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Sample records for acid-labile temperature-responsive copolymers

  1. Acid-Labile Amphiphilic PEO-b-PPO-b-PEO Copolymers: Degradable Poloxamer Analogs.

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

    2016-05-01

    Poly ((ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)) triblock copolymers commonly known as poloxamers or Pluronics constitute an important class of nonionic, biocompatible surfactants. Here, a method is reported to incorporate two acid-labile acetal moieties in the backbone of poloxamers to generate acid-cleavable nonionic surfactants. Poly(propylene oxide) is functionalized by means of an acetate-protected vinyl ether to introduce acetal units. Three cleavable PEO-PPO-PEO triblock copolymers (Mn,total = 6600, 8000, 9150 g·mol(-1) ; Mn,PEO = 2200, 3600, 4750 g·mol(-1) ) have been synthesized using anionic ring-opening polymerization. The amphiphilic copolymers exhibit narrow molecular weight distributions (Ð = 1.06-1.08). Surface tension measurements reveal surface-active behavior in aqueous solution comparable to established noncleavable poloxamers. Complete hydrolysis of the labile junctions after acidic treatment is verified by size exclusion chromatography. The block copolymers have been employed as surfactants in a miniemulsion polymerization to generate polystyrene (PS) nanoparticles with mean diameters of ≈200 nm and narrow size distribution, as determined by dynamic light scattering and scanning electron microscopy. Acid-triggered precipitation facilitates removal of surfactant fragments from the nanoparticles, which simplifies purification and enables nanoparticle precipitation "on demand." PMID:27000789

  2. Novel poly(ethylene oxide monomethyl ether)-b-poly(.epsilon.-caprolactone) diblock copolymers containing a pH-acid labile ketal group as a block linkage

    Petrova, Svetlana; Jäger, Eliezer; Konefal, Rafal; Jäger, Alessandro; Venturini, Cristina Garcia; Štěpánek, Petr

    Sofia : Institute of Polymers BAS, 2015. P2-25. [Challenges in Science and Technology of Polymer Materials. 19.05.2015-23.05.2015, Bansko] R&D Projects: GA MŠk(CZ) LH14292 Institutional support: RVO:61389013 Keywords : acid-labile degradable linkage * MPEO-b-PCL diblock copolymers Subject RIV: CC - Organic Chemistry

  3. PEG-detachable and acid-labile cross-linked micelles based on orthoester linked graft copolymer for paclitaxel release

    Yuan, Zhefan; Huang, Jingyi; Liu, Jing; Cheng, Sixue; Zhuo, Renxi; Li, Feng

    2011-08-01

    Polyethylene glycol detachable graft copolymer, mPEG-g-p(NAS-co-BMA), was synthesized by grafting 2-(ω-methoxy)PEGyl-1,3-dioxan-5-ylamine onto poly(N-(acryloyloxy)succinimide-co-butyl methacrylate). Pseudo in situ cross-linking of the mPEG-g-p(NAS-co-BMA) was performed in dimethylformamide phosphate buffer (v/v = 1/1) by an acid-labile diamine cross-linker bearing two symmetrical cyclic orthoesters. The cross-linked (CL) micelles with different contents of mPEG segments represented different morphologies. The CL micelles containing approximately one mPEG segment exhibited 'echini' morphology whereas the CL micelle with approximately three mPEG segments formed nanowires. The hydrolysis rate of the CL micelles is highly pH-dependent and much more rapid at mild acid than physiological conditions. Hydrolyzates of the CL micelles formed vesicles because new amphiphilic copolymers were formed. Paclitaxel (PTX) was successfully loaded into the CL micelles and a controlled and pH-dependent release behavior was observed. No obvious cytotoxicity was found for the CL micelles at concentration as high as 800 mg l - 1.

  4. Novel poly(ethylene oxide monomethyl ether)-b-poly(.epsilon.-caprolactone) diblock copolymers containing a pH-acid labile ketal group as a block linkage

    Petrova, Svetlana; Jäger, Eliezer; Konefal, Rafal; Jäger, Alessandro; Venturini, Cristina Garcia; Spěváček, Jiří; Pavlova, Ewa; Štěpánek, Petr

    2014-01-01

    Roč. 5, č. 12 (2014), s. 3884-3893. ISSN 1759-9954 R&D Projects: GA ČR GAP208/10/1600; GA TA ČR TE01020118 Institutional support: RVO:61389013 Keywords : MPOE-b-PCL diblock copolymer s * ring-opening polymerization * "click" chemistry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.520, year: 2014

  5. Synthesis and Properties of pH and Temperature Responsive Copolymer with Pesudorotaxane Structure

    MA Qiang; YANG Hui; XU Wen-chao; TAN Ye-bang

    2012-01-01

    pH and temperature responsive copolymers PNAM4VBCB of N-isopropyl acrylamide(NAM) and complex pseudorotaxane monomer N1-(4-vinylbenzyl)-1,4-diaminobutane dihydrochloride with cucurbit[6]uril(CB[6])threaded(4VBCB) were prepared via free-radical polymerization in aqueous solution.The copolymers were characterized by 1H NMR,Fourier transform infrared(FTIR) spectrometry,elemental analysis,and static light scattering.The thermodynamic properties of the copolymers were studied by thermogravimetric analysis(TGA),and the effects of pH and the concentration of the copolymer on the average hydrodynamic radius(Rh) were studied by dynamic light scattering(DLS).In addition,the thermal sensitivities of the copolymers were studied by DLS and UV-Vis.The experiment data show that CB[6] beads are localized on 1,4-diaminobutane units in the side chains of the copolymer.TGA data show that thermal stability of the copolymers increases with the adding of CB[6] threaded because of the enhanced rigidity and the bulky steric hindrance of 4VBCB in the side chain of PNAM4VBCB.DLS data show that the average hydrodynamic radius of copolymer increases with the increase of the copolymer concentration and has a jump with adjusting pH due to the existing of the small size CB[6] dethreaded from the copolymer with increasing pH.Both pH and electrical conductivity curves of the solution of PNAM4VBCB-4 have a jump because CB[6] could dethread from the copolymers with the addition of NaOH.In addition,the copolymers have thermal sensitivity and their phase-change temperatures could be controlled by adjusting the molar ratio of NAM to 4VBCB in the copolymers.

  6. Temperature-responsive liquid chromatography. 2. Effects of hydrophobic groups in N-isopropylacrylamide copolymer-modified silica.

    Kanazawa, H; Kashiwase, Y; Yamamoto, K; Matsushima, Y; Kikuchi, A; Sakurai, Y; Okano, T

    1997-03-01

    We recently reported the new concept of temperature-responsive liquid chromatography using temperature-responsive poly(N-isopropylacrylamide)-modified surfaces as high-performance liquid chromatography media with aqueous mobile phases. Incorporation of hydrophobic sites is an important factor to improve the efficacy (selectivity and retention) of temperature-responsive chromatography. Toward this goal, we have synthesized semitelechelic copolymers of N-isopropylacrylamide (IPAAm) and butyl methacrylate (BMA) having reactive terminal functional groups using telomerization. The lower critical solution temperatures of the copolymers shift to lower temperatures with increasing hydrophobic BMA content in the poly(IPAAm-co-BMA) relative to that of the IPAAm homopolymer. This temperature-responsive semitelechelic copolymer was grafted to the surface of (aminopropyl)silica through the reaction of activated ester-amine coupling. The polymer-modified silica was used as a column packing material. Separation of a mixture of five steroids having various hydrophobicities was investigated. Retention of steroids on poly(IPAAm-co-BMA)-modified columns is increased with an increase in column temperature. The capacity factors for steroids on the copolymer-modified silica beads was much larger than that on homopolymer PIPAAm-modified columns. The capacity factor for testosterone at 50 degrees C was 33.8 for poly(IPAAm-co-BMA) containing 5 mol% BMA, while that for the PIPAAm homopolymer was 15.0 at the same temperature. The influence of column temperature on steroid retention behavior on copolymer-modified stationary phases was significant compared with the case of homopolymer-modified columns. Furthermore, retention times for steroids increased remarkably with increasing BMA composition. The temperature-responsive elution behavior for the steroids was strongly affected by the hydrophobicity of the grafted polymer chains on silica surfaces. Possible protein separation in temperature-responsive

  7. Temperature-Responsive Biocompatible Copolymers Incorporating Hyperbranched Polyglycerols for Adjustable Functionality

    Alan J. House

    2011-08-01

    Full Text Available Temperature-triggered copolymers are proposed for a number of bio-applications but there is no ideal material platform, especially for injectable drug delivery. Options are needed for degradable biomaterials that not only respond to temperature but also easily accommodate linkage of active molecules. A first step toward realizing this goal is the design and synthesis of the novel materials reported herein. A multifunctional macromer, methacrylated hyperbranched polyglycerol (HPG-MA with an average of one acrylate unit per copolymer, was synthesized and copolymerized with N-isopropylacrylamide (NIPAAm, hydroxyethyl methacrylate-polylactide (HEMAPLA and acrylic acid (AAc. The potential to fully exploit the copolymers by modification of the multiple HPG hydroxyl groups will not be discussed here. Instead, this report focuses on the thermoresponsive, biocompatible, and degradation properties of the material. Poly(NIPAAm-co-HEMAPLA-co-AAc-co-HPG-MA displayed increasing lower critical solution temperatures (LCST as the HPG content increased over a range of macromer ratios. For the copolymer with the maximum HPG incorporation (17%, the LCST was ~30 °C. In addition, this sample showed no toxicity when human uterine fibroid cells were co-cultured with the copolymer for up to 72 h. This copolymer lost approximately 92% of its mass after 17 hours at 37 °C. Thus, the reported biomaterials offer attractive properties for the design of drug delivery systems where orthogonally triggered mechanisms of therapeutic release in relatively short time periods would be attractive.

  8. Human acid-labile subunit deficiency: clinical, endocrine and metabolic consequences.

    Domene, H.M.; Hwa, V.; Argente, J.; Wit, J.M.; Camacho-Hubner, C.; Jasper, H.G.; Pozo, J.; Duyvenvoorde, H.A. van; Yakar, S.; Fofanova-Gambetti, O.V.; Rosenfeld, R.G.; Hermus, A.R.M.M.; Twickler, T.B.; Kempers, M.J.E.

    2009-01-01

    The majority of insulin-like growth factor (IGF)-I and IGF-II circulate in the serum as a complex with the insulin-like growth factor binding protein (IGFBP)-3 or IGFBP-5, and an acid-labile subunit (ALS). The function of ALS is to prolong the half-life of the IGF-I-IGFBP-3/IGFBP-5 binary complexes.

  9. Internal Nanoparticle Structure of Temperature-Responsive Self-Assembled PNIPAM-b-PEG-b-PNIPAM Triblock Copolymers in Aqueous Solutions: NMR, SANS, and Light Scattering Studies.

    Filippov, Sergey K; Bogomolova, Anna; Kaberov, Leonid; Velychkivska, Nadiia; Starovoytova, Larisa; Cernochova, Zulfiya; Rogers, Sarah E; Lau, Wing Man; Khutoryanskiy, Vitaliy V; Cook, Michael T

    2016-05-31

    In this study, we report detailed information on the internal structure of PNIPAM-b-PEG-b-PNIPAM nanoparticles formed from self-assembly in aqueous solutions upon increase in temperature. NMR spectroscopy, light scattering, and small-angle neutron scattering (SANS) were used to monitor different stages of nanoparticle formation as a function of temperature, providing insight into the fundamental processes involved. The presence of PEG in a copolymer structure significantly affects the formation of nanoparticles, making their transition to occur over a broader temperature range. The crucial parameter that controls the transition is the ratio of PEG/PNIPAM. For pure PNIPAM, the transition is sharp; the higher the PEG/PNIPAM ratio results in a broader transition. This behavior is explained by different mechanisms of PNIPAM block incorporation during nanoparticle formation at different PEG/PNIPAM ratios. Contrast variation experiments using SANS show that the structure of nanoparticles above cloud point temperatures for PNIPAM-b-PEG-b-PNIPAM copolymers is drastically different from the structure of PNIPAM mesoglobules. In contrast with pure PNIPAM mesoglobules, where solidlike particles and chain network with a mesh size of 1-3 nm are present, nanoparticles formed from PNIPAM-b-PEG-b-PNIPAM copolymers have nonuniform structure with "frozen" areas interconnected by single chains in Gaussian conformation. SANS data with deuterated "invisible" PEG blocks imply that PEG is uniformly distributed inside of a nanoparticle. It is kinetically flexible PEG blocks which affect the nanoparticle formation by prevention of PNIPAM microphase separation. PMID:27159129

  10. The acid-labile subunit of human ternary insulin-like growth factor binding protein complex in serum

    Juul, A; Møller, S; Mosfeldt-Laursen, E; Rasmussen, M H; Scheike, Thomas Harder; Pedersen, S A; Kastrup, K W; Yu, Hao; Mistry, J; Rasmussen, S; Müller, J; Henriksen, J; Skakkebaek, N E

    1998-01-01

    not measurable by this approach or, alternatively, that the liver is not the primary source of circulating ALS, IGF-I, or IGFBP-3 in humans. In conclusion, we have provided extensive normal data for a novel ALS assay and found that circulating ALS levels exhibit minor diurnal variation. We suggest......Circulating insulin-like growth factor-I (IGF-I) is predominantly bound in the trimeric complex comprised of IGF binding protein-3 (IGFBP-3) and acid-labile subunit (ALS). Circulating concentrations of IGF-I, IGFBP-3 and ALS are believed to reflect the GH secretory status, but the clinical use of...

  11. The acid-labile subunit of the ternary insulin-like growth factor complex in cirrhosis: relation to liver dysfunction

    Møller, S; Juul, A; Becker, U; Henriksen, Jens Henrik Sahl

    2000-01-01

    BACKGROUND/AIMS: In the circulation, insulin-like growth factor-I (IGF-I) is bound in a trimeric complex of 150 kDa with IGF binding protein-3 (IGFBP-3) and the acid-labile subunit (ALS). Whereas circulating IGF-I and IGFBP-3 are reported to be low in patients with chronic liver failure, the leve...... significant relations to liver dysfunction and other components of the IGF complex. A small hepatic extraction was found in controls, which suggests extrahepatic production of ALS. Future studies should focus on organ-specific removal of ALS.......BACKGROUND/AIMS: In the circulation, insulin-like growth factor-I (IGF-I) is bound in a trimeric complex of 150 kDa with IGF binding protein-3 (IGFBP-3) and the acid-labile subunit (ALS). Whereas circulating IGF-I and IGFBP-3 are reported to be low in patients with chronic liver failure, the level...... of ALS has not been described in relation to hepatic dysfunction. The aim of the present study was therefore to measure circulating and hepatic venous concentrations of ALS in relation to hepatic function and the IGF axis. METHODS: Twenty-five patients with cirrhosis (Child class A/B/C:5/10/10) and...

  12. The acid-labile subunit of human ternary insulin-like growth factor binding protein complex in serum

    Juul, A; Møller, S; Mosfeldt-Laursen, E;

    1998-01-01

    Circulating insulin-like growth factor-I (IGF-I) is predominantly bound in the trimeric complex comprised of IGF binding protein-3 (IGFBP-3) and acid-labile subunit (ALS). Circulating concentrations of IGF-I, IGFBP-3 and ALS are believed to reflect the GH secretory status, but the clinical use of...... adults; and 4) ALS levels were below -2 SD in 57 of 79 GHD patients (sensitivity 72%) and above 2 SD in 22 of 29 patients with normal GH response (specificity 76%), which was similar, compared with the diagnostic utility of IGF-I and IGFBP-3. Finally, our findings indicate that hepatic ALS production is...... not measurable by this approach or, alternatively, that the liver is not the primary source of circulating ALS, IGF-I, or IGFBP-3 in humans. In conclusion, we have provided extensive normal data for a novel ALS assay and found that circulating ALS levels exhibit minor diurnal variation. We suggest...

  13. The ortho backbone amide linker (o-BAL) is an easily prepared and highly acid-labile handle for solid-phase synthesis

    Boas, Ulrik; Brask, Jesper; Christensen, J.B.;

    2002-01-01

    , followed by purification through steam distillation, Cleavage studies of Leu-enkephalin anchored to either o-BAL or p-BAL handles revealed that both handles were surprisingly acid-labile and released the peptide with dilute TFA (5% and even 1% TFA in CH2Cl2). This useful property allowed the synthesis of...

  14. Direct imaging of nanoscopic plastic deformation below bulk Tg and chain stretching in temperature-responsive block copolymer hydrogels by Cryo-TEM

    Nykänen, Antti; Nuopponen, Markus; Hiekkataipale, Panu; Hirvonen, Sami-Pekka; Soininen, Antti; Tenhu, Heikki; Ikkala, Olli; Mezzenga, Raffaele

    2008-01-01

    This work describes the thermoresponsive transition in polystyrene-block-poly(N-isopropylacrylamide)-block-polystyrene (PS-block-PNIPAM-block-PS) triblock copolymer hydrogels, as observed by both direct and reciprocal space in-situ characterization. The hydrogel morphology was studied in both the dry and wet state, at temperatures below and beyond the coil−globule transition of PNIPAM, using vitrified ice cryo-transmission electron microscopy (cryo-TEM), in-situ freeze-drying technique, and s...

  15. Interaction between acid-labile subunit and insulin-like growth factor binding protein 3 expressed in Xenopus oocytes.

    Choi, Kyung-Yi; Lee, Dong-Hee

    2002-03-31

    The acid-labile subunit (ALS) associates with the insulinlike growth factor (IGF)-I or II, and the IGF binding protein-3 (IGFBP-3) in order to form a 150-kD complex in the circulation. This complex may regulate the serum IGFs by restricting them in the vascular system and promoting their endocrine actions. Little is known about how ALS binds to IGFBP3, which connects the IGFs to ALS. Xenopus oocyte was utilized to study the function of ALS in assembling IGFs into the ternary complexes. Xenopus oocyte was shown to correctly translate in vitro transcribed mRNAs of ALS and IGFBP3. IGFBP3 and ALS mRNAs were injected in a mixture, and their products were immunoprecipitated by antisera against ALS and IGFBP3. Contrary to traditional reports that ALS interacts only with IGF-bound IGFBP3, this study shows that ALS is capable of forming a binary complex with IGFBP3 in the absence of IGF. When cross-linked by disuccinimidyl suberate, the band that represents the ALSIGFBP3 complex was evident on the PAGE. IGFBP3 movement was monitored according to the distribution between the hemispheres. Following a localized translation in the vegetal hemisphere, IGFBP3 remained in the vegetal half in the presence of ALS. However, the mutant IGFBP3 freely diffused into the animal half, despite the presence of ALS, which is different from the wild type IGFBP3. This study, therefore, suggests that ALS may play an important role in sequestering IGFBP3 polypeptides via the intermolecular aggregation. Studies using this heterologous model will lead to a better understanding of the IGFBP3 and ALS that assemble into the ternary structure and circulate the IGF system. PMID:12297028

  16. A simple and inexpensive enteric-coated capsule for delivery of acid-labile macromolecules to the small intestine*

    Miller, Darren S.; Parsons, Anne Michelle; Bresland, John; Herde, Paul; Pham, Duc Minh; Tan, Angel; Hsu, Hung-yao; Prestidge, Clive A.; Kuchel, Tim; Begg, Rezaul; Aziz, Syed Mahfuzul; Butler, Ross N.

    2015-01-01

    Understanding the ecology of the gastrointestinal tract and the impact of the contents on the host mucosa is emerging as an important area for defining both wellness and susceptibility to disease. Targeted delivery of drugs to treat specific small intestinal disorders such as small bowel bacterial overgrowth and targeting molecules to interrogate or to deliver vaccines to the remote regions of the small intestine has proven difficult. There is an unmet need for methodologies to release probes/drugs to remote regions of the gastrointestinal tract in furthering our understanding of gut health and pathogenesis. In order to address this concern, we need to know how the regional delivery of a surrogate labeled test compound is handled and in turn, if delivered locally as a liquid or powder, the dynamics of its subsequent handling and metabolism. In the studies we report on in this paper, we chose 13C sodium acetate (13C-acetate), which is a stable isotope probe that once absorbed in the small intestine can be readily measured non-invasively by collection and analysis of 13CO2 in the breath. This would provide information of gastric emptying rates and an indication of the site of release and absorptive capacity. In a series of in vitro and in vivo pig experiments, we assessed the enteric-protective properties of a commercially available polymer EUDRAGIT®L100-55 on gelatin capsules and also on DRcaps®. Test results demonstrated that DRcaps®coated with EUDRAGIT®L100-55 possessed enhanced enteric-protective properties, particularly in vivo. These studies add to the body of knowledge regarding gastric emptying in pigs and also begin the process of gathering specifications for the design of a simple and cost-effective enteric-coated capsule for delivery of acid-labile macromolecules to the small intestine. PMID:26160716

  17. Combination of acid labile detergent and C18 Empore™ disks for improved identification and sequence coverage of in-gel digested proteins.

    Koehn, Henning; Lau, Benjamin; Clerens, Stefan; Plowman, Jeffrey E; Dyer, Jolon M; Ramli, Umi Salamah; Deb-Choudhury, Santanu

    2011-04-01

    A protocol for improved extraction of peptides from in-gel protein digests, using a combination of the acid labile surfactant, sodium deoxycholate (SDC) and C18 Empore™ membranes, is presented. This approach results in better mass spectrum quality, higher numbers of identified peptide peaks and improved identification scores compared to standard tryptic digestion protocols, or protocols using only SDC or only C18 Empore™ disks. The advantages of the new protocol are demonstrated for two different types of samples: Merino wool intermediate filament proteins and Elaeis guineensis (oil palm) mesocarp proteins. PMID:21327873

  18. Temperature responsive shape memory hybrids

    Ponyrko, Sergii; Matějka, Libor

    Montpellier: L2C, Université de Montpellier, 2015. Mo-P12. [International workshop on "Structure and dynamics of polymer nanocomposites". 22.06.2015-24.06.2015, Montpellier] Grant ostatní: AV ČR(CZ) M200501203 Institutional support: RVO:61389013 Keywords : temperature-responsive * shape memory polymer * nanocomposite Subject RIV: CD - Macromolecular Chemistry

  19. Total and free insulin-like growth factor I, insulin-like growth factor binding protein 3 and acid-labile subunit reflect clinical activity in acromegaly

    Sneppen, S B; Lange, Merete Wolder; Pedersen, L M; Kristensen L, L Ø; Main, K M; Juul, A; Skakkebaek, N E; Feldt-Rasmussen, U

    2001-01-01

    insulin-like growth factor binding protein-3 (IGFBP-3) with PV(pos) of 0.69 and 0.71 and PV(neg) of 0.91 and 0.92 respectively. We conclude that free IGF-I is more closely related than total IGF-I to perceived disease activity and is as such useful when evaluating previously treated acromegaly for disease...... the inactive and the active groups, we found that positive and negative predictive values (PV(pos), PV(neg)) for clinical disease activity of total and free insulin-like growth factor-I (IGF-I) were 0.59, 0.90 and 1.00, 0.82 respectively. Acid-labile subunit (ALS) showed diagnostic merit similar to...... activity. Total IGF-I, IGFBP-3 and ALS possess a higher PV(neg) for the clinical disease activity. None of the parameters can at present be claimed to be superior to the others and thus all the measured parameters are recommended to be part of the evaluation of acromegalic patients....

  20. Temperature responsive shape memory nanocomposites

    Ponyrko, Sergii; Matějka, Libor

    Ljubljana: Jožef Stefan Institute, 2015. s. 39. [HINT Training School "Bottom-up Approaches of Hybrid Materials: Preparation and Design". 26.05.2015-28.05.2015, Ljubljana] R&D Projects: GA MŠk(CZ) LD14010 Grant ostatní: AV ČR(CZ) M200501203; European Commission(XE) COST Action MP1202 HINT Institutional support: RVO:61389013 Keywords : temperature-responsive * shape memory polymer * nanocomposite Subject RIV: CD - Macromolecular Chemistry

  1. Application of nanoparticles for oral delivery of acid-labile lansoprazole in the treatment of gastric ulcer: in vitro and in vivo evaluations

    Alai M

    2015-06-01

    Full Text Available Milind Alai,1 Wen Jen Lin1,2 1Graduate Institute of Pharmaceutical Sciences, School of Pharmacy, 2Drug Research Center, College of Medicine, National Taiwan University, Taipei, Taiwan Abstract: The aim of this study was to develop nanoparticles for oral delivery of an acid-labile drug, lansoprazole (LPZ, for gastric ulcer therapy. LPZ-loaded positively charged Eudragit® RS100 nanoparticles (ERSNPs-LPZ and negatively charged poly(lactic-co-glycolic acid nanoparticles (PLGANPs-LPZ were prepared. The effect of charge on nanoparticle deposition in ulcerated and non-ulcerated regions of the stomach was investigated. The cellular uptake of nanoparticles in the intestine was evaluated in a Caco-2 cell model. The pharmacokinetic performance and ulcer healing response of LPZ-loaded nanoparticles following oral administration were evaluated in Wistar rats with induced ulcers. The prepared drug-loaded ERSNPs-LPZ and PLGANPs-LPZ possessed opposite surface charge (+38.5±0.3 mV versus -27.3±0.3 mV, respectively and the particle size was around 200 nm with a narrow size distribution. The negatively charged PLGANPs adhered more readily to the ulcerated region (7.22%±1.21% per cm2, whereas the positively charged ERSNPs preferentially distributed in the non-ulcerated region (8.29%±0.35% per cm2. Both ERSNPs and PLGANPs were prominent uptake in Caco-2 cells, too. The nanoparticles sustained and prolonged LPZ concentrations up to 24 hours, and the half-life and mean residence time of LPZ were prolonged by 3.5-fold and 4.5-fold, respectively, as compared with LPZ solution. Oral administration of LPZ-loaded nanoparticles healed 92.6%–95.7% of gastric ulcers in Wistar rats within 7 days. Keywords: nanoparticles, lansoprazole, Eudragit® RS100, PLGA

  2. Application of nanoparticles for oral delivery of acid-labile lansoprazole in the treatment of gastric ulcer: in vitro and in vivo evaluations

    Alai, Milind; Lin, Wen Jen

    2015-01-01

    The aim of this study was to develop nanoparticles for oral delivery of an acid-labile drug, lansoprazole (LPZ), for gastric ulcer therapy. LPZ-loaded positively charged Eudragit® RS100 nanoparticles (ERSNPs-LPZ) and negatively charged poly(lactic-co-glycolic acid) nanoparticles (PLGANPs-LPZ) were prepared. The effect of charge on nanoparticle deposition in ulcerated and non-ulcerated regions of the stomach was investigated. The cellular uptake of nanoparticles in the intestine was evaluated in a Caco-2 cell model. The pharmacokinetic performance and ulcer healing response of LPZ-loaded nanoparticles following oral administration were evaluated in Wistar rats with induced ulcers. The prepared drug-loaded ERSNPs-LPZ and PLGANPs-LPZ possessed opposite surface charge (+38.5±0.3 mV versus −27.3±0.3 mV, respectively) and the particle size was around 200 nm with a narrow size distribution. The negatively charged PLGANPs adhered more readily to the ulcerated region (7.22%±1.21% per cm2), whereas the positively charged ERSNPs preferentially distributed in the non-ulcerated region (8.29%±0.35% per cm2). Both ERSNPs and PLGANPs were prominent uptake in Caco-2 cells, too. The nanoparticles sustained and prolonged LPZ concentrations up to 24 hours, and the half-life and mean residence time of LPZ were prolonged by 3.5-fold and 4.5-fold, respectively, as compared with LPZ solution. Oral administration of LPZ-loaded nanoparticles healed 92.6%–95.7% of gastric ulcers in Wistar rats within 7 days. PMID:26124659

  3. Acid-labile protein-adducted heterocyclic aromatic amines in human blood are not viable biomarkers of dietary exposure: A systematic study.

