, we demonstrate that those regulate the swelling when exposing the biomimetic hybrids to water, and they allow engineering the photonic response. Moreover, the amount of hydrogen bonds and the polymer fraction are decisive in defining the mechanical properties. An Ashby plot comparing previous ordered CNC-based nanocomposites with our new hierarchical ones reveals that molecular engineering allows us to span an unprecedented mechanical property range from highest inelastic deformation (strain up to ∼13%) to highest stiffness (E ∼ 15 GPa) and combinations of both. We envisage that further rational design of the molecular interactions will provide efficient tools for enhancing the multifunctional property profiles of such bioinspired nanocomposites. PMID:27067311

  11. Combining modular ligation and supramolecular self-assembly for the construction of star-shaped macromolecules.

    Science.gov (United States)

    Altintas, Ozcan; Muller, Thierry; Lejeune, Elise; Plietzsch, Oliver; Bräse, Stefan; Barner-Kowollik, Christopher

    2012-06-14

    A well-defined random copolymer of styrene (S) and chloromethylstyrene (CMS) featuring lateral chlorine moieties with an alkyne terminal group is prepared (P(S-co-CMS), M(n) = 5500 Da, PDI = 1.13). The chloromethyl groups are converted into Hamilton wedge (HW) entities (P(S-co-HWS), M(n) = 6200 Da, PDI = 1.13). The P(S-co-HWS) polymer is subsequently ligated with tetrakis(4-azidophenyl)methane to give HW-functional star-shaped macromolecules (P(S-co-HWS))(4), M(n) = 25,100 Da, PDI = 1.08). Supramolecular star-shaped copolymers are then prepared via self-assembly between the HW-functionalized four-arm star-shaped macromolecules (P(S-co-HW))(4) and cyanuric acid (CA) end-functionalized PS (PS-CA, M(n) = 3700 Da, PDI = 1.04), CA end-functionalized poly(methyl methacrylate) (PMMA-CA, M(n) = 8500 Da, PDI = 1.13) and CA end-functionalized polyethylene glycol (PEG-CA, M(n) = 1700 Da, PDI = 1.05). The self-assembly is monitored by (1)H NMR spectroscopy and light scattering analyses.

  12. H-bonding directed programmed supramolecular assembly of naphthalene-diimide (NDI) derivatives.

    Science.gov (United States)

    Das, Anindita; Ghosh, Suhrit

    2016-05-25

    In this review we have collated various supramolecular designs, all surrounding H-bonding among well-known functional groups (peptides, nucleic acids, amides, ureas, carboxylic acids, pyridine-hydroxyls, urethanes, imides and others), to dictate self-assembly of naphthalenediimide (NDI) π-systems (both small molecules and polymeric building blocks) that exhibit several exciting features including strong propensity for π-π interactions, π-acidity, excellent n-type semiconductivity, CT-complexation, ion-π interactions, ring-substitution dependent redox properties and photophysical properties. This article reveals that H-bonding can indeed serve as a very powerful and versatile tool to programmed self-assembly of a single or multiple dye system producing a wide range of tailored soft materials, including fibrillar gels, chromonic mesophases, foldamers, nanotubes, vesicles, reverse micelles and polymersomes, both in water and organic medium with distinct photophysical properties, charge transport properties, conductivity properties and functional group displays that are highly relevant in the fields of biology and organic electronics. PMID:27100059

  13. Nanophotonics and supramolecular chemistry

    Science.gov (United States)

    Ariga, Katsuhiko; Komatsu, Hirokazu; Hill, Jonathan P.

    2013-10-01

    Supramolecular chemistry has become a key area in emerging bottom-up nanoscience and nanotechnology. In particular, supramolecular systems that can produce a photonic output are increasingly important research targets and present various possibilities for practical applications. Accordingly, photonic properties of various supramolecular systems at the nanoscale are important in current nanotechnology. In this short review, nanophotonics in supramolecular chemistry will be briefly summarized by introducing recent examples of control of photonic responses of supramolecular systems. Topics are categorized according to the fundamental actions of their supramolecular systems: (i) self-assembly; (ii) recognition; (iii) manipulation.

  14. A luminescent supramolecular assembly composed of a single-walled carbon nanotube and a molecular magnet precursor

    Energy Technology Data Exchange (ETDEWEB)

    Safar, G. A. M., E-mail: gamsafar@yahoo.com.br; Simoes, T. R. G. [Universidade Federal de Minas Gerais, Departamento de Quimica (Brazil); Paula, A. M. de [Universidade Federal de Minas Gerais, Departamento de Fisica (Brazil); Gratens, X.; Chitta, V. A. [Instituto de Fisica, Universidade de Sao Paulo (Brazil); Stumpf, H. O. [Universidade Federal de Minas Gerais, Departamento de Quimica (Brazil)

    2013-02-15

    Magnetism of supramolecular assemblies of single-walled carbon nanotubes (SWCNTS) with a magnetic dinuclear molecule is investigated. Raman, optical absorption and confocal fluorescence images are used to probe the interaction of the dinuclear compound and the SWCNT. The supramolecular assembly shows antiferromagnetism, on the contrary to the case when strong electronic doping of the SWCNT occurs, yielding a spin-glass system, and contrary to the case of the dinuclear molecular crystal, which is ferromagnetic. The SWCNT imposes the antiferromagnetic order to the dinuclear molecule, corroborating recent findings that antiferromagnetism is present in pure SWCNTs. Two theoretical models are used to fit the data, both yielding good fitting results. The nanoparticle size range is around 2-10 nm.

  15. A Ferrocene-Based Catecholamide Ligand: the Consequences of Ligand Swivel for Directed Supramolecular Self-Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Mugridge, Jeffrey; Fiedler, Dorothea; Raymond, Kenneth

    2010-02-04

    A ferrocene-based biscatecholamide ligand was prepared and investigated for the formation of metal-ligand supramolecular assemblies with different metals. Reaction with Ge(IV) resulted in the formation of a variety of Ge{sub n}L{sub m} coordination complexes, including [Ge{sub 2}L{sub 3}]{sup 4-} and [Ge{sub 2}L{sub 2}({mu}-OMe){sub 2}]{sup 2-}. The ligand's ability to swivel about the ferrocenyl linker and adopt different conformations accounts for formation of many different Ge{sub n}L{sub m} species. This study demonstrates why conformational ligand rigidity is essential in the rational design and directed self-assembly of supramolecular complexes.

  16. Supra-molecular assembly of aromatic proton sponges to direct the crystallization of extra-large-pore zeotypes

    OpenAIRE

    Martinez Franco, Raquel; Sun, Junliang; SASTRE NAVARRO, GERMAN IGNACIO; Yun, Yifeng; Zou, Xiaodong; Moliner Marin, Manuel; Corma Canós, Avelino

    2014-01-01

    The combination of different experimental techniques, such as solid C-13 and H-1 magic-angle spinning NMR spectroscopy, fluorescence spectroscopy and powder X-ray diffraction, together with theoretical calculations allows the determination of the unique structure directing the role of the bulky aromatic proton sponge 1,8-bis(dimethylamino)naphthalene (DMAN) towards the extra-large-pore ITQ-51 zeolite through supra-molecular assemblies of those organic molecules. Spanish Government SEV 20...

  17. Assembly of three organic–inorganic hybrid supramolecular materials based on reduced molybdenum(V) phosphates

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, He [Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025 (China); Key Laboratory of Synthesis of Functional Materials and Green Catalysis, Colleges of Heilongjiang Province, Harbin Normal University, Harbin 150025 (China); Yu, Kai, E-mail: hlyukai188@163.com [Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025 (China); Key Laboratory of Synthesis of Functional Materials and Green Catalysis, Colleges of Heilongjiang Province, Harbin Normal University, Harbin 150025 (China); Lv, Jing-Hua; Wang, Chun-Mei; Wang, Chun-Xiao [Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025 (China); Key Laboratory of Synthesis of Functional Materials and Green Catalysis, Colleges of Heilongjiang Province, Harbin Normal University, Harbin 150025 (China); Zhou, Bai-Bin, E-mail: zhou_bai_bin@163.com [Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025 (China); Key Laboratory of Synthesis of Functional Materials and Green Catalysis, Colleges of Heilongjiang Province, Harbin Normal University, Harbin 150025 (China)

    2014-09-15

    Three supramolecular materials based on (P{sub 4}Mo{sub 6}) polyoxoanions, (Hbbi){sub 2}(H{sub 2}bbi)[Cu{sub 3}Mo{sub 12}{sup V}O{sub 24}(OH){sub 6}(H{sub 2}O){sub 6}(HPO{sub 4}){sub 4}(H{sub 2}PO{sub 4}){sub 2}(PO{sub 4}){sub 2}]·3H{sub 2}O (1), (Hbbi){sub 2}(H{sub 2}bbi)[Ni{sub 3}Mo{sub 12}{sup V}O{sub 24}(OH){sub 6}(H{sub 2}O){sub 2}(HPO{sub 4}){sub 4}(H{sub 2}PO{sub 4}){sub 2}(PO{sub 4}){sub 2}]·9H{sub 2}O (2), (Hbpy)(bpy){sub 3}[Ni{sub 2}(H{sub 2}O){sub 10}Na(PCA){sub 2}][NiMo{sub 12}{sup V}O{sub 24}(OH){sub 6}(H{sub 2}PO{sub 4}){sub 6}(PO{sub 4}){sub 2}]·6H{sub 2}O (3) (bbi=1,1′-(1,4-butanediyl)bis(imidazole), bpy=4,4′-bipyridine, PCA=pyridine-4-carboxylic acid), have been hydrothermally synthesized and structurally characterized by the elemental analysis, TG, IR, UV–vis, PXRD and the single-crystal X-ray diffraction. Compounds 1 and 2 exhibit covalent 1-D chains constructed from M[P{sub 4}Mo{sub 6}]{sub 2} dimeric cluster and (M(H{sub 2}O){sub n}) (M=Cu, n=3 for 1 and M=Ni, n=1 for 2) linker. Compound 3 possesses an unusual POMMOF supramolecular layers based on [Ni(P{sub 4}Mo{sub 6})]{sub 2} dimeric units and 1-D metal–organic strings [Ni(H{sub 2}O){sub 5}Na(PCA)]{sub n}, in which an in situ ligand of PCA from 1,3-bis(4-pyridyl)propane (bpp) precursor was observed. Furthermore, the electrochemical behavior of 1–3-CPE and magnetic properties of 1–3 have been investigated in detail. - Graphical abstract: As new linking unit, Cu(H{sub 2}O){sub 3}, Ni(H{sub 2}O), and (Ni{sub 2}(H{sub 2}O){sub 10}Na(PCA){sub 2}) are introduced into (TM(P{sub 4}Mo{sub 6}){sub 2}) reaction systems to assemble three supramolecular materials under hydrothermal conditions via changing organic ligand and transition metal. - Highlights: • Tree new supramolecular hybrids based on (P{sub 4}Mo{sub 6}) cluster are reported. • Cu(H{sub 2}O){sub 3} and Ni(H{sub 2}O) as linker are introduced into the (TM(P{sub 4}Mo{sub 6}){sub 2}) systems. • 3 shows unusual layers based on

  18. Self-assembly of supramolecular triarylamine nanowires in mesoporous silica and biocompatible electrodes thereof

    Science.gov (United States)

    Licsandru, Erol-Dan; Schneider, Susanne; Tingry, Sophie; Ellis, Thomas; Moulin, Emilie; Maaloum, Mounir; Lehn, Jean-Marie; Barboiu, Mihail; Giuseppone, Nicolas

    2016-03-01

    Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes. Here we show that we can grow supramolecular stacks of triarylamine molecules in the confined space of oriented mesopores of a silica nanolayer covering a gold electrode. This addressable bottom-up construction is triggered from solution simply by light irradiation. The resulting self-assembled nanowires act as highly conducting electronic pathways crossing the silica layer. They allow very efficient charge transfer from the redox species in solution to the gold surface. We demonstrate the potential of these hybrid constitutional materials by implementing them as biocathodes and by measuring laccase activity that reduces dioxygen to produce water.Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes. Here we show that we can grow supramolecular stacks of triarylamine molecules in the confined space of oriented mesopores of a silica nanolayer covering a gold electrode. This addressable bottom-up construction is triggered from solution simply by light irradiation. The resulting self-assembled nanowires act as highly conducting

  19. Structure-Property Relationship for Two-Photon Absorbing Multiporphyrins: Supramolecular Assembly of Highly-Conjugated Multiporphyrinic Ladders and Prisms

    Energy Technology Data Exchange (ETDEWEB)

    Easwaramoorthi, Shanmugam; Jang, So Young; Yoon, Zin Seok; Lim, Jong Min; Lee, Cheng-Wei; Mai, Chi-Lun; Liu, Yen-Chun; Yeh, Chen-Yu; Vura-Weis, Josh; Wasielewski, Michael R.; Kim, Dongho (NWU); (Yonsei); (NSHU)

    2008-10-03

    Two-photon absorption (TPA) phenomena of a series of single-strand as well as supramolecular self-assembled ladders and prisms of highly conjugated ethyne bridged multiporphyrin dimer, trimer, and star shaped pentamer have been investigated. The ligand mediated self-assembled supramolecular structures were characterized by UV-visible spectroscopy and small- and wide-angle X-ray scattering (SAXS/WAXS) analysis. The TPA cross section values of multiporphyrins increase nonlinearly from {approx}100 to {approx}18000 GM with an increased number of porphyrin units and elongated ?-conjugation length by virtue of charge transfer and excited-state cumulenic configurations. The observed opposite TPA behavior between their supramolecular ladder and prism configurations necessitates the importance of interstrand interactions between the multiporphyrinic units and the overall shape of the assembly. Furthermore, the diminished TPA cross section of the pentamer, despite the increased ?-conjugation resulting from duplex formation suggests that destabilizing the essential functional configurations at the cost of elongation of ?-delocalization pathway must cause unfavorable effects. We have also shown that one- and two-photon allowed energy-levels of linear multiporphyrins are nearly isoenergetic and the latter transition originates exclusively from the extent of ?-delocalization within the molecule. The identical TPA maximum position of the trimer and pentamer indicates that the TPA of the pentamer arises only from its basic trimer unit in spite of its extended two-dimensional {pi}-conjugation pathway involving five porphyrinic units.

  20. Steric hindrance regulated supramolecular assembly between β-cyclodextrin polymer and pyrene for alkaline phosphatase fluorescent sensing

    Science.gov (United States)

    Song, Chunxia; Yang, Xiaohai; Wang, Kemin; Wang, Qing; Liu, Jianbo; Huang, Jin; Zhou, Maogui; Guo, Xiaochen

    2016-03-01

    We herein report a strategy for sensitive alkaline phosphatase (ALP) fluorescent sensing based on steric hindrance regulated supramolecular assembly between β-cyclodextrin polymer (polyβ-CD) and pyrene. The fluorescence of pyrene was enhanced more than 10 times through supramolecular assembly with polyβ-CD. The 5‧-phosphorylated dsDNA probe with pyrene attached on the 3‧-terminal could be cleaved by λ exonuclease (λ exo), yielding pyrene attached on mononucleotides. Pyrene attached on mononucleotides could easily enter the cavity of polyβ-CD, resulting in fluorescence enhancement. When ALP was introduced, it could remove 5‧-phosphate groups from dsDNA and then prevented the cleavage of dsDNA. Pyrene attached on dsDNA was difficult to enter the cavity of polyβ-CD because of steric hindrance, resulting in an inconspicuous fluorescence enhancement. Owing to the excellent fluorescence enhancement during steric hindrance regulated supramolecular assembly, excellent performance of the assay method was achieved for ALP with a detection limit of 0.04 U mL- 1. The detection limit was superior or comparable with the reported methods. Besides, this method was simple in design, avoiding double-labeling of probe.

  1. Self-healing supramolecular bioelastomers with shape memory property as a multifunctional platform for biomedical applications via modular assembly.

    Science.gov (United States)

    Wu, Yaobin; Wang, Ling; Zhao, Xin; Hou, Sen; Guo, Baolin; Ma, Peter X

    2016-10-01

    Mimicking native functional dynamics for traditional biomaterials such as thermoset elastomers is limited due to their lack of responsiveness to biological stimuli and difficulties to incorporate biofunctionalities. Furthermore, the mechanical fracture of traditional thermoset elastomers caused by irreversible covalent bond rupture would lead to their permanent loss of properties. To overcome these challenges, degradable self-healed supramolecular bioelastomers are designed by an elastic poly(glycerol sebacate) (PGS) backbone and multiple hydrogen-bonding ureido-pyrimidinone (UPy) grafts. These supramolecular elastic polymers exhibit efficient self-healing, rapid shape-memory abilities and highly tunable mechanical properties due to the dynamic supramolecular interactions, and perform a good biocompatibility in vitro and a mild host response in vivo. By combining modular approaches, these supramolecular bioelastomers have been further assembled into a multifunctional platform to expand their applications in different biomedical fields. These include a complex 3D scaffold with shape-memory capacity and anisotropic mechanical properties, a controllable drug delivery model via a layer-by-layer technique, a surface antibacterial composite by physical modification, and a spatial oriented cell co-culture system via incorporating different cell-laden self-healing films, demonstrating their potential as building blocks in a wide range of biomedical applications where dynamic properties and biological functions are desired.

  2. Self-healing supramolecular bioelastomers with shape memory property as a multifunctional platform for biomedical applications via modular assembly.

    Science.gov (United States)

    Wu, Yaobin; Wang, Ling; Zhao, Xin; Hou, Sen; Guo, Baolin; Ma, Peter X

    2016-10-01

    Mimicking native functional dynamics for traditional biomaterials such as thermoset elastomers is limited due to their lack of responsiveness to biological stimuli and difficulties to incorporate biofunctionalities. Furthermore, the mechanical fracture of traditional thermoset elastomers caused by irreversible covalent bond rupture would lead to their permanent loss of properties. To overcome these challenges, degradable self-healed supramolecular bioelastomers are designed by an elastic poly(glycerol sebacate) (PGS) backbone and multiple hydrogen-bonding ureido-pyrimidinone (UPy) grafts. These supramolecular elastic polymers exhibit efficient self-healing, rapid shape-memory abilities and highly tunable mechanical properties due to the dynamic supramolecular interactions, and perform a good biocompatibility in vitro and a mild host response in vivo. By combining modular approaches, these supramolecular bioelastomers have been further assembled into a multifunctional platform to expand their applications in different biomedical fields. These include a complex 3D scaffold with shape-memory capacity and anisotropic mechanical properties, a controllable drug delivery model via a layer-by-layer technique, a surface antibacterial composite by physical modification, and a spatial oriented cell co-culture system via incorporating different cell-laden self-healing films, demonstrating their potential as building blocks in a wide range of biomedical applications where dynamic properties and biological functions are desired. PMID:27424213

  3. Controllable optical activity of gold nanorod and chiral quantum dot assemblies.

    Science.gov (United States)

    Zhu, Zhening; Guo, Jun; Liu, Wenjing; Li, Zhengtao; Han, Bing; Zhang, Wei; Tang, Zhiyong

    2013-12-16

    The optical coupling between Au nanorods (Au NRs) and chiral quantum dots (QDs) in assemblies is investigated by both experiment and theoretical calculations. The coupled optical activity in the visible-light region can be manipulated by changing either the aspect ratio of Au NRs or the size of QDs (left). PMID:24346941

  4. Autonomous oscillation in supramolecular assemblies: Role of free energy landscape and fluctuations

    Science.gov (United States)

    Sereda, Yuriy V.; Ortoleva, Peter J.

    2015-11-01

    Molecular dynamics studies demonstrated that a supramolecular assembly can express autonomous structural oscillations about equilibrium. It is demonstrated here that for nanosystems such oscillations can result from the interplay of free energy landscape and structural fluctuations. Furthermore, these oscillations have intermittent character, reflecting the conflict between a tendency to oscillate due to features in the free energy landscape, and the Second Law's repression of perpetual oscillation in an isothermal, equilibrium system. The demonstration system is a T = 1 icosahedral structure constituted of 12 protein pentamers in contact with a bath at fixed temperature. The oscillations are explained in terms of a Langevin model accounting for interactions among neighboring pentamers. The model is based on a postulated free energy landscape in the 24-dimensional space of variables describing the centrifugal and rotational motion of each pentamer. The model includes features such as basins of attraction and low free energy corridors. When the system is driven slightly out of equilibrium, the oscillations are transformed into a limit cycle, as expressed in terms of power spectrum narrowing.

  5. Template Syntheses, Crystal Structures and Supramolecular Assembly of Hexaaza Macrocyclic Copper(II) Complexes

    International Nuclear Information System (INIS)

    Two new hexaaza macrocyclic copper(II) complexes were prepared by a template method and structurally characterized. In the solid state, they were self-assembled by intermolecular interactions to form the corresponding supramolecules 1 and 2, respectively. In the structure of 1, the copper(II) macrocycles are bridged by a tp ligand to form a macrocyclic copper(II) dimer. The dimer extends its structure by intermolecular forces such as hydrogen bonds and C-H···π interactions, resulting in the formation of a double stranded 1D supramolecule. In 2, the basic structure is a monomeric copper(II) macrocycle with deprotonated imidazole pendants. An undulated 1D hydrogen bonded array is achieved through hydrogen bonds between imidazole pendants and secondary amines, where the imidazole pendants act as a hydrogen bond acceptor. The 1D hydrogen bonded supramolecular chain is supported by C-H···π interactions between the methyl groups of acetonitrile ligands and imidazole pendants of the copper(II) macrocycles. In both complexes, the introduction of imidazoles to the macrocycle as a pendant plays an important role for the formation of supramolecules, where they act as intermolecular hydrogen bond donors and/or acceptors, C-H···π and π-π interactions

  6. Self-Healing Supramolecular Self-Assembled Hydrogels Based on Poly(L-glutamic acid).

    Science.gov (United States)

    Li, Guifei; Wu, Jie; Wang, Bo; Yan, Shifeng; Zhang, Kunxi; Ding, Jianxun; Yin, Jingbo

    2015-11-01

    Self-healing polymeric hydrogels have the capability to recover their structures and functionalities upon injury, which are extremely attractive in emerging biomedical applications. This research reports a new kind of self-healing polypeptide hydrogels based on self-assembly between cholesterol (Chol)-modified triblock poly(L-glutamic acid)-block-poly(ethylene glycol)-block-poly(L-glutamic acid) ((PLGA-b-PEG-b-PLGA)-g-Chol) and β-cyclodextrin (β-CD)-modified poly(L-glutamic acid) (PLGA-g-β-CD). The hydrogel formation relied on the host and guest linkage between β-CD and Chol. This study demonstrates the influences of polymer concentration and β-CD/Chol molar ratio on viscoelastic behavior of the hydrogels. The results showed that storage modulus was highest at polymer concentration of 15% w/v and β-CD/Chol molar ratio of 1:1. The effect of the PLGA molecular weight in (PLGA-b-PEG-b-PLGA)-g-Chol on viscoelastic behavior, mechanical properties and in vitro degradation of the supramolecular hydrogels was also studied. The hydrogels showed outstanding self-healing capability and good cytocompatibility. The multilayer structure was constructed using hydrogels with self-healing ability. The developed hydrogels provide a fascinating glimpse for the applications in tissue engineering. PMID:26414083

  7. Fabrication of CO2 Facilitated Transport Channels in Block Copolymer through Supramolecular Assembly

    Directory of Open Access Journals (Sweden)

    Yao Wang

    2014-05-01

    Full Text Available In this paper, the molecule 12-amidine dodecanoic acid (M with ending groups of carboxyl and amidine groups respectively was designed and synthesized as CO2-responsive guest molecules. The block copolymer polystyrene-b-polyethylene oxide (PS-b-PEO was chosen as the host polymer to fabricate a composite membrane through H-bonding assembly with guest molecule M. We attempted to tune the phase separation structure of the annealed film by varying the amount of M added, and investigated the nanostructures via transmission electron microscope (TEM, fourier transform infrared (FT-IR etc. As a result, a reverse worm-like morphology in TEM image of bright PS phase in dark PEO/M matrix was observed for PS-b-PEO/M1 membrane in which the molar ratio of EO unit to M was 1:1. The following gas permeation measurement indicated that the gas flux of the annealed membranes dramatically increased due to the forming of ordered phase separation structure. As we expected, the obtained composite membrane PS-b-PEO/M1 with EO:M mole ratio of 1:1 presented an evident selectivity for moist CO2 permeance, which is identical with our initial proposal that the guest molecule M in the membranes will play the key role for CO2 facilitated transportation since the amidine groups of M could react reversibly with CO2 molecules in membranes. This work provides a supramolecular approach to fabricating CO2 facilitated transport membranes.

  8. Self-Assembly of Polyoxometalate and Polyelectrolyte Macroions into Mechanically Strong Supramolecular Hydrogels

    Science.gov (United States)

    Jing, Benxin; Zhu, Y. Elaine

    Polyoxometalate (POM) macroions are the nanoclusters of transition metal oxide with size 1-10 nm and well-defined structure at the atom level. Because of their stoichiometric surface groups and high solubility in polar solvents to form thermodynamically stable solution, POMs are studied as excellent model macroions at nanoscale. In this work, we explore the electrostatic controlled self-assembly of anionic POMs and cationic or zwitterionic polyelectrolytes (PEs) in aqueous solution. Specifically we examine the complex formation of zwitterionic poly (3-(methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonium hydroxide) (PSBMA) and cationic poly(diallyldimethylammonium chloride) (PDADMAC) with tungstate based POMs of varied valence. The phase diagram of POM/polyelectrolyte complexes is determined with varied POM/PE charge ratios. It is interesting to observe the coacervation of POMs with PSBMA. With cationic PDADMAC, hybrid POM-PDADMAC hydrogels can be formed. Nevertheless, POM-PDADMAC complexes exhibit much enhanced mechanical properties in comparison to polymer hydrogel. The viscoelastic properties of hybrid macroion complexes strongly depend on PDADMAC concentration, POM-to-PDADMAC molar ratio, the size and valence of POMs. At the intermediate range of POM-to-PDADMAC concentration ratio, shear thickening and strain hardening are observed with soft supramolecular hydrogels, which is resulted from the non-Gaussian stretching of polymer chains.

  9. Self-Healing Supramolecular Self-Assembled Hydrogels Based on Poly(L-glutamic acid).

    Science.gov (United States)

    Li, Guifei; Wu, Jie; Wang, Bo; Yan, Shifeng; Zhang, Kunxi; Ding, Jianxun; Yin, Jingbo

    2015-11-01

    Self-healing polymeric hydrogels have the capability to recover their structures and functionalities upon injury, which are extremely attractive in emerging biomedical applications. This research reports a new kind of self-healing polypeptide hydrogels based on self-assembly between cholesterol (Chol)-modified triblock poly(L-glutamic acid)-block-poly(ethylene glycol)-block-poly(L-glutamic acid) ((PLGA-b-PEG-b-PLGA)-g-Chol) and β-cyclodextrin (β-CD)-modified poly(L-glutamic acid) (PLGA-g-β-CD). The hydrogel formation relied on the host and guest linkage between β-CD and Chol. This study demonstrates the influences of polymer concentration and β-CD/Chol molar ratio on viscoelastic behavior of the hydrogels. The results showed that storage modulus was highest at polymer concentration of 15% w/v and β-CD/Chol molar ratio of 1:1. The effect of the PLGA molecular weight in (PLGA-b-PEG-b-PLGA)-g-Chol on viscoelastic behavior, mechanical properties and in vitro degradation of the supramolecular hydrogels was also studied. The hydrogels showed outstanding self-healing capability and good cytocompatibility. The multilayer structure was constructed using hydrogels with self-healing ability. The developed hydrogels provide a fascinating glimpse for the applications in tissue engineering.

  10. Facile Isolation of Adsorbent-Free Long and Highly-Pure Chirality-Selected Semiconducting Single-Walled Carbon Nanotubes Using A Hydrogen-bonding Supramolecular Polymer

    Science.gov (United States)

    Toshimitsu, Fumiyuki; Nakashima, Naotoshi

    2015-12-01

    The ideal form of semiconducting-single-walled carbon nanotubes (sem-SWNTs) for science and technology is long, defect-free, chirality pure and chemically pure isolated narrow diameter tubes. While various techniques to solubilize and purify sem-SWNTs have been developed, many of them targeted only the chiral- or chemically-purity while sacrificing the sem-SWNT intrinsic structural identities by applying strong ultra-sonication and/or chemical modifications. Toward the ultimate purification of the sem-SWNTs, here we report a mild-conditioned extraction of the sem-SWNTs using removable supramolecular hydrogen-bonding polymers (HBPs) that are composed of dicarboxylic- or diaminopyridyl-fluorenes with ~70%-(8,6)SWNT selective extraction. Replacing conventional strong sonication techniques by a simple shaking using HPBs was found to provide long sem-SWNTs (>2.0 μm) with a very high D/G ratio, which was determined by atomic force microscopy observations. The HBPs were readily removed from the nanotube surfaces by an outer stimulus, such as a change in the solvent polarities, to provide chemically pure (8,6)-enriched sem-SWNTs. We also describe molecular mechanics calculations to propose possible structures for the HBP-wrapped sem-SWNTs, furthermore, the mechanism of the chiral selectivity for the sorted sem-SWNTs is well explained by the relationship between the molecular surface area and mass of the HBP/SWNT composites.

  11. Supramolecularly assembled water layers stabilized by sebacic anions in complexes of Zn(II) and Co(II)

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Two three-dimensional supramolecular water architectures,[Zn(phen)3]2 ·[Zn(C10H16O4)·(H2O)3]·(C10H16O4)2·20H2O(1) and [Co(phen)3]2 ·[Co(H2O)6]·(C10H16O4)3·30H2O(2)[phen=1,10-Phenanthroline,C10H16O4=sebacic dianion],have been synthesized and characterized by IR,elemental analysis,thermogravimetric analysis,and single-crystal X-ray diffractions.The two structures both contain extensive hydrogen bonding between water molecules as well as between water molecules and sebacic anions.The water molecules and sebacic acid O atoms assembled 2D supramolecular corrugated sheets with different morphology in the two complexes.

  12. Supramolecular Assemblies in Salts of 2,2'-Biimidazole with 5-Sulfosalicylic Acid and 3,4,5-Trihydroxybenzoic Acid

    Institute of Scientific and Technical Information of China (English)

    LI Yan-Ping; YANG Pin

    2007-01-01

    Supramolecular assemblies of 2,2'-biimidazole with 5-sulfosalicylic acid and 3,4,5-trihydroxybenzoic acid, have been synthesized and characterized by single-crystal X-ray diffraction methods. Both the two proton-transfer compounds of 2,2'-biimidazole with 3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid, 5-SSA) [namely structures having significant interlayer π-π interactions between the cation and anion species. In Ⅰ, a 5-SSA2- dianionic species results from deprotonation of both the sulfonic and the carboxylic acid groups, all available O-atom acceptors interact with all cation and water molecule donors by hydrogen bonds. In Ⅱ, the formula unit displays a crystallographic inversion symmetry. The structural information about the two complexes between 2,2'-biimidazole compound and benzenecarboxylic acids obtained in this work will be particularly important for the rational design of supramolecular organic functional materials.

  13. Hierarchical self-assembly of a striped gyroid formed by threaded chiral mesoscale networks

    DEFF Research Database (Denmark)

    Kirkensgaard, Jacob Judas Kain; Evans, Myfanwy; de Campo, Lilliana;

    2014-01-01

    the gyroid film are densely packed and contain either graphitic hcb nets (chicken wire) or srs nets, forming convoluted intergrowths of multiple nets. Furthermore, each net is ideally a single chiral enantiomer, induced by the gyroid architecture. However, the numerical simulations result in defect......Numerical simulations reveal a family of hierarchical and chiral multicontinuous network structures self-assembled from a melt blend of Y-shaped ABC and ABD three-miktoarm star terpolymers, constrained to have equal-sized A/B and C/D chains, respectively. The C and D majority domains within...

  14. Supramolecular polymers in inhomogeneous systems

    OpenAIRE

    Zweistra, H.J.A.

    2007-01-01

    This thesis describes theoretical results of supramolecular polymers in inhomogeneous systems. Supramolecular polymers are linear assemblies of which the monomers are joined by reversible bonds. Many types of supramolecular polymers have been synthesized in recent years. Moreover, there are numerous compounds in nature which exhibit similar behavior. Simulations of coarse-grained models of supramolecular polymers yielded new insights into the properties of supramolecular polymers in inhomogen...

  15. Investigation of Porphyrin and Lipid Supramolecular Assemblies for Cancer Imaging and Therapy

    Science.gov (United States)

    Ng, Kenneth Ka-Seng

    Aerobic life on earth is made possible through the functions of the porphyrin. These colorful and ubiquitous chromophores are efficient at concentrating and converting sunlight into chemical energetic potential which sustain biological life. Humans have had a longstanding fascination with these molecules, especially for their applications in photodynamic therapy. The photophysical properties of porphyrins are highly influenced by their surrounding environment. Intermolecular interactions between these pigments can lead to excited state quenching, energy transfer and large changes to their absorption and fluorescence spectra. This thesis is focused on utilizing molecular self-assembly strategies to develop nanoscale porphyrin and phospholipid structures. The rationale being that intermolecular interactions between porphyrins in these nanostructures can induce changes which can be exploited in novel biomedical imaging and therapeutic applications. Four lipid-based structural platforms are studied including: nanoemulsions, bilayer discs and nanovesicles. In Chapter 1, I provide a background on the photophysics of porphyrins and the effect of intermolecular porphyrin interactions on photophysical properties. I also discuss phospholipids and their self-assembly process. Lastly I review current biomedical photonics techniques and discuss how these strategies can be used in conjugation with porphyrin and lipid supramolecular assemblies. In Chapter 2, I investigate the influence that loading a novel bacteriochlorin photosensitizer into a protein-stabilized lipid emulsion has on its spectral properties. I discovered that while the dye can be incorporated into the lipid emulsion, no changes were observed in its spectral properties. In Chapter 3, an amphipathic alpha-helical protein is used to stabilize and organize porphyrin-lipid molecules into bilayer discs. Close packing between porphyrin molecules causes quenching, which can be reversed by structural degradation of the

  16. A unique quinolineboronic acid-based supramolecular structure that relies on double intermolecular B-N bonds for self-assembly in solid state and in solution.

    Science.gov (United States)

    Zhang, Yanling; Li, Minyong; Chandrasekaran, Sekar; Gao, Xingming; Fang, Xikui; Lee, Hsiau-Wei; Hardcastle, Kenneth; Yang, Jenny; Wang, Binghe

    2007-04-16

    The boronic acid functional group plays very important roles in sugar recognition, catalysis, organic synthesis, and supramolecular assembly. Therefore, understanding the unique properties of this functional group is very important. 8-Quinolineboronic acid (8-QBA) is found to be capable of self-assembling in solid state through a unique intermolecular B-N bond mechanism reinforced by intermolecular boronic anhydride formation, π-π stacking, and hydrogen bond formation. NMR NOE and diffusion studies indicate that intermolecular B-N interaction also exists in solution with 8-QBA. In contrast, a positional isomer of 8-QBA, 5-quinolineboronic acid (5-QBA) showed very different behaviors in crystal packing and in solution and therefore different supramolecular network. Understanding the structural features of this unique 8-QBA assembly could be very helpful for the future design of new sugar sensors, molecular catalysts, and supramolecular assemblies. PMID:18414645

  17. Supra-molecular assembly of a lumican-derived peptide amphiphile enhances its collagen-stimulating activity.

    Science.gov (United States)

    Walter, Merlin N M; Dehsorkhi, Ashkan; Hamley, Ian W; Connon, Che J

    2016-02-01

    C16-YEALRVANEVTLN, a peptide amphiphile (PA) incorporating a biologically active amino acid sequence found in lumican, has been examined for its influence upon collagen synthesis by human corneal fibroblasts in vitro, and the roles of supra-molecular assembly and activin receptor-like kinase ALK receptor signaling in this effect were assessed. Cell viability was monitored using the Alamar blue assay, and collagen synthesis was assessed using Sirius red. The role of ALK signaling was studied by receptor inhibition. Cultured human corneal fibroblasts synthesized significantly greater amounts of collagen in the presence of the PA over both 7-day and 21-day periods. The aggregation of the PA to form nanotapes resulted in a notable enhancement in this activity, with an approximately two-fold increase in collagen production per cell. This increase was reduced by the addition of an ALK inhibitor. The data presented reveal a stimulatory effect upon collagen synthesis by the primary cells of the corneal stroma, and demonstrate a direct influence of supra-molecular assembly of the PA upon the cellular response observed. The effects of PA upon fibroblasts were dependent upon ALK receptor function. These findings elucidate the role of self-assembled nanostructures in the biological activity of peptide amphiphiles, and support the potential use of a self-assembling lumican derived PA as a novel biomaterial, intended to promote collagen deposition for wound repair and tissue engineering purposes. PMID:26626506

  18. Electrochemically controlled supramolecular systems

    NARCIS (Netherlands)

    Nijhuis, Christian A.; Ravoo, Bart Jan; Huskens, Jurriaan; Reinhoudt, David N.

    2007-01-01

    Large and complex molecular structures can be assembled by supramolecular chemistry and self-organization. For practical purposes it is required that the assembly and disassembly of supramolecular complexes and materials can be directed and controlled by external stimuli in order to build, for insta

  19. Enantioselective analysis of non-steroidal anti-inflammatory drugs in freshwater fish based on microextraction with a supramolecular liquid and chiral liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Caballo, Carmen; Sicilia, Maria Dolores; Rubio, Soledad

    2015-06-01

    Toxicity of pharmaceuticals to aquatic biota is still largely unknown, and no research on the stereoselective toxicity of chiral drugs to these organisms has been undertaken to date. Because of the lack of analytical methods available for this purpose, this manuscript deals, for the first time, with the enantioselective analysis of the non-steroidal anti-inflammatory drugs (NSAIDs) ibuprofen, naproxen and ketoprofen in freshwater fish. The method was based on the microextraction of NSAIDs from fish muscle with a supramolecular liquid made up of inverted hexagonal aggregates of decanoic acid, their enantiomeric separation by liquid chromatography onto a (R)-1-naphthylglycine and 3,5-dinitrobenzoic acid stationary phase and quantification by tandem mass spectrometry. Limits of quantitation (LOQs) for NSAID enantiomers were in the range 1.7-3.3 ng g(-1). Absolute recoveries were from 97 to 104 %, which indicated the high extraction efficiency of the supramolecular solvent. Extraction equilibrium conditions were reached after 10 min which permitted fast sample treatment. Relative standard deviations for enantiomers in fish muscle were always below 6 %. Isotopically labelled internal standards were used to compensate for matrix interferences. The method in-house validation was carried out with the Oncorhynchus mykiss species, and it was applied to the determination of NSAID enantiomers in different fortified freshwater fish species (Alburnus alburnus, Lepomis gibbosus, Micropterus salmoides, O. mykiss and Cyprinus carpio). PMID:25869485

  20. Supramolecular Assemblies of(±)-2,2'-Dihydroxy-1,1'-binaphthyl with 2,2'-Bipyridine and Naphthodiazine

    Institute of Scientific and Technical Information of China (English)

    JI Bao-Ming吉保明; CHEN Hua-Ting陈花婷; DU Chen-Xia杜晨霞; DING Kui-Ling丁奎岭

    2004-01-01

    Supramolecular assemblies of (±)-2,2'-dihydroxy-l,l'-binaphthyl (BINOL, A), with aza donor molecules including 2,2'-bipyridine (B) and naphthodiazine (C), have been synthesized and characterized by single-crystal X-ray diffraction methods. Two inclusion complexes crystallize in the triclinic system with P-1 space group. In the inclusion complex between A and B, two molecules of A and two molecules of B are linked each other by intermolecular hydrogen bonds with two molecules of water as the bridges, forming a centrosymmetric dimer with formula of A2(H2O)2B2; while in the inclusion complex between A and C, the molecule C virtually acts as a bridge to link molecules A through intermolecular O-H...N hydrogen bonds, forming a short-chain supramolecular block with interactions also play an important role in the solid-state packing of these two inclusion complexes. The structural information disclosed on the complex between dihydroxy compound and aza hydrogen bond acceptors in this work would be particularly important for the rational design of supramolecular organic functional materials.

  1. Two 3D supramolecular frameworks assembled from the dinuclear building block: A crystallographic evidence of carboxylate(O)$\\ldots$ interaction

    Indian Academy of Sciences (India)

    Sudip Mohapatra; Syamantak Roy; Debajyoti Ghoshal; Tapas Kumar Maji

    2014-07-01

    Two new complexes of Mn(II) and Zn(II) have been synthesized using a mixed ligand system and characterized by IR spectroscopy, elemental analysis, single crystal x-ray diffraction and variable temperature magnetic study for one of the compounds. Dimeric coordination structures of [Mn2(2,4-pyrdc)2(bpe)(H2O)6]·2H2O (1) and [Zn2(2,4-pyrdc)2(azpy)(H2O)6]·2H2O (2) [2,4-pyrdc = 2,4-pyridinedicarboxylate; bpe = 1,2-bis(4-pyridyl)ethane; azpy = 4, 4' azopyridine] are constructed by the bridging of bpe and azpy, respectively and both are extended to a 3D supramolecular structure by non-covalent interactions. In both the cases, unprecedented carboxylate(O)$\\ldots$ interactions played a crucial role in the organization of the 3D supramolecular assembly. The carboxylate(O)$\\ldots$ interactions are controlled by the C-H$\\ldots$ interactions which were accomplished by the proper modulation of the organic linkers. The formation of these supramolecular frameworks revealed that control of weak interactions can be achieved by the interplay of both energetically strong (covalent) and weak forces (non-covalent).

  2. Biocatalytic self-assembly of supramolecular charge-transfer nanostructures based on n-type semiconductor-appended peptides.

    Science.gov (United States)

    Nalluri, Siva Krishna Mohan; Berdugo, Cristina; Javid, Nadeem; Frederix, Pim W J M; Ulijn, Rein V

    2014-06-01

    The reversible in situ formation of a self-assembly building block (naphthalenediimide (NDI)-dipeptide conjugate) by enzymatic condensation of NDI-functionalized tyrosine (NDI-Y) and phenylalanine-amide (F-NH2) to form NDI-YF-NH2 is described. This coupled biocatalytic condensation/assembly approach is thermodynamically driven and gives rise to nanostructures with optimized supramolecular interactions as evidenced by substantial aggregation induced emission upon assembly. Furthermore, in the presence of di-hydroxy/alkoxy naphthalene donors, efficient charge-transfer complexes are produced. The dynamic formation of NDI-YF-NH2 and electronic and H-bonding interactions are analyzed and characterized by different methods. Microscopy (TEM and AFM) and rheology are used to characterize the formed nanostructures. Dynamic nanostructures, whose formation and function are driven by free-energy minimization, are inherently self-healing and provide opportunities for the development of aqueous adaptive nanotechnology. PMID:24788665

  3. The Self-Assembly of Nano-Objects Code: Applications to supramolecular organic monolayers adsorbed on metal surfaces

    CERN Document Server

    Roussel, Thomas

    2012-01-01

    The Self-Assembly of Nano-Objects (SANO) code we implemented demonstrates the ability to predict the molecular self-assembly of different structural motifs by tuning the molecular building blocks as well as the metallic substrate. It consists in a two-dimensional Grand Canonical Monte-Carlo (GCMC) approach developed to perform atomistic simulations of thousands of large organic molecules self-assembling on metal surfaces. Computing adsorption isotherms at room temperature and spanning over the characteristic sub-micrometric scales, we confront the robustness of the approach with three different well-known systems: ZnPcCl8 on Ag(111), CuPcF16 on Au(111) and PTBC on Ag(111). We retrieve respectively their square, oblique and hexagonal supramolecular tilling. The code incorporates generalized force fields to describe the molecular interactions, which provides transferability and versatility to many organic building blocks and metal surfaces.

  4. Chiral expression at the solid-liquid interface: a joint experimental and theoretical study of the self-assembly of chiral porphyrins on graphite.

    Science.gov (United States)

    Linares, Mathieu; Iavicoli, Patrizia; Psychogyiopoulou, Krystallia; Beljonne, David; De Feyter, Steven; Amabilino, David B; Lazzaroni, Roberto

    2008-09-01

    The chiral organization of an enantiopure functional molecule on an achiral surface has been studied with the aim of understanding the influence of stereogenic centers on the self-assembly in two dimensions. A chiral tetra meso-amidophenyl-substituted porphyrin containing long hydrophobic tails at the periphery of the conjugated pi-electron system was prepared for this purpose. Scanning tunneling microscopy (STM) images of the compound at the graphite-heptanol interface reveal a chiral arrangement of the molecules, with the porphyrin rows tilted by 13 degrees with respect to the normal to the graphite axes. In terms of molecular modeling, a combination of molecular dynamics simulations on systems constrained by periodic boundary conditions and on unconstrained large molecular aggregates has been applied to reach a quantitative interpretation on both the density of the layer and its orientation with respect to the graphite surface. The results show clearly that (i) the methyl groups of the stereogenic point toward the graphite surface and (ii) the porphyrin molecules self-assemble into an interdigitated structure where the alkyl chains align along one of the graphite axes and the porphyrin cores are slightly shifted with respect to one another. The direction of this shift, which defines the chirality of the monolayer, is set by the chirality of the stereogenic centers. Such an arrangement results in the formation of a dense chiral monolayer that is further stabilized by hydrogen bonding with protic solvents.

  5. A supramolecular Janus hyperbranched polymer and its photoresponsive self-assembly of vesicles with narrow size distribution.

    Science.gov (United States)

    Liu, Yong; Yu, Chunyang; Jin, Haibao; Jiang, Binbin; Zhu, Xinyuan; Zhou, Yongfeng; Lu, Zhongyuan; Yan, Deyue

    2013-03-27

    Herein, we report a novel Janus particle and supramolecular block copolymer consisting of two chemically distinct hyperbranched polymers, which is coined as Janus hyperbranched polymer. It is constructed by the noncovalent coupling between a hydrophobic hyperbranched poly(3-ethyl-3-oxetanemethanol) with an apex of an azobenzene (AZO) group and a hydrophilic hyperbranched polyglycerol with an apex of a β-cyclodextrin (CD) group through the specific AZO/CD host-guest interactions. Such an amphiphilic supramolecular polymer resembles a tree together with its root very well in the architecture and can further self-assemble into unilamellar bilayer vesicles with narrow size distribution, which disassembles reversibly under the irradiation of UV light due to the trans-to-cis isomerization of the AZO groups. In addition, the obtained vesicles could further aggregate into colloidal crystal-like close-packed arrays under freeze-drying conditions. The dynamics and mechanism for the self-assembly of vesicles as well as the bilayer structure have been disclosed by a dissipative particle dynamics simulation. PMID:23464832

  6. Fabrication of Highly Ordered Polymeric Nanodot and Nanowire Arrays Templated by Supramolecular Assembly Block Copolymer Nanoporous Thin Films

    Directory of Open Access Journals (Sweden)

    Liu Xikui

    2009-01-01

    Full Text Available Abstract Realizing the vast technological potential of patternable block copolymers requires both the precise controlling of the orientation and long-range ordering, which is still a challenging topic so far. Recently, we have demonstrated that ordered nanoporous thin film can be fabricated from a simple supramolecular assembly approach. Here we will extend this approach and provide a general route to fabricate large areas of highly ordered polymeric nanodot and nanowire arrays. We revealed that under a mixture solvent annealing atmosphere, a near-defect-free nanoporous thin film over large areas can be achieved. Under the direction of interpolymer hydrogen bonding and capillary action of nanopores, this ordered porous nanotemplate can be properly filled with phenolic resin precursor, followed by curation and pyrolysis at middle temperature to remove the nanotemplate, a perfect ordered polymer nanodot arrays replication was obtained. The orientation of the supramolecular assembly thin films can be readily re-aligned parallel to the substrate upon exposure to chloroform vapor, so this facile nanotemplate replica method can be further extend to generate large areas of polymeric nanowire arrays. Thus, we achieved a successful sub-30 nm patterns nanotemplates transfer methodology for fabricating polymeric nanopattern arrays with highly ordered structure and tunable morphologies.

  7. Self-assembly and supramolecular liquid crystals based on organic cation encapsulated polyoxometalate hybrid reverse micelles and pyridine derivatives.

    Science.gov (United States)

    Yin, Shengyan; Sun, Hang; Yan, Yi; Zhang, Hui; Li, Wen; Wu, Lixin

    2011-09-15

    The controlled self-assembly of multi-components in one system represents the capability integrating intermolecular interactions and functions of components and is believed the key procedure leading to multifunctional materials finally. In pursuing this goal, we used a double-chain cationic surfactant with a benzoic acid group at the end of one tail to encapsulate Keggin-type polyanion clusters via electrostatic interaction, obtaining uniform supramolecular hybrid reverse micelles, which served as hydrogen-bonding donors. Five pyridine derivatives containing conjugated and non-conjugated groups were chosen as hydrogen-bonding acceptors to bind with reverse micelles. Through mixing with these components according to chemical stoichiometry, the hybrid reverse micelle changed to a new self-assembly precursor through intermolecular hydrogen bonding. The as-prepared reverse micelles bearing conjugated pyridine groups exhibit supramolecular liquid crystal properties, which were characterized by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction. The length and number of the alky chain in the pyridine derivatives, as well as the charges of polyoxometalates were also studied with regard to the liquid crystal structure. The synergistic effect of among three components was analyzed, and the liquid crystal properties could be conveniently adjusted through the modification of the hydrogen-bonding acceptor components.

  8. Modeling Textural Processes during Self-Assembly of Plant-Based Chiral-Nematic Liquid Crystals

    Directory of Open Access Journals (Sweden)

    Yogesh K. Murugesan

    2010-12-01

    Full Text Available Biological liquid crystalline polymers are found in cellulosic, chitin, and DNA based natural materials. Chiral nematic liquid crystalline orientational order is observed frozen-in in the solid state in plant cell walls and is known as a liquid crystal analogue characterized by a helicoidal plywood architecture. The emergence of the plywood architecture by directed chiral nematic liquid crystalline self assembly has been postulated as the mechanism that leads to optimal cellulose fibril organization. In natural systems, tissue growth and development takes place in the presence of inclusions and secondary phases leaving behind characteristic defects and textures, which provide a unique testing ground for the validity of the liquid crystal self-assembly postulate. In this work, a mathematical model, based on the Landau-de Gennes theory of liquid crystals, is used to simulate defect textures arising in the domain of self assembly, due to presence of secondary phases representing plant cells, lumens and pit canals. It is shown that the obtained defect patterns observed in some plant cell walls are those expected from a truly liquid crystalline phase. The analysis reveals the nature and magnitude of the viscoelastic material parameters that lead to observed patterns in plant-based helicoids through directed self-assembly. In addition, the results provide new guidance to develop biomimetic plywoods for structural and functional applications.

  9. Chiral-induced self-assembly sphere phase liquid crystal with fast switching time

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Ji-Liang; Ni, Shui-Bin; Ping Chen, Chao; Lu, Jian-Gang, E-mail: lujg@sjtu.edu.cn; Su, Yikai [National Engineering Lab for TFT-LCD Materials and Technologies, Department of Electronic Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Wu, Dong-Qing [College of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Song, Xiao-Long; Chen, Chao-Yuan [The Jiangsu Hecheng Display Technology Co., Ltd., Nanjing 211300 (China); Shieh, Han-Ping D. [National Engineering Lab for TFT-LCD Materials and Technologies, Department of Electronic Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Department of Photonics and Display Institute, National Chiao Tung University, Hsinchu 300, Taiwan (China)

    2014-03-03

    A fluid self-assembly sphere phase (SP) of liquid crystal induced by chiral dopant is observed in a narrow temperature range between isotropic and blue phase or between isotropic and chiral nematic phase. The SP consists of three-dimensional twist spheres (3-DTSs) and disclinations among 3-DTSs. The temperature range of the SP has been broadened to more than 85 °C by stabilizing the disclinations with amorphous polymer chains. The electro-optical switching time of the polymer-stabilized SP is demonstrated in sub-millisecond with a low switching electric field of 4.4 V μm{sup −1}, which is of promising applications in displays, 3-D tunable photonic crystals, and phase modulators.