    Cooper, Kevin M; Brennan, Sarah F; Woodside, Jayne V; Cantwell, Marie; Guo, Xiaoxiao; Mooney, Mark; Elliott, Christopher T; Cuskelly, Geraldine J

    2016-05-01

    Heterocyclic aromatic amines (HCA) are carcinogenic mutagens formed during cooking of protein-rich foods. HCA residues adducted to blood proteins have been postulated as biomarkers of HCA exposure. However, the viability of quantifying HCAs following hydrolytic release from adducts in vivo and correlation with dietary intake are unproven. To definitively assess the potential of labile HCA-protein adducts as biomarkers, a highly sensitive UPLC-MS/MS method was validated for four major HCAs: 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx) and 2-amino-3,7,8-trimethylimidazo[4,5-f]quinoxaline (7,8-DiMeIQx). Limits of detection were 1-5 pg/ml plasma and recoveries 91-115%. Efficacy of hydrolysis was demonstrated by HCA-protein adducts synthesised in vitro. Plasma and 7-day food diaries were collected from 122 fasting adults consuming their habitual diets. Estimated HCA intakes ranged from 0 to 2.5 mg/day. An extensive range of hydrolysis conditions was examined for release of adducted HCAs in plasma. HCA was detected in only one sample (PhIP, 9.7 pg/ml), demonstrating conclusively for the first time that acid-labile HCA adducts do not reflect dietary HCA intake and are present at such low concentrations that they are not feasible biomarkers of exposure. Identification of biomarkers remains important. The search should concentrate on stabilised HCA-peptide markers and use of untargeted proteomic and metabolomic approaches. PMID:26993956

  4. Monoclonal anti-acid-labile subunit oligopeptide antibodies and their use in a two-site immunoassay for ALS measurement in humans.

    Stadler, S; Wu, Z; Dressendörfer, R A; Morrison, K M; Khare, A; Lee, P D; Strasburger, C J

    2001-06-01

    Quantification of the acid-labile subunit (ALS) has to date been restricted to immunoassays utilizing polyclonal antibodies. By immunization with N-terminal and C-terminal specific ALS oligopeptides, we generated monoclonal antibodies (mAbs) that target ALS-specific sequences outside the nonspecific leucine-rich repeats in the ALS molecule. For mAb selection, a special screening method was developed. Monoclonal antibody 5C9, which targets the N-terminus of ALS, is immobilized and the anti-ALS mAb 7H3, directed against the C-terminus, is biotinylated and used as tracer Ab. Due to the extreme pH-lability of ALS, changes in immunorecognition of ALS were investigated after acidification for protein unfolding in different pH ranges and in a time-dependent manner. It was determined that acidification of the serum samples to pH 2.7 for 30 min, followed by neutralization and dilution to 1:100 was the optimal acid-neutralization method. For standardization purposes, a serum pool derived from healthy volunteers was assigned the value 1 U/ml ALS. The sandwich assay has a working range with a linear dose-response curve in a log/log system between 0.005 and 10 U/ml. ALS levels in seven acromegalic patients ranged from 2.0 to 4.2 U/ml, and in 12 untreated growth hormone deficient patients from 0.036 to 0.986 U/ml (mean=0.45 U/ml). After 12 months of growth hormone therapy, ALS levels increased significantly to 1.18+/-0.45 U/ml (mean+/-SD; p<0.0006). The increase ranged from 0.48 to 1.4 U/ml. The change in ALS with growth hormone (GH) therapy correlated closer with the change in IGF-I (r=0.798, p=0.0057; Spearman rank correlation) than with the change in insulin-like growth factor binding protein (IGFBP3; r=0.549, p=0.057). This specific sandwich assay for the measurement of ALS provides a potentially valuable indicator of growth hormone secretory status. With this mAb-based immunofluorometric assay, the nonspecific detection of other proteins containing leucine-rich repeat

  5. Effects of short-term caloric restriction on circulating free IGF-I, acid-labile subunit, IGF-binding proteins (IGFBPs)-1-4, and IGFBPs-1-3 protease activity in obese subjects

    Rasmussen, Michael Højby; Juul, Anders; Kjems, Lise Lund;

    2006-01-01

    Decreased levels of GH and total IGF-I have been reported in obesity. It has been hypothesized that increased free (biologically active) IGF-I levels generated from IGF-binding protein (IGFBP) protease activity could be the mechanism for the low GH release in dieting obese subjects. However, no...... published data exist on free IGF-I levels, acid labile subunit (ALS), or IGFBP protease activity in relation to GH release during a hypocaloric diet. The main purpose of this study was to determine free IGF-I, ALS, IGFBPs-1-4, and IGFBPs-1-3 protease activity in relation to 24-h GH release before and after...

  6. Effects of short-term caloric restriction on circulating free IGF-I, acid-labile subunit, IGF-binding proteins (IGFBPs)-1-4, and IGFBPs-1-3 protease activity in obese subjects

    Rasmussen, Michael Højby; Juul, Anders; Kjems, Lise Lund;

    2006-01-01

    Decreased levels of GH and total IGF-I have been reported in obesity. It has been hypothesized that increased free (biologically active) IGF-I levels generated from IGF-binding protein (IGFBP) protease activity could be the mechanism for the low GH release in dieting obese subjects. However, no...... published data exist on free IGF-I levels, acid labile subunit (ALS), or IGFBP protease activity in relation to GH release during a hypocaloric diet. The main purpose of this study was to determine free IGF-I, ALS, IGFBPs-1-4, and IGFBPs-1-3 protease activity in relation to 24-h GH release before and after...... a short-term very low-calorie diet (VLCD)....

  7. Temperature-responsive intelligent interfaces for biomolecular separation and cell sheet engineering.

    Nagase, Kenichi; Kobayashi, Jun; Okano, Teruo

    2009-06-01

    Temperature-responsive intelligent surfaces, prepared by the modification of an interface with poly(N-isopropylacrylamide) and its derivatives, have been used for biomedical applications. Such surfaces exhibit temperature-responsive hydrophilic/hydrophobic alterations with external temperature changes, which, in turn, result in thermally modulated interactions with biomolecules and cells. In this review, we focus on the application of these intelligent surfaces to chromatographic separation and cell cultures. Chromatographic separations using several types of intelligent surfaces are mentioned briefly, and various effects related to the separation of bioactive compounds are discussed, including wettability, copolymer composition and graft polymer architecture. Similarly, we also summarize temperature-responsive cell culture substrates that allow the recovery of confluent cell monolayers as contiguous living cell sheets for tissue-engineering applications. The key factors in temperature-dependent cell adhesion/detachment control are discussed from the viewpoint of grafting temperature-responsive polymers, and new methodologies for effective cell sheet culturing and the construction of thick tissues are summarized. PMID:19324682

  8. Novel temperature-responsive polymer brushes with carbohydrate residues facilitate selective adhesion and collection of hepatocytes

    Naokazu Idota, Mitsuhiro Ebara, Yohei Kotsuchibashi, Ravin Narain and Takao Aoyagi

    2012-01-01

    Full Text Available Temperature-responsive glycopolymer brushes were designed to investigate the effects of grafting architectures of the copolymers on the selective adhesion and collection of hypatocytes. Homo, random and block sequences of N-isopropylacrylamide and 2-lactobionamidoethyl methacrylate were grafted on glass substrates via surface-initiated atom transfer radical polymerization. The galactose/lactose-specific lectin RCA120 and HepG2 cells were used to test for specific recognition of the polymer brushes containing galactose residues over the lower critical solution temperatures (LCSTs. RCA120 showed a specific binding to the brush surfaces at 37 °C. These brush surfaces also facilitated the adhesion of HepG2 cells at 37 °C under nonserum conditions, whereas no adhesion was observed for NIH-3T3 fibroblasts. When the temperature was decreased to 25 °C, almost all the HepG2 cells detached from the block copolymer brush, whereas the random copolymer brush did not release the cells. The difference in releasing kinetics of cells from the surfaces with different grafting architectures can be explained by the correlated effects of significant changes in LCST, mobility, hydrophilicity and mechanical properties of the grafted polymer chains. These findings are important for designing 'on–off' cell capture/release substrates for various biomedical applications such as selective cell separation.

  9. Silicone/Acrylate Copolymers

    Dennis, W. E.

    1982-01-01

    Two-step process forms silicone/acrylate copolymers. Resulting acrylate functional fluid is reacted with other ingredients to produce copolymer. Films of polymer were formed by simply pouring or spraying mixture and allowing solvent to evaporate. Films showed good weatherability. Durable, clear polymer films protect photovoltaic cells.

  10. Temperature response of bundle-sheath conductance in maize leaves.

    Yin, Xinyou; van der Putten, Peter E L; Driever, Steven M; Struik, Paul C

    2016-04-01

    A small bundle-sheath conductance (g bs) is essential for the C4 CO2-concentrating mechanism to suppress photorespiration effectively. To predict the productivity of C4 crops accurately under global warming, it is necessary to examine whether and how g bs responds to temperature. We investigated the temperature response of g bs in maize by fitting a C4 photosynthesis model to combined gas exchange and chlorophyll fluorescence measurements of irradiance and CO2 response curves at 21% and 2% O2 within the range of 13.5-39 °C. The analysis was based on reported kinetic constants of C4 Rubisco and phosphoenolpyruvate carboxylase and temperature responses of C3 mesophyll conductance (g m). The estimates of g bs varied greatly with leaf temperature. The temperature response of g bs was well described by the peaked Arrhenius equation, with the optimum temperature being ~34 °C. The assumed temperature responses of g m had only a slight impact on the temperature response of g bs In contrast, using extreme values of some enzyme kinetic constants changed the shape of the response, from the peaked optimum response to the non-peaked Arrhenius pattern. Further studies are needed to confirm such an Arrhenius response pattern from independent measurement techniques and to assess whether it is common across C4 species. PMID:26969744

  11. Silicon containing copolymers

    Amiri, Sahar; Amiri, Sanam

    2014-01-01

    Silicones have unique properties including thermal oxidative stability, low temperature flow, high compressibility, low surface tension, hydrophobicity and electric properties. These special properties have encouraged the exploration of alternative synthetic routes of well defined controlled microstructures of silicone copolymers, the subject of this Springer Brief. The authors explore the synthesis and characterization of notable block copolymers. Recent advances in controlled radical polymerization techniques leading to the facile synthesis of well-defined silicon based thermo reversible blo

  12. Antimicrobial Graft Copolymer Gels.

    Harvey, Amanda C; Madsen, Jeppe; Douglas, C W Ian; MacNeil, Sheila; Armes, Steven P

    2016-08-01

    In view of the growing worldwide rise in microbial resistance, there is considerable interest in designing new antimicrobial copolymers. The aim of the current study was to investigate the relationship between antimicrobial activity and copolymer composition/architecture to gain a better understanding of their mechanism of action. Specifically, the antibacterial activity of several copolymers based on 2-(methacryloyloxy)ethyl phosphorylcholine [MPC] and 2-hydroxypropyl methacrylate (HPMA) toward Staphylococcus aureus was examined. Both block and graft copolymers were synthesized using either atom transfer radical polymerization or reversible addition-fragmentation chain transfer polymerization and characterized via (1)H NMR, gel permeation chromatography, rheology, and surface tensiometry. Antimicrobial activity was assessed using a range of well-known assays, including direct contact, live/dead staining, and the release of lactate dehydrogenase (LDH), while transmission electron microscopy was used to study the morphology of the bacteria before and after the addition of various copolymers. As expected, PMPC homopolymer was biocompatible but possessed no discernible antimicrobial activity. PMPC-based graft copolymers comprising PHPMA side chains (i.e. PMPC-g-PHPMA) significantly reduced both bacterial growth and viability. In contrast, a PMPC-PHPMA diblock copolymer comprising a PMPC stabilizer block and a hydrophobic core-forming PHPMA block did not exhibit any antimicrobial activity, although it did form a biocompatible worm gel. Surface tensiometry studies and LDH release assays suggest that the PMPC-g-PHPMA graft copolymer exhibits surfactant-like activity. Thus, the observed antimicrobial activity is likely to be the result of the weakly hydrophobic PHPMA chains penetrating (and hence rupturing) the bacterial membrane. PMID:27409712

  13. Temperature response of Earth to the annual solar irradiance cycle

    We directly determine the sensitivity and time delay of Earth's surface temperature response to annual solar irradiance variations from 60 years of data. A two-layer energy balance model is developed to interpret the results. Explaining both the resulting low sensitivity and time delay of 1-2 months requires negative feedback

  14. Preparation of temperature responsive fragrance release membranes by UV curing

    The authors have studied the preparation and the function of intelligent drug release membranes by UV curing. Temperature responsive fragrance release membranes were prepared by UV curing process and the release functions were investigated as the function of thickness and composition of membrane. Microscopic observations were used to prove the postulated release mechanism

  15. Preparation of temperature responsive fragrance release membranes by UV curing

    Nakayama, Hiroshi E-mail: nakayama@ned.kindai.ac.jp; Kaetsu, Isao; Uchida, Kumao; Okuda, Jyunya; Kitami, Toshiaki; Matsubara, Yoshio

    2003-06-01

    The authors have studied the preparation and the function of intelligent drug release membranes by UV curing. Temperature responsive fragrance release membranes were prepared by UV curing process and the release functions were investigated as the function of thickness and composition of membrane. Microscopic observations were used to prove the postulated release mechanism.

  16. Global temperature responses to current emissions from the transport sectors

    Berntsen, Terje; Fuglestvedt, Jan

    2008-01-01

    Transport affects climate directly and indirectly through mechanisms that cause both warming and cooling of climate, and the effects operate on very different timescales. We calculate climate responses in terms of global mean temperature and find large differences between the transport sectors with respect to the size and mix of short- and long-lived effects, and even the sign of the temperature response. For year 2000 emissions, road transport has the largest effect on global mean temperatur...

  17. Synthesis and Characterization of Stimuli Responsive Block Copolymers, Self-Assembly Behavior and Applications

    Michael Duane Determan

    2005-12-17

    The central theme of this thesis work is to develop new block copolymer materials for biomedical applications. While there are many reports of stimuli-responsive amphiphilic [19-21] and crosslinked hydrogel materials [22], the development of an in situ gel forming, pH responsive pentablock copolymer is a novel contribution to the field, Figure 1.1 is a sketch of an ABCBA pentablock copolymer. The A blocks are cationic tertiary amine methacrylates blocked to a central Pluronic F127 triblock copolymer. In addition to the prerequisite synthetic and macromolecular characterization of these new materials, the self-assembled supramolecular structures formed by the pentablock were experimentally evaluated. This synthesis and characterization process serves to elucidate the important structure property relationships of these novel materials, The pH and temperature responsive behavior of the pentablock copolymer were explored especially with consideration towards injectable drug delivery applications. Future synthesis work will focus on enhancing and tuning the cell specific targeting of DNA/pentablock copolymer polyplexes. The specific goals of this research are: (1) Develop a synthetic route for gel forming pentablock block copolymers with pH and temperature sensitive properties. Synthesis of these novel copolymers is accomplished with ATRP, yielding low polydispersity and control of the block copolymer architecture. Well defined macromolecular characteristics are required to tailor the phase behavior of these materials. (2) Characterize relationship between the size and shape of pentablock copolymer micelles and gel structure and the pH and temperature of the copolymer solutions with SAXS, SANS and CryoTEM. (3) Evaluate the temperature and pH induced phase separation and macroscopic self-assembly phenomenon of the pentablock copolymer. (4) Utilize the knowledge gained from first three goals to design and formulate drug delivery formulations based on the multi

  18. Bactericidal block copolymer micelles.

    Vyhnalkova, Renata; Eisenberg, Adi; van de Ven, Theo

    2011-05-12

    Block copolymer micelles with bactericidal properties were designed to deactivate pathogens such as E. coli bacteria. The micelles of PS-b-PAA and PS-b-P4VP block copolymers were loaded with biocides TCMTB or TCN up to 20 or 30 wt.-%, depending on the type of antibacterial agent. Bacteria were exposed to loaded micelles and bacterial deactivation was evaluated. The micelles loaded with TCN are bactericidal; bacteria are killed in less than two minutes of exposure. The most likely interpretation of the data is that the biocide is transferred to the bacteria by repeated micelle/bacteria contacts, and not via the solution. PMID:21275041

  19. Additive Driven Self Assembly and Photo-induced Ordering in Poly(ethylene glycol)monomethyl ether monomethacrylate-block-Poly(ethyl methacrylate) Copolymers

    Li, Cheng; Watkins, James

    2013-03-01

    Recent work in our labs has shown that blending of hydrogen-bond donating polymers, small molecules or nanoparticles with a block copolymer that contains poly(ethylene oxide) (PEO) can enhance microphase segregation strength and yield well ordered morphologies. While PEO crystallization in these polymers is suppressed by strong interactions between the additive and the PEO segments at high additive loadings, crystallization of the PEO block in the absence of these interactions or at low additive loadings is highly undesirable for many applications. To remedy this issue, poly[poly(ethylene glycol) monomethyl ether monomethacrylate]-block-poly(ethyl methacrylate) was prepared using reversible addition-fragmentation chain transfer polymerization(RAFT). This block copolymer is a phase mixed, non-crystallizable system at room temperature. We find that incorporation of organic additives with multiple carboxylic acid groups such as mellitic acid induces phase segregation in this system. Furthermore, the use of additives in which the hydrogen bond donating group is protected with an acid labile group in combination with a photo acid generator enables photo-induced microphase segregation of the composite to yield well ordered films.

  20. Controlled Delivery of Human Cells by Temperature Responsive Microcapsules

    W.C. Mak

    2015-06-01

    Full Text Available Cell therapy is one of the most promising areas within regenerative medicine. However, its full potential is limited by the rapid loss of introduced therapeutic cells before their full effects can be exploited, due in part to anoikis, and in part to the adverse environments often found within the pathologic tissues that the cells have been grafted into. Encapsulation of individual cells has been proposed as a means of increasing cell viability. In this study, we developed a facile, high throughput method for creating temperature responsive microcapsules comprising agarose, gelatin and fibrinogen for delivery and subsequent controlled release of cells. We verified the hypothesis that composite capsules combining agarose and gelatin, which possess different phase transition temperatures from solid to liquid, facilitated the destabilization of the capsules for cell release. Cell encapsulation and controlled release was demonstrated using human fibroblasts as model cells, as well as a therapeutically relevant cell line—human umbilical vein endothelial cells (HUVECs. While such temperature responsive cell microcapsules promise effective, controlled release of potential therapeutic cells at physiological temperatures, further work will be needed to augment the composition of the microcapsules and optimize the numbers of cells per capsule prior to clinical evaluation.

  1. Temperature-Responsive Polymer Modified Surface for Cell Sheet Engineering

    Teruo Okano

    2012-08-01

    Full Text Available In the past two decades, as a novel approach for tissue engineering, cell sheet engineering has been proposed by our laboratory. Poly(N-isopropylacrylamide (PIPAAm, which is a well-known temperature-responsive polymer, has been grafted on tissue culture polystyrene (TCPS surfaces through an electron beam irradiated polymerization. At 37 °C, where the PIPAAm modified surface is hydrophobic, cells can adhere, spread on the surface and grow to confluence. By decreasing temperature to 20 °C, since the surface turns to hydrophilic, cells can detach themselves from the surface spontaneously and form an intact cell sheet with extracellular matrix. For obtaining a temperature-induced cell attachment and detachment, it is necessary to immobilize an ultra thin PIPAAm layer on the TCPS surfaces. This review focuses on the characteristics of PIAPAm modified surfaces exhibiting these intelligent properties. In addition, PIPAAm modified surfaces giving a rapid cell-sheet recovery has been further developed on the basis of the characteristic of the PIPAAm surface. The designs of temperature-responsive polymer layer have provided an enormous potential to fabricate clinically applicable regenerative medicine.

  2. Block copolymer battery separator

    Wong, David; Balsara, Nitash Pervez

    2016-04-26

    The invention herein described is the use of a block copolymer/homopolymer blend for creating nanoporous materials for transport applications. Specifically, this is demonstrated by using the block copolymer poly(styrene-block-ethylene-block-styrene) (SES) and blending it with homopolymer polystyrene (PS). After blending the polymers, a film is cast, and the film is submerged in tetrahydrofuran, which removes the PS. This creates a nanoporous polymer film, whereby the holes are lined with PS. Control of morphology of the system is achieved by manipulating the amount of PS added and the relative size of the PS added. The porous nature of these films was demonstrated by measuring the ionic conductivity in a traditional battery electrolyte, 1M LiPF.sub.6 in EC/DEC (1:1 v/v) using AC impedance spectroscopy and comparing these results to commercially available battery separators.

  3. Synthesis and Thermosensitive Behavior of Polyacrylamide Copolymers and Their Applications in Smart Textiles

    Tao Chen

    2015-05-01

    Full Text Available We tuned the lower critical solution temperature (LCST of amphiphilic poly(N-isopropylacrylamide (PNIPAAm via copolymerization with a hydrophilic comonomer of N-hydroxymethyl acrylamide (NHMAAm. A series of copolymers P(NIPAAm-co-NHMAAm were synthesized by atom transfer radical polymerization (ATRP using CuBr/(N,N,N',N',N''-Pentamethyldiethylenetriamine (PMDETA as a catalyst system and 2-bromo ethyl isobutyrate (EBiB as an initiator. The copolymers were well characterized by Fourier transform infrared spectroscopy (FT-IR, 1H Nuclear magnetic resonance (NMR, and Thermogravimetric analysis (TGA. The copolymers followed a simple rule in their thermosensitive behaviors and have a linear increase in the LCST as a function of NHMAAm mol%. The thermosensitive properties of the copolymer films were investigated and demonstrated hydrophilic-hydrophobic transitions. Finally, the copolymer was grafted onto cotton fabrics using citric acid (CA as a crosslinking agent and sodium hypophosphite (SHP as a catalyst following a two dipping, two padding process. The large number of hydroxyl groups in the copolymer makes grafting convenient and firm. The grafted cotton fabrics show obvious thermosensitive behaviors. The results demonstrate that the cotton fabrics become more hydrophobic when the temperature is higher than the LCST. This study presents a valuable route towards temperature-responsive smart textiles and their potential applications.

  4. Rheological and Mechanical behaviour of Block copolymers, Multigraft copolymers and Block copolymer Nanocomposites

    Thunga, Mahendra

    2009-01-01

    Block copolymers are commercially significant and fundamentally interesting class of polymeric materials. The ability to undergo interfacial thermodynamics-controlled microphase separation from a completely disordered state in the melt to a specifically defined ordered structure through self-organization makes the block copolymers based materials unique. Block copolymer are strongly replacing many of the commercially available polymers due to their unique microstructure and properties. The mo...

  5. PEG-b-PCL copolymer micelles with the ability of pH-controlled negative-to-positive charge reversal for intracellular delivery of doxorubicin.

    Deng, Hongzhang; Liu, Jinjian; Zhao, Xuefei; Zhang, Yuming; Liu, Jianfeng; Xu, Shuxin; Deng, Liandong; Dong, Anjie; Zhang, Jianhua

    2014-11-10

    The application of PEG-b-PCL micelles was dampened by their inherent low drug-loading capability and relatively poor cell uptake efficiency. In this study, a series of novel PEG-b-PCL copolymers methoxy poly(ethylene glycol)-b-poly(ε-caprolactone-co-γ-dimethyl maleamidic acid -ε-caprolactone) (mPEG-b-P(CL-co-DCL)) bearing different amounts of acid-labile β-carboxylic amides on the polyester moiety were synthesized. The chain structure and chemical composition of copolymers were characterized by (1)H NMR, Fourier transform infrared spectroscopy (FT-IR), and gel permeation chromatography (GPC). mPEG-b-P(CL-co-DCL) with critical micellar concentrations (CMCs) of 3.2-6.3 μg/mL could self-assemble into stable micelles in water with diameters of 100 to 150 nm. Doxorubicin (DOX), a cationic hydrophobic drug, was successfully encapsulated into the polymer micelles, achieving a very high loading content due to electrostatic interaction. Then the stability, charge-conversional behavior, loading and release profiles, cellular uptake and in vitro cytotoxicity of free drug and drug-loaded micelles were evaluated. The β-carboxylic amides functionalized polymer micelles are negatively charged and stable in neutral solution but quickly become positively charged at pH 6.0, due to the hydrolysis of β-carboxylic amides in acidic conditions. The pH-triggered negative-to-positive charge reversal not only resulted in a very fast drug release in acidic conditions, but also effectively enhanced the cellular uptake by electrostatic absorptive endocytosis. The MTT assay demonstrated that mPEG-b-P(CL-co-DCL) micelles were biocompatible to HepG2 cells while DOX-loaded micelles showed significant cytotoxicity. In sum, the introduction of acid-labile β-carboxylic amides on the polyester block in mPEG-b-P(CL-co-DCL) exhibited great potentials for the modifications in the stability in blood circulation, drug solubilization, and release properties, as well as cell internalization and

  6. Polyether/Polyester Graft Copolymers

    Bell, Vernon L., Jr.; Wakelyn, N.; Stoakley, D. M.; Proctor, K. M.

    1986-01-01

    Higher solvent resistance achieved along with lower melting temperature. New technique provides method of preparing copolymers with polypivalolactone segments grafted onto poly (2,6-dimethyl-phenylene oxide) backbone. Process makes strong materials with improved solvent resistance and crystalline, thermally-reversible crosslinks. Resulting graft copolymers easier to fabricate into useful articles, including thin films, sheets, fibers, foams, laminates, and moldings.

  7. Tensile actuators of carbon nanotube coiled yarn based on polydiacetylene–pluronic copolymers as temperature indicators

    Lee, Hee Uk; Kim, Hyunsoo; Chun, Kyoung-Yong; Kwon, Cheong Hoon; Lima, Márcio D.; Baughman, Ray H.; Kim, Seon Jeong

    2016-07-01

    Most polydiacetylenes (PDAs) have been studied as chromatic sensors or temperature indicators because of their phase transition that is accompanied by a color change from blue to red. Here, we focus on the structural change based on the polydiacetylene phase transition for a temperature-responsive tensile actuator at low temperature using a copolymer composed of PDA and pluronic in a multi-walled carbon nanotube (MWCNT) coiled yarn. In this paper, we do not focus on the general color change phenomenon of PDA. We demonstrate that the volume change of PDA in the MWCNT coiled yarn provides ∼180% tensile strain at low temperature (∼53 °C). Insertion of the pluronic copolymer into the coiled yarn composed of PDA and MWCNT caused the tensile actuation temperature to decrease by ∼6 °C (with tensile actuation of ∼230%) compared to an actuator without pluronic copolymer. Furthermore, we could verify that the large tensile actuation was also predominantly affected by the melting of the nonpolymerized diacetylene (DA) monomer and the pluronic copolymer. MWCNT coiled yarn actuators with PDA-pluronic copolymer can be easily prepared, have a large tensile actuation, and are actuated at low temperature. It could be used as temperature indicators in the food, drugs, and medical fields.

  8. Non-monotonic temperature response of polymer mediated interactions.

    Xie, Fei; Woodward, Clifford E; Forsman, Jan

    2016-01-21

    In a recent publication, Feng et al. [Feng et al., Nat. Mater., 2015, 14, 61] reported a very interesting re-entrant solidification behaviour of colloidal particles in an aqueous solution containing polyethylene oxide (PEO). In this system, a crystalline colloidal phase, which is present at low temperatures, melts to a homogeneous fluid upon increasing the temperature. Further raising the temperature, however, eventually gives rise to a flocculated colloidal phase. Feng et al. proposed that the low-temperature crystalline phase is caused by polymer depletion while, at higher temperature, an increased attraction between polymers and particles leads to bridging attractions, and colloidal flocculation. The intermediate temperature regime sees the colloidal interactions dominated by charge repulsion, giving rise to a fluid phase. In the model by Feng et al., polymers are treated as hard spheres, which interact with the colloids via a phenomenological, temperature dependent potential. In this work, we develop a more detailed polymer density functional treatment, based on a model for aqueous PEO solutions that was originally developed by Karlström [Karlström, J. Phys. Chem., 1985, 89, 4962] for bulk solutions. In this model, monomers are assumed to be in either of two classes of states, labelled A and B, where B is more solvophobic than A. On the other hand, the degeneracy of the B states exceed that of A, causing the population of solvophobic monomers to increase with temperature. If the colloidal particles are also solvophobic, then this model displays the same qualitative temperature response as was observed by Feng et al. That is, at low temperatures, A type monomers predominate and one observes depletion interactions, whereas polymer bridging dominates at higher temperatures, due to the attraction between B-type monomers and the colloidal surface. Interestingly, the intermediate temperature regime is characterized by a polymer mediated interaction between colloids

  9. Xanthate-Functional Temperature-Responsive Polymers: Effect on Lower Critical Solution Temperature Behavior and Affinity toward Sulfide Surfaces.

    Ng, Wei Sung; Forbes, Elizaveta; Franks, George V; Connal, Luke A

    2016-08-01

    Xanthate-functional polymers represent an exciting opportunity to provide temperature-responsive materials with the ability to selectively attach to specific metals, while also modifying the lower critical solution temperature (LCST) behavior. To investigate this, random copolymers of poly(N-isopropylacrylamide) (PNIPAM) with xanthate incorporations ranging from 2 to 32% were prepared via free radical polymerization. Functionalization with 2% xanthate increased the LCST by 5 °C relative to the same polymer without xanthate. With increasing xanthate composition, the transition temperature increased and the transition range broadened until a critical composition of the hydrophilic xanthate groups (≥18%) where the transition disappeared completely. The adsorption of the polymers at room temperature onto chalcopyrite (CuFeS2) surfaces increased with xanthate composition, while adsorption onto quartz (SiO2) was negligible. These findings demonstrate the affinity of these functional smart polymers toward copper iron sulfide relative to quartz surfaces, presumably due to the interactions between xanthate and specific metal centers. PMID:27434760

  10. BARRIER PROPERTIES OF VINYLIDENE CHLORIDE COPOLYMERS

    LI Yuesheng; WENG Zhixue; HUANG Zhiming; PAN Zuren

    1996-01-01

    The permeability coefficients of a series of copolymers of vinylidene chloride (VDC)with methyl acrylate (MA), butyl acrylate (BA) or vinyl chloride (VC) (as comonomer)to oxygen and carbon dioxide have been measured at 1.0 MPa and 30℃, while those to water vapor have been measured at 30℃ and 100% relative humidity. All the copolymers are semicrystalline. VDC/MA copolymers have lower melting temperature compared with VDC/BA copolymers, while that melting temperature of VDC/VC copolymer is higher than that of VDC/acrylate copolymers with the same VDC content. The barrier property of the copolymers is predominantly controlled by crystallite, free volume fraction, and cohesive energy. The permeability coefficients of VDC/MA copolymers to oxygen, carbon dioxide, and water vapor were successfully correlated with the ratio of free volume to cohesive energy.

  11. A simple and inexpensive enteric-coated capsule for delivery of acid-labile macromolecules to the small intestine%题目:一种用于递送酸度敏感大分子到小肠的简易且廉价的肠溶胶囊

    Darren S MILLER; Rezaul BEGG; Syed Mahfuzul AZIZ; Ross N BUTLER; Anne Michelle PARSONS; John BRESLAND; Paul HERDE; Duc Minh PHAM; Angel TAN; Hung-yao HSU; Clive A PRESTIDGE; Tim KUCHEL

    2015-01-01

    enteric-protective properties of a commercialy available polymer EUDRAGIT® L100-55 on gelatin capsules and also on DRcaps®. Test results demonstrated that DRcaps® coated with EUDRAGIT® L100-55 possessed enhanced enteric-protective properties, particularlyin vivo. These studies add to the body of knowledge regarding gastric emptying in pigs and also begin the process of gathering specifications for the design of a simple and cost-effective enteric-coated capsule for delivery of acid-labile macromolecules to the smal intestine.

  12. Micellization and Dynamics of a Block Copolymer

    Hvidt, Søren

    2006-01-01

    Triblock copolymers of the type EPE, where E and P denote ethylene oxide and propylene oxide blocks, respectively, are industrially important copolymers often called Pluronics or Poloxamers. EPE copolymers form micelles with a core of P blocks and different micellar shapes depending on block length...... copolymer mixtures, and evidence in favor of a multi-equilibria unimer-micelle model will be presented. Results obtained by liquid chromatographic methods will be shown and it will be demonstrated that commercial EPE copolymers are inhomogeneous at several levels and many of their unusual properties reflect...

  13. The role of spatial scale and background climate in the latitudinal temperature response to deforestation

    Li, Y.; de Noblet-Ducoudré, N.; E. L. Davin; Zeng, N; S. Motesharrei; S.C. Li; Kalnay, E.

    2015-01-01

    Previous modeling and empirical studies have shown that the biophysical impact of deforestation is to warm the tropics and cool the extra-tropics. In this study, we use an earth system model to investigate how deforestation at various spatial scales affects ground temperature, with an emphasis on the latitudinal temperature response and its underlying mechanisms. Results show that the latitudinal pattern of temperature response depends non-linearly on the s...

  14. The role of spatial scale and background climate in the latitudinal temperature response to deforestation

    Li, Yan; De Noblet-Ducoudré, Nathalie; Davin, Edouard L.; Motesharrei, Safa; Zeng, Ning; Li, Shuangcheng; Kalnay, Eugenia

    2016-01-01

    Previous modeling and empirical studies have shown that the biophysical impact of deforestation is to warm the tropics and cool the extratropics. In this study, we use an earth system model of intermediate complexity to investigate how deforestation on various spatial scales affects ground temperature, with an emphasis on the latitudinal temperature response and its underlying mechanisms. Results show that the latitudinal pattern of temperature response depends nonlinearly o...

  15. Polyether-polyester graft copolymer

    Bell, Vernon L. (Inventor)

    1987-01-01

    Described is a polyether graft polymer having improved solvent resistance and crystalline thermally reversible crosslinks. The copolymer is prepared by a novel process of anionic copolymerization. These polymers exhibit good solvent resistance and are well suited for aircraft parts. Previous aromatic polyethers, also known as polyphenylene oxides, have certain deficiencies which detract from their usefulness. These commercial polymers are often soluble in common solvents including the halocarbon and aromatic hydrocarbon types of paint thinners and removers. This limitation prevents the use of these polyethers in structural articles requiring frequent painting. In addition, the most popular commercially available polyether is a very high melting plastic. This makes it considerably more difficult to fabricate finished parts from this material. These problems are solved by providing an aromatic polyether graft copolymer with improved solvent resistance and crystalline thermally reversible crosslinks. The graft copolymer is formed by converting the carboxyl groups of a carboxylated polyphenylene oxide polymer to ionic carbonyl groups in a suitable solvent, reacting pivalolactone with the dissolved polymer, and adding acid to the solution to produce the graft copolymer.

  16. Design, syntheses, and properties of tunable, dual-stimuli (temperature and pH) responsive copolymers

    Manokruang, Kiattikhun

    polymer aggregates for each pH, rather than random/polydisperse structures. TEM images of the collapsed morphology showed polymer aggregates that included numerous small hydrophobic cores, demonstrating that the phase transition of these copolymers involved the formation of micelles with many hydrophobic clusters. Finally, these copolymers were used to prepare hollow microcapsules that provided an exceptional protection and a prolonged stability of an encapsulated matter at acidic conditions (pH 2) and a sharp and fast pH-triggered release at physiological conditions (pH 7). A second series of copolymers was synthesized to compose of ethylene glycol oligomers (EOm) connected in an alternating fashion with hydrophobic alkyls (EEn), (EOm-alt-EE n). Also, terpolymers were synthesized to compose of EOm connected in an alternating fashion with EEn and lysine ethyl ester (LyE), (EOm-alt-(EEn;LyE). Both copolymers and terpolymers demonstrated temperature responsive LCST phase behavior in aqueous solution, whose critical temperature is dictated by the thermodynamics of the hydrophilic/hydrophobic balance. In addition, the terpolymers' LCST can be further tuned by tailoring the ratio of EEn to LyE yielding dual responsive, viz. temperature and pH responsive, polymers upon conversion of LyE to ionizable Lysine (Lys). These last polymers that included ionizable units showed a reversible temperature and pH sensitive phase transition, allowing for such polymers to exhibit a phase separation with both-or-either temperature increase and pH-decrease. The extended phase diagrams, collected from turbidity measurements and modulated differential scanning callorimetry (MDSC), showed that the phase diagram remained a genuine LCST binodal throughout the complete concentration range. In addition, 1H-NMR provided additional strong evidence that the phase transition proceeded without micelle formation. Finally, hydrogels were prepared from EOm-alt-EEn, which exhibited reversible swelling

  17. Blends of Styrene-Butadiene-Styrene Triblock Copolymer with Random Styrene-Maleic Anhydride Copolymers

    Piccini, Maria Teresa; Ruggeri, Giacomo; Passaglia, Elisa; Picchioni, Francesco; Aglietto, Mauro

    2002-01-01

    Blends of styrene-butadiene-styrene triblock copolymer (SBS) with random styrene-maleic anhydride copolymers (PS-co-MA), having different MA content, were prepared in a Brabender Plastigraph mixer. The presence of polystyrene (PS) blocks in the SBS copolymer and the high styrene content (93 and 86 w

  18. Photo-Induced Micellization of Block Copolymers

    Satoshi Kuwayama; Eri Yoshida

    2010-01-01

    We found novel photo-induced micellizations through photolysis, photoelectron transfer, and photo-Claisen rearrangement. The photolysis-induced micellization was attained using poly(4-tert-butoxystyrene)-block-polystyrene diblock copolymer (PBSt-b-PSt). BSt-b-PSt showed no self-assembly in dichloromethane and existed as isolated copolymers. Dynamic light scattering demonstrated that the copolymer produced spherical micelles in this solvent due to irradiation with a high-pressure mercury lamp ...

  19. Synthesis of ester-siloxane multiblock copolymers

    Antić Vesna V.; Vučković Marija V.; Govedarica Milutin N.

    2004-01-01

    It was shown that the two-stage transesterification/polycondensation reaction in the melt, can successfully be applied for the preparation of poly(butylene terephtalate-dimethylsiloxane) multiblock copolymers. Three series of co-polymers were synthesized, using poly(dimethylsiloxanes) bearing ester (two series) and hydroxy -end groups as reactants. The structure and composition of the obtained copolymers were determined by 1H NMR spectroscopy A mechanism, i.e. an order of reaction steps, invo...

  20. Silica reinforced triblock copolymer gels

    Theunissen, E.; Overbergh, N.; Reynaers, H.;

    2004-01-01

    scattering at very low q, but no structure and formfactor information. However, on heating above the viscoelastic to plastic transition, the 'typical' scattering pattern of the copolymer gel builds-up. All reinforced gels are strengthened by the addition of the reinforcing agent. The transitions from a...... viscoclastic rubber to a plastic fluid and from a plastic fluid to a viscoelastic liquid are shifted to more elevated temperatures when silica is added to the triblock copolymer gel. (C) 2004 Elsevier Ltd. All rights reserved.......The effect of silica and polymer coated silica particles as reinforcing agents on the structural and mechanical properties of polystyrene-poly(ethylene/butylene)-polystyrene (PS-PEB-PS) triblock gel has been investigated. Different types of chemically modified silica have been compared in order to...

  1. Copolymer nanoparticles for biomedical applications

    Štěpánek, Petr; Jäger, Eliezer; Jäger, Alessandro; Petrova, Svetlana; Venturini, Cristina Garcia

    Saint-Petersburg: Institute of Macromolecular Compounds RAS, 2014. s. 26. ISBN 978-5-98340-329-1. [International Symposium "Molecular Order and Mobility in Polymer Systems" /8./. 02.06.2014-06.06.2014, St. Petersburg] R&D Projects: GA ČR GAP208/10/1600 Institutional support: RVO:61389013 Keywords : copolymer self-assembly * light scattering * nanoparticles Subject RIV: CF - Physical ; Theoretical Chemistry

  2. Interfaces between Block Copolymer Domains

    Kim, Jaeup; Jeong, Seong-Jun; Kim, Sang Ouk

    2011-03-01

    Block copolymers naturally form nanometer scale structures which repeat their geometry on a larger scale. Such a small scale periodic pattern can be used for various applications such as storage media, nano-circuits and optical filters. However, perfect alignment of block copolymer domains in the macroscopic scale is still a distant dream. The nanostructure formation usually occurs with spontaneously broken symmetry; hence it is easily infected by topological defects which sneak in due to entropic fluctuation and incomplete annealing. Careful annealing can gradually reduce the number of defects, but once kinetically trapped, it is extremely difficult to remove all the defects. One of the main reasons is that the defect finds a locally metastable morphology whose potential depth is large enough to prohibit further morphology evolution. In this work, the domain boundaries between differently oriented lamellar structures in thin film are studied. For the first time, it became possible to quantitatively study the block copolymer morphology in the transitional region, and it was shown that the twisted grain boundary is energetically favorable compared to the T-junction grain boundary. [Nano Letters, 9, 2300 (2010)]. This theoretical method successfully explained the experimental results.

  3. Preparation and Investigation of Poly (N-isopropylacrylamide-acrylamide Membranes in Temperature Responsive Drug Delivery

    Elham Khodaverdi

    2010-06-01

    Full Text Available Objective(sPhysiological changes in the body may be utilized as potential triggers for controlled drug delivery. Based on these mechanisms, stimulus–responsive drug delivery has been developed.Materials and MethodsIn this study, a kind of poly (N-isopropylacrylamide-acrylamide membrane was prepared by radical copolymerization. Changes in swelling ratios and diameters of the membrane were investigated in terms of temperature. On-off regulation of drug permeation through the membrane was then studied at temperatures below and above the phase transition temperature of the membrane. Two drugs, vitamin B12 and acetaminophen were chosen as models of high and low molecular weights here, respectively. ResultsIt was indicated that at temperatures below the phase transition temperature of the membrane, copolymer was in a swollen state. Above the phase transition temperature, water was partially expelled from the functional groups of the copolymer. Permeation of high molecular weight drug models such as vitamin B12 was shown to be much more distinct at temperatures below the phase transition temperature when the copolymer was in a swollen state. At higher temperatures when the copolymer was shrunken, drug permeation through the membrane was substantially decreased. However for acetaminophen, such a big change in drug permeation around the phase transition temperature of the membrane was not observed. ConclusionAccording to the pore mechanism of drug transport through hydrogels, permeability of solutes decreased with increasing molecular size. As a result, the relative permeability, around the phase transition temperature of the copolymer, was higher for solutes of high molecular weight.

  4. Stability Analysis of Temperature Response of a Heated Cylinder Subject to Side Cooling

    Abdulsatar Mohammed Ibrahim

    2014-04-01

    Full Text Available This article presents a linear stability analysis for temperature response of a heated cylinder subject to side cooling. Interestingly, this complex dynamical system has two clearly separated stability regions. More precisely, the system is stable when k>π and unstable otherwise.

  5. Thermochemical characteristics of chitosan-polylactide copolymers

    Goruynova, P. E.; Larina, V. N.; Smirnova, N. N.; Tsverova, N. E.; Smirnova, L. A.

    2016-05-01

    The energies of combustion of chitosan and its block-copolymers with different polylactide contents are determined in a static bomb calorimeter. Standard enthalpies of combustion and formation are calculated for these substances. The dependences of the thermochemical characteristics on block-copolymer composition are determined and discussed.

  6. 21 CFR 177.2470 - Polyoxymethylene copolymer.

    2010-04-01

    ...-ylene copolymer can be identified by its characteristic infrared spectrum. (2) Minimum number average molecular weight of the copolymer is 15,000 as determined by a method titled “Number Average Molecular... product of trioxane (cyclic trimer of formaldehyde) and a maximum of 5 percent by weight of...

  7. Copolymers at the solid-liquid interface.

    Wijmans, C.M.

    1994-01-01

    Copolymers consisting of both adsorbing and nonadsorbing segments can show an adsorption behaviour which is very different from that of homopolymers. We have mainly investigated the adsorption of AB diblock copolymers, which have one adsorbing block (anchor) and one nonadsorbing block (buoy). The an

  8. PEO-related block copolymer surfactants

    Mortensen, K.

    2001-01-01

    Non-ionic block copolymer systems based on hydrophilic poly(ethylene oxide) and more hydrophobic co-polymer blocks are used intensively in a variety of industrial and personal applications. A brief description on the applications is presented. The physical properties of more simple model systems ...

  9. STUDY ON POLYSULFONE-POLYESTER BLOCK COPOLYMERS

    DING Youjun; QI Daquan

    1988-01-01

    Synthesis and characterization of a series of Polysulfone (PSF)-Polyester (PEs) block copolymers were studied.The degree of randomness (B) of these block copolymers was calculated from the intensities of their proton signals in 1H NMR spectra and lies in the region of 0 < B < 1. It was shown that the degree of randomness (B) and the average sequence length (L) in block copolymers were relatively dependent on the reaction conditions, various feed ratios and structure of diols.The phenomenon was observed, when the PSF-PEs block copolymers dissolved in different solvents they had different viscosities and molecular conformations.The PSF-PEs block copolymers had better solvent resistance than homo-polysulfone.

  10. Copolymer Melts in Disordered Media

    Stepanow, S.; Dobrynin, A.; Vilgis, T.; Binder, K.

    1996-01-01

    We have considered a symmetric AB block copolymer melt in a gel matrix with preferential adsorption of A monomers on the gel. Near the point of the microphase separation transition such a system can be described by the random field Landau-Brazovskii model, where randomness is built into the system during the polymerization of the gel matrix. By using the technique of the 2-nd Legendre transform, the phase diagram of the system is calculated. We found that preferential adsorption of the copoly...

  11. Rapid self-assembly of block copolymers to photonic crystals

    Xia, Yan; Sveinbjornsson, Benjamin R; Grubbs, Robert H; Weitekamp, Raymond; Miyake, Garret M; Atwater, Harry A; Piunova, Victoria; Daeffler, Christopher Scot; Hong, Sung Woo; Gu, Weiyin; Russell, Thomas P.

    2016-07-05

    The invention provides a class of copolymers having useful properties, including brush block copolymers, wedge-type block copolymers and hybrid wedge and polymer block copolymers. In an embodiment, for example, block copolymers of the invention incorporate chemically different blocks comprising polymer size chain groups and/or wedge groups that significantly inhibit chain entanglement, thereby enhancing molecular self-assembly processes for generating a range of supramolecular structures, such as periodic nanostructures and microstructures. The present invention also provides useful methods of making and using copolymers, including block copolymers.

  12. NANOSTRUCTURES OF FUNCTIONAL BLOCK COPOLYMERS

    Guojun Liu

    2000-01-01

    Nanostructure fabrication from block copolymers in my group normally involves polymer design, synthesis, selfassembly, selective domain crosslinking, and sometimes selective domain removal. Preparation of thin films with nanochannels was used to illustrate the strategy we took. In this particular case, a linear triblock copolymer polyisopreneblock-poly(2-cinnamoylethyl methacrylate)-block-poly(t-butyl acrylate), PI-b-PCEMA-b-PtBA, was used. Films, 25 to50μm thick, were prepared from casting on glass slides a toluene solution of PI-b-PCEMA-b-PtBA and PtBA homopolymer,hPtBA, where hPtBA is shorter than the PtBA block. At the hPtBA mass fraction of 20% relative to the triblock or the total PtBA (hPtBA and PtBA block) volume fraction of 0.44, hPtBA and PtBA formed a seemingly continuous phase in the matrix of PCEMA and PI. Such a block segregation pattern was locked in by photocrosslinking the PCEMA domain. Nanochannels were formed by extracting out hPtBA with solvent. Alternatively, larger channels were obtained from extracting out hPtBA and hydrolyzing the t-butyl groups of the PtBA block. Such membranes were not liquid permeable but had gas permeability constants ~6 orders of magnitude higher than that of low-density polyethylene films.

  13. Block copolymer membranes for aqueous solution applications

    Nunes, Suzana Pereira

    2016-03-22

    Block copolymers are known for their intricate morphology. We review the state of the art of block copolymer membranes and discuss perspectives in this field. The main focus is on pore morphology tuning with a short introduction on non-porous membranes. The two main strategies for pore formation in block copolymer membranes are (i) film casting and selective block sacrifice and (ii) self-assembly and non-solvent induced phase separation (SNIPS). Different fundamental aspects involved in the manufacture of block copolymer membranes are considered, including factors affecting the equilibrium morphology in solid films, self-assembly of copolymer in solutions and macrophase separation by solvent-non-solvent exchange. Different mechanisms are proposed for different depths of the SNIPS membrane. Block copolymer membranes can be prepared with much narrower pore size distribution than homopolymer membranes. Open questions and indications of what we consider the next development steps are finally discussed. They include the synthesis and application of new copolymers and specific functionalization, adding characteristics to respond to stimuli and chemical environment, polymerization-induced phase separation, and the manufacture of organic-inorganic hybrids.

  14. Future CO2 concentrations, though not warmer temperatures, enhance wheat photosynthesis temperature responses

    Alonso, Aitor; Pérez, P.; Morcuende, R.; Martínez-Carrasco, R.

    2008-01-01

    The temperature dependence of C3 photosynthesis is known to vary according to the growth environment. Atmospheric CO2 concentration and temperature are predicted to increase with climate change. To test whether long-term growth in elevated CO2 and temperature modifies photosynthesis temperature response, wheat (Triticum aestivum L.) was grown in ambient CO2 (370 µmol mol-1) and elevated CO2 (700 µmol mol-1)combined with ambient and 4 ºC warmer temperatures, using temperature gradient ch...

  15. Growth in elevated CO2 enhances temperature response of photosynthesis in wheat

    Alonso, Aitor; Pérez, P.; Martínez-Carrasco, R.

    2008-01-01

    The temperature dependence of C3 photosynthesis may be altered by the growth environment. The effects of long-term growth in elevated CO2 on photosynthesis temperature response have been investigated in wheat (Triticum aestivum L.) grown in controlled chambers with 370 or 700 µmol mol-1 CO2 from sowing through to anthesis. Gas exchange was measured in flag leaves at ear emergence, and the parameters of a biochemical photosynthesis model were determined along with their temperat...

  16. Temperature response of methane production in liquid manures and co-digestates

    Elsgaard, Lars; Olsen, Anna Berg; Petersen, Søren O.

    2016-01-01

    Intensification of livestock production makes correct estimation of methanogenesis in liquidmanure increasingly important for inventories of CH4 emissions. Such inventories currently rely on fixed methane conversion factors as knowledge gaps remain with respect to detailed temperature responses o...... and rice paddies (89.3 kJmol−1). This supports that the derived temperature sensitivity parameters may be applicable to dynamic modelling of CH4 emissions from livestock manure....

  17. Measurement of temperature response to a pressure change of a supercooled liquid at the dynamic glasstransition

    Samsøe-Petersen, Anders; Xiao, Wence; Byskov, Sedi; Sand Ottsen, Tobias; Aagaard, Johanne

    2011-01-01

    This report introduces an approach to characterizing thermal and mechanical properties of viscous liquids, by using a specific set up utilizing the coupling of a piezoelectric bulk modulus gauge (PBG) and a thermistor placed on a transverse wire through the PBG. More specifically we are using this set-up to investigate the temperature response to a pressure change of a supercooled liquid at the dynamic glass transition, as is also stated in the title. Physically this is achieved b...

  18. Germination rates of Solanum sisymbriifolium: temperature response models, effects of temperature fluctuations and soil water potential

    Timmermans, B.G.H.; Vos, J.; Nieuwburg, van, J.G.W.; Stomph, T. J.; Putten, van, T.

    2007-01-01

    Four temperature response models were compared describing the emergence rate of Solanum sisymbriifolium (L.) over a broad range of suboptimal temperatures and at different soil water potentials. In the laboratory, the effects were tested on germination rates at constant (9.1-21.8 degrees C) and diurnally fluctuating temperatures at different soil water potentials. Linear, 010, expolinear and quadratic models were fitted to the data on rate of emergence against temperature. For model validatio...

  19. Growth in elevated CO{sub 2} enhances temperature response of photosynthesis in wheat

    Alonso, A.; Perez, P.; Martinez-Carrasco, R. (Inst. of Natural Resources and Agrobiology of Salamanca, CSIC (Spain))

    2009-07-01

    The temperature dependence of C{sub 3} photosynthesis may be altered by the growth environment. The effects of long-term growth in elevated CO{sub 2} on photosynthesis temperature response have been investigated in wheat (Triticum aestivum L.) grown in controlled chambers with 370 or 700 mumol mol-1 CO{sub 2} from sowing through to anthesis. Gas exchange was measured in flag leaves at ear emergence, and the parameters of a biochemical photosynthesis model were determined along with their temperature responses. Elevated CO{sub 2} slightly decreased the CO{sub 2} compensation point and increased the rate of respiration in the light and ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) V{sub cmax}, although the latter effect was reversed at 15 degrees C. With elevated CO{sub 2}, J{sub max} decreased in the 15-25 degrees C temperature range and increased at 30 and 35 degrees C. The temperature response (activation energy) of V{sub cmax} and J{sub max} increased with growth in elevated CO{sub 2}. CO{sub 2} enrichment decreased the ribulose 1,5-bisphosphate (RuBP)-limited photosynthesis rates at lower temperatures and increased Rubisco- and RuBP-limited rates at higher temperatures. The results show that the photosynthesis temperature response is enhanced by growth in elevated CO{sub 2}. We conclude that if temperature acclimation and factors such as nutrients or water availability do not modify or negate this enhancement, the effects of future increases in air CO{sub 2} on photosynthetic electron transport and Rubisco kinetics may improve the photosynthetic response of wheat to global warming. (au)

  20. Switchable photoluminescence of CdTe nanocrystals by temperature-responsive microgels

    Agrawal, M.; Rubio-Retama, J.; Zafeiropoulos, N. E.; Gaponik, N.; Gupta, S.; Cimrová, Věra; Lesnyak, V.; López-Cabarcos, E.; Tzavalas, S.; Rojas-Reyna, R.; Eychmuller, A.; Stamm, M.