  10. Lanthanide-directed synthesis of luminescent self-assembly supramolecular structures and mechanically bonded systems from acyclic coordinating organic ligands.

    Science.gov (United States)

    Barry, Dawn E; Caffrey, David F; Gunnlaugsson, Thorfinnur

    2016-06-01

    Herein some examples of the use of lanthanide ions (f-metal ions) to direct the synthesis of luminescent self-assembly systems (architectures) will be discussed. This area of lanthanide supramolecular chemistry is fast growing, thanks to the unique physical (magnetic and luminescent) and coordination properties of the lanthanides, which are often transferred to the resulting supermolecule. The emphasis herein will be on systems that are luminescent, and hence, generated by using either visibly emitting ions (such as Eu(III), Tb(III) and Sm(III)) or near infrared emitting ions (like Nd(III), Yb(III) and Er(III)), formed through the use of templating chemistry, by employing structurally simple ligands, possessing oxygen and nitrogen coordinating moieties. As the lanthanides have high coordination requirements, their use often allows for the formation of coordination compounds and supramolecular systems such as bundles, grids, helicates and interlocked molecules that are not synthetically accessible through the use of other commonly used templating ions such as transition metal ions. Hence, the use of the rare-earth metal ions can lead to the formation of unique and stable species in both solution and in the solid state, as well as functional and responsive structures.

  11. Dissolved oxygen amperometric sensor based on layer-by-layer assembly using host-guest supramolecular interactions

    International Nuclear Information System (INIS)

    The development of a simple, efficient and sensitive sensor for dissolved oxygen is proposed using the host-guest binding of a supramolecular complex at a host surface by combining a self-assembled monolayer (SAM) of mono-(6-deoxy-6-mercapto)-β-cyclodextrin (βCDSH), iron (III) tetra-(N-methyl-4-pyridyl)-porphyrin (FeTMPyP) and cyclodextrin-functionalized gold nanoparticles (CDAuNP). The supramolecular modified electrode showed excellent catalytic activity for oxygen reduction. The reduction potential of oxygen was shifted about 200 mV toward less negative values with this modified electrode, presenting a peak current much higher than those observed on a bare gold electrode. Cyclic voltammetry and rotating disk electrode (RDE) experiments indicated that the oxygen reduction reaction involves probably 4-electrons with a rate constant (kobs) of 7 x 104 mol-1 L s-1. A linear response range from 0.2 up to 6.5 mg L-1, with a sensitivity of 5.5 μA L mg-1 (or 77.5 μA cm-2 L mg-1) and a detection limit of 0.02 mg L-1 was obtained with this sensor. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation was 3.0% for 10 measurements of a solution of 6.5 mg L-1 oxygen.

  12. A unique quinolineboronic acid-based supramolecular structure that relies on double intermolecular B-N bonds for self-assembly in solid state and in solution

    OpenAIRE

    Zhang, Yanling; Li, Minyong; Chandrasekaran, Sekar; Gao, Xingming; Fang, Xikui; Lee, Hsiau-Wei; Hardcastle, Kenneth; Yang, Jenny; Wang, Binghe

    2007-01-01

    The boronic acid functional group plays very important roles in sugar recognition, catalysis, organic synthesis, and supramolecular assembly. Therefore, understanding the unique properties of this functional group is very important. 8-Quinolineboronic acid (8-QBA) is found to be capable of self-assembling in solid state through a unique intermolecular B-N bond mechanism reinforced by intermolecular boronic anhydride formation, π-π stacking, and hydrogen bond formation. NMR NOE and diffusion s...

  13. Molecular-Level Design of Heterogeneous Chiral Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Francisco Zaera

    2012-03-21

    The following is a proposal to continue our multi-institutional research on heterogeneous chiral catalysis. Our team combines the use of surface-sensitive analytical techniques for the characterization of model systems with quantum and statistical mechanical calculations to interpret experimental data and guide the design of future research. Our investigation focuses on the interrelation among the three main mechanisms by which enantioselectivity can be bestowed to heterogeneous catalysts, namely: (1) by templating chirality via the adsorption of chiral supramolecular assemblies, (2) by using chiral modifiers capable of forming chiral complexes with the reactant and force enantioselective surface reactions, and (3) by forming naturally chiral surfaces using imprinting chiral agents. Individually, the members of our team are leaders in these various aspects of chiral catalysis, but the present program provides the vehicle to generate and exploit the synergies necessary to address the problem in a comprehensive manner. Our initial work has advanced the methodology needed for these studies, including an enantioselective titration procedure to identify surface chiral sites, infrared spectroscopy in situ at the interface between gases or liquids and solids to mimic realistic catalytic conditions, and DFT and Monte Carlo algorithms to simulate and understand chirality on surfaces. The next step, to be funded by the monies requested in this proposal, is to apply those methods to specific problems in chiral catalysis, including the identification of the requirements for the formation of supramolecular surface structures with enantioselective behavior, the search for better molecules to probe the chiral nature of the modified surfaces, the exploration of the transition from supramolecular to one-to-one chiral modification, the correlation of the adsorption characteristics of one-to-one chiral modifiers with their physical properties, in particular with their configuration

  14. Electrostatic-assembly-driven formation of supramolecular rhombus microparticles and their application for fluorescent nucleic acid detection.

    Directory of Open Access Journals (Sweden)

    Hailong Li

    Full Text Available In this paper, we report on the large-scale formation of supramolecular rhombus microparticles (SRMs driven by electrostatic assembly, carried out by direct mixing of an aqueous HAuCl(4 solution and an ethanol solution of 4,4'-bipyridine at room temperature. We further demonstrate their use as an effective fluorescent sensing platform for nucleic acid detection with a high selectivity down to single-base mismatch. The general concept used in this approach is based on adsorption of the fluorescently labeled single-stranded DNA (ssDNA probe by SRM, which is accompanied by substantial fluorescence quenching. In the following assay, specific hybridization with its target to form double-stranded DNA (dsDNA results in desorption of ssDNA from SRM surface and subsequent fluorescence recovery.

  15. Exploring the complexity of supramolecular interactions for patterning at the liquid-solid interface.

    Science.gov (United States)

    Mali, Kunal S; Adisoejoso, Jinne; Ghijsens, Elke; De Cat, Inge; De Feyter, Steven

    2012-08-21

    The use of self-assembly to fabricate surface-confined adsorbed layers (adlayers) from molecular components provides a simple means of producing complex functional surfaces. The molecular self-assembly process relies on supramolecular interactions sustained by noncovalent forces such as van der Waals, electrostatic, dipole-dipole, and hydrogen bonding interactions. Researchers have exploited these noncovalent bonding motifs to construct well-defined two-dimensional (2D) architectures at the liquid-solid interface. Despite myriad examples of 2D molecular assembly, most of these early findings were serendipitous because the intermolecular interactions involved in the process are often numerous, subtle, cooperative, and multifaceted. As a consequence, the ability to tailor supramolecular patterns has evolved slowly. Insight gained from various studies over the years has contributed significantly to the knowledge of supramolecular interactions, and the stage is now set to systematically engineer the 2D supramolecular networks in a "preprogrammed" fashion. The control over 2D self-assembly of molecules has many important implications. Through appropriate manipulation of supramolecular interactions, one can "encode" the information at the molecular level via structural features such as functional groups, substitution patterns, and chiral centers which could then be retrieved, transferred, or amplified at the supramolecular level through well-defined molecular recognition processes. This ability allows for precise control over the nanoscale structure and function of patterned surfaces. A clearer understanding and effective use of these interactions could lead to the development of functional surfaces with potential applications in molecular electronics, chiral separations, sensors based on host-guest systems, and thin film materials for lubrication. In this Account, we portray our various attempts to achieve rational design of self-assembled adlayers by exploiting the

  16. Supramolecular catalysis: Refocusing catalysis

    NARCIS (Netherlands)

    P.W.N.M. van Leeuwen; Z. Freixa

    2008-01-01

    This chapter contains sections titled: * Introduction: A Brief Personal History * Secondary Phosphines or Phosphites as Supramolecular Ligands * Host-Guest Catalysis * Ionic Interactions as a Means to Form Heterobidentate Assembly Ligands * Ditopic Ligands for the Construction of Bidentate Phosphine

  17. Encapsulation and Characterization of Proton-Bound Amine Homodimers in a Water Soluble, Self-Assembled Supramolecular Host

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael; Fiedler, Dorothea; Mugridge, Jeffrey; Bergman, Robert; Raymond, Kenneth

    2008-10-01

    Cyclic amines can be encapsulated in a water-soluble self-assembled supramolecular host upon protonation. The hydrogen bonding ability of the cyclic amines, as well as the reduced degrees of rotational freedom, allows for the formation of proton-bound homodimers inside of the assembly which are otherwise not observable in aqueous solution. The generality of homodimer formation was explored with small N-alkyl aziridines, azetidines, pyrrolidines and piperidines. Proton-bound homodimer formation is observed for N-alkylaziridines (R = methyl, isopropyl, tert-butyl), N-alkylazetidines (R = isopropyl, tertbutyl), and N-methylpyrrolidine. At high concentration, formation of a proton-bound homotrimer is observed in the case of N-methylaziridine. The homodimers stay intact inside the assembly over a large concentration range, thereby suggesting cooperative encapsulation. Both G3(MP2)B3 and G3B3 calculations of the proton-bound homodimers were used to investigate the enthalpy of the hydrogen bond in the proton-bound homodimers and suggest that the enthalpic gain upon formation of the proton-bound homodimers may drive guest encapsulation.

  18. Controlled Assembly of Endohedrally-Functionalized Metal-Ligand Supramolecular Complexes

    OpenAIRE

    Johnson, Amber

    2014-01-01

    An area of supramolecular chemistry that has recently been growing in popularity is the synthesis of metal-ligand cages. These are most commonly comprised of organic ligands and transition metal ions. Cage complexes often take the form of geometric polyhedra such as tetrahedra and octahedra, where the ligands act as the edges or faces and the metals serve as the vertices. Because these complexes have a polyhedral design, there is a central cavity in the cage, and this has been exploited for g...

  19. Supramolecular clippers for controlling photophysical processes through preorganized chromophores.

    Science.gov (United States)

    Kumar, Mohit; Ushie, Onumashi Afi; George, Subi J

    2014-04-22

    A novel supramolecular clipping design for influencing the photophysical properties of functional molecular assemblies, by the preorganization (clipping) of chromophores, is described. Several chromophores end functionalized with molecular recognition units were designed. These molecular recognition units serve as handles to appropriately position these systems upon noncovalent interactions with multivalent guest molecules (supramolecular clippers). Towards this goal, we have synthesized 1,5-dialkoxynaphthalene (DAN) and naphthalenediimide (NDI) functionalized with dipicolylethylenediamine (DPA) motifs. These molecules could preorganize upon noncovalent clipping with adenosine di- or triphosphates, which resulted in preassociated excimers and mixed (cofacial) charge-transfer (CT) assemblies. Chiral guest binding could also induce supramolecular chirality, not only into the individual chromophoric assembly but also into the heteromeric CT organization, as seen from the strong circular dichroism (CD) signal of the CT transition. The unique ability of this design to influence the intermolecular interactions by changing the binding strength of the clippers furthermore makes it very attractive for controlling the bimolecular photophysical processes. PMID:24623564

  20. Design, synthesis, and self-assembly of optically active perylenetetracarboxylic diimide bearing two peripheral chiral binaphthyl moieties

    International Nuclear Information System (INIS)

    An optically active perylenetetracarboxylic diimide (PTCDI) bearing two optically active binaphthyl moieties has been designed and synthesized. The self-assembly properties of these novel PTCDI derivatives in DMF/H2O were systematically investigated by electronic absorption, circular dichroism (CD) spectra, IR spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray diffraction (XRD) technique. Observation of CD signal in the whole absorption region of PTCDI chromophore, indicates effective chiral information transfer from the chiral binaphthyl units to the central PTCDI chromophore at molecular level. The intermolecular π–π interaction between PTCDI rings together with the additionally formed hydrogen bonds between the crown ether moieties of (S)-1 and additional water molecules and the chiral discrimination of periphery chiral side chains induces further intensified asymmetrical perturbation of the chiral binaphthyl units to the central PTCDI chromophore during the self-assembly process, resulting in the formation of right-handed helical arrangement of corresponding molecules in a stack of PTCDI chromophores in aggregates. In addition, the formed nanostructures were revealed to show good semiconducting properties. - Graphical abstract: An optically active perylenetetracarboxylic diimide bearing two optically active binaphthyl moieties has been prepared. Self-assembly properties of this novel PTCDI derivative in DMF/H2O were systematically investigated. Experimental results indicate the effective chiral information transfer and expression at molecular and intermolecular level. Highlights: ► An optically active perylenetetracarboxylic diimide bearing two optically active binaphthyl moieties has been prepared. ► Self-assembly properties of this novel PTCDI derivative in DMF/H2O were systematically investigated. ► Experimental results indicate the effective chiral information transfer and expression at molecular

  1. The formation of right-handed and left-handed chiral nanopores within a single domain during amino acid self-assembly on Au(111).

    Science.gov (United States)

    Yang, Sena; Jeon, Aram; Driver, Russell W; Kim, Yeonwoo; Jeon, Eun Hee; Kim, Sehun; Lee, Hee-Seung; Lee, Hangil

    2016-05-25

    We report the formation of both right- and left-handed chiral nanopores within a single domain during the self-assembly of an amino acid derivative on an inert Au(111) surface using STM. DFT calculations employed to rationalize this unusual result identified that intermolecular interactions between chiral, windmill-shaped tetramers are crucial for self-assembly.

  2. Construction of diverse supramolecular assemblies of dimetal subunits differing in coordinated water molecules via strong hydrogen bonding interactions: Synthesis, crystal structures and spectroscopic properties

    Indian Academy of Sciences (India)

    Sadhika Khullar; Sanjay K Mandal

    2014-09-01

    Three new supramolecular assemblies (constructed through strong hydrogen bonding) of [Co2(bpta)2(adc)(H2O)4](ClO4)2.2H2O (1), [Cu2(bpta)2(fum)(H2O)2](ClO4)2 (2) and [Cu2(bpta)2(tdc)(H2O) (ClO4)](ClO4).3H2O (3), which are synthesised by one pot self-assembly of the metal salt, bpta ligand and the corresponding dicarboxylate under the same reaction conditions, are reported (where adc = acetylene dicarboxylate, fum = fumarate, tdc = 2,5-thiophenedicarboxylate and bpta = N,N'-bis(2-pyridylmethyl)-tertbutylamine). These compounds have varying degrees of coordinatedwater molecules per dimetal subunits (four for 1, two for 2 and one for 3, respectively). Furthermore, the orientation of the coordinated water molecules in 1 and 2, with respect to the mono (carboxylato)-bridged dimetal subunit, is different (cis and trans, respectively). On the other hand, there is a coordinated perchlorate ion in 3 making the two metal centers inequivalent. Unlike 1 and 3, there are no lattice water molecules in 2. This difference in the dimetal subunit in 1-3 and the presence or absence of the lattice water molecules are the keys to forming the diverse supramolecular assemblies. In 1 and 3, the involvement of lattice water molecules in the construction of such assemblies is distinctly different. In case of 2, the formation of supramolecular assembly depends on the coordinated water molecule (trans to each other) and thus a ladder shaped supramolecular assembly is the result. The strength of hydrogen bonding observed in the networks of 1-3 is indicated in the O…O distances (2.596 Å to 3.160 Å) and the OH…O angles 124° to 176°. All are characterised by elemental analysis, FTIR spectroscopy and single crystal X-ray diffraction studies.

  3. Synthesis, Crystal Structure and Photocatalytic Properties of a Supramolecular Assembly Based on Keggin Polyoxotungstate

    Institute of Scientific and Technical Information of China (English)

    CHEN Shun-Yu; CHEN Xin-Qin; LIN Shen

    2012-01-01

    A new supramolecular compound (4,4'-bipyH)4[SiW12O40](4,4'-bipy) (4,4'-bipy = 4,4'-bipyridine) was synthesized hydrothermally and characterized by single-crystal X-ray diffraction and IR spectrum. The crystallography analysis for the title compound reveals that the crystal crystallizes in monoclinic, space group C2/m with a = 22.2767(12), b = 21.1879(11), c = 15.6942(8) A, β = 97.068(3)°, V = 7351.3(7) A3, Cs0H44N10040SiW12, Mr = 3659.24, Z = 4, Dc = 3.306 g/cm3, F(000) = 6544, GOOF = 1.137, R = 0.0577 and wR = 0.1579. The title compound consists of a discrete Keggin-type [SiWl2O40]4- anion, one 4,4'-bipy and four protonated (4,4'-bipyH)+ cations. The [SiWl2O40]4- anion and protonated 4,4'-bipy are connected to form a supramolecular structure by hydrogen bonds. Meanwhile, the title compound exhibits good photocatalytic activity for color degradation of Rhodamine-B dye solution under visible-light irradiation.

  4. Aqueous cholesteric liquid crystals using uncharged rodlike polypeptides. Polypeptide vesicles by conformation-specific assembly. Ordered chiral macroporous hybrid silica-polypeptide composites

    Science.gov (United States)

    Bellomo, Enrico Giuseppe

    2005-07-01

    Aqueous cholesteric liquid crystals using uncharged rodlike polypeptides . The aqueous, lyotropic liquid-crystalline phase behavior of an alpha helical polypeptide, has been studied using optical microscopy and X-ray scattering. Solutions of optically pure polypeptide were found to form cholesteric liquid crystals at volume fractions that decreased with increasing average chain length. At very high volume fractions, the formation of a hexagonal mesophase was observed. The pitch of the cholesteric phase could be varied by a mixture of enantiomeric samples, where the pitch increased as the mixture approached equimolar. The cholesteric phases could be untwisted, using either magnetic field or shear flow, into nematic phases, which relaxed into cholesterics upon removal of field or shear. We have found that the phase diagram of this polypeptide in aqueous solution parallels that of poly(gamma-benzyl glutamate) in organic solvents, thus providing a useful system for liquid-crystal applications requiring water as solvent. Polypeptide vesicles by conformation-specific assembly. We have found that block copolymers composed of polypeptide segments provide significant advantages in controlling both the function and supramolecular structure of bioinspired self-assemblies. Incorporation of the stable chain conformations found in proteins into block copolymers was found to provide an additional element of control, beyond amphiphilicity and composition that defines self-assembled architecture. The abundance of functionality present in amino acids, and the ease by which they can be incorporated into these materials, also provides a powerful mechanism to impart block copolypeptides with function. This combination of structure and function work synergistically to enable significant advantages in the preparation of therapeutic agents as well as provide insight into design of self-assemblies beginning to approach the complexity of natural structures such as virus capsids. Ordered

  5. Predicting Chiral Nanostructures, Lattices and Superlattices in Complex Multicomponent Nanoparticle Self-Assembly

    KAUST Repository

    Hur, Kahyun

    2012-06-13

    "Bottom up" type nanoparticle (NP) self-assembly is expected to provide facile routes to nanostructured materials for various, for example, energy related, applications. Despite progress in simulations and theories, structure prediction of self-assembled materials beyond simple model systems remains challenging. Here we utilize a field theory approach for predicting nanostructure of complex and multicomponent hybrid systems with multiple types of short- and long-range interactions. We propose design criteria for controlling a range of NP based nanomaterial structures. In good agreement with recent experiments, the theory predicts that ABC triblock terpolymer directed assemblies with ligand-stabilized NPs can lead to chiral NP network structures. Furthermore, we predict that long-range Coulomb interactions between NPs leading to simple NP lattices, when applied to NP/block copolymer (BCP) assemblies, induce NP superlattice formation within the phase separated BCP nanostructure, a strategy not yet realized experimentally. We expect such superlattices to be of increasing interest to communities involved in research on, for example, energy generation and storage, metamaterials, as well as microelectronics and information storage. © 2012 American Chemical Society.

  6. Functionalized Nanostructures: Redox-Active Porphyrin Anchors for Supramolecular DNA Assemblies

    KAUST Repository

    Börjesson, Karl

    2010-09-28

    We have synthesized and studied a supramolecular system comprising a 39-mer DNA with porphyrin-modified thymidine nucleosides anchored to the surface of large unilamellar vesicles (liposomes). Liposome porphyrin binding characteristics, such as orientation, strength, homogeneity, and binding site size, was determined, suggesting that the porphyrin is well suited as a photophysical and redox-active lipid anchor, in comparison to the inert cholesterol anchor commonly used today. Furthermore, the binding characteristics and hybridization capabilities were studied as a function of anchor size and number of anchoring points, properties that are of importance for our future plans to use the addressability of these redox-active nodes in larger DNA-based nanoconstructs. Electron transfer from photoexcited porphyrin to a lipophilic benzoquinone residing in the lipid membrane was characterized by steady-state and time-resolved fluorescence and verified by femtosecond transient absorption. © 2010 American Chemical Society.

  7. Influence of Dissolved O2 in Organic Solvents on CuOEP Supramolecular Self-Assembly on Graphite.

    Science.gov (United States)

    Hao, Yibo; Weatherup, Robert S; Eren, Baran; Somorjai, Gabor A; Salmeron, Miquel

    2016-06-01

    The supramolecular self-assembly of copper(II) octaethylporphyrin (CuOEP) and octaethylporphyrin (H2OEP) on graphitic surfaces immersed in organic solvents (dichlorobenzene, dodecane) is studied using scanning tunneling microscopy (STM) and Raman spectroscopy. STM reveals that the self-assembled structure of CuOEP in 1,2-dichlorobenzene is significantly altered by dissolved oxygen within the solvent. Raman spectroscopy reveals that the presence of the oxygen alters the molecule-substrate interaction, which is attributed to the adsorption of oxygen on the Cu center of the CuOEP, which is facilitated by electron transfer from the graphitic surface. Such oxygen-induced changes are not observed for H2OEP, indicating that the metal center of CuOEP plays a critical role. When the solvent is dodecane, we find that solvation effects dominate. CuOEP adsorbed on graphitic surfaces provides a model system relevant to the study of the transport and activation of oxygen by enzymes and other complexes. PMID:27180868

  8. A molecular simulation probing of structure and interaction for supramolecular sodium dodecyl sulfate/single-wall carbon nanotube assemblies.

    Science.gov (United States)

    Xu, Zhijun; Yang, Xiaoning; Yang, Zhen

    2010-03-10

    Here we report a larger-scale atomic-level molecular dynamics (MD) simulation for the self-assembly of sodium dodecyl sulfate (SDS) surfactant on single-walled carbon nanotube (SWNT) surfaces and the interaction between supramolecular SDS/SWNT aggregates. We make an effort to address several important problems in regard to carbon nanotube dispersion/separation. At first, the simulation provides comprehensive direct evidence for SDS self-assembly structures on carbon nanotube surfaces, which can help to clarify the relevant debate over the exact adsorption structure. We also, for the first time, simulated the potential of mean force (PMF) between two SWNTs embedded in SDS surfactant micelles. A novel unified PMF approach has been applied to reveal various cooperative interactions between the SDS/SWNT aggregates, which is different from the previous electrostatic repulsion explanation. The unique role of sodium ions revealed here provides a new microscopic understanding of the recent experiments in the electrolyte tuning of the interfacial forces on the selective fractionation of SDS surrounding SWNTs.

  9. Chiral Nanoscience and Nanotechnology

    OpenAIRE

    Dibyendu S. Bag; T.C. Shami; K.U. Bhasker Rao

    2008-01-01

    The paper reviews nanoscale science and technology of chiral molecules/macromolecules-under twosubtopics-chiral nanotechnology and nano-chiral technology. Chiral nanotechnology discusses thenanotechnology, where molecular chirality plays a role in the properties of materials, including molecularswitches, molecular motors, and other molecular devices; chiral supramolecules and self-assembled nanotubesand their functions are also highlighted. Nano-chiral technology  describes the nanoscale appr...

  10. A versatile strategy towards non-covalent functionalization of graphene by surface-confined supramolecular self-assembly of Janus tectons

    Directory of Open Access Journals (Sweden)

    Ping Du

    2015-03-01

    Full Text Available Two-dimensional (2D, supramolecular self-assembly at surfaces is now well-mastered with several existing examples. However, one remaining challenge to enable future applications in nanoscience is to provide potential functionalities to the physisorbed adlayer. This work reviews a recently developed strategy that addresses this key issue by taking advantage of a new concept, Janus tecton materials. This is a versatile, molecular platform based on the design of three-dimensional (3D building blocks consisting of two faces linked by a cyclophane-type pillar. One face is designed to steer 2D self-assembly onto C(sp2-carbon-based flat surfaces, the other allowing for the desired functionality above the substrate with a well-controlled lateral order. In this way, it is possible to simultaneously obtain a regular, non-covalent paving as well as supramolecular functionalization of graphene, thus opening interesting perspectives for nanoscience applications.

  11. Supramolecular Au Nanoparticle Assemblies as Optical Probes for Enzyme-Linked Immunoassays

    NARCIS (Netherlands)

    Rica, de la Roberto; Velders, Aldrik H.

    2011-01-01

    A novel enzyme-linked immunoassay with nanoparticle assemblies as optical probes is presented. The macrocycle cucurbit[7]uril assembles gold nanoparticles, and the enzymatic generation of ammonium by urease as the label of the immunoassay disperses the probes to yield variations of plasmon absorbanc

  12. Reversible supramolecular assembly at specific DNA sites: nickel-promoted bivalent DNA binding with designed peptide and bipyridyl-bis(benzamidine) components.

    Science.gov (United States)

    Sánchez, Mateo I; Mosquera, Jesús; Vázquez, M Eugenio; Mascareñas, José L

    2014-09-01

    At specific DNA sites, nickel(II) salts promote the assembly of designed components, namely a bis(histidine)-modified peptide that is derived from a bZIP transcription factor and a bis(benzamidine) unit that is equipped with a bipyridine. This programmed supramolecular system with emergent properties reproduces some key characteristics of naturally occurring DNA-binding proteins, such as bivalence, selectivity, responsiveness to external agents, and reversibility.

  13. Magnetism: a supramolecular function

    Energy Technology Data Exchange (ETDEWEB)

    Decurtins, S.; Pellaux, R.; Schmalle, H.W. [Zurich Univ., Inst. fuer Anorganische Chemie, Zurich (Switzerland)

    1996-11-01

    The field of molecule-based magnetism has developed tremendously in the last few years. Two different extended molecular - hence supramolecular -systems are presented. The Prussian-blue analogues show some of the highest magnetic ordering temperature of any class of molecular magnets, T{sub c} = 315 K, whereas the class of transition-metal oxalate-bridged compounds exhibits a diversity of magnetic phenomena. Especially for the latter compounds, the elastic neutron scattering technique has successfully been proven to trace the magnetic structure of these supramolecular and chiral compounds. (author) 18 figs., 25 refs.

  14. Supramolecular Self-Assembled Chaos: Polyphenolic Lignin’s Barrier to Cost-Effective Lignocellulosic Biofuels

    OpenAIRE

    Shawn Matthew Dirk; Jason Carl Harper; Blake Alexander Simmons; Anup Kumar Singh; Paul David Adams; Ann Mary Achyuthan; Komandoor Elayavalli Achyuthan

    2010-01-01

    Phenylpropanoid metabolism yields a mixture of monolignols that undergo chaotic, non-enzymatic reactions such as free radical polymerization and spontaneous self-assembly in order to form the polyphenolic lignin which is a barrier to cost-effective lignocellulosic biofuels. Post-synthesis lignin integration into the plant cell wall is unclear, including how the hydrophobic lignin incorporates into the wall in an initially hydrophilic milieu. Self-assembly, self-organization and aggregation gi...

  15. Supramolecular assembly of macroscopic building blocks through self-propelled locomotion by dissipating chemical energy.

    Science.gov (United States)

    Cheng, Mengjiao; Ju, Guannan; Zhang, Yingwei; Song, Mengmeng; Zhang, Yajun; Shi, Feng

    2014-10-15

    Chemical energy supplied by the catalytic decomposition of H2O2 is introduced into macroscopic building blocks, which self-propel, interact with each other, and finally assemble into ordered and advanced structures. The geometry is highly dependent on the way that the catalyst is loaded. The integration of catalyst and building block provides assembling component as well as its energy of motion. PMID:24838346

  16. Luminescent lanthanide complexes with 4-acetamidobenzoate: Synthesis, supramolecular assembly via hydrogen bonds, crystal structures and photoluminescence

    Science.gov (United States)

    Yin, Xia; Fan, Jun; Wang, Zhi Hong; Zheng, Sheng Run; Tan, Jing Bo; Zhang, Wei Guang

    2011-07-01

    Four new luminescent complexes, namely, [Eu(aba) 2(NO 3)(C 2H 5OH) 2] ( 1), [Eu(aba) 3(H 2O) 2]·0.5 (4, 4'-bpy)·2H 2O ( 2), [Eu 2(aba) 4(2, 2'-bpy) 2(NO 3) 2]·4H 2O ( 3) and [Tb 2(aba) 4(phen) 2(NO 3) 2]·2C 2H 5OH ( 4) were obtained by treating Ln(NO 3) 3·6H 2O and 4-acetamidobenzoic acid (Haba) with different coligands (4, 4'-bpy=4, 4'-bipyridine, 2, 2'-bpy=2, 2'-bipyridine, and phen=1, 10-phenanthroline). They exhibit 1D chains ( 1- 2) and dimeric structures ( 3- 4), respectively. This structural variation is mainly attributed to the change of coligands and various coordination modes of aba molecules. Moreover, the coordination units are further connected via hydrogen bonds to form 2D even 3D supramolecular networks. These complexes show characteristic emissions in the visible region at room temperature. In addition, thermal behaviors of four complexes have been investigated under air atmosphere. The relationship between the structures and physical properties has been discussed.

  17. Self-assembly of hydrogen-bonded supramolecular complexes of nucleic-acid-base and fatty-acid at the liquid-solid interface.

    Science.gov (United States)

    Zhao, Huiling; Song, Xin; Aslan, Hüsnü; Liu, Bo; Wang, Jianguo; Wang, Li; Besenbacher, Flemming; Dong, Mingdong

    2016-06-01

    Self-assembly provides an effective approach for the fabrication of supramolecular complexes or heterojunction materials, which have unique properties and potential applications in many fields. In this study, the self-assembled structures of stearic acid (SA) and nucleic acid base, guanine (G), are formed at the liquid-solid interface. Two main configurations, namely SA-G-SA and SA-G-G-SA, are observed and the intermolecular recognition mechanism between G and SA is proposed from the hydrogen-bonding point of view. PMID:27170421

  18. Supramolecular assembly of biological molecules purified from bovine nerve cells: from microtubule bundles and necklaces to neurofilament networks

    International Nuclear Information System (INIS)

    With the completion of the human genome project, the biosciences community is beginning the daunting task of understanding the structures and functions of a large number of interacting biological macromolecules. Examples include the interacting molecules involved in the process of DNA condensation during the cell cycle, and in the formation of bundles and networks of filamentous actin proteins in cell attachment, motility and cytokinesis. In this proceedings paper we present examples of supramolecular assembly based on proteins derived from the vertebrate nerve cell cytoskeleton. The axonal cytoskeleton in vertebrate neurons provides a rich example of bundles and networks of neurofilaments, microtubules (MTs) and filamentous actin, where the nature of the interactions, structures, and structure-function correlations remains poorly understood. We describe synchrotron x-ray diffraction, electron microscopy, and optical imaging data, in reconstituted protein systems purified from bovine central nervous system, which reveal unexpected structures not predicted by current electrostatic theories of polyelectrolyte bundling, including three-dimensional MT bundles and two-dimensional MT necklaces

  19. Eight supramolecular assemblies constructed from bis(benzimidazole) and organic acids through strong classical hydrogen bonding and weak noncovalent interactions

    Science.gov (United States)

    Jin, Shouwen; Wang, Daqi

    2014-05-01

    Eight crystalline organic acid-base adducts derived from alkane bridged bis(N-benzimidazole) and organic acids (2,4,6-trinitrophenol, p-nitrobenzoic acid, m-nitrobenzoic acid, 3,5-dinitrobenzoic acid, 5-sulfosalicylic acid and oxalic acid) were prepared and characterized by X-ray diffraction analysis, IR, mp, and elemental analysis. Of the eight compounds five are organic salts (1, 4, 6, 7 and 8) and the other three (2, 3, and 5) are cocrystals. In all of the adducts except 1 and 8, the ratio of the acid and the base is 2:1. All eight supramolecular assemblies involve extensive intermolecular classical hydrogen bonds as well as other noncovalent interactions. The role of weak and strong noncovalent interactions in the crystal packing is ascertained. These weak interactions combined, all the complexes displayed 3D framework structure. The results presented herein indicate that the strength and directionality of the classical N+-H⋯O-, O-H⋯O, and O-H⋯N hydrogen bonds (ionic or neutral) and other nonbonding associations between acids and ditopic benzimidazoles are sufficient to bring about the formation of cocrystals or organic salts.

  20. Microphase Separation in Thin Films of Block Copolymer Supramolecular Assemblies: Composition Dependent Morphological Transitions and Molecular Architecture Effect

    Science.gov (United States)

    Nandan, Bhanu; Stamm, Manfred

    2010-03-01

    Block copolymer based supramolecular assemblies (SMAs) recently have attracted lot of attention because of their potential application as nanotemplates. These SMAs are prepared by attaching small molecules selectively to one of the blocks of the copolymer through physical interactions. In the present study, the phase behavior of SMAs formed by polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) with 2-(4'-hydroxybenzeneazo)benzoic acid (HABA) was investigated with respect to the molar ratio (X) between HABA and 4VP monomer unit in bulk as well as in thin films. It will be shown that these SMAs show some interesting composition dependent and solvent induced pathway dependent phase transitions. Moreover, the orientation of cylindrical or lamellar microdomains of P4VP(HABA) depends on the selectivity of the solvent as well as on the degree of swelling of the thin film. Furthermore, it will be shown that the molecular architecture of the block copolymer influences the orientation and ordering of microdomains in the SMA. Hence, whereas, the cylindrical and lamellar microdomains of SMA composed of a P4VP-b-PS-b-P4VP triblock copolymer were perpendicular to the substrate, those composed from a PS-b-P4VP diblock of similar composition had in-plane orientation of the microdomains.

  1. Direct Biomolecules Binding on Nonfouling Surface via Newly Discovered Supramolecular Self-assembly of Lysozyme under Physiological Condition

    Science.gov (United States)

    Yang, Peng

    2013-01-01

    A major challenge in the development of low cost and practical strategies for biomolecules immobilization on solid supports is that the multi-step chemical/physical activating and following deactivating procedures on nonfouling substrates often increase the cost and complexity of surface functional group types as well as deteriorate the surface integrity. Herein, we show a novel phase transition of lysozyme could be used to constitute a major step to address the above problem. It is found that when lysozyme is dissolved in a neutral buffer solution of 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES, pH 7.4) with 1–50 mM tris(2-carboxyethyl)phosphine (TCEP) added, a fast phase transition process occurs and the resulting novel fibra-like hierarchical supramolecular assemblies made by primary spherical particles aggregation would function as a “superglue” that strongly and quickly bind onto non-fouling coatings. This binding is highly selective towards lysozyme, and excludes completely tedious synthetical, chemical/physical activation/deactivation (blocking) steps. When biotin is conjugated with lysozyme, such phase transition quickly constructs a perfect biotinylated surface on nonfouling surface for avidin binding, showing great potential for the development of low-cost and practical biochips. PMID:22707360

  2. Six hydrogen-bonded supramolecular frameworks assembled from organic acids and p-dimethylaminobenzaldehyde

    Science.gov (United States)

    Jin, Shouwen; Wang, Lanqing; Lou, Yulei; Liu, Li; Li, Bin; Li, Linyu; Feng, Chao; Liu, Hui; Wang, Daqi

    2016-03-01

    Cocrystallization of the commonly available organic compound, p-dimethylaminobenzaldehyde, with a series of organic acids gave a total of six molecular adducts with the compositions: p-dimethylaminobenzaldehyde : (3,5-dinitrosalicylic acid) [(L) · (Hdsa), Hdsa = 3,5-dinitrosalicylic acid] (1), p-dimethylaminobenzaldehyde : (3-nitrophthalic acid) [(L) · (3-H2npa), 3-H2npa = 3-nitrophthalic acid] (2), p-dimethylaminobenzaldehyde : (4-nitrophthalic acid) [(L) · (4-H2npa), 4-H2npa = 4-nitrophthalic acid] (3), p-dimethylaminobenzaldehyde : (1,5-naphthalenedisulfonic acid) : (NH3)2 [NH4 · (HL) · (nds2-) · NH3, nds- = 1,5-naphthalenedisulfonate] (4), p-dimethylaminobenzaldehyde : (oxalic acid)0.5 [(L) · (H2oa)0.5, H2oa = oxalic acid] (5), and p-dimethylaminobenzaldehyde : (fumaric acid)0.5 [(L) · (H2fum)0.5, H2fum = fumaric acid] (6). The six molecular adducts have been characterized by X-ray diffraction technique, IR, and elemental analysis, and the melting points of all adducts were also reported. And their structural and supramolecular aspects are fully analyzed. Of the six adducts, only 4 is an organic salt and the other five are cocrystals. The crystal packing is interpreted in terms of the strong classical hydrogen bonds as well as other weak non-classical hydrogen bonds. The different families of non-covalent bonds contribute to the stabilization and expansion of the total high-dimensional (2D-3D) frameworks.

  3. Self-assembled peptide nanotubes are uniquely rigid bioinspired supramolecular structures.

    Science.gov (United States)

    Kol, Nitzan; Adler-Abramovich, Lihi; Barlam, David; Shneck, Roni Z; Gazit, Ehud; Rousso, Itay

    2005-07-01

    We recently presented a novel class of self-assembled diphenylalanine-based peptide nanotubes. Here, for the first time, we present their mechanical properties, which we directly measured through indentation type experiments using atomic force microscopy. We find that the averaged point stiffness of the nanotubes is 160 N/m, and that they have a correspondingly high Young's modulus of approximately 19 GPa, as calculated by finite element analysis. This high value places these peptide nanotubes among the stiffest biological materials presently known, making them attractive building blocks for the design and assembly of biocompatible nanodevices. PMID:16178235

  4. Dragging Human Mesenchymal Stem Cells with the Aid of Supramolecular Assemblies of Single-Walled Carbon Nanotubes, Molecular Magnets, and Peptides in a Magnetic Field

    Directory of Open Access Journals (Sweden)

    Ana Cláudia C. de Paula

    2015-01-01

    Full Text Available Human adipose-derived stem cells (hASCs are an attractive cell source for therapeutic applicability in diverse fields for the repair and regeneration of damaged or malfunctioning tissues and organs. There is a growing number of cell therapies using stem cells due to their characteristics of modulation of immune system and reduction of acute rejection. So a challenge in stem cells therapy is the delivery of cells to the organ of interest, a specific site. The aim of this paper was to investigate the effects of a supramolecular assembly composed of single-walled carbon nanotubes (SWCNT, molecular magnets (lawsone-Co-phenanthroline, and a synthetic peptide (FWYANHYWFHNAFWYANHYWFHNA in the hASCs cultures. The hASCs were isolated, characterized, expanded, and cultured with the SWCNT supramolecular assembly (SWCNT-MA. The assembly developed did not impair the cell characteristics, viability, or proliferation. During growth, the cells were strongly attached to the assembly and they could be dragged by an applied magnetic field of less than 0.3 T. These assemblies were narrower than their related allotropic forms, that is, multiwalled carbon nanotubes, and they could therefore be used to guide cells through thin blood capillaries within the human body. This strategy seems to be useful as noninvasive and nontoxic stem cells delivery/guidance and tracking during cell therapy.

  5. Self-organized ureido substituted diacetylenic organogel. Photopolymerization of one-dimensional supramolecular assemblies to give conjugated nanofibers.

    Science.gov (United States)

    Dautel, Olivier J; Robitzer, Mike; Lère-Porte, Jean-Pierre; Serein-Spirau, Françoise; Moreau, Joël J E

    2006-12-20

    The introduction of the urea function as structure directing agent of diacetylene organogels (DA-OGs) has been achieved. Despite the urea function being one of the most frequently used structure directing agents for the formation of organogels, it has never been exploited in the fabrication and photopolymerization of DA-OGs. The self-association of ureas involving two hydrogen bonds is much stronger than that of urethanes or amides, and the resulting supramolecular assemblies are completely insoluble. In this context, 1,1'-(hexa-2,4-diyne-1,6-diyl)bis(3-(10-(triethoxysilyl)decyl)urea) 2 was synthesized. Compound 2 was soluble owing to the triethoxysilane function that we recently used in the fabrication of a silylated bis-urea-stilbene organogel. It formed an organogel, and its photopolymerization was studied in cyclohexane. The loss of the gel state and the formation of a red solution resulting from the polymerization were found to be the result of the constraints introduced by the urea function in close vicinity to the polymerizable function. To obtain an ureido substituted diacetylenic organogelator affording a blue highly conjugated polydiacetylene (PDA) without a sol-gel transition, a propylene spacer was introduced to move the urea function away from the polymerizable function (derivative 3). The thermochromism exhibited by the latter in the solid state was studied. Using the same setup and the same sample, UV-vis and FTIR spectra were simultaneously recorded as a function of the temperature to highlight a relation between color changes and urea association mode changes. The data showed that the reversible thermochromic transition must be associated with a reversible supramolecular modification and, conversely, that irreversible chromic transitions are the result of irreversible structural modifications. The chromic effects of the acidic hydrolysis-polycondensation of the trialkoxysilyl groups to form a siloxane network were studied on a thin film of 3. In

  6. Supramolecular self-assembly of metal- free naphthalocyanine on Au(111)

    NARCIS (Netherlands)

    Pham, Tuan Anh; Song, Fei; Stöhr, Meike

    2014-01-01

    The self-assembly of metal-free naphthalocyanine (H(2)Nc) on the Au(111) surface is studied under ultrahigh vacuum conditions at room temperature using a combination of scanning tunnelling microscopy (STM), low-energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS). The STM me

  7. The supramolecular organization of self-assembling chlorosomal bacteriochlorophyll c, d, or e mimics.

    Science.gov (United States)

    Jochum, Tobias; Reddy, Chilla Malla; Eichhöfer, Andreas; Buth, Gernot; Szmytkowski, Jedrzej; Kalt, Heinz; Moss, David; Balaban, Teodor Silviu

    2008-09-01

    Bacteriochlorophylls (BChls) c, d, and e are the main light-harvesting pigments of green photosynthetic bacteria that self-assemble into nanostructures within the chlorosomes forming the most efficient antennas of photosynthetic organisms. All previous models of the chlorosomal antennae, which are quite controversially discussed because no single crystals could be grown so far from these organelles, involve a strong hydrogen-bonding interaction between the 3(1) hydroxyl group and the 13(1) carbonyl group. We have synthesized different self-assemblies of BChl c mimics having the same functional groups as the natural counterparts, that is, a hydroxyethyl substituent, a carbonyl group and a divalent metal atom ligated by a tetrapyrrole. These artificial BChl mimics have been shown by single crystal x-ray diffraction to form extended stacks that are packed by hydrophobic interactions and in the absence of hydrogen bonding. Time-resolved photoluminescence proves the ordered nature of the self-assembled stacks. FT-IR spectra show that on self-assembly the carbonyl frequency is shifted by approximately 30 cm(-1) to lower wavenumbers. From the FT-IR data we can infer the proximal interactions between the BChls in the chlorosomes consistent with a single crystal x-ray structure that shows a weak electrostatic interaction between carbonyl groups and the central zinc atom. PMID:18755898

  8. Supramolecular nanostructuring of silver surfaces via self-assembly of [60]fullerene and porphyrin modules

    NARCIS (Netherlands)

    Bonifazi, Davide; Kiebele, Andreas; Stöhr, Meike; Cheng, Fuyong; Jung, Thomas; Diederich, Francois; Spillmann, Hannes

    2007-01-01

    Recent achievements in our laboratory toward the "bottom-up" fabrication of addressable multicomponent molecular entities obtained by self-assembly of C-60 and porphyrins on Ag(100) and Ag(111) surfaces are described.. Scanning tunneling microscopy (STM) studies on ad-layers constituting monomeric a

  9. Assembling and releasing performance of supramolecular hydrogels formed from simple drug molecule as the hydrogelator

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A simple drug compound, 4-oxo-4-(2-pyridinylamino) butanoic acid (defined as AP), was able to gel water at 4 wt%concentration under various conditions. In the superstructure, AP molecules assembled into fibrous aggregates driving by hydrogen bonds and π-π stacking interaction. The gels with different backbone structures released drug molecules in different speeds.

  10. Exploring the Transferability of Large Supramolecular Assemblies to the Vacuum-Solid Interface

    DEFF Research Database (Denmark)

    Xu, W.; Dong, M. D.; Gersen, H.;

    2009-01-01

    We present an interplay of high-resolution scanning tunneling microscopy imaging and the corresponding theoretical calculations based on elastic scattering quantum chemistry techniques of the adsorption of a gold-functionalized rosette assembly and its building blocks on a Au(111) surface...

  11. Supramolecular Photochemistry Controlling Photochemical Processes

    CERN Document Server

    Ramamurthy, V

    2011-01-01

    This is the most updated, comprehensive collection of monographs on all aspects of photochemistry and photophysics related to natural and synthetic, inorganic, organic, and biological supramolecular systems. Supramolecular Photochemistry: Controlling Photochemical Processes addresses reactions in crystals, organized assemblies, monolayers, zeolites, clays, silica, micelles, polymers, dendrimers, organic hosts, supramolecular structures, organic glass, proteins and DNA, and applications of photosystems in confined media. This landmark publication describes the past, present, and future of this

  12. Self-assembled supramolecular nano vesicles for safe and highly efficient gene delivery to solid tumors

    Directory of Open Access Journals (Sweden)

    Li W

    2012-08-01

    Full Text Available Wei Li,1,2,* Huafei Li,1,* Jinfeng Li,1,* Huajing Wang,1,* He Zhao,1 Li Zhang,1 Yu Xia,1 Zengwei Ye,1 Jie Gao,1,2 Jianxin Dai,1–3 Hao Wang,1–3 Yajun Guo1–31International Joint Cancer Institute, The Second Military Medical University, Shanghai, 2National Engineering Research Center for Antibody Medicine, State Key Laboratory of Antibody Medicine and Targeting Therapy and Shanghai Key Laboratory of Cell Engineering, Shanghai, 3PLA General Hospital Cancer Center, PLA Graduate School of Medicine, Beijing, People's Republic of China*These authors contributed equally to this workAbstract: The main obstacles for cationic polyplexes in gene delivery are in vivo instability and low solid-tumor accumulation. Safe vectors with high transfection efficiency and in vivo tumor accumulation are therefore highly desirable. In this study, the amphiphilic block copolymer poly(n-butyl methacrylate-b-poly(N-acryloylmorpholine was synthesized by reversible addition–fragmentation chain-transfer (RAFT radical polymerization. The corresponding well-defined vesicles with narrow size distribution were tailored by finely regulating the packing parameter (β of copolymer (1/2 < β < 1. Compared with traditional "gold-standard" polycation (polyethylenimine, 25 kDa, plasmid DNA condensing efficiency, DNase I degradation protection, and cellular uptake were improved by the supramolecular nano vesicles. In addition, the plasmid DNA transferring efficiency in 10% fetal bovine serum medium was enlarged five times to that of polyethylenimine in renal tubular epithelial and human hepatocellular carcinoma cell lines. This improved in vitro transfection was mainly attributed to the densely packed bilayer. This stealth polyplex showed high serum stability via entropic repulsion, which further protected the polyplex from being destroyed during sterilization. As indicated by the IVIS® Lumina II Imaging System (Caliper Life Sciences, Hopkinton, MA 24 hours post

  13. Hierarchical Self-Assembly of Polyoxometalate-Based Hybrids Driven by Metal Coordination and Electrostatic Interactions: From Discrete Supramolecular Species to Dense Monodisperse Nanoparticles.

    Science.gov (United States)

    Izzet, Guillaume; Abécassis, Benjamin; Brouri, Dalil; Piot, Madeleine; Matt, Benjamin; Serapian, Stefano Artin; Bo, Carles; Proust, Anna

    2016-04-20

    The metal-driven self-assembly processes of a covalent polyoxometalate (POM)-based hybrid bearing remote terpyridine binding sites have been investigated. In a strongly dissociating solvent, a discrete metallomacrocycle, described as a molecular triangle, is formed and characterized by 2D diffusion NMR spectroscopy (DOSY), small-angle X-ray scattering (SAXS), and molecular modeling. In a less dissociating solvent, the primary supramolecular structure, combining negatively charged POMs and cationic metal linkers, further self-assemble through intermolecular electrostatic interactions in a reversible process. The resulting hierarchical assemblies are dense monodisperse nanoparticles composed of ca. 50 POMs that were characterized by SAXS and transmission electron microscopy (TEM). This multiscale organized system directed by metal coordination and electrostatic interactions constitutes a promising step for the future design of POM self-assemblies with controllable structure-directing factors. PMID:27019075

  14. Experimental and theoretical analysis of H-bonded supramolecular assemblies of PTCDA molecules

    OpenAIRE

    Mura, M; X. Sun; F. Silly; Jonkman, H. T.; Briggs, G. A. D.; Castell, M. R.; Kantorovich, L. N.

    2010-01-01

    Using a systematic method based on considering all possible hydrogen bond connections between molecules and subsequent density-functional theory (DFT) calculations, we investigated planar superstructures that the perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride (PTCDA) molecules can form in one and two dimensions. Structures studied are mostly based on two molecule unit cells and all assemble in flat periodic arrays. We show that 42 different monolayer structures are possible, which can...

  15. Yielding and flow of solutions of thermoresponsive surfactant tubes: tuning macroscopic rheology by supramolecular assemblies

    OpenAIRE

    Fameau, Anne-Laure; Saint-Jalmes, Arnaud

    2014-01-01

    International audience In this article, we show that stimuli-induced microscopic transformations of self-assembled surfactant structures can be used to tune the macroscopic bulk and interfacial rheological properties. Previously, we had described the formation of micron-sized 12-hydroxystearic acid tubes having a temperaturetunable diameter in the bulk, and also adsorbing at the air-water interface. We report now a detailed study of the bulk and interfacial rheological properties of this s...

  16. Self-assembly of 2,3-dihydroxycholestane steroids into supramolecular organogels as a soft template for the in-situ generation of silicate nanomaterials

    Directory of Open Access Journals (Sweden)

    Valeria C. Edelsztein

    2013-09-01

    Full Text Available Supramolecular gels are an important and interesting class of soft materials that show great potential for many applications. Most of them have been discovered serendipitously, and understanding the supramolecular self-assembly that leads to the formation of the gel superstructure is the key to the directed design of new organogels. We report herein the organogelating property of four stereoisomers of the simple steroid 2,3-dihydroxycholestane. Only the isomer with the trans-diaxial hydroxy groups had the ability to gelate a broad variety of liquids and, thus, to be a super-organogelator for hydrocarbons. The scope of solvent gelation was analysed with regard to two solvent parameters, namely the Kamlet–Taft and the Hansen solubility parameters. The best correlation was observed with the Hansen approach that revealed the existence of two clear gelation zones. We propose a general model of self-assembly through multiple intermolecular hydrogen bonds between the 1,2-dihydroxy system, which is based on experimental data and computational simulations revealing the importance of the di-axial orientation of the hydroxy groups for the one-dimensional self-assembly. Under controlled conditions, the fibrillar superstructure of the organogel was successfully used as a template for the in-situ sol–gel polymerization of tetraethoxysilane and the further preparation of silica nanotubes. We propose that the driving forces for templating are hydrogen bonding and electrostatic interactions between the anionic silicate intermediate species and the self-assembled fibrillar network.

  17. Supramolecular self-assembly of metal- free naphthalocyanine on Au(111)

    OpenAIRE

    Pham, Tuan Anh; Song, Fei; Stöhr, Meike

    2014-01-01

    The self-assembly of metal-free naphthalocyanine (H(2)Nc) on the Au(111) surface is studied under ultrahigh vacuum conditions at room temperature using a combination of scanning tunnelling microscopy (STM), low-energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS). The STM measurements reveal that the molecules form a well-ordered, defect-free structure with a square-like unit cell at monolayer coverage with their molecular plane parallel to the substrate plane. The mo...

  18. Supramolecular chemistry and technology

    Directory of Open Access Journals (Sweden)

    HENRIQUE E. TOMA

    2000-03-01

    Full Text Available Supramolecular chemistry deals with the association of several chemical species, in an organized way and according to well defined purposes. Based on a molecular engineering approach, supramolecular structures can be designed from pre-formed building blocks, providing a promising route from chemistry to molecular nanotechnology. New supramolecular systems have been assembled in our laboratory with the use of bridging unities such as tetrapyridylporphyrins, porphyrazines and polypyrazines, connecting transition metal complexes and clusters. These systems display a very exciting electrochemical and catalytic behavior, and interact with DNA, generating ¹O2 and leading to efficient oxidative clivage for photodynamic terapy applications. Molecular interfaces have been developed, exhibiting photocurrent response in the presence of visible-UV light, and rectifying properties in the presence of electroactive species. Successful applications of the supramolecular species in chemical and bio-sensors have been developed.

  19. Self-Assemblies of Single-Walled Carbon Nanotubes through Tunable Tethering of Pyrenes by Dextrin for Rapidly Chiral Sensing

    Directory of Open Access Journals (Sweden)

    Wei-Li Wei

    2011-01-01

    Full Text Available Pyrene-modified dextrin (Py-Dex was synthesized via the Schiff base reaction between reducing end of dextrins and 1-aminopyrene, and then self-assemblies of single-walled carbon nanotubes (SWNTs were fabricated through the tunable tethering of pyrene to SWNTs by dextrin chains. The Py-Dex-SWNTs assemblies were found to be significantly water-soluble because of the synergistic effect of dextrin chains and pyrene moieties. Py-Dex and Py-Dex-SWNTs were adequately characterized by NMR, UV-vis, fluorescence spectroscopy, Raman spectroscopy, matrix-assisted laser desorption/ionization-time of flight mass spectroscopy, and transmission electron microscopy. The tethering effect of dextrin toward pyrene moieties was clearly revealed and was found to be tunable by adjusting the length of dextrin chains. The fluorescence of pyrene moieties was sufficiently quenched by SWNTs with the support of dextrin chains. Furthermore, the Py-Dex-SWNTs assemblies were used for chiral selective sensing by introducing cyclodextrins as chiral binding sites. The rapid chiral sensing was successfully tested for different enantiomers.

  20. Supramolecular Chemistry And Self-assembly Special Feature: Virus-assisted loading of polymer nanocontainer

    Science.gov (United States)

    Graff, Alexandra; Sauer, Marc; van Gelder, Patrick; Meier, Wolfgang

    2002-04-01

    We present a DNA-containing polymeric nanocontainer using the self-assembled superstructure of amphiphilic block copolymers in aqueous solutions. To demonstrate that DNA translocation is possible across a completely synthetic block copolymer membrane, we have used a phage transfection strategy as a DNA-transfer model system. For this purpose the bacterial channel forming protein LamB was reconstituted in ABA-triblock copolymer vesicles. The outer membrane protein LamB is a specific transporter for maltodextrins but also serves as a receptor for phage to trigger the ejection of phage DNA. We demonstrate that the functionality of the LamB protein is fully preserved despite the artificial surrounding. This leads to a type of polymeric vehicle for DNA that could be useful for gene therapy.

  1. Supramolecular Coordination Assemblies Constructed From Multifunctional Azole-Containing Carboxylic Acids

    Directory of Open Access Journals (Sweden)

    Yuheng Deng

    2010-05-01

    Full Text Available This paper provides a brief review of recent progress in the field of metal coordination polymers assembled from azole-containing carboxylic acids and gives a diagrammatic summary of the diversity of topological structures in the resulting infinite metal-organic coordination networks (MOCNs. Azole-containing carboxylic acids are a favorable kind of multifunctional ligand to construct various metal complexes with isolated complexes and one, two and three dimensional structures, whose isolated complexes are not the focus of this review. An insight into the topology patterns of the infinite coordination polymers is provided. Analyzed topologies are compared with documented topologies and catalogued by the nature of nodes and connectivity pattern. New topologies which are not available from current topology databases are described and demonstrated graphically.

  2. Supramolecular Cationic Assemblies against Multidrug-Resistant Microorganisms: Activity and Mechanism of Action

    Directory of Open Access Journals (Sweden)

    Letícia Dias de Melo Carrasco

    2015-03-01

    Full Text Available The growing challenge of antimicrobial resistance to antibiotics requires novel synthetic drugs or new formulations for old drugs. Here, cationic nanostructured particles (NPs self-assembled from cationic bilayer fragments and polyelectrolytes are tested against four multidrug-resistant (MDR strains of clinical importance. The non-hemolytic poly(diallyldimethylammonium chloride (PDDA polymer as the outer NP layer shows a remarkable activity against these organisms. The mechanism of cell death involves bacterial membrane lysis as determined from the leakage of inner phosphorylated compounds and possibly disassembly of the NP with the appearance of multilayered fibers made of the NP components and the biopolymers withdrawn from the cell wall. The NPs display broad-spectrum activity against MDR microorganisms, including Gram-negative and Gram-positive bacteria and yeast.

  3. Supramolecular Assemblies of Poly(propyleneimine) Dendrimers Driven by Simple Monovalent Counterions

    Science.gov (United States)

    Eghtesadi, Seyed Ali; Haso, Fadi; Kashfipour, Marjan Alsadat; Lillard, Robert, , Dr.; Liu, Tianbo, , Dr.; Tianbo Liu's group Team, Dr.; Lillard's group Collaboration, Dr.

    Polyelectrolytes (PE) are fascinating class of polymers carrying dissociative ionic groups which give them unique properties in solutions and at charged surfaces. The properties of these polymers in solution are mainly depending on the fraction of dissociated ionic groups, the quality of solvent and salt concentration. Describing the solution properties of polyelectrolytes have always been an obstacle for polymer scientists due to their different behavior as a result of their dual character of being highly charged electrolytes and at macromolecular size. The question we tried to address was what happens to solution behavior of charged polyelectrolytes when they reach to the nano-scale size which can neither be considered as point charges nor colloids. Second generation of poly(propyleneimine) dendrimer in different solvent qualities, salt concentrations, pH and temperatures were studied using techniques such as LLS, TEM, AFM and zeta-potential, and dominant controlling factors over their self-assembly into hollow spherical ``Blackberry'' like nanoparticles was investigated.

  4. Altering the inclusion properties of CTV through crystal engineering: CTV, carborane, and DMF supramolecular assemblies

    Science.gov (United States)

    Hardie; Raston; Wells

    2000-09-01

    The complexes [Na(CTV)2(OH)(H2O)](H2O)(DMF)2(o-carborane) (3; CTV = cyclotriveratrylene), [K(OH)(CTV)(DMF)]2(o-carborane) (4), [(DMF)(CTV)]2(H2O)4(o-carborane) (5), and (o-carborane)(CTV)(DMF)2 (6) all form as crystalline inclusion complexes from N,N'-dimethylformamide (DMF) solution. Complexes 3 and 4 are the first reported examples of CTV acting as a chelating ligand, with two CTV molecules coordinating cis to the six-coordinate M+ centers (M=Na, K). The extended structures of complexes 3-5 are similar, forming extended coordinate and/or hydrogen-bonding interactions and all feature intracavity complexation of DMF by CTV, while the complex 6 forms an assembly of (o-carborane) intersection of two sets (CTV) ball-and-socket supermolecules with DMF as a channel-type included guest. PMID:11003008

  5. The physical properties of supramolecular peptide assemblies: from building block association to technological applications.

    Science.gov (United States)

    Adler-Abramovich, Lihi; Gazit, Ehud

    2014-01-01

    Bio-inspired nano-materials can be formed by the ordered assembly of elementary building blocks using recognition modules and structural elements. Among the biological sources, peptides and proteins are of special interest due to their role as major structural elements in all living systems, ranging from bacteria to humans in a continuum of magnitudes, from the nano-scale to the macro-scale. Peptides, as short as dipeptides, contain all the molecular information needed to form well-ordered structures at the nano-scale. Here, in light of the significant advancements in the field of peptide nanostructures in the last few years, we provide an updated overview of this subject. The use of these nanostructures was indeed recently demonstrated in various fields including the design of molecular motors based on nanostructure complexation with a metal-organic framework, the delivery of therapeutic agents, the development of energy storage devices and the fabrication of piezoelectric-based sensors. PMID:25099656

  6. 环糊精相关的超分子自组装最新进展%Recent Progress in Supramolecular Self-Assembly Based on Cyclodextrin

    Institute of Scientific and Technical Information of China (English)

    周冬香; 孙涛; 邓维

    2012-01-01

    The supramolecular material has been widely used as a type of drug/gene delivery, molecule device, molecule sensor and catalysis. Due to their excellent biologic and optical properties, cyclodextrins have recently attracted increasingly more attention. In this review the newest development of the supramolecular self-assembly based on cyclodextrin is summarized. The article provided detail information about the synthesis and applications of both of rotaxanes formed by cyclodextrin ring and polymer axes, and supramolecular polymer without polymer backbone.%对基于环糊精的超分子自组装的最新研究进展作了综述.详细介绍了环糊精为轮、高分子为轴的聚轮烷的制备及其修饰的方法,同时还介绍了无高分子参与的环糊精的超分子自组装高分子化合物的制备.并且对这些超分子在智能材料、生物医药和聚合催化等方面的应用进行了介绍.

  7. Progress of Rod-like Chiral Supramolecular Liquid Crystals Based on Intermolecular Hydrogen Bonding%基于分子间氢键的棒状手性液晶的研究进展

    Institute of Scientific and Technical Information of China (English)

    左飞龙; 吴奕环; 时志强; 武长城

    2012-01-01

    Due to its unique optical-electro properties, facile synthesis and stimuli responsiveness to the environment, chiral supramolecular liquid crystals based on intermolecular hydrogen bonding have been becoming one of the hot topics in domain of supramolecular chemistry and been winning more application in functional materials, nonlinear optics and biomedical science, etc. This paper presents a brief review on the rod-like hydrogen-bonding chiral liquid crystals (RHCLC). The molecular structure, chiral group, substituent group, flexible chain, stability of these hydrogen-bonded supramolecular complexes and their relation to the observed liquid crystalline phases are the main topics of this review. Recent research achievements about RHCLC sorted by hydrogen bonds groups such as carboxylic acid and pyridine are introduced. At last the future development of RHCLC is prospected.%分子间氢键棒状手性液晶因其兼具手性液晶奇特的光电性能和氢键液晶的便捷制备以及独特的外界刺激响应性,在功能材料、非线性光学、生物医学等领域具有潜在的应用价值,一直是超分子液晶领域的研究热点.文章按照形成氢键互补基团的不同,将其划分为3种类型,即羧酸-羧酸类、羧酸吡啶类和其他类型氢键,介绍了此三类氢键棒状手性液晶近年来的研究进展.详细归纳了氢键质子给受体的分子结构、氢键稳定性、手性中心位置、取代基、柔性链长度等对液晶性能的影响,并在此基础上,对其未来发展做了展望.

  8. Supramolecular Self-Assembly of Histidine-Capped-Dialkoxy-Anthracene: A Visible Light Triggered Platform for facile siRNA Delivery

    KAUST Repository

    Patil, Sachin

    2016-06-29

    Supramolecular self-assembly of histidine-capped-dialkoxy-anthracene (HDA) results in the formation of light responsive nanostructures.Single-crystal X-ray diffraction analysis of HDA shows two types of hydrogen bonding. The first hydrogen bond is established between the imidazole moieties while the second involves the oxygen atom of one amide group and the hydrogen atom of a second amide group. When protonated in acidic aqueous media, HDA successfully complexes siRNA yielding spherical nanostructures. This biocompatible platform controllably delivers siRNA with high efficacy upon visible light irradiation leading up to 90% of gene silencing in live cells.

  9. Explosive decomposition of a melamine-cyanuric acid supramolecular assembly for fabricating defect-rich nitrogen-doped carbon nanotubes with significantly promoted catalysis.

    Science.gov (United States)

    Zhao, Zhongkui; Dai, Yitao; Ge, Guifang; Wang, Guiru

    2015-05-26

    A facile and scalable approach for fabricating structural defect-rich nitrogen-doped carbon nanotubes (MCSA-CNTs) through explosive decomposition of melamine-cyanuric acid supramolecular assembly is presented. In comparison to pristine carbon nanotubes, MCSA-CNT exhibits significantly enhanced catalytic performance in oxidant- and steam-free direct dehydrogenation of ethylbenzene, demonstrating the potential for metal-free clean and energy-saving styrene production. This finding also opens a new horizon for preparing highly-efficient carbocatalysts rich in structural defect sites for diverse transformations. PMID:25900736

  10. Chlorophylls, Symmetry, Chirality, and Photosynthesis

    Directory of Open Access Journals (Sweden)

    Mathias O. Senge

    2014-09-01

    Full Text Available Chlorophylls are a fundamental class of tetrapyrroles and function as the central reaction center, accessory and photoprotective pigments in photosynthesis. Their unique individual photochemical properties are a consequence of the tetrapyrrole macrocycle, the structural chemistry and coordination behavior of the phytochlorin system, and specific substituent pattern. They achieve their full potential in solar energy conversion by working in concert in highly complex, supramolecular structures such as the reaction centers and light-harvesting complexes of photobiology. The biochemical function of these structures depends on the controlled interplay of structural and functional principles of the apoprotein and pigment cofactors. Chlorophylls and bacteriochlorophylls are optically active molecules with several chiral centers, which are necessary for their natural biological function and the assembly of their supramolecular complexes. However, in many cases the exact role of chromophore stereochemistry in the biological context is unknown. This review gives an overview of chlorophyll research in terms of basic function, biosynthesis and their functional and structural role in photosynthesis. It highlights aspects of chirality and symmetry of chlorophylls to elicit further interest in their role in nature.

  11. A biocompatible cobaltporphyrin-based complex micelle constructed via supramolecular assembly for oxygen transfer.

    Science.gov (United States)

    Shen, Liangliang; Qu, Rui; Shi, Hejin; Huang, Fan; An, Yingli; Shi, Linqi

    2016-05-26

    Herein, a complex micelle as an oxygen nano-carrier is constructed through the hierarchical assembly of the diblock copolymer poly(ethylene glycol)-block-poly(l-lysine) (PEG-b-PLys), tetrakis(4-sulfonatophenyl)porphinato cobalt(ii) (Co(ii)TPPS), a heptapeptide (Cys-His-His-His-His-His-His) and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin (TM-β-CD). Co(ii)TPPS was encapsulated into the cavities of TM-β-CDs driven by the host-guest interaction so that the irreversible formation of a μ-oxo-dimer of Co(ii)TPPS can be effectively prevented. The imidazole groups of the heptapeptide were selected as good axial ligands coordinating to the centric cobalt of Co(ii)TPPS, which subtly constituted the five-coordinated precursor serving as an active functional centre for oxygen binding. The sixth position of Co(ii)TPPS can bind oxygen. Furthermore, the host-guest inclusion (TM-β-CD/Co(ii)TPPS) was loaded into the hydrophobic core of the complex micelle and tightly fixed with PLys chains. The hydrophilic PEG blocks stretched in the aqueous solution constitute the shells which stabilize the structure of the complex micelle as well as impart the complex micelle sufficient blood circulation time. Moreover, the complex micelle exhibited excellent biocompatibility and cellular uptake. Therefore, the rationally designed amphiphilic structure can work as promising artificial O2 carriers in vivo. Potentially, the complex micelle can be expected to change the anaerobic microenvironment and find applications in the repair of the cells damaged by cellular hypoxia. PMID:27009911

  12. Supramolecular recognition of heteropairs of lanthanide ions: a step toward self-assembled bifunctional probes.

    Science.gov (United States)

    André, Nicolas; Jensen, Thomas B; Scopelliti, Rosario; Imbert, Daniel; Elhabiri, Mourad; Hopfgartner, Gérard; Piguet, Claude; Bünzli, Jean-Claude G

    2004-01-26

    Three unsymmetrical ditopic hexadentate ligands coded for the recognition of trivalent lanthanide ions have been synthesized, L(AB), L(AC), and L(BC), where A represents a benzimidazole-pyridine-benzimidazole coordination unit, B a benzimidazole-pyridine-carboxamide one, and C a benzimidazole-pyridine-carboxylic acid moiety. Under stoichiometric 2:3 (Ln:L) conditions, these ligands self-assemble with lanthanide ions to yield triple-stranded bimetallic helicates having a sizable stability in acetonitrile: log beta(23) values for Eu are equal to 23.9 +/- 0.5 (L(AB)), 23.3 +/- 0.7 (deprotonated L(AC)), and 29.8 +/- 0.5 (deprotonated L(BC)). The crystal structure of the EuEu helicate with L(AB) shows 9-coordinate metal ions and an HHH (H stands for head) configuration of the helically wrapped ligand strands. In the presence of equimolar quantities of Ln and Ln' ions, L(AB) displays a remarkable predisposition to form HHH-heterobimetallic edifices, as proved both in the solid state by the crystal structures of the LaEu, LaTb, PrEr, and PrLu helicates and in solution by NMR spectroscopy. In all cases, the benzimidazole-pyridine-carboxamide units of the three ligands are bound to the smaller lanthanide ion, a fact further ascertained by high-resolution luminescence data on LaEu and by (1)H NMR. Analysis of the lanthanide-induced (1)H NMR shifts and of the spin-lattice relaxation times of the [LnLu(L(AB))(3)](6+) series (Ln = Ce, Pr, Nd, Sm, Eu) demonstrates the isostructural nature of the complexes in solution and that the crystal structure of LaTb is a good model for the solution structure. The selectivity of L(AB) for heteropairs of Ln(III) ions increases with increasing difference in ionic radius, resulting in 70% of the heterobimetallic species for deltar(i) = 0.1 A and up to 90% for LaLu (deltar(i) = 0.18 A), and corresponding to delta(deltaG) in the range 3-10 kJ.mol(-)(1). The origins of this stabilization are discussed in terms of the donor properties of the

  13. 新型超分子化合物的合成自组装及应用研究的新进展%Recent Research Achievements on Synthesis,Self-assembly and Applications of New Supramolecular Compounds

    Institute of Scientific and Technical Information of China (English)

    张来新; 胡小兵

    2014-01-01

    This paper briefly introduced the definition, concept, generation and application of supramolecular chemistry. Emphases were put on three parts:① synthesis and self-assembly of new supramolecular compounds;② synthesis and selective recognition effects of new supramolecular compounds;③synthesis and application of su-pramolecular crown ether metal complexes.%简要介绍了超分子化学的定义、概念、产生及应用,详细介绍了:①新型超分子化合物合成及自组装;②新型超分子化合物的合成及选择性识别作用;③超分子冠醚金属配合物的合成及应用。

  14. Surface-Confined Supramolecular Self-Assembly of Molecular Nanocranes for Chemically Lifting and Positioning C60 above a Conducting Substrate.

    Science.gov (United States)

    Du, Ping; Kreher, David; Mathevet, Fabrice; Maldivi, Pascale; Charra, Fabrice; Attias, André-Jean

    2015-12-21

    2D supramolecular self-assembly is a good way to form well-defined nanostructures on various substrates. One of the current challenges is to extend this approach to 3D functional building blocks. Here, we address this issue by providing a strategy for the controlled lifting and positioning of functional units above a graphitic substrate. This is the first time that multistory cyclophane-based 3D tectons incorporating C60 units have been designed and synthesized. Molecular modelling provides a description of the 3D geometries and evidences the flexible character of the building blocks. Despite this later feature, the supramolecular self-assembly of Janus tectons on HOPG yields well-ordered adlayers incorporating C60 arrays at well-defined mean distances from the surface. As our approach is not limited to C60 , the results reported here open-up possibilities for applications where the topological and electronic interactions between the substrate and the functional unit are of prime importance.

  15. Patchy Supramolecular Bottle-Brushes Formed by Solution Self-Assembly of Bis(urea)s and Tris(urea)s Decorated by Two Incompatible Polymer Arms.

    Science.gov (United States)

    Catrouillet, Sylvain; Bouteiller, Laurent; Boyron, Olivier; Lorthioir, Cédric; Nicol, Erwan; Pensec, Sandrine; Colombani, Olivier

    2016-09-01

    In an attempt to design urea-based Janus nanocylinders through a supramolecular approach, nonsymmetrical bis(urea)s and tris(urea)s decorated by two incompatible polymer arms, namely, poly(styrene) (PS) and poly(isobutylene) (PIB), were synthesized using rather straightforward organic and polymer chemistry techniques. Light scattering experiments revealed that these molecules self-assembled in cyclohexane by cooperative hydrogen bonds. The extent of self-assembly was limited for the bis(urea)s. On the contrary, reasonably anisotropic 1D structures (small nanocylinders) could be obtained with the tris(urea)s (Nagg ∼ 50) which developed six cooperative hydrogen bonds per molecule. (1)H transverse relaxation measurements and NOESY NMR experiments in cyclohexane revealed that perfect Janus nanocylinders with one face consisting of only PS and the other of PIB were not obtained. Nevertheless, phase segregation between the PS and PIB chains occurred to a large extent, resulting in patchy cylinders containing well separated domains of PIB and PS chains. Reasons for this behavior were proposed, paving the way to improve the proposed strategy toward true urea-based supramolecular Janus nanocylinders.

  16. The fabrication and enhanced nonlinear optical properties of electrostatic self-assembled film containing water-soluble chiral polymers

    Energy Technology Data Exchange (ETDEWEB)

    Ouyang Qiuyun, E-mail: qyouyang7823@yahoo.cn [College of Science, Harbin Engineering University, Harbin 150001 (China); Chen Yujin; Li Chunyan [College of Science, Harbin Engineering University, Harbin 150001 (China)

    2012-05-15

    Highlights: Black-Right-Pointing-Pointer The ultra-thin film containing the chiral PPV and oligo-thiophene derivatives was fabricated. Black-Right-Pointing-Pointer The third-order NLO properties were studied of the ultra-thin film. Black-Right-Pointing-Pointer The reverse saturable absorption and self-defocusing were observed. Black-Right-Pointing-Pointer The nonlinear optical mechanism was discussed. - Abstract: An ultra-thin film containing a water-soluble chiral PPV derivative and oligo-thiophene derivative was fabricated through the electrostatic self-assembly technique. The PPV and thiophene derivatives are poly{l_brace}(2,5-bis(3-bromotrimethylammoniopropoxy)-phenylene-1,4-divinylene) -alt-1,4-(2,5-bis((3-hydroxy-2-(S)-methyl)propoxy)phenylenevinylene) (BHP-PPV) and 4 Prime ,3 Double-Prime -dipentyl-5,2 Prime :5 Prime ,2 Double-Prime :5 Double-Prime ,2 Double-Prime Prime -quaterthiophene-2,5 Double-Prime Prime -dicarboxylic acid (QTDA), respectively. The circular dichroism (CD) spectrum of BHP-PPV cast film on quartz substrate proved the chirality of BHP-PPV. The UV-vis spectra showed a continuous deposition process of BHP-PPV and QTDA. The film structure was characterized by small angle X-ray diffraction (XRD) measurement and atomic force microscopy (AFM) images. The nonlinear optical (NLO) properties of BHP-PPV/QTDA ultra-thin film with different number of bilayers were investigated by the Z-scan technique with 8 ns laser pulse at 532 nm. The Z-scan experimental data were analyzed with the double-sided film Z-scan theory. The BHP-PPV/QTDA film exhibits enhanced reverse saturable absorption (RSA) and self-defocusing effects, which may be attributed to the conjugated strength, chirality and well-ordered film structure. The chirality may lead to the RSA of BHP-PPV/QTDA film contrary to the SA of the other electrostatic self-assembled films without chiral units. The self-defocusing effect should be due to the thermal effect.

  17. Engineering of supramolecular photoactive protein architectures: the defined co-assembly of photosystem I and cytochrome c using a nanoscaled DNA-matrix.

    Science.gov (United States)

    Stieger, Kai R; Ciornii, Dmitri; Kölsch, Adrian; Hejazi, Mahdi; Lokstein, Heiko; Feifel, Sven C; Zouni, Athina; Lisdat, Fred

    2016-05-19

    The engineering of renewable and sustainable protein-based light-to-energy converting systems is an emerging field of research. Here, we report on the development of supramolecular light-harvesting electrodes, consisting of the redox protein cytochrome c working as a molecular scaffold as well as a conductive wiring network and photosystem I as a photo-functional matrix element. Both proteins form complexes in solution, which in turn can be adsorbed on thiol-modified gold electrodes through a self-assembly mechanism. To overcome the limited stability of self-grown assemblies, DNA, a natural polyelectrolyte, is used as a further building block for the construction of a photo-active 3D architecture. DNA acts as a structural matrix element holding larger protein amounts and thus remarkably improving the maximum photocurrent and electrode stability. On investigating the photophysical properties, this system demonstrates that effective electron pathways have been created.

  18. Engineering of supramolecular photoactive protein architectures: the defined co-assembly of photosystem I and cytochrome c using a nanoscaled DNA-matrix

    Science.gov (United States)

    Stieger, Kai R.; Ciornii, Dmitri; Kölsch, Adrian; Hejazi, Mahdi; Lokstein, Heiko; Feifel, Sven C.; Zouni, Athina; Lisdat, Fred

    2016-05-01

    The engineering of renewable and sustainable protein-based light-to-energy converting systems is an emerging field of research. Here, we report on the development of supramolecular light-harvesting electrodes, consisting of the redox protein cytochrome c working as a molecular scaffold as well as a conductive wiring network and photosystem I as a photo-functional matrix element. Both proteins form complexes in solution, which in turn can be adsorbed on thiol-modified gold electrodes through a self-assembly mechanism. To overcome the limited stability of self-grown assemblies, DNA, a natural polyelectrolyte, is used as a further building block for the construction of a photo-active 3D architecture. DNA acts as a structural matrix element holding larger protein amounts and thus remarkably improving the maximum photocurrent and electrode stability. On investigating the photophysical properties, this system demonstrates that effective electron pathways have been created.The engineering of renewable and sustainable protein-based light-to-energy converting systems is an emerging field of research. Here, we report on the development of supramolecular light-harvesting electrodes, consisting of the redox protein cytochrome c working as a molecular scaffold as well as a conductive wiring network and photosystem I as a photo-functional matrix element. Both proteins form complexes in solution, which in turn can be adsorbed on thiol-modified gold electrodes through a self-assembly mechanism. To overcome the limited stability of self-grown assemblies, DNA, a natural polyelectrolyte, is used as a further building block for the construction of a photo-active 3D architecture. DNA acts as a structural matrix element holding larger protein amounts and thus remarkably improving the maximum photocurrent and electrode stability. On investigating the photophysical properties, this system demonstrates that effective electron pathways have been created. Electronic supplementary information

  19. Stimuli-Directed Helical Chirality Inversion and Bio-Applications

    Directory of Open Access Journals (Sweden)

    Ziyu Lv

    2016-08-01

    Full Text Available Helical structure is a sophisticated ubiquitous motif found in nature, in artificial polymers, and in supramolecular assemblies from microscopic to macroscopic points of view. Significant progress has been made in the synthesis and structural elucidation of helical polymers, nevertheless, a new direction for helical polymeric materials, is how to design smart systems with controllable helical chirality, and further use them to develop chiral functional materials and promote their applications in biology, biochemistry, medicine, and nanotechnology fields. This review summarizes the recent progress in the development of high-performance systems with tunable helical chirality on receiving external stimuli and discusses advances in their applications as drug delivery vesicles, sensors, molecular switches, and liquid crystals. Challenges and opportunities in this emerging area are also presented in the conclusion.

  20. Carbohydrates in Supramolecular Chemistry.

    Science.gov (United States)

    Delbianco, Martina; Bharate, Priya; Varela-Aramburu, Silvia; Seeberger, Peter H

    2016-02-24

    Carbohydrates are involved in a variety of biological processes. The ability of sugars to form a large number of hydrogen bonds has made them important components for supramolecular chemistry. We discuss recent advances in the use of carbohydrates in supramolecular chemistry and reveal that carbohydrates are useful building blocks for the stabilization of complex architectures. Systems are presented according to the scaffold that supports the glyco-conjugate: organic macrocycles, dendrimers, nanomaterials, and polymers are considered. Glyco-conjugates can form host-guest complexes, and can self-assemble by using carbohydrate-carbohydrate interactions and other weak interactions such as π-π interactions. Finally, complex supramolecular architectures based on carbohydrate-protein interactions are discussed. PMID:26702928

  1. Thioamides: versatile bonds to induce directional and cooperative hydrogen bonding in supramolecular polymers.

    Science.gov (United States)

    Mes, Tristan; Cantekin, Seda; Balkenende, Dirk W R; Frissen, Martijn M M; Gillissen, Martijn A J; De Waal, Bas F M; Voets, Ilja K; Meijer, E W; Palmans, Anja R A

    2013-06-24

    The amide bond is a versatile functional group and its directional hydrogen-bonding capabilities are widely applied in, for example, supramolecular chemistry. The potential of the thioamide bond, in contrast, is virtually unexplored as a structuring moiety in hydrogen-bonding-based self-assembling systems. We report herein the synthesis and characterisation of a new self-assembling motif comprising thioamides to induce directional hydrogen bonding. N,N',N''-Trialkylbenzene-1,3,5-tris(carbothioamide)s (thioBTAs) with either achiral or chiral side-chains have been readily obtained by treating their amide-based precursors with P2S5. The thioBTAs showed thermotropic liquid crystalline behaviour and a columnar mesophase was assigned. IR spectroscopy revealed that strong, three-fold, intermolecular hydrogen-bonding interactions stabilise the columnar structures. In apolar alkane solutions, thioBTAs self-assemble into one-dimensional, helical supramolecular polymers stabilised by three-fold hydrogen bonding. Concentration- and temperature-dependent self-assembly studies performed by using a combination of UV and CD spectroscopy demonstrated a cooperative supramolecular polymerisation mechanism and a strong amplification of supramolecular chirality. The high dipole moment of the thioamide bond in combination with the anisotropic shape of the resulting cylindrical aggregate gives rise to sufficiently strong depolarised light scattering to enable depolarised dynamic light scattering (DDLS) experiments in dilute alkane solution. The rotational and translational diffusion coefficients, D(trans) and D(rot), were obtained from the DDLS measurements, and the average length, L, and diameter, d, of the thioBTA aggregates were derived (L = 490 nm and d = 3.6 nm). These measured values are in good agreement with the value L(w) = 755 nm obtained from fitting the temperature-dependent CD data by using a recently developed equilibrium model. This experimental verification

  2. Growth of Optically Active Chiral Inorganic Films through DNA Self-Assembly and Silica Mineralisation

    Science.gov (United States)

    Liu, Ben; Han, Lu; Duan, Yingying; Cao, Yunayuan; Feng, Ji; Yao, Yuan; Che, Shunai

    2014-05-01

    The circularly polarized reflection of nature is due to their distinct azimuthally twisted or helical character in the nanostructure of the surface films. Although many chiral inorganic powders have been successfully synthesised, the artificial synthesis of chiral inorganic films is rare. Herein, we reported a facile synthetic route for the growth of monolayered chiral film on the quaternary ammonium-modified silicon substrate. The films grew on the substrate surface because of the strong electrostatic interaction between positively charged quaternary ammonium groups and negatively charged phosphate groups of DNA, with subsequent growth to right-handed, vertically aligned, impeller-like helical architectures with left-handed two-dimensional square p4mm-structured DNA chiral packing. The DNA-silica composite films exhibited strong optical activity at 295 nm and in the range of 400-800 nm, corresponding to DNA chiral packing (absorption) and to the helical blade in the impeller (scattering), respectively. Upon removal of DNA templates, the pure inorganic impeller-like helical morphology was maintained; consequently, the scattering-based optical response was blue-shifted approximately 200 nm as a result of a decrease in the effective average refractive index. The hierarchical structures were reflected from the surfaces by cross-polarised light, which confirmed that the films were strongly birefringent, with long-range anisotropy.

  3. Magnetic structure of two- and three-dimensional supramolecular compounds

    Energy Technology Data Exchange (ETDEWEB)

    Decurtins, S.; Schmalle, H.W.; Pellaux, R. [Zurich Univ. (Switzerland); Fischer, P.; Fauth, F. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Ouladdiaf, B. [Institut Max von Laue - Paul Langevin, 75 - Paris (France)

    1997-09-01

    Supramolecular chiral networks of oxalato-bridged transition metals show either two- or three-dimensional structural features. The magnetic structures of such compounds have been investigated by means of elastic neutron powder diffraction. (author) 2 figs., 2 refs.

  4. Supramolecular Assembly of Biobased Graphene Oxide Quantum Dots Controls the Morphology of and Induces Mineralization on Poly(ε-caprolactone) Films.

    Science.gov (United States)

    Hassanzadeh, Salman; Adolfsson, Karin H; Wu, Duo; Hakkarainen, Minna

    2016-01-11

    Biobased 2D graphene oxide quantum dots (GOQDs) were synthesized from waste paper via carbon nanosphere intermediates and evaluated as property-enhancing additives for poly(ε-caprolactone) (PCL). The morphology of PCL films was controlled by supramolecular assembly of the small, 2D GOQDs in the polymer matrix. Phase behavior studies of PCL-GOQD in the solid state indicated concentration-dependent self-association of GOQD sheets, which was confirmed by SEM observations. Depending on the GOQD concentration, the formation of, e.g., spheres and stacked sheets was observed. GOQDs also induced mineralization on the surface of the films. A calcium phosphate (CaP) mineralization test revealed that the density of growing CaP crystals was controlled by the type of GOQD aggregates formed. Thus, utilization of the aggregation behavior of small GOQD sheets in polymeric matrices paves the way for tuning the morphology and properties of nanocomposites. PMID:26650535

  5. Supramolecular assembly of (Z)-ethyl 2-cyano-3-((4-fluorophenyl)amino) acrylate, crystal structure, Hirshfeld surface analysis and DFT studies

    Science.gov (United States)

    Matos, Catiúcia R. M. O.; Vitorino, Letícia S.; de Oliveira, Pedro H. R.; de Souza, Maria Cecília B. V.; Cunha, Anna C.; Boechat, Fernanda da C. S.; Resende, Jackson A. L. C.; Carneiro, José Walkimar de M.; Ronconi, Célia M.

    2016-09-01

    A mixture of the E and Z isomers of ethyl 2-cyano-3-((4-fluorophenyl)amino) acrylate was synthesized and characterized by elemental analysis, attenuated total reflectance-Fourier transform infrared spectroscopy, 1H and 13C nuclear magnetic resonance spectroscopy. The structure of the Z isomer was determined by single crystal X-ray diffraction, which revealed a three-dimensional supramolecular network governed by Csbnd H⋯N, Csbnd H⋯O, and Csbnd H⋯F hydrogen bonds and π⋯π stacking interactions. The combination of these interactions plays an important role in stabilizing the self-assembly process and the molecular conformation. Hirshfeld surface analysis indicated the roles of the noncovalent interactions in the crystal packing, which were quantified by fingerprint plots and DFT calculations.

  6. Understanding complex chiral plasmonics

    Science.gov (United States)

    Duan, Xiaoyang; Yue, Song; Liu, Na

    2015-10-01

    Chiral nanoplasmonics exhibits great potential for novel nanooptical devices due to the generation of a strong chiroptical response within nanoscale metallic structures. Recently, a number of different approaches have been utilized to create chiral nanoplasmonic structures. However, particularly for tailoring nanooptical chiral sensing devices, the understanding of the resulting chiroptical response when coupling chiral and achiral structures together is crucial and has not been completely understood to date. Here, we present a thorough and step-by-step experimental study to understand the intriguing chiral-achiral coupling scheme. We set up a hybrid plasmonic system, which bears resemblance to the `host-guest' system in supramolecular chemistry to analyze and explain the complex chiral response both at the chiral and achiral plasmonic resonances. We also provide an elegant and simple analytical model, which can describe, predict, and comprehend the chiroptical spectra in detail. Our study will shed light on designing well-controlled chiral-achiral coupling platforms for reliable chiral sensing.Chiral nanoplasmonics exhibits great potential for novel nanooptical devices due to the generation of a strong chiroptical response within nanoscale metallic structures. Recently, a number of different approaches have been utilized to create chiral nanoplasmonic structures. However, particularly for tailoring nanooptical chiral sensing devices, the understanding of the resulting chiroptical response when coupling chiral and achiral structures together is crucial and has not been completely understood to date. Here, we present a thorough and step-by-step experimental study to understand the intriguing chiral-achiral coupling scheme. We set up a hybrid plasmonic system, which bears resemblance to the `host-guest' system in supramolecular chemistry to analyze and explain the complex chiral response both at the chiral and achiral plasmonic resonances. We also provide an elegant

  7. Hierarchical self-assembly of switchable nucleolipid supramolecular gels based on environmentally-sensitive fluorescent nucleoside analogs

    Science.gov (United States)

    Nuthanakanti, Ashok; Srivatsan, Seergazhi G.

    2016-02-01

    Exquisite recognition and folding properties have rendered nucleic acids as useful supramolecular synthons for the construction of programmable architectures. Despite their proven applications in nanotechnology, scalability and fabrication of nucleic acid nanostructures still remain a challenge. Here, we describe a novel design strategy to construct new supramolecular nucleolipid synthons by using environmentally-sensitive fluorescent nucleoside analogs, based on 5-(benzofuran-2-yl)uracil and 5-(benzo[b]thiophen-2-yl)uracil cores, as the head group and fatty acids, attached to the ribose sugar, as the lipophilic group. These modified nucleoside-lipid hybrids formed organogels driven by hierarchical structures such as fibers, twisted ribbons, helical ribbons and nanotubes, which depended on the nature of fatty acid chain and nucleobase modification. NMR, single crystal X-ray and powder X-ray diffraction studies revealed the coordinated interplay of various non-covalent interactions invoked by modified nucleobase, sugar and fatty acid chains in setting up the pathway for the gelation process. Importantly, these nucleolipid gels retained or displayed aggregation-induced enhanced emission and their gelation behavior and photophysical properties could be reversibly switched by external stimuli such as temperature, ultrasound and chemicals. Furthermore, the switchable nature of nucleolipid gels to chemical stimuli enabled the selective two channel recognition of fluoride and Hg2+ ions through visual phase transition and fluorescence change. Fluorescent organogels exhibiting such a combination of useful features is rare, and hence, we expect that this innovative design of fluorescent nucleolipid supramolecular synthons could lead to the emergence of a new family of smart optical materials and probes.Exquisite recognition and folding properties have rendered nucleic acids as useful supramolecular synthons for the construction of programmable architectures. Despite their

  8. Nano-self-assemblies based on synthetic analogues of mycobacterial monomycoloyl glycerol and DDA: Supramolecular structure and adjuvant efficacy

    DEFF Research Database (Denmark)

    Martin-Bertelsen, Birte; Korsholm, Karen Smith; Christensen, Dennis;

    2016-01-01

    responses. In the present study, we investigated the supramolecular structure and in vivo adjuvant activity of dispersions based on binary mixtures of DDA and an array of synthetic MMG-1 analogues (MMG- 2/3/5/6) displaying longer (MMG-2) or shorter (MMG-3) alkyl chain lengths, or polar headgroup (MMG-5...... for DDA:MMG-3, depending on the DDA:MMG molar ratio. The studies also showed that ULVs were formed, regardless of the structural characteristics of the neat MMG analogues in excess buffer [lamellar (MMG-1/2/5) or inverse hexagonal (MMG-3/6) phases]. Immunization of mice with a chlamydia antigen surface...

  9. Design of bio-based supramolecular structures through self-assembly of α-lactalbumin and lysozyme

    OpenAIRE

    Monteiro, Adenilson A.; Monteiro, Marcia R.; Pereira, Ricardo N.; Diniz, Renata; Costa, Angélica R.; Malcata, F. Xavier; J. A. Teixeira; Teixeira, Álvaro V.; Oliveira, Eduardo B.; Coimbra, Jane S.; Vicente, A.A.; Ramos, Óscar L.

    2016-01-01

    Bovine α-lactalbumin (α-La) and lysozyme (Lys), two globular proteins with highly homologous tertiary structures and opposite isoelectric points, were used to produce bio-based supramolecular structures under various pH values (3, 7 and 11), temperatures (25, 50 and 75 °C) and times (15, 25 and 35 min) of heating. Isothermal titration calorimetry experiments showed protein interactions and demonstrated that structures were obtained from the mixture of α-La/Lys in molar ratio of 0.546. Structu...

  10. Self-sorting in two-dimensional assemblies of simple chiral molecules

    OpenAIRE

    Woszczyk, A.; Szabelski, P.

    2016-01-01

    Structural modification of adsorbed overlayers by means of external factors is an important objective in the fabrication of stimuli-responsive materials with adjustable physicochemical properties. In this contribution we present a coarse-grained Monte Carlo model of the confinement-induced chiral self-sorting of hockey stick-shaped enantiomers adsorbed on a triangular lattice. It is assumed that the adsorbed overlayer consists of "normal" molecules that are capable of adopting any of the six ...

  11. Chiral amplification of oligopeptides in two-dimensional crystalline self-assemblies on water

    DEFF Research Database (Denmark)

    Zepik, H.; Shavit, E.; Tang, M.;

    2002-01-01

    from chiral nonracemic mixtures. The crystalline structures on the water surface were determined by grazing incidence x-ray diffraction and the diastereomeric composition of the oligopeptides by matrix-assisted laser desorption time-of-flight mass spectrometry with enantio-labeling. These results...... suggest that reactivity of ordered clusters at interfaces might have played a role in the generation of early homochiral biopolymers....

  12. Applications of supramolecular chemistry

    CERN Document Server

    Schneider, Hans-Jörg

    2012-01-01

    ""The time is ripe for the present volume, which gathers thorough presentations of the numerous actually realized or potentially accessible applications of supramolecular chemistry by a number of the leading figures in the field. The variety of topics covered is witness to the diversity of the approaches and the areas of implementation…a broad and timely panorama of the field assembling an eminent roster of contributors.""-Jean-Marie Lehn, 1987 Noble Prize Winner in Chemistry

  13. Ionic supramolecular bonds preserve mechanical properties and enable synergetic performance at high humidity in water-borne, self-assembled nacre-mimetics

    Science.gov (United States)

    Das, Paramita; Walther, Andreas

    2013-09-01

    Although tremendous effort has been focused on enhancing the mechanical properties of nacre-mimetic materials, conservation of high stiffness and strength against hydration-induced decay of mechanical properties at high humidity remains a fundamental challenge in such water-borne high-performance materials. Herein, we demonstrate that ionic supramolecular bonds, introduced by infiltration of divalent Cu2+ ions, allow efficient stabilization of the mechanical properties of self-assembled water-borne nacre-mimetics based on sustainable sodium carboxymethylcellulose (Na+CMC) and natural sodium montmorillonite nanoclay (Na+MTM) against high humidity (95% RH). The mechanical properties in the highly hydrated state (Young's modulus up to 13.5 GPa and tensile strength up to 125 MPa) are in fact comparable to a range of non-crosslinked nacre-mimetic materials in the dry state. Moreover, the Cu2+-treated nacre-inspired materials display synergetic mechanical properties as found in a simultaneous improvement of stiffness, strength and toughness, as compared to the pristine material. Significant inelastic deformation takes place considering the highly reinforced state. This contrasts the typical behaviour of tight, covalent crosslinks and is suggested to originate from a sacrificial, dynamic breakage and rebinding of transient supramolecular ionic bonds. Considering easy access to a large range of ionic interactions and alteration of counter-ion charge via external stimuli, we foresee responsive and adaptive mechanical properties in highly reinforced and stiff bio-inspired bulk nanocomposites and in other bio-inspired materials, e.g. nanocellulose papers and peptide-based materials.Although tremendous effort has been focused on enhancing the mechanical properties of nacre-mimetic materials, conservation of high stiffness and strength against hydration-induced decay of mechanical properties at high humidity remains a fundamental challenge in such water-borne high

  14. Fluorescence turn-on recognition of chiral amino acids using dye incorporated β-CD functionalized AuNPs assembly

    Energy Technology Data Exchange (ETDEWEB)

    Aswathy, B., E-mail: aswathybv@gmail.com; Sony, G., E-mail: emailtosony@gmail.com

    2014-10-15

    An assembly of dye incorporated β-cyclodextrin (βCD) functionalized AuNPs for the fluorescent probing of chiral amino acids is presented. Gold nanoparticles (AuNPs) possessing a high extinction coefficient function can be used as excellent fluorescent quenchers in AuNP–fluorophore system. Inclusion of fluorescein (FL) into β-cyclodextrin (βCD) makes energy transfer to occur through the donor and quencher nearby. This energy transfer switches off by virtue of the analyte induced release of FL from β-CD cavity, which results in the fluorescence recovery of the quenched dye. Analysis suggests that the assembly of AuNPs–βCDs–FL is effective as a turn-on fluorescent probe for the chiroselective optical discrimination between D,L-tryptophan, D,L-phenyl alanine and D,L-tyrosine. The detection limits for analyzing L-tryptophan, L-phenyl alanine and L-tyrosine were found to be 0.59, 1.2 and 1.5 μM respectively. - Highlights: • Fluorescence quenching AuNP–βCD–dye assembly via energy transfer. • Energy transfer from dye to AuNPs is a SET process. • Fluorescence turn-on detection of amino acids by the competitive binding method. • Chiroselective discrimination between enantiomeric amino acids.

  15. Supramolecular architectures from the self-assembly of lanthanide ions with 6-hydroxypicolinic acid and 1,10-phenanthroline

    Science.gov (United States)

    Sun, Chang-Yan; Jin, Lin-Pei

    2005-05-01

    Three new lanthanide complexes, [La(HpicO) 3(phen)(H 2O)] n ( 1) and Ln 3(picO) 4(phen) 3(H 2O) 2·HpicO·0.5H 2O (Ln=Er ( 2), Yb ( 3)) were synthesized by the hydrothermal reactions and characterized by single crystal X-ray diffraction, elemental analysis and IR spectrum. In complex 1, each La(III) ion is 10-coordinated and HpicO - ligands link the metal ions into 1D zigzag chains. Complexes 2 and 3 are isomorphous, and there are three crystallographically independent Ln(III) ions in the asymmetric unit. The N-H⋯O and O-H⋯O hydrogen bonds and π-π stacking interactions in these complexes result in the formation of 3D supramolecular architectures.

  16. Applying low-molecular weight supramolecular gelators in an environmental setting - self-assembled gels as smart materials for pollutant removal.

    Science.gov (United States)

    Okesola, Babatunde O; Smith, David K

    2016-07-25

    This review explores supramolecular gels as materials for environmental remediation. These soft materials are formed by self-assembling low-molecular-weight building blocks, which can be programmed with molecular-scale information by simple organic synthesis. The resulting gels often have nanoscale 'solid-like' networks which are sample-spanning within a 'liquid-like' solvent phase. There is intimate contact between the solvent and the gel nanostructure, which has a very high effective surface area as a result of its dimensions. As such, these materials have the ability to bring a solid-like phase into contact with liquids in an environmental setting. Such materials can therefore remediate unwanted pollutants from the environment including: immobilisation of oil spills, removal of dyes, extraction of heavy metals or toxic anions, and the detection or removal of chemical weapons. Controlling the interactions between the gel nanofibres and pollutants can lead to selective uptake and extraction. Furthermore, if suitably designed, such materials can be recyclable and environmentally benign, while the responsive and tunable nature of the self-assembled network offers significant advantages over other materials solutions to problems caused by pollution in an environmental setting. PMID:27241027

  17. The Self-Assembly of Nano-Objects Code: Applications to supramolecular organic monolayers adsorbed on metal surfaces

    OpenAIRE

    Roussel, Thomas; Vega, Lourdes F.

    2012-01-01

    The Self-Assembly of Nano-Objects (SANO) code we implemented demonstrates the ability to predict the molecular self-assembly of different structural motifs by tuning the molecular building blocks as well as the metallic substrate. It consists in a two-dimensional Grand Canonical Monte-Carlo (GCMC) approach developed to perform atomistic simulations of thousands of large organic molecules self-assembling on metal surfaces. Computing adsorption isotherms at room temperature and spanning over th...

  18. Enantioselective Formation of a Dynamic Hydrogen-Bonded Assembly Based on the Chiral Memory Concept

    NARCIS (Netherlands)

    Ishi-i, Tsutomu; Crego Calama, Mercedes; Timmerman, Peter; Reinhoudt, David N.; Shinkai, Seiji

    2002-01-01

    In this paper, we report the enantioselective formation of a dynamic noncovalent double rosette assembly 1a3·(CYA)6 composed of three 2-pyridylcalix[4]arene dimelamines (1a) and six butylcyanuric acid molecules (BuCYA). The six 2-pyridyl functionalities of the assembly interact stereoselectively wit

  19. Self-formation of highly aligned metallic, semiconducting and single chiral single-walled carbon nanotubes assemblies via a crystal template method

    Energy Technology Data Exchange (ETDEWEB)

    Kawai, Hideki; Hasegawa, Kai; Yanagi, Kazuhiro, E-mail: yanagi-kazuhiro@tmu.ac.jp [Department of Physics, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397 (Japan); Oyane, Ayako [Nanosystem Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8562 (Japan); Naitoh, Yasuhisa [Nanosystem Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8564 (Japan)

    2014-09-01

    The fabrication of an aligned array of single-walled carbon nanotubes (SWCNTs) with a single chiral state has been a significant challenge for SWCNT applications as well as for basic science research. Here, we developed a simple, unique technique to produce assemblies in which metallic, semiconducting, and single chiral state SWCNTs were densely and highly aligned. We utilized a crystal of surfactant as a template on which mono-dispersed SWCNTs in solution self-assembled. Micro-Raman measurements and scanning electron microscopy measurements clearly showed that the SWCNTs were highly and densely aligned parallel to the crystal axis, indicating that approximately 70% of the SWCNTs were within 7° of being parallel. Moreover, the assemblies exhibited good field effect transistor characteristics with an on/off ratio of 1.3 × 10{sup 5}.

  20. Self-sorting in two-dimensional assemblies of simple chiral molecules

    Directory of Open Access Journals (Sweden)

    A. Woszczyk

    2016-02-01

    Full Text Available Structural modification of adsorbed overlayers by means of external factors is an important objective in the fabrication of stimuli-responsive materials with adjustable physicochemical properties. In this contribution we present a coarse-grained Monte Carlo model of the confinement-induced chiral self-sorting of hockey stick-shaped enantiomers adsorbed on a triangular lattice. It is assumed that the adsorbed overlayer consists of "normal" molecules that are capable of adopting any of the six planar orientations imposed by the symmetry of the lattice and molecular directors having only one permanent orientation, that reflect the coupling of these species with an external directional field. Our investigations focus on the influence of the amount fraction of the molecular directors, temperature and surface coverage on the extent of the chiral segregation. The simulated results demonstrate that the molecular directors can have a significant effect on the ordering in enantiopure overlayers, while for the corresponding racemates their role is largely diminished. These findings can be helpful in designing strategies to improve methods of fabrication of homochiral surfaces and enantioselective adsorbents.