    2008-01-01

    Roč. 24, č. 17 (2008), s. 9820-9824. ISSN 0743-7463 R&D Projects: GA AV ČR IAA4050409; GA MŠk(CZ) 1M06031 Institutional research plan: CEZ:AV0Z40500505 Keywords : switchable photoluminescence * temperature-responsive microgels * CdTe nanocrystals Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.097, year: 2008

  1. Block Copolymer Membranes for Biofuel Purification

    Evren Ozcam, Ali; Balsara, Nitash

    2012-02-01

    Purification of biofuels such as ethanol is a matter of considerable concern as they are produced in complex multicomponent fermentation broths. Our objective is to design pervaporation membranes for concentrating ethanol from dilute aqueous mixtures. Polystyrene-b-polydimethylsiloxane-b-polystyrene block copolymers were synthesized by anionic polymerization. The polydimethylsiloxane domains provide ethanol-transporting pathways, while the polystyrene domains provide structural integrity for the membrane. The morphology of the membranes is governed by the composition of the block copolymer while the size of the domains is governed by the molecular weight of the block copolymer. Pervaporation data as a function of these two parameters will be presented.

  2. Spectroelectrochemistry of aniline-o-aminophenol copolymers

    Shah, Anwar-ul-Haq Ali [Institute fuer Chemie, AG Elektrochemie, Technische Universitaet Chemnitz, 09107 Chemnitz (Germany); Holze, Rudolf [Institute fuer Chemie, AG Elektrochemie, Technische Universitaet Chemnitz, 09107 Chemnitz (Germany)]. E-mail: rudolf.holze@chemie.tu-chemnitz.de

    2006-11-12

    Electroactive copolymers of aniline and o-aminophenol (OAP) with varying concentration ratios prepared by potential cycling in acidic aqueous solutions of the monomers on indium-doped tin oxide (ITO) coated glass and gold electrodes were studied with in situ UV-vis and Raman spectroscopy. Characteristic UV-vis and Raman features have been identified and their dependencies on the electrode potential are discussed. Spectroelectrochemical results reveal the formation of polyaniline-based copolymers at low concentration of OAP in the feed but incorporation of more OAP units into the copolymer with higher concentration of OAP in the comonomer feed. Spectroelectrochemical features are significantly different from those of both homopolymers.

  3. PEO-related block copolymer surfactants

    Mortensen, K.

    Non-ionic block copolymer systems based on hydrophilic poly(ethylene oxide) and more hydrophobic co-polymer blocks are used intensively in a variety of industrial and personal applications. A brief description on the applications is presented. The physical properties of more simple model systems of...... such PEG-based block copolymers in aqueous suspensions are reviewed. Based on scattering experiments using either X-ray or neutrons, the phase behavior is characterized, showing that the thermo-reversible gelation is a result of micellar ordering into mesoscopic crystalline phases of cubic, hexagonal...

  4. Convergence in the temperature response of leaf respiration across biomes and plant functional types.

    Heskel, Mary A; O'Sullivan, Odhran S; Reich, Peter B; Tjoelker, Mark G; Weerasinghe, Lasantha K; Penillard, Aurore; Egerton, John J G; Creek, Danielle; Bloomfield, Keith J; Xiang, Jen; Sinca, Felipe; Stangl, Zsofia R; Martinez-de la Torre, Alberto; Griffin, Kevin L; Huntingford, Chris; Hurry, Vaughan; Meir, Patrick; Turnbull, Matthew H; Atkin, Owen K

    2016-04-01

    Plant respiration constitutes a massive carbon flux to the atmosphere, and a major control on the evolution of the global carbon cycle. It therefore has the potential to modulate levels of climate change due to the human burning of fossil fuels. Neither current physiological nor terrestrial biosphere models adequately describe its short-term temperature response, and even minor differences in the shape of the response curve can significantly impact estimates of ecosystem carbon release and/or storage. Given this, it is critical to establish whether there are predictable patterns in the shape of the respiration-temperature response curve, and thus in the intrinsic temperature sensitivity of respiration across the globe. Analyzing measurements in a comprehensive database for 231 species spanning 7 biomes, we demonstrate that temperature-dependent increases in leaf respiration do not follow a commonly used exponential function. Instead, we find a decelerating function as leaves warm, reflecting a declining sensitivity to higher temperatures that is remarkably uniform across all biomes and plant functional types. Such convergence in the temperature sensitivity of leaf respiration suggests that there are universally applicable controls on the temperature response of plant energy metabolism, such that a single new function can predict the temperature dependence of leaf respiration for global vegetation. This simple function enables straightforward description of plant respiration in the land-surface components of coupled earth system models. Our cross-biome analyses shows significant implications for such fluxes in cold climates, generally projecting lower values compared with previous estimates. PMID:27001849

  5. The role of spatial scale and background climate in the latitudinal temperature response to deforestation

    Li, Yan; De Noblet-Ducoudré, Nathalie; Davin, Edouard L.; Motesharrei, Safa; Zeng, Ning; Li, Shuangcheng; Kalnay, Eugenia

    2016-03-01

    Previous modeling and empirical studies have shown that the biophysical impact of deforestation is to warm the tropics and cool the extratropics. In this study, we use an earth system model of intermediate complexity to investigate how deforestation on various spatial scales affects ground temperature, with an emphasis on the latitudinal temperature response and its underlying mechanisms. Results show that the latitudinal pattern of temperature response depends nonlinearly on the spatial extent of deforestation and the fraction of vegetation change. Compared with regional deforestation, temperature change in global deforestation is greatly amplified in temperate and boreal regions but is dampened in tropical regions. Incremental forest removal leads to increasingly larger cooling in temperate and boreal regions, while the temperature increase saturates in tropical regions. The latitudinal and spatial patterns of the temperature response are driven by two processes with competing temperature effects: decrease in absorbed shortwave radiation due to increased albedo and decrease in evapotranspiration. These changes in the surface energy balance reflect the importance of the background climate in modifying the deforestation impact. Shortwave radiation and precipitation have an intrinsic geographical distribution that constrains the effects of biophysical changes and therefore leads to temperature changes that are spatially varying. For example, wet (dry) climate favors larger (smaller) evapotranspiration change; thus, warming (cooling) is more likely to occur. Our analysis reveals that the latitudinal temperature change largely results from the climate conditions in which deforestation occurs and is less influenced by the magnitude of individual biophysical changes such as albedo, roughness, and evapotranspiration efficiency.

  6. Preparation and properties of fast temperature-responsive soy protein/PNIPAAm IPN hydrogels

    Liu Yong

    2014-01-01

    Full Text Available The interpenetrating polymer network of fast temperature-responsive hydrogels based on soy protein and poly(N-isopropylacrylamide were successfully prepared using the sodium bicarbonate (NaHCO3 solutions as the reaction medium. The structure and properties of the hydrogels were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry and thermal gravimetric analysis. The swelling and deswelling kinetics were also investigated in detail. The results have shown that the proposed hydrogels had high porous structure, good miscibility and thermal stability, and fast temperature responsivity. The presence of NaHCO3 had little effect on the volume phase transition temperature (VPTT of the hydrogels, and the VPTTs were at about 32°C. Compared with the traditional hydrogels, the proposed hydrogels had much faster swelling and deswelling rate. The swelling mechanism of the hydrogels was the non-Fickian diffusion. This fast temperature-responsive hydrogels may have potential applications in the field of biomedical materials.

  7. Gyroid Membranes made from Nanoporous Blck Copolymers

    Szewczykowski, Piotr Plzemystaw; Vigild, Martin Etchells; Ndoni, Sokol;

    2007-01-01

    Nanoporous materials are interesting and exciting materials in view of their many potential applications, especially as ultrafiltration membranes. One way of preparing nanoporous polymeric materials is to use block copolymers. Block copolymers have the great advantage that they organize them......-selves into different morphologies on the nano scale. Block copolymer synthesis controls the molecular weight and volume fraction of blocks, which determine the resulting nano-structures. From a membrane application point of view one very suitable morphology is the bicontinuous gyroid. Mechanical stability of...... the membrane and its nanoporosity is e.g. obtained by cross-linking the majority blocks and selectively etching the minority blocks. Here we report on ultrafiltration membranes prepared from a 1,2-polybutadiene-b-polydimethylsiloxane diblock copolymer with gyroid structure. Different experimental...

  8. 21 CFR 180.22 - Acrylonitrile copolymers.

    2010-04-01

    ..., distilled water, 8 percent or 50 percent ethanol, 3 percent acetic acid, and either n-heptane or an... conditions for the use of acrylonitrile copolymers have been, or soon will be, undertaken. Toxicity...

  9. Self-assembly of block copolymers

    Hidenori Otsuka

    2001-05-01

    Full Text Available Block copolymers in a selective solvent have a tendency to self-assemble at surfaces and into micelles1–4. At an aqueous interface, the amphiphilic property of block copolymers composed of hydrophilic and hydrophobic segments can cause the distal end of the hydrophilic chain to extend into the bulk aqueous solution, anchoring the hydrophilic block to the substrate surface through hydrophobic segments1, 2. In an aqueous solution, micelles with core-shell structure are formed by the segregation of insoluble blocks into the core, which is surrounded by a hydrophilic shell composed of hydrophilic blocks3, 4. This interfacial activity of amphiphilic block copolymers provides their utility in the biomedical field as colloidal dispersants, surface modifiers and drug carriers, prompting many studies of block copolymer adsorption on solid surfaces5, 6, 7, 8, force measurements between tethered layers9, 10, 11 and the characterization of micelle properties12, 13, 14.

  10. TRANSITION IN THE MELT OF FEP COPOLYMER

    SHI Guanyi; YUE Junshi

    1983-01-01

    The nature of the transition in molten FEP copolymer was examined in relation to the enthalpy change, mechanical damping and melt viscosity. For a pre-heat-treated FEP copolymer sample a small endothermic peak appeared at 309-312 ℃ in DSC trace with enthalpy change 0.03-0.05cal/g. A peak was also detected in damping versus temperature curve at the same temperature range.The rheological property of FEP copolymer melt was similar to that of liquid crystal, but no birefrigence was viewed in the melt. Therefore the transition was explained as the melting of small crystallites which persist in typical copolymer beyond its melting temperature. These crystallites can act as nuclei for crystallization upon cooling.

  11. Functional Nanoporous Polymers from Block Copolymer Precursors

    Guo, Fengxiao

    functionalities remains a great challenge due to the limitation of available polymer synthesis and the nanoscale confinement of the porous cavities. The main topic of this thesis is to develop methods for fabrication of functional nanoporous polymers from block copolymer precursors. A method has been developed......Abstract Self-assembly of block copolymers provides well-defined morphologies with characteristic length scales in the nanometer range. Nanoporous polymers prepared by selective removal of one block from self-assembled block copolymers offer great technological promise due to their many potential......, where living anionic polymerization and atom transfer radical polymerization (ATRP) are combined to synthesize a polydimethylsiloxane-b-poly(tert-butyl acrylate)-b-polystyrene (PDMS-b-PtBA-b-PS) triblock copolymer precursor. By using either anhydrous hydrogen fluoride or trifluoroacetic acid, PtBA block...

  12. Biosensor for Pesticides Based on Valerolacton Copolymer

    Yotova L.; Mateva R.; Yaneva S.; Marinkova D.

    2007-01-01

    A construction of amperometric biosensor based on immobilized acetycholinesterase and cholin oxidase is described and its application in the detection of organophosphate pesticides through enzyme inhibition measurements is discussed. The bioactive component of the sensor consists of acetycholinesterase or cholin oxidase covalently immobilized on two types new polymeric synthetic membranes. Two types of the copolymers were used for the synthesis of membranes - the copolymer of polyacrylamide a...

  13. Functional Nanoporous Polymers from Block Copolymer Precursors

    Guo, Fengxiao

    2010-01-01

    Abstract Self-assembly of block copolymers provides well-defined morphologies with characteristic length scales in the nanometer range. Nanoporous polymers prepared by selective removal of one block from self-assembled block copolymers offer great technological promise due to their many potential applications as, e.g., membranes for separation and purification, templates for nanostructured materials, sensors, substrates for catalysis, low dielectric constant materials, photonic materials, and...

  14. Silicone containing copolymers: Synthesis, properties and applications

    Yılgör, Emel; Yılgör, İskender

    2013-01-01

    Accepted Manuscript Title: Silicone containing copolymers: Synthesis, properties and applications Author: Emel Yilgor Iskender Yilgor PII: S0079-6700(13)00141-X DOI: http://dx.doi.org/doi:10.1016/j.progpolymsci.2013.11.003 Reference: JPPS 848 To appear in: Progress in Polymer Science Received date: 1-8-2013 Revised date: 4-11-2013 Accepted date: 8-11-2013 Please cite this article as: Yilgor E, Yilgor I, Silicone containing copolymers: Synthesis, properties ...

  15. Responsive Copolymers for Enhanced Petroleum Recovery

    McCormick, C.; Hester, R.

    2001-02-27

    The objectives of this work was to: synthesize responsive copolymer systems; characterize molecular structure and solution behavior; measure rheological properties of aqueous fluids in fixed geometry flow profiles; and to tailor final polymer compositions for in situ rheology control under simulated conditions. This report focuses on the synthesis and characterization of novel stimuli responsive copolymers, the investigation of dilute polymer solutions in extensional flow and the design of a rheometer capable of measuring very dilute aqueous polymer solutions at low torque.

  16. The role of spatial scale and background climate in the latitudinal temperature response to deforestation

    Y. Li

    2015-10-01

    Full Text Available Previous modeling and empirical studies have shown that the biophysical impact of deforestation is to warm the tropics and cool the extra-tropics. In this study, we use an earth system model to investigate how deforestation at various spatial scales affects ground temperature, with an emphasis on the latitudinal temperature response and its underlying mechanisms. Results show that the latitudinal pattern of temperature response depends non-linearly on the spatial extent of deforestation and the fraction of vegetation change. Compared with regional deforestation, temperature change in global deforestation is greatly amplified in temperate and boreal regions, but is dampened in tropical regions. Incremental forest removal leads to increasingly larger cooling in temperate and boreal regions, while the temperature increase saturates in tropical regions. The latitudinal and spatial patterns of the temperature response are driven by two processes with competing temperature effects: decreases in absorbed shortwave radiation due to increased albedo and decreases in evapotranspiration. These changes in the surface energy balance reflect the importance of the background climate on modifying the deforestation impact. Shortwave radiation and precipitation have an intrinsic geographical distribution that constrains the effects of biophysical changes and therefore leads to temperature changes that are spatially varying. For example, wet (dry climate favors larger (smaller evapotranspiration change, thus warming (cooling is more likely to occur. Further analysis on the contribution of individual biophysical factors (albedo, roughness, and evapotranspiration efficiency reveals that the latitudinal signature embodied in the temperature change probably result from the background climate conditions rather than the initial biophysical perturbation.

  17. Regional and global temperature response to anthropogenic SO2 emissions from China in three climate models

    Kasoar, Matthew; Voulgarakis, Apostolos; Lamarque, Jean-François; Shindell, Drew T.; Bellouin, Nicolas; Collins, William J.; Faluvegi, Greg; Tsigaridis, Kostas

    2016-08-01

    We use the HadGEM3-GA4, CESM1, and GISS ModelE2 climate models to investigate the global and regional aerosol burden, radiative flux, and surface temperature responses to removing anthropogenic sulfur dioxide (SO2) emissions from China. We find that the models differ by up to a factor of 6 in the simulated change in aerosol optical depth (AOD) and shortwave radiative flux over China that results from reduced sulfate aerosol, leading to a large range of magnitudes in the regional and global temperature responses. Two of the three models simulate a near-ubiquitous hemispheric warming due to the regional SO2 removal, with similarities in the local and remote pattern of response, but overall with a substantially different magnitude. The third model simulates almost no significant temperature response. We attribute the discrepancies in the response to a combination of substantial differences in the chemical conversion of SO2 to sulfate, translation of sulfate mass into AOD, cloud radiative interactions, and differences in the radiative forcing efficiency of sulfate aerosol in the models. The model with the strongest response (HadGEM3-GA4) compares best with observations of AOD regionally, however the other two models compare similarly (albeit poorly) and still disagree substantially in their simulated climate response, indicating that total AOD observations are far from sufficient to determine which model response is more plausible. Our results highlight that there remains a large uncertainty in the representation of both aerosol chemistry as well as direct and indirect aerosol radiative effects in current climate models, and reinforces that caution must be applied when interpreting the results of modelling studies of aerosol influences on climate. Model studies that implicate aerosols in climate responses should ideally explore a range of radiative forcing strengths representative of this uncertainty, in addition to thoroughly evaluating the models used against

  18. A balance between radiative forcing and climate feedback in the modeled 20th century temperature response

    Crook, Julia A.; Forster, Piers M.

    2011-09-01

    In this paper, we breakdown the temperature response of coupled ocean-atmosphere climate models into components due to radiative forcing, climate feedback, and heat storage and transport to understand how well climate models reproduce the observed 20th century temperature record. Despite large differences between models' feedback strength, they generally reproduce the temperature response well but for different reasons in each model. We show that the differences in forcing and heat storage and transport give rise to a considerable part of the intermodel variability in global, Arctic, and tropical mean temperature responses over the 20th century. Projected future warming trends are much more dependent on a model's feedback strength, suggesting that constraining future climate change by weighting these models on the basis of their 20th century reproductive skill is not possible. We find that tropical 20th century warming is too large and Arctic amplification is unrealistically low in the Geophysical Fluid Dynamics Laboratory CM2.1, Meteorological Research Institute CGCM232a, and MIROC3.2(hires) models because of unrealistic forcing distributions. The Arctic amplification in both National Center for Atmospheric Research models is unrealistically high because of high feedback contributions in the Arctic compared to the tropics. Few models reproduce the strong observed warming trend from 1918 to 1940. The simulated trend is too low, particularly in the tropics, even allowing for internal variability, suggesting there is too little positive forcing or too much negative forcing in the models at this time. Over the whole of the 20th century, the feedback strength is likely to be underestimated by the multimodel mean.

  19. Studies on the application of temperature-responsive ion exchange polymers with whey proteins.

    Maharjan, Pankaj; Campi, Eva M; De Silva, Kirthi; Woonton, Brad W; Jackson, W Roy; Hearn, Milton T W

    2016-03-18

    Several new types of temperature-responsive ion exchange resins of different polymer composition have been prepared by grafting the products from the co-polymerisation of N-phenylacrylamide, N-iso-propylacrylamide and acrylic acid derivatives onto cross-linked agarose. Analysis of the binding isotherms for these different resins obtained under batch adsorption conditions indicated that the resin based on N-iso-propylacrylamide containing 5% (w/w) N-phenylacrylamide and 5% (w/w) acrylic acid resulted in the highest adsorption capacity, Bmax, for the whey protein, bovine lactoferrin, e.g. 14 mg bovine lactoferrin/mL resin at 4 °C and 62 mg bovine lactoferrin/mL resin at 40 °C, respectively. Under dynamic loading conditions at 40 °C, 94% of the loaded bovine lactoferrin on a normalised mg protein per mL resin basis was adsorbed by this new temperature-responsive ion-exchanger, and 76% was eluted by a single cycle temperature shift to 4 °C without varying the composition of the 10mM sodium dihydrogen phosphate buffer, pH 6.5, or the flow rate. The binding characteristics of these different ion exchange resins with bovine lactoferrin were also compared to results obtained using other resins based on N-isopropylacrylamide but contained N-tert-butylacrylamide rather than N-phenylacrylamide, where the corresponding dynamic capture and release properties for bovine lactoferrin required different temperature conditions of 20 °C and 50 °C, respectively for optimal desorption/adsorption. The cationic protein, bovine lactoperoxidase, was also adsorbed and desorbed with these temperature-responsive resins under similar conditions of changing temperature, whereas the anionic protein, bovine β-lactoglobulin, was not adsorbed under this regime of temperature conditions but instead eluted in the flow-through. PMID:26905884

  20. Temperature response of photosynthesis in different drug and fiber varieties of Cannabis sativa L.

    Chandra, Suman; Lata, Hemant; Khan, Ikhlas A.; Mahmoud A. ElSohly

    2011-01-01

    The temperature response on gas and water vapour exchange characteristics of three medicinal drug type (HP Mexican, MX and W1) and four industrial fiber type (Felinq 34, Kompolty, Zolo 11 and Zolo 15) varieties of Cannabis sativa, originally from different agro-climatic zones worldwide, were studied. Among the drug type varieties, optimum temperature for photosynthesis (Topt) was observed in the range of 30–35 °C in high potency Mexican HPM whereas, it was in the range of 25–30 °C in W1. A co...

  1. Ion and temperature sensitive polypeptide block copolymer.

    Joo, Jae Hee; Ko, Du Young; Moon, Hyo Jung; Shinde, Usha Pramod; Park, Min Hee; Jeong, Byeongmoon

    2014-10-13

    A poly(ethylene glycol)/poly(L-alanine) multiblock copolymer incorporating ethylene diamine tetraacetic acid ([PA-PEG-PA-EDTA(m)) was synthesized as an ion/temperature dual stimuli-sensitive polymer, where the effect of different metal ions (Cu(2+), Zn(2+), and Ca(2+)) on the thermogelation of the polymer aqueous solution was investigated. The dissociation constants between the metal ions and the multiblock copolymer were calculated to be 1.2 × 10(-7), 6.6 × 10(-6), and 1.2 × 10(-4) M for Cu(2+), Zn(2+), and Ca(2+), respectively, implying that the binding affinity of the multiblock copolymer for Cu(2+) is much greater than that for Zn(2+) or Ca(2+). Atomic force microscopy and dynamic light scattering of the multiblock copolymer containing metal ions suggested micelle formation at low temperature, which aggregated as the temperature increased. Circular dichroism spectra suggested that changes in the α-helical secondary structure of the multiblock copolymer were more pronounced by adding Cu(2+) than other metal ions. The thermogelation of the multiblock copolymer aqueous solution containing Cu(2+) was observed at a lower temperature, and the modulus of the gel was significantly higher than that of the system containing Ca(2+) or Zn(2+), in spite of the same concentration of the metal ions and their same ionic valence of +2. The above results suggested that strong ionic complexes between Cu(2+) and the multiblock copolymer not only affected the secondary structure of the polymer but also facilitated the thermogelation of the polymer aqueous solution through effective salt-bridge formation even in a millimolar range of the metal ion concentration. Therefore, binding affinity of metal ions for polymers should be considered first in designing an effective ion/temperature dual stimuli-sensitive polymer. PMID:25178662

  2. Preparation and catalytic performance of temperature-responsive cell-like particles.

    Yang, Qiufeng; Dai, Zhao; Guo, Wenjuan; Chu, Yuanyuan; Chen, Guangping

    2014-09-01

    A novel kind of cell-like particles as temperature-responsive catalysts was presented in this paper. First, uniform α-Fe₂O₃shuttle-like nanoparticles were prepared by homogeneous hydrolysis. Then, these α-Fe₂O₃particles were coated by Au nanoparticles (AuNPs), SiO₂and poly (N-isopropylacrylamide) (PNIPAM), respectively. After the removal of SiO₂layer by etching with HF solution, the cell-like particles were prepared when the α-Fe₂O₃, AuNPs, and PNIPAM were as cell nucleus, catalysts, and cell membranes, respectively. These cell-like particles showed a novel temperature-responsively catalytic performance because the PNIPAM shell could change its hydrophilicity and swelling capacity under different temperature. When the temperature was 25°C, the yield of 4-aminophenol (4-AP) from 4-nitrophenol (4-NP) by reduction of NaBH₄was about 100% in 15 min, while the yield of 4-AP was about 90.5% in 40 min. when the temperature was 40°C. PMID:25262506

  3. Modeling and Experimental Analysis on the Temperature Response of AlN-Film Based SAWRs.

    Chen, Shuo; You, Zheng

    2016-01-01

    The temperature responses of aluminum nitride (AlN) based surface acoustic wave resonator (SAWR) are modeled and tested. The modeling of the electrical performance is based on a modified equivalent circuit model introduced in this work. For SAWR consisting of piezoelectric film and semiconducting substrate, parasitic parameters from the substrate is taken into consideration for the modeling. By utilizing the modified model, the high temperature electrical performance of the AlN/Si and AlN/6H-SiC based SAWRs can be predicted, indicating that a substrate with a wider band gap will lead to a more stable high temperature behavior, which is further confirmed experimentally by high temperature testing from 300 K to 725 K with SAWRs having a wavelength of 12 μm. Temperature responses of SAWR's center frequency are also calculated and tested, with experimental temperature coefficient factors (TCF) of center frequency being -29 ppm/K and -26 ppm/K for the AlN/Si and AlN/6H-SiC based SAWRs, which are close to the predicted values. PMID:27483286

  4. Diblock Copolymers for Nanoscale Patterning

    Russell, Thomas

    2006-03-01

    As the size scale of device features becomes increasingly smaller, conventional lithographic processes become increasingly more difficult and expensive, especially at a minimum feature size of less than 50 nm. Consequently, to achieve higher density circuits, storage devices or displays, it is evident that alternative routes need to be developed to circumvent both cost and manufacturing issues. An ideal process would be compatible with existing technological processes/manufacturing techniques and these strategies, together with novel materials, could allow significant advances to be made in meeting both short-term and long-term demands for higher density and faster devices. The self-assembly of block copolymers (BCP), two polymer chains covalently linked together at one end, provides a robust solution to these challenges. As thin films, immiscible BCP self-assemble into a range of highly-ordered morphologies where with size scale of the features is limited to the size of the polymers chains and are, therefore, nanoscopic in size. While self-assembly alone is sufficient for a number of applications in fabricating advanced microelectronics, directed self-orienting self-assembly processes are also required to produce complex devices with the required density and addressability of elements to meet future demands. By combining tailored self-assembly processes, a bottom-up approach, with micro-fabrication processes, a top-down approach, the ever-present thirst of the consumer for faster, better and cheaper devices can be met in very simple, yet robust, ways.

  5. Oil recovery with vinyl sulfonic acid-acrylamide copolymers

    Norton, C.J.; Falk, D.O.

    1973-12-18

    An aqueous polymer flood containing sulfomethylated alkali metal vinyl sulfonate-acrylamide copolymers was proposed for use in secondary or tertiary enhanced oil recovery. The sulfonate groups on the copolymers sustain the viscosity of the flood in the presence of brine and lime. Injection of the copolymer solution into a waterflooded Berea core, produced 30.5 percent of the residual oil. It is preferred that the copolymers are partially hydrolyzed.

  6. Metallo-supramolecular block copolymers : from synthesis to smart nanomaterials

    Guillet, Pierre

    2008-01-01

    Supramolecular copolymers have become of increasing interest in recent years for the search of new materials with tunable properties. In particular, metallo-supramolecular block copolymers have seen important progresses since the last five years. In this thesis, a library of metallo-supramolecular amphiphilic block copolymers containing a hydrophilic block, linked to a hydrophobic block, through a metal-ligand complex has been investigated. The micelles formed in water from these copolymers...

  7. Dynamic Processes in Diblock Copolymer Micelles

    Robertson, Megan; Singh, Avantika

    2013-03-01

    Diblock copolymers, which form micelle structures in selective solvents, offer advantages of robustness and tunability of micelle characteristics as compared to small molecule surfactants. Diblock copolymer micelles in water have been a subject of great interest in drug delivery applications based on their high loading capacity and targeted drug delivery. The aim of this work is to understand the dynamic processes which underlie the self-assembly of diblock copolymer micelle systems which have a semi-crystalline core. Due to the large size of the molecules, the self-assembly of block copolymer micelles occurs on significantly longer time scales than small molecule analogues. The present work focuses on amphiphilic diblock copolymers containing blocks of poly(ethylene oxide) (a hydrophilic polymer) and polycaprolactone (a hydrophobic, semi-crystalline polymer), which spontaneously self-assemble into spherical micelles in water. A variety of experimental techniques are used to probe the kinetic processes relevant to micelle self-assembly, including time-resolved neutron scattering, dynamic light scattering, pulsed field gradient nuclear magnetic resonance, and fluorescence resonance energy transfer experiments.