  1. Surfactant assisted self-assembly of zinc 5,10-bis (4-pyridyl)-15,20-bis (4-octadecyloxyphenyl) porphyrin into supramolecular nanoarchitectures

    Energy Technology Data Exchange (ETDEWEB)

    Gautam, Renu; Chauhan, S.M.S., E-mail: smschauhan@chemistry.du.ac.in

    2014-10-01

    The surfactant assisted self-assembly (SAS) method has been used in the formation of nanocubes, nanorods and microrods from zinc 5,10-bis (4-pyridyl)-15,20-bis (4-octadecyloxyphenyl) porphyrin. By the dropwise addition of chloroform solution of the zinc porphyrin into an aqueous solution of cetyltrimethylammonium bromide (CTAB), cuboidal nanostructures are formed at the initial stage. The nanocubes are transformed into nanorods and microrods by aging under ambient conditions. The longer nanorods with well defined edges have been formed with lower concentration of porphyrin solution whereas the shorter nanorods have been formed with higher concentration of zinc porphyrin. The synergistic effect of hydrophobic interactions by the long alkyl chains substituted on the peripheral phenyl rings of porphyrin and axial coordination of pyridyl nitrogen atoms with central zinc is mainly responsible for the formation of different nanostructures. The nanostructures were characterized by UV–visible spectra, fluorescence spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), IR spectroscopy and X-ray diffraction (XRD) pattern. - Graphical abstract: Supramolecular nanocubes, nanorods and microrods have been controllably fabricated by a simple surfactant-assisted solution route using unsymmetrical porphyrin bearing self assembly motifs. - Highlights: • Nanoaggregates from unsymmetrical porphyrin using surfactant were fabricated. • Zn–N axial interaction and hydrophobic interaction play a major role in aggregation. • Self-assembly can be controlled via porphyrin concentration and aging time. • A possible explanation for the fabrication of nanoaggregates has been proposed. • Highly ordered J type of aggregation takes place.

  2. Supramolecular biomaterials

    Science.gov (United States)

    Webber, Matthew J.; Appel, Eric A.; Meijer, E. W.; Langer, Robert

    2016-01-01

    Polymers, ceramics and metals have historically dominated the application of materials in medicine. Yet rationally designed materials that exploit specific, directional, tunable and reversible non-covalent interactions offer unprecedented advantages: they enable modular and generalizable platforms with tunable mechanical, chemical and biological properties. Indeed, the reversible nature of supramolecular interactions gives rise to biomaterials that can sense and respond to physiological cues, or that mimic the structural and functional aspects of biological signalling. In this Review, we discuss the properties of several supramolecular biomaterials, as well as their applications in drug delivery, tissue engineering, regenerative medicine and immunology. We envision that supramolecular biomaterials will contribute to the development of new therapies that combine highly functional materials with unmatched patient- and application-specific tailoring of both material and biological properties.

  3. Synthesis, double-helix formation, and higher-assembly formation of chiral polycyclic aromatic compounds: conceptual development of polyketide aldol synthesis.

    Science.gov (United States)

    Yamaguchi, Masahiko; Shigeno, Masanori; Saito, Nozomi; Yamamoto, Koji

    2014-02-01

    Polycyclic aromatic compounds are an important group of substances in chemistry, and the study of their properties is a subject of interest in the development of drugs and materials. We have been conducting studies to develop chiral polycyclic aromatic compounds, i.e., helicenes and equatorenes. These helical molecules showed notable aggregate-forming properties and the capability for chiral recognition exerted by noncovalent bond interactions, which were not observed in compounds with central chirality. Homo- and hetero-double-helix-forming helicene oligomers were developed, and the latter self-assembled to form gels and vesicles. In this article, we describe such hierarchical studies of polycyclic aromatic compounds, which were started from polyketide aldol synthesis.

  4. Chiral hierarchical self-assembly in Langmuir monolayers of diacetylenic lipids

    KAUST Repository

    Basnet, Prem B.

    2013-01-01

    When compressed in the intermediate temperature range below the chain-melting transition yet in the low-pressure liquid phase, Langmuir monolayers made of chiral lipid molecules form hierarchical structures. Using Brewster angle microscopy to reveal this structure, we found that as the liquid monolayer is compressed, an optically anisotropic condensed phase nucleates in the form of long, thin claws. These claws pack closely to form stripes. This appears to be a new mechanism for forming stripes in Langmuir monolayers. In the lower temperature range, these stripes arrange into spirals within overall circular domains, while near the chain-melting transition, the stripes arrange into target patterns. We attributed this transition to a change in boundary conditions at the core of the largest-scale circular domains. © 2013 The Royal Society of Chemistry.

  5. Influences of hydrophilic and hydrophobic substituents on the organization of supramolecular assemblies of porphyrin derivatives formed at the air/water interface

    International Nuclear Information System (INIS)

    Monolayers and Langmuir-Blodgett (LB) films of several kinds of porphyrin derivatives that have different substituted alkyl chain length, chain numbers and central metals were studied by π-A isotherms, UV-Vis, polarized UV-Vis and fluorescence spectroscopy and low angle X-ray diffractometry (LAXD). The orientation angles of porphyrin rings and alkyl chains were derived from the polarized UV-Vis spectra and LAXD patterns of the monolayers or LB films, respectively. The rings of the freebase porphyrins with different alkyl chain length or number have similar orientation angles in the films due to the same hydrophilic groups on the rings, and those of metal porphyrins have different orientation angles from each other. The orientation of the alkyl chains is related to the special positions of the chains on the rings and the orientation of the rings. The influences of the hydrophilicity of the hydrophilic groups and the alkyl chain number and length on the organization of the supramolecular assemblies of the porphyrin derivatives were discussed

  6. Metal-organic and supramolecular networks driven by 5-chloronicotinic acid: Hydrothermal self-assembly synthesis, structural diversity, luminescent and magnetic properties

    Science.gov (United States)

    Gao, Zhu-Qing; Li, Hong-Jin; Gu, Jin-Zhong; Zhang, Qing-Hua; Kirillov, Alexander M.

    2016-09-01

    Four new crystalline solids, namely [Co2(μ2-5-Clnic)2(μ3-5-Clnic)2(μ2-H2O)]n (1), [Co(5-Clnic)2(H2O)4]·2(5-ClnicH) (2), [Pb(μ2-5-Clnic)2(phen)]n (3), and [Cd(5-Clnic)2(phen)2]·3H2O (4) were generated by hydrothermal self-assembly methods from the corresponding metal(II) chlorides, 5-chloronicotinic acid (5-ClnicH) as a principal building block, and 1,10-phenanthroline (phen) as an ancillary ligand (optional). All the products 1-4 were characterized by IR spectroscopy, elemental analysis, thermogravimetric (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. Their structures range from an intricate 3D metal-organic network 1 with the 3,6T7 topology to a ladder-like 1D coordination polymer 3 with the 2C1 topology, whereas compounds 2 and 4 are the discrete 0D monomers. The structures of 2 and 4 are further extended (0D→2D or 0D→3D) by hydrogen bonds, generating supramolecular networks with the 3,8L18 and ins topologies, respectively. Synthetic aspects, structural features, thermal stability, magnetic (for 1) and luminescent (for 3 and 4) properties were also investigated and discussed.

  7. Supramolecular assembly and nanostructures of a series of luminol derivatives with aromatic/alkyl substituted groups in Langmuir-Blodgett films.

    Science.gov (United States)

    Jiao, Tifeng; Xing, Yuanyuan; Zhang, Qingrui; Zhang, Li; Liu, Minghua; Zhou, Jingxin; Gao, Faming

    2014-06-01

    A series of functional luminol derivatives with aromatic and alkyl substituted groups has been designed and synthesized from the reaction of the corresponding chloride precursors with luminol. These compounds can be spread on water surface to form stable Langmuir films at the air-water interface. It has been found that UV and IR spectra confirmed the characteristic aromatic segment, imide group, and aromatic/alkyl substituted groups. In addition, for the interfacial assembly process of compounds with alkyl substituted groups, there are obvious spectral changes for the alkyl chains. AFM results indicated that various different aggregated domains may be fabricated in the transferred LB films. For all cases, the substituted groups in molecular structures have an important effect in regulating the aggregation mode and spectral changes in organized molecular films. The present results showed that the modified luminol derivatives may have potential application in functional material fields such as ECL sensor, which may give some insight to study the relationship between the molecular structures and supramolecular aggregation of amphiphiles in organized molecular films.

  8. Supramolecular Assembly of Molecular Rare-Earth-3,5-Dichlorobenzoic Acid-2,2':6',2″-Terpyridine Materials: Structural Systematics, Luminescence Properties, and Magnetic Behavior.

    Science.gov (United States)

    Carter, Korey P; Thomas, Kara E; Pope, Simon J A; Holmberg, Rebecca J; Butcher, Ray J; Murugesu, Muralee; Cahill, Christopher L

    2016-07-18

    The syntheses and crystal structures of 16 new rare-earth (RE = La(3+)-Y(3+))-3,5-dichlorobenzoic acid-terpyridine molecular materials characterized via single-crystal and powder X-ray diffraction are reported. These 16 complexes consist of four unique structure types ranging from molecular dimers (La(3+) and Ce(3+)) to tetramers (Pr(3+)-Y(3+)) as one moves across the RE(3+) series. This structural evolution is accompanied by subsequent changes in modes of supramolecular assembly (halogen bonding, halogen-π, halogen-halogen, and π-π interactions). Solid-state visible and near-infrared lifetime measurements were performed on complexes 6 (Sm(3+)), 7 (Eu(3+)), 9 (Tb(3+)), 10 (Dy(3+)), 11 (Ho(3+)), 12 (Er(3+)), and 14 (Yb(3+)), and characteristic emission was observed for all complexes except 11. Lifetime data for 11, 12, and 14 suggest sensitization by the terpy antenna does occur in near-infrared systems, although not as efficiently as in the visible region. Additionally, direct current magnetic susceptibility measurements were taken for complexes 10 (Dy(3+)) and 12 (Er(3+)) and showed dominant ferromagnetic behavior. PMID:27347607

  9. Enzyme-catalyzed preparation of supramolecular structured hydrogel of polypseudorotaxanes derived from the self-assembly of α-CDs with 3-arm p-hydroxyphenylpropionate terminated PEG

    Institute of Scientific and Technical Information of China (English)

    XIE Zhiguo; HOU Dandan; YE Lin; ZHANG Aiying; FENG Zengguo

    2007-01-01

    A kind of novel 3-D cross-1inked supramolecular structured hydrogels has been fabricated via enzymatic oxidative coupling of polypseudorotaxanes (PPRs) derived from the self-assembly of α-cyclodextrins (α-CDs) with 3-arm p-hydroxyphenylpropionate terminated PEG (3-HPPP) as a macromer by using horseradish peroxidase (HRP)/H2O2 catalytic system.The enzymatic cross-1inking of the macromer or PPRs made with a smaller amount of α-CDs was found to be much faster than that by ordinary chemical pathways,showing the promise to be used as the surgical adhesive and sealant which are needed to rapidly function in vivo.The gelation time was highly extended and the gel content was considerably decreased by increasing the α-CDs to macromer feeding molar ratio.Thereby these hydrogels exhibited a decreasing trend in dynamical mechanical properties with increasing the amount of α-CDs in regard to the blank hydrogel made without α-CD addition.

  10. Supramolecular perspectives in colloid science

    NARCIS (Netherlands)

    Cohen Stuart, M.A.

    2008-01-01

    Supramolecular chemistry puts emphasis on molecular assemblies held together by non-covalent bonds. As such, it is very close in spirit to colloid science which also focuses on objects which are small, but beyond the molecular scale, and for which other forces than covalent bonds are crucial. We dis

  11. Enantioselective self-assembly of antiferromagnetic hexacopper(II) wheels with chiral amino acid oxamates.

    Science.gov (United States)

    Grancha, Thais; Ferrando-Soria, Jesús; Cano, Joan; Lloret, Francesc; Julve, Miguel; De Munno, Giovanni; Armentano, Donatella; Pardo, Emilio

    2013-07-01

    The Cu(2+)-mediated self-assembly of oxamato-based ligands derived from either the (S)- or (R)-enantiomers of the amino acid valine leads to the formation of two antiferromagnetically coupled homochiral anionic hexacopper(II) wheels in the presence of templating tetramethylammonium countercations.

  12. Supramolecular assemblies based on complexes of nonionic amphiphilic cyclodextrins and a meso-tetra(4-sulfonatophenyl)porphine tributyltin(IV) derivative: potential nanotherapeutics against melanoma.

    Science.gov (United States)

    Mazzaglia, Antonino; Bondì, Maria Luisa; Scala, Angela; Zito, Francesca; Barbieri, Giovanna; Crea, Francesco; Vianelli, Giuseppina; Mineo, Placido; Fiore, Tiziana; Pellerito, Claudia; Pellerito, Lorenzo; Costa, Maria Assunta

    2013-11-11

    Amphiphilic cyclodextrin (ACyD) provides water-soluble and adaptable nanovectors by modulating the balance between the hydrophobic and hydrophilic chains at both CyD sides. This work aimed to design nanoassemblies based on nonionic and hydrophilic ACyD (SC6OH) for the delivery of a poor-water-soluble organotin(IV)-porphyrin derivative [(Bu3Sn)4TPPS] to melanoma cancer cells. To characterize the porphyrin derivatives under simulated physiological conditions, a speciation was performed using complementary techniques. In aqueous solution (≤ 20 μM), (Bu3Sn)4TPPS primarily exists as a monomer (2 in Figure 1), as suggested by the low static anisotropy (ρ ≈ 0.02) with a negligible formation of porphyrin supramolecular aggregates. MALDI-TOF spectra indicate the presence of moieties (i.e., [(Bu3Sn)3TPPS](-)) that are derivatives of the monomeric species. Spectrofluorimetry coupled with potentiometric measurements primarily assesses the presence of the hydrolytic [(Bu3Sn)4TPPS (OH)4](4-) species under physiological conditions. Nanoassemblies of (Bu3Sn)4TPPS/SC6OH were prepared by dispersion of organic films in PBS at pH 7.4 and were investigated using a combination of spectroscopic and morphological techniques. The UV-vis and emission fluorescence spectra of the (Bu3Sn)4TPPS/SC6OH reveal shifts in the peculiar bands of the organotin(IV)-porphyrin derivative due to its interaction with the ACyD supramolecular assemblies in aqueous solution. The mean size was within the range of 100-120 nm. The ξ-potential was negative (-16 mV) for the (Bu3Sn)4TPPS/SC6OH nanoassemblies, with an entrapment efficiency of approximately 67%. The intracellular delivery, cytotoxicity, nuclear morphology and cell growth kinetics were evaluated via fluorescence microscopy on A375 human melanoma cells. The delivery of (Bu3Sn)4TPPS by ACyD with respect to free (Bu3Sn)4TPPS increases the internalization efficiency and cytotoxicity to induce apoptotic cell death and, at lower concentrations

  13. Supramolecular synthons on surfaces : Controlling dimensionality and periodicity of tetraarylporphyrin assemblies by the interplay of cyano and alkoxy substituents

    NARCIS (Netherlands)

    Wintjes, Nikolai; Hornung, Jens; Lobo-Checa, Jorge; Voigt, Tobias; Samuely, Tomáš; Thilgen, Carlo; Stöhr, Meike; Diederich, François; Jung, Thomas A.

    2008-01-01

    The self-assembly of three porphyrin derivatives was studied in detail on a Cu(111) substrate by means of scanning tunneling microscopy (STM). All derivatives have two 4-cyanophenyl substituents in diagonally opposed meso-positions of the porphyrin core. but differ in the nature of the other two mes

  14. Self-Assembled Ionophores from Isoguanosine: Diffusion NMR Spectroscopy Clarifies Cation's and Anion's Influence on Supramolecular Structure

    NARCIS (Netherlands)

    Evan-Salem, Tamar; Frish, Limor; Leeuwen, van Fijs W.B.; Reinhoudt, David N.; Verboom, Willem; Kaucher, Mark S.; Davis, Jeffery T.; Cohen, Yoram

    2007-01-01

    Cation-templated self-assembly of the lipophilic isoguanosine (isoG 1) with different monovalent cations (M+=Li+, Na+, K+, NH4+, and Cs+) was studied in solvents of different polarity by using diffusion NMR spectroscopy. Previous studies that did not use diffusion NMR techniques concluded that isoG

  15. Unraveling the nanostructure of supramolecular assemblies of hydrogen-bonded rosettes on graphite: An atomic force microscopy study

    Science.gov (United States)

    Schönherr, Holger; Paraschiv, Vasile; Zapotoczny, Szczepan; Crego-Calama, Mercedes; Timmerman, Peter; Frank, Curtis W.; Vancso, G. Julius; Reinhoudt, David N.

    2002-01-01

    The self-organization of multicomponent tetrarosette assemblies into ordered nanostructures on graphite surfaces has been studied by atomic force microscopy (AFM). Real-space information on the level of individual molecules allowed us to analyze the underlying structure in unprecedented detail. In highly ordered nanorod domains, tetrarosettes 13⋅(DEB)12 arrange in the form of parallel rows with a spacing of 4.6 ± 0.1 nm. High resolution AFM revealed the internal packing of the tetrarosette assemblies in these rows, which can be described by an oblique lattice with a = 2.5 ± 0.3 nm, b = 5.0 ± 0.1 nm, and γ = 122 ± 3°. The results, together with recent improvements in synthetic approaches, contribute to the development of a general strategy to develop H-bonding-based nanostructures with molecular precision. PMID:11929980

  16. Supramolecular assembly with ionic, redox-responsive poly(ferrocenylsilanes) : engineering of interfaces and molecular release applications

    OpenAIRE

    Ma, Yujie

    2008-01-01

    This thesis describes the synthesis and electrostatic assembly of organometallic poly(ferrocenylsilane) (PFS) strong polyelectrolytes. The distinctive structural features of poly(ferrocenylsilanes) come from the silicon and iron atoms in the main chain. The presence of redox-active ferrocene units in the polymer backbone provides unique redox-responsive properties to PFS. The charged nature and redox-responsiveness of these organometallic polyelectrolytes makes them particularly useful in the...

  17. Hydrodynamic-induced enantiomeric enrichment of self-assemblies: Role of the solid-liquid interface in chiral nucleation and seeding

    Science.gov (United States)

    Raudino, Antonio; Pannuzzo, Martina

    2012-10-01

    A simple hydrodynamic model has been developed to explain the experimentally observed chirality selection in stirred solutions of self-assembling achiral dyes. Selection depends on the stirring direction: the dichroic signal reverses its shape in clockwise or anti-clockwise rotations. Our model investigates the possible role of the liquid-solid interface in nucleating, growing, and transferring to the bulk of chiral seeds. The nucleation step requires a double modulation of the hydrodynamic field exhibiting different velocity along two orthogonal axes. Under a series of restrictions, such a condition is easily met at the solid-liquid interface and it is dictated by the boundary conditions and geometry of stirring. In stagnant conditions, growing helices made-up of self-assembled achiral dyes have no chiral preference forming a racemic mixture that contains identical amount of right-handed (R) and left-handed (L) configurations. The application of a hydrodynamic torque (related to the velocity gradient and width of the helix) breaks down the original symmetry, a further velocity gradient perpendicular to the first one ensures, after averaging, a slightly different population of R and L conformations. The yields of the hydrodynamic-induced chirality excess are extremely tiny, hence the suggested mechanism is significant only if next chirality amplification processes are efficient. Again, hydrodynamics provides a tool for the detachment of weakly bound aggregates once they have reached a critical length. Aggregates are transported in the bulk where the ripening process goes to completion. The efficiency of the surface catalytic effect strongly depends on the aggregate-surface sticking energy, reaching a maximum at intermediate sticking energies (of order of 10 kT). Numerical estimates show that the proposed mechanism is rather efficient, giving rise to entatiomeric excesses near (but smaller than) those experimentally found.

  18. A TEMPERATURE AND pH DOUBLE SENSITIVE CHOLESTERIC POLYMER FILM FROM A PHOTOPOLYMERIZABLE CHIRAL HYDROGEN-BONDED ASSEMBLY

    Institute of Scientific and Technical Information of China (English)

    Feng-jin Chen; Jin-bao Guo; Ou-yu Jin; Jie Wei

    2013-01-01

    In this study,a novel H-bonded cholesteric polymer film responding to temperature and pH by changing the reflection color was fabricated.The H-bonded cholesteric polymer film was achieved by UV-photopolymerizing a cholesteric liquid crystal (Ch-LC) monomers mixture containing a photopolymerizable chiral H-bonded assembly (PCHA).The cholesteric polymer film based on PCHA can be thermally switched to reflect red color from the initial green/yellow color as temperature is increased,which is due to a change in helical pitch induced by the weakening of H-bonded interaction in the polymer film.Additionally,the selective reflection band (SRB) of the cholesteric polymer film in solution with pH > 7showed an obvious red shift with increasing pH values.While the SRB of the cholesteric polymer film in solutions with pH =7 and pH < 7 hardly changed.This pH sensitivity in solutions with pH > 7 could be explained by the breakage of H-bonds in the cholesteric polymer film and the structure changes induced by-OFF and-K+ ions in the alkaline solution.In contrast,it couldn't happen in the neutral and acidic solutions.The cholesteric polymer film in this study can be used as optical/photonic papers,optical sensors and LCs displays,etc.

  19. Molecular recognition on supramolecular systems (XXXV)——Synthesis of novel β-cyclodextrin derivative bearing pyridinio group and its chiral discrimination of amino acids

    Institute of Scientific and Technical Information of China (English)

    刘育; 康诗钊

    2001-01-01

    A novel p-cyclodextrin derivative 4 bearing a pyridinio group on the primary side was synthesized by the reaction of 2-aminopyridine with 6-p-cyclodextrin monoaldehyde 3, and its complexation stability constants with several aliphatic amino acids have been determined in phosphate buffer solution ( pH = 7.2, 0.1 mol ?L-1) at 25℃by using spectrofluorometric titrations. The stoichiometry is 1 : 1 for the inclusion complexation of amino acids with compound 4. Circular dichroism study indicates that the aromatic moiety was embedded shallowly into the cyclodextrin cavity. As a spectral probe, the pyridinio group in the modified cyclodextrin can recognize not only differences of the size and shape of amino acid molecules, but also the L/D-amino acid chiral iso-mer. As compared with mono-[6-(1-pyridinio)-6-deoxy]-p-cyclodextrin 5, compound 4 switched the enantiomer preference for L- to D-isomer, and showed the highest enantioselectivity of 5.4 for D/L-serine. These results are discussed from the viewpoints of ge

  20. Molecular recognition on supramolecular systems (XXXV)-- Synthesis of novel b-cyclodextrin derivative bearing pyridinio group and its chiral discrimination of amino acids

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A novel b-cyclodextrin derivative 4 bearing a pyridinio group on the primary side was synthesized by the reaction of 2-aminopyridine with 6-b-cyclodextrin monoaldehyde 3, and its complexation stability constants with several aliphatic amino acids have been determined in phosphate buffer solution ( pH = 7.2, 0.1 mol·L-1) at 25 ℃ by using spectrofluormetric titrations. The stoichiometry is 1︰1 for the inclusion complexation of amino acids with compound 4. Circular dichroism study indicates that the aromatic moiety was embedded shallowly into the cyclodextrin cavity. As a spectral probe, the pyridinio group in the modified cyclodextrin can recognize not only differences of the size and shape of amino acid molecules, but also the L/D-amino acid chiral isomer. As com-pared with mono-[6-(1-pyridinio)-6-deoxy]-b-cyclodextrin 5, compound 4 switched the enantiomer preference for L- to D-isomer, and showed the highest enantioselectivity of 5.4 for D/L-serine. The-se results are discussed from the viewpoints of geometric compensation, induced-fit concept and cooperation of several weak interactions.

  1. Structure and energetics of diphenylalanine self-assembling on Cu(110).

    Science.gov (United States)

    Tomba, Giulia; Lingenfelder, Magalí; Costantini, Giovanni; Kern, Klaus; Klappenberger, Florian; Barth, Johannes V; Ciacchi, Lucio Colombi; De Vita, Alessandro

    2007-12-13

    We investigate the dynamical features of the adsorption of diphenylalanine molecules on the Cu(110) surface and of their assembling into supramolecular structures by a combination of quantum and classical atomistic modeling with dynamic scanning tunneling microscopy and spectroscopic experiments. Our results reveal a self-assembling mechanism in which isolated adsorbed molecules change their conformation and adsorption mode as a consequence of their mutual interactions. In particular, the formation of zwitterions after proton transfer between initially neutral molecules is found to be the key event of the assembling process, which stabilizes the supramolecular structures. Because of the constraints on the intermolecular bonds exerted by the surface-molecule interactions, the assembly process is strictly stereoselective, and may suggest a general model for patterning and functionalization of bare metal surfaces with short chiral peptides. PMID:17999478

  2. Self-assembled supramolecular hydrogel based on PCL-PEG-PCL triblock copolymer and γ-cyclodextrin inclusion complex for sustained delivery of dexamethasone.

    Science.gov (United States)

    Khodaverdi, Elham; Gharechahi, Marzieh; Alibolandi, Mona; Tekie, Farnaz Sadat Mirzazadeh; Khashyarmanesh, Bibi Zahra; Hadizadeh, Farzin

    2016-01-01

    In this study, thermosensitive, water-soluble, and biodegradable triblock copolymer PCL600-PEG6000-PCL600 was used to form supramolecular hydrogel (SMGel) by inclusion complexation with γ-cyclodextrin (γ-CD). The prepared SMGel was investigated as a carrier for sustained release of dexamethasone. The triblock copolymer PCL-PEG-PCL [where PCL = polycaprolactone, PEG = poly(ethylene glycol)] was synthesized by the ring-opening polymerization method using microwave irradiation. The polymerization reaction and the copolymer structures were evaluated by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). SMGel was prepared in aqueous solution by blending an aqueous γ-CD solution with aqueous solution of PCL-PEG-PCL triblock copolymer at room temperature. The sol-to-gel transition time was measured at various concentrations of copolymer and γ-CD. As-prepared SMGel was used to prepare a sustained, controllable drug delivery system of dexamethasone sodium phosphate. The SMGel was also characterized in terms of rheological, morphological, and structural properties. Results obtained from proton nuclear magnetic resonance ( (1)H-NMR) and GPC demonstrated that microwave irradiation is a simple and reliable method for synthesis of PEG-PCL copolymer. The SMGel with excellent syringability was prepared by mixing of 20% wt γ-CD and 10% wt of copolymer within 4 s. The SMGel containing 10% wt copolymer, 20% wt γ-CD, and 0.5% or 0.1% wt dexamethasone released approximately 100% and 45% of drug over up to 23 days, respectively. It could be concluded that SMGel based on self-assembly of inclusion complexes between PCL-PEG-PCL copolymer and γ-CD could be used as a basis for injectable drug delivery systems that provide sustained and controlled release of macromolecular drugs such as dexamethasone. PMID:27051627

  3. Shuttle-like supramolecular nanostructures formed by self-assembly of a porphyrin via an oil/water system

    Directory of Open Access Journals (Sweden)

    Guo Peipei

    2011-01-01

    Full Text Available Abstract In this paper, in terms of the concentration of an aqueous solution of a surfactant, we investigate the self-assembly behavior of a porphyrin, 5, 10, 15, 20-tetra(4-pyridyl-21H, 23H-porphine [H2TPyP], by using an oil/water system as the medium. We find that when a chloroform solution of H2TPyP is dropwise added into an aqueous solution of cetyltrimethylammonium bromide [CTAB] with a lower concentration, a large amount of irregular nanoarchitectures, together with a small amount of well-defined shuttle-like nanostructures, hollow nanospheres, and nanotubes, could be produced. While a moderate amount of shuttle-like nanostructures accompanied by a few irregular nanoarchitectures, solid nanospheres, and nanorods are produced when a CTAB aqueous solution in moderate concentration is employed, in contrast, a great quantity of shuttle-like nanostructures together with a negligible amount of solid nanospheres, nanofibers, and irregular nanostructures are manufactured when a high-concentration CTAB aqueous solution is involved. An explanation on the basis of the molecular geometry of H2TPyP and in terms of the intermolecular π-π interactions between H2TPyP units, and hydrophobic interactions between CTAB and H2TPyP has been proposed. The investigation gives deep insights into the self-assembly behavior of porphyrins in an oil/water system and provides important clues concerning the design of appropriate porphyrins when related subjects are addressed. Our investigation suggests that an oil/aqueous system might be an efficient medium for producing unique organic-based nanostructures.

  4. Supramolecular approaches for drug development.

    Science.gov (United States)

    Kawakami, K; Ebara, M; Izawa, H; Sanchez-Ballester, N M; Hill, J P; Ariga, K

    2012-01-01

    Various supramolecular systems can be used as drug carriers to alter physicochemical and pharmacokinetic characteristics of drugs. Representative supramolecular systems that can be used for this purpose include surfactant/polymer micelles, (micro)emulsions, liposomes, layer-by-layer assemblies, and various molecular conjugates. Notably, liposomes are established supramolecular drug carriers, which have already been marketed in formulations including AmBisome(®) (for treatment of fungal infection), Doxil(®) (for Kaposi's sarcoma), and Visudyne(®) (for age-related macular degeneration and choroidal neovascularization). Microemulsions have been used oral drug delivery of poorly soluble drugs due to improvements in bioavailability and predictable of absorption behavior. Neoral(®), an immunosuppressant used after transplant operations, is one of the most famous microemulsion-based drugs. Polymer micelles are being increasingly investigated as novel drug carriers and some formulations have already been tested in clinical trials. Supramolecular systems can be functionalized by designing the constituent molecules to achieve efficient delivery of drugs to desired sites in the body. In this review, representative supramolecular drug delivery systems, that may improve usability of candidate drugs or add value to existing drugs, are introduced. PMID:22455591

  5. Chirality in Nonlinear Optics

    Science.gov (United States)

    Haupert, Levi M.; Simpson, Garth J.

    2009-05-01

    The past decade has witnessed the emergence of new measurement approaches and applications for chiral thin films and materials enabled by the observations of the high sensitivity of second-order nonlinear optical measurements to chirality. In thin films, the chiral response to second harmonic generation and sum frequency generation (SFG) from a single molecular monolayer is often comparable with the achiral response. The chiral specificity also allows for symmetry-allowed SFG in isotropic chiral media, confirming predictions made ˜50 years ago. With these experimental demonstrations in hand, an important challenge is the construction of intuitive predictive models that allow the measured chiral response to be meaningfully related back to molecular and macromolecular structure. This review defines and considers three distinct mechanisms for chiral effects in uniaxially oriented assemblies: orientational chirality, intrinsic chirality, and isotropic chirality. The role of each is discussed in experimental and computational studies of bacteriorhodopsin films, binaphthol, and collagen. Collectively, these three model systems support a remarkably simple framework for quantitatively recovering the measured chiral-specific activity.

  6. Supramolecular self-assembly of graphene oxide and metal nanoparticles into stacked multilayers by means of a multitasking protein ring

    Science.gov (United States)

    Ardini, Matteo; Golia, Giordana; Passaretti, Paolo; Cimini, Annamaria; Pitari, Giuseppina; Giansanti, Francesco; Leandro, Luana Di; Ottaviano, Luca; Perrozzi, Francesco; Santucci, Sandro; Morandi, Vittorio; Ortolani, Luca; Christian, Meganne; Treossi, Emanuele; Palermo, Vincenzo; Angelucci, Francesco; Ippoliti, Rodolfo

    2016-03-01

    Graphene oxide (GO) is rapidly emerging worldwide as a breakthrough precursor material for next-generation devices. However, this requires the transition of its two-dimensional layered structure into more accessible three-dimensional (3D) arrays. Peroxiredoxins (Prx) are a family of multitasking redox enzymes, self-assembling into ring-like architectures. Taking advantage of both their symmetric structure and function, 3D reduced GO-based composites are hereby built up. Results reveal that the ``double-faced'' Prx rings can adhere flat on single GO layers and partially reduce them by their sulfur-containing amino acids, driving their stacking into 3D multi-layer reduced GO-Prx composites. This process occurs in aqueous solution at a very low GO concentration, i.e. 0.2 mg ml-1. Further, protein engineering allows the Prx ring to be enriched with metal binding sites inside its lumen. This feature is exploited to both capture presynthesized gold nanoparticles and grow in situ palladium nanoparticles paving the way to straightforward and ``green'' routes to 3D reduced GO-metal composite materials.Graphene oxide (GO) is rapidly emerging worldwide as a breakthrough precursor material for next-generation devices. However, this requires the transition of its two-dimensional layered structure into more accessible three-dimensional (3D) arrays. Peroxiredoxins (Prx) are a family of multitasking redox enzymes, self-assembling into ring-like architectures. Taking advantage of both their symmetric structure and function, 3D reduced GO-based composites are hereby built up. Results reveal that the ``double-faced'' Prx rings can adhere flat on single GO layers and partially reduce them by their sulfur-containing amino acids, driving their stacking into 3D multi-layer reduced GO-Prx composites. This process occurs in aqueous solution at a very low GO concentration, i.e. 0.2 mg ml-1. Further, protein engineering allows the Prx ring to be enriched with metal binding sites inside its

  7. Multivalent supramolecular dendrimer-based drugs.

    Science.gov (United States)

    Galeazzi, Simone; Hermans, Thomas M; Paolino, Marco; Anzini, Maurizio; Mennuni, Laura; Giordani, Antonio; Caselli, Gianfranco; Makovec, Francesco; Meijer, E W; Vomero, Salvatore; Cappelli, Andrea

    2010-01-11

    Supramolecular complexes consisting of a hydrophobic dendrimer host [DAB-dendr-(NHCONH-Ad)(64)] as well as solubilizing and bioactive guest molecules have been synthesized using a noncovalent approach. The guest-host supramolecular assembly is first preassembled in chloroform and transferred via the neat phase to aqueous solution. The bioactive guest molecules can bind to a natural (serotonin 5-HT(3)) receptor with nanomolar affinity as well as to the synthetic dendrimer receptor in aqueous solution, going toward a dynamic multivalent supramolecular construct capable of adapting itself to a multimeric receptor motif.

  8. Supramolecular assembly based on a heteropolyanion: Synthesis and crystal structure of Na3(H2O)6[Al(OH)6Mo6O18]$\\cdot$2H2O

    Indian Academy of Sciences (India)

    Vaddypally Shivaiah; Samar K Das

    2005-05-01

    Synthesis and structural characterization of a polyoxometalate compound Na3(H2O)6 [Al(OH)6Mo6O18]$\\cdot$2H2O (1) have been described. Compound 1 exhibits three-dimensional network structure in the solid state, which is assembled by Anderson-type heteropolyanions, [Al(OH)6Mo6O18]$_n^{3n-}$, as building blocks sharing sodium cations. 1 possesses ``sinuous" channels occupied by supramolecular water dimers as guests. Anderson anions, sodium-coordinated water and crystal water are additionally involved in an intricate hydrogen-bonding network in the crystal of 1.

  9. Assembly of polymeric silver(I) complexes of isomeric phenylenediethynides with the supramolecular synthons Agn subset C2-R-C2 superset Agn (R = p-, m-, o-C6H4; n = 4, 5).

    Science.gov (United States)

    Zhao, Liang; Mak, Thomas C W

    2005-11-01

    New Agn subset C2-R-C2 supersetAgn (R = p-, m-, o-C6H4; n = 4, 5) supramolecular synthons have been explored in the coordination network assembly of silver(I) complexes of the isomeric phenylenediethynides. An unprecedented mu5-eta1-coordination mode for the ethynide moiety and a mixed mu4,mu5-coordination mode for the o-phenylenediethynide group are observed, providing a rationale for the abundant occurrence of C2@Agn (n

  10. Hydrogen Bonded Supramolecular Polymers in Both Apolar and Aqueous Media: Self-Assembly and Reversible Conversion of Vesicles and Gels%Hydrogen Bonded Supramolecular Polymers in Both Apolar and Aqueous Media: Self-Assembly and Reversible Conversion of Vesicles and Gels

    Institute of Scientific and Technical Information of China (English)

    杜平; 孔军; 王贵涛; 赵新; 李光玉; 蒋锡夔; 黎占亭

    2011-01-01

    In a preliminary letter (Tetrahedron Lett. 2010, 51, 188), we reported two new hydrazide-based quadruple hydrogen-bonding motifs, this is, two monopodal (la and lb) and five dipodal (2a, 2b and 3a--3c) aromatic hydrazide derivatives, and the formation of supramolecular polymers and vesicles from the dipodal motifs in hydrocarbons. In this paper, we present a full picture on the properties of these hydrogen-bonding motifs with an emphasis on their self-assembling behaviors in aqueous media. SEM, AFM, TEM and fluorescent micrographs indicate that all the dipodal compounds also form vesicles in polar methanol and water-methanol (up to 50% of water) mixtures. Control experiments show that lb does not form vesicles in same media. Addition of lb to the solution of the dipodal compounds inhibits the latter's capacity of forming vesicles. At high concentrations, 3b and 3c also gelate discrete solvents, including hydrocarbons, esters, methanol, and methanol-water mixture. Concentration-dependent SEM investigations reveal that the vesicles of 3b and 3c fuse to form gels and the gel of 3c can de-aggregate to form the vesicles reversibly.

  11. Topological dynamics in supramolecular rotors.

    Science.gov (United States)

    Palma, Carlos-Andres; Björk, Jonas; Rao, Francesco; Kühne, Dirk; Klappenberger, Florian; Barth, Johannes V

    2014-08-13

    Artificial molecular switches, rotors, and machines are set to establish design rules and applications beyond their biological counterparts. Herein we exemplify the role of noncovalent interactions and transient rearrangements in the complex behavior of supramolecular rotors caged in a 2D metal-organic coordination network. Combined scanning tunneling microscopy experiments and molecular dynamics modeling of a supramolecular rotor with respective rotation rates matching with 0.2 kcal mol(-1) (9 meV) precision, identify key steps in collective rotation events and reconfigurations. We notably reveal that stereoisomerization of the chiral trimeric units entails topological isomerization whereas rotation occurs in a topology conserving, two-step asynchronous process. In supramolecular constructs, distinct displacements of subunits occur inducing a markedly lower rotation barrier as compared to synchronous mechanisms of rigid rotors. Moreover, the chemical environment can be instructed to control the system dynamics. Our observations allow for a definition of mechanical cooperativity based on a significant reduction of free energy barriers in supramolecules compared to rigid molecules. PMID:25078022

  12. Data Mining as a Guide for the Construction of Crosslinked Nanoparticles with Low Immunotoxicity via Controlling Polymer Chemistry and Supramolecular Assembly

    Science.gov (United States)

    Elsabahy, Mahmoud; Wooley, Karen L.

    2015-01-01

    CONSPECTUS The potential immunotoxicity of nanoparticles that are currently being approved or in different phases of clinical trials or under rigorous in vitro and in vivo characterizations in several laboratories has recently raised special attention. Products with no apparent in vitro or in vivo toxicity may still trigger the various components of the immune system, unintentionally, and lead to serious adverse reactions. Cytokines are one of the useful biomarkers to predict the effect of biotherapeutics on modulating the immune system and for screening the immunotoxicity of nanoparticles, both in vitro and in vivo, and were found recently to partially predict the in vivo pharmacokinetics and biodistribution of nanomaterials. Control of polymer chemistry and supramolecular assembly provides a great opportunity for construction of biocompatible nanoparticles for biomedical clinical applications. However, the sources of data collected regarding immunotoxicities of nanomaterials are diverse and experiments are usually conducted using different assays and under specific conditions, making direct comparisons nearly impossible and, thus, tailoring properties of nanomaterials based on the available data is challenging. In this account, the effects of chemical structure, crosslinking, degradability, morphology, concentration and surface chemistry on the immunotoxicity of an expansive array of polymeric nanomaterials will be highlighted, with focus being given on assays conducted using the same in vitro and in vivo models and experimental conditions. Furthermore, numerical descriptive values have been utilized, uniquely, to stand for induction of cytokines by nanoparticles. This treatment of available data provides a simple and easy way to compare the immunotoxicity of various nanomaterials, and the values were found to correlate-well with published data. Based on the investigated polymeric systems in this study, valuable information has been collected that aids in the

  13. Self-assembled cyclodextrin-modified gold nanoparticles on silica beads as stationary phase for chiral liquid chromatography and hydrophilic interaction chromatography.

    Science.gov (United States)

    Li, Yuanyuan; Wei, Manman; Chen, Tong; Zhu, Nan; Ma, Yulong

    2016-11-01

    A facile strategy based on self-assembly of Au nanoparticles (AuNPs) (60±10nm in size) on the surfaces of amino-functionalized porous silica spheres under mild conditions was proposed. The resulting material possessed a core-shell structure in which AuNPs were the shell and silica spheres were the core. Then, thiolated-β-cyclodextrin (SH-β-CD) was covalently attached onto the AuNPs as chiral selector for the enantioseparation. The resultant packing material was evaluated by high-performance liquid chromatography (HPLC). The separations of nine pairs of enantiomers were achieved by using the new chiral stationary phase (CSP) in the reversed-phase liquid chromatography (RPLC) mode, respectively. The results showed the new CSP have more sufficient interaction with the analytes due to the existence of AuNPs on silica surfaces, resulting in faster mass transfer rate, compared with β-CD modified silica column. The result shed light on potential usage of chemical modified NPs as chiral selector for enantioseparation based on HPLC. In addition, the new phase was also used in hydrophilic interaction liquid chromatography (HILIC) to separate polar compounds and highly hydrophilic compounds. PMID:27591589

  14. Coordination of alkaline earth metal ions in the inverted cucurbit[7]uril supramolecular assemblies formed in the presence of [ZnCl4]2- and [CdCl4]2-.

    Science.gov (United States)

    Li, Qing; Zhang, Yun-Qian; Zhu, Qian-Jiang; Xue, Sai-Feng; Tao, Zhu; Xiao, Xin

    2015-05-01

    A convenient method to isolate inverted cucurbit[7]uril (iQ[7]) from a mixture of water-soluble Q[n]s was established by eluting the soluble mixture of Q[n]s on a Dowex (H(+) form) column so that iQ[7] could be selected as a ligand for coordination and supramolecular assembly with alkaline earth cations (AE(2+)) in aqueous HCl solutions in the presence of [ZnCl(4)](2-) and [CdCl(4)](2-) anions as structure-directing agents. Single-crystal X-ray diffraction analysis revealed that both iQ[7]-AE(2+) -[ZnCl(4)](2-) -HCl and iQ[7]-AE(2+) -[CdCl(4)](2-) -HCl interaction systems yielded supramolecular assemblies, in which the [ZnCl(4)](2-) and [CdCl(4)](2-) anions presented a honeycomb effect, and this resulted in the formation of linear iQ[7]/AE(2+) coordination polymers through outer-surface interactions of Q[n]s.

  15. Catalysis of Supramolecular Hydrogelation.

    Science.gov (United States)

    Trausel, Fanny; Versluis, Frank; Maity, Chandan; Poolman, Jos M; Lovrak, Matija; van Esch, Jan H; Eelkema, Rienk

    2016-07-19

    One often thinks of catalysts as chemical tools to accelerate a reaction or to have a reaction run under more benign conditions. As such, catalysis has a role to play in the chemical industry and in lab scale synthesis that is not to be underestimated. Still, the role of catalysis in living systems (cells, organisms) is much more extensive, ranging from the formation and breakdown of small molecules and biopolymers to controlling signal transduction cascades and feedback processes, motility, and mechanical action. Such phenomena are only recently starting to receive attention in synthetic materials and chemical systems. "Smart" soft materials could find many important applications ranging from personalized therapeutics to soft robotics to name but a few. Until recently, approaches to control the properties of such materials were largely dominated by thermodynamics, for instance, looking at phase behavior and interaction strength. However, kinetics plays a large role in determining the behavior of such soft materials, for instance, in the formation of kinetically trapped (metastable) states or the dynamics of component exchange. As catalysts can change the rate of a chemical reaction, catalysis could be used to control the formation, dynamics, and fate of supramolecular structures when the molecules making up these structures contain chemical bonds whose formation or exchange are susceptible to catalysis. In this Account, we describe our efforts to use synthetic catalysts to control the properties of supramolecular hydrogels. Building on the concept of synthesizing the assembling molecule in the self-assembly medium from nonassembling precursors, we will introduce the use of catalysis to change the kinetics of assembler formation and thereby the properties of the resulting material. In particular, we will focus on the synthesis of supramolecular hydrogels where the use of a catalyst provides access to gel materials with vastly different appearance and mechanical

  16. Ordered supramolecular assembly of bis[3,4,12,13,21,22,30, 31-octa(dodecylthio)-2,3-naphthalocyaninato] erbium at the air/water interface

    Institute of Scientific and Technical Information of China (English)

    CHEN; Ya; nli

    2001-01-01

    -type (na)phthalocyaninato and porphyrinato rare earth complexes, Polyhedron, 2000, 19:1381.[12]Jiang. J.. Kasuga, K., Dennis, P. et al., Supramolecular Photosensitive and Electroactive Materials, New York: Academic Press. 2001. 113-210.[13]Van Nostrum. C. F., Nolte, R. J. M., Functional supramolecular material: self-assembly of phthalocyanines and porphyraszines. Chem. Commun., 1996: 2385.[14]Liu. Y., Shigehara, K., Yamada, A., Purification of lutetium diphthalocyanine and electrochromism of its Langmuir-Blodgett films, Thin Solid Films, 1989, 179: 303.[15]Liu. Y.. Shigehara, K., Hara, M. et al., Electrochemistry and electrochromic behavior of Langmuir-Blodgett films of octakis-substituted rare-earth metal diphthalocyanines, J. Am. Chem. Soc., 1991,113: 440.[16]Jones, R., Hunter, R. A., Davidson, K., Ordered Langmuir-Blodgett films of a substituted lutetium bisphthalocyanine, Thin Solid Films,1994, 250: 249.[17]Jones, R., Krier, A., Davidosn, K., Structure electrical conductivity and electrochromism in thin film of substituted and unsubstituted lanthanide bisphthalocyanines, Thin Solid Films, 1997, 298: 228.[18]Qian, D. -J., Liu, H. -G., Jiang, J., Monolayers and Langmuir-Blodgett films of (phthalocyaninato)(tetra-4-pyridylporphyrinato) cerium double-decker heteto complex, Colloids and Surfaces A, 2000,163:191.[19]Honig, E. P., Hengst, J. H. T., Engelsen, D. D., Langmuir-Blodgett deposition ratios, J. Colloid Interface Sci., 1973, 45:92.[20]Smolenyak, P., Peterson, R., Nesesny, K. et al., Highly ordered thin films of octasubstituted phthalocyanines, J. Am. Chem.Soc., 1999, 121: 8628.[21]Kasha, M., Rawls, H. R., E1-Bayoumi, M. A., The excition model in molecular spectroscopy, Pure Appl. Chem., 1965, 11: 371.[22]Fujiki, M., Tabei, H., Kurihara, T., Self-assembling features of soluble nickel phthalocyanines, J. Phys. Chem., 1988, 92:1281.[23]Osburn, E. J., Chau, L. -K., Chen, S. -Y. et al., Novel amphiphilic phthalocyanines

  17. Supramolecular science: A new way to understand the matter world

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xi; SHEN Jiacong

    2003-01-01

    @@ After over 20 years' rapid development, supramolecular chemistry has exceeded the original realm of organic host-guest chemistry, and formed its own unique concepts and systems, such as molecular recognition, molecular self-assembly, supramolecular devices and materials[1,2]. These branches have organized into a charming new subject in the whole family of chemistry.

  18. Supramolecular fibres: Self-sorting shows its true colours

    Science.gov (United States)

    Draper, Emily R.; Adams, Dave J.

    2016-08-01

    Self-sorting events in supramolecular assembly lead to complex systems that are attractive for the design of functional materials, but have remained difficult to understand and control. Now, the growth of self-sorted supramolecular nanofibres has been elucidated by direct imaging through real-time in situ confocal microscopy.

  19. Supramolecular chemistry and crystal engineering

    Indian Academy of Sciences (India)

    Ashwini Nangia

    2010-05-01

    Advances in supramolecular chemistry and crystal engineering reported from India within the last decade are highlighted in the categories of new intermolecular interactions, designed supramolecular architectures, network structures, multi-component host-guest systems, cocrystals, and polymorphs. Understanding self-assembly and crystallization through X-ray crystal structures is illustrated by two important prototypes - the large unit cell of elusive saccharin hydrate, Na16(sac)16 . 30H2O, which contains regular and irregular domains in the same structure, and by the Aufbau build up of zinc phosphate framework structures, e.g. ladder motif in [C3N2H12][Zn(HPO4)2] to layer structure in [C3N2H12][Zn2(HPO4)3] upon prolonged hydrothermal conditions. The pivotal role of accurate X-ray diffraction in supramolecular and structural studies is evident in many examples. Application of the bottomup approach to make powerful NLO and magnetic materials, design of efficient organogelators, and crystallization of novel pharmaceutical polymorphs and cocrystals show possible future directions for interdisciplinary research in chemistry with materials and pharmaceutical scientists. This article traces the evolution of supramolecular chemistry and crystal engineering starting from the early nineties and projects a center stage for chemistry in the natural sciences.

  20. A Supramolecular Hydrogel Inspired by Elastin

    Institute of Scientific and Technical Information of China (English)

    丁磊; 王淑芳; 武文洁; 胡月晗; 杨翠红; 谭鸣; 孔德领; 杨志谋

    2011-01-01

    Self-assembly prevails in nature and learning from nature will lead to biofunctional materials. Inspired by the protein of elastin, we reported in this study on a supramolecular hydrogel beating the elastin repeating peptide of VPGAG. The visco-elasticity property, morphology of the nanostructures, and aromatic stacking in the self-assembled nanostructure were characterized by a rheometry, transmission electron microscope (TEM), and fluorescence microscope, respectively. The biocompatibility of the gelator was also proved by an MTT assay. Though the supramolecular hydrogel failed to exhibit a high elasticity like elastin, the thixotropic hydrogel might have potentials for the applications in fields of cell culture, controlled-drug release, etc.

  1. Enantioselective binding of amino acids and amino alcohols by self-assembled chiral basket-shaped receptors

    NARCIS (Netherlands)

    Escuder, B.; Rowan, A.E.; Feiters, M.C.; Nolte, R.J.M.

    2004-01-01

    Amino acid appended diphenylglycoluril-based chiral molecular receptors 2 and 3 have been prepared and their aggregation has been studied in water at various pH's and in chloroform. The binding of several biologically relevant guests with aromatic moieties to these aggregates has been studied with U

  2. Three-dimensional hydrogen-bonded supramolecular assembly in tetrakis(1,3,5-triaza-7-phosphaadamantanecopper(I chloride hexahydrate

    Directory of Open Access Journals (Sweden)

    Armando J. L. Pombeiro

    2008-05-01

    Full Text Available The structure of the title compound, [Cu(PTA4]Cl·6H2O (PTA is 1,3,5-triaza-7-phosphaadamantane, C6H12N3P, is composed of discrete monomeric [Cu(PTA4]+ cations, chloride anions and uncoordinated water molecules. The CuI atom exhibits tetrahedral coordination geometry, involving four symmetry-equivalent P–bound PTA ligands. The structure is extended to a regular three-dimensional supramolecular framework via numerous equivalent O—H...N hydrogen bonds between all solvent water molecules (six per cation and all PTA N atoms, thus simultaneously bridging each [Cu(PTA4]+ cation with 12 neighbouring units in multiple directions. The study also shows that PTA can be a convenient ligand in crystal engineering for the construction of supramolecular architectures.

  3. Fibonacci Sequence and Supramolecular Structure of DNA.

    Science.gov (United States)

    Shabalkin, I P; Grigor'eva, E Yu; Gudkova, M V; Shabalkin, P I

    2016-05-01

    We proposed a new model of supramolecular DNA structure. Similar to the previously developed by us model of primary DNA structure [11-15], 3D structure of DNA molecule is assembled in accordance to a mathematic rule known as Fibonacci sequence. Unlike primary DNA structure, supramolecular 3D structure is assembled from complex moieties including a regular tetrahedron and a regular octahedron consisting of monomers, elements of the primary DNA structure. The moieties of the supramolecular DNA structure forming fragments of regular spatial lattice are bound via linker (joint) sequences of the DNA chain. The lattice perceives and transmits information signals over a considerable distance without acoustic aberrations. Linker sequences expand conformational space between lattice segments allowing their sliding relative to each other under the action of external forces. In this case, sliding is provided by stretching of the stacked linker sequences.

  4. Fibonacci Sequence and Supramolecular Structure of DNA.

    Science.gov (United States)

    Shabalkin, I P; Grigor'eva, E Yu; Gudkova, M V; Shabalkin, P I

    2016-05-01

    We proposed a new model of supramolecular DNA structure. Similar to the previously developed by us model of primary DNA structure [11-15], 3D structure of DNA molecule is assembled in accordance to a mathematic rule known as Fibonacci sequence. Unlike primary DNA structure, supramolecular 3D structure is assembled from complex moieties including a regular tetrahedron and a regular octahedron consisting of monomers, elements of the primary DNA structure. The moieties of the supramolecular DNA structure forming fragments of regular spatial lattice are bound via linker (joint) sequences of the DNA chain. The lattice perceives and transmits information signals over a considerable distance without acoustic aberrations. Linker sequences expand conformational space between lattice segments allowing their sliding relative to each other under the action of external forces. In this case, sliding is provided by stretching of the stacked linker sequences. PMID:27265133

  5. Self-Assembly Supramolecular Systems toward Molecular Machines and Motors%具有分子机器、分子开关功能的自组装超分子体系

    Institute of Scientific and Technical Information of China (English)

    陈慧兰

    2001-01-01

    Self-assembly, self-organization and self-replication, that are central to nature' s forms and functions, are now becoming feasible to construct large and intricate, yet highly ordered functioning molecular and supramolecular entities. This paper introduced the recently new progress for a kind of special rotaxane and catenane supramoculars having functions of molecular shuttle or molecular switch, as well as the chemical and biological systems toward molecular machines and motors.%本文介绍了具有分子梭或分子开关性质的新型轮烷和索烃超分子以及具有分子机器功能的其它类型化学和生物分子的国际研究最新动态。

  6. Chiral (6,3) Network Assembled by Lanthanide and Changeful Dihydroxyfumaric Acid%Chiral (6,3) Network Assembled by Lanthanide and Changeful Dihydroxyfumaric Acid

    Institute of Scientific and Technical Information of China (English)

    Zhang, Manbo; Lu, Jing; Hu, Ruixiang

    2012-01-01

    A series of chiral two-dimensional lanthanide coordination polymers, [Ln2(L)3(H2O)6]n·n/3H2O[Ln=Nd (la, lb), Sm (2), Eu (3), Tb (4), Dy (5), Ho (6), Er (7); H2L=2,2-dihydroxylmalonic acid], have been hydrothermally synthesized by using dihydroxyfumaric acid as a source of polydentate O-donor ligands. The luminescence behav- iors of 3 and 4 have been investigated, and they exhibit strong red and green fluorescence in the visible region respectively.

  7. Robust excitons inhabit soft supramolecular nanotubes

    NARCIS (Netherlands)

    Eisele, Doerthe M.; Arias, Dylan H.; Fu, Xiaofeng; Bloemsma, Erik A.; Steiner, Colby P.; Jensen, Russell A.; Rebentrost, Patrick; Eisele, Holger; Tokmakoff, Andrei; Lloyd, Seth; Nelson, Keith A.; Nicastro, Daniela; Knoester, Jasper; Bawendi, Moungi G.

    2014-01-01

    Nature's highly efficient light-harvesting antennae, such as those found in green sulfur bacteria, consist of supramolecular building blocks that self-assemble into a hierarchy of close-packed structures. In an effort to mimic the fundamental processes that govern nature's efficient systems, it is i

  8. Chirality imprinting and direct asymmetric reaction screening using a stereodynamic Brønsted/Lewis acid receptor

    Science.gov (United States)

    Bentley, Keith W.; Proano, Daysi; Wolf, Christian

    2016-08-01

    Molecular recognition, activation and dynamic self-assembly with Brønsted and Lewis acids play a central role across the chemical sciences including catalysis, crystal engineering, supramolecular architectures and drug design. Despite this general advance, the utilization of the corresponding binding motifs for fast and robust quantitative chemosensing of chiral compounds in a complicate matrix has remained challenging. Here we show that a stereodynamic probe carrying complementary boronic acid and urea units achieves this goal with hydroxy carboxylic acids. Synergistic dual-site binding and instantaneous chirality imprinting result in characteristic ultraviolet and CD readouts that allow instantaneous determination of the absolute configuration, enantiomeric excess and concentration of the target compound even in complex mixtures. The robustness and practicality of this strategy for high-throughput screening purposes is demonstrated. Comprehensive sensing of only 0.5 mg of a crude reaction mixture of an asymmetric reduction eliminates cumbersome work-up protocols and minimizes analysis time, labour and waste production.

  9. Tailoring two-dimensional PTCDA-melamine self-assembled architectures at room temperature by tuning molecular ratio

    Energy Technology Data Exchange (ETDEWEB)

    Sun Xiaonan; Jonkman, Harry T; Silly, Fabien, E-mail: fabien.silly@cea.fr [Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, NL-9747 AG Groningen (Netherlands)

    2010-04-23

    Engineering and tuning multi-component supramolecular self-assemblies on surfaces is one of the challenges of nanotechnology. We use scanning tunneling microscopy to investigate the influence of molecular ratio on the self-assembly of PTCDA-melamine structures on Au(111)-(22x{radical}3). Our observations reveal that three different chiral supramolecular networks having a PTCDA:melamine ratio of 3:2, 1:2, 1:4 can be selectively created by tuning the ratio of molecules deposited on the surface. The 1:2 ratio network having melamine in excess has been observed previously but the 1:4 network has not yet been reported. In comparison, the multi-component 3:2 network having PTCDA in excess is a completely new structure.

  10. Tailoring two-dimensional PTCDA-melamine self-assembled architectures at room temperature by tuning molecular ratio.

    Science.gov (United States)

    Sun, Xiaonan; Jonkman, Harry T; Silly, Fabien

    2010-04-23

    Engineering and tuning multi-component supramolecular self-assemblies on surfaces is one of the challenges of nanotechnology. We use scanning tunneling microscopy to investigate the influence of molecular ratio on the self-assembly of PTCDA-melamine structures on Au(111)-(22 x complex square root of 3). Our observations reveal that three different chiral supramolecular networks having a PTCDA:melamine ratio of 3:2, 1:2, 1:4 can be selectively created by tuning the ratio of molecules deposited on the surface. The 1:2 ratio network having melamine in excess has been observed previously but the 1:4 network has not yet been reported. In comparison, the multi-component 3:2 network having PTCDA in excess is a completely new structure. PMID:20348601

  11. Tailoring two-dimensional PTCDA-melamine self-assembled architectures at room temperature by tuning molecular ratio

    International Nuclear Information System (INIS)

    Engineering and tuning multi-component supramolecular self-assemblies on surfaces is one of the challenges of nanotechnology. We use scanning tunneling microscopy to investigate the influence of molecular ratio on the self-assembly of PTCDA-melamine structures on Au(111)-(22x√3). Our observations reveal that three different chiral supramolecular networks having a PTCDA:melamine ratio of 3:2, 1:2, 1:4 can be selectively created by tuning the ratio of molecules deposited on the surface. The 1:2 ratio network having melamine in excess has been observed previously but the 1:4 network has not yet been reported. In comparison, the multi-component 3:2 network having PTCDA in excess is a completely new structure.

  12. Assembly of organic moiety with metal-oxide cluster to generate a new three dimensional supramolecular/hydrogen bonded network based on isopolymolybdate

    Indian Academy of Sciences (India)

    DONIA ZAMMEL; ICHRAF NAGAZI; AMOR HADDAD

    2016-07-01

    A new octa-molybdate formulated as (C₂H₆N₄)₂ [β-Mo₈O₂₆].4H₂O (1) has been isolated by conventional solution method and structurally characterized by single-crystal X-ray diffraction method, IR spectroscopy, UV-Vis absorption, thermogravimetric analysis and cyclic voltammetry. Compound 1 crystallizes in the Triclinic system, space group P-1 with unit cell dimensions, a = 8.348 (2)Å, b = 10.154 (2)Å, c = 10.823 (3)Å, α = 68.35◦ (2), β = 71.59◦ (2), γ= 78.55◦ (2), V = 805.5 (3)ų, and Z = 2. The crystal structure of 1 is built up from octa-molybdate [β-Mo₈O₂₆]⁴⁻ clusters connected through hydrogen-bonding interactions into a three-dimensional supramolecular network.

  13. New Supramolecular Complex Assembled through Hydrogen Bonds.Crystal Structure of Co(PMBP-tsc)2·2DMF·2H2O

    Institute of Scientific and Technical Information of China (English)

    UU,Lang(刘浪); JIA,Dian-Zeng(贾殿赠); QIAO,Yong-Min(乔永民); YU,Kai-Bei(郁开北)

    2002-01-01

    The structure of the complex [Co(PMBP-tsc)2.2DMF@2H2O]( PMBP-tsc= 1-phenyl-3-methyl-4-benzoylpyrazol-5-one-thiosemicarbazone) has been determined by X-ray crystallography. It crystallizes in the orthorhombic system, space group Pna21, with lattice parameters a=2.1170(3) nm, b =1.2780(10) nm, c = 1.8956(2) nm, V= 4.5258(9) nm3 and Z=4. The structure shows that Co2+ in the complex is hexacoordinated with a distorted octahedral coordination sphere.The water molecules bridge the adjacent stacks through hydrogen bonds and lead to supramolecular formation with three-dimensional network structure.

  14. Energy landscapes and functions of supramolecular systems

    Science.gov (United States)

    Tantakitti, Faifan; Boekhoven, Job; Wang, Xin; Kazantsev, Roman V.; Yu, Tao; Li, Jiahe; Zhuang, Ellen; Zandi, Roya; Ortony, Julia H.; Newcomb, Christina J.; Palmer, Liam C.; Shekhawat, Gajendra S.; de La Cruz, Monica Olvera; Schatz, George C.; Stupp, Samuel I.

    2016-04-01

    By means of two supramolecular systems--peptide amphiphiles engaged in hydrogen-bonded β-sheets, and chromophore amphiphiles driven to assemble by π-orbital overlaps--we show that the minima in the energy landscapes of supramolecular systems are defined by electrostatic repulsion and the ability of the dominant attractive forces to trap molecules in thermodynamically unfavourable configurations. These competing interactions can be selectively switched on and off, with the order of doing so determining the position of the final product in the energy landscape. Within the same energy landscape, the peptide-amphiphile system forms a thermodynamically favoured product characterized by long bundled fibres that promote biological cell adhesion and survival, and a metastable product characterized by short monodisperse fibres that interfere with adhesion and can lead to cell death. Our findings suggest that, in supramolecular systems, functions and energy landscapes are linked, superseding the more traditional connection between molecular design and function.

  15. A combined experimental and theoretical study of the supramolecular self-assembly of Cu(II) malonate complex assisted by various weak forces and water dimer

    International Nuclear Information System (INIS)

    A Cu(II) malonate complex with formula [Cu(C3H2O4)(C6H8N2)(H2O)]2·4H2O (1) [C6H8N2=2-picolylamine, C3H2O42−=malonate dianion] has been synthesized by mixing the reactants in their stoichiometric proportion and its crystal structure has been determined by single-crystal X-ray diffraction. In 1, monomeric neutral metal malonate units [Cu(C3H2O4)(C6H8N2)(H2O)] are interlinked with each other through hydrogen bonds, weak lone pair⋯π and cuprophilic interactions to generate supramolecular dimers, which in turn further associated through hydrogen bonding to form infinite 1D chains. Water dimers, through series of hydrogen bonds and weak π–stacking forces are found to be responsible for interconnection of 1D chains, which resulted in a 3D network. A density functional (DFT) study of the energetic features of several noncovalent interactions observed in the solid state have been analyzed and characterized using Bader's theory of “atoms-in-molecules”. We also present here Hirshfeld surface analysis to investigate the close intermolecular contacts. - Graphical Abstract: Interplay of weak forces like hydrogen bonding, lone pair⋯π, Cu⋯Cu and π–stacking interactions leading to the formation of supramolecular network in [Cu(C3H2O4)(C6H8N2)(H2O)]2·4H2O complex. - Highlights: • A complex of Cu(II) with malonate and 2-picolylamine is synthesized and X-ray characterized. • We report a density functional study of the energetic features of several noncovalent interactions • We perform Hirshfeld surface analysis to investigate the close intermolecular contacts

  16. Tuning the 1D-self-assembly of dicyano-functionalized helicene building-blocks

    International Nuclear Information System (INIS)

    Full text: Effective control of chirality in supramolecular systems is an important challenge towards the assembly of well-defined nano-architectures from the bottom-up. The chirality transfer from single molecules onto 3D- and 2D-crystals is well known, however chirality in case of the 1D-objects (wires) is largely unexplored. Here we present a study based on Scanning Tunnelling Microscopy (STM) and X-Ray Photoelectron Spectroscopy (XPS) measurements and Density Functional Theory (DFT) calculations to understand the formation of 1D conglomerates from enantiopure dicyano functionalized heptahelicene molecules of both chiralities at different, well defined single-crystal surfaces. We show that the main bonding motif can be switched by temperature, substrate or adatom stimuli. We discuss the key driving forces for the formation of well-ordered long-range arrays and the chirality transfer on the single molecule scale as well as onto the 1D conglomerate as a whole. In comparison of experiment and theory, we deepen the insight into the chirality transfer in competition between molecule-molecule and surface-molecule interactions. (author)

  17. Self-assembly of metallosupramolecular rhombi from chiral concave 9,9’-spirobifluorene-derived bis(pyridine ligands

    Directory of Open Access Journals (Sweden)

    Rainer Hovorka

    2014-02-01

    Full Text Available Two new 9,9’-spirobifluorene-based bis(4-pyridines were synthesised in enantiopure and one also in racemic form. These ligands act as concave templates and form metallosupramolecular [(dppp2M2L2] rhombi with cis-protected [(dpppPd]2+ and [(dpppPt]2+ ions. The self-assembly process of the racemic ligand preferably occurs in a narcissistic self-recognising manner. Hence, a mixture of all three possible stereoisomers [(dppp2M2{(R-L}2](OTf4, [(dppp2M2{(S-L}2](OTf4, and [(dppp2M2{(R-L}{(S-L}](OTf4 was obtained in an approximate 1.5:1.5:1 ratio which corresponds to an amplification of the homochiral assemblies by a factor of approximately three as evidenced by NMR spectroscopy and mass spectrometry. The racemic homochiral assemblies could also be characterised by single crystal X-ray diffraction.

  18. Preface to the special issue: Macrocyclic and supramolecular chemistry

    Institute of Scientific and Technical Information of China (English)

    LIU Yu

    2009-01-01

    @@ The 14th Conference of Macrocyclic Chemistry and the 6th Conference of Supramolecular Chemistry was held in Northwest Normal University in Lanzhou, Gansu Province, China, from 11 to 13 August, 2008. More than 200 participants from 40 universities and institutes dis-cussed the development of macrocyclic and su-pramolecular chemistry in China. More than 50 plenary and oral presentations concerning the synthesis, recogni-tion, assembly and functions of macrocyclic and su-pramolecular systems were held, presenting significant achievements in these areas.

  19. Supramolecular control of [2 + 2] photodimerization via hydrogen bonding.

    Science.gov (United States)

    Darcos, Vincent; Griffith, Kirsten; Sallenave, Xavier; Desvergne, Jean-Pierre; Guyard-Duhayon, Carine; Hasenknopf, Bernold; Bassani, Dario M

    2003-11-01

    The use of supramolecular catalysis to control the photoinduced dimerization of styrene, cinnamate, and stilbene chromophores is reported. The strategy employs the formation of a 2:1 supramolecular assembly in the presence of 5,5-dihexylbarbituric acid (DHB). A 3- to 10-fold increase in dimerization efficiency is observed in its presence, concomitant with accrued selectivity for the syn photodimers. The origin of the regioselectivity in the presence of DHB is discussed in terms of topochemical control within the supramolecular architecture. PMID:14690228

  20. Simulation of self-organization processes in crystal-forming systems: Supramolecular cyclic R6 cluster precursors and self-assembly of TeO2- TEL ( Tellurite) and TeO2- PAR ( Paratellurite) structures

    Science.gov (United States)

    Ilyushin, G. D.

    2014-11-01

    The supramolecular chemistry of oxides of sp elements (SO2, SeO2, and TeO2) is considered. The self-assembly of TeO2- TEL ( Tellurite) and TeO2- PAR ( Paratellurite) crystal structures is simulated. Methods of combinatorial and topological analysis (TOPOS program package) are applied which are based on constructing a basis 3D network of the structure in the form of a graph, the sites of which correspond to the positions of centroids of TeO2 molecules and the edges characterize bonds between them. The topological type of the basis 2D network in the TeO2- TEL structure corresponds to graphite (C- GRA), while in the TeO2- PAR structure the basis network corresponds to the 3D diamond network (C- DIA). A nanocluster precursor of cyclic type ( R6) composed of six covalently bound TeO2 molecules (chair conformation) is established for both structures. The desymmetrization of the cyclic structure of the R6 cluster in TeO2- PAR is related to the formation of Te-Te bonds with lengths of 3.824 and 4.062 Å. The symmetry and topology code of the processes of self-assembly of 3D structures from nanocluster precursors is completely reconstructed into the form "primary chain → microlayer → microframework." In both structures R6 clusters form 2D packings with a coordination number of 6. The cluster self-assembly model explains the specific features of the morphogenesis of TeO2- TEL and TeO2- PAR (phases with low and high crystallization temperatures, respectively): platelike shape, perfect cleavage in the (110) plane, and preferred growth in the primar-chain direction [100] in the former case and growth in the direction of the primary [001] axis with the preferred formation of tetragonal prism faces (110) in the latter case.

  1. Three-Dimensionally Isotropic Negative Refractive Index Materials from Block Copolymer Self-Assembled Chiral Gyroid Networks

    KAUST Repository

    Hur, Kahyun

    2011-10-17

    Metamaterials are engineered artificial materials that offer new functionalities such as super-resolution imaging and cloaking. Calculations of the photonic properties of three-dimensionally isotropic metamaterials with cubic double gyroid and alternating gyroid morphologies from block copolymer self-assembly are presented.

  2. Self-assembly, Dynamics and Chirality of Conformational Switches on Metal Surfaces Studied by UHV-STM

    DEFF Research Database (Denmark)

    Nuermaimaiti, Ajiguli

    2013-01-01

    Molecular self-assembly is essential in the bottom-up design of nanostructures. Molecular conformational switches are highly interesting both from the basic science of view to enhance our understanding of molecular dynamics in adsorption systems, and also due to potential applications such as mol...

  3. A combined experimental and theoretical study of the supramolecular self-assembly of Cu(II) malonate complex assisted by various weak forces and water dimer

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Prankrishna [Department of Chemistry, Jadavpur University, Kolkata 700 032 (India); Ray Choudhury, Somnath [Central Chemical Laboratory, Geological Survey of India, 15 A and B Kyd Street, Kolkata 700 016 (India); Mitra, Monojit [Department of Chemistry, Jadavpur University, Kolkata 700 032 (India); Kumar Seth, Saikat [Department of Physics, M. G. Mahavidyalaya, Bhupatinagar, Purba Medinipur, West Bengal 721 425 (India); Helliwell, Madeleine [School of Chemistry, The University of Manchester, Brunswick Street, Manchester M13 9PL (United Kingdom); Bauzá, Antonio [Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma (Baleares) (Spain); Frontera, Antonio, E-mail: toni.frontera@uib.es [Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma (Baleares) (Spain); Mukhopadhyay, Subrata, E-mail: smukhopadhyay@chemistry.jdvu.ac.in [Department of Chemistry, Jadavpur University, Kolkata 700 032 (India)

    2014-12-15

    A Cu(II) malonate complex with formula [Cu(C{sub 3}H{sub 2}O{sub 4})(C{sub 6}H{sub 8}N{sub 2})(H{sub 2}O)]{sub 2}·4H{sub 2}O (1) [C{sub 6}H{sub 8}N{sub 2}=2-picolylamine, C{sub 3}H{sub 2}O{sub 4}{sup 2−}=malonate dianion] has been synthesized by mixing the reactants in their stoichiometric proportion and its crystal structure has been determined by single-crystal X-ray diffraction. In 1, monomeric neutral metal malonate units [Cu(C{sub 3}H{sub 2}O{sub 4})(C{sub 6}H{sub 8}N{sub 2})(H{sub 2}O)] are interlinked with each other through hydrogen bonds, weak lone pair⋯π and cuprophilic interactions to generate supramolecular dimers, which in turn further associated through hydrogen bonding to form infinite 1D chains. Water dimers, through series of hydrogen bonds and weak π–stacking forces are found to be responsible for interconnection of 1D chains, which resulted in a 3D network. A density functional (DFT) study of the energetic features of several noncovalent interactions observed in the solid state have been analyzed and characterized using Bader's theory of “atoms-in-molecules”. We also present here Hirshfeld surface analysis to investigate the close intermolecular contacts. - Graphical Abstract: Interplay of weak forces like hydrogen bonding, lone pair⋯π, Cu⋯Cu and π–stacking interactions leading to the formation of supramolecular network in [Cu(C{sub 3}H{sub 2}O{sub 4})(C{sub 6}H{sub 8}N{sub 2})(H{sub 2}O)]{sub 2}·4H{sub 2}O complex. - Highlights: • A complex of Cu(II) with malonate and 2-picolylamine is synthesized and X-ray characterized. • We report a density functional study of the energetic features of several noncovalent interactions • We perform Hirshfeld surface analysis to investigate the close intermolecular contacts.

  4. Enzymatic induction of supramolecular order and bioactivity

    Science.gov (United States)

    Yang, Chengbiao; Ren, Xinrui; Ding, Dan; Wang, Ling; Yang, Zhimou

    2016-05-01

    We showed in this study that enzymatic triggering is a totally different pathway for the preparation of self-assembling nanomaterials to the heating-cooling process. Because the molecules were under lower energy levels and the molecular conformation was more ordered during the enzymatic triggeration under mild conditions, nanomaterials with higher supramolecular order could be obtained through biocatalytic control. In this study, nanoparticles were obtained by an enzymatic reaction and nanofibers were observed through the heating-cooling process. We observed a distinct trough at 318 nm from the CD spectrum of a particle sample but not a fiber sample, suggesting the long range arrangement of molecules and helicity in the nanoparticles. The nanoparticles with higher supramolecular order possessed much better potency as a protein vaccine adjuvant because it accelerated the DC maturation and elicited stronger T-cells cytokine production than the nanofibers. Our study demonstrated that biocatalytic triggering is a useful method for preparing supramolecular nanomaterials with higher supramolecular order and probably better bioactivity.We showed in this study that enzymatic triggering is a totally different pathway for the preparation of self-assembling nanomaterials to the heating-cooling process. Because the molecules were under lower energy levels and the molecular conformation was more ordered during the enzymatic triggeration under mild conditions, nanomaterials with higher supramolecular order could be obtained through biocatalytic control. In this study, nanoparticles were obtained by an enzymatic reaction and nanofibers were observed through the heating-cooling process. We observed a distinct trough at 318 nm from the CD spectrum of a particle sample but not a fiber sample, suggesting the long range arrangement of molecules and helicity in the nanoparticles. The nanoparticles with higher supramolecular order possessed much better potency as a protein vaccine

  5. Single-step coacervate-mediated preconcentration of metals and metal-chelates in supramolecular vesicular surfactant assemblies and determination by flame atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Tsogas, George Z. [Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, 45110 Ioannina (Greece); Giokas, Dimosthenis L. [Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, 45110 Ioannina (Greece)]. E-mail: dgiokas@cc.uoi.gr; Paleologos, Evangelos K. [Laboratory of Food Chemistry, Department of Chemistry, University of Ioannina, 45110 Ioannina (Greece); Vlessidis, Athanasios G. [Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, 45110 Ioannina (Greece); Evmiridis, Nicholaos P. [Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, 45110 Ioannina (Greece)

    2005-04-29

    The use of ionic surfactant supramolecular aggregates is described, as means for accomplishing the concentration of analytes with different polarities using the same extraction pattern. The proposed method is based on the phase separation of an anionic surfactant through the formation of perplexed lamellar phases, allowing for the extraction of hydrated metal cations by complexation and metal-chelates by hydrophobic interactions. The data suggest that both extraction and phase separation are controlled by the presence of ionic surfactant as a function of the degree of phase divergence from the lamellar to bilayer phase. This again is determined by the composition of the phase-forming parameters, these are the surfactant concentration, the kind and amount of metallic counterparts and ionic strength. On the basis of these findings, the proposed method was successfully applied to the determination of metal species in natural waters. The limits of detection were easily brought down to the low microgram per liter levels by simply preconcentrating 10 mL of sample volume in the presence of at least 0.45% (w/v) of anionic surfactant. The method provided extraction recoveries higher than 94.0% with standard deviations well below 7.0%.

  6. Supramolecular Langmuir monolayers and multilayered vesicles of self-assembling DNA–lipid surface structures and their further implications in polyelectrolyte-based cell transfections

    Energy Technology Data Exchange (ETDEWEB)

    Demirsoy, Fatma Funda Kaya [Ankara University, The Central Laboratory of The Institute of Biotechnology (Turkey); Eruygur, Nuraniye [Gazi University, Department of Pharmacognosy, Faculty of Pharmacy (Turkey); Süleymanoğlu, Erhan, E-mail: erhans@mail.ru [Gazi University, Department of Pharmaceutical Chemistry, Faculty of Pharmacy (Turkey)

    2015-01-15

    The basic interfacial characteristics of DNA–lipid recognitions have been studied. The complex structures of individual unbound DNA molecules and their binary and ternary complexes with zwitterionic lipids and divalent cations were followed by employing lipid monolayers at the air–liquid interfaces, as well as by performing various microscopic, spectroscopic, and thermodynamic measurements with multilayered vesicles. The pressure-area isotherms depicted that Mg{sup 2+}-ions increase the surface pressure of lipid films and thus give rise to electrostatic and hydrophobic lipid–DNA interactions in terms of DNA adsorption, adhesion, and compaction. These features were further approached by using multilamellar vesicles with a mean diameter of 850 nm, where a metal ion-directed nucleic acid compaction and condensation effects were shown. The data obtained show the effectiveness of Langmuir monolayers and lipid multilayers in studying nucleic acid–lipid recognitions. The data provide with further details and support previous reports on mainly structural features of these recognitions. Biomolecular surface recognition events were presented in direct link with spectral and thermodynamic features of lipid vesicle–polynucleotide complex formations. The results serve to build a theoretical model considering the use of neutral lipids in lipoplex designs as a polyelectrolyte alternatives to the currently employed cytotoxic cationic liposomes. The supramolecular structures formed and their possible roles in interfacial electrostatic and hydrophobic mechanisms of endosomal escape in relevant cell transfection assays are particularly emphasized.

  7. Redox-Robust Pentamethylferrocene Polymers and Supramolecular Polymers, and Controlled Self-Assembly of Pentamethylferricenium Polymer-Embedded Ag, AgI, and Au Nanoparticles.

    Science.gov (United States)

    Gu, Haibin; Ciganda, Roberto; Castel, Patricia; Vax, Amélie; Gregurec, Danijela; Irigoyen, Joseba; Moya, Sergio; Salmon, Lionel; Zhao, Pengxiang; Ruiz, Jaime; Hernández, Ricardo; Astruc, Didier

    2015-12-01

    We report the first pentamethylferrocene (PMF) polymers and the redox chemistry of their robust polycationic pentamethylferricenium (PMFium) analogues. The PMF polymers were synthesized by ring-opening metathesis polymerization (ROMP) of a PMF-containing norbornene derivative by using the third-generation Grubbs ruthenium metathesis catalyst. Cyclic voltammetry studies allowed us to determine confidently the number of monomer units in the polymers through the Bard-Anson method. Stoichiometric oxidation by using ferricenium hexafluorophosphate quantitatively and instantaneously provided fully stable (even in aerobic solutions) blue d(5) Fe(III) metallopolymers. Alternatively, oxidation of the PMF-containing polymers was conducted by reactions with Ag(I) or Au(III) , to give PMFium polymer-embedded Ag and Au nanoparticles (NPs). In the presence of I2 , oxidation by using Ag(I) gave polymer-embedded Ag/AgI NPs and AgNPs at the surface of AgI NPs. Oxidation by using Au(III) also produced an Au(I) intermediate that was trapped and characterized. Engineered single-electron transfer reactions of these redox-robust nanomaterial precursors appear to be a new way to control their formation, size, and environment in a supramolecular way.

  8. Hydrogen bonded supramolecular structures

    CERN Document Server

    Li, Zhanting

    2015-01-01

    This book covers the advances in the studies of hydrogen-bonding-driven supramolecular systems  made over the past decade. It is divided into four parts, with the first introducing the basics of hydrogen bonding and important hydrogen bonding patterns in solution as well as in the solid state. The second part covers molecular recognition and supramolecular structures driven by hydrogen bonding. The third part introduces the formation of hollow and giant macrocycles directed by hydrogen bonding, while the last part summarizes hydrogen bonded supramolecular polymers. This book is designed to b

  9. 超分子化合物的合成自组装应用研究的新进展%Recent Research Achievements on Synthesis and Self-assembly Applications of New Supramolecular Compounds

    Institute of Scientific and Technical Information of China (English)

    张来新; 赵卫星

    2013-01-01

    简要介绍了超分子化学的产生、发展及应用,重点介绍了:①新型超分子化合物的合成及自组装;②新型超分子金属配合物的合成及应用;③新型超分子化合物的合成及药理作用。并对超分子化学的发展进行了展望。%This paper briefly introduces the generation ,development,and application of supramolecular chemis-try.Emphases are put on three parts:①synthesis and applications of new supramolecular compounds;②synthesis and applications of new supramolecular metal complexes;③synthesis and pharmacological effects of new supramo-lecular compounds.Future developments of supramolecular chemistry are prospected in the end.

  10. Molecular and supramolecular control of the work function of an inorganic electrode with self-assembled monolayer of umbrella-shaped fullerene derivatives.

    Science.gov (United States)

    Lacher, Sebastian; Matsuo, Yutaka; Nakamura, Eiichi

    2011-10-26

    The surface properties of inorganic substrates can be altered by coating with organic molecules, which may result in the improvement of the properties suitable for electronic or biological applications. This article reports a systematic experimental study on the influence of the molecular and supramolecular properties of umbrella-shaped penta(organo)[60]fullerene derivatives, and on the work function and the water contact angle of indium-tin oxide (ITO) and gold surfaces. We could relate these macroscopic characteristics to single-molecular level properties, such as ionization potential and molecular dipole. The results led us to conclude that the formation of a SAM of a polar compound generates an electronic field through intermolecular interaction of the molecular charges, and this field makes the overall dipole of the SAM much smaller than the one expected from the simple sum of the dipoles of all molecules in the SAM. This effect, which was called depolarization and previously discussed theoretically, is now quantitatively probed by experiments. The important physical properties in surface science such as work function, ionization potential, and water contact angles have been mutually correlated at the level of molecular structures and molecular orientations on the substrate surface. We also found that the SAMs on ITO and gold operate under the same principle except that the "push-back" effect operates specifically for gold. The study also illustrates the ability of the photoelectron yield spectroscopy technique to rapidly measure the work function of a SAM-covered substrate and the ionization potential value of a molecule on the surface. PMID:21923177

  11. Supramolecular Photodimerization of Coumarins

    Directory of Open Access Journals (Sweden)

    Koichi Tanaka

    2012-02-01

    Full Text Available Stereoselective photodimerization of coumarin and its derivatives in supra-molecular systems is reviewed. The enantioselective photodimerization of coumarin and thiocoumarin in inclusion crystals with optically active host compounds is also described.

  12. A switchable self-assembling and disassembling chiral system based on a porphyrin-substituted phenylalanine-phenylalanine motif

    Science.gov (United States)

    Charalambidis, Georgios; Georgilis, Evangelos; Panda, Manas K.; Anson, Christopher E.; Powell, Annie K.; Doyle, Stephen; Moss, David; Jochum, Tobias; Horton, Peter N.; Coles, Simon J.; Linares, Mathieu; Beljonne, David; Naubron, Jean-Valère; Conradt, Jonas; Kalt, Heinz; Mitraki, Anna; Coutsolelos, Athanassios G.; Balaban, Teodor Silviu

    2016-09-01

    Artificial light-harvesting systems have until now not been able to self-assemble into structures with a large photon capture cross-section that upon a stimulus reversibly can switch into an inactive state. Here we describe a simple and robust FLFL-dipeptide construct to which a meso-tetraphenylporphyrin has been appended and which self-assembles to fibrils, platelets or nanospheres depending on the solvent composition. The fibrils, functioning as quenched antennas, give intense excitonic couplets in the electronic circular dichroism spectra which are mirror imaged if the unnatural FDFD-analogue is used. By slightly increasing the solvent polarity, these light-harvesting fibres disassemble to spherical structures with silent electronic circular dichroism spectra but which fluoresce. Upon further dilution with the nonpolar solvent, the intense Cotton effects are recovered, thus proving a reversible switching. A single crystal X-ray structure shows a head-to-head arrangement of porphyrins that explains both their excitonic coupling and quenched fluorescence.

  13. A switchable self-assembling and disassembling chiral system based on a porphyrin-substituted phenylalanine–phenylalanine motif

    Science.gov (United States)

    Charalambidis, Georgios; Georgilis, Evangelos; Panda, Manas K.; Anson, Christopher E.; Powell, Annie K.; Doyle, Stephen; Moss, David; Jochum, Tobias; Horton, Peter N.; Coles, Simon J.; Linares, Mathieu; Beljonne, David; Naubron, Jean-Valère; Conradt, Jonas; Kalt, Heinz; Mitraki, Anna; Coutsolelos, Athanassios G.; Balaban, Teodor Silviu

    2016-01-01

    Artificial light-harvesting systems have until now not been able to self-assemble into structures with a large photon capture cross-section that upon a stimulus reversibly can switch into an inactive state. Here we describe a simple and robust FLFL-dipeptide construct to which a meso-tetraphenylporphyrin has been appended and which self-assembles to fibrils, platelets or nanospheres depending on the solvent composition. The fibrils, functioning as quenched antennas, give intense excitonic couplets in the electronic circular dichroism spectra which are mirror imaged if the unnatural FDFD-analogue is used. By slightly increasing the solvent polarity, these light-harvesting fibres disassemble to spherical structures with silent electronic circular dichroism spectra but which fluoresce. Upon further dilution with the nonpolar solvent, the intense Cotton effects are recovered, thus proving a reversible switching. A single crystal X-ray structure shows a head-to-head arrangement of porphyrins that explains both their excitonic coupling and quenched fluorescence. PMID:27582363

  14. A One-Pot Self-Assembly Reaction to Prepare a Supramolecular Palladium(II) Cyclometalated Complex: An Undergraduate Organometallic Laboratory Experiment

    Science.gov (United States)

    Fernandez, Alberto; Lopez-Torres, Margarita; Fernandez, Jesus J.; Vazquez-Garcia, Digna; Vila, Jose M.

    2012-01-01

    A laboratory experiment for students in advanced inorganic chemistry is described. Students prepare palladium(II) cyclometalated complexes. A terdentate [C,N,O] Schiff base ligand is doubly deprotonated upon reaction with palladium(II) acetate in a self-assembly process to give a palladacycle with a characteristic tetranuclear structure. This…

  15. Chiral Electronics

    OpenAIRE

    Kharzeev, Dmitri E.; Yee, Ho-Ung

    2012-01-01

    We consider the properties of electric circuits involving Weyl semimetals. The existence of the anomaly-induced chiral magnetic current in a Weyl semimetal subjected to magnetic field causes an interesting and unusual behavior of such circuits. We consider two explicit examples: i) a circuit involving the "chiral battery" and ii) a circuit that can be used as a "quantum amplifier" of magnetic field. The unique properties of these circuits stem from the chiral anomaly and may be utilized for c...

  16. Chiral photochemistry

    CERN Document Server

    Inoue, Yoshihisa

    2004-01-01

    Direct Asymmetric Photochemistry with Circularly Polarized Light, H. RauCoherent Laser Control of the Handedness of Chiral Molecules, P. Brumer and M. ShapiroMagnetochiral Anisotropy in Asymmetric Photochemistry, G.L.J.A.RikkenEnantiodifferentiating Photosensitized Reactions, Y. InoueDiastereodifferentiating Photoreactions, N. Hoffmann and J.-P. PeteChirality in Photochromism, Y. Yokoyama and M. SaitoChiral Photochemistry with Transition Metal Complexes, S. Sakaki and T. HamadaTemplate-Induced Enantioselective Photochemical Reactions in S

  17. Supramolecular photochemistry and solar cells

    Directory of Open Access Journals (Sweden)

    IHA NEYDE YUKIE MURAKAMI

    2000-01-01

    Full Text Available Supramolecular photochemistry as well as solar cells are fascinating topics of current interest in Inorganic Photochemistry and very active research fields which have attracted wide attention in last two decades. A brief outline of the investigations in these fields carried out in our Laboratory of Inorganic Photochemistry and Energy Conversion is given here with no attempt of an exhaustive coverage of the literature. The emphasis is placed on recent work and information on the above mentioned subjects. Three types of supramolecular systems have been the focus of this work: (i cage-type coordination compounds; (ii second-sphere coordination compounds, exemplified by ion-pair photochemistry of cobalt complexes and (iii covalently-linked systems. In the latter, modulation of the photoluminescence and photochemistry of some rhenium complexes are discussed. Solar energy conversion and development of thin-layer photoelectrochemical solar cells based on sensitization of nanocrystalline semiconductor films by some ruthenium polypyridyl complexes are presented as an important application that resulted from specifically engineered artificial assemblies.

  18. Versatile Supramolecular Gene Vector Based on Host-Guest Interaction.

    Science.gov (United States)

    Liu, Jia; Hennink, Wim E; van Steenbergen, Mies J; Zhuo, Renxi; Jiang, Xulin

    2016-04-20

    It is a great challenge to arrange multiple functional components into one gene vector system to overcome the extra- and intracellular obstacles for gene therapy. In this study, we developed a supramolecular approach for constructing a versatile gene delivery system composed of adamantyl-terminated functional polymers and a β-cyclodextrin based polymer. Adamantyl-functionalized low molecular weight PEIs (PEI-Ad) and PEG (Ad-PEG) as well as poly(β-cyclodextrin) (PCD) were synthesized by one-step chemical reactions. The supramolecular inclusion complex formed from PCD to assemble LMW PEI-Ad4 via host-guest interactions can condense plasmid DNA to form nanopolyplexes by electrostatic interactions. The supramolecular polyplexes can be further PEGylated with Ad-PEG to form inclusion complexes, which showed increased salt and serum stability. In vitro experiments revealed that these supramolecular assembly polyplexes had good cytocompatibility and showed high transfection activity close to that of the commercial ExGen 500 at high dose of DNA. Also, the supramolecular vector system exhibited about 60% silencing efficiency as a siRNA vector. Thus, a versatile effective supramolecular gene vector based on host-guest complexes was fabricated with good cytocompatbility and transfection activity. PMID:27019340

  19. Supramolecular Luminescence from Oligofluorenol-Based Supramolecular Polymer Semiconductors

    OpenAIRE

    Guang-Wei Zhang; Long Wang; Ling-Hai Xie; Jin-Yi Lin; Wei Huang

    2013-01-01

    Supramolecular luminescence stems from non-covalent exciton behaviors of active π-segments in supramolecular entities or aggregates via intermolecular forces. Herein, a π-conjugated oligofluorenol, containing self-complementary double hydrogen bonds, was synthesized using Suzuki coupling as a supramolecular semiconductor. Terfluorenol-based random supramolecular polymers were confirmed via concentration-dependent nuclear magnetic resonance (NMR) and dynamic light scattering (DLS). The photolu...

  20. Ag+ labeling: a convenient new tool for the characterization of hydrogen-bonded supramolecular assemblies by MALDI-TOF mass spectrometry.

    Science.gov (United States)

    Timmerman, P; Jolliffe, K A; Calama, M C; Weidmann, J L; Prins, L J; Cardullo, F; Snellink-Ruël, B H; Fokkens, R H; Nibbering, N M; Shinkai, S; Reinhoudt, D N

    2000-11-17

    Herein we describe our results on the characterization of a wide variety of different hydrogen-bonded assemblies by means of a novel matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) technique with Ag+ labeling. The labeling technique with Ag+ ions is extremely mild and provides a nondestructive way to generate charged assemblies that can be detected by mass spectrometry. Up to now more than 25 different single (1(3).2(3)), double (3(3).2(6)), and tetrarosettes (4(3).2(12)) have been successfully characterized by the use of this method. The success of the method entirely depends on the presence of a suitable binding site for the Ag+ ion. A variety of functionalities has been identified that provide strong binding sites for Ag+, either acting in a cooperative way (pi-arene and pi-alkene donor functionalities) or individually (cyano and crown ether functionalities). The method works well for assemblies with molecular weights between 2,000 and 8,000 Da, and most likely far beyond this limit.

  1. Chiral Cyclobutane β-Amino Acid-Based Amphiphiles: Influence of Cis/Trans Stereochemistry on Solution Self-Aggregation and Recognition.

    Science.gov (United States)

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

    2015-09-01

    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

  2. X-ray studies of crystalline complexes involving amino acids and peptides. XLIV. Invariant features of supramolecular association and chiral effects in the complexes of arginine and lysine with tartaric acid.

    Science.gov (United States)

    Selvaraj, M; Thamotharan, S; Roy, Siddhartha; Vijayan, M

    2007-06-01

    The tartaric acid complexes with arginine and lysine exhibit two stoichiometries depending upon the ionization state of the anion. The structures reported here are DL-argininium DL-hydrogen tartrate, bis(L-argininium) L-tartrate, bis(DL-lysinium) DL-tartrate monohydrate, L-lysinium D-hydrogen tartrate and L-lysinium L-hydrogen tartrate. During crystallization, L-lysine preferentially interacts with D-tartaric acid to form a complex when DL-tartaric acid is used in the experiment. The anions and the cations aggregate into separate alternating layers in four of the five complexes. In bis(L-argininium) L-tartrate, the amino acid layers are interconnected by individual tartrate ions which do not interact among themselves. The aggregation of argininium ions in the DL- and the L-arginine complexes is remarkably similar, which is in turn similar to those observed in other dicarboxylic acid complexes of arginine. Thus, argininium ions have a tendency to assume similar patterns of aggregation, which are largely unaffected by a change in the chemistry of partner molecules such as the introduction of hydroxyl groups or a change in chirality or stoichiometry. On the contrary, the lysinium ions exhibit fundamentally different aggregation patterns in the DL-DL complexes on the one hand and L-D and L-L complexes on the other. Interestingly, the pattern in the L-D complex is similar to that in the L-L complex. The lysinium ions in the DL-DL complex exhibit an aggregation pattern similar to those observed in the DL-lysine complexes involving other dicarboxylic acids. Thus, the effect of change in the chirality of a subset of the component complexes could be profound or marginal, in an unpredictable manner. The relevant crystal structures appear to indicate that the preference of L-lysine for D-tartaric acid is perhaps caused by chiral discrimination resulting from the amplification of a small energy difference.

  3. Supramolecular Luminescence from Oligofluorenol-Based Supramolecular Polymer Semiconductors

    Directory of Open Access Journals (Sweden)

    Guang-Wei Zhang

    2013-11-01

    Full Text Available Supramolecular luminescence stems from non-covalent exciton behaviors of active π-segments in supramolecular entities or aggregates via intermolecular forces. Herein, a π-conjugated oligofluorenol, containing self-complementary double hydrogen bonds, was synthesized using Suzuki coupling as a supramolecular semiconductor. Terfluorenol-based random supramolecular polymers were confirmed via concentration-dependent nuclear magnetic resonance (NMR and dynamic light scattering (DLS. The photoluminescent spectra of the TFOH-1 solution exhibit a green emission band (g-band at approximately ~520 nm with reversible features, as confirmed through titration experiments. Supramolecular luminescence of TFOH-1 thin films serves as robust evidence for the aggregates of g-band. Our results suggest that the presence of polyfluorene ketone defects is a sufficient condition, rather than a sufficient-necessary condition for the g-band. Supramolecular electroluminescence will push organic devices into the fields of supramolecular optoelectronics, spintronics, and mechatronics.

  4. Controlling and imaging biomimetic self-assembly

    Science.gov (United States)

    Aliprandi, Alessandro; Mauro, Matteo; de Cola, Luisa

    2016-01-01

    The self-assembly of chemical entities represents a very attractive way to create a large variety of ordered functional structures and complex matter. Although much effort has been devoted to the preparation of supramolecular nanostructures based on different chemical building blocks, an understanding of the mechanisms at play and the ability to monitor assembly processes and, in turn, control them are often elusive, which precludes a deep and comprehensive control of the final structures. Here the complex supramolecular landscape of a platinum(II) compound is characterized fully and controlled successfully through a combination of supramolecular and photochemical approaches. The supramolecular assemblies comprise two kinetic assemblies and their thermodynamic counterpart. The monitoring of the different emission properties of the aggregates, used as a fingerprint for each species, allows the real-time visualization of the evolving self-assemblies. The control of multiple supramolecular pathways will help the design of complex systems in and out of their thermodynamic equilibrium.

  5. Coordination polymers with the chiral ligand N-p-tolylsulfonyl-L-glutamic acid: Influence of metal ions and different bipyridine ligands on structural chirality

    International Nuclear Information System (INIS)

    Four new polymers, namely [Ni(-tsgluO)(2,4'-bipy)2(H2O)2]n.5nH2O (1), [Co(-tsgluO)(2,4'-bipy)2(H2O)2]n.5nH2O (2), [Ni(-tsgluO)(4,4'-bipy)]n.0.5nH2O (3), and [Co(-tsgluO)(4,4'-bipy)]n.0.5nH2O (4), where tsgluO2-=(+)-N-p-tolylsulfonyl-L-glutamate dianion, 2,4'-bipy=2,4'-bipyridine, and 4,4'-bipy=4,4'-bipyridine, have been prepared and structurally characterized. Compounds 1 and 2 are isostructural and mononuclear, and crystallize in the acentric monoclinic space group Cc, forming 1D chain structures. Compound 3 is also mononuclear, but crystallizes in the chiral space group P21, forming a homochiral 2D architecture. In contrast to the other complexes, compound 4 crystallizes in the space group P-1 and is composed of binuclear [Co2O6N2]n4- units, which give rise to a 2D bilayer framework. Moreover, compounds 1, 2, and 4 self-assemble to form 3D supramolecular structures through π-π stacking and hydrogen-bonding interactions, while compound 3 is further hydrogen-bonded to form 3D frameworks. We have demonstrated the influence of the central metal and bipyridine ligands on the framework chirality of the coordination complexes. - Graphical abstract: Four novel polymers based on a chiral ligand were prepared and structurally characterized; it represents the first series of investigations about the effect of central metals and bipyridine ligands on framework chirality.

  6. Supramolecular Nanoparticles for Molecular Diagnostics and Therapeutics

    Science.gov (United States)

    Chen, Kuan-Ju

    Over the past decades, significant efforts have been devoted to explore the use of various nanoparticle-based systems in the field of nanomedicine, including molecular imaging and therapy. Supramolecular synthetic approaches have attracted lots of attention due to their flexibility, convenience, and modularity for producing nanoparticles. In this dissertation, the developmental story of our size-controllable supramolecular nanoparticles (SNPs) will be discussed, as well as their use in specific biomedical applications. To achieve the self-assembly of SNPs, the well-characterized molecular recognition system (i.e., cyclodextrin/adamantane recognition) was employed. The resulting SNPs, which were assembled from three molecular building blocks, possess incredible stability in various physiological conditions, reversible size-controllability and dynamic disassembly that were exploited for various in vitro and in vivo applications. An advantage of using the supramolecular approach is that it enables the convenient incorporation of functional ligands onto SNP surface that confers functionality ( e.g., targeting, cell penetration) to SNPs. We utilized SNPs for molecular imaging such as magnetic resonance imaging (MRI) and positron emission tomography (PET) by introducing reporter systems (i.e., radio-isotopes, MR contrast agents, and fluorophores) into SNPs. On the other hand, the incorporation of various payloads, including drugs, genes and proteins, into SNPs showed improved delivery performance and enhanced therapeutic efficacy for these therapeutic agents. Leveraging the powers of (i) a combinatorial synthetic approach based on supramolecular assembly and (ii) a digital microreactor, a rapid developmental pathway was developed that is capable of screening SNP candidates for the ideal structural and functional properties that deliver optimal performance. Moreover, SNP-based theranostic delivery systems that combine reporter systems and therapeutic payloads into a

  7. Supramolecular interactions in the solid state

    Directory of Open Access Journals (Sweden)

    Giuseppe Resnati

    2015-11-01

    Full Text Available In the last few decades, supramolecular chemistry has been at the forefront of chemical research, with the aim of understanding chemistry beyond the covalent bond. Since the long-range periodicity in crystals is a product of the directionally specific short-range intermolecular interactions that are responsible for molecular assembly, analysis of crystalline solids provides a primary means to investigate intermolecular interactions and recognition phenomena. This article discusses some areas of contemporary research involving supramolecular interactions in the solid state. The topics covered are: (1 an overview and historical review of halogen bonding; (2 exploring non-ambient conditions to investigate intermolecular interactions in crystals; (3 the role of intermolecular interactions in morphotropy, being the link between isostructurality and polymorphism; (4 strategic realisation of kinetic coordination polymers by exploiting multi-interactive linker molecules. The discussion touches upon many of the prerequisites for controlled preparation and characterization of crystalline materials.

  8. Supramolecular interactions in the solid state.

    Science.gov (United States)

    Resnati, Giuseppe; Boldyreva, Elena; Bombicz, Petra; Kawano, Masaki

    2015-11-01

    In the last few decades, supramolecular chemistry has been at the forefront of chemical research, with the aim of understanding chemistry beyond the covalent bond. Since the long-range periodicity in crystals is a product of the directionally specific short-range intermolecular interactions that are responsible for molecular assembly, analysis of crystalline solids provides a primary means to investigate intermolecular interactions and recognition phenomena. This article discusses some areas of contemporary research involving supramolecular interactions in the solid state. The topics covered are: (1) an overview and historical review of halogen bonding; (2) exploring non-ambient conditions to investigate intermolecular interactions in crystals; (3) the role of intermolecular interactions in morphotropy, being the link between isostructurality and polymorphism; (4) strategic realisation of kinetic coordination polymers by exploiting multi-interactive linker molecules. The discussion touches upon many of the prerequisites for controlled preparation and characterization of crystalline materials.

  9. Porphyrinic supramolecular daisy chains incorporating pillar[5]arene-viologen host-guest interactions

    KAUST Repository

    Fathalla, Maher

    2015-05-18

    A porphyrin functionalised with pillar[5]arene and a viologen at its 5- and 15-meso positions assembles in a head-to-tail manner, producing linear supramolecular daisy chains in dichloromethane. At high concentrations, it forms an organogel which has been investigated by electron microscopy and rheological measurements, paving the way for the preparation of other functional supramolecular assemblies which harness viologen"⊂" pillararene host-guest interactions.