  8. 21 CFR 175.210 - Acrylate ester copolymer coating.

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylate ester copolymer coating. 175.210 Section... COATINGS Substances for Use as Components of Coatings § 175.210 Acrylate ester copolymer coating. Acrylate ester copolymer coating may safely be used as a food-contact surface of articles intended for...

  9. SCATTERING BY CYCLIC POLYMERS AND COPOLYMERS AT LARGE SCATTERING VECTORS

    KOSMAS, M; BENOIT, H; HADZIIOANNOU, G

    1994-01-01

    General formulae allowing the evaluation of the form factors of cyclic block copolymers are established and graphs for cyclic copolymers of the form (A-B)(N) are shown. When N is large, the linear and the cyclic copolymer have the same behaviour. It is possible to extend at large angle an analytical

  10. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

    2010-04-01

    ... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified as... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Cross-linked polyacrylate copolymers. 177.1211... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1211 Cross-linked...

  11. Blends of Styrene-Butadiene-Styrene Triblock Copolymer with Random Styrene-Maleic Anhydride Copolymers

    Piccini, Maria Teresa; Ruggeri, Giacomo; Passaglia, Elisa; Picchioni, Francesco; Aglietto, Mauro

    2002-01-01

    Blends of styrene-butadiene-styrene triblock copolymer (SBS) with random styrene-maleic anhydride copolymers (PS-co-MA), having different MA content, were prepared in a Brabender Plastigraph mixer. The presence of polystyrene (PS) blocks in the SBS copolymer and the high styrene content (93 and 86 wt.-%, respectively) in the two kinds of used PS-co-MA samples afforded a good compatibility between the PS phases of the two polymers. On the other hand, the presence of polar anhydride groups allo...

  12. Polyimide nanofoams from aliphatic polyester based copolymers

    Hedrick, J.L.; Carter, K.R.; Richter, R.; Russell, T.P. [Almaden Research Center, San Jose, CA (United States)] [and others

    1996-10-01

    High temperature polymer foams were prepared using microphase separated block copolymers where the major component is thermally stable block and the minor component is thermally labile. Upon thermal treatment, the dispersed minor component undergoes thermolysis leaving pores the size and shape of which are dictated by the initial copolymer morphology. The driving force behind the survey of aliphatic polyesters as possible labile blocks stems from their quantitative degradation into low boiling, polar degradation products via a backbiting process. Block copolymers were prepared using either a monofunctional caprolactone or a valerolactone oligomer and a high T. polyimide. Microphase morphologies were observed in each case. Thermal decomposition of the polyester blocks was accomplished by a thermal treatment at 370{degrees}C for 5 h. Significant density reductions were measured, and the resulting foams showed pore sizes in the 60-70 {Angstrom} range.

  13. Functionalization of Block Copolymer Vesicle Surfaces

    Wolfgang Meier

    2011-01-01

    Full Text Available In dilute aqueous solutions certain amphiphilic block copolymers self-assemble into vesicles that enclose a small pool of water with a membrane. Such polymersomes have promising applications ranging from targeted drug-delivery devices, to biosensors, and nanoreactors. Interactions between block copolymer membranes and their surroundings are important factors that determine their potential biomedical applications. Such interactions are influenced predominantly by the membrane surface. We review methods to functionalize block copolymer vesicle surfaces by chemical means with ligands such as antibodies, adhesion moieties, enzymes, carbohydrates and fluorophores. Furthermore, surface-functionalization can be achieved by self-assembly of polymers that carry ligands at their chain ends or in their hydrophilic blocks. While this review focuses on the strategies to functionalize vesicle surfaces, the applications realized by, and envisioned for, such functional polymersomes are also highlighted.

  14. Thermodynamic Interactions in Organometallic Block Copolymers

    The thermodynamic interactions in anionically synthesized poly(styrene-block-ferrocenyldimethylsilane) (SF) copolymers were examined using birefringence, small angle X-ray and neutron scattering (SAXS and SANS). We show that birefringence detection of the order-disorder transition is possible in colored samples provided the wavelength of the incident beam is in the tail of the absorption spectrum. The location of the order-disorder transition was confirmed by SAXS. The temperature-dependence of the Flory-Huggins parameter, χ, of SF copolymers, determined by SAXS, is similar in magnitude to that between polystyrene and polyisoprene chains. We find that χ is independent of block copolymer composition (within experimental error). We also demonstrate that the neutron scattering length densities of styrene and ferrocenyldimethylsilane moieties are identical due to a surprising cancellation of factors related to density and atomic composition

  15. Micellization and Characterization of Block Copolymer Detergents

    Hvidt, Søren

    Triblock copolymers of the type EPE, where E and P denote ethylene oxide and propylene oxide blocks, respectively, are used widely in industry as emulsifiers, anti-foaming agents, and in delayed drug release. EPE copolymers form micelles with a core of P blocks and different micellar shapes...... depending on block length ratios and temperature. The micellization process with increasing temperature or concentration has been followed by a number of techniques including differential scanning calorimetry and surface tension measurements. The detailed micellar mechanism is not well understood and...... different models have been proposed. Results obtained by a range of liquid chromatographic methods will be shown and it will be demonstrated that commercial EPE copolymers are inhomogeneous at several levels and many of their unusual properties reflect the presence of impurities....

  16. Biosensor for Pesticides Based on Valerolacton Copolymer

    Yotova L.

    2007-12-01

    Full Text Available A construction of amperometric biosensor based on immobilized acetycholinesterase and cholin oxidase is described and its application in the detection of organophosphate pesticides through enzyme inhibition measurements is discussed. The bioactive component of the sensor consists of acetycholinesterase or cholin oxidase covalently immobilized on two types new polymeric synthetic membranes. Two types of the copolymers were used for the synthesis of membranes - the copolymer of polyacrylamide and acrylonitrile and the new copolymer of poly- (hexanlactam-co-block-poly-(delta-valerolactone with aliphatic polyester. It is investigated the technical characteristics of biosensor like, response time, linear range and operating stability. The factors affecting the inhibition and reactivation processes were investigated too.

  17. Temperature response to reactant concentration perturbations in a packed-bed reactor

    Unsteady-state operations are known to enhance the performance of some packed-bed reactor systems. However, negative effects of this type of operation should not be neglected. Temperature excursions developed during transients may accelerate some deactivation mechanisms, reducing catalyst lifetime and selectivity. Temperature response to perturbations in reactant concentration was studied for CO oxidation over Pt/Al2O3, in a packed-bed reactor. Experiments were conducted in the CO concentration range for which multiple steady states are observed. Temperature and concentration profiles in the packed-bed reactor at steady state were found to depend on the dynamic history of the reactor prior to the steady-state condition. (author)

  18. Temperature-Responsive Tensile Actuator Based on Multi-walled Carbon Nanotube Yarn

    Hyunsoo Kim; Jae Ah Lee; Hyeon Jun Sim; Ma rcio D Lima; Ray H Baughman; Seon Jeong Kim

    2016-01-01

    Many temperature indicators or sensors show color changes for materials used in food and medical fields. However, they are not helpful for a color-blind person or children who lack judgment. In this paper, we introduce simply fabricated and more useful low-temperature indicator (*30 ?C) for devices that actuates using paraffin-infiltrated multi-walled carbon nanotube (MWCNT) coiled yarn. The density difference of MWCNT yarn provides large strain (*330%) when heat causes the melted polymer to move. Furthermore, the MWCNT yarn decreases the melting point of paraffin. These properties allow control of the actuating temperature. In addition, mechanical strength was enhanced by MWCNT than previously reported temperature-responsive actuators based on shape memory polymers. This simply fabricated temperature indicator can be applied in latching devices for medical and biological fields.

  19. Kuosheng BWR/6 containment pressure and temperature responses after recirculation line break using GOTHIC code

    In this study, we presented the calculated results of the containment P/T (pressure and temperature) response after the recirculation line break (RCLB) accident of a GE-designed twin-unit BWR/6 plant, which can be served as the design basis for the containment system. During the simulation, a power of SPU (stretch power uprate) range was used and a model of the Mark III type containment was built using the GOTHIC (Generation of Thermal-Hydraulic Information for Containments) code. The calculated results, similar to the FSAR (Final Safety Analysis Report) results, indicate the GOTHIC code has the capability to simulate the containment P/T response to the RCLB accident. (author)

  20. [Hydrodynamic properties of exopolysaccharide-acrylamide copolymer].

    Votselko, S K

    2000-01-01

    The method for producing copolymer EPAA of exopolysaccharide (EPS)--polyacrylamide (PAA) has been presented which was based on microbial exopolysaccharides (enposane, xampane), their mixture and model EPS (xanthane sigma, rodopol P-23). The copolymer was produced by acrylamide polymerization in 1-2% water solutions of polysaccharides, the concentration of acrylamide in the reaction mixture being 4.7-2% and that of polysaccharides 0.1-1% of the weight. Hydrodynamic parameters of the studied polymers have been determined, their heterogenity as to molecular-weight characteristics has been demonstrated. Molecular-weight distribution of copolymers showed that the content of low-molecular fractions decreased, thus the Mw values were (0.08-0.2) x 10(6) Da in contrast to that of exopolysaccharides possessing Mw (1.2-0.4) x 10(6) Da and of polyacrylamide possessing Mw within (2-30) x 10(6) Da. The value of efficient viscosity of copolymers ranged from 120 to 131 mPa.s that was lower than that of polyacrylamide (500 mPa.s), and higher than that of exopolysaccharides (42 mPa.s), and it depended on the sample, raw material, production conditions. A possibility has been shown to produce a new copolymer based on microbial polysaccharides enposane and xampane in the process of acrylamide polymerization. It has been found out that the studied copolymers EPAA differ from initial ones as to their hydrodynamical properties, which determines their preference: better solubility, good glueing properties, prolonged term of preservation, resistance to bacterial pollution. PMID:11300081

  1. Long- and short-term temperature responses of microbially-mediated boreal soil organic matter transformations

    Min, K.; Buckeridge, K. M.; Edwards, K. A.; Ziegler, S. E.; Billings, S. A.

    2015-12-01

    Microorganisms use exoenzymes to decay soil organic matter into assimilable substrates, some of which are transformed into CO2. Microbial CO2 efflux contributes up to 60% of soil respiration, a feature that can change with temperature due to altered exoenzyme activities (short-term) and microbial communities producing different exoenzymes (longer-term). Often, however, microbial temperature responses are masked by factors that also change with temperature in soil, making accurate projections of microbial CO2 efflux with warming challenging. Using soils along a natural climate gradient similar in most respects except for temperature regime (Newfoundland Labrador Boreal Ecosystem Latitudinal Transect), we investigated short-vs. long-term temperature responses of microbially-mediated organic matter transformations. While incubating soils at 5, 15, and 25°C for 84 days, we measured exoenzyme activities, CO2 efflux rates and biomass, and extracted DNA at multiple times. We hypothesized that short-term, temperature-induced increases in exoenzyme activities and CO2 losses would be smaller in soils from warmer regions, because microbes presumably adapted to warmer regions should use assimilable substrates more efficiently and thus produce exoenzymes at a lower rate. While incubation temperature generally induced greater exoenzyme activities (pDNA sequencing will reveal how microbial community abundance and composition change with short-vs. longer-term temperature change. Though short-term microbial responses to temperature suggest higher CO2 efflux and thus lower efficiency of resource use with warming, longer-term adaptations of microbial communities to warmer climates remain unknown; this work helps fill that knowledge gap.

  2. Temperature response functions introduce high uncertainty in modelled carbon stocks in cold temperature regimes

    H. Portner

    2009-08-01

    Full Text Available Models of carbon cycling in terrestrial ecosystems contain formulations for the dependence of respiration on temperature, but the sensitivity of predicted carbon pools and fluxes to these formulations and their parameterization is not understood. Thus, we made an uncertainty analysis of soil organic matter decomposition with respect to its temperature dependency using the ecosystem model LPJ-GUESS.

    We used five temperature response functions (Exponential, Arrhenius, Lloyd-Taylor, Gaussian, Van't Hoff. We determined the parameter uncertainty ranges of the functions by nonlinear regression analysis based on eight experimental datasets from northern hemisphere ecosystems. We sampled over the uncertainty bounds of the parameters and run simulations for each pair of temperature response function and calibration site. The uncertainty in both long-term and short-term soil carbon dynamics was analyzed over an elevation gradient in southern Switzerland.

    The function of Lloyd-Taylor turned out to be adequate for modelling the temperature dependency of soil organic matter decomposition, whereas the other functions either resulted in poor fits (Exponential, Arrhenius or were not applicable for all datasets (Gaussian, Van't Hoff. There were two main sources of uncertainty for model simulations: (1 the uncertainty in the parameter estimates of the response functions, which increased with increasing temperature and (2 the uncertainty in the simulated size of carbon pools, which increased with elevation, as slower turn-over times lead to higher carbon stocks and higher associated uncertainties. The higher uncertainty in carbon pools with slow turn-over rates has important implications for the uncertainty in the projection of the change of soil carbon stocks driven by climate change, which turned out to be more uncertain for higher elevations and hence higher latitudes, which are of key importance for the global terrestrial carbon

  3. Dynamics of Block Copolymer Nanocomposites

    Mochrie, Simon G. J.

    2014-09-09

    A detailed study of the dynamics of cadmium sulfide nanoparticles suspended in polystyrene homopolymer matrices was carried out using X-ray photon correlation spectroscopy for temperatures between 120 and 180 °C. For low molecular weight polystyrene homopolymers, the observed dynamics show a crossover from diffusive to hyper-diffusive behavior with decreasing temperatures. For higher molecular weight polystyrene, the nanoparticle dynamics appear hyper-diffusive at all temperatures studied. The relaxation time and characteristic velocity determined from the measured hyper-diffusive dynamics reveal that the activation energy and underlying forces determined are on the order of 2.14 × 10-19 J and 87 pN, respectively. We also carried out a detailed X-ray scattering study of the static and dynamic behavior of a styrene– isoprene diblock copolymer melt with a styrene volume fraction of 0.3468. At 115 and 120 °C, we observe splitting of the principal Bragg peak, which we attribute to phase coexistence of hexagonal cylindrical and cubic double- gyroid structure. In the disordered phase, above 130 °C, we have characterized the dynamics of composition fluctuations via X-ray photon correlation spectroscopy. Near the peak of the static structure factor, these fluctuations show stretched-exponential relaxations, characterized by a stretching exponent of about 0.36 for a range of temperatures immediately above the MST. The corresponding characteristic relaxation times vary exponentially with temperature, changing by a factor of 2 for each 2 °C change in temperature. At low wavevectors, the measured relaxations are diffusive with relaxation times that change by a factor of 2 for each 8 °C change in temperature.

  4. Observed frustration in confined block copolymers

    Symmetric diblock copolymers confined between two solid surfaces were studied by neutron reflectivity. A multilayered morphology with an integral number of layers oriented parallel to the solid interfaces was found in all cases. The period of the confined multilayers deviated from the bulk period in a cyclic manner as a function of the confined film thickness. A first-order transition occurred between the expanded and contracted states of the copolymer chains. The data suggest that the deviation of the period from the bulk value decreases with increasing separation distance

  5. Substrate tolerant direct block copolymer nanolithography

    Li, Tao; Wang, Zhongli; Schulte, Lars;

    2016-01-01

    simplifies the main stream BC lithography process, showing a broad substrate tolerance and allowing for efficient pattern transfer over wafer scale. PDMS-rich poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) copolymers are directly applied on substrates including polymers, silicon and graphene. A single oxygen......Block copolymer (BC) self-assembly constitutes a powerful platform for nanolithography. However, there is a need for a general approach to BC lithography that critically considers all the steps from substrate preparation to the final pattern transfer. We present a procedure that significantly...... plasma treatment enables formation of the oxidized PDMS hard mask, PS block removal and polymer or graphene substrate patterning....

  6. Co-polymer Films for Sensors

    Ryan, Margaret A. (Inventor); Homer, Margie L. (Inventor); Yen, Shiao-Pin S. (Inventor); Kisor, Adam (Inventor); Jewell, April D. (Inventor); Shevade, Abhijit V. (Inventor); Manatt, Kenneth S. (Inventor); Taylor, Charles (Inventor); Blanco, Mario (Inventor); Goddard, William A. (Inventor)

    2012-01-01

    Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

  7. BARRIER PROPERTIES OF VINYLIDENE CHLORIDE/METHYL ACRYLATE COPOLYMER

    LI Yuesheng; WENG Zhixue; PAN Zuren

    1997-01-01

    A series of vinylidene dichloride (VDC) copolymers with methyl acrylate (MA) as comonomer (3-12 wt%), was prepared by free-radical suspension copolymerization. The permeability coefficients of the copolymers to oxygen and carbon dioxide were measured at1.0 MPa and at 30℃, and those to water vapor were measured at 30℃ and 100% relative humidity. All the VDC/MA copolymers studied are semicrystalline. As the MA content increases, the permeability coefficients of the copolymers to oxygen, carbon dioxide, and water vapor are progressively increased, caused by decrease in crystalline fraction and increase in free volume of VDC/MA copolymers.

  8. Block Copolymers of Ethylene Oxide and Styrene Oxide.New Copolymer Surfactants(Ⅱ)

    Zhuo Yang; David Attwood; Colin Booth

    2003-01-01

    @@ 3.2. Association Number Figure 5 shows the dependence of the weight-average association number (Nw,measured by static light scattering, solution temperature 30 °C) on hydrophobe block length for ES and ESEblock copolymers.

  9. Synthesis of amphiphilic diblock copolymer for surface modification of Ethylene-Norbornene copolymers

    Levinsen, Simon; Svendsen, Winnie Edith; Horsewell, Andy; Almdal, Kristoffer

    2014-01-01

    The aim of this work is to produce polymer modifiers in order to develop hydrophilic polymeric surfaces for use in microfluidics. The use of hydrophilic polymers in microfluidics will have many advantages e.g. preventing protein absorbance. Here we present an amphiphilic diblock copolymer...... consisting of a bulk material compatible block and a hydrophilic block. To utilize the possibility of incorporating diblock copolymers into ethylenenorbornene copolymers, we have in this work developed a model poly(ethylene-1-butene) polymer compatible with the commercial available ethylene......-norbornene copolymer TOPAS. Through matching of the radius of gyration for the model polymer and TOPAS the miscibility was achieved. The poly(ethylene-1-butene) polymer was synthesized from a hydrogenated anionic polymerized polybutadiene polymer. As hydrophilic block poly(ethylene oxide) was subsequently added also...

  10. Molecular Interaction Control in Diblock Copolymer Blends and Multiblock Copolymers with Opposite Phase Behaviors

    Cho, Junhan

    2014-03-01

    Here we show how to control molecular interactions via mixing AB and AC diblock copolymers, where one copolymer exhibits upper order-disorder transition and the other does lower disorder-order transition. Linear ABC triblock copolymers possessing both barotropic and baroplastic pairs are also taken into account. A recently developed random-phase approximation (RPA) theory and the self-consistent field theory (SCFT) for general compressible mixtures are used to analyze stability criteria and morphologies for the given systems. It is demonstrated that the copolymer systems can yield a variety of phase behaviors in their temperature and pressure dependence upon proper mixing conditions and compositions, which is caused by the delicate force fields generated in the systems. We acknowledge the financial support from National Research Foundation of Korea and Center for Photofunctional Energy Materials.

  11. A temperature response function for modeling leaf growth and development of the African violet (Saintpaulia ionantha Wendl.

    Streck Nereu Augusto

    2004-01-01

    Full Text Available Response functions used in crop simulation models are usually different for different physiological processes and cultivars, resulting in many unknown coefficients in the response functions. This is the case of African violet (Saintpaulia ionantha Wendl., where a generalized temperature response for leaf growth and development has not been developed yet. The objective of this study was to develop a generalized nonlinear temperature response function for leaf appearance rate and leaf elongation rate in African violet. The nonlinear function has three coefficients, which are the cardinal temperatures (minimum, optimum, and maximum temperatures. These coefficients were defined as 10, 24, and 33ºC, based on the cardinal temperatures of other tropical species. Data of temperature response of leaf appearance rate and leaf elongation rate in African violet, cultivar Utah, at different light levels, which are from published research, were used as independent data for evaluating the performance of the nonlinear temperature response function. The results showed that a generalized nonlinear response function can be used to describe the temperature response of leaf growth and development in African violet. These results imply that a reduction in the number of input data required in African violet simulation models is possible.

  12. HPMA copolymer conjugates designed for combination chemotherapy

    Krakovičová, Hana; Etrych, Tomáš; Ulbrich, Karel; Jelínková, Markéta; Říhová, Blanka

    Brno : Veterinary Research Institute, 2008. s. 26. [International Workshop on Drug Delivery Systems for Nanomedicine: Nanostructures and their Biomedical Applications. 03.10.2008-06.10.2008, Liblice] R&D Projects: GA AV ČR IAA400500806 Institutional research plan: CEZ:AV0Z40500505 Keywords : HPMA copolymers * drug carriers * doxorubicin Subject RIV: CD - Macromolecular Chemistry

  13. Ordering phenomena in ABA triblock copolymer gels

    Reynders, K.; Mischenko, N.; Kleppinger, R.; Reynaers, H.; Koch, M.H.J.; Mortensen, K.

    1997-01-01

    Temperature and concentration dependencies of the degree of order in ABA triblock copolymer gels are discussed. Two factors can influence the ordering phenomena: the conformation of the midblocks (links of the network) and the polydispersity of the endblock domains (nodes of the network). The...

  14. Shear instability of a gyroid diblock copolymer

    Eskimergen, Rüya; Mortensen, Kell; Vigild, Martin Etchells

    2005-01-01

    -induced destabilization is discussed in relation to analogous observations on shear-induced order-to-order and disorder-to-order transitions observed in related block copolymer systems and in microemulsions. It is discussed whether these phenomena originate in shear-reduced fluctuations or shear-induced dislocations....

  15. Cyclic olefin copolymer-silica nanocomposites foams

    Pegoretti, A.; Dorigato, A.; Biani, A.; Šlouf, Miroslav

    2016-01-01

    Roč. 51, č. 8 (2016), s. 3907-3916. ISSN 0022-2461 R&D Projects: GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 Keywords : cyclic olefin copolymer * nanocomposites * silica Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.371, year: 2014

  16. An isotopic investigation of the temperature response of young and old soil organic matter respiration

    Burns, Nancy; Cloy, Joanna; Garnett, Mark; Reay, David; Smith, Keith; Otten, Wilfred

    2010-05-01

    The effect of temperature on rates of soil respiration is critical to our understanding of the terrestrial carbon cycle and potential feedbacks to climate change. The relative temperature sensitivity of labile and recalcitrant soil organic matter (SOM) is still controversial; different studies have produced contrasting results, indicating limited understanding of the underlying relationships between stabilisation processes and temperature. Current global carbon cycle models still rely on the assumption that SOM pools with different decay rates have the same temperature response, yet small differences in temperature response between pools could lead to very different climate feedbacks. This study examined the temperature response of soil respiration and the age of soil carbon respired from radiocarbon dated fractions of SOM (free, intra-aggregate and mineral-bound) and whole soils (organic and mineral layers). Samples were collected from a peaty gley soil from Harwood Forest, Northumberland, UK. SOM fractions were isolated from organic layer (5 - 17 cm) material using high density flotation and ultrasonic disaggregation - designated as free ( 1.8 g cm-3) and mineral-bound (> 1.8 g cm-3) SOM. Fractions were analysed for chemical composition (FTIR, CHN analysis, ICP-OES), 14C (AMS), δ13C and δ15N (MS) and thermal properties (DSC). SOM fractions and bulk soil from the organic layer and the mineral layer (20 - 30 cm) were incubated in sealed vessels at 30 ° C and 10 ° C for 3 or 9 months to allow accumulation of CO2 sufficient for sampling. Accumulated respired CO2 samples were collected on zeolite molecular sieve cartridges and used for AMS radiocarbon dating. In parallel, material from the same fractions and layers were incubated at 10 ° C, 15 ° C, 25 ° C and 30 ° C for 6 months and sampled weekly for CO2 flux measurements using GC chromatography. Initial data have shown radiocarbon ages ranging from modern to 219 y BP in bulk soil from the organic layer (5

  17. Global temperature response to the major volcanic eruptions in multiple reanalysis data sets

    Fujiwara, M.; Hibino, T.; Mehta, S. K.; Gray, L.; Mitchell, D.; Anstey, J.

    2015-12-01

    The global temperature responses to the eruptions of Mount Agung in 1963, El Chichón in 1982, and Mount Pinatubo in 1991 are investigated using nine currently available reanalysis data sets (JRA-55, MERRA, ERA-Interim, NCEP-CFSR, JRA-25, ERA-40, NCEP-1, NCEP-2, and 20CR). Multiple linear regression is applied to the zonal and monthly mean time series of temperature for two periods, 1979-2009 (for eight reanalysis data sets) and 1958-2001 (for four reanalysis data sets), by considering explanatory factors of seasonal harmonics, linear trends, Quasi-Biennial Oscillation, solar cycle, and El Niño Southern Oscillation. The residuals are used to define the volcanic signals for the three eruptions separately, and common and different responses among the older and newer reanalysis data sets are highlighted for each eruption. In response to the Mount Pinatubo eruption, most reanalysis data sets show strong warming signals (up to 2-3 K for 1-year average) in the tropical lower stratosphere and weak cooling signals (down to -1 K) in the subtropical upper troposphere. For the El Chichón eruption, warming signals in the tropical lower stratosphere are somewhat smaller than those for the Mount Pinatubo eruption. The response to the Mount Agung eruption is asymmetric about the equator with strong warming in the Southern Hemisphere midlatitude upper troposphere to lower stratosphere. Comparison of the results from several different reanalysis data sets confirms the atmospheric temperature response to these major eruptions qualitatively, but also shows quantitative differences even among the most recent reanalysis data sets. The consistencies and differences among different reanalysis data sets provide a measure of the confidence and uncertainty in our current understanding of the volcanic response. The results of this intercomparison study may be useful for validation of climate model responses to volcanic forcing and for assessing proposed geoengineering by stratospheric

  18. Global temperature response to the major volcanic eruptions in multiple reanalysis data sets

    M. Fujiwara

    2015-12-01

    Full Text Available The global temperature responses to the eruptions of Mount Agung in 1963, El Chichón in 1982, and Mount Pinatubo in 1991 are investigated using nine currently available reanalysis data sets (JRA-55, MERRA, ERA-Interim, NCEP-CFSR, JRA-25, ERA-40, NCEP-1, NCEP-2, and 20CR. Multiple linear regression is applied to the zonal and monthly mean time series of temperature for two periods, 1979–2009 (for eight reanalysis data sets and 1958–2001 (for four reanalysis data sets, by considering explanatory factors of seasonal harmonics, linear trends, Quasi-Biennial Oscillation, solar cycle, and El Niño Southern Oscillation. The residuals are used to define the volcanic signals for the three eruptions separately, and common and different responses among the older and newer reanalysis data sets are highlighted for each eruption. In response to the Mount Pinatubo eruption, most reanalysis data sets show strong warming signals (up to 2–3 K for 1-year average in the tropical lower stratosphere and weak cooling signals (down to −1 K in the subtropical upper troposphere. For the El Chichón eruption, warming signals in the tropical lower stratosphere are somewhat smaller than those for the Mount Pinatubo eruption. The response to the Mount Agung eruption is asymmetric about the equator with strong warming in the Southern Hemisphere midlatitude upper troposphere to lower stratosphere. Comparison of the results from several different reanalysis data sets confirms the atmospheric temperature response to these major eruptions qualitatively, but also shows quantitative differences even among the most recent reanalysis data sets. The consistencies and differences among different reanalysis data sets provide a measure of the confidence and uncertainty in our current understanding of the volcanic response. The results of this intercomparison study may be useful for validation of climate model responses to volcanic forcing and for assessing proposed

  19. Transient temperature response of in-vessel components due to pulsed operation in tokamak fusion experimental reactor (FER)

    A transient temperature response of the in-vessel components (first wall, blanket, divertor/limiter and shielding) surrounding plasma in Tokamak Fusion Experimental Reactor (FER) has been analysed. Transient heat load during start up/shut down and pulsed operation cycles causes the transient temperature response in those components. The fatigue lifetime of those components significantly depends upon the resulting cyclic thermal stress. The burn time affects the temperature control in the solid breeder (Li2O) and also affects the thermo-mechanical design of the blanket and shielding which are constructed with thick structure. In this report, results of the transient temperature response obtained by the heat transfer and conduction analyses for various pulsed operation scenarios (start up, shut down, burn and dwell times) have been investigated in view of thermo-mechanical design of the in-vessel components. (author)

  20. The use of infrared thermography to detect the skin temperature response to physical activity

    Tanda, G.