  10. Glassy carbon electrodes modified with supramolecular assemblies generated by π-stacking of Cobalt (II) octaethylporphyrins. A 4 electrons-dioxygen reduction reaction occurring at positive potentials

    International Nuclear Information System (INIS)

    A new method of modifying previously oxidized glassy carbon electrode (GCE) using commercial cobalt (II) porphyrin is proposed. This novel assembly presents a significant improvement in terms of electroactivity towards the oxygen reduction reaction (ORR), as compared to other reported systems. The device reduces molecular oxygen at positive potentials involving 4 electrons, as corroborated by kinetic studies. In addition, a 46 mV per decade Tafel slope was obtained, evidencing that the ORR mechanism would involve a chemical step following the first electron transfer, or, the rate determining step would be the transfer of a second electron. Concomitant to this, studies with different metalloporphirins were accomplished in order to compare the central metal ion effect. Morphological studies conducted using Atomic Force Microscopy (AFM) consistent with the proposed modification based on the structural changes found on the GCE surface, as well as to the obtained differences of roughness parameters (Rq values). Finally, it was demonstrated that this new system is better, in terms of electroactivity, than previously reported arrays

  11. Isotopic chirality

    Energy Technology Data Exchange (ETDEWEB)

    Floss, H.G. [Univ. of Washington, Seattle, WA (United States)

    1994-12-01

    This paper deals with compounds that are chiral-at least in part, due to isotope substitution-and their use in tracing the steric course of enzyme reaction in vitro and in vivo. There are other applications of isotopically chiral compounds (for example, in analyzing the steric course of nonenzymatic reactions and in probing the conformation of biomolecules) that are important but they will not be discussed in this context.

  12. Chiral Superconductors

    OpenAIRE

    Kallin, Catherine; Berlinsky, John

    2015-01-01

    Chiral superconductivity is a striking quantum phenomenon in which an unconventional superconductor spontaneously develops an angular momentum and lowers its free energy by eliminating nodes in the gap. It is a topologically non-trivial state and, as such, exhibits distinctive topological modes at surfaces and defects. In this paper we discuss the current theory and experimental results on chiral superconductors, focusing on two of the best-studied systems, Sr2RuO4, which is thought to be a c...

  13. Supramolecular Chemistry in Water

    NARCIS (Netherlands)

    Oshovsky, Gennady V.; Reinhoudt, David N.; Verboom, Willem

    2007-01-01

    Supramolecular chemistry in water is a constantly growing research area because noncovalent interactions in aqueous media are important for obtaining a better understanding and control of the major processes in nature. This Review offers an overview of recent advances in the area of water-soluble sy

  14. Supramolecular bacterial systems

    NARCIS (Netherlands)

    Sankaran, Shrikrishnan

    2015-01-01

    For nearly over a decade, a wide variety of dynamic and responsive supramolecular architectures have been investigated and developed to address biological systems. Since the non-covalent interactions between individual molecular components in such architectures are similar to the interactions found

  15. Chiral crystal of a C2v-symmetric 1,3-diazaaulene derivative showing efficient optical second harmonic generation

    KAUST Repository

    Ma, Xiaohua

    2011-03-01

    Achiral nonlinear optical (NLO) chromophores 1,3-diazaazulene derivatives, 2-(4â€-aminophenyl)-6-nitro-1,3-diazaazulene (APNA) and 2-(4â€-N,N-diphenylaminophenyl)-6-nitro-1,3-diazaazulene (DPAPNA), were synthesized with high yield. Despite the moderate static first hyperpolarizabilities (β0) for both APNA [(136 ± 5) à - 10-30 esu] and DPAPNA [(263 ± 20) à - 10-30 esu], only APNA crystal shows a powder efficiency of second harmonic generation (SHG) of 23 times that of urea. It is shown that the APNA crystallization driven cooperatively by the strong H-bonding network and the dipolar electrostatic interactions falls into the noncentrosymmetric P2 12121 space group, and that the helical supramolecular assembly is solely responsible for the efficient SHG response. To the contrary, the DPAPNA crystal with centrosymmetric P-1 space group is packed with antiparalleling dimmers, and is therefore completely SHG-inactive. 1,3-Diazaazulene derivatives are suggested to be potent building blocks for SHG-active chiral crystals, which are advantageous in high thermal stability, excellent near-infrared transparency and high degree of designing flexibility. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011 Optical crystals based on 1,3-diazaazulene derivatives are reported as the first example of organic nonlinear optical crystal whose second harmonic generation activity is found to originate solely from the chirality of their helical supramolecular orientation. The strong H-bond network forming between adjacent choromophores is found to act cooperatively with dipolar electrostatic interactions in driving the chiral crystallization of this material. Copyright © 2011 Wiley Periodicals, Inc.

  16. From structure to function via complex supramolecular dendrimer systems.

    Science.gov (United States)

    Sun, Hao-Jan; Zhang, Shaodong; Percec, Virgil

    2015-06-21

    This tutorial review summarizes strategies elaborated for the discovery and prediction of programmed primary structures derived from quasi-equivalent constitutional isomeric libraries of self-assembling dendrons, dendrimers and dendronized polymers. These libraries demonstrate an 82% predictability, defined as the percentage of similar primary structures resulting in at least one conserved supramolecular shape with internal order. A combination of structural and retrostructural analysis that employs methodologies transplanted from structural biology, adapted to giant supramolecular assemblies was used for this process. A periodic table database of programmed primary structures was elaborated and used to facilitate the emergence of a diversity of functions in complex dendrimer systems via first principles. Assemblies generated by supramolecular and covalent polymer backbones were critically compared. Although by definition complex functional systems cannot be designed, this tutorial hints to a methodology based on database analysis principles to facilitate design principles that may help to mediate an accelerated emergence of chemical, physical and most probably also societal, political and economic complex systems on a shorter time scale and lower cost than by the current methods. This tutorial review is limited to the simplest, synthetically most accessible self-assembling minidendrons, minidendrimers and polymers dendronized with minidendrons that are best analyzed and elucidated at molecular, supramolecular and theoretical levels, and most used in other laboratories. These structures are all interrelated, and their principles expand in a simple way to their higher generations. PMID:25325787

  17. Chemical Equilibrium in Supramolecular Systems as Studied by NMR Spectrometry

    Science.gov (United States)

    Gonzalez-Gaitano, Gustavo; Tardajos, Gloria

    2004-01-01

    Undergraduate students are required to study the chemical balance in supramolecular assemblies constituting two or more interacting species, by using proton NMR spectrometry. A good knowledge of physical chemistry, fundamentals of chemical balance, and NMR are pre-requisites for conducting this study.

  18. Supramolecular Filaments Containing a Fixed 41% Paclitaxel Loading

    OpenAIRE

    Lin, Ran; Cheetham, Andrew G.; Zhang, Pengcheng; Lin, Yi-An; Cui, Honggang

    2013-01-01

    We report here the self-assembly of a rationally designed paclitaxel drug amphiphile into well-defined supramolecular filaments that possess a fixed 41% paclitaxel loading. These filaments can exert effective cytotoxicity against a number of cell lines comparable to that of free paclitaxel.

  19. Protein Camouflage: Supramolecular Anion Recognition by Ubiquitin.

    Science.gov (United States)

    Mallon, Madeleine; Dutt, Som; Schrader, Thomas; Crowley, Peter B

    2016-04-15

    Progress in the field of bio-supramolecular chemistry, the bottom-up assembly of protein-ligand systems, relies on a detailed knowledge of molecular recognition. To address this issue, we have characterised complex formation between human ubiquitin (HUb) and four supramolecular anions. The ligands were: pyrenetetrasulfonic acid (4PSA), p-sulfonato-calix[4]arene (SCLX4), bisphosphate tweezers (CLR01) and meso-tetrakis (4-sulfonatophenyl)porphyrin (TPPS), which vary in net charge, size, shape and hydrophobicity. All four ligands induced significant changes in the HSQC spectrum of HUb. Chemical shift perturbations and line-broadening effects were used to identify binding sites and to quantify affinities. Supporting data were obtained from docking simulations. It was found that these weakly interacting ligands bind to extensive surface patches on HUb. A comparison of the data suggests some general indicators for the protein-binding specificity of supramolecular anions. Differences in binding were observed between the cavity-containing and planar ligands. The former had a preference for the arginine-rich, flexible C terminus of HUb. PMID:26818656

  20. Chiral symmetry

    CERN Document Server

    Ecker, G

    1999-01-01

    Broken chiral symmetry has become the basis for a unified treatment of hadronic interactions at low energies. After reviewing mechanisms for spontaneous chiral symmetry breaking, I outline the construction of the low--energy effective field theory of the Standard Model called chiral perturbation theory. The loop expansion and the renormalization procedure for this nonrenormalizable quantum field theory are developed. Evidence for the standard scenario with a large quark condensate is presented, in particular from high--statistics lattice calculations of the meson mass spectrum. Elastic pion--pion scattering is discussed as an example of a complete calculation to O(p^6) in the low--energy expansion. The meson--baryon system is the subject of the last lecture. After a short summary of heavy baryon chiral perturbation theory, a recent analysis of pion--nucleon scattering to O(p^3) is reviewed. Finally, I describe some very recent progress in the chiral approach to the nucleon--nucleon interaction.

  1. Supramolecular chemistry-general principles and selected examples from anion recognition and metallosupramolecular chemistry.

    Science.gov (United States)

    Albrecht, Markus

    2007-12-01

    This review gives an introduction into supramolecular chemistry describing in the first part general principles, focusing on terms like noncovalent interaction, molecular recognition, self-assembly, and supramolecular function. In the second part those will be illustrated by simple examples from our laboratories. Supramolecular chemistry is the science that bridges the gap between the world of molecules and nanotechnology. In supramolecular chemistry noncovalent interactions occur between molecular building blocks, which by molecular recognition and self-assembly form (functional) supramolecular entities. It is also termed the "chemistry of the noncovalent bond." Molecular recognition is based on geometrical complementarity based on the "key-and-lock" principle with nonshape-dependent effects, e.g., solvatization, being also highly influential. Self-assembly leads to the formation of well-defined aggregates. Hereby the overall structure of the target ensemble is controlled by the symmetry features of the certain building blocks. Finally, the aggregates can possess special properties or supramolecular functions, which are only found in the ensemble but not in the participating molecules. This review gives an introduction on supramolecular chemistry and illustrates the fundamental principles by recent examples from our group.

  2. Constructing supramolecular nanostructure by hydrogen-bonding

    Institute of Scientific and Technical Information of China (English)

    LI YiBao; ZENG QingDao; WANG ZhiHui; QI GuiCun; GUAN Li; FAN XiaoLin; WANG Chen

    2008-01-01

    The diquinoxalino (2.3-2'.3'-a.c) phenazine (DQP), containing 6 nitrogen atoms, was synthesized, and its adsorption and self-assembling behavior on highly oriented pyrolytic graphite (HOPG) was studied by scanning tunneling microscopy (STM) under ambient conditions. With 1,14-tetradecanedioic acid as a bridge, uniform two-dimensional arrays of 1,14-tetradecanedioic acid/DQP nanostrueture were suc-cessfully fabricated. The result illustrates that it is possible to construct and control supramolecular nanostructure by intermolecular hydrogen-bonding.

  3. Supramolecular chemistry of cucurbiturils

    International Nuclear Information System (INIS)

    The main principles of the design of supramolecular compounds starting from organic macrocyclic cavitands, viz., cucurbit[n]urils [C6H6N4O2]n (n=5-10), are considered. The presence of the hydrophobic inner cavity along with polar carbonyl groups forming the cucurbituril portals are responsible for high specificity of the formation of host-guest complexes. The unique ability of cucurbiturils to act as synthetic molecular containers is discussed. In these containers, bimolecular reactions between specially selected guests proceed with high regio- and stereoselectivity. The review surveys new data on the directed construction of supramolecular organic-inorganic compounds through the formation of an extensive network of hydrogen bonds between the portal oxygen atoms of cucurbiturils and water molecules of metal aqua complexes. The bibliography includes 108 references.

  4. Punctuated Chirality

    Science.gov (United States)

    Gleiser, Marcelo; Thorarinson, Joel; Walker, Sara Imari

    2008-12-01

    Most biomolecules occur in mirror, or chiral, images of each other. However, life is homochiral: proteins contain almost exclusively L-amino acids, while only D-sugars appear in RNA and DNA. The mechanism behind this fundamental asymmetry of life remains an open problem. Coupling the spatiotemporal evolution of a general autocatalytic polymerization reaction network to external environmental effects, we show through a detailed statistical analysis that high intensity and long duration events may drive achiral initial conditions towards chirality. We argue that life’s homochirality resulted from sequential chiral symmetry breaking triggered by environmental events, thus extending the theory of punctuated equilibrium to the prebiotic realm. Applying our arguments to other potentially life-bearing planetary platforms, we predict that a statistically representative sampling will be racemic on average.

  5. Punctuated Chirality

    CERN Document Server

    Gleiser, Marcelo; Walker, Sara Imari

    2008-01-01

    Most biomolecules occur in mirror, or chiral, images of each other. However, life is homochiral: proteins contain almost exclusively levorotatory (L) amino acids, while only dextrorotatory (R) sugars appear in RNA and DNA. The mechanism behind this fundamental asymmetry of life remains an open problem. Coupling the spatiotemporal evolution of a general autocatalytic polymerization reaction network to external environmental effects, we show through a detailed statistical analysis that high intensity and long duration events may drive achiral initial conditions towards chirality. We argue that life's homochirality resulted from sequential chiral symmetry breaking triggered by environmental events, thus extending the theory of punctuated equilibrium to the prebiotic realm. Applying our arguments to other potentially life-bearing planetary platforms, we predict that a statistically representative sampling will be racemic on average.

  6. A supramolecular tubular nanoreactor.

    Science.gov (United States)

    Li, Zhi-Qiang; Zhang, Ying-Ming; Chen, Yong; Liu, Yu

    2014-07-01

    The extremely strong noncovalent complexation between the rigid host of phthalocyanine-bridged β-cyclodextrins and the amphiphilic guest carboxylated porphyrin is employed to construct a hollow tubular structure as a supramolecular nanoreactor. A representative coupling reaction occurs in the hydrophobic interlayers of the tubular walls in pure water at room temperature, leading to an enhancement of ten times higher reaction rate without any adverse effect on catalytic activity and conversion. PMID:24890802

  7. Supramolecular chemistry in silico

    OpenAIRE

    Sheehan, Rosemary; Cragg, Peter J.

    2008-01-01

    Abstract Computational protocols capable of modelling supramolecular complexes have been evaluated. The complexation of cations by crown ethers and quaternary ammonium ions by an oxacalix[3]arene are presented as examples. In the latter case reliable qualitative results were obtained using the semi-empirical PM3 method where guest LUMO and electrostatic potential energies have been shown to correlate with experimental binding data. The optimal method for more accurate results combi...

  8. Supramolecular bacterial systems

    OpenAIRE

    Sankaran, Shrikrishnan

    2015-01-01

    For nearly over a decade, a wide variety of dynamic and responsive supramolecular architectures have been investigated and developed to address biological systems. Since the non-covalent interactions between individual molecular components in such architectures are similar to the interactions found in living systems, it was possible to integrate chemically-synthesized and naturally-occurring components to create platforms with interesting bioactive properties. Bacterial cells and recombinant ...

  9. Flourishing Development in Supramolecular Chemistry%蓬勃发展的超分子化学

    Institute of Scientific and Technical Information of China (English)

    张来新; 朱海云

    2014-01-01

    This paper briefly introduces the concepts and applications of supramolecular chemistry.Emphases are put on three parts:①selective anion recognition of supramolecular self-assembly;②synthesis and applications of supramolecular metal complexes;③synthesis and applications of supramolecular receptor in medicine.Future de-velopments of supramolecular chemistry are prospected in the end.%本文简要介绍了超分子化学的概念及应用,详细综述了:①超分子自组装对阴离子的选择性识别作用;②超分子金属配合物的合成及应用;③医用超分子受体的合成及应用。并对超分子化学的发展进行了展望。

  10. Anion induced modulation of self-assembly and optical properties in urea end-capped oligo(p-phenylenevinylene)s.

    Science.gov (United States)

    Varghese, Reji; George, Subi J; Ajayaghosh, Ayyappanpillai

    2005-02-01

    The non-emissive supramolecular assembly of urea end-capped oligo(p-phenylenevinylene) flourophores turned strongly emissive in the presence of tetrabutylammonium flouride which has implications in the anion controlled design of supramolecular architectures with tunable emission properties.

  11. Constitutional dynamic chemistry: bridge from supramolecular chemistry to adaptive chemistry.

    Science.gov (United States)

    Lehn, Jean-Marie

    2012-01-01

    Supramolecular chemistry aims at implementing highly complex chemical systems from molecular components held together by non-covalent intermolecular forces and effecting molecular recognition, catalysis and transport processes. A further step consists in the investigation of chemical systems undergoing self-organization, i.e. systems capable of spontaneously generating well-defined functional supramolecular architectures by self-assembly from their components, thus behaving as programmed chemical systems. Supramolecular chemistry is intrinsically a dynamic chemistry in view of the lability of the interactions connecting the molecular components of a supramolecular entity and the resulting ability of supramolecular species to exchange their constituents. The same holds for molecular chemistry when the molecular entity contains covalent bonds that may form and break reversibility, so as to allow a continuous change in constitution by reorganization and exchange of building blocks. These features define a Constitutional Dynamic Chemistry (CDC) on both the molecular and supramolecular levels.CDC introduces a paradigm shift with respect to constitutionally static chemistry. The latter relies on design for the generation of a target entity, whereas CDC takes advantage of dynamic diversity to allow variation and selection. The implementation of selection in chemistry introduces a fundamental change in outlook. Whereas self-organization by design strives to achieve full control over the output molecular or supramolecular entity by explicit programming, self-organization with selection operates on dynamic constitutional diversity in response to either internal or external factors to achieve adaptation.The merging of the features: -information and programmability, -dynamics and reversibility, -constitution and structural diversity, points to the emergence of adaptive and evolutive chemistry, towards a chemistry of complex matter.

  12. NMR investigation of the complexation and chiral discrimination of pyrazole sulfonamide derivatives with cyclodextrins.

    Science.gov (United States)

    Rogez-Florent, Tiphaine; Azaroual, Nathalie; Goossens, Laurence; Goossens, Jean-François; Danel, Cécile

    2015-01-22

    The complexes formed between six original chiral diaryl-pyrazole sulfonamide derivatives, displaying poor solubility, and various CDs (native α-, β- and γ-CDs, hydroxypropylated HP-β-CD, methylated Me-β-CD or amino NH2-β-CD) were studied by 1D and 2D (1)H NMR at physiological pH in order to determine their apparent binding constant, stoichiometry and structure of the supramolecular assembly. For some complexes, the spectra obtained for free racemic compound and for racemic compound in presence of CD indicate a splitting of signal(s). Additional experiments with pure enantiomer and enriched enantiomer allow us to attribute this behavior to chiral discrimination. The complexing ability of the native β-CD towards our compounds appears the most promising since binding values around 7×10(2)M(-1) are obtained. The two-dimensional ROESY ((1)H-(1)H) experiments prove the inclusion of the aliphatic part of the compound in the CD cavity. It is noteworthy that this inclusion occurs via the smaller opening of the cavity.

  13. Toward Modular Analysis of Supramolecular Protein Assemblies.

    Science.gov (United States)

    Kim, Jaehoon; Kim, Jin-Gyun; Yun, Giseok; Lee, Phill-Seung; Kim, Do-Nyun

    2015-09-01

    Despite recent advances in molecular simulation technologies, analysis of high-molecular-weight structures is still challenging. Here, we propose an automated model reduction procedure aiming to enable modular analysis of these structures. It employs a component mode synthesis for the reduction of finite element protein models. Reduced models may consist of real biological subunits or artificial partitions whose dynamics is described using the degrees of freedom at the substructural interfaces and a small set of dominant vibrational modes only. Notably, the proper number of dominant modes is automatically determined using a novel estimator for eigenvalue errors without calculating the reference eigensolutions of the full model. The performance of the proposed approach is thoroughly investigated by analyzing 50 representative structures including a crystal structure of GroEL and an electron density map of a ribosome. PMID:26575921

  14. On Chiral Space Groups and Chiral Molecules

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    This note explains the relationship (as well as the absence of a relationship) between chiral space groups and chiral molecules (which have absolute configurations). For a chiral molecule, which must crystallize in a chiral space group, the outcome of the absolute configuration determination must be linked to some other properties of the chiral crystal such as its optical activity for the observation to the relevant.

  15. Self-assembly of multinuclear coordination species with chiral bipyridine ligands: silver complexes of 5,6-CHIRAGEN(o,m,p-xylidene) ligands and equilibrium behaviour in solution.

    Science.gov (United States)

    Mamula, O; Monlien, F J; Porquet, A; Hopfgartner, G; Merbach, A E; von Zelewsky, A

    2001-01-19

    The complexation reactions between Ag- and a series of enantiopure ligands belonging to the CHIRAGEN (from CHIRAlity GENerator) family (L1, L2, L3, based on (-)-5,6-pinene bipyridine) have been studied in solution. It has been shown that the length of the bridge plays a fundamental role in the self-assembly processes leading to different compounds: mononuclear complexes (with L3), mixtures of polynuclear complexes (with L2) and circular helicates (with L 1). Although the absolute configuration of the chiral centres in all three ligands is the same, the metal-centred chirality of L3 (delta) is inverted with respect to that in the other two complexes with L1 and L2 (delta). The metal configuration is thus opposite in the mononuclear complex with respect to the polynuclear species. Detailed thermodynamic studies were carried out for the Ag+ and L1 ligand system by 1H and 109Ag NMR spectroscopy (as a function of concentration, temperature and pressure). At low temperature and high pressure, the [Ag6L1(6)]6+ hexanuclear circular helicate forms a tetranuclear circular helicate [Ag4L1(4)]4+: 2[Ag6L1(6)]6+ 3 [Ag4L1(4)]4+. The thermodynamics parameters, obtained by temperature and pressure variation, have the following values: K298 = (8.7 +/- 0.7) x 10(-5) mol x kg(-1), deltaHo = -15.65 +/- 0.8 kJ x mol(-1), deltaSo = -130.2 +/- 3 J x mol(-1) x K(-1) and deltaVo(256 K)= -160 +/- 12 cm3 x mol(-1). The reaction volume calculated according to Connolly's method indicates that the calculated structure of [Ag4L1(4)]4+ is plausible. Both the signs and large magnitudes of deltaSo and deltaVo are counterintuitive, yet can be understood by modelling methods. PMID:11271539

  16. Self-assembly behaviour of conjugated terthiophene surfactants in water

    NARCIS (Netherlands)

    van Rijn, Patrick; Janeliunas, Dainius; Brizard, Aurelie M.; Stuart, Marc C. A.; Koper, Ger J. M.; Eelkema, Rienk; van Esch, Jan H.

    2011-01-01

    Conjugated self-assembled systems in water are of great interest because of their potential application in biocompatible supramolecular electronics, but so far their supramolecular chemistry remains almost unexplored. Here we present amphiphilic terthiophenes as a general self-assembling platform fo

  17. Synthesis and photophysical studies of chiral helical macrocyclic scaffolds via coordination-driven self-assembly of 1,8,9,16-tetraethynyltetraphenylene. formation of monometallic platinum(II) and dimetallic platinum(II)-ruthenium(II) complexes.

    Science.gov (United States)

    Lin, Fang; Peng, Hai-Yan; Chen, Jing-Xing; Chik, David T W; Cai, Zongwei; Wong, Keith M C; Yam, Vivian W W; Wong, Henry N C

    2010-11-24

    This paper is concerned with the synthesis and reactions of enantiopure 1,8,9,16-tetraethynyltetraphenylene (3). We obtained 3 in 34% yield through four steps starting from 1,8,9,16-tetrahydroxytetraphenylene (2a) via a functional group interconversion strategy. On the basis of this chiral "helical" building block, three rigid helical macrocycles 14, 15, and 22 were designed. Complexes 14 and 15 were constructed via coordination-driven self-assembly with platinum(II) complexes 8 and 9b, while 22 cannot be obtained successfully. Then macrocycle 28 was designed on the structural basis of 22 to which octyl chains were introduced, in the hope of improving the solubility of the complex. Macrocycle 28 was finally formed and was characterized by NMR spectroscopy, elemental analysis, and electrospray mass spectrometry. For the enantiopure 15 and 28, circular dichroism (CD) spectra also exhibited chiral properties. Complexes 27 and 28 both exhibited an intense emission band at 621 nm in acetonitrile at 298 K upon excitation at λ > 420 nm. PMID:21033663

  18. Molecular self-assembly advances and applications

    CERN Document Server

    Dequan, Alex Li

    2012-01-01

    In the past several decades, molecular self-assembly has emerged as one of the main themes in chemistry, biology, and materials science. This book compiles and details cutting-edge research in molecular assemblies ranging from self-organized peptide nanostructures and DNA-chromophore foldamers to supramolecular systems and metal-directed assemblies, even to nanocrystal superparticles and self-assembled microdevices

  19. Supramolecular polymer transformation: a kinetic study.

    Science.gov (United States)

    Baram, Jonathan; Weissman, Haim; Rybtchinski, Boris

    2014-10-16

    Investigation of supramolecular kinetics is essential for elucidating self-assembly mechanisms. Recently, we reported on a noncovalent system involving a bolaamphiphilic perylene diimide dimer that is kinetically trapped in water but can rearrange into a different, more ordered assembly in water/THF mixtures ( Angew. Chem. Int. Ed. 2014 , 53 , 4123 ). Here we present a kinetic mechanistic study of this process by employing UV-vis spectroscopy. The transformation exhibits a rapid decrease in the red-shifted absorption band, which is monitored in order to track the kinetics at different temperatures (15-50 °C) and concentrations. Fitting the data with the 1D KJMA (Kolmogorov-Johnson-Mehl-Avrami) model affords the activation parameters. The latter as well as seeding experiments indicates that the transformation occurs without the detachment of covalent units, and that hydration dynamics plays a significant role in nucleation, with entropic factors being dominant. Switching off the transformation, and the formation of off-pathway intermediates were observed upon heating to temperatures above 55 °C. These insights into kinetically controlled supramolecular polymer transformations provide mechanistic information that is needed for a fundamental understanding of noncovalent processes, and the rational design of noncovalent materials. PMID:25238603

  20. Freestanding 3D supramolecular particle bridges: fabrication and mechanical behavior.

    Science.gov (United States)

    Ling, Xing Yi; Phang, In Yee; Schönherr, Holger; Reinhoudt, David N; Vancso, G Julius; Huskens, Jurriaan

    2009-06-01

    Freestanding particle bridges with controlled composition and macroscopic robustness are demonstrated by the use of supramolecular nanoparticle assembly. Self-assembly of nanoparticles, templating, and supramolecular glue infiltration are combined to form stable and ordered three-dimensional polystyrene particle composites on a polydimethylsiloxane stamp. Freestanding hybrid polystyrene nanoparticle bridges are obtained by transfer printing of the hybrid structures onto topographically patterned substrates via host-guest interactions. The mechanical robustness and rigidity of the particle bridges can be controlled by manipulating the layer-by-layer cycles of supramolecular glues of gold nanoparticles and dendrimers. Atomic force microscopy-based microbending results, in particular the location and force-dependent deflection behavior, confirm that the particle bridge fulfills the classical supported-beam characteristics. As estimated from classical beam theory, the bending moduli of the particle bridges vary between 0.8 and 1.1 GPa, depending on the degree of filling by the supramolecular glues. Failure analysis on the particle structure indicates linear elastic behavior and a plastic deformation upon failure. PMID:19373830

  1. Versatile types of polysaccharide-based supramolecular polycation/pDNA nanoplexes for gene delivery

    Science.gov (United States)

    Hu, Yang; Zhao, Nana; Yu, Bingran; Liu, Fusheng; Xu, Fu-Jian

    2014-06-01

    Different polysaccharide-based supramolecular polycations were readily synthesized by assembling multiple β-cyclodextrin-cored star polycations with an adamantane-functionalized dextran via host-guest interaction in the absence or presence of bioreducible linkages. Compared with nanoplexes of the starting star polycation and pDNA, the supramolecular polycation/pDNA nanoplexes exhibited similarly low cytotoxicity, improved cellular internalization and significantly higher gene transfection efficiencies. The incorporation of disulfide linkages imparted the supramolecular polycation/pDNA nanoplexes with the advantage of intracellular bioreducibility, resulting in better gene delivery properties. In addition, the antitumor properties of supramolecular polycation/pDNA nanoplexes were also investigated using a suicide gene therapy system. The present study demonstrates that the proper assembly of cyclodextrin-cored polycations with adamantane-functionalized polysaccharides is an effective strategy for the production of new nanoplex delivery systems.Different polysaccharide-based supramolecular polycations were readily synthesized by assembling multiple β-cyclodextrin-cored star polycations with an adamantane-functionalized dextran via host-guest interaction in the absence or presence of bioreducible linkages. Compared with nanoplexes of the starting star polycation and pDNA, the supramolecular polycation/pDNA nanoplexes exhibited similarly low cytotoxicity, improved cellular internalization and significantly higher gene transfection efficiencies. The incorporation of disulfide linkages imparted the supramolecular polycation/pDNA nanoplexes with the advantage of intracellular bioreducibility, resulting in better gene delivery properties. In addition, the antitumor properties of supramolecular polycation/pDNA nanoplexes were also investigated using a suicide gene therapy system. The present study demonstrates that the proper assembly of cyclodextrin-cored polycations

  2. Punctuated Chirality

    OpenAIRE

    Gleiser, Marcelo; Thorarinson, Joel; Walker, Sara Imari

    2008-01-01

    Most biomolecules occur in mirror, or chiral, images of each other. However, life is homochiral: proteins contain almost exclusively levorotatory (L) amino acids, while only dextrorotatory (R) sugars appear in RNA and DNA. The mechanism behind this fundamental asymmetry of life remains an open problem. Coupling the spatiotemporal evolution of a general autocatalytic polymerization reaction network to external environmental effects, we show through a detailed statistical analysis that high int...

  3. Chiral streamers

    Energy Technology Data Exchange (ETDEWEB)

    Zou, Dandan; Cao, Xin [State Key Laboratory of Advanced Electromagnetic Engineering and Technology, Huazhong University of Science and Technology, Wuhan, Hubei 430074 (China); Lu, Xinpei, E-mail: luxinpei@hotmail.com [State Key Laboratory of Advanced Electromagnetic Engineering and Technology, Huazhong University of Science and Technology, Wuhan, Hubei 430074 (China); IFSA Collaborative Innovation Center, Shanghai Jiao Tong University, Shanghai 200240 (China); Ostrikov, Kostya [School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology, Brisbane, Queensland 4000 (Australia); Comonwealth Scientific and Industrial Research Organization, P.O. Box 218, Sydney, New South Wales 2070 (Australia)

    2015-10-15

    The interaction of time-varying electromagnetic fields and solid, liquid, and gaseous matter may lead to electrical breakdown phenomena through the excitation of ionization waves or streamers that control the dynamics of localized plasma propagation through the media. The streamers usually propagate along straight lines, either between random points in space or along a certain direction in a guided mode. Here, we report on a new type of plasma discharges with the regular helical propagation pattern driven by a pulsed dc voltage in nitrogen at sub-atmospheric-pressure conditions. The helical guided streamers, named chiral streamers or chi-streamers, are excited without any external magnetic fields, which commonly cause helical plasma motions. We also demonstrate a hybrid propagation mode involving the interchangeable chiral streamers and the straight-line propagating plasmas. High-speed, time-resolved optical imaging reveals that the chiral streamers and the hybrid patterns are made of spatially localized discrete plasma bullets, similar to the straight-line guided streamers. These results may enable effective control of propagation of confined plasmas and electromagnetic energy along pre-determined, potentially deterministic paths, which have important implications for the development of next-generation plasma-based radiation sources, communication devices, and medical treatments.

  4. Chiral streamers

    Science.gov (United States)

    Zou, Dandan; Cao, Xin; Lu, Xinpei; Ostrikov, Kostya Ken

    2015-10-01

    The interaction of time-varying electromagnetic fields and solid, liquid, and gaseous matter may lead to electrical breakdown phenomena through the excitation of ionization waves or streamers that control the dynamics of localized plasma propagation through the media. The streamers usually propagate along straight lines, either between random points in space or along a certain direction in a guided mode. Here, we report on a new type of plasma discharges with the regular helical propagation pattern driven by a pulsed dc voltage in nitrogen at sub-atmospheric-pressure conditions. The helical guided streamers, named chiral streamers or chi-streamers, are excited without any external magnetic fields, which commonly cause helical plasma motions. We also demonstrate a hybrid propagation mode involving the interchangeable chiral streamers and the straight-line propagating plasmas. High-speed, time-resolved optical imaging reveals that the chiral streamers and the hybrid patterns are made of spatially localized discrete plasma bullets, similar to the straight-line guided streamers. These results may enable effective control of propagation of confined plasmas and electromagnetic energy along pre-determined, potentially deterministic paths, which have important implications for the development of next-generation plasma-based radiation sources, communication devices, and medical treatments.

  5. Fragmentation and Coagulation in Supramolecular (Co)polymerization Kinetics.

    Science.gov (United States)

    Markvoort, Albert J; Eikelder, Huub M M Ten; Hilbers, Peter A J; de Greef, Tom F A

    2016-04-27

    The self-assembly of molecular building blocks into one-dimensional supramolecular architectures has opened up new frontiers in materials science. Due to the noncovalent interactions between the monomeric units, these architectures are intrinsically dynamic, and understanding their kinetic driving forces is key to rationally programming their morphology and function. To understand the self-assembly dynamics of supramolecular polymerizations (SP), kinetic models based on aggregate growth by sequential monomer association and dissociation have been analyzed. However, fragmentation and coagulation events can also play a role, as evident from studies on peptide self-assembly and the fact that aggregations can be sensitive to mechanical agitations. Here, we analyze how fragmentation and coagulation events influence SP kinetics by theoretical analysis of self-assembling systems of increasing complexity. Our analysis starts with single-component systems in which aggregates are able to grow via an isodesmic or cooperative nucleation-elongation mechanism. Subsequently, equilibration dynamics in cooperative two-component supramolecular copolymerizations are investigated. In the final part, we reveal how aggregate growth in the presence of competing, kinetically controlled pathways is influenced by fragmentation and coagulation reactions and reveal how seed-induced growth can give rise to block copolymers. Our analysis shows how fragmentation and coagulation reactions are able to modulate SP kinetics in ways that are highly system dependent. PMID:27163054

  6. Supramolecular spin valves.

    Science.gov (United States)

    Urdampilleta, M; Klyatskaya, S; Cleuziou, J-P; Ruben, M; Wernsdorfer, W

    2011-07-01

    Magnetic molecules are potential building blocks for the design of spintronic devices. Moreover, molecular materials enable the combination of bottom-up processing techniques, for example with conventional top-down nanofabrication. The development of solid-state spintronic devices based on the giant magnetoresistance, tunnel magnetoresistance and spin-valve effects has revolutionized magnetic memory applications. Recently, a significant improvement of the spin-relaxation time has been observed in organic semiconductor tunnel junctions, single non-magnetic molecules coupled to magnetic electrodes have shown giant magnetoresistance and hybrid devices exploiting the quantum tunnelling properties of single-molecule magnets have been proposed. Herein, we present an original spin-valve device in which a non-magnetic molecular quantum dot, made of a single-walled carbon nanotube contacted with non-magnetic electrodes, is laterally coupled through supramolecular interactions to TbPc(2) single-molecule magnets (Pc=phthalocyanine). Their localized magnetic moments lead to a magnetic field dependence of the electrical transport through the single-walled carbon nanotube, resulting in magnetoresistance ratios up to 300% at temperatures less than 1 K. We thus demonstrate the functionality of a supramolecular spin valve without magnetic leads. Our results open up prospects of new spintronic devices with quantum properties. PMID:21685902

  7. Ostwald's rule of stages governs structural transitions and morphology of dipeptide supramolecular polymers.

    Science.gov (United States)

    Levin, Aviad; Mason, Thomas O; Adler-Abramovich, Lihi; Buell, Alexander K; Meisl, George; Galvagnion, Celine; Bram, Yaron; Stratford, Samuel A; Dobson, Christopher M; Knowles, Tuomas P J; Gazit, Ehud

    2014-01-01

    The self-assembly of molecular building blocks into nano- and micro-scale supramolecular architectures has opened up new frontiers in polymer science. Such supramolecular species not only possess a rich set of dynamic features as a consequence of the non-covalent nature of their core interactions, but also afford unique structural characteristics. Although much is now known about the manner in which such structures adopt their morphologies and size distributions in response to external stimuli, the kinetic and thermodynamic driving forces that lead to their transformation from soluble monomeric species into ordered supramolecular entities have remained elusive. Here we focus on Boc-diphenylalanine, an archetypical example of a peptide with a high propensity towards supramolecular self-organization, and describe the pathway through which it forms a range of nano-assemblies with different structural characteristics. Our results reveal that the nucleation process is multi-step in nature and proceeds by Ostwald's step rule through which coalescence of soluble monomers leads to the formation of nanospheres, which then undergo ripening and structural conversions to form the final supramolecular assemblies. We characterize the structures and thermodynamics of the different phases involved in this process and reveal the intricate nature of the transitions that can occur between discrete structural states of this class of supramolecular polymers. PMID:25391268

  8. Ostwald’s rule of stages governs structural transitions and morphology of dipeptide supramolecular polymers

    Science.gov (United States)

    Levin, Aviad; Mason, Thomas O.; Adler-Abramovich, Lihi; Buell, Alexander K.; Meisl, George; Galvagnion, Celine; Bram, Yaron; Stratford, Samuel A.; Dobson, Christopher M.; Knowles, Tuomas P. J.; Gazit, Ehud

    2014-11-01

    The self-assembly of molecular building blocks into nano- and micro-scale supramolecular architectures has opened up new frontiers in polymer science. Such supramolecular species not only possess a rich set of dynamic features as a consequence of the non-covalent nature of their core interactions, but also afford unique structural characteristics. Although much is now known about the manner in which such structures adopt their morphologies and size distributions in response to external stimuli, the kinetic and thermodynamic driving forces that lead to their transformation from soluble monomeric species into ordered supramolecular entities have remained elusive. Here we focus on Boc-diphenylalanine, an archetypical example of a peptide with a high propensity towards supramolecular self-organization, and describe the pathway through which it forms a range of nano-assemblies with different structural characteristics. Our results reveal that the nucleation process is multi-step in nature and proceeds by Ostwald’s step rule through which coalescence of soluble monomers leads to the formation of nanospheres, which then undergo ripening and structural conversions to form the final supramolecular assemblies. We characterize the structures and thermodynamics of the different phases involved in this process and reveal the intricate nature of the transitions that can occur between discrete structural states of this class of supramolecular polymers.

  9. S-Shaped Conformation of the Quaterthiophene Molecular Backbone in Two-Dimensional Bisterpyridine-Derivative Self-Assembled Nanoarchitecture.

    Science.gov (United States)

    Kervella, Yann; Shilova, Ekaterina; Latil, Sylvain; Jousselme, Bruno; Silly, Fabien

    2015-12-15

    The conformation and the two-dimensional self-assembly of 4'-(3',4″-dihexyloxy-5,2':5',2″:5″,2‴-quaterthien-2,5‴-diyl)-bis(2,2':6',2″-terpyridine) molecules are theoretically and experimentally investigated. This molecular building block forms a hydrogen-bonded chiral supramolecular nanoarchitecture on graphite at the solid/liquid interface. Scanning tunneling microscopy (STM) shows that the molecule adopts an S-shaped conformation in this structure. DFTB+ calculations reveal that this conformation is not the lowest-energy conformation. The molecular nanoarchitecture appears to be stabilized by hydrogen bonding as well as van der Waals interactions. I-, L-, and D-shaped molecular conformations are, however, locally observed at the domain boundary, but these conformations do not self-assemble into organized 2D structures. PMID:26624809

  10. Transfer-printing and host-guest properties of 3D supramolecular particle structures.

    Science.gov (United States)

    Ling, Xing Yi; Phang, In Yee; Reinhoudt, David N; Vancso, G Julius; Huskens, Jurriaan

    2009-04-01

    Mechanically robust and crystalline supramolecular particle structures have been constructed by decoupling nanoparticle assembly and supramolecular glue infiltration into a sequential process. First, beta-cyclodextrin (CD)-functionalized polystyrene particles (d approximately 500 nm) were assembled on a CD-functionalized surface via convective assembly to form highly ordered, but mechanically unstable, particle crystals. Subsequently, the crystals were infiltrated by a solution of adamantyl-functionalized dendrimers, functioning as a supramolecular glue to bind neighboring particles together and to couple the entire particle crystal to the CD surface, both in a noncovalent manner. The supramolecular particle crystals are highly robust, as witnessed by their ability to withstand agitation by ultrasonication. When assembled on a poly(dimethylsiloxane) (PDMS) stamp, the dendrimer-infiltrated particle crystals could be transfer-printed onto a CD-functionalized target surface. By variation of the geometry and size of the PDMS stamps, single particle lines, interconnected particle rings, and V-shaped particle assemblies were obtained. The particle structures served as 3D receptors for the binding of (multiple) complementary guest molecules, indicating that the supramolecular host functionalities of the particle crystals were retained throughout the fabrication process. PMID:20356024

  11. Helical chirality induction of expanded porphyrin analogues

    Indian Academy of Sciences (India)

    Jun-Ichiro Setsune

    2012-11-01

    Expanded porphyrin analogues with unique figure-eight conformation were prepared by way of useful pyrrole intermediates such as bis(azafulvene)s and 2-borylpyrrole. Supramolecular chirogenesis of cyclooctapyrrole O1 with 32-cycloconjugation was successfully applied to determine absolute configuration of chiral carboxylic acids. Dinuclear CuII complex of cyclooctapyrrole O2 with interrupted -conjugation was resolved by HPLC into enantiomers and their helical handedness was determined by theoretical simulation of their CD spectral pattern. Enantioselective induction of helicity in the metal helicate formation in the presence of a chiral promoter was demonstrated by using ()-(+)-1-(1-phenyl)ethylamine that favoured , helicity. Dinuclear CoII complexes of cyclotetrapyrroletetrapyridine O3 were found to be substitution labile and pick up amino acid anions in water. Those amino acid complexes of O3Co2 were rendered to adopt a particular unidirectional helical conformation preferentially depending on the ligated amino acid anion.

  12. Cristais líquidos colestéricos: a quiralidade revela as suas cores Cholesteric liquid crstals: chirality shows its colors

    Directory of Open Access Journals (Sweden)

    Fernando Ely

    2007-01-01

    Full Text Available Chirality deeply impacts the macroscopic properties on all scales of the universe from elemental particles through biological structures up to astronomic systems. Specifically, chiral liquid crystals give rise to self-organized macrostructures with unparalleled properties. Here we present easy experiments with a special class of chiral liquid crystals that show temperature-induced selective reflection of light (thermochromic effect. Understanding this thermochromic effect allows undergraduate students better realize important properties of super and supramolecular systems.

  13. Chiral geometry in multiple chiral doublet bands

    CERN Document Server

    Zhang, Hao

    2015-01-01

    The chiral geometry of the multiple chiral doublet bands with identical configuration is discussed for different triaxial deformation parameters $\\gamma$ in the particle rotor model with $\\pi h_{11/2}\\otimes \

  14. Orientation-Dependent Handedness and Chiral Design

    Science.gov (United States)

    Efrati, Efi; Irvine, William T. M.

    2014-01-01

    Chirality occupies a central role in fields ranging from biological self-assembly to the design of optical metamaterials. The definition of chirality, as given by Lord Kelvin, associates chirality with the lack of mirror symmetry: the inability to superpose an object on its mirror image. While this definition has guided the classification of chiral objects for over a century, the quantification of handed phenomena based on this definition has proven elusive, if not impossible, as manifest in the paradox of chiral connectedness. In this work, we put forward a quantification scheme in which the handedness of an object depends on the direction in which it is viewed. While consistent with familiar chiral notions, such as the right-hand rule, this framework allows objects to be simultaneously right and left handed. We demonstrate this orientation dependence in three different systems—a biomimetic elastic bilayer, a chiral propeller, and optical metamaterial—and find quantitative agreement with chirality pseudotensors whose form we explicitly compute. The use of this approach resolves the existing paradoxes and naturally enables the design of handed metamaterials from symmetry principles.

  15. Prion-like nanofibrils of small molecules (PriSM): A new frontier at the intersection of supramolecular chemistry and cell biology

    OpenAIRE

    Zhou, Jie; Du, Xuewen; Xu, Bing

    2015-01-01

    Formed by non-covalent interactions and not defined at genetic level, the assemblies of small molecules in biology are complicated and less explored. A common morphology of the supramolecular assemblies of small molecules is nanofibrils, which coincidentally resembles the nanofibrils formed by proteins such as prions. So these supramolecular assemblies are termed as prion-like nanofibrils of small molecules (PriSM). Emerging evidence from several unrelated fields over the past decade implies ...

  16. Simple chiral urea gelators, (R)- and (S)-2-heptylurea: their gelling ability enhanced by chirality.

    Science.gov (United States)

    Kim, Jong-Uk; Schollmeyer, Dieter; Brehmer, Martin; Zentel, Rudolf

    2011-05-15

    We present the first report on the synthesis of chiral ureas, (R)- and (S)-2-heptylurea, and their gelling behaviors. The ureas were prepared by the reactions of chiral amines and phenyl carbamate in the presence of triethylamine. On cooling from homogeneous solutions, the chiral ureas form gels in water and various nonpolar organic solvents, such as cyclohexane, toluene, and tetrachloromethane, while the racemate gelatinize only toluene and tetrachloromethane among the solvents we examined. The gelling ability of the enantiomeric urea is higher than the racemate, as the critical gelling concentrations in toluene, for example, were 0.2% and 0.7% (wt/wt), respectively. The enhanced gelling ability of the enantiomeric ureas is due to the 1D supramolecular structure formed during gelation. In contrast, the racemate crystallizes into two-dimensional lamellae, where the (R)- and (S)-2-heptylurea exist alternatingly in a plane (P2(1)/c space group). Powder X-ray diffraction pattern of the enantiomeric urea showed that it has a different crystal lattice from that of the racemate, implying that the steric effect by the methyl group at the chiral center prevents the pure enantiomers from having 2D hydrogen bonding networks, which lead to sheet-like structures for the racemate and the achiral analog. Thus the pure enantiomers self-organize into one-dimensional fibrous structures. The simplicity and the ambidextrous gelling behaviors of the chiral ureas in forming both hydrogels and organogels present numerous possibilities for future applications. PMID:21396655

  17. Supramolecular Polymers in DNA Nanotechnology

    OpenAIRE

    Vyborna, Yuliia; Vybornyi, Mykhailo; Häner, Robert

    2016-01-01

    Creation of biocompatible functional materials is an important task in supramolecular chemistry. In this contribution, we report on noncovalent synthesis of DNA-grafted supramolecular polymers (SPs). DNA-grafted SPs enable programmed arrangement of oligonucleotides in a regular, tightly packed one-dimensional array. Further interactions of DNA-grafted SPs with complementary DNA strands leads to the formation of networks through highly cooperative G-C blunt-end stacking interactions. The struc...

  18. The Resolution of Chiral, Tetrahedral M4L6 Metal-LigandHosts

    Energy Technology Data Exchange (ETDEWEB)

    Davis, Anna V.; Fiedler, Dorothea; Ziegler, Marco; Terpin,Andreas; Raymond, Kenneth N.

    2007-08-28

    The supramolecular metal-ligand assemblies of M{sub 4}1{sub 6} stoichiometry are chiral (M = Ga{sup III}, Al{sup III}, In{sup III}, Fe{sup III}, Ti{sup IV}, or Ge{sup IV}, H{sub 4}1 = N,N'-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene). The resolution process of {Delta}{Delta}{Delta}{Delta}- and {Lambda}{Lambda}{Lambda}{Lambda}-[M{sub 4}1{sub 6}]{sup 12-} by the chiral cation s-nicotinium (S-nic{sup +}) is described for the Ga{sup III}, Al{sup III}, and Fe{sup III} assemblies, and the resolution is shown to be proton dependent. From a methanol solution of M(acac){sub 3}, H{sub 4}1, S-nicI, and KOH, the {Delta}{Delta}{Delta}{Delta}-KH{sub 3}(S-nic){sub 7}[(S-nic) {contained_in}M{sub 4}1{sub 6}] complexes precipitate, and the {Lambda}{Lambda}{Lambda}{Lambda}-K{sub 6}(S-nic){sub 5}[(S-nic) {contained_in} M{sub 4}1{sub 6}] complexes subsequently can be isolated from the supernatant. Ion exchange enables the isolation of the (NEt{sub 4}{sup +}){sub 12}, (NMe{sub 4}{sup +}){sub 12} and K{sub 12}{sup +} salts of the resolved structures, which have been characterized by CD and NMR spectroscopies. Resolution can also be accomplished with one equivalent of NEt{sub 4}{sup +} blocking the cavity interior, demonstrating that external binding sites are responsible for the difference in S-nic{sup +} enantiomer interactions. Circular dichroism data demonstrate that the (NMe{sub 4}{sup +}){sub 12} and (NEt{sub 4}{sup +}){sub 12} salts of the resolved [Ga{sub 4}1{sub 6}]{sup 12-} and [Al{sub 4}1{sub 6}]{sup 12-} structures retain their chirality over extended periods of time (>20 d) at room temperature; heating the (NEt{sub 4}{sup +}){sub 12}[Ga{sub 4}1{sub 6}] assembly to 75 C also had no effect on its CD spectrum. Finally, experiments with the resolved K{sub 12}[Ga{sub 4}1{sub 6}] assemblies point to the role of a guest in stabilizing the resolved framework.

  19. Probing the Intact Cluster Catalysis Concept by Tetrahedral Clusters With Framework Chirality

    Institute of Scientific and Technical Information of China (English)

    G. Süss-Fink; L. Vieille-Petit

    2005-01-01

    @@ 1Results and Discussion In order to bring evidence for or against the hypothesis of catalytic hydrogenation by intact trinuclear arene ruthenium clusters containing an oxo cap, the substrate being hydrogenated inside the hydrophobic pocket spanned by the three arene ligands ("supramolecular cluster catalysis")[1], we synthesized cationic Ru3O clusters (See Fig. 1) with three different arene ligands (intrinsically chiral tetrahedra).

  20. Supramolecular nanofibrils inhibit cancer progression in vitro and in vivo

    OpenAIRE

    Kuang, Yi; Du, Xuewen; Zhou, Jie; Xu, Bing

    2014-01-01

    The recent discovery of the inverse comorbidity between cancer and Alzheimer’s disease implies that one may use amyloids to inhibit tumors. During the conversion of a dipeptide segment (Phe-Phe) in β-amyloid into a supramolecular hydrogelator, we obtained a small molecule (1) that can self-assembly into nanofibrils via multiple intermolecular hydrogen bonding and aromatic-aromatic interactions. Interestingly, while the monomers of 1 are innocuous, the nanofibrils formed by 1 can selectively i...

  1. Transfer of chirality from adsorbed chiral molecules to the substrates highlighted by circular dichroism in angle-resolved valence photoelectron spectroscopy

    DEFF Research Database (Denmark)

    Contini, G.; Turchini, S.; Sanna, Simone;

    2012-01-01

    state, that the presence of molecular chiral domains induces asymmetry in the interaction with the substrate and locally transfers the chiral character to the underlying metal atoms participating in the adsorption process; combined information related to the asymmetry of the initial electronic state......Studies of self-assembled chiral molecules on achiral metallic surfaces have mostly focused on the determination of the geometry of adsorbates and their electronic structure. The aim of this paper is to provide direct information on the chirality character of the system and on the chirality......, which is expected to be chiral, and the final electronic state, which locally probes the asymmetry of the potential, has been obtained. Identification of chirality in the adsorption footprint sheds new light on the transfer of chirality from a chiral modifier to a symmetric metal surface and represents...