    2015-11-01

    Physical activity has a noticeable effect on skin blood flow and temperature. The thermal regulatory and hemodynamic processes during physical activity are controlled by two conflicting mechanisms: the skin vasoconstriction induced by the blood flow demand to active muscles and the skin vasodilation required by thermoregulation to increase warm blood flow and heat conduction to the skin. The time-evolution of skin temperature during exercise can give useful information about the adaptation of the subject as a function of specific type, intensity and duration of exercise. In this paper, infrared thermography is used to investigate the thermal response of skin temperature during running exercise on treadmill for a group of seven healthy and trained runners. Two different treadmill exercises are considered: a graded load exercise and a constant load exercise; for both exercises the duration was 30 minutes. Within the limits due to the relatively small size of the sample group, results typically indicate a fall in skin temperature during the initial stage of running exercise. As the exercise progresses, the dynamics of the skin temperature response depends on the type of exercise (graded versus constant load) and probably on the level of training of the subject.

  1. Light- and temperature-responsive liposomes incorporating cinnamoyl Pluronic F127.

    Wang, MinHui; Kim, Jin-Chul

    2014-07-01

    Light- and temperature-responsive liposomes were prepared by immobilizing cinnamoyl Pluronic F127 (CP F127) on the surface of egg phosphatidylcholine liposomes. CP F127 was prepared by a condensation reaction, and the molar ratio of cinnamoyl group to Pluronic F127 was calculated to be 1:1.4 on (1)H NMR spectrum. The cinnamoyl group of CP F127 was readily dimerized under the irradiation of a UV light (254 nm, 6 W). CP F127 decreased the absolute value of the zeta potential of liposome possibly because it can shift the hydrodynamic plane away from the liposome surface. The size of liposome decorated with CP F127, measured on a dynamic light scattering machine and observed on a TEM, was larger than that of bare liposome. The liposome bearing CP F127 seemed to fuse and aggregate each other. The liposome released calcein, a fluorescence dye, in response to a UV irradiation, possibly because the photo-dimerization of cinnamoyl group perturbs the liposomal membrane. Moreover, the liposome released the dye in response to a temperature change, possible due to the phase transition of Pluronic F127 layer on the liposomal surface or the hydrophobic interaction of the polymer with liposomal membrane. PMID:24709213

  2. A reusable electrochemical immunosensor fabricated using a temperature-responsive polymer for cancer biomarker proteins.

    Hong, Wooyoung; Lee, Sooyeon; Jae Kim, Eun; Lee, Maria; Cho, Youngnam

    2016-04-15

    In the present study, we describe a reusable electrochemical immunosensor for the repeated detection of cancer biomarkers using a single platform. The integration of a temperature-responsive polymer on the electrode surface enables easy manipulation of the biological sensing interface (i.e., addition of biotin, streptavidin, and antibody), thus allowing for temperature-induced regeneration and disruption of the interface architecture of the electrode surface. Using our immunosensor, we demonstrate sequential amperometric detection of three tumor markers: CA125, CEA, and PSA. Interestingly, greatly amplified signals are achieved by immersing the immunosensor in a solution of horseradish peroxidase (HRP) and antibody-labeled nanoparticles, resulting in a linear range of 0.0064 to 256 U/mL, 1 pg/mL to 100 ng/mL, and 10 pg/mL to 10 ng/mL with a detection limit of 0.007 U/mL, 0.7 pg/mL, and 0.9 pg/mL for CA125, CEA, and PSA, respectively. By alternating temperature, the immunosensor adsorbs and desorbs the biological elements without damage. Our proposed methodology can be expanded to measure other relevant biological species by repeated detection and thus has enormous potential for industrial and clinical applications. PMID:26606310

  3. Surface modification of uniaxial cyclic strain cell culture platform with temperature-responsive polymer for cell sheet detachment†

    Lee, E L; Bendre, H. H.; Kalmykov, A.; Wong, J Y

    2015-01-01

    Current cell sheet-based blood vessels lack biomimetic structure and require excessively long culture times that may compromise smooth muscle cell phenotype. We modified a commercially available product for uniaxial cell sheet conditioning with thermoresponsive copolymers. Thus, culture of detachable conditioned cell sheets is shortened while retaining structural integrity and contractility.

  4. Phase behavior of model ABC triblock copolymers

    Chatterjee, Joon

    The phase behavior of poly(isoprene-b-styrene- b-ethylene oxide) (ISO), a model ABC triblock copolymer has been studied. This class of materials exhibit self-assembly, forming a large array of ordered morphologies at length scales of 5-100 nm. The formation of stable three-dimensionally continuous network morphologies is of special interest in this study. Since these nanostructures considerably impact the material properties, fundamental knowledge for designing ABC systems have high technological importance for realizing applications in the areas of nanofabrication, nanoporous media, separation membranes, drug delivery and high surface area catalysts. A comprehensive framework was developed to describe the phase behavior of the ISO triblock copolymers at weak to intermediate segregation strengths spanning a wide range of composition. Phases were characterized through a combination of characterization techniques, including small angle x-ray scattering, dynamic mechanical spectroscopy, transmission electron microscopy, and birefringence measurements. Combined with previous investigations on ISO, six different stable ordered state symmetries have been identified: lamellae (LAM), Fddd orthorhombic network (O70), double gyroid (Q230), alternating gyroid (Q214), hexagonal (HEX), and body-centered cubic (BCC). The phase map was found to be somewhat asymmetric around the fI = fO isopleth. This work provides a guide for theoretical studies and gives insight into the intricate effects of various parameters on the self-assembly of ABC triblock copolymers. Experimental SAXS data evaluated with a simple scattering intensity model show that local mixing varies continuously across the phase map between states of two- and three-domain segregation. Strategies of blending homopolymers with ISO triblock copolymer were employed for studying the swelling properties of a lamellar state. Results demonstrate that lamellar domains swell or shrink depending upon the type of homopolymer that

  5. Synthesis and Characterization of New Poly(silole-fluorene) Copolymers.

    Lee, Yun-Ji; Park, Jeong Cheol; Yun, Hui-Jun; Park, Jong-Man; Kim, Yun-Hi

    2015-02-01

    New poly(silole-fluorene) copolymers were designed and synthesized. Copolymers were obtained by Suzuki coupling reaction with different ratio of fluorene and silole. The obtained copolymers were characterized by the spectroscopic methods such as FT-IR and 1H-NMR spectroscopies. The resulting copolymers were soluble in common organic solvents such as toluene, tetrahydrofurane, chloroform, chlorobenzene, etc. The obtained copolymers showed thermal stabilities, which were characterized by TGA and DSC. PLEDs with device configurations of ITO/PEDOT:PSS/Copolymer I~VI/LiF/AI. The best device performances, with maximum brightness of 231.5 cd/m2 at a current density (J) of 408.3 mA/cm2, and a maximum luminance efficiency of 0.115 cd/A, were achieved in the composition of fluorene and silole moiety (0.9:0.1). PMID:26353724

  6. COMPOSITIONAL HETEROGENEITY OF ETHYLENE OXIDE-BUTYLENE TEREPHTHALATE SEGMENTED COPOLYMER

    De-zhu Ma; Dong-sheng Li; Ming-chuan Zhao; Mo-zhen Wang; Ran Ye; Xiao-lie Luo

    1999-01-01

    A series of ethylene oxide-butylene terephthalate (EOBT) segmented copolymers with different soft segment length and hard segment content were synthesized. The compositional heterogeneity was studied by solvent extraction. The results show that the compositional heterogeneity increases when soft segment length and hard segment content increase. The compositional heterogeneity is also reflected in the crystallization behavior and morphology of soft and hard segment in EOBT segmented copolymer. The more compositional heterogeneous the EOBT segmented copolymer is, the more different the morphology and the crystallization behavior between separated fractions. Compared with ethylene oxide-ethylene terephthalate (EOET) segmented copolymer, compositional heterogeneity in EOBT segmented copolymer is weaker. But the compositional heterogeneity in EOBT segmented copolymer with long soft segment and high hard segment content is still obvious.

  7. Temperature response of photosynthesis in different drug and fiber varieties of Cannabis sativa L.

    Chandra, Suman; Lata, Hemant; Khan, Ikhlas A; Elsohly, Mahmoud A

    2011-07-01

    The temperature response on gas and water vapour exchange characteristics of three medicinal drug type (HP Mexican, MX and W1) and four industrial fiber type (Felinq 34, Kompolty, Zolo 11 and Zolo 15) varieties of Cannabis sativa, originally from different agro-climatic zones worldwide, were studied. Among the drug type varieties, optimum temperature for photosynthesis (Topt) was observed in the range of 30-35 °C in high potency Mexican HPM whereas, it was in the range of 25-30 °C in W1. A comparatively lower value (25 °C) for Topt was observed in MX. Among fiber type varieties, Topt was around 30 °C in Zolo 11 and Zolo 15 whereas, it was near 25 °C in Felinq 34 and Kompolty. Varieties having higher maximum photosynthesis (PN max) had higher chlorophyll content as compared to those having lower PN max. Differences in water use efficiency (WUE) were also observed within and among the drug and fiber type plants. However, differences became less pronounced at higher temperatures. Both stomatal and mesophyll components seem to be responsible for the temperature dependence of photosynthesis (PN) in this species, however, their magnitude varied with the variety. In general, a two fold increase in dark respiration with increase in temperature (from 20 °C to 40 °C) was observed in all the varieties. However, a greater increase was associated with the variety having higher rate of photosynthesis, indicating a strong association between photosynthetic and respiratory rates. The results provide a valuable indication regarding variations in temperature dependence of PN in different varieties of Cannabis sativa L. PMID:23573022

  8. Temperature responsive hydrogel magnetic nanocomposites for hyperthermia and metal extraction applications

    Reddy, N. Narayana, E-mail: nagireddynarayana@gmail.com [Center for Advanced Biomaterials for Healthcare, Istituto Italiano di Tecnologia@CRIB, Largo Barsanti e Matteucci 53, 80125 Napoli (Italy); Ravindra, S. [Department of Physics, College of Science, Engineering and Technology, University of South Africa, Johannesburg 1709 (South Africa); Reddy, N. Madhava [Department of Environmental Science, Gates Institute of Technology, NH-7, Gooty, Anantapuram, Andhra Pradesh (India); Rajinikanth, V. [Department of Physics, College of Science, Engineering and Technology, University of South Africa, Johannesburg 1709 (South Africa); Raju, K. Mohana [Synthetic Polymer Laboratory, Department of Polymer Science & Technology, S.K. University, Anantapuram, Andhra Pradesh (India); Vallabhapurapu, Vijaya Srinivasu [Department of Physics, College of Science, Engineering and Technology, University of South Africa, Johannesburg 1709 (South Africa)

    2015-11-15

    The present work deals with the development of temperature and magnetic responsive hydrogel networks based on poly (N-isopropylacrylamide)/acrylamido propane sulfonic acid. The hydrogel matrices are synthesized by polymerizing N-isopropylacrylamide (NIPAM) monomer in the presence of acrylamido propane sulphonicacid (AMPS) using a cross-linker (N,N-methylenebisacrylamide, MBA) and redox initiating system [ammonium persulphate (APS)/tetramethylethylenediamine (TMEDA)]. The magnetic nanoparticles are generated throughout the hydrogel networks using in situ method by incorporating iron ions and subsequent treatment with ammonia. A series of hydrogel-magnetic nanocomposites (HGMNC) are developed by varying AMPS composition. The synthesized hydrogel magnetic nanocomposites (HGMNC) are characterized by using Fourier Transform Infrared (FTIR) Spectroscopy, X-ray diffraction (XRD), Thermal Analyses and Electron Microscopy analysis (Scanning and Transmission Electron Microscope). The metal extraction capacities of the prepared hydrogel (HG) and hydrogel magnetic nanocomposites (HGMNC) were studied at different temperatures. The results suggest that HGMNCs have higher extraction capacity compared to HG and HG loaded iron ions. This data also reveals that the extraction of metals by hydrogel magnetic nanocomposites (HGMNCs) is higher at higher temperatures than room temperature. The prepared HGMNCs are also subjected to hyperthermia (cancer therapy) studies. - Highlights: • We have developed temperature responsive hydrogel magnetic nanocomposites. • Addition of AMPS monomer to this magnetic hydrogel enhances the temperature sensitivity to 40–43 °C. • Similarly the sulfonic groups present in the AMPS units enhances the swelling ratio of magnetic hydrogels. • AMPS acts as good stabilizing agent for nanoparticles in the magnetic nanogel.

  9. Highly temperature responsive core-shell magnetic particles: synthesis, characterization and colloidal properties.

    Rahman, Md Mahbubor; Chehimi, Mohamed M; Fessi, Hatem; Elaissari, Abdelhamid

    2011-08-15

    Temperature responsive magnetic polymer submicron particles were prepared by two step seed emulsion polymerization process. First, magnetic seed polymer particles were obtained by emulsion polymerization of styrene using potassium persulfate (KPS) as an initiator and divinylbenzne (DVB) as a cross-linker in the presence of oil-in-water magnetic emulsion (organic ferrofluid droplets). Thereafter, DVB cross-linked magnetic polymer particles were used as seed in the precipitation polymerization of N-isopropylacrylamide (NIPAM) to induce thermosensitive PNIPAM shell onto the hydrophobic polymer surface of the cross-linked magnetic polymer particles. To impart cationic functional groups in the thermosensitive PNIPAM backbone, the functional monomer aminoethylmethacrylate hydrochloride (AEMH) was used to polymerize with NIPAM while N,N'-methylenebisacrylamide (MBA) and 2, 2'-azobis (2-methylpropionamidine) dihydrochloride (V-50) were used as a cross-linker and as an initiator respectively. The effect of seed to monomer (w/w) ratio along with seed nature on the final particle morphology was investigated. Dynamic light scattering (DLS) results demonstrated particles swelling at below volume phase transition temperature (VPTT) and deswelling above the VPTT. The perfect core (magnetic) shell (polymer) structure of the particles prepared was confirmed by Transmission Electron Microscopy (TEM). The chemical composition of the particles were determined by thermogravimetric analysis (TGA). The effect of temperature, pH, ionic strength on the colloidal properties such as size and zeta potential of the micron sized thermo-sensitive magnetic particles were also studied. In addition, a short mechanistic discussion on the formation of core-shell morphology of magnetic polymer particles has also been discussed. PMID:21570083

  10. Temperature responsive hydrogel magnetic nanocomposites for hyperthermia and metal extraction applications

    The present work deals with the development of temperature and magnetic responsive hydrogel networks based on poly (N-isopropylacrylamide)/acrylamido propane sulfonic acid. The hydrogel matrices are synthesized by polymerizing N-isopropylacrylamide (NIPAM) monomer in the presence of acrylamido propane sulphonicacid (AMPS) using a cross-linker (N,N-methylenebisacrylamide, MBA) and redox initiating system [ammonium persulphate (APS)/tetramethylethylenediamine (TMEDA)]. The magnetic nanoparticles are generated throughout the hydrogel networks using in situ method by incorporating iron ions and subsequent treatment with ammonia. A series of hydrogel-magnetic nanocomposites (HGMNC) are developed by varying AMPS composition. The synthesized hydrogel magnetic nanocomposites (HGMNC) are characterized by using Fourier Transform Infrared (FTIR) Spectroscopy, X-ray diffraction (XRD), Thermal Analyses and Electron Microscopy analysis (Scanning and Transmission Electron Microscope). The metal extraction capacities of the prepared hydrogel (HG) and hydrogel magnetic nanocomposites (HGMNC) were studied at different temperatures. The results suggest that HGMNCs have higher extraction capacity compared to HG and HG loaded iron ions. This data also reveals that the extraction of metals by hydrogel magnetic nanocomposites (HGMNCs) is higher at higher temperatures than room temperature. The prepared HGMNCs are also subjected to hyperthermia (cancer therapy) studies. - Highlights: • We have developed temperature responsive hydrogel magnetic nanocomposites. • Addition of AMPS monomer to this magnetic hydrogel enhances the temperature sensitivity to 40–43 °C. • Similarly the sulfonic groups present in the AMPS units enhances the swelling ratio of magnetic hydrogels. • AMPS acts as good stabilizing agent for nanoparticles in the magnetic nanogel

  11. Temperature response of carbon isotope discrimination and mesophyll conductance in tobacco.

    Evans, John R; von Caemmerer, Susanne

    2013-04-01

    The partial pressure of CO2 at the sites of carboxylation within chloroplasts depends on the conductance to CO2 diffusion from intercellular airspace to the sites of carboxylation, termed mesophyll conductance (gm ). We investigated the temperature response of gm in tobacco (Nicotiana tabacum) by combining gas exchange in high light, ambient CO2 in either 2 or 21% O2 with carbon isotope measurements using tuneable diode laser spectroscopy. The gm increased linearly with temperature in 2 or 21% O2 . In 21% O2 , isotope discrimination associated with gm decreased from 5.0 ± 0.2 to 1.8 ± 0.2‰ as temperature increased from 15 to 40 °C, but the photorespiratory contribution to the isotopic signal is significant. While the fractionation factor for photorespiration (f = 16.2 ± 0.7‰) was independent of temperature between 20 and 35 °C, discrimination associated with photorespiration increased from 1.1 ± 0.01 to 2.7 ± 0.02‰ from 15 to 40 °C. Other mitochondrial respiration contributed around 0.2 ± 0.03‰. The drawdown in CO2 partial pressure from ambient air to intercellular airspaces was nearly independent of leaf temperature. By contrast, the increase in gm with increasing leaf temperature resulted in the drawdown in CO2 partial pressure between intercellular airspaces and the sites of carboxylation decreasing substantially at high temperature. PMID:22882584

  12. Protein-Reactive, Thermoresponsive Copolymers with High Flexibility and Biodegradability

    Guan, Jianjun; Hong, Yi; Ma, Zuwei; Wagner, William R.

    2008-01-01

    A family of injectable, biodegradable, and thermosensitive copolymers based on N-isopropylacrylamide, acrylic acid, N-acryloxysuccinimide, and a macromer polylactide–hydroxyethyl methacrylate were synthesized by free radical polymerization. Copolymers were injectable at or below room temperature and formed robust hydrogels at 37 °C. The effects of monomer ratio, polylactide length, and AAc content on the chemical and physical properties of the hydrogel were investigated. Copolymers exhibited ...

  13. Free energy of a copolymer in a micro-emulsion

    den Hollander, F.; Petrelis, N.

    2012-01-01

    In this paper we consider a two-dimensional model of a copolymer consisting of a random concatenation of hydrophilic and hydrophobic monomers, immersed in a micro-emulsion of random droplets of oil and water. The copolymer interacts with the micro-emulsion through an interaction Hamiltonian that favors matches and disfavors mismatches between the monomers and the solvents, in such a way that the interaction with the oil is stronger than with the water. The configurations of the copolymers are...

  14. A mathematical model for a copolymer in an emulsion

    2007-01-01

    In this paper we review some recent results, obtained jointly with Stu Whittington, for a mathematical model describing a copolymer in an emulsion. The copolymer consists of hydrophobic and hydrophilic monomers, concatenated randomly with equal density. The emulsion consists of large blocks of oil and water, arranged in a percolation-type fashion. To make the model mathematically tractable, the copolymer is allowed to enter and exit a neighboring pair of blocks only at diagonally opposite cor...

  15. Reversible geling co-polymer and method of making

    Gutowska, Anna

    2005-12-27

    The present invention is a thereapeutic agent carrier having a thermally reversible gel or geling copolymer that is a linear random copolymer of an [meth-]acrylamide derivative and a hydrophilic comonomer, wherein the linear random copolymer is in the form of a plurality of linear chains having a plurality of molecular weights greater than or equal to a minimum geling molecular weight cutoff and a therapeutic agent.

  16. Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

    Hoarfrost, Megan Lane

    2012-01-01

    Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the additio...

  17. Hybrid, Nanoscale Phospholipid/Block Copolymer Vesicles

    Bo Liedberg

    2013-09-01

    Full Text Available Hybrid phospholipid/block copolymer vesicles, in which the polymeric membrane is blended with phospholipids, display interesting self-assembly behavior, incorporating the robustness and chemical versatility of polymersomes with the softness and biocompatibility of liposomes. Such structures can be conveniently characterized by preparing giant unilamellar vesicles (GUVs via electroformation. Here, we are interested in exploring the self-assembly and properties of the analogous nanoscale hybrid vesicles (ca. 100 nm in diameter of the same composition prepared by film-hydration and extrusion. We show that the self-assembly and content-release behavior of nanoscale polybutadiene-b-poly(ethylene oxide (PB-PEO/1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC hybrid phospholipid/block copolymer vesicles can be tuned by the mixing ratio of the amphiphiles. In brief, these hybrids may provide alternative tools for drug delivery purposes and molecular imaging/sensing applications and clearly open up new avenues for further investigation.

  18. Nanostructured Polysulfone-Based Block Copolymer Membranes

    Xie, Yihui

    2016-05-01

    The aim of this work is to fabricate nanostructured membranes from polysulfone-based block copolymers through self-assembly and non-solvent induced phase separation. Block copolymers containing polysulfone are novel materials for this purpose providing better mechanical and thermal stability to membranes than polystyrene-based copolymers, which have been exclusively used now. Firstly, we synthesized a triblock copolymer, poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) through polycondensation and reversible addition-fragmentation chain-transfer polymerization. The obtained membrane has a highly porous interconnected skin layer composed of elongated micelles with a flower-like arrangement, on top of the graded finger-like macrovoids. Membrane surface hydrolysis was carried out in a combination with metal complexation to obtain metal-chelated membranes. The copper-containing membrane showed improved antibacterial capability. Secondly, a poly(acrylic acid)-b-polysulfone-b-poly(acrylic acid) triblock copolymer obtained by hydrolyzing poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) formed a thin film with cylindrical poly(acrylic acid) microdomains in polysulfone matrix through thermal annealing. A phase inversion membrane was prepared from the same polymer via self-assembly and chelation-assisted non-solvent induced phase separation. The spherical micelles pre-formed in a selective solvent mixture packed into an ordered lattice in aid of metal-poly(acrylic acid) complexation. The space between micelles was filled with poly(acrylic acid)-metal complexes acting as potential water channels. The silver0 nanoparticle-decorated membrane was obtained by surface reduction, having three distinct layers with different particle sizes. Other amphiphilic copolymers containing polysulfone and water-soluble segments such as poly(ethylene glycol) and poly(N-isopropylacrylamide) were also synthesized through coupling reaction and copper0-mediated

  19. Morphology of diblock copolymers in porous media

    Maniadis, Panagiotis; Tsimpanogiannis, I. N.; Kober, E.M.; Lookman, T.

    2014-01-01

    Roč. 112, č. 17 (2014), s. 2297-2309. ISSN 0026-8976 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0068; GA MŠk(CZ) EE2.3.20.0214 Institutional support: RVO:68081723 Keywords : confinement * diblock copolymer s * porous media * self-assembly * self-consistent field theory Subject RIV: BE - Theoretical Physics Impact factor: 1.720, year: 2014

  20. Static wetting behaviour of diblock copolymers

    Ausserre, D.; Raghunathan, V.; Maaloum, M.

    1993-01-01

    Thin liquid films of ordered diblock copolymers deposited on a solid substrate form a multilayer stacking parallel to the solid surface. A multilayer with a finite extend can be stable, metastable, or unstable, depending on the relative values of the surface energies of the various interfaces. The spreading parameter and chemical potential of a n-layer are derived, and used for classifying all possible situations. It is shown that only mono- and bilayers can be stable, and that non-wetting mu...

  1. Critical adsorption of copolymer tethered on selective surfaces

    Li, Hong; Qian, Chang-Ji; Luo, Meng-Bo

    2016-04-01

    Critical adsorption behaviors of flexible copolymer chains tethered to a flat homogeneous surface are studied by using Monte Carlo simulations. We have compared the critical adsorption temperature Tc, estimated by a finite-size scaling method, for different AB copolymer sequences with A the attractive monomer and B the inert monomer. We find that Tc increases with an increase in the fraction of monomers A, fA, in copolymers, and it increases with an increase in the length of block A for the same fA. In particular, Tc of copolymer (AnBn)r can be expressed as a function of the block length, n, and Tc of copolymer (AnB)r and (ABm)r can be expressed as a linear function of fA. Tc of random copolymer chains also can be expressed as a linear function of fA and it can be estimated by using weight-average of Tc of different diblocks in the random copolymer. However, the crossover exponent is roughly independent of AB sequence distributions either for block copolymers or for random copolymers.

  2. Solubility and self-assembly of amphiphilic gradient and block copolymers in supercritical CO2

    This work aims at demonstrating the interest of gradient copolymers in supercritical CO2 in comparison with block copolymers. Gradient copolymers exhibit a better solubility in supercritical CO2 than block copolymers, as attested by cloud point data. The self-assembly of gradient and block copolymers in dense CO2 has been characterized by Small-Angle Neutron Scattering (SANS); and it is shown that it is not fundamentally modified when changing from block copolymers to gradient copolymers. Therefore, gradient copolymers are advantageous thanks to their easier synthesis and their solubility at lower pressure while maintaining a good ability for self-organization in dense CO2. (authors)

  3. Regulating block copolymer phases via selective homopolymers

    The phase behavior of strongly segregated AB diblock copolymer and selective C homopolymer blends is examined theoretically using a combination of strong stretching theory (SST) and self-consistent field theory (SCFT). The C-homopolymer is immiscible with the B-blocks but strongly attractive with the A-blocks. The effect of homopolymer content on the order-order phase transitions is analyzed. It is observed that, for AB diblock copolymers with majority A-blocks, the addition of the C-homopolymers results in lamellar to cylindrical to spherical phase transitions because of the A/C complexation. For diblock copolymers with minor A-blocks, adding C-homopolymers leads to transitions from spherical or cylindrical morphology with A-rich core to lamellae to inverted cylindrical and spherical morphologies with B-rich core. The results from analytical SST and numerical SCFT are in good agreement within most regions of the phase diagram. But the deviation becomes more obvious when the composition of A-blocks is too small and the content of added C-homopolymers is large enough, where the SCFT predicts a narrow co-existence region between different ordered phases. Furthermore, it is found that the phase behavior of the system is insensitive to the molecular weight of C-homopolymer

  4. Comparing Fluid and Elastic Block Copolymer Shells

    Rozairo, Damith; Croll, Andrew B.

    2014-03-01

    Emulsions can be stabilized with the addition of an amphiphilic diblock copolymer, resulting in droplets surrounded and protected by a polymer monolayer. Such droplets show considerable promise as advanced cargo carriers in pharmaceuticals or cosmetics due to their strength and responsiveness. Diblock copolymer interfaces remain mostly fluid and may not be able to attain the mechanical performance desired by industry. To strengthen block copolymer emulsion droplets we have developed a novel method for creating thin elastic shells using polystyrene-b-poly(acrylic acid)-b-polystyrene (PS-PAA-PS). Characterization of the fluid filled elastic shells is difficult with traditional means which lead us to develop a new and general method of mechanical measurement. Specifically, we use laser scanning confocal microscopy to achieve a high resolution measure of the deformation of soft spheres under the influence of gravity. To prove the resilience of the technique we examine both a polystyrene-b-poly(ethylene oxide) (PS-PEO) stabilized emulsion and the PS-PAA-PS emulsion. The mechanical measurement allows the physics of the polymer at the interface to be examined, which will ultimately lead to the rational development of these technologies.

  5. Block and Graft Copolymers of Polyhydroxyalkanoates

    Marchessault, Robert H.; Ravenelle, François; Kawada, Jumpei

    2004-03-01

    Polyhydroxyalkanoates (PHAs) were modified for diblock copolymer and graft polymer by catalyzed transesterification in the melt and by chemical synthesis to extend the side chains of the PHAs, and the polymers were studied by transmission electron microscopy (TEM) X-ray diffraction, thermal analysis and nuclear magnetic resonance (NMR). Catalyzed transesterification in the melt is used to produce diblock copolymers of poly[3-hydroxybutyrate] (PHB) and monomethoxy poly[ethylene glycol] (mPEG) in a one-step process. The resulting diblock copolymers are amphiphilic and self-assemble into sterically stabilized colloidal suspensions of PHB crystalline lamellae. Graft polymer was synthesized in a two-step chemical synthesis from biosynthesized poly[3-hydroxyoctanoate-co-3-hydroxyundecenoate] (PHOU) containing ca. 25 mol chains. 11-mercaptoundecanoic acid reacts with the side chain alkenes of PHOU by the radical addition creating thioether linkage with terminal carboxyl functionalities. The latter groups were subsequently transformed into the amide or ester linkage by tridecylamine or octadecanol, respectively, producing new graft polymers. The polymers have different physical properties than poly[3-hydroxyoctanoate] (PHO) which is the main component of the PHOU, such as non-stickiness and higher thermal stability. The combination of biosynthesis and chemical synthesis produces a hybrid thermoplastic elastomer with partial biodegradability.

  6. Crystallization in Ordered Polydisperse Polyolefin Diblock Copolymers

    The morphologies of polydisperse ethylene-octene diblock copolymers, synthesized via a novel coordinative chain transfer polymerization process, are examined using two-dimensional synchrotron small-angle and wide-angle X-ray scattering on flow-aligned specimens. The diblock copolymers comprise one amorphous block with high 1-octene content and one semicrystalline block with relatively low 1-octene content, and each block ideally exhibits the most-probable distribution. Near-symmetric diblocks with a sufficiently large octene differential between the amorphous and semicrystalline blocks show well-ordered lamellar domain structures with long periods exceeding 100 nm. Orientation of these domain structures persists through multiple melting/recrystallization cycles, reflecting a robust structure which self-assembles in the melt. The domain spacings are nearly 3-fold larger than those in near-monodisperse polyethylene block copolymers of similar molecular weights. Although the well-ordered lamellar domain structure established in the melt is preserved in the solid state, the crystallites are isotropic in orientation. These materials display crystallization kinetics consistent with a spreading growth habit, indicating that the lamellae do not confine or template the growing crystals. The exceptionally large domain spacings and isotropic crystal growth are attributed to interblock mixing resulting from the large polydispersity; short hard blocks dissolved in the soft-block-rich domains swell the domain spacing in the melt and allow hard block crystallization to proceed across the lamellar domain interfaces.

  7. A NOVEL THERMOSENSITIVE POLYMER WITH pH-DEPENDENT DEGRADATION FOR DRUG DELIVERY

    Garripelli, Vivek Kumar; Kim, Jin-Ki; Namgung, Ran; Kim, Won Jong; Repka, Michael A.; Jo, Seongbong

    2009-01-01

    A class of thermosensitive biodegradable multiblock copolymers with acid-labile acetal linkages were synthesized from Pluronic® triblock copolymers (Pluronic® P85 and P104) and di-(ethylene glycol) divinyl ether. The novel polymers were engineered to form thermogels at body temperature and degrade in acidic environment. The Pluronic®-based acid-labile polymers were characterized using nuclear magnetic resonance, gel permeation chromatography and differential scanning calorimetry. In vitro bio...

  8. Siloxane modified polyurea and polyurethane urea segmented copolymers

    Kim, Regina H.

    1989-01-01

    High molecular weight polyether urea copolymers were synthesized using perfectly difunctional aromatic amine terminated polypropylene oxide (PPO) (2800 ) prepared via aluminum porphorin initiated coordination polymerization. The resulting segmented copolymer showed much higher tensile strength and better thermal stability than polyureas based on commercial PPO which contains some terminal unsaturation. This was attributed to the achievement of both higher molecular weight and t...

  9. Positively charged co-polymers for use as antimicrobial agents

    2016-01-01

    The present invention provides a positively charged co-polymer for use as an antimicrobial agent, wherein said positively charged co-polymer is composed of amino acids and/or derivatives thereof and wherein at least 75 molar percent of said amino acids are selected from the group consisting of...

  10. Microphase separation of diblock copolymers with amphiphilic segment

    Kriksin, Yury A.; Khalatur, Pavel G.; Erukhimovich, Igor Ya.; ten Brinke, Gerrit; Khokhlov, Alexei R.

    2009-01-01

    We present a statistical mechanical approach for predicting the self-assembled morphologies of amphiphilic diblock copolymers in the melt. We introduce two conformationally asymmetric linear copolymer models with a local structural asymmetry, one of a "comb-tail'' type and another that we call "cont

  11. From Block Copolymers to Nano-porous Materials

    Vigild, Martin Etchells; Ndoni, Sokol; Berg, Rolf Henrik

    2003-01-01

    Quantitative etching of the polydimethylsiloxane block in a series of polystyrene-polydimethylsiloxane (PS-PDMS) block copolymers is reported. Reacting the block copolymer with anhydrous hydrogen fluoride (HF) renders a nanoporous material with the remaining PS maintaining the original morphology...

  12. Antimicrobial activity of poly(acrylic acid) block copolymers

    Gratzl, Günther, E-mail: guenther.gratzl@jku.at [Johannes Kepler University Linz, Institute for Chemical Technology of Organic Materials, Altenberger Str. 69, 4040 Linz (Austria); Paulik, Christian [Johannes Kepler University Linz, Institute for Chemical Technology of Organic Materials, Altenberger Str. 69, 4040 Linz (Austria); Hild, Sabine [Johannes Kepler University Linz, Institute of Polymer Science, Altenberger Str. 69, 4040 Linz (Austria); Guggenbichler, Josef P.; Lackner, Maximilian [AMiSTec GmbH and Co. KG, Leitweg 13, 6345 Kössen, Tirol (Austria)

    2014-05-01

    The increasing number of antibiotic-resistant bacterial strains has developed into a major health problem. In particular, biofilms are the main reason for hospital-acquired infections and diseases. Once formed, biofilms are difficult to remove as they have specific defense mechanisms against antimicrobial agents. Antimicrobial surfaces must therefore kill or repel bacteria before they can settle to form a biofilm. In this study, we describe that poly(acrylic acid) (PAA) containing diblock copolymers can kill bacteria and prevent from biofilm formation. The PAA diblock copolymers with poly(styrene) and poly(methyl methacrylate) were synthesized via anionic polymerization of tert-butyl acrylate with styrene or methyl methacrylate and subsequent acid-catalyzed hydrolysis of the tert-butyl ester. The copolymers were characterized via nuclear magnetic resonance spectroscopy (NMR), size-exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and acid–base titrations. Copolymer films with a variety of acrylic acid contents were produced by solvent casting, characterized by atomic force microscopy (AFM) and tested for their antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The antimicrobial activity of the acidic diblock copolymers increased with increasing acrylic acid content, independent of the copolymer-partner, the chain length and the nanostructure. - Highlights: • Acrylic acid diblock copolymers are antimicrobially active. • The antimicrobial activity depends on the acrylic acid content in the copolymer. • No salts, metals or other antimicrobial agents are needed.

  13. Surface morphology of PS-PDMS diblock copolymer films

    Andersen, T.H.; Tougaard, S.; Larsen, N.B.;

    2001-01-01

    Spin coated thin films (∼400 Å) of poly(styrene)–poly(dimethylsiloxane) (PS–PDMS) diblock copolymers have been investigated using X-ray Photoelectron Spectroscopy and Atomic Force Microscopy. Surface segregation of the poly(dimethylsiloxane) blocks was studied for five diblock copolymers which...

  14. Radiation crosslinked block copolymer blends with improved impact resistance

    Polymer blends having high impact resistance after mechanical working are produced by blending together a non-elastomeric monovinylidene aromatic polymer such as polystyrene with an elastomeric copolymer, such as a block copolymer of styrene and butadiene, in the form of crosslinked, colloidal size particles

  15. Morphological studies on block copolymer modified PA 6 blends

    Poindl, M., E-mail: marcus.poindl@ikt.uni-stuttgart.de, E-mail: christian.bonten@ikt.uni-stuttgart.de; Bonten, C., E-mail: marcus.poindl@ikt.uni-stuttgart.de, E-mail: christian.bonten@ikt.uni-stuttgart.de [Institut für Kunststofftechnik, University of Stuttgart (Germany)

    2014-05-15

    Recent studies show that compounding polyamide 6 (PA 6) with a PA 6 polyether block copolymers made by reaction injection molding (RIM) or continuous anionic polymerization in a reactive extrusion process (REX) result in blends with high impact strength and high stiffness compared to conventional rubber blends. In this paper, different high impact PA 6 blends were prepared using a twin screw extruder. The different impact modifiers were an ethylene propylene copolymer, a PA PA 6 polyether block copolymer made by reaction injection molding and one made by reactive extrusion. To ensure good particle matrix bonding, the ethylene propylene copolymer was grafted with maleic anhydride (EPR-g-MA). Due to the molecular structure of the two block copolymers, a coupling agent was not necessary. The block copolymers are semi-crystalline and partially cross-linked in contrast to commonly used amorphous rubbers which are usually uncured. The combination of different analysis methods like atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) gave a detailed view in the structure of the blends. Due to the partial cross-linking, the particles of the block copolymers in the blends are not spherical like the ones of ethylene propylene copolymer. The differences in molecular structure, miscibility and grafting of the impact modifiers result in different mechanical properties and different blend morphologies.

  16. Self-assembled materials from thermosensitive and biohybrid block copolymers

    de Graaf, A.J.

    2012-01-01

    In this research, several block copolymers were synthesized and characterized with regard to possible pharmaceutical applications. All block copolymers were thermosensitive and self-assembled at 37 °C into structures like micelles and hydrogels, which can be used for innovative drug delivery purpose

  17. Functional Block Copolymers via Anionic Polymerization for Electroactive Membranes

    Schultz, Alison

    2013-01-01

           Ion-containing block copolymers blend ionic liquid properties with well-defined polymer architectures. This provides conductive materials with robust mechanical stability, efficient processability, and tunable macromolecular design. Conventional free radical polymerization and anion exchange achieved copolymers containing n-butyl acrylate and phosphonium ionic liquids. These compositions incorporated vinylbenzyl triphenyl phosphonium and vinylbenzyl tricyclohexyl phosphonium cations be...

  18. Stereo block copolymers of L- and D-lactides

    Yui, Nobuhiko; Dijkstra, Pieter J.; Feijen, Jan

    1990-01-01

    Sequential diblock copolymers composed of L- and D-lactic acid residues were synthesized through a living ring-opening polymerization of L- and D-lactide initiated by aluminium tris(2-propanolate). The composition of the block copolymers was varied by changing the reaction conditions and monomer ove

  19. Antimicrobial activity of poly(acrylic acid) block copolymers

    The increasing number of antibiotic-resistant bacterial strains has developed into a major health problem. In particular, biofilms are the main reason for hospital-acquired infections and diseases. Once formed, biofilms are difficult to remove as they have specific defense mechanisms against antimicrobial agents. Antimicrobial surfaces must therefore kill or repel bacteria before they can settle to form a biofilm. In this study, we describe that poly(acrylic acid) (PAA) containing diblock copolymers can kill bacteria and prevent from biofilm formation. The PAA diblock copolymers with poly(styrene) and poly(methyl methacrylate) were synthesized via anionic polymerization of tert-butyl acrylate with styrene or methyl methacrylate and subsequent acid-catalyzed hydrolysis of the tert-butyl ester. The copolymers were characterized via nuclear magnetic resonance spectroscopy (NMR), size-exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and acid–base titrations. Copolymer films with a variety of acrylic acid contents were produced by solvent casting, characterized by atomic force microscopy (AFM) and tested for their antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The antimicrobial activity of the acidic diblock copolymers increased with increasing acrylic acid content, independent of the copolymer-partner, the chain length and the nanostructure. - Highlights: • Acrylic acid diblock copolymers are antimicrobially active. • The antimicrobial activity depends on the acrylic acid content in the copolymer. • No salts, metals or other antimicrobial agents are needed

  20. A Preliminary Study on Mechanisms of Well Water Temperature Responses Based on the Modes of Stress Loading

    Chen Daqing; Wan Yongfang

    2011-01-01

    Based on the studies of the predecessors, and contrasting the modes of stress loading with water level and water temperature response characteristics of a well-aquifer system, this paper draws a preliminary conclusion on the mechanisms of water temperature responses in a well caused by three modes of stress loading, i.e. gas escape, heat dispersion and cold water penetration mechanisms for elastic seismic wave stress loading; the fracture seepage mechanism for seismic wave stress loading and the hydrodynamic mechanism for earth tide stress loading and stress-dissipative heat mechanism for long period slow stress loading in the earthquake preparation stage. This paper illustrates the typical observation examples for each mode of stress loading and makes a preliminary study on their mechanisms.

  1. Temperature response of litter and soil organic matter decomposition is determined by chemical composition of organic material.

    Erhagen, Björn; Öquist, Mats; Sparrman, Tobias; Haei, Mahsa; Ilstedt, Ulrik; Hedenström, Mattias; Schleucher, Jürgen; Nilsson, Mats B

    2013-12-01

    The global soil carbon pool is approximately three times larger than the contemporary atmospheric pool, therefore even minor changes to its integrity may have major implications for atmospheric CO2 concentrations. While theory predicts that the chemical composition of organic matter should constitute a master control on the temperature response of its decomposition, this relationship has not yet been fully demonstrated. We used laboratory incubations of forest soil organic matter (SOM) and fresh litter material together with NMR spectroscopy to make this connection between organic chemical composition and temperature sensitivity of decomposition. Temperature response of decomposition in both fresh litter and SOM was directly related to the chemical composition of the constituent organic matter, explaining 90% and 70% of the variance in Q10 in litter and SOM, respectively. The Q10 of litter decreased with increasing proportions of aromatic and O-aromatic compounds, and increased with increased contents of alkyl- and O-alkyl carbons. In contrast, in SOM, decomposition was affected only by carbonyl compounds. To reveal why a certain group of organic chemical compounds affected the temperature sensitivity of organic matter decomposition in litter and SOM, a more detailed characterization of the (13) C aromatic region using Heteronuclear Single Quantum Coherence (HSQC) was conducted. The results revealed considerable differences in the aromatic region between litter and SOM. This suggests that the correlation between chemical composition of organic matter and the temperature response of decomposition differed between litter and SOM. The temperature response of soil decomposition processes can thus be described by the chemical composition of its constituent organic matter, this paves the way for improved ecosystem modeling of biosphere feedbacks under a changing climate. PMID:23907960

  2. Sulfomethylated graft copolymers of xanthan gum and polyacrylamide

    Cottrell, I.W.; Empey, R.A.; Racciato, J.S.

    1978-08-08

    A water-soluble anionic graft copolymer of xanthan gum and polyacrylamide is described in which at least part of the amide function of the acrylamide portion of the copolymer is sulfomethylated and the xanthan gum portion of the copolymer is unreacted with formaldehyde. The copolymer is sulfomethylated by reaction with formaldehyde and sodium metabisulfite. The formaldehyde does not cause any appreciable cross-linking between hydroxyl groups of the xanthan moieties. The sulfomethylation of the acrylamido group takes place at temperatures from 35 to 70 C. The pH is 10 or higher, typically from 12 to 13. The degree of anionic character may be varied by adjusting the molar ratio of formaldehyde and sodium metabisulfite with respect to the copolymer. 10 claims.

  3. Block Copolymer Metastability: Scientific Nightmare or Engineering Dream?

    Bates, Frank S.

    1997-03-01

    Most experimental studies and almost all theories that deal with block copolymers, or mixtures of block copolymers and homopolymers, have been designed from an equilibrium perspective. Yet a myriad of factors conspire to retard approach to equilibrium in these systems, including: subtle features in the free energy surface that are controlled by ordered state symmetry; a coupling between microphase separation and entanglement dynamics; complex molecular architectures such as multiblock, starblock, and miktoarm. Even unentangled low molecular weight diblock copolymers, the simplest and dynamically least encumbered materials, exhibit long-lived metastable states that confound attempts to validate equilibrium theories. However, this apparent dilemma can be exploited through clever processing strategies. This lecture will address two opposing consequences of block copolymer metastability. The first is a potential nightmare: Can we ever establish universal block copolymer phase diagrams? The second is the stuff of dreams: Self-assembled thermoset nanocomposites.

  4. Multicompartment Micelles From π-Shaped ABC Block Copolymers

    XIA Jun; ZHONG Chong-Li

    2007-01-01

    Dissipative particle dynamics simulations were performed on the morphology and structure of multicompartment micelles formed from n-shaped ABC block copolymers in water. The influences of chain architectures were studied in a systematic way, and a rich variety of morphologies were observed, such as spherical, wormlike,X-shaped, Y-shaped, ribbon-like, layered rod-like, layered disk-like, as well as network morphologies. The simulations show that the distance between the two grafts plays an important role in control of the morphology. Since π-shaped ABC block copolymers can be reduced to linear ABC and star ABC block copolymers, they are good model copolymers for studying the self-assembly of complex block copolymers into micelles. The knowledge obtained in this work as well as the new morphologies identified provide useful information for future rational design and synthesis of novel multicompartment micelles.

  5. Temperature response of denitrification and anaerobic ammonium oxidation rates and microbial community structure in Arctic fjord sediments.

    Canion, Andy; Overholt, Will A; Kostka, Joel E; Huettel, Markus; Lavik, Gaute; Kuypers, Marcel M M

    2014-10-01

    The temperature dependency of denitrification and anaerobic ammonium oxidation (anammox) rates from Arctic fjord sediments was investigated in a temperature gradient block incubator for temperatures ranging from -1 to 40°C. Community structure in intact sediments and slurry incubations was determined using Illumina SSU rRNA gene sequencing. The optimal temperature (Topt ) for denitrification was 25-27°C, whereas anammox rates were optimal at 12-17°C. Both denitrification and anammox exhibited temperature responses consistent with a psychrophilic community, but anammox bacteria may be more specialized for psychrophilic activity. Long-term (1-2 months) warming experiments indicated that temperature increases of 5-10°C above in situ had little effect on the microbial community structure or the temperature response of denitrification and anammox. Increases of 25°C shifted denitrification temperature responses to mesophilic with concurrent community shifts, and anammox activity was eliminated above 25°C. Additions of low molecular weight organic substrates (acetate and lactate) caused increases in denitrification rates, corroborating the hypothesis that the supply of organic substrates is a more dominant control of respiration rates than low temperature. These results suggest that climate-related changes in sinking particulate flux will likely alter rates of N removal more rapidly than warming. PMID:25115991

  6. A method for achieving monotonic frequency-temperature response for langasite surface-acoustic-wave high-temperature sensor

    Shaoming, Bao; Yabing, Ke; Yanqing, Zheng; Lina, Cheng; Honglang, Li

    2016-02-01

    To achieve the monotonic frequency-temperature response for a high-temperature langasite (LGS) surface-acoustic-wave (SAW) sensor in a wide temperature range, a method utilizing two substrate cuts with different propagation angles on the same substrate plane was proposed. In this method, the theory of effective permittivity is adopted to calculate the temperature coefficients of frequency (TCF), electromechanical coupling coefficients (k2), and power flow angle (PFA) for different propagation angles on the same substrate plane, and then the two substrate cuts were chosen to have large k2 and small PFA, as well as the difference in their TCFs (ΔTCF) to always have the same sign of their values. The Z-cut LGS substrate plane was taken as an example, and the two suitable substrate cuts with propagation angles of 74 and 80° were chosen to derive a monotonic frequency-temperature response for LGS SAW sensors at -50 to 540 °C. Experiments on a LGS SAW sensor using the above two substrate cuts were designed, and its measured frequency-temperature response at -50 to 540 °C agreed well with the theory, demonstrating the high accuracy of the proposed method.

  7. Improvement in transdermal drug delivery performance by graphite oxide/temperature-responsive hydrogel composites with micro heater

    Transdermal drug delivery system (TDDS) was prepared with temperature-responsive hydrogel. The graphite was oxidized and incorporated into hydrogel matrix to improve the thermal response of hydrogel. The micro heater was fabricated to control the temperature precisely by adopting a joule heating method. The drug in hydrogel was delivered through a hairless mouse skin by controlling temperature. The efficiency of drug delivery was improved obviously by incorporation of graphite oxide due to the excellent thermal conductivity and the increased interfacial affinity between graphite oxide and hydrogel matrix. The fabricated micro heater was effective in controlling the temperature over lower critical solution temperature of hydrogel precisely with a small voltage less than 1 V. The cell viability test on graphite oxide composite hydrogel showed enough safety for using as a transdermal drug delivery patch. The performance of TDDS could be improved noticeably based on temperature-responsive hydrogel, thermally conductive graphite oxide, and efficient micro heater. - Graphical abstract: The high-performance transdermal drug delivery system could be prepared by combining temperature-responsive hydrogel, thermally conductive graphite oxide with improved interfacial affinity, and efficient micro heater fabricated by a joule heating method. Highlights: ► High performance of transdermal drug delivery system with an easy control of voltage. ► Improved thermal response of hydrogel by graphite oxide incorporation. ► Efficient micro heater fabricated by a joule heating method.

  8. Materials Design for Block Copolymer Lithography

    Sweat, Daniel Patrick

    Block copolymers (BCPs) have attracted a great deal of scientific and technological interest due to their ability to spontaneously self-assemble into dense periodic nanostructures with a typical length scale of 5 to 50 nm. The use of self-assembled BCP thin-films as templates to form nanopatterns over large-area is referred to as BCP lithography. Directed self-assembly of BCPs is now viewed as a viable candidate for sub-20 nm lithography by the semiconductor industry. However, there are multiple aspects of assembly and materials design that need to be addressed in order for BCP lithography to be successful. These include substrate modification with polymer brushes or mats, tailoring of the block copolymer chemistry, understanding thin-film assembly and developing epitaxial like methods to control long range alignment. The rational design, synthesis and self-assembly of block copolymers with large interaction parameters (chi) is described in the first part of this dissertation. Two main blocks were chosen for introducing polarity into the BCP system, namely poly(4-hydroxystyrene) and poly(2-vinylpyridine). Each of these blocks are capable of ligating Lewis acids which can increase the etch contrast between the blocks allowing for facile pattern transfer to the underlying substrate. These BCPs were synthesized by living anionic polymerization and showed excellent control over molecular weight and dispersity, providing access to sub 5-nm domain sizes. Polymer brushes consist of a polymer chain with one end tethered to the surface and have wide applicability in tuning surface energy, forming responsive surfaces and increasing biocompatibility. In the second part of the dissertation, we present a universal method to grow dense polymer brushes on a wide range of substrates and combine this chemistry with BCP assembly to fabricate nanopatterned polymer brushes. This is the first demonstration of introducing additional functionality into a BCP directing layer and opens up

  9. Surface tension of micellar block copolymer films

    Surface tensions of micellar block copolymers of poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) films are obtained by X-ray diffuse scattering. PS-b-PDMS films on Si substrates with the thicknesses from 36 to 588 nm were investigated at temperatures of 30 - 215 .deg. C. The surface tension reflects the concentration of PDMS micelles which are preferably located at the surface. The molar fraction of PDMS micelles near the surface is estimated by using angle-resolved X-ray photoelectron spectroscopy.