  2. Supramolecular cyclodextrin-based drug nanocarriers.

    Science.gov (United States)

    Simões, Susana M N; Rey-Rico, Ana; Concheiro, Angel; Alvarez-Lorenzo, Carmen

    2015-04-14

    Supramolecular systems formed by the binding of several cyclodextrins (CDs) to polymers or lipids, either via non-covalent or covalent links, open a wide range of possibilities for the delivery of active substances. CDs can perform as multifunctionalizable cores to which very diverse (macro)molecules and drugs can be conjugated. Grafting with amphiphilic molecules can lead to nanoassemblies exhibiting a variety of architectures. CDs can also polymerize with other CDs or can be used to functionalize preexisting polymers to form polymers/networks with enhanced capability to form inclusion complexes. Alternatively, CDs can be exploited as transient cross-linkers to form poly(pseudo)rotaxane-based networks or zipper-like assemblies. Combination of mutifunctionality and complexation ability of CDs has been shown to be useful to develop depot-like formulations and colloidal nanocarriers with improved performances regarding easiness of administration, protection of the encapsulated substances, control of the delivery rate, and cell interactions. The aim of this review is to provide an overall view of the diversity of designs of CD-based supramolecular nanosystems with a special focus on the advances materialized in the last five years, including clinical trials. PMID:25679097

  3. Supramolecular approach to new inkjet printing inks.

    Science.gov (United States)

    Hart, Lewis R; Harries, Josephine L; Greenland, Barnaby W; Colquhoun, Howard M; Hayes, Wayne

    2015-04-29

    Electronically complementary, low molecular weight polymers that self-assemble through tunable π-π stacking interactions to form extended supramolecular polymer networks have been developed for inkjet printing applications and successfully deposited using three different printing techniques. Sequential overprinting of the complementary components results in supramolecular network formation through complexation of π-electron rich pyrenyl or perylenyl chain-ends in one component with π-electron deficient naphthalene diimide residues in a chain-folding polyimide. The complementary π-π stacked polymer blends generate strongly colored materials as a result of charge-transfer absorption bands in the visible spectrum, potentially negating the need for pigments or dyes in the ink formulation. Indeed, the final color of the deposited material can be tailored by varying the end-groups of the π-electron rich polymer component. Piezoelectric printing techniques were employed in a proof of concept study to allow characterization of the materials deposited, and a thermal inkjet printer adapted with imaging software enabled in situ analysis of the ink drops as they formed and of their physical properties. Finally, continuous inkjet printing allowed greater volumes of material to be deposited, on a variety of different substrate surfaces, and demonstrated the utility and versatility of this novel type of ink for industrial applications.

  4. Chirality imprinting and direct asymmetric reaction screening using a stereodynamic Brønsted/Lewis acid receptor.

    Science.gov (United States)

    Bentley, Keith W; Proano, Daysi; Wolf, Christian

    2016-01-01

    Molecular recognition, activation and dynamic self-assembly with Brønsted and Lewis acids play a central role across the chemical sciences including catalysis, crystal engineering, supramolecular architectures and drug design. Despite this general advance, the utilization of the corresponding binding motifs for fast and robust quantitative chemosensing of chiral compounds in a complicate matrix has remained challenging. Here we show that a stereodynamic probe carrying complementary boronic acid and urea units achieves this goal with hydroxy carboxylic acids. Synergistic dual-site binding and instantaneous chirality imprinting result in characteristic ultraviolet and CD readouts that allow instantaneous determination of the absolute configuration, enantiomeric excess and concentration of the target compound even in complex mixtures. The robustness and practicality of this strategy for high-throughput screening purposes is demonstrated. Comprehensive sensing of only 0.5 mg of a crude reaction mixture of an asymmetric reduction eliminates cumbersome work-up protocols and minimizes analysis time, labour and waste production. PMID:27549926

  5. Supramolecular Drug Delivery Systems Based on Water-Soluble Pillar[n]arenes.

    Science.gov (United States)

    Wu, Xuan; Gao, Lei; Hu, Xiao-Yu; Wang, Leyong

    2016-06-01

    Supramolecular drug delivery systems (SDDSs), including various kinds of nanostructures that are assembled by reversible noncovalent interactions, have attracted considerable attention as ideal drug carriers owing to their fascinating ability to undergo dynamic switching of structure, morphology, and function in response to various external stimuli, which provides a flexible and robust platform for designing and developing functional and smart supramolecular nano-drug carriers. Pillar[n]arenes represent a new generation of macrocyclic hosts, which have unique structures and excellent properties in host-guest chemistry. This account describes recent progress in our group to develop pillararene-based stimuli-responsive supramolecular nanostructures constructed by reversible host-guest interactions for controllable anticancer drug delivery. The potential applications of these supramolecular drug carriers in cancer treatment and the fundamental questions facing SDDSs are also discussed.

  6. 蓬勃发展的超分子化学∗%Flourishing Development in Supramolecular Chemistry

    Institute of Scientific and Technical Information of China (English)

    张来新; 陈琦

    2015-01-01

    The generation,development,and applications of supramolecular chemistry were briefly introduced in this paper. Emphases were put on from three parts:① synthesis and applications of new supramolecular com-pounds;② constructions of supramolecular polymer self-assembly and their applications;③ preparation and me-dicinal use of new supramolecular compounds. Future developments of supramolecular chemistry were prospected in the end.%简要介绍了超分子化学的产生发展及应用。详细介绍了:①新型超分子化合物的合成及应用;②超分子聚合物自组装的构筑及应用;③新型超分子化合物的制备及药用。并对超分子化学的发展进行了展望。

  7. Supramolecular fabrication of multilevel graphene-based gas sensors with high NO2 sensibility

    Science.gov (United States)

    Chen, Zhuo; Umar, Ahmad; Wang, Shiwei; Wang, Yao; Tian, Tong; Shang, Ying; Fan, Yuzun; Qi, Qi; Xu, Dongmei; Jiang, Lei

    2015-05-01

    This study reports the supramolecular assembly of a silver nanoparticle-naphthalene-1-sulphonic acid-reduced graphene oxide composite (Ag-NA-rGO) and its utilization to fabricate a highly sensitive and selective gas sensor. The prepared supramolecular assembly acted not only as a non-covalent functionalization platform (π-π interaction) but was also an excellent scaffold to fabricate a highly sensitive and selective low concentration NO2 gas sensor. The prepared composites were characterized using several techniques, which revealed that the graphene sheets were dispersed as ultrathin monolayers with a uniform distribution of silver nanoparticles. The fabricated multilevel structure exhibited an excellent sensing performance, i.e. 2.8 times better, towards 10 ppm NO2 compared to the NA-rGO and rGO based sensors. Apart from its high sensitivity, superior reversibility and selectivity, the prepared supramolecular assembly exhibited an outstanding linear response over the large concentration range from 1 ppm to 10 ppm. The obtained results demonstrate that the prepared supramolecular assembly holds great potential in the fabrication of efficient and effective low-concentration NO2 gas sensors for practical applications.This study reports the supramolecular assembly of a silver nanoparticle-naphthalene-1-sulphonic acid-reduced graphene oxide composite (Ag-NA-rGO) and its utilization to fabricate a highly sensitive and selective gas sensor. The prepared supramolecular assembly acted not only as a non-covalent functionalization platform (π-π interaction) but was also an excellent scaffold to fabricate a highly sensitive and selective low concentration NO2 gas sensor. The prepared composites were characterized using several techniques, which revealed that the graphene sheets were dispersed as ultrathin monolayers with a uniform distribution of silver nanoparticles. The fabricated multilevel structure exhibited an excellent sensing performance, i.e. 2.8 times better

  8. Chiral mirrors

    Energy Technology Data Exchange (ETDEWEB)

    Plum, Eric, E-mail: erp@orc.soton.ac.uk [Optoelectronics Research Centre and Centre for Photonic Metamaterials, University of Southampton, Highfield, Southampton SO17 1BJ (United Kingdom); Zheludev, Nikolay I., E-mail: niz@orc.soton.ac.uk [Optoelectronics Research Centre and Centre for Photonic Metamaterials, University of Southampton, Highfield, Southampton SO17 1BJ (United Kingdom); The Photonics Institute and Centre for Disruptive Photonic Technologies, Nanyang Technological University, Singapore 637378 (Singapore)

    2015-06-01

    Mirrors are used in telescopes, microscopes, photo cameras, lasers, satellite dishes, and everywhere else, where redirection of electromagnetic radiation is required making them arguably the most important optical component. While conventional isotropic mirrors will reflect linear polarizations without change, the handedness of circularly polarized waves is reversed upon reflection. Here, we demonstrate a type of mirror reflecting one circular polarization without changing its handedness, while absorbing the other. The polarization-preserving mirror consists of a planar metasurface with a subwavelength pattern that cannot be superimposed with its mirror image without being lifted out of its plane, and a conventional mirror spaced by a fraction of the wavelength from the metasurface. Such mirrors enable circularly polarized lasers and Fabry-Pérot cavities with enhanced tunability, gyroscopic applications, polarization-sensitive detectors of electromagnetic waves, and can be used to enhance spectroscopies of chiral media.

  9. Electrochemical redox responsive polymeric micelles formed from amphiphilic supramolecular brushes.

    Science.gov (United States)

    Feng, Anchao; Yan, Qiang; Zhang, Huijuan; Peng, Liao; Yuan, Jinying

    2014-05-11

    The end-decorated homopolymer poly(ε-caprolactone)-ferrocene threaded onto a β-cyclodextrin-functionalized main-chain polymer can form a class of amphiphilic noncovalent graft copolymers based on the host-guest interactions of the terminal groups on the side chains. These new supramolecular polymer brushes can further self-assemble into micellar aggregates that exhibit reversible assembly and disassembly behavior under an electrochemical redox trigger, which opens up a new route to building dynamic block copolymer topologies. PMID:24681929

  10. Physical Organic Chemistry of Supramolecular Polymers

    Science.gov (United States)

    Serpe, Michael J.; Craig, Stephen L.

    2008-01-01

    Unlike the case of traditional covalent polymers, the entanglements that determine properties of supramolecular polymers are defined by very specific, intermolecular interactions. Recent work using modular molecular platforms to probe the mechanisms underlying mechanical response of supramolecular polymers is reviewed. The contributions of supramolecular kinetics, thermodynamics, and conformational flexibility to supramolecular polymer properties in solutions of discrete polymers, in networks, and at interfaces, are described. Molecule-to-material relationships are established through methods reminiscent of classic physical organic chemistry. PMID:17279638

  11. Supramolecular Packing Controls H₂ Photocatalysis in Chromophore Amphiphile Hydrogels.

    Science.gov (United States)

    Weingarten, Adam S; Kazantsev, Roman V; Palmer, Liam C; Fairfield, Daniel J; Koltonow, Andrew R; Stupp, Samuel I

    2015-12-01

    Light harvesting supramolecular assemblies are potentially useful structures as components of solar-to-fuel conversion materials. The development of these functional constructs requires an understanding of optimal packing modes for chromophores. We investigated here assembly in water and the photocatalytic function of perylene monoimide chromophore amphiphiles with different alkyl linker lengths separating their hydrophobic core and the hydrophilic carboxylate headgroup. We found that these chromophore amphiphiles (CAs) self-assemble into charged nanostructures of increasing aspect ratio as the linker length is increased. The addition of salt to screen the charged nanostructures induced the formation of hydrogels and led to internal crystallization within some of the nanostructures. For linker lengths up to seven methylenes, the CAs were found to pack into 2D crystalline unit cells within ribbon-shaped nanostructures, whereas the nine methylene CAs assembled into long nanofibers without crystalline molecular packing. At the same time, the different molecular packing arrangements after charge screening led to different absorbance spectra, despite the identical electronic properties of all PMI amphiphiles. While the crystalline CAs formed electronically coupled H-aggregates, only CAs with intermediate linker lengths showed evidence of high intermolecular orbital overlap. Photocatalytic hydrogen production using a nickel-based catalyst was observed in all hydrogels, with the highest turnovers observed for CA gels having intermediate linker lengths. We conclude that the improved photocatalytic performance of the hydrogels formed by supramolecular assemblies of the intermediate linker CA molecules likely arises from improved exciton splitting efficiencies due to their higher orbital overlap. PMID:26593389

  12. Chiral Gravitational Waves from Chiral Fermions

    CERN Document Server

    Anber, Mohamed M

    2016-01-01

    We report on a new mechanism that leads to the generation of primordial chiral gravitational waves, and hence, the violation of the parity symmetry in the Universe. We show that nonperturbative production of fermions with a definite helicity is accompanied by the generation of chiral gravitational waves. This is a generic and model-independent phenomenon that can occur during inflation, reheating and radiation eras, and can leave imprints in the cosmic microwave background polarization and may be observed in future ground- and space-based interferometers. We also discuss a specific model where chiral gravitational waves are generated via the production of light chiral fermions during pseudoscalar inflation.

  13. Chiral solitons in a coupled double Peierls chain.

    Science.gov (United States)

    Cheon, Sangmo; Kim, Tae-Hwan; Lee, Sung-Hoon; Yeom, Han Woong

    2015-10-01

    Chiral edge states are the hallmark of two- and three-dimensional topological materials, but their one-dimensional (1D) analog has not yet been found. We report that the 1D topological edge states, solitons, of the charge density wave system of indium atomic wires self-assembled on a silicon surface have chirality. The system is described by a coupled double Peierls-dimerized atomic chain, where the interchain coupling induces dynamical sublattice symmetry breaking. This changes its topological symmetry from Z₂× Z₂to Z₄ and endows solitons with a chiral degree of freedom. Chiral solitons can produce quantized charge transport across the chain that is topologically protected and controllable by the soliton's chirality. Individual right- and left-chiral solitons in indium wires are directly identified by scanning tunneling microscopy. PMID:26450206

  14. Emergence of Chirality from Isotropic Interactions of Three Length Scales

    Science.gov (United States)

    Mkhonta, S. K.; Elder, K. R.; Huang, Zhi-Feng

    2016-05-01

    Chirality is known to play a pivotal role in determining material properties and functionalities. However, it remains a great challenge to understand and control the emergence of chirality and the related enantioselective process particularly when the building components of the system are achiral. Here we explore the generic mechanisms driving the formation of two-dimensional chiral structures in systems characterized by isotropic interactions and three competing length scales. We demonstrate that starting from isotropic and rotationally invariant interactions, a variety of chiral ordered patterns and superlattices with anisotropic but achiral units can self-assemble. The mechanisms for selecting specific states are related to the length-scale coupling and the selection of resonant density wave vectors. Sample phase diagrams and chiral elastic properties are identified. These findings provide a viable route for predicting chiral phases and selecting the desired handedness.

  15. 3D Printing of Biocompatible Supramolecular Polymers and their Composites.

    Science.gov (United States)

    Hart, Lewis R; Li, Siwei; Sturgess, Craig; Wildman, Ricky; Jones, Julian R; Hayes, Wayne

    2016-02-10

    A series of polymers capable of self-assembling into infinite networks via supramolecular interactions have been designed, synthesized, and characterized for use in 3D printing applications. The biocompatible polymers and their composites with silica nanoparticles were successfully utilized to deposit both simple cubic structures, as well as a more complex twisted pyramidal feature. The polymers were found to be not toxic to a chondrogenic cell line, according to ISO 10993-5 and 10993-12 standard tests and the cells attached to the supramolecular polymers as demonstrated by confocal microscopy. Silica nanoparticles were then dispersed within the polymer matrix, yielding a composite material which was optimized for inkjet printing. The hybrid material showed promise in preliminary tests to facilitate the 3D deposition of a more complex structure.

  16. 3D Printing of Biocompatible Supramolecular Polymers and their Composites.

    Science.gov (United States)

    Hart, Lewis R; Li, Siwei; Sturgess, Craig; Wildman, Ricky; Jones, Julian R; Hayes, Wayne

    2016-02-10

    A series of polymers capable of self-assembling into infinite networks via supramolecular interactions have been designed, synthesized, and characterized for use in 3D printing applications. The biocompatible polymers and their composites with silica nanoparticles were successfully utilized to deposit both simple cubic structures, as well as a more complex twisted pyramidal feature. The polymers were found to be not toxic to a chondrogenic cell line, according to ISO 10993-5 and 10993-12 standard tests and the cells attached to the supramolecular polymers as demonstrated by confocal microscopy. Silica nanoparticles were then dispersed within the polymer matrix, yielding a composite material which was optimized for inkjet printing. The hybrid material showed promise in preliminary tests to facilitate the 3D deposition of a more complex structure. PMID:26766139

  17. A small MRI contrast agent library of gadolinium(III)-encapsulated supramolecular nanoparticles for improved relaxivity and sensitivity**

    OpenAIRE

    Chen, Kuan-Ju; Wolahan, Stephanie M.; Wang, Hao; Hsu, Chao-Hsiung; Chang, Hsing-Wei; Durazo, Armando; Hwang, Lian-Pin; Garcia, Mitch A.; Jiang, Ziyue Karen; Wu, Lily; Lin, Yung-Ya; Tseng, Hsian-Rong

    2010-01-01

    We introduce a new category of nanoparticle-based T1 MRI contrast agents (CAs) by encapsulating paramagnetic chelated gadolinium(III), i.e., Gd3+·DOTA, through supramolecular assembly of molecular building blocks that carry complementary molecular recognition motifs, including adamantane (Ad) and β-cyclodextrin (CD). A small library of Gd3+·DOTA-encapsulated supramolecular nanoparticles (Gd3+·DOTA⊂SNPs) was produced by systematically altering the molecular building block mixing ratios. A broa...

  18. An electrochemical aptasensor for chiral peptide detection using layer-by-layer assembly of polyelectrolyte-methylene blue/polyelectrolyte-graphene multilayer

    Energy Technology Data Exchange (ETDEWEB)

    Qin Haixia; Liu Jiyang; Chen Chaogui [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Wang Jiahi, E-mail: jhwang@ciac.jl.cn [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Wang Erkang, E-mail: ekwang@ciac.jl.cn [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China)

    2012-01-27

    Highlights: Black-Right-Pointing-Pointer An electrochemical aptasensor for selective detection of peptide is constructed. Black-Right-Pointing-Pointer This aptasensor is based on grapheme multilayer via layer-by-layer assembly. Black-Right-Pointing-Pointer Such multilayer facilitates electron transfer and provides more adsorption sites. - Abstract: Here we demonstrate for the first time that by physically adsorbing aptamer onto conductive film assembled via alternate adsorption of graphene/polyelectrolyte and methylene blue/polyelectrolyte, a label-free electrochemical aptasensor with high sensitivity and selectivity for peptide detection is constructed. Graphene multilayer derived from layer-by-layer assembly has played significant roles in this sensing strategy: allowing accumulation of methylene blue, facilitating electron transfer and providing much more adsorption site. As compared to previous electrochemical aptasensors, the current sensor based on graphene multilayer alternated with electroactive molecule layer offers extremely high capability for sensitive detection of target without interference of environmental surrounding. This electroactive probe-confined graphene multilayer confers great flexibility to combine with differential pulse voltammetry (DPV) together. In the presence of target D entiomer of arginine vasopressin (D-VP), the binding of peptide to aptamer block the electron transfer process of MB, leading to decreased current peak of DPV. By this way, this electrochemical aptasensor based on electroactive molecule-intercalated graphene multilayer provide highly sensitive and specific detection of D-VP with the lowest detectable concentration of 1 ng mL{sup -1} and a wide detection range from 1 to 265 ng mL{sup -1}.

  19. 一种由[Ag(CN)2]-和Mn(Ⅱ)建筑块组装的三个三维网穿插的超分子配合物的结构和荧光性质%Three Interpenetrating 3D Related Networks and Luminescence of a Supramolecular Assembly Containing [Ag(CN)2]- and Mn(Ⅱ) Tectons

    Institute of Scientific and Technical Information of China (English)

    张建华; 董文

    2006-01-01

    Three interpenetrating 3D related networks of a cyano-bridged heterometallic supramolecular complexstate of 1 displays interesting luminescence determined by argentophilicity at room temperature. CCDC: 197205.

  20. Anomalous Chiral Superfluidity

    OpenAIRE

    Lublinsky, Michael(Physics Department, Ben-Gurion University of the Negev, Beer Sheva 84105, Israel); Zahed, Ismail

    2009-01-01

    We discuss both the anomalous Cartan currents and the energy-momentum tensor in a left chiral theory with flavour anomalies as an effective theory for flavored chiral phonons in a chiral superfluid with the gauged Wess-Zumino-Witten term. In the mean-field (leading tadpole) approximation the anomalous Cartan currents and the energy momentum tensor take the form of constitutive currents in the chiral superfluid state. The pertinence of higher order corrections and the Adler-Bardeen theorem is ...

  1. Selective Organic and Organometallic Reactions in Water-Soluble Host-Guest Supramolecular Systems

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael D.; Raymond, Kenneth N.; Bergman, Robert G.

    2008-02-16

    Inspired by the efficiency and selectivity of enzymes, synthetic chemists have designed and prepared a wide range of host molecules that can bind smaller molecules with their cavities; this area has become known as 'supramolecular' or 'host-guest' chemistry. Pioneered by Lehn, Cram, Pedersen, and Breslow, and followed up by a large number of more recent investigators, it has been found that the chemical environment in each assembly - defined by the size, shape, charge, and functional group availability - greatly influences the guest-binding characteristics of these compounds. In contrast to the large number of binding studies that have been carried out in this area, the exploration of chemistry - especially catalytic chemistry - that can take place inside supramolecular host cavities is still in its infancy. For example, until the work described here was carried out, very few examples of organometallic reactivity inside supramolecular hosts were known, especially in water solution. For that reason, our group and the group directed by Kenneth Raymond decided to take advantage of our complementary expertise and attempt to carry out metal-mediated C-H bond activation reactions in water-soluble supramolecular systems. This article begins by providing background from the Raymond group in supramolecular coordination chemistry and the Bergman group in C-H bond activation. It goes on to report the results of our combined efforts in supramolecular C-H activation reactions, followed by extensions of this work into a wider range of intracavity transformations.

  2. Photonic properties of organic molecular assemblies

    Science.gov (United States)

    Huggins, Kevin Edward

    1997-12-01

    This work attempts to characterize various photonic properties of spontaneously created organic molecular objects. A novel diacetylene monomer was synthesized and found to polymerize forming two-dimensional supramolecular assemblies. The two-dimensional structure self assembles when UV light generates polydiacetylene comb polymers. The material forms blue solid thin films which have been characterized by x-ray diffraction, infrared spectroscopy and Raman scattering. The photopolymerization rate of the monomer was followed by Raman scattering and was shown to be of second order. A reaction rate threshold was observed between 300 and 400mW of incident 647.1nm laser radiation where the reaction rate increased substantially. The material generates high third order nonlinear optical signals and have remarkable photochemical stability to 1064nm radiation from a Q-switched Nd:YAG laser. Upon heating to 62oC, the material turns bright red reversibly while maintaining its two-dimensional structure, characterized by differential scanning calorimetry. Heating to 180oC results in an irreversible color change to bright orange characterized by UV-Vis-NIR spectrophotometry. Variable temperature sum frequency generation experiments show that the third harmonic generation signals retain much of their original intensity through the thermochromic transitions. A system of novel rodcoil materials self assembles into mushroom-shaped supramolecular objects. These nanophase separated aggregates form oblique-plane superlattices exhibiting long-range order. The superlattice is composed of isolated crystallized rod domains surrounded by amorphous coil which form from simple solvent casting techniques. Second harmonic generation was used to confirm the polar head-to-tail stacking of the aggregates and to determine the average physical tilt of (5/pm 5)o of the aggregates relative to the film plane. A novel chiral oligomer synthesized in our group gave rise to interesting phase behavior

  3. Supramolecular assemblies of tetrafluoroterephthalic acid and N-heterocycles via various strong hydrogen bonds and weak Csbnd H⋯F interactions: Synthons cooperation, robust motifs and structural diversity

    Science.gov (United States)

    Hu, Yanjing; Hu, Hanbin; Li, Yingying; Chen, Ruixin; Yang, Yu; Wang, Lei

    2016-10-01

    A series of organic solid states including three salts, two co-crystals, and three hydrates based on tetrafluoroterephthalic acid (H2tfBDC) and N-bearing ligands (2,4-(1H,3H)-pyrimidine dione (PID), 2,4-dihydroxy-6-methyl pyrimidine (DHMPI), 2-amino-4,6-dimethyl pyrimidine (ADMPI), 2-amino-4,6-dimenthoxy pyrimidine (ADMOPI), 5,6-dimenthyl benzimidazole (DMBI), 2-aminobenzimidazole (ABI), 3,5-dimethyl pyrazole (DMP), and 3-cyanopyridine (3-CNpy)), namely, [(PID)2·(H2tfBDC)] (1), [(DHMPI)2·(H2tfBDC)] (2), [(H-ADMPI+)2·(tfBDC2-)·2(H2O)] (3), [(H-ADMOPI+)2·(tfBDC2-)·(H2O)] (4), [(H-DMBI+)2·(tfBDC2-)·2(H2O)] (5), [(H-ABI+)2·(tfBDC2-)] (6), [(H-DMP+)·(HtfBDC-)] (7), and [(H-3-CNpy+)·(HtfBDC-)] (8), were synthesized by solvent evaporation method. Crystal structures analyses show that the F atom of the H2tfBDC participates in multiple Csbnd H⋯F hydrogen bond formations, producing different supramolecular synthons. The weak hydrogen bonding Csbnd H⋯F and Nsbnd H⋯F play an important part in constructing the diversity structures 2-8, except in crystal 1. In complexes 1-3, they present the same synthon R22(8) with different N-heterocyclic compounds, which may show the strategy in constructing the supramolecular. Meanwhile, the complex 3 exhibits a 2D layer, and the independent molecules of water exist in the adjacent layers. In complexes 4 and 5, the water molecules connect the neighboring layers to form 3D network by strong Osbnd H⋯O hydrogen bonding. These crystals 1-8 were fully characterized by single-crystal X-ray crystallography, elemental analysis, infrared spectroscopy (IR), and thermogravimetric analysis (TGA).

  4. Graphene controlled H- and J-stacking of perylene dyes into highly stable supramolecular nanostructures for enhanced photocurrent generation

    DEFF Research Database (Denmark)

    Gan, Shiyu; Zhong, Lijie; Engelbrekt, Christian;

    2014-01-01

    We report a new method for controlling H- and J-stacking in supramolecular self-assembly. Graphene nanosheets act as structure inducers to direct the self-assembly of a versatile organic dye, perylene into two distinct types of functional nanostructures, i.e. one-dimensional nanotubes via J-stack...

  5. Supramolecular Organic Nanowires as Plasmonic Interconnects.

    Science.gov (United States)

    Armao, Joseph J; Domoto, Yuya; Umehara, Teruhiko; Maaloum, Mounir; Contal, Christophe; Fuks, Gad; Moulin, Emilie; Decher, Gero; Javahiraly, Nicolas; Giuseppone, Nicolas

    2016-02-23

    Metallic nanostructures are able to interact with an incident electromagnetic field at subwavelength scales by plasmon resonance which involves the collective oscillation of conduction electrons localized at their surfaces. Among several possible applications of this phenomenon, the theoretical prediction is that optical circuits connecting multiple plasmonic elements will surpass classical electronic circuits at nanoscale because of their much faster light-based information processing. However, the placement and coupling of metallic elements smaller than optical wavelengths currently remain a formidable challenge by top-down manipulations. Here, we show that organic supramolecular triarylamine nanowires of ≈1 nm in diameter are able to act as plasmonic waveguides. Their self-assembly into plasmonic interconnects between arrays of gold nanoparticles leads to the bottom-up construction of basic optical nanocircuits. When the resonance modes of these metallic nanoparticles are coupled through the organic nanowires, the optical conductivity of the plasmonic layer dramatically increases from 259 to 4271 Ω(-1)·cm(-1). We explain this effect by the coupling of a hot electron/hole pair in the nanoparticle antenna with the half-filled polaronic band of the organic nanowire. We also demonstrate that the whole hybrid system can be described by using the abstraction of the lumped circuit theory, with a far field optical response which depends on the number of interconnects. Overall, our supramolecular bottom-up approach opens the possibility to implement processable, soft, and low cost organic plasmonic interconnects into a large number of applications going from sensing to metamaterials and information technologies.

  6. Supramolecular Organic Nanowires as Plasmonic Interconnects.

    Science.gov (United States)

    Armao, Joseph J; Domoto, Yuya; Umehara, Teruhiko; Maaloum, Mounir; Contal, Christophe; Fuks, Gad; Moulin, Emilie; Decher, Gero; Javahiraly, Nicolas; Giuseppone, Nicolas

    2016-02-23

    Metallic nanostructures are able to interact with an incident electromagnetic field at subwavelength scales by plasmon resonance which involves the collective oscillation of conduction electrons localized at their surfaces. Among several possible applications of this phenomenon, the theoretical prediction is that optical circuits connecting multiple plasmonic elements will surpass classical electronic circuits at nanoscale because of their much faster light-based information processing. However, the placement and coupling of metallic elements smaller than optical wavelengths currently remain a formidable challenge by top-down manipulations. Here, we show that organic supramolecular triarylamine nanowires of ≈1 nm in diameter are able to act as plasmonic waveguides. Their self-assembly into plasmonic interconnects between arrays of gold nanoparticles leads to the bottom-up construction of basic optical nanocircuits. When the resonance modes of these metallic nanoparticles are coupled through the organic nanowires, the optical conductivity of the plasmonic layer dramatically increases from 259 to 4271 Ω(-1)·cm(-1). We explain this effect by the coupling of a hot electron/hole pair in the nanoparticle antenna with the half-filled polaronic band of the organic nanowire. We also demonstrate that the whole hybrid system can be described by using the abstraction of the lumped circuit theory, with a far field optical response which depends on the number of interconnects. Overall, our supramolecular bottom-up approach opens the possibility to implement processable, soft, and low cost organic plasmonic interconnects into a large number of applications going from sensing to metamaterials and information technologies. PMID:26814600

  7. 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

    2012-01-01

    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.

  8. A Supramolecular Sensing Platform for Phosphate Anions and an Anthrax Biomarker in a Microfluidic Device

    NARCIS (Netherlands)

    Eker, Bilge; Yilmaz, Mahmut Deniz; Schlautmann, Stefan; Gardeniers, Johannes G.E.; Huskens, Jurriaan

    2011-01-01

    A supramolecular platform based on self-assembled monolayers (SAMs) has been implemented in a microfluidic device. The system has been applied for the sensing of two different analyte types: biologically relevant phosphate anions and aromatic carboxylic acids, which are important for anthrax detecti

  9. Light Responsive Two-Component Supramolecular Hydrogel: A Sensitive Platform for Humidity Sensors

    KAUST Repository

    Samai, Suman

    2016-02-15

    The supramolecular assembly of anionic azobenzene dicarboxylate and cationic cetyltrimethylammonium bromide (CTAB) formed a stimuli responsive hydrogel with a critical gelation concentration (CGC) of 0.33 wt%. This self-sustainable two-component system was able to repair damage upon light irradiation. Moreover, it was successfully employed in the fabrication of highly sensitive humidity sensors for the first time.

  10. Baryons and Chiral Symmetry

    CERN Document Server

    Liu, Keh-Fei

    2016-01-01

    The relevance of chiral symmetry in baryons is highlighted in three examples in the nucleon spectroscopy and structure. The first one is the importance of chiral dynamics in understanding the Roper resonance. The second one is the role of chiral symmetry in the lattice calculation of $\\pi N \\sigma$ term and strangeness. The third one is the role of chiral $U(1)$ anomaly in the anomalous Ward identity in evaluating the quark spin and the quark orbital angular momentum. Finally, the chiral effective theory for baryons is discussed.

  11. Regulating Competing Supramolecular Interactions Using Ligand Concentration.

    Science.gov (United States)

    Teunissen, Abraham J P; Paffen, Tim F E; Ercolani, Gianfranco; de Greef, Tom F A; Meijer, E W

    2016-06-01

    The complexity of biomolecular systems inevitably leads to a degree of competition between the noncovalent interactions involved. However, the outcome of biological processes is generally very well-defined often due to the competition of these interactions. In contrast, specificity in synthetic supramolecular systems is usually based on the presence of a minimum set of alternative assembly pathways. While the latter might simplify the system, it prevents the selection of specific structures and thereby limits the adaptivity of the system. Therefore, artificial systems containing competing interactions are vital to stimulate the development of more adaptive and lifelike synthetic systems. Here, we present a detailed study on the self-assembly behavior of a C2v-symmetrical tritopic molecule, functionalized with three self-complementary ureidopyrimidinone (UPy) motifs. Due to a shorter linker connecting one of these UPys, two types of cycles with different stabilities can be formed, which subsequently dimerize intermolecularly via the third UPy. The UPy complementary 2,7-diamido-1,8-naphthyridine (NaPy) motif was gradually added to this mixture in order to examine its effect on the cycle distribution. As a result of the C2v-symmetry of the tritopic UPy, together with small differences in binding strength, the cycle ratio can be regulated by altering the concentration of NaPy. We show that this ratio can be increased to an extent where one type of cycle is formed almost exclusively. PMID:27163942

  12. Remote control of helical chirality: thermodynamic resolution of a racemic mixture of CTV units by remote stereogenic centers.

    Science.gov (United States)

    Chatelet, Bastien; Joucla, Lionel; Padula, Daniele; Di Bari, Lorenzo; Pilet, Guillaume; Robert, Vincent; Dufaud, Véronique; Dutasta, Jean-Pierre; Martinez, Alexandre

    2015-02-01

    Enantiopure hemicryptophanes designed from the cyclotriveratrylene (CTV) unit display remarkable properties in selective host-guest recognition or as supramolecular catalysts. The unprecedented control of the helical chirality of the CTV unit by remote stereogenic centers of a tren moiety is reported, providing an original access to this highly promising class of host molecules. Although the chiral centers and the CTV unit are separated by more than 10 Å, one single diastereomer is formed; the nature of the diastereoselective process is discussed and the procedure is exemplified using different enantiopure tren derivatives. This work also highlights the influence of the chirality of the CTV unit on the whole cage structure. PMID:25629235

  13. Chiral Rotational Spectroscopy

    CERN Document Server

    Cameron, Robert P; Barnett, Stephen M

    2015-01-01

    We introduce chiral rotational spectroscopy: a new technique that enables the determination of the individual optical activity polarisability components $G_{XX}'$, $G_{YY}'$, $G_{ZZ}'$, $A_{X,YZ}$, $A_{Y,ZX}$ and $A_{Z,XY}$ of chiral molecules, in a manner that reveals the enantiomeric constitution of a sample whilst yielding an incisive signal even for a racemate. Chiral rotational spectroscopy could find particular use in the analysis of molecules that are chiral by virtue of their isotopic constitution and molecules with multiple chiral centres. The principles that underpin chiral rotational spectroscopy can also be exploited in the search for molecular chirality in space, which, if found, may add weight to hypotheses that biological homochirality and indeed life itself are of cosmic origin.

  14. On chiral and non chiral 1D supermultiplets

    Energy Technology Data Exchange (ETDEWEB)

    Toppan, Francesco, E-mail: toppan@cbpf.b [Centro Brasileiro de Pesquisas Fisicas (TEO/CBPF), Rio de Janeiro, RJ (Brazil). Coordenacao de Fisica Teorica

    2011-07-01

    In this talk I discuss and clarify some issues concerning chiral and non chiral properties of the one-dimensional supermultiplets of the N-extended supersymmetry. Quaternionic chirality can be defined for N = 4, 5, 6, 7, 8. Octonionic chirality for N = 8 and beyond. Inequivalent chiralities only arise when considering several copies of N = 4 or N = 8 supermultiplets. (author)

  15. Orthogonal Enzymatic Reactions to Control Supramolecular Hydrogelations%Orthogonal Enzymatic Reactions to Control Supramolecular Hydrogelations

    Institute of Scientific and Technical Information of China (English)

    陈国钦; 任春华; 王玲; 徐兵; 杨志谋

    2012-01-01

    Enzyme-responsive hydrogels have great potential in applications of controlled drug release, tissue engineering, etc. In this study, we reported on a supramolecular hydrogel that showed responses to two enzymes, phosphatase which was used to form the hydrogels and esterase which could trigger gelsol phase transitions. The gelation process and visco-elasticity property of the resulting gel, morphology of the nanostructures in hydrogel, and peptide conformation in the self-assembled nanostructure were characterized by theology, transmission electron microscope (TEM), and circular dichroism (CD), respectively. Potential application of the enzyme-responsive hydrogel in drug release was also demonstrated in this study. Though only one potential application of drug release was proved in this study, the responsive hydrogel system in this study might have potentials for the applications in fields of cell culture, controlled-drug release, etc.

  16. Chiral symmetry and chiral-symmetry breaking

    Energy Technology Data Exchange (ETDEWEB)

    Peskin, M.E.

    1982-12-01

    These lectures concern the dynamics of fermions in strong interaction with gauge fields. Systems of fermions coupled by gauge forces have a very rich structure of global symmetries, which are called chiral symmetries. These lectures will focus on the realization of chiral symmetries and the causes and consequences of thier spontaneous breaking. A brief introduction to the basic formalism and concepts of chiral symmetry breaking is given, then some explicit calculations of chiral symmetry breaking in gauge theories are given, treating first parity-invariant and then chiral models. These calculations are meant to be illustrative rather than accurate; they make use of unjustified mathematical approximations which serve to make the physics more clear. Some formal constraints on chiral symmetry breaking are discussed which illuminate and extend the results of our more explicit analysis. Finally, a brief review of the phenomenological theory of chiral symmetry breaking is presented, and some applications of this theory to problems in weak-interaction physics are discussed. (WHK)

  17. Supramolecular nanoreactors for intracellular singlet-oxygen sensitization

    Science.gov (United States)

    Swaminathan, Subramani; Fowley, Colin; Thapaliya, Ek Raj; McCaughan, Bridgeen; Tang, Sicheng; Fraix, Aurore; Burjor, Captain; Sortino, Salvatore; Callan, John F.; Raymo, Françisco M.

    2015-08-01

    An amphiphilic polymer with multiple decyl and oligo(ethylene glycol) chains attached to a common poly(methacrylate) backbone assembles into nanoscaled particles in aqueous environments. Hydrophobic anthracene and borondipyrromethene (BODIPY) chromophores can be co-encapsulated within the self-assembling nanoparticles and transported across hydrophilic media. The reversible character of the noncovalent bonds, holding the supramolecular containers together, permits the exchange of their components with fast kinetics in aqueous solution. Incubation of cervical cancer (HeLA) cells with a mixture of two sets of nanoparticles, pre-loaded independently with anthracene or BODIPY chromophores, results in guest scrambling first and then transport of co-entrapped species to the intracellular space. Alternatively, incubation of cells with the two sets of nanocarriers in consecutive steps permits the sequential transport of the anthracene and BODIPY chromophores across the plasma membrane and only then allows their co-encapsulation within the same supramolecular containers. Both mechanisms position the two sets of chromophores with complementary spectral overlap in close proximity to enable the efficient transfer of energy intracellularly from the anthracene donors to the BODIPY acceptors. In the presence of iodine substituents on the BODIPY platform, intersystem crossing follows energy transfer. The resulting triplet state can transfer energy further to molecular oxygen with the concomitant production of singlet oxygen to induce cell mortality. Furthermore, the donor can be excited with two near-infrared photons simultaneously to permit the photoinduced generation of singlet oxygen intracellularly under illumination conditions compatible with applications in vivo. Thus, these supramolecular strategies to control the excitation dynamics of multichromophoric assemblies in the intracellular environment can evolve into valuable protocols for photodynamic therapy.An amphiphilic

  18. Art, auto-mechanics, and supramolecular chemistry. A merging of hobbies and career

    OpenAIRE

    Eric V. Anslyn

    2016-01-01

    While the strict definition of supramolecular chemistry is “chemistry beyond the molecule”, meaning having a focus on non-covalent interactions, the field is primarily associated with the creation of synthetic receptors and self-assembly. For synthetic ease, the receptors and assemblies routinely possess a high degree of symmetry, which lends them an aspect of aesthetic beauty. Pictures of electron orbitals similarly can be seen as akin to works of art. This similarity was an early draw for m...

  19. Photoinduced formation of an azobenzene-based CD-active supramolecular cyclic dimer.

    Science.gov (United States)

    Sogawa, Hiromitsu; Terada, Kayo; Miyagi, Yu; Shiotsuki, Masashi; Inai, Yoshihito; Masuda, Toshio; Sanda, Fumio

    2015-04-27

    A series of new photo-responsive amino acid-derived azobenzenedicarboxylic acid derivatives (S)-1 a-e were synthesized. Compound (S)-1 a in the trans form exhibited no circular dichroism (CD) signal in DMF under ambient conditions, whereas intense Cotton effects were observed upon UV irradiation, indicating the formation of a chiral supramolecular structure in the cis form. The CD signals disappeared when trifluoroacetic acid (TFA) was added to the solution. The ester counterpart [(S)-1 a'] showed no CD signal. Hydrogen bonding between the carboxy groups seemed necessary for constructing the supramolecular structure. The kinetic studies of cis to trans isomerization of (S)-1 a demonstrated that the formation of a chiral supramolecule enhances the stability of the cis-azobenzene structure. The ESI mass spectrum of stilbenedicarboxylic acid (S)-4, an analogue of (S)-1 b, confirmed the formation of a dimer. A theoretical CD study revealed that (S)-1 a in the cis form should be present as a cyclic chiral dimer.

  20. The supramolecular organization of the C. elegans nuclear lamin filament.

    Science.gov (United States)

    Ben-Harush, Kfir; Wiesel, Naama; Frenkiel-Krispin, Daphna; Moeller, Dorothee; Soreq, Eyal; Aebi, Ueli; Herrmann, Harald; Gruenbaum, Yosef; Medalia, Ohad

    2009-03-13

    Nuclear lamins are involved in most nuclear activities and are essential for retaining the mechano-elastic properties of the nucleus. They are nuclear intermediate filament (IF) proteins forming a distinct meshwork-like layer adhering to the inner nuclear membrane, called the nuclear lamina. Here, we present for the first time, the three-dimensional supramolecular organization of lamin 10 nm filaments and paracrystalline fibres. We show that Caenorhabditis elegans nuclear lamin forms 10 nm IF-like filaments, which are distinct from their cytoplasmic counterparts. The IF-like lamin filaments are composed of three and four tetrameric protofilaments, each of which contains two partially staggered anti-parallel head-to-tail polymers. The beaded appearance of the lamin filaments stems from paired globular tail domains, which are spaced regularly, alternating between 21 nm and 27 nm. A mutation in an evolutionarily conserved residue that causes Hutchison-Gilford progeria syndrome in humans alters the supramolecular structure of the lamin filaments. On the basis of our structural analysis, we propose an assembly pathway that yields the observed 10 nm IF-like lamin filaments and paracrystalline fibres. These results serve also as a platform for understanding the effect of laminopathic mutations on lamin supramolecular organization.

  1. Encoding complexity within supramolecular analogues of frustrated magnets

    Science.gov (United States)

    Cairns, Andrew B.; Cliffe, Matthew J.; Paddison, Joseph A. M.; Daisenberger, Dominik; Tucker, Matthew G.; Coudert, François-Xavier; Goodwin, Andrew L.

    2016-05-01

    The solid phases of gold(I) and/or silver(I) cyanides are supramolecular assemblies of inorganic polymer chains in which the key structural degrees of freedom—namely, the relative vertical shifts of neighbouring chains—are mathematically equivalent to the phase angles of rotating planar (‘XY’) spins. Here, we show how the supramolecular interactions between chains can be tuned to mimic different magnetic interactions. In this way, the structures of gold(I) and/or silver(I) cyanides reflect the phase behaviour of triangular XY magnets. Complex magnetic states predicted for this family of magnets—including collective spin-vortices of relevance to data storage applications—are realized in the structural chemistry of these cyanide polymers. Our results demonstrate how chemically simple inorganic materials can behave as structural analogues of otherwise inaccessible ‘toy’ spin models and also how the theoretical understanding of those models allows control over collective (‘emergent’) phenomena in supramolecular systems.

  2. TOPICAL REVIEW: Metallo-supramolecular modules as a paradigm for materials science

    Directory of Open Access Journals (Sweden)

    Dirk G Kurth

    2008-01-01

    Full Text Available Metal ion coordination in discrete or extended metallo-supramolecular assemblies offers ample opportunity to fabricate and study devices and materials that are equally important for fundamental research and new technologies. Metal ions embedded in a specific ligand field offer diverse thermodynamic, kinetic, chemical, physical and structural properties that make these systems promising candidates for active components in functional materials. A key challenge is to improve and develop methodologies for placing these active modules in suitable device architectures, such as thin films or mesophases. This review highlights recent developments in extended, polymeric metallo-supramolecular systems and discrete polyoxometalates with an emphasis on materials science.

  3. Directing the Crystallization of Dehydro[24]annulenes into Supramolecular Nanotubular Scaffolds.

    Science.gov (United States)

    Suzuki, Mitsuharu; Kotyk, Juliet F Khosrowabadi; Khan, Saeed I; Rubin, Yves

    2016-05-11

    The self-assembly of a series of dehydro[24]annulene derivatives into columnar stacks has been examined for its latent ability to form π-conjugated carbon-rich nanotubular structures through topochemical polymerizations. We have studied the parameters affecting self-assembly, including the nature of the substituent and crystallization conditions, using 10 different dehydro[24]annulene derivatives. In particular, hydrogen-bonding interactions through carbamate groups were found to be especially useful at directing the formation of nanotubular supramolecular assemblies. We have also evaluated the electronic coupling between neighboring dehydroannulene molecules within these supramolecular assemblies. Density functional calculations on the stacked supramolecular nanotube assemblies show that transfer integrals vary considerably between the three columnar assemblies, ranging from moderate to high (59-98 meV for the highest occupied molecular orbitals, 63-97 meV for the lowest unoccupied molecular orbitals), depending on the local molecular topology. In addition, the dehydro[24]annulene derivatives afforded distinct architectures in the crystal, including nanochannel arrays, sheets with solvent-filled pores, and lamellae. This work is an essential step toward a controlled formation of covalently linked carbon-rich nanostructures generated from molecular precursors with a latent diacetylene reactivity. PMID:27088651

  4. Supramolecular-templated synthesis of mesoporous silica-zirconia nanocomposite

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Mesoporous SiO2-ZrO2 nanocomposite was successfully prepared by using supramolecular triblock copolymer as the template through evaporation-induced self-assembly approach. The textural and structural properties were characterized by X-ray diffraction, nitrogen adsorption analysis, and transmission electron microscope.Comparison between pure mesoporous silica and mesoporous silica-zirconia nanocomposite was also presented in this work. The surface area, pore size, and pore volume decreased as the Zr doping in the mesoporous silica framework. But the obtained nanocomposite maintained the cubic Im3m-type mesoporous structure.

  5. Construction of tunable supramolecular networks studied by scanning tunneling microscopy

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    In this review we describe a family of organic-based host frameworks which can accommodate guest molecules. The aim of the study is to test the adjustability of this class of mimic structures that may lead to new interesting functions. Emphasis of our research is placed upon four aspects: 1) thermal properties, 2) surface photochemistry, 3) fullerene adsorption, and 4) guest inclusion. It is envisioned that such approach of nanoporous molecular networks might be developed into a new family of useful soft frameworks for studies toward shape-selective catalysis, molecular recognition, self-assembly, and host-guest supramolecular chemistry.

  6. Supramolecular control over thermoresponsive polymers

    OpenAIRE

    Victor R. de la Rosa; Patrice Woisel; Richard Hoogenboom

    2016-01-01

    Thermoresponsive polymers facilitate the development of a wide range of applications in multiple areas spanning from construction or water management to lab-on-a-chip technologies and biomedical sciences. The combination of thermoresponsive polymers with supramolecular chemistry, inspired by the molecular mechanisms behind natural systems, is resulting in adaptive and smart materials with unprecedented properties. This work reviews the past advances on the combination of this young field of r...

  7. Self-healing supramolecular nanocomposites

    OpenAIRE

    Liu, Z.

    2015-01-01

    The aim of this thesis is to execute a bottom-up design of the intrinsically self-healing nanocomposites. We briefly introduced the self-healing materials in chapter 1, covering classification and basic self-healing mechanism. In chapter 2, we have synthesized polyborosiloxane (PBS) according to the last century recipe as the self-healing supramolecular matrix. Additionally, we provided the long existing recipe with exclusive supplementary details, such as reaction kinetics, structural refine...

  8. Chiral Superfluidity for QCD

    CERN Document Server

    Kalaydzhyan, Tigran

    2014-01-01

    We argue that the strongly coupled quark-gluon plasma formed at LHC and RHIC can be considered as a chiral superfluid. The "normal" component of the fluid is the thermalized matter in common sense, while the "superfluid" part consists of long wavelength (chiral) fermionic states moving independently. We use the bosonization procedure with a finite cut-off and obtain a dynamical axion-like field out of the chiral fermionic modes. Then we use relativistic hydrodynamics for macroscopic description of the effective theory obtained after the bosonization. Finally, solving the hydrodynamic equations in gradient expansion, we find that in the presence of external electromagnetic fields or rotation the motion of the "superfluid" component gives rise to the chiral magnetic, chiral vortical, chiral electric and dipole wave effects. Latter two effects are specific for a two-component fluid, which provides us with crucial experimental tests of the model.

  9. Mechanical separation of chiral dipoles by chiral light

    CERN Document Server

    Canaguier-Durand, Antoine; Genet, Cyriaque; Ebbesen, Thomas W

    2013-01-01

    Optical forces take on a specific form when involving chiral light fields interacting with chiral objects. We show that optical chirality density and flow can have mechanical effects through reactive and dissipative components of chiral forces exerted on chiral dipoles. Remarkably, these force components are directly related to standard observables: optical rotation and circular dichroism, respectively. As a consequence, resulting forces and torques are dependent on the enantiomeric form of the chiral dipole. This leads to promising strategies for the mechanical separation of chiral objects using chiral light forces.

  10. What Triggers Supramolecular Isomerism in Nonmolecular Solids? A case study of Copper Pyridazine Halides

    Indian Academy of Sciences (India)

    JENCY THOMAS; ARUNACHALAM RAMANAN

    2016-11-01

    Molecular recognition and aggregation occurring in solution are critical events towards the nucleation and growth of a crystal. However, controlling aggregation towards a particular supramolecular assembly is difficult due to lack of information on its thermodynamics and kinetics. Hence, the occurrence of supramolecularisomers is hardly recognized. In this paper, therefore, we demonstrate a retrosynthetic analysis to interpret the occurrence of isostructures and supramolecular isomers and predict the possibility of new phases in copperhalide-pyridazine- H₂O system. A significant feature of this paper is the use of crystal engineering tools, namely, synthons and tectons to interpret the phase diagram of a system. The structure-synthesis correlation discussed here provides chemical insight to evolve a synthetic protocol to interpret and predict the possibilityof supramolecular isomers in metal organic solids.

  11. Biocompatible fluorescent supramolecular nanofibrous hydrogel for long-term cell tracking and tumor imaging applications

    Science.gov (United States)

    Wang, Huaimin; Mao, Duo; Wang, Youzhi; Wang, Kai; Yi, Xiaoyong; Kong, Deling; Yang, Zhimou; Liu, Qian; Ding, Dan

    2015-11-01

    Biocompatible peptide-based supramolecular hydrogel has recently emerged as a new and promising system for biomedical applications. In this work, Rhodamine B is employed as a new capping group of self-assembling peptide, which not only provides the driving force for supramolecular nanofibrous hydrogel formation, but also endows the hydrogel with intrinsic fluroescence signal, allowing for various bioimaging applications. The fluorescent peptide nanofibrous hydrogel can be formed via disulfide bond reduction. After dilution of the hydrogel with aqueous solution, the fluorescent nanofiber suspension can be obtained. The resultant nanofibers are able to be internalized by the cancer cells and effectively track the HeLa cells for as long as 7 passages. Using a tumor-bearing mouse model, it is also demonstrated that the fluorescent supramolecular nanofibers can serve as an efficient probe for tumor imaging in a high-contrast manner.

  12. Supramolecular Rotor and Translator at Work: On-Surface Movement of Single Atoms.

    Science.gov (United States)

    Ohmann, Robin; Meyer, Jörg; Nickel, Anja; Echeverria, Jorge; Grisolia, Maricarmen; Joachim, Christian; Moresco, Francesca; Cuniberti, Gianaurelio

    2015-08-25

    A supramolecular nanostructure composed of four 4-acetylbiphenyl molecules and self-assembled on Au (111) was loaded with single Au adatoms and studied by scanning tunneling microscopy at low temperature. By applying voltage pulses to the supramolecular structure, the loaded Au atoms can be rotated and translated in a controlled manner. The manipulation of the gold adatoms is driven neither by mechanical interaction nor by direct electronic excitation. At the electronic resonance and driven by the tunneling current intensity, the supramolecular nanostructure performs a small amount of work of about 8 × 10(-21) J, while transporting the single Au atom from one adsorption site to the next. Using the measured average excitation time necessary to induce the movement, we determine the mechanical motive power of the device, yielding about 3 × 10(-21) W. PMID:26158314

  13. Chiral atomically thin films

    Science.gov (United States)

    Kim, Cheol-Joo; Sánchez-Castillo, A.; Ziegler, Zack; Ogawa, Yui; Noguez, Cecilia; Park, Jiwoong

    2016-06-01

    Chiral materials possess left- and right-handed counterparts linked by mirror symmetry. These materials are useful for advanced applications in polarization optics, stereochemistry and spintronics. In particular, the realization of spatially uniform chiral films with atomic-scale control of their handedness could provide a powerful means for developing nanodevices with novel chiral properties. However, previous approaches based on natural or grown films, or arrays of fabricated building blocks, could not offer a direct means to program intrinsic chiral properties of the film on the atomic scale. Here, we report a chiral stacking approach, where two-dimensional materials are positioned layer-by-layer with precise control of the interlayer rotation (θ) and polarity, resulting in tunable chiral properties of the final stack. Using this method, we produce left- and right-handed bilayer graphene, that is, a two-atom-thick chiral film. The film displays one of the highest intrinsic ellipticity values (6.5 deg μm-1) ever reported, and a remarkably strong circular dichroism (CD) with the peak energy and sign tuned by θ and polarity. We show that these chiral properties originate from the large in-plane magnetic moment associated with the interlayer optical transition. Furthermore, we show that we can program the chiral properties of atomically thin films layer-by-layer by producing three-layer graphene films with structurally controlled CD spectra.

  14. Anomalous chiral superfluidity

    Energy Technology Data Exchange (ETDEWEB)

    Lublinsky, Michael, E-mail: lublinsky@phys.uconn.ed [Department of Physics and Astronomy, Stony Brook University, Stony Brook, NY 11794 (United States); Physics Department, Ben-Gurion University, Beer Sheva 84105 (Israel); Zahed, Ismail [Department of Physics and Astronomy, Stony Brook University, Stony Brook, NY 11794 (United States)

    2010-02-08

    We discuss both the anomalous Cartan currents and the energy-momentum tensor in a left chiral theory with flavor anomalies as an effective theory for flavored chiral phonons in a chiral superfluid with the gauged Wess-Zumino-Witten term. In the mean-field (leading tadpole) approximation the anomalous Cartan currents and the energy-momentum tensor take the form of constitutive currents in the chiral superfluid state. The pertinence of higher order corrections and the Adler-Bardeen theorem is briefly noted.

  15. Chiral Shock Waves

    CERN Document Server

    Sen, Srimoyee

    2016-01-01

    We study shock waves in relativistic chiral matter. We argue that the conventional Rankine- Hugoinot relations are modified due to the presence of chiral transport phenomena. We show that the entropy discontinuity in a weak shock wave is linearly proportional to the pressure discontinuity when the effect of chiral transport becomes sufficiently large. We also show that rarefaction shock waves, which do not exist in usual nonchiral fluids, can appear in chiral matter. These features are exemplified by shock propagation in dense neutrino matter in the hydrodynamic regime.

  16. Doped Chiral Polymer Metamaterials Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Doped Chiral Polymer Metamaterials (DCPM) with tunable resonance frequencies have been developed by adding plasmonic inclusions into chiral polymers with variable...

  17. Supramolecular donor-acceptor hybrids of porphyrins/phthalocyanines with fullerenes/carbon nanotubes: electron transfer, sensing, switching, and catalytic applications.

    Science.gov (United States)

    D'Souza, Francis; Ito, Osamu

    2009-09-01

    Since the three-dimensional electron-accepting fullerene has been found to be an excellent building block for self-assembled supramolecular systems, we have investigated photoinduced electron transfer processes in supramolecular fullerene systems with porphyrins and phthalocyanines as electron donors to mimic natural photosynthesis. We have successfully formed self-assembled supramolecular dyads and triads via metal-ligand coordination, crown-ether inclusion, ion pairing, hydrogen-bonding, or pi-pi stacking interactions. Although the single mode of binding gives usually flexible supramolecular structures, the newly developed strategy of multiple modes of binding results in conjugates of defined distance and orientation between the donor and acceptor entities, which influences the overall electron transfer reactions. In these conjugates, we observe the anticipated acceleration of the charge separation process and deceleration of the charge recombination process. Applications of these supramolecular systems for reversible photoswitching of inter- and intramolecular electron transfer events open up new opportunities in the area of photosensors. Extension of the self-assembly approaches to single wall carbon nanotubes (SWNT) results in SWNT-porphyrin/phthalocyanine nanohybrids capable of undergoing photoinduced electron transfer. These photochemical processes lead to photocatalytic reactions accumulating redox active substances of electron acceptor/mediator entities with the help of a sacrificial electron donor. Studies on these self-assembled supramolecular dyads, triads, tetrads, etc., are only in the beginning stages and future studies anticipate involvement of more complex systems targeted for better performances in light-driven devices. PMID:19668806

  18. Elastic instability-mediated actuation by a supra-molecular polymer

    Science.gov (United States)

    Levin, Aviad; Michaels, Thomas C. T.; Adler-Abramovich, Lihi; Mason, Thomas O.; Müller, Thomas; Zhang, Bohan; Mahadevan, L.; Gazit, Ehud; Knowles, Tuomas P. J.

    2016-10-01

    In nature, fast, high-power-density actuation can be achieved through the release of stored elastic energy by exploiting mechanical instabilities in systems including the closure of the Venus flytrap and the dispersal of plant or fungal spores. Here, we use droplet microfluidics to tailor the geometry of a nanoscale self-assembling supra-molecular polymer to create a mechanical instability. We show that this strategy allows the build-up of elastic energy as a result of peptide self-assembly, and its release within milliseconds when the buckled geometry of the nanotube confined within microdroplets becomes unstable with respect to the straight form. These results overcome the inherent limitations of self-assembly for generating large-scale actuation on the sub-second timescale and illuminate the possibilities and performance limits of irreversible actuation by supra-molecular polymers.

  19. [Study on meridian tropism of medicinal property theory for Chines medicines by supramolecular chemistry (I)].

    Science.gov (United States)

    He, Fu-yuan; Deng, Kai-wen; Yang, Yan-tao; Zhou, Yi-qun; Shi, Ji-lian; Liu, Wen-long; Tang, Yu

    2015-04-01

    In this paper, based on the special influence of supramolecular chemistry on the basic theory of Chinese medicines ( CM) , the authors further analyzed the history of meridian tropism and natural origins of CM organisms and explained CM ingredients and the universal regularity of the automatic action of the supramolecular "imprinting templates" hole channel structure. After entering human bodies, CMs, as the aggregation of supramolecular "imprinting templates" , automatically seek supramolecular subjects that are matched with their "imprinting templates" in human meridians and organs for the purpose of self-recognition, self-organization, self-assembly and self-replication, so as to generate specific efficacy in meridians and organs, which is reflected as the meridian tropism phenomena at macro level. This regularity can be studied by in vitro and in vivo experimental studies. In vitro methods are mostly supra molecular structure analysis and kinetic and thermodynamic parameter calculation; Whereas in vivo methods are dominated by the analysis on object component distribution, chromatopharmacodynamic parameters and network chromatopharmacodynamic parameters; Particularly, the acupoint-medicine method can simplify to study the supramolecular subject-object relations. Consequently, CM's'meridian tropism reveals the universal regularity for interactions of macromolecular and micromolecular "imprinting templates" of subjects and objects in natural organisms. As the first barrier for the material base of the CM theory and breakthrough in the modernization of the basic CM theory, meridian tropism plays an important role in studies on basic theories of the basic CM theory.

  20. A redox responsive, fluorescent supramolecular metallohydrogel consists of nanofibers with single-molecule width

    KAUST Repository

    Zhang, Ye

    2013-04-03

    The integration of a tripeptide derivative, which is a versatile self-assembly motif, with a ruthenium(II)tris(bipyridine) complex affords the first supramolecular metallo-hydrogelator that not only self assembles in water to form a hydrogel but also exhibits gel-sol transition upon oxidation of the metal center. Surprisingly, the incorporation of the metal complex in the hydrogelator results in the nanofibers, formed by the self-assembly of the hydrogelator in water, to have the width of a single molecule of the hydrogelator. These results illustrate that metal complexes, besides being able to impart rich optical, electronic, redox, or magnetic properties to supramolecular hydrogels, also offer a unique geometrical control to prearrange the self-assembly motif prior to self-assembling. The use of metal complexes to modulate the dimensionality of intermolecular interactions may also help elucidate the interactions of the molecular nanofibers with other molecules, thus facilitating the development of supramolecular hydrogel materials for a wide range of applications. © 2013 American Chemical Society.

  1. Experimental Binding Energies in Supramolecular Complexes.

    Science.gov (United States)

    Biedermann, Frank; Schneider, Hans-Jörg

    2016-05-11

    On the basis of many literature measurements, a critical overview is given on essential noncovalent interactions in synthetic supramolecular complexes, accompanied by analyses with selected proteins. The methods, which can be applied to derive binding increments for single noncovalent interactions, start with the evaluation of consistency and additivity with a sufficiently large number of different host-guest complexes by applying linear free energy relations. Other strategies involve the use of double mutant cycles, of molecular balances, of dynamic combinatorial libraries, and of crystal structures. Promises and limitations of these strategies are discussed. Most of the analyses stem from solution studies, but a few also from gas phase. The empirically derived interactions are then presented on the basis of selected complexes with respect to ion pairing, hydrogen bonding, electrostatic contributions, halogen bonding, π-π-stacking, dispersive forces, cation-π and anion-π interactions, and contributions from the hydrophobic effect. Cooperativity in host-guest complexes as well as in self-assembly, and entropy factors are briefly highlighted. Tables with typical values for single noncovalent free energies and polarity parameters are in the Supporting Information. PMID:27136957

  2. Stabilization of reactive species by supramolecular encapsulation.

    Science.gov (United States)

    Galan, Albano; Ballester, Pablo

    2016-03-14

    Molecular containers have attracted the interest of supramolecular chemists since the early beginnings of the field. Cavitands' inner cavities were quickly exploited by Cram and Warmuth to construct covalent containers able to stabilize and assist the characterization of short-lived reactive species such as cyclobutadiene or o-benzyne. Since then, more complex molecular architectures have been prepared able to store and isolate a myriad of fleeting species (i.e. organometallic compounds, cationic species, radical initiators…). In this review we cover selected examples of the stabilization of reactive species by encapsulation in molecular containers from the first reports of covalent containers described by Cram et al. to the most recent examples of containers with self-assembled structure (metal coordination cages and hydrogen bonded capsules). Finally, we briefly review examples reported by Rebek et al. in which elusive reaction intermediates could be detected in the inner cavities of self-folding resorcin[4]arene cavitands by the formation of covalent host-guest complexes. The utilization of encapsulated reactive species in catalysis or synthesis is not covered. PMID:26797259

  3. Engineering Functionalization in a Supramolecular Polymer: Hierarchical Self-Organization of Triply Orthogonal Non-covalent Interactions on a Supramolecular Coordination Complex Platform.

    Science.gov (United States)

    Zhou, Zhixuan; Yan, Xuzhou; Cook, Timothy R; Saha, Manik Lal; Stang, Peter J

    2016-01-27

    Here we present a method for the construction of functionalizable supramolecular polymers by controlling three orthogonal interactions within a single system: (i) coordination-driven self-assembly; (ii) H-bonding; and (iii) host-guest interactions between crown ether and dialkylammonium substrates. Three unique molecules constitute the supramolecular construct, including a 2-ureido-4-pyrimidinone (UPy)-functionalized rigid dipyridyl donor and a complementary organoplatinum(II) acceptor decorated with a crown ether moiety that provide the basis for self-assembly and polymerization. The final host-guest interaction is demonstrated by using one of two dialkylammonium molecules containing fluorophores that bind to the benzo-21-crown-7 (B21C7) groups of the acceptors, providing a spectroscopic handle to evaluate the functionalization. An initial coordination-driven self-assembly yields hexagonal metallacycles with alternating UPy and B21C7 groups at their vertices. The assembly does not interfere with H-bonding between the UPy groups, which link the discrete metallacycles into a supramolecular network, leaving the B21C7 groups free for functionalization via host-guest chemistry. The resultant network results in a cavity-cored metallogel at high concentrations or upon solvent swelling. The light-emitting properties of the dialkylammonium substrates were transferred to the network upon host-guest binding. This method is compatible with any dialkylammonium substrate that does not disrupt coordination nor H-bonding, and thus, the unification of these three orthogonal interactions represents a simple yet highly efficient strategy to obtain supramolecular polymeric materials with desirable functionality.

  4. Chiral geometry in multiple chiral doublet bands

    Science.gov (United States)

    Zhang, Hao; Chen, Qibo

    2016-02-01

    The chiral geometry of multiple chiral doublet bands with identical configuration is discussed for different triaxial deformation parameters γ in the particle rotor model with . The energy spectra, electromagnetic transition probabilities B(M1) and B(E2), angular momenta, and K-distributions are studied. It is demonstrated that the chirality still remains not only in the yrast and yrare bands, but also in the two higher excited bands when γ deviates from 30°. The chiral geometry relies significantly on γ, and the chiral geometry of the two higher excited partner bands is not as good as that of the yrast and yrare doublet bands. Supported by Plan Project of Beijing College Students’ Scientific Research and Entrepreneurial Action, Major State 973 Program of China (2013CB834400), National Natural Science Foundation of China (11175002, 11335002, 11375015, 11461141002), National Fund for Fostering Talents of Basic Science (NFFTBS) (J1103206), Research Fund for Doctoral Program of Higher Education (20110001110087) and China Postdoctoral Science Foundation (2015M580007)

  5. Supramolecular core–shell nanoparticles for photoconductive device applications

    Science.gov (United States)

    Cheng, Chih-Chia; Chen, Jem-Kun; Shieh, Yeong-Tarng; Lee, Duu-Jong

    2016-08-01

    We report a breakthrough discovery involving supramolecular-based strategies to construct novel core–shell heterojunction nanoparticles with hydrophilic adenine-functionalized polythiophene (PAT) as the core and hydrophobic phenyl-C61-butyric acid methyl ester (PCBM) as the shell, which enables the conception of new functional supramolecular assemblies for constructing functional nanomaterials for applications in optoelectronic devices. The generated nanoparticles exhibit uniform spherical shape, well-controlled tuning of particle size with narrow size distributions, and excellent electrochemical stability in solution and the solid state owing to highly efficient energy transfer from PAT to PCBM. When the PAT/PCBM nanoparticles were fabricated into a photoconducting layer in an electronic device, the resulting device showed excellent electric conduction characteristics, including an electrically-tunable voltage-controlled switch, and high short-circuit current and open-circuit voltage. These observations demonstrate how the self-assembly of PAT/PCBM into specific nanostructures may help to promote efficient charge generation and transport processes, suggesting potential for a wide variety of applications as a promising candidate material for bulk heterojunction polymer devices.

  6. Supramolecular core-shell nanoparticles for photoconductive device applications

    Science.gov (United States)

    Cheng, Chih-Chia; Chen, Jem-Kun; Shieh, Yeong-Tarng; Lee, Duu-Jong

    2016-08-01

    We report a breakthrough discovery involving supramolecular-based strategies to construct novel core-shell heterojunction nanoparticles with hydrophilic adenine-functionalized polythiophene (PAT) as the core and hydrophobic phenyl-C61-butyric acid methyl ester (PCBM) as the shell, which enables the conception of new functional supramolecular assemblies for constructing functional nanomaterials for applications in optoelectronic devices. The generated nanoparticles exhibit uniform spherical shape, well-controlled tuning of particle size with narrow size distributions, and excellent electrochemical stability in solution and the solid state owing to highly efficient energy transfer from PAT to PCBM. When the PAT/PCBM nanoparticles were fabricated into a photoconducting layer in an electronic device, the resulting device showed excellent electric conduction characteristics, including an electrically-tunable voltage-controlled switch, and high short-circuit current and open-circuit voltage. These observations demonstrate how the self-assembly of PAT/PCBM into specific nanostructures may help to promote efficient charge generation and transport processes, suggesting potential for a wide variety of applications as a promising candidate material for bulk heterojunction polymer devices.

  7. Supramolecular core-shell nanoparticles for photoconductive device applications.

    Science.gov (United States)

    Cheng, Chih-Chia; Chen, Jem-Kun; Shieh, Yeong-Tarng; Lee, Duu-Jong

    2016-08-12

    We report a breakthrough discovery involving supramolecular-based strategies to construct novel core-shell heterojunction nanoparticles with hydrophilic adenine-functionalized polythiophene (PAT) as the core and hydrophobic phenyl-C61-butyric acid methyl ester (PCBM) as the shell, which enables the conception of new functional supramolecular assemblies for constructing functional nanomaterials for applications in optoelectronic devices. The generated nanoparticles exhibit uniform spherical shape, well-controlled tuning of particle size with narrow size distributions, and excellent electrochemical stability in solution and the solid state owing to highly efficient energy transfer from PAT to PCBM. When the PAT/PCBM nanoparticles were fabricated into a photoconducting layer in an electronic device, the resulting device showed excellent electric conduction characteristics, including an electrically-tunable voltage-controlled switch, and high short-circuit current and open-circuit voltage. These observations demonstrate how the self-assembly of PAT/PCBM into specific nanostructures may help to promote efficient charge generation and transport processes, suggesting potential for a wide variety of applications as a promising candidate material for bulk heterojunction polymer devices. PMID:27353003

  8. Wormholes from Chiral Fields

    International Nuclear Information System (INIS)

    In this paper, Lorentzian wormholes with a phantom field and chiral matter fields have been obtained. In addition, it is shown that for different values of the gravitational coupling of the chiral fields, the wormhole geometry changes. Finally, the stability of the corresponding wormholes is studied and it is shown that are unstable (eg. Ellis's wormhole instability)

  9. Spectral signatures of chirality

    DEFF Research Database (Denmark)

    Pedersen, Jesper Goor; Mortensen, Asger

    2009-01-01

    We present a new way of measuring chirality, via the spectral shift of photonic band gaps in one-dimensional structures. We derive an explicit mapping of the problem of oblique incidence of circularly polarized light on a chiral one-dimensional photonic crystal with negligible index contrast to t...

  10. Supramolecular Structure and Function 9

    CERN Document Server

    Pifat-Mrzljak, Greta

    2007-01-01

    The book is based on International Summer Schools on Biophysics held in Croatia which, contrary to other workshops centered mainly on one topic or technique, has very broad scope providing advanced training in areas related to biophysics. This volume is presenting papers in the field of biophysics for studying biological phenomena by using physical methods (NMR, EPR, FTIR, Mass Spectrometry, etc.) and/or concepts (predictions of protein-protein interactions, virtual ligand screening etc.). The interrelationship of supramolecular structures and there functions is enlightened by applications of principals of these physical methods in the biophysical and molecular biology context.

  11. Chiral Magnetic "Superfluidity"

    CERN Document Server

    Sadofyev, Andrey V

    2015-01-01

    We study a heavy impurity moving longitudinal with the direction of an external magnetic field in an anomalous chiral medium. Such system would carry a non-dissipative current of chiral magnetic effect associated with the anomaly. We show, by generalizing Landau's criterion for superfluidity, that the "anomalous component" which gives rise to the anomalous transport will {\\it not} contribute to the drag experienced by an impurity. We argue on very general basis that those systems with a strong magnetic field would exhibit the behavior of 'superfluidity" -- the motion of the heavy impurity is frictionless, in analog to the case of a superfluid. However, this "superfluidity" exists even for chiral media at finite temperature and only in the directional longitudinal with the magnetic field, in contrast to the ordinary superfluid. We will call this novel phenomenon as the Chiral Magnetic "Superfluidity". We demonstrate and confirm our general results with two complementary examples: weakly coupled chiral fermion ...

  12. Hydrothermal Synthesis and Characterization of a Novel Supramolecular Network Compound [Co(IN2)(H2O)4](IN=Isonicotinate)

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A novel supramolecular compound, [Co(IN)2(H2O)4](1), was synthesized by means of the hydrothermal method and its structure was characterized with elemental analysis, FT-IR spectrum, TGA and X-ray diffraction. Though the unit cell structure of the title compound is only monomeric, all these units as building blocks are assembled into a novel three-dimensional supramolecular network via the widely hydrogen-bonding and π-π stacking interactions.

  13. 3D Supramolecular Network Based on Hydrogen Bonds Between 1D [ Ni(μ2 -C2O4 ) (Him) 2 ] Zigzag Chains

    Institute of Scientific and Technical Information of China (English)

    ZHANG Jing; HUANG Ru-dan; ZHU Qin-lei; HU Chang-wen

    2007-01-01

    @@ Introduction In recent years, considerable attention has been paid to supramolecular networks based on metal organic building blocks because of their potential applications in diverse fields, such as, catalysis, optics, sensors,magnetism, and molecular recognition[1-3]. On the basis of the principles of crystal engineering and special synthesis strategies, several novel supramolecular frameworks have been assembled from various organic,inorganic and metal-organic moieties, which largely enriches the structure chemistry of solid state materials[4-9].

  14. Development of self-assembling nanowires containing electronically active oligothiophenes

    Science.gov (United States)

    Tsai, Wei-Wen

    modification of a class of peptide lipids. The tripeptide segments in the molecular structure promote beta-sheet formation in nonpolar organic solvents, which is the main driving force for their self-assembly into 1D nanowires. Left-handed helical nanowires were formed with diameters of 8.9 nm and pitches between 50--150 nm. Substitutions of oligothiophenes lead to unprecedented supercoiling phenomena manifested as the transformation from helical to coiled or curved nanowires. We proposed that the curving of the nanowires is the consequence of relaxation from torsionally strained nanohelices, a process similar to supercoiling of strained DNA double helix. This process is governed by the mismatch in intermolecular distances required for peptide beta-sheets vs. pi-pi interactions of the conjugated segments decorating the periphery of the nanowires. Circular dichroism revealed helical arrangements of the conjugated moieties in these peptide lipids manifesting supercoiling phenomena. Peptide lipids without helical arrangement of the conjugated segments only exhibit helical morphologies. The self-assembly process of peptide lipids also leads to hierarchical assemblies of energetically favored single, double, and triple-helical nanostructures with well-defined dimensions. Self-assembled nanowires from oligothiophene-substituted peptide lipids revealed increased conductivity of 1.39--1.41 x 10-5 S/cm, two orders of magnitude higher than unassembled films and one order of magnitude higher than unsubstituted peptide lipids. The role of the primary beta-helix in controlling supramolecular organization was investigated by varying the chirality of the tripeptide segments, GAA. Four diastereomers of a peptide lipid substituted with p-toluene carboxylates were compared using L or D-alanines. Molecules with all L residues self-assemble into left-handed helical nanofibers with a pitch of 160 +/- 30 nm. Substitution of one or two D-alanines leads to assemblies of cylindrical nanofibers without

  15. Chirality of 4,4'-Biphenylene Bridged Polybissilsesquioxane Nanotubes Using the Dipeptides Derived from Valine.

    Science.gov (United States)

    Sang, Yunsen; Guo, Yongmin; Wang, Hairui; Li, Yi; Li, Baozong; Yang, Yonggang

    2015-03-01

    Four dipeptides with alkyl chains derived from L- and D-valines were synthesized, the handedness of their self-assemblies were controlled by the valine chirality at the terminals. The stacking of the carbonyl groups plays an important in the formation of chiral organic self-assemblies. Chiral 4,4'-biphenylene bridged polybissilsesquioxane nanotubes were prepared using the self-assemblies of these dipeptides as the templates. The chirality of the polysilsesquioxane nanotubes was mainly controlled by the valines at the terminals of the dipeptides, which was transferred from the valines at the terminals through electrostatic interaction. The valines near the alkyl chains could also affect the polysilsesquioxane chirality through hydrogen bonding.

  16. Chiral Magnetic Effect and Chiral Phase Transition

    Institute of Scientific and Technical Information of China (English)

    FU Wei-Jie; LIU Yu-Xin; WU Yue-Liang

    2011-01-01

    We study the influence of the chiral phase transition on the chiral magnetic effect.The azimuthal chargeparticle correlations as functions of the temperature are calculated.It is found that there is a pronounced cusp in the correlations as the temperature reaches its critical value for the QCD phase transition.It is predicted that there will be a drastic suppression of the charge-particle correlations as the collision energy in RHIC decreases to below a critical value.We show then the azimuthal charge-particle correlations can be the signal to identify the occurrence of the QCD phase transitions in RHIC energy scan experiments.

  17. Fluorescent supramolecular micelles for imaging-guided cancer therapy

    Science.gov (United States)

    Sun, Mengmeng; Yin, Wenyan; Dong, Xinghua; Yang, Wantai; Zhao, Yuliang; Yin, Meizhen

    2016-02-01

    A novel smart fluorescent drug delivery system composed of a perylene diimide (PDI) core and block copolymer poly(d,l-lactide)-b-poly(ethyl ethylene phosphate) is developed and named as PDI-star-(PLA-b-PEEP)8. The biodegradable PDI-star-(PLA-b-PEEP)8 is a unimolecular micelle and can self-assemble into supramolecular micelles, called as fluorescent supramolecular micelles (FSMs), in aqueous media. An insoluble drug camptothecin (CPT) can be effectively loaded into the FSMs and exhibits pH-responsive release. Moreover, the FSMs with good biocompatibility can also be employed as a remarkable fluorescent probe for cell labelling because the maximum emission of PDI is beneficial for bio-imaging. The flow cytometry and confocal laser scanning microscopy analysis demonstrate that the micelles are easily endocytosed by cancer cells. In vitro and in vivo tumor growth-inhibitory studies reveal a better therapeutic effect of FSMs after CPT encapsulation when compared with the free CPT drug. The multifunctional FSM nanomedicine platform as a nanovehicle has great potential for fluorescence imaging-guided cancer therapy.A novel smart fluorescent drug delivery system composed of a perylene diimide (PDI) core and block copolymer poly(d,l-lactide)-b-poly(ethyl ethylene phosphate) is developed and named as PDI-star-(PLA-b-PEEP)8. The biodegradable PDI-star-(PLA-b-PEEP)8 is a unimolecular micelle and can self-assemble into supramolecular micelles, called as fluorescent supramolecular micelles (FSMs), in aqueous media. An insoluble drug camptothecin (CPT) can be effectively loaded into the FSMs and exhibits pH-responsive release. Moreover, the FSMs with good biocompatibility can also be employed as a remarkable fluorescent probe for cell labelling because the maximum emission of PDI is beneficial for bio-imaging. The flow cytometry and confocal laser scanning microscopy analysis demonstrate that the micelles are easily endocytosed by cancer cells. In vitro and in vivo tumor growth

  18. Applications of chiral symmetry

    Energy Technology Data Exchange (ETDEWEB)

    Pisarski, R.D.

    1995-03-01

    The author discusses several topics in the applications of chiral symmetry at nonzero temperature. First, where does the rho go? The answer: up. The restoration of chiral symmetry at a temperature T{sub {chi}} implies that the {rho} and a{sub 1} vector mesons are degenerate in mass. In a gauged linear sigma model the {rho} mass increases with temperature, m{sub {rho}}(T{sub {chi}}) > m{sub {rho}}(0). The author conjectures that at T{sub {chi}} the thermal {rho} - a{sub 1}, peak is relatively high, at about {approximately}1 GeV, with a width approximately that at zero temperature (up to standard kinematic factors). The {omega} meson also increases in mass, nearly degenerate with the {rho}, but its width grows dramatically with temperature, increasing to at least {approximately}100 MeV by T{sub {chi}}. The author also stresses how utterly remarkable the principle of vector meson dominance is, when viewed from the modern perspective of the renormalization group. Secondly, he discusses the possible appearance of disoriented chiral condensates from {open_quotes}quenched{close_quotes} heavy ion collisions. It appears difficult to obtain large domains of disoriented chiral condensates in the standard two flavor model. This leads to the last topic, which is the phase diagram for QCD with three flavors, and its proximity to the chiral critical point. QCD may be very near this chiral critical point, and one might thereby generated large domains of disoriented chiral condensates.

  19. The covariant chiral ring

    Science.gov (United States)

    Bourget, Antoine; Troost, Jan

    2016-03-01

    We construct a covariant generating function for the spectrum of chiral primaries of symmetric orbifold conformal field theories with N = (4 , 4) supersymmetry in two dimensions. For seed target spaces K3 and T 4, the generating functions capture the SO(21) and SO(5) representation theoretic content of the chiral ring respectively. Via string dualities, we relate the transformation properties of the chiral ring under these isometries of the moduli space to the Lorentz covariance of perturbative string partition functions in flat space.

  20. The Covariant Chiral Ring

    CERN Document Server

    Bourget, Antoine

    2015-01-01

    We construct a covariant generating function for the spectrum of chiral primaries of symmetric orbifold conformal field theories with N=(4,4) supersymmetry in two dimensions. For seed target spaces K3 and T4, the generating functions capture the SO(21) and SO(5) representation theoretic content of the chiral ring respectively. Via string dualities, we relate the transformation properties of the chiral ring under these isometries of the moduli space to the Lorentz covariance of perturbative string partition functions in flat space.

  1. Protein-based polymers that bond to DNA : design of virus-like particles and supramolecular nanostructures

    NARCIS (Netherlands)

    Hernandez Garcia, A.

    2014-01-01

     In this thesis it is demonstrated that it is possible to use Protein-based Polymers (PbPs) as synthetic binders of DNA (or any other negatively charged polyelectrolyte). The PbPs co-assemble with their DNA templates to form highly organized virus-like particles and supramolecular structures. A

  2. Hydrolytic and oxidative degradation of electrospun supramolecular biomaterials: In vitro degradation pathways.

    Science.gov (United States)

    Brugmans, M C P; Sӧntjens, S H M; Cox, M A J; Nandakumar, A; Bosman, A W; Mes, T; Janssen, H M; Bouten, C V C; Baaijens, F P T; Driessen-Mol, A

    2015-11-01

    The emerging field of in situ tissue engineering (TE) of load bearing tissues places high demands on the implanted scaffolds, as these scaffolds should provide mechanical stability immediately upon implantation. The new class of synthetic supramolecular biomaterial polymers, which contain non-covalent interactions between the polymer chains, thereby forming complex 3D structures by self assembly. Here, we have aimed to map the degradation characteristics of promising (supramolecular) materials, by using a combination of in vitro tests. The selected biomaterials were all polycaprolactones (PCLs), either conventional and unmodified PCL, or PCL with supramolecular hydrogen bonding moieties (either 2-ureido-[1H]-pyrimidin-4-one or bis-urea units) incorporated into the backbone. As these materials are elastomeric, they are suitable candidates for cardiovascular TE applications. Electrospun scaffold strips of these materials were incubated with solutions containing enzymes that catalyze hydrolysis, or solutions containing oxidative species. At several time points, chemical, morphological, and mechanical properties were investigated. It was demonstrated that conventional and supramolecular PCL-based polymers respond differently to enzyme-accelerated hydrolytic or oxidative degradation, depending on the morphological and chemical composition of the material. Conventional PCL is more prone to hydrolytic enzymatic degradation as compared to the investigated supramolecular materials, while, in contrast, the latter materials are more susceptible to oxidative degradation. Given the observed degradation pathways of the examined materials, we are able to tailor degradation characteristics by combining selected PCL backbones with additional supramolecular moieties. The presented combination of in vitro test methods can be employed to screen, limit, and select biomaterials for pre-clinical in vivo studies targeted to different clinical applications. PMID:26316031

  3. Hydrolytic and oxidative degradation of electrospun supramolecular biomaterials: In vitro degradation pathways.

    Science.gov (United States)

    Brugmans, M C P; Sӧntjens, S H M; Cox, M A J; Nandakumar, A; Bosman, A W; Mes, T; Janssen, H M; Bouten, C V C; Baaijens, F P T; Driessen-Mol, A

    2015-11-01

    The emerging field of in situ tissue engineering (TE) of load bearing tissues places high demands on the implanted scaffolds, as these scaffolds should provide mechanical stability immediately upon implantation. The new class of synthetic supramolecular biomaterial polymers, which contain non-covalent interactions between the polymer chains, thereby forming complex 3D structures by self assembly. Here, we have aimed to map the degradation characteristics of promising (supramolecular) materials, by using a combination of in vitro tests. The selected biomaterials were all polycaprolactones (PCLs), either conventional and unmodified PCL, or PCL with supramolecular hydrogen bonding moieties (either 2-ureido-[1H]-pyrimidin-4-one or bis-urea units) incorporated into the backbone. As these materials are elastomeric, they are suitable candidates for cardiovascular TE applications. Electrospun scaffold strips of these materials were incubated with solutions containing enzymes that catalyze hydrolysis, or solutions containing oxidative species. At several time points, chemical, morphological, and mechanical properties were investigated. It was demonstrated that conventional and supramolecular PCL-based polymers respond differently to enzyme-accelerated hydrolytic or oxidative degradation, depending on the morphological and chemical composition of the material. Conventional PCL is more prone to hydrolytic enzymatic degradation as compared to the investigated supramolecular materials, while, in contrast, the latter materials are more susceptible to oxidative degradation. Given the observed degradation pathways of the examined materials, we are able to tailor degradation characteristics by combining selected PCL backbones with additional supramolecular moieties. The presented combination of in vitro test methods can be employed to screen, limit, and select biomaterials for pre-clinical in vivo studies targeted to different clinical applications.

  4. Catalysis of Dynamical Chiral Symmetry Breaking by Chiral Chemical Potential

    CERN Document Server

    Braguta, V V

    2016-01-01

    In this paper we study the properties of media with chiral imbalance parameterized by chiral chemical potential. It is shown that depending on the strength of interaction between constituents in the media the chiral chemical potential either creates or enhances dynamical chiral symmetry breaking. Thus the chiral chemical potential plays a role of the catalyst of dynamical chiral symmetry breaking. Physically this effect results from the appearance of the Fermi surface and additional fermion states on this surface which take part in dynamical chiral symmetry breaking. An interesting conclusion which can be drawn is that at sufficiently small temperature chiral plasma is unstable with respect to condensation of Cooper pairs and dynamical chiral symmetry breaking even for vanishingly small interactions between constituents.

  5. Rapid fabrication of hierarchically structured supramolecular nanocomposite thin films in one minute.

    Science.gov (United States)

    Kao, Joseph; Thorkelsson, Kari; Bai, Peter; Zhang, Zhen; Sun, Cheng; Xu, Ting

    2014-01-01

    Functional nanocomposites containing nanoparticles of different chemical compositions may exhibit new properties to meet demands for advanced technology. It is imperative to simultaneously achieve hierarchical structural control and to develop rapid, scalable fabrication to minimize degradation of nanoparticle properties and for compatibility with nanomanufacturing. Here we show that the assembly kinetics of supramolecular nanocomposites in thin films are governed by the energetic cost arising from defects, the chain mobility and the activation energy for inter-domain diffusion. By optimizing only one parameter, the solvent fraction in the film, the assembly kinetics can be precisely tailored to produce hierarchically structured thin films of supramolecular nanocomposites in one minute. Moreover, the strong wavelength-dependent optical anisotropy in the nanocomposite highlights their potential applications for light manipulation and information transmission. The present study may open a new avenue in designing manufacture-friendly continuous processing for the fabrication of functional nanocomposite thin films. PMID:24887144

  6. Unveiling the molecular mechanism of self-healing in a telechelic, supramolecular polymer network

    Science.gov (United States)

    Yan, Tingzi; Schröter, Klaus; Herbst, Florian; Binder, Wolfgang H.; Thurn-Albrecht, Thomas

    2016-09-01

    Reversible polymeric networks can show self-healing properties due to their ability to reassemble after application of stress and fracture, but typically the relation between equilibrium molecular dynamics and self-healing kinetics has been difficult to disentangle. Here we present a well-characterized, self-assembled bulk network based on supramolecular assemblies, that allows a clear distinction between chain dynamics and network relaxation. Small angle x-ray scattering and rheological measurements provide evidence for a structurally well-defined, dense network of interconnected aggregates giving mechanical strength to the material. Different from a covalent network, the dynamic character of the supramolecular bonds enables macroscopic flow on a longer time scale and the establishment of an equilibrium structure. A combination of linear and nonlinear rheological measurements clearly identifies the terminal relaxation process as being responsible for the process of self-healing.

  7. A recyclable supramolecular membrane for size-selective separation of nanoparticles

    Science.gov (United States)

    Krieg, Elisha; Weissman, Haim; Shirman, Elijah; Shimoni, Eyal; Rybtchinski, Boris

    2011-03-01

    Most practical materials are held together by covalent bonds, which are irreversible. Materials based on noncovalent interactions can undergo reversible self-assembly, which offers advantages in terms of fabrication, processing and recyclability, but the majority of noncovalent systems are too fragile to be competitive with covalent materials for practical applications, despite significant attempts to develop robust noncovalent arrays. Here, we report nanostructured supramolecular membranes prepared from fibrous assemblies in water. The membranes are robust due to strong hydrophobic interactions, allowing their application in the size-selective separation of both metal and semiconductor nanoparticles. A thin (12 µm) membrane is used for filtration (~5 nm cutoff), and a thicker (45 µm) membrane allows for size-selective chromatography in the sub-5 nm domain. Unlike conventional membranes, our supramolecular membranes can be disassembled using organic solvent, cleaned, reassembled and reused multiple times.

  8. Color chiral solitons

    CERN Document Server

    Novozhilov, V Yu; Novozhilov, Victor; Novozhilov, Yuri

    2002-01-01

    We discuss specific features of color chiral solitons (asymptotics, possibility of confainment, quantization) at example of isolated SU(2) color skyrmions, i.e. skyrmions in a background field which is the vacuum field forming the gluon condensate.

  9. Information processing in the CNS: a supramolecular chemistry?

    Science.gov (United States)

    Tozzi, Arturo

    2015-10-01

    How does central nervous system process information? Current theories are based on two tenets: (a) information is transmitted by action potentials, the language by which neurons communicate with each other-and (b) homogeneous neuronal assemblies of cortical circuits operate on these neuronal messages where the operations are characterized by the intrinsic connectivity among neuronal populations. In this view, the size and time course of any spike is stereotypic and the information is restricted to the temporal sequence of the spikes; namely, the "neural code". However, an increasing amount of novel data point towards an alternative hypothesis: (a) the role of neural code in information processing is overemphasized. Instead of simply passing messages, action potentials play a role in dynamic coordination at multiple spatial and temporal scales, establishing network interactions across several levels of a hierarchical modular architecture, modulating and regulating the propagation of neuronal messages. (b) Information is processed at all levels of neuronal infrastructure from macromolecules to population dynamics. For example, intra-neuronal (changes in protein conformation, concentration and synthesis) and extra-neuronal factors (extracellular proteolysis, substrate patterning, myelin plasticity, microbes, metabolic status) can have a profound effect on neuronal computations. This means molecular message passing may have cognitive connotations. This essay introduces the concept of "supramolecular chemistry", involving the storage of information at the molecular level and its retrieval, transfer and processing at the supramolecular level, through transitory non-covalent molecular processes that are self-organized, self-assembled and dynamic. Finally, we note that the cortex comprises extremely heterogeneous cells, with distinct regional variations, macromolecular assembly, receptor repertoire and intrinsic microcircuitry. This suggests that every neuron (or group of

  10. Self-organized internal architectures of chiral micro-particles

    International Nuclear Information System (INIS)

    The internal architecture of polymeric self-assembled chiral micro-particles is studied by exploring the effect of the chirality, of the particle sizes, and of the interface/surface properties in the ordering of the helicoidal planes. The experimental investigations, performed by means of different microscopy techniques, show that the polymeric beads, resulting from light induced polymerization of cholesteric liquid crystal droplets, preserve both the spherical shape and the internal self-organized structures. The method used to create the micro-particles with controlled internal chiral architectures presents great flexibility providing several advantages connected to the acquired optical and photonics capabilities and allowing to envisage novel strategies for the development of chiral colloidal systems and materials

  11. Chiral Odd GPDs

    Directory of Open Access Journals (Sweden)

    Goldstein Gary R.

    2015-01-01

    Full Text Available Nucleon spin structure, transversity and the tensor charge are of central importance to understanding the role of QCD in hadronic physics. A new approach to measuring orbital angular momenta of quarks in the proton via twist 3 GPDs is shown. The “flexible parametrization” of chiral even GPDs is reviewed and its transformation into the chiral odd sector is discussed. The resulting parametrization is applied to recent data on π0 and η electroproduction.

  12. Chiral separation in microflows

    OpenAIRE

    Kostur, Marcin; Schindler, Michael; Talkner, Peter; Hänggi, Peter

    2005-01-01

    Molecules that only differ by their chirality, so called enantiomers, often possess different properties with respect to their biological function. Therefore, the separation of enantiomers presents a prominent challenge in molecular biology and belongs to the ``Holy Grail'' of organic chemistry. We suggest a new separation technique for chiral molecules that is based on the transport properties in a microfluidic flow with spatially variable vorticity. Because of their size the thermal fluctua...

  13. The quest for chirality

    Energy Technology Data Exchange (ETDEWEB)

    Bonner, W.A. [Department of Chemistry Stanford University, Stanford, California 94305 (United States)

    1996-07-01

    The indispensable role played by homochirality and chiral homogeneity in the self-replication of crucial biomolecules is stressed, with the conclusion that life could neither exist nor originate without these chiral molecular attributes. Hypotheses historically proposed for the origin of chiral molecules on Earth are reviewed, including biogenic theories as well as abiotic theories embracing both indeterminate and determinate mechanisms. Indeterminate mechanisms, including autocatalytic symmetry breaking, asymmetric adsorption on quartz and clay minerals, and asymmetric syntheses in chiral crystals, are discussed and evaluated in the context of the prebiotic environment. Abiotic determinate mechanisms based on electric, magnetic and gravitational fields, on circularly polarized light (CPL), and on parity violation effects are summarized, with the emphasis that only CPL has proved practicable experimentally, but that it would be implausible on the primitive Earth. Mechanisms for the amplification of small, indigenous enantiomeric excesses are discussed, with one involving the partial polymerization of amino acids and the partial hydrolysis of polypeptides suggested as potentially viable prebiotically. Aspects of the turbulent, chirality-destructive primeval environment are described, with the conclusion that all of the above mechanisms for the {ital terrestrial} prebiotic origin of chirality would be non-viable, and that an alternative extraterrestrial source for the accumulation of chiral molecules on primitive Earth must have been operative. A scenario for this is outlined, in which we postulate that asymmetric photolysis of the organic mantles on interstellar grains in molecular clouds by circularly polarized ultraviolet synchrotron radiation from the neutron star remnants of supernovae produces chiral molecules in the grain mantles. (Abstract Truncated)

  14. Supramolecular organic frameworks: engineering periodicity in water through host-guest chemistry.

    Science.gov (United States)

    Tian, Jia; Chen, Lan; Zhang, Dan-Wei; Liu, Yi; Li, Zhan-Ting

    2016-05-11

    The development of homogeneous, water-soluble periodic self-assembled structures comprise repeating units that produce porosity in two-dimensional (2D) or three-dimensional (3D) spaces has become a topic of growing interest in the field of supramolecular chemistry. Such novel self-assembled entities, known as supramolecular organic frameworks (SOFs), are the result of programmed host-guest interactions, which allows for the thermodynamically controlled generation of monolayer sheets or a diamondoid architecture with regular internal cavities or pores under mild conditions. This feature article aims at propagating the conceptually novel SOFs as a new entry into conventional supramolecular polymers. In the first section, we will describe the background of porous solid frameworks and supramolecular polymers. We then introduce the self-assembling behaviour of several multitopic flexible molecules, which is closely related to the design of periodic SOFs from rigid multitopic building blocks. This is followed by a brief discussion of cucurbit[8]uril (CB[8])-encapsulation-enhanced aromatic stacking in water. The three-component host-guest pattern based on this stacking motif has been utilized to drive the formation of most of the new SOFs. In the following two sections, we will highlight the main advances in the construction of 2D and 3D SOFs and the related functional aspects. Finally, we will offer our opinions on future directions for both structures and functions. We hope that this article will trigger the interest of researchers in the field of chemistry, physics, biology and materials science, which should help accelerate the applications of this new family of soft self-assembled organic frameworks.

  15. Nanocellulose Derivative/Silica Hybrid Core-Shell Chiral Stationary Phase: Preparation and Enantioseparation Performance

    OpenAIRE

    Xiaoli Zhang; Litao Wang; Shuqing Dong; Xia Zhang; Qi Wu; Liang Zhao; Yanping Shi

    2016-01-01

    Core-shell silica microspheres with a nanocellulose derivative in the hybrid shell were successfully prepared as a chiral stationary phase by a layer-by-layer self-assembly method. The hybrid shell assembled on the silica core was formed using a surfactant as template by the copolymerization reaction of tetraethyl orthosilicate and the nanocellulose derivative bearing triethoxysilyl and 3,5-dimethylphenyl groups. The resulting nanocellulose hybrid core-shell chiral packing materials (CPMs) we...

  16. Bottom-up graphene-nanoribbon fabrication reveals chiral edges and enantioselectivity.

    Science.gov (United States)

    Han, Patrick; Akagi, Kazuto; Federici Canova, Filippo; Mutoh, Hirotaka; Shiraki, Susumu; Iwaya, Katsuya; Weiss, Paul S; Asao, Naoki; Hitosugi, Taro

    2014-09-23

    We produce precise chiral-edge graphene nanoribbons on Cu{111} using self-assembly and surface-directed chemical reactions. We show that, using specific properties of the substrate, we can change the edge conformation of the nanoribbons, segregate their adsorption chiralities, and restrict their growth directions at low surface coverage. By elucidating the molecular-assembly mechanism, we demonstrate that our method constitutes an alternative bottom-up strategy toward synthesizing defect-free zigzag-edge graphene nanoribbons.

  17. Principles of self-assembly of helical pores from dendritic dipeptides

    Science.gov (United States)

    Percec, Virgil; Dulcey, Andrés E.; Peterca, Mihai; Ilies, Monica; Nummelin, Sami; Sienkowska, Monika J.; Heiney, Paul A.

    2006-01-01

    The self-assembly of the dendritic dipeptides (4-3,4-3,5)nG2-CH2-Boc-l-Tyr-l-Ala-OMe and their achiral dendritic alcohol (4-3,4-3,5)nG2-CH2OH precursors, both with n = 1–16, where n represents the number of methylenic units in the alkyl groups of the dendron, are reported. All chiral dendritic dipeptides and achiral dendritic alcohols self-assemble into helical porous columns that are stable in both solution and solid state. The pore diameter (Dpore) of the columns self-assembled from dendritic dipeptides is ≈10 Å larger than that of structures assembled from dendritic alcohols. The increase of the Dpore at the transition from dendritic alcohol to dendritic dipeptide is accompanied by a decreased solid angle of the building block. This trend is in agreement with previous pore size-solid angle dependences observed with different protective groups of the dipeptide and primary structures of the dendron. However, within the series of dendritic alcohols and dendritic dipeptides with various n, the Dpore increases when the solid angle increases. The results of these investigations together with those of previous studies on the role of dipeptide stereochemistry and protective groups on this self-assembly process provide the molecular principles required to program the construction of supramolecular helical pores with diameter controlled at the Å level from a single dendritic dipeptide architecture. These principles are expected to be valid for libraries of dendritic dipeptides based on dendrons and dipeptides with various primary structures. PMID:16469843

  18. Supramolecular nanofibrils inhibit cancer progression in vitro and in vivo

    Science.gov (United States)

    Kuang, Yi; Du, Xuewen; Zhou, Jie; Xu, Bing

    2014-01-01

    The recent discovery of the inverse comorbidity between cancer and Alzheimer’s disease implies that one may use amyloids to inhibit tumors. During the conversion of a dipeptide segment (Phe-Phe) in β-amyloid into a supramolecular hydrogelator, we obtained a small molecule (1) that can self-assembly into nanofibrils via multiple intermolecular hydrogen bonding and aromatic-aromatic interactions. Interestingly, while the monomers of 1 are innocuous, the nanofibrils formed by 1 can selectively inhibit the growth of glioblastoma cells over neuronal cells. To further assess the potential of this small molecular nanofibrils as anti-cancer agent, we exam the biological activity of the nanofibrils and demonstrate that the nanofibrils of 1 efficiently inhibit the progression of cancer cells (e.g., HeLa cells) both in cell assays and on xenograft mice model. This work suggests that nanofibrils derived from core motif of amyloid are effective agents for inhibiting cancer progression. Thus, this work contributes to a new approach that uses supramolecular nanofibrils as de novo molecular amyloids for inhibiting the growth of cancer cells. PMID:24574174

  19. Supramolecular architecture of endoplasmic reticulum-plasma membrane contact sites.

    Science.gov (United States)

    Fernández-Busnadiego, Rubén

    2016-04-15

    The endoplasmic reticulum (ER) forms membrane contact sites (MCS) with most other cellular organelles and the plasma membrane (PM). These ER-PM MCS, where the membranes of the ER and PM are closely apposed, were discovered in the early days of electron microscopy (EM), but only recently are we starting to understand their functional and structural diversity. ER-PM MCS are nowadays known to mediate excitation-contraction coupling (ECC) in striated muscle cells and to play crucial roles in Ca(2+)and lipid homoeostasis in all metazoan cells. A common feature across ER-PM MCS specialized in different functions is the preponderance of cooperative phenomena that result in the formation of large supramolecular assemblies. Therefore, characterizing the supramolecular architecture of ER-PM MCS is critical to understand their mechanisms of function. Cryo-electron tomography (cryo-ET) is a powerful EM technique uniquely positioned to address this issue, as it allows 3D imaging of fully hydrated, unstained cellular structures at molecular resolution. In this review I summarize our current structural knowledge on the molecular organization of ER-PM MCS and its functional implications, with special emphasis on the emerging contributions of cryo-ET. PMID:27068966

  20. Dynamic Chirality in Nuclei

    International Nuclear Information System (INIS)

    Chirality has recently been proposed as a novel feature of rotating nuclei [1]. Because the chiral symmetry is dichotomic, its spontaneous breaking by the axial angular momentum vector leads to doublets of closely lying rotational bands of the same parity. To investigate nuclear chirality, next to establish the existence of almost degenerate rotational bands, it is necessary to measure also other observables and compare them to the model predictions. The crucial test for the suggested nuclei as candidates to express chirality is based on precise lifetime measurements. Two lifetime experiments and theoretical approaches for the description of the experimental results will be presented. Lifetimes of exited states in 134Pr were measured [2,3] by means of the recoil distance Doppler-shift and Doppler-shift attenuation techniques. The branching ratios and the electric or magnetic character of the transitions were also investigated [3]. The experiments were performed at IReS, Strasbourg, using the EUROBALL IV spectrometer, in conjunction with the inner bismuth germanate ball and the Cologne coincidence plunger apparatus. Exited states in 134Pr were populated in the fusion-evaporation reaction 119Sn(19F, 4n)134Pr. The possible chiral interpretation of twin bands was investigated in the two-quasiparticle triaxial rotor [1] and interacting boson-fermion-fermion models [4]. Both theoretical approaches can describe the level-scheme of 134Pr. The analysis of the wave functions has shown that the possibility for the angular momenta of the proton, neutron, and core to find themselves in the favorable, almost orthogonal geometry, is present but is far from being dominant [3,5]. The structure is characterized by large β and γ fluctuations. The existence of doublets of bands in 134Pr can be attributed to weak chirality dominated by shape fluctuations. In a second experiment branching ratios and lifetimes in 136Pm were measured by means of the recoil distance Doppler-shift and