  10. Preparation of Impact and Weather Resistant Copolymer

    LIANG; Tao

    2001-01-01

    Synthesis method of the resin is that crosslinked polybutyl acrylate latex is used as base latex. Styrene (St) and acrylonitrile (AN) are grafted onto polybutyl acrylate latex particle and turn into core-shell copolymer. The resin is a good resin's impact modifier. There are study of influence regularity about additive emulsifier, initiator, monomer concentration, the ratio of St to AN, chain transfer to graft polymerization. A kind of core-shell resin used as impact modifier is obtained. (A) Preparation of Crosslinked Butyl Acrylate Rubber Latex  ……

  11. Preparation of Impact and Weather Resistant Copolymer

    2001-01-01

    @@ Synthesis method of the resin is that crosslinked polybutyl acrylate latex is used as base latex. Styrene (St) and acrylonitrile (AN) are grafted onto polybutyl acrylate latex particle and turn into core-shell copolymer. The resin is a good resin's impact modifier. There are study of influence regularity about additive emulsifier, initiator, monomer concentration, the ratio of St to AN, chain transfer to graft polymerization. A kind of core-shell resin used as impact modifier is obtained. (A) Preparation of Crosslinked Butyl Acrylate Rubber Latex

  12. Oriented Protein Nanoarrays on Block Copolymer Template.

    Shen, Lei; Zhu, Jintao

    2016-03-01

    Here, a simple yet robust method is developed to fabricate oriented protein nanoarrays by employing a block copolymer (BCP) template, which presents nano-scaled spot areas at high-density arrays. Unlike the conventional BCP nanolithography, the BCP platform described here resists nonspecific protein adsorption and prevents the denaturation of immobilized proteins in aqueous solution. The orderly arranged array areas are functionalized by linking chemistry which allows for the precise control of protein orientation. This approach allows us to generate potentially oriented protein nanoarrays at high-density array spots, which is useful for miniaturized nanoarrays within high-throughput proteomic applications. PMID:26785818

  13. Heat exchanger temperature response for duty-cycle transients in the NGNP/HTE

    Control system studies were performed for the Next Generation Nuclear Plant (NGNP) interfaced to the High Temperature Electrolysis (HTE) plant. Temperature change and associated thermal stresses are important factors in determining plant lifetime. In the NGNP the design objective of a 40 year lifetime for the Intermediate Heat Exchanger (IHX) in particular is seen as a challenge. A control system was designed to minimize temperature changes in the IHX and more generally at all high-temperature locations in the plant for duty-cycle transients. In the NGNP this includes structures at the reactor outlet and at the inlet to the turbine. This problem was approached by identifying those high-level factors that determine temperature rates of change. First are the set of duty cycle transients over which the control engineer has little control but which none-the-less must be addressed. Second is the partitioning of the temperature response into a quasi-static component and a transient component. These two components are largely independent of each other and when addressed as such greater understanding of temperature change mechanisms and how to deal with them is achieved. Third is the manner in which energy and mass flow rates are managed. Generally one aims for a temperature distribution that minimizes spatial non-uniformity of thermal expansion in a component with time. This is can be achieved by maintaining a fixed spatial temperature distribution in a component during transients. A general rule of thumb for heat exchangers is to maintain flow rate proportional to thermal power. Additionally the product of instantaneous flow rate and heat capacity should be maintained the same on both sides of the heat exchanger. Fourth inherent mechanisms for stable behavior should not be compromised by active controllers that can introduce new feedback paths and potentially create under-damped response. Applications of these principles to the development of a plant control strategy for

  14. Nanostructure controlled sustained delivery of human growth hormone using injectable, biodegradable, pH/temperature responsive nanobiohybrid hydrogel

    Singh, Narendra K.; Nguyen, Quang Vinh; Kim, Bong Sup; Lee, Doo Sung

    2015-02-01

    The clinical efficacy of a therapeutic protein, the human growth hormone (hGH), is limited by its short plasma half-life and premature degradation. To overcome this limitation, we proposed a new protein delivery system by the self-assembly and intercalation of a negatively charged hGH onto a positively charged 2D-layered double hydroxide nanoparticle (LDH). The LDH-hGH ionic complex, with an average particle size of approximately 100 nm, retards hGH diffusion. Nanobiohybrid hydrogels (PAEU/LDH-hGH) were prepared by dispersing the LDH-hGH complex into a cationic pH- and temperature-sensitive injectable PAEU copolymer hydrogel to enhance sustained hGH release by dual ionic interactions. Biodegradable copolymer hydrogels comprising poly(β-amino ester urethane) and triblock poly(ε-caprolactone-lactide)-poly(ethylene glycol)-poly-(ε-caprolactone-lactide) (PCLA-PEG-PCLA) were synthesized and characterized. hGH was self-assembled and intercalated onto layered LDH nanoparticles through an anion exchange technique. X-ray diffraction and zeta potential results showed that the LDH-hGH complex was prepared successfully and that the PAEU/LDH-hGH nanobiohybrid hydrogel had a disordered intercalated nanostructure. The biocompatibility of the nanobiohybrid hydrogel was confirmed by an in vitro cytotoxicity test. The in vivo degradation of pure PAEU and its nanobiohybrid hydrogels was investigated and it showed a controlled degradation of the PAEU/LDH nanobiohybrids compared with the pristine PAEU copolymer hydrogel. The LDH-hGH loaded injectable hydrogels suppressed the initial burst release of hGH and extended the release period for 13 days in vitro and 5 days in vivo. The developed nanohybrid hydrogel has the potential for application as a protein carrier to improve patient compliance.The clinical efficacy of a therapeutic protein, the human growth hormone (hGH), is limited by its short plasma half-life and premature degradation. To overcome this limitation, we proposed a new

  15. Chain exchange in triblock copolymer micelles

    Lu, Jie; Lodge, Timothy; Bates, Frank

    2015-03-01

    Block polymer micelles offer a host of technological applications including drug delivery, viscosity modification, toughening of plastics, and colloidal stabilization. Molecular exchange between micelles directly influences the stability, structure and access to an equilibrium state in such systems and this property recently has been shown to be extraordinarily sensitive to the core block molecular weight in diblock copolymers. The dependence of micelle chain exchange dynamics on molecular architecture has not been reported. The present work conclusively addresses this issue using time-resolved small-angle neutron scattering (TR-SANS) applied to complimentary S-EP-S and EP-S-EP triblock copolymers dissolved in squalane, a selective solvent for the EP blocks, where S and EP refer to poly(styrene) and poly(ethylenepropylene), respectively. Following the overall SANS intensity as a function of time from judiciously deuterium labelled polymer and solvent mixtures directly probes the rate of molecular exchange. Remarkably, the two triblocks display exchange rates that differ by approximately ten orders of magnitude, even though the solvophobic S blocks are of comparable size. This discovery is considered in the context of a model that successfully explains S-EP diblock exchange dynamics.

  16. Controlling Structure in Sulfonated Block Copolymer Membranes

    Truong, Phuc; Stein, Gila; Strzalka, Joe

    2015-03-01

    In many ionic block copolymer systems, the strong incompatibility between ionic and non-ionic segments will trap non-equilibrium structures in the film, making it difficult to engineer the optimal domain sizes and transport pathways. The goal of this work is to establish a framework for controlling the solid-state structure of sulfonated pentablock copolymer membranes. They have ABCBA block sequence, where A is poly(t-butyl styrene), B is poly(hydrogenated isoprene), and C is poly(styrene sulfonate). To process into films, the polymer is dissolved in toluene/n-propanol solvent mixtures, where the solvent proportions and the polymer loading were both varied. Solution-state structure was measured with small angle X-ray scattering (SAXS). We detected micelles with radii that depend on the solvent composition and polymer loading. Film structure was measured with grazing-incidence SAXS, which shows (i) domain periodicity is constant throughout film thickness; (ii) domain periodicity depends on solvent composition and polymer loading, and approximately matches the micelle radii in solutions. The solid-state packing is consistent with a hard sphere structure factor. Results suggest that solid-state structure can be tuned by manipulating the solution-state self-assembly.

  17. Interface-enforced complexation between copolymer blocks.

    Steinschulte, Alexander A; Xu, Weinan; Draber, Fabian; Hebbeker, Pascal; Jung, Andre; Bogdanovski, Dimitri; Schneider, Stefanie; Tsukruk, Vladimir V; Plamper, Felix A

    2015-05-14

    Binary diblock copolymers and corresponding ternary miktoarm stars are studied at oil-water interfaces. All polymers contain oil-soluble poly(propylene oxide) PPO, water-soluble poly(dimethylaminoethyl methacrylate) PDMAEMA and/or poly(ethylene oxide) PEO. The features of their Langmuir compression isotherms are well related to the ones of the corresponding homopolymers. Within the Langmuir-trough, PEO-b-PPO acts as the most effective amphiphile compared to the other PPO-containing copolymers. In contrast, the compression isotherms show a complexation of PPO and PDMAEMA for PPO-b-PDMAEMA and the star, reducing their overall amphiphilicity. Such complex formation between the blocks of PPO-b-PDMAEMA is prevented in bulk water but facilitated at the interface. The weakly-interacting blocks of PPO-b-PDMAEMA form a complex due to their enhanced proximity in such confined environments. Scanning force microscopy and Monte Carlo simulations with varying confinement support our results, which are regarded as compliant with the mathematical random walk theorem by Pólya. Finally, the results are expected to be of relevance for e.g. emulsion formulation and macromolecular engineering. PMID:25807174

  18. Anomalous Micellization of Pluronic Block Copolymers

    Leonardi, Amanda; Ryu, Chang Y.

    2014-03-01

    Poly(ethylene oxide) - poly(propylene oxide) - poly(ethylene oxide) (PEO-PPO-PEO) block copolymers, commercially known as Pluronics, are a unique family of amphiphilic triblock polymers, which self-assemble into micelles in aqueous solution. These copolymers have shown promise in therapeutic, biomedical, cosmetic, and nanotech applications. As-received samples of Pluronics contain low molecular weight impurities (introduced during the manufacturing and processing), that are ignored in most applications. It has been observed, however, that in semi-dilute aqueous solutions, at concentrations above 1 wt%, the temperature dependent micellization behavior of the Pluronics is altered. Anomalous behavior includes a shift of the critical micellization temperature and formation of large aggregates at intermediate temperatures before stable sized micelles form. We attribute this behavior to the low molecular weight impurities that are inherent to the Pluronics which interfere with the micellization process. Through the use of Dynamic Light Scattering and HPLC, we compared the anomalous behavior of different Pluronics of different impurity levels to their purified counterparts.

  19. Block copolymer ion gels for gas separation

    Gu, Yuanyan; Lodge, Timothy

    2012-02-01

    Carbon dioxide removal from light gases (eg. N2, CH4, and H2) is a very important technology for industrial applications such as natural gas sweetening, CO2 capture from coal-fire power plant exhausts and hydrogen production. Current CO2 separation method uses amine-absorption, which is energy-intensive and requires frequent maintenance. Membrane separation is a cost-effective solution to this problem, especially in small-scale applications. Ionic liquids have recently received increasing interest in this area because of their selective solubility for CO2 and non-volatility. However, ionic liquid itself lacks the persistent structure and mechanical integrity to withstand the high pressure for gas separation. Here, we report the development and gas separation performances of physically crosslinked ion gels based on self-assembly of ABA-triblock copolymers in ionic liquids. Three different types of polymers was used to achieve gelation in ionic liquids. Specifically, a triblock copolymer ion gel with a polymerized ionic liquid mid-block shows performances higher than the upper bound of well-known ``Robeson Plot'' for CO2/N2.

  20. Sequence-Specific Copolymer Compatibilizers designed via a Genetic Algorithm

    Meenakshisundaram, Venkatesh; Patra, Tarak; Hung, Jui-Hsiang; Simmons, David

    For several decades, block copolymers have been employed as surfactants to reduce interfacial energy for applications from emulsification to surface adhesion. While the simplest approach employs symmetric diblocks, studies have examined asymmetric diblocks, multiblock copolymers, gradient copolymers, and copolymer-grafted nanoparticles. However, there exists no established approach to determining the optimal copolymer compatibilizer sequence for a given application. Here we employ molecular dynamics simulations within a genetic algorithm to identify copolymer surfactant sequences yielding maximum reductions the interfacial energy of model immiscible polymers. The optimal copolymer sequence depends significantly on surfactant concentration. Most surprisingly, at high surface concentrations, where the surfactant achieves the greatest interfacial energy reduction, specific non-periodic sequences are found to significantly outperform any regularly blocky sequence. This emergence of polymer sequence-specificity within a non-sequenced environment adds to a recent body of work suggesting that specific sequence may have the potential to play a greater role in polymer properties than previously understood. We acknowledge the W. M. Keck Foundation for financial support of this research.

  1. Synthesis and morphological characterization of block copolymers for improved biomaterials

    Biocompatible polymers are known to act as scaffolds for the regeneration and growth of bone. Block copolymers are of interest as scaffold materials because a number of the blocks are biocompatible, and their nanostructure is easily tunable with synthetic techniques. In this paper, we report the synthesis of a novel class of biomaterials from block copolymers containing a hydrophobic block of methyl methacrylate and a hydrophilic block of either acrylic acid, dimethyl acrylamide, or 2-hydroxyethyl methacrylate. The block copolymers were synthesized using a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and click chemistry. Since the surface morphology is critical for successful cell growth, atomic force microscopy (AFM) studies were conducted for selected block copolymers. The topography, phase angle and friction maps were obtained in dry and physiological buffer environments to study the morphology. Results of AFM imaging identified the presence of polymer domains corresponding to the copolymer components. The distribution of nanoscale features in these block copolymers is comparable to those found on other surfaces that exhibit favorable cell adhesion and growth. In physiological buffer medium, the hydrophilic component of the block copolymer (acrylic acid or hydroxyethyl methacrylate) appears to be present in greater amounts on the surface as a consequence of water absorption and swelling.

  2. Synthesis and morphological characterization of block copolymers for improved biomaterials

    Schricker, Scott, E-mail: Schricker.1@osu.edu [Restorative and Prosthetic Dentistry Section, College of Dentistry, The Ohio State University, Columbus, OH 43210 (United States); Palacio, Manuel [Nanoprobe Laboratory for Bio- and Nanotechnology and Biomimetics, The Ohio State University, Columbus, OH 43210 (United States); Thirumamagal, B.T.S. [Restorative and Prosthetic Dentistry Section, College of Dentistry, The Ohio State University, Columbus, OH 43210 (United States); Bhushan, Bharat [Nanoprobe Laboratory for Bio- and Nanotechnology and Biomimetics, The Ohio State University, Columbus, OH 43210 (United States)

    2010-05-15

    Biocompatible polymers are known to act as scaffolds for the regeneration and growth of bone. Block copolymers are of interest as scaffold materials because a number of the blocks are biocompatible, and their nanostructure is easily tunable with synthetic techniques. In this paper, we report the synthesis of a novel class of biomaterials from block copolymers containing a hydrophobic block of methyl methacrylate and a hydrophilic block of either acrylic acid, dimethyl acrylamide, or 2-hydroxyethyl methacrylate. The block copolymers were synthesized using a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and click chemistry. Since the surface morphology is critical for successful cell growth, atomic force microscopy (AFM) studies were conducted for selected block copolymers. The topography, phase angle and friction maps were obtained in dry and physiological buffer environments to study the morphology. Results of AFM imaging identified the presence of polymer domains corresponding to the copolymer components. The distribution of nanoscale features in these block copolymers is comparable to those found on other surfaces that exhibit favorable cell adhesion and growth. In physiological buffer medium, the hydrophilic component of the block copolymer (acrylic acid or hydroxyethyl methacrylate) appears to be present in greater amounts on the surface as a consequence of water absorption and swelling.

  3. Thermo-Responsive Injectable MPEG-Polyester Diblock Copolymers for Sustained Drug Release

    Hoon Hyun

    2014-10-01

    Full Text Available Thermo-responsive diblock copolymers composed of hydrophilic methoxy poly(ethylene glycol (MPEG and hydrophobic biodegradable polyesters were prepared for application as injectable drug delivery systems, because they show a thermo-responsive sol-to-gel transition, especially around body temperature, when dispersed in aqueous solutions. The thermogelling hydrogels formed by hydrophobic aggregation could be varied by changing the components of the hydrophobic polyester part. For the polyester block in the present study, 95 mol% of ε-caprolactone (CL was used for the main polyester chain and 5 mol% of p-dioxanone (DO was copolymerized randomly by the MPEG initiator in the presence of HCl as the catalyst. By adding a small portion of DO into the poly ε-caprolactone (PCL chains, the temperature range of gelation, the intensity of viscosity and the drug release behavior were changed. The MPEG-b-poly(ε-caprolactone-ran-p-dioxanone (MPEG-b-PCDO hydrogel showed the enhanced drug release in vitro and in vivo compared to MPEG-b-PCL hydrogel. Therefore, MPEG-polyester hydrogels may serve as minimally invasive and therapeutic, injectable hydrogel systems with adjustable temperature-responsive and biodegradable windows, as well as sustained release of drugs over a certain time period.

  4. Viscometric Studies of Graft Copolymers of Methylcellulose and Polyacrylamide

    Krishna Kohli (Bardhan

    1985-01-01

    Full Text Available Viscometric studies of graft copolymers (methyl cellulose g polyacrylamide were made at four temperatures. The values of intrinsic viscosity of the graft copolymers were found to be much less than the linear methyl cellulose which was used as a backbone polymer. Intrinsic viscosity also decreased with the increase in the number and length of the branches.Huggin's slope constant k' was found to be much higher than the linear methyl cellulose. k' values also increased with increase in the number of the branches as well as the length of the branches and are temperature dependent. These observations clearly indicate the branched nature of the copolymer.

  5. Controlled Synthesis of Fluorinated Copolymers with Pendant Sulfonates

    Dimitrov, Ivaylo; Jankova Atanasova, Katja; Hvilsted, Søren

    2008-01-01

    Novel fluorinated copolymers of different architectures and bearing sulfopropyl groups were synthesized by atom transfer radical polymerization (ATRP) of aromatic fluorinated monomers and two modification reactions performed on the polymer chain - demethylation followed by sulfopropylation. As a....... The second type copolymers have diblock architecture with one.of the blocks being sulfopropyl~ed. They were synthesized via ATRP of 2,3,4,5,6pentafluorostyrene (FS) initiated by PTFMS-macroinitiator followed by demethylation and sulfopropylation performed on the TFMS-block (Scheme 1). The) copolymers...

  6. Synthesis and properties of polystyrene/polydimethylsiloxane graft copolymers

    Wu Ningjing; Huang Likan; Zheng Anna

    2006-01-01

    Polystyrene-graft-polydimethylsiloxane (PS-g-PDMS) copolymers with different PDMS content were synthesized by the radical bulk copolymerization of PDMS macromonomer and styrene.The copolymers were characterized by Fourier transform infrared (FT-IR),1H-nuclear magnetic resonance (NMR),thermogravimetric analysis (TGA),dynamic mechanical analysis (DMA),transmission electron microscopy (TEM) and the mechanical properties of the copolymers were also carried out.It was indicated that the notched impact strength and elongation at break of the polymers increased with the increase of PDMS content.The thermal stability of PS-g-PDMS is better than that of PS.

  7. Preparation and Characterization of Acrylonitrile Copolymers by Emulsion Technique

    Acrylonitrile (AN) binary copolymers with styrene (St) and maleic acid (MA) of different compositions were prepared by free radical emulsion copolymerization using potassium persulfate and sodium bisulfite as a redox pair initiation system and sodium dodecyl benzene sulfonate as an emulsifier. Based on the copolymerization data of the (AN/St) and (AN/MA) in emulsion polymerization process, the reactivity ratios of the prepared copolymers were investigated by different methods. Thermogravimetric analysis and X-ray diffraction were studied to characterize the prepared copolymers. Physicomechanical properties of some copolymeric lattices films were also identified

  8. Radiation-induced oxidation of polyethylene, ethylene-butene copolymer, and ethylene-propylene copolymer

    Oxygen consumption and yield of oxidation products during ν-irradiation were studied on five types of polyethylene (PE), ethylene-butene copolymer (EB), and ethylene-propylene copolymer (EPR) using gas chromatography, mass spectrography, and high-resolution NMR. Samples were irradiated in oxygen under pressure from 0 to 500 torr by 60Co ν-rays up to 20 Mrad at 22-250C. In enough oxygen, oxygen consumption and yield of oxidation products are independent of oxygen pressure for low-density PE, EB, and EPR. The G values of oxygen consumption were 14-18.4 for PE, 11.6 for EB at 1 x 106 rad/h, and 8.3 for EPR at 2 x 105 rad/h. The oxidation products determined were carboxylic acid (-CH2-CO-OH), H2O, CO2, and CO. The oxygen consumption and oxidation products for PE were found to increase with increasing crystallinity

  9. Polycationic graft copolymers as carriers for oligonucleotide delivery. Complexes of oligonucleotides with polycationic graft copolymers

    Dautzenberg, H.; Zintchenko, A.; Koňák, Čestmír; Reschel, Tomáš; Šubr, Vladimír; Ulbrich, Karel

    2001-01-01

    Roč. 17, č. 10 (2001), s. 3096-3102. ISSN 0743-7463 R&D Projects: GA MŠk ME 362; GA ČR GV307/96/K226; GA AV ČR KSK2055603 Grant ostatní: XE(XC) ERBIC 20CT97005 Institutional research plan: CEZ:AV0Z4050913 Keywords : drug delivery * oligonuclotides * polycationic graft copolymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.963, year: 2001

  10. Mechanical properties of weakly segregated block copolymers : 1. Synergism on tensile properties of poly(styrene-b-n-butylmethacrylate) diblock copolymers

    Weidisch, R.; Michler, G.H.; Fischer, H.; Arnold, M.; Hofmann, S.; Stamm, M.

    1999-01-01

    Mechanical properties of poly(styrene-b-n-butylmethacrylate) diblock copolymers, PS-b-PBMA, with different lengths of the polystyrene block were investigated. The copolymers display a composition range where the tensile strength of the block copolymers exceeds the values of the corresponding homopol

  11. Thermal Stability of Poly (acrylonitrile-methyl acrylate) Copolymers

    HAN Na; ZHANG Xing-xiang; WANG Xue-chen

    2008-01-01

    Poly (acrylonitrile-methyl acrylate) copolymer was synthesized by water depositing polymerization and has a typical feed ratio of 85/15. And then 1 - 3 wt% lauryl alcohol maleic anhydride (LAM) was adopted as stabilizer to mix with the acrylonitrile based copolymer. The mixtures were characterized by using Fourier Transform Infrared Spectroscopy (FTIR), Nuclear Magnetic Resonance (1H NMR ), Gel Permeation Chromatography ( GPC ), Differential Scanning Calorimetry (DSC), optic microscope and Ubbelohde viscosimetryr etc. The melting point (Tm) and glass transition temperature (Tg) of the 85/15 AN/MA copolymer mixed with LAM all decrease with the increase of stabilizer content. The lowest Tg and Tm were 116.1 ℃ and 209. 1℃ respectively at the heating rate of 100℃/min when the content of LAM is 2 wt%. The 85°/15 AN/MA copolymer mixed with 1 - 3 w t% LAM possess good thermal stability up to 30 min at 220 ℃.

  12. Stimuli-Responsive Peptide-based Triblock and Star Copolymers

    Ray, Jacob; Naik, Sandeep; Johnson, Ashley; Ly, Jack; Savin, Daniel

    2011-03-01

    Stimuli-responsive copolymers demonstrate diverse aggregation behavior in aqueous solution. In general, the molecular architecture and the balance of hydrophilic and hydrophobic volumes influence morphology. This study involves polypeptide-based ABA linear triblock and AB2 star copolymer (which structurally resemble phospholipids) amphiphiles. Model systems for this study are poly(L-lysine)-b-poly(propylene oxide)-b-poly(L-lysine) (KPK) triblocks and poly(L-glutamate) (PE) based star copolymers. Extensive studies with KPK systems have resulted in morphological transitions by modifying pH, and we hypothesize that a change in individual chain conformation is the driving force for these transitions. Preliminary results for PE-based star copolymers with various hydrophobic moieties suggest polymersome (vesicle) formation. Light scattering (dynamic and static) and TEM were used to determine aggregate size and morphology as a function of pH; furthermore, circular dichroism (CD) spectroscopy was used to measure helix-to-coil transitions of the polypeptide blocks.

  13. Synthesis of Polyacrylate/Polysiloxane Copolymer and Its Damping Performance

    夏宇正; 石淑先; 焦书科; 李素青

    2003-01-01

    The copolymer of polyacrylate/polysiloxane for vibration damping materials was synthesized through emulsion polymerization. The effects of the amount of methyl methacrylate (MMA),polysiloxane containing vinyl, initiator and emulsifier on the conversion, stability of polyacrylate/polysiloxane emulsion were discussed when the emulsion was prepared by pre-emulsifying half continuous method. The graft copolymer has good vibration damping performance. The widest glass transition region of the copolymer spans 100℃, and the highest value of tanδ reached 2.0. The glass transition of the samples was examined by dynamic mechanical analysis (DMA). The vibration damping performance of the graft copolymer was affected by the amount of poly-vinyl dimethylsiloxane (PVMS).

  14. CHARACTERIZATION OF IMPACT POLYPROPYLENE COPOLYMERS BY SOLVENT FRACTIONATION

    Xiao-ying Lu; Jian-jun Yi; Shang-tao Chen; Feng-hua Zu; Rong-bo Li

    2012-01-01

    The compositional heterogeneity of two impact polypropylcne copolymers (IPCs) was studied by a combinatory investigation of temperature rising elution fractionation (TREF) and solvent fractionation.The chain structures and composition of fractions obtained from solvent fractionation were examined in detail.The TREF results shows that there are much more E-P segmented copolymer and more uniform distribution of ethylene sequence in IPC-1,which is responsible for its better comprehensive mechanical performance.The fractions from hexane and heptane are ethylene-propylene rubber phase and E-P block copolymers respectively.The result of solvent fractionation method also shows that custom hexane or heptaae extractions can not extract the E-P copolymer completely.

  15. Molecular weight and its distribution of tetrafluoroethylene and propylene copolymer

    In comparison of molecular structure of tetrafluoroethylene and propylene copolymer produced by radiation and chemical initiators respectively, both were fractionated by elution method and fine structure was examined. For the fractionated sample by radiation, the relation between molecular weight anti Mn and intrinsic viscosity ( eta] is ( eta] = 3.97 x 10-4 anti Mnsup(0.630) The result is not in agreement with that of the unfractionated sample by radiation, and similar to those of samples by chemical initiators. There is no difference, however, in the elution method of GPC between both these copolymers; the elution behavior agrees with that of standard polystyrene. Long chain branching thus exists little in the copolymer of tetrafluoroethylene and propylene. To reveal the relations between reaction conditions and molecular weight and its distribution of the copolymer produced by flow apparatus, the molecular weight distribution was measured by GPC. The method of analysis could evaluate molecular weight distribution changing constantly. (auth.)

  16. Synthesis and interfacial behavior of polystyrene-polysaccharide diblock copolymers

    Bosker, W.T.E.; Ágoston, K.; Cohen Stuart, M.A.; Norde, W.; Timmermans, J.W.; Slaghek, T.M.

    2003-01-01

    Linear block copolymers of polystyrene and polysaccharide were synthesized using a block synthesis method with amino-terminated polystyrene and sodium cyanoborohydride as reducing agent. Different types of polysaccharides, dextrans, and maltodextrins with various molecular weights were used. IR spec

  17. Synthesis of Amylose-b-P2 VP Block Copolymers.

    Kumar, Kamlesh; Woortman, Albert J J; Loos, Katja

    2015-12-01

    A new class of rod-coil block copolymers is synthesized by chemoenzymatic polymerization. In the first step, maltoheptaose, which acts as a primer for the synthesis of amylose, is attached to poly(2-vinyl pyridine) (P2 VP). The enzymatic polymerization of maltoheptaose is carried out by phosphorylase to obtain amylose-b-P2 VP block copolymers. The block copolymer is characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance, gel permeation chromatography, and wide-angle X-ray scattering techniques. The designed molecules combine the inclusion complexation ability of amylose with the supramolecular complexation ability of P2 VP and therefore this kind of rod-coil block copolymers can be used to generate well-organized novel self-assembled structures. PMID:26437256

  18. BARRIER PROPERTY AND STRUCTURE OF ACRYLONITRILE/ACRYLIC COPOLYMERS

    YANG Zhenghua; LI Yuesheng

    1997-01-01

    A series of acrylonitrile (AN) copolymers with methyl acrylate (MA) or ethyl acrylate (EA) as comonomer (5-23 wt%) was prepared by free-radical copolymerization. The permeability coefficients of the copolymers to oxygen and carbon dioxide were measured at 1.0 MPa and at 30 ℃, and those to water vapor also measured at 100% relative humidity and at 30 ℃. All the AN/acrylic copolymers are semicrystalline. As the acrylate content increase, the permeability coefficients of the copolymers to oxygen and carbon dioxide are increased progressively, but those to water vapor are decreased progressively. The gas permeability coefficients of the polymers were correlated with free-volume fractions or the ratio of free volume to cohesive energy.

  19. Nanopatterned articles produced using surface-reconstructed block copolymer films

    Russell, Thomas P.; Park, Soojin; Wang, Jia-Yu; Kim, Bokyung

    2016-06-07

    Nanopatterned surfaces are prepared by a method that includes forming a block copolymer film on a substrate, annealing and surface reconstructing the block copolymer film to create an array of cylindrical voids, depositing a metal on the surface-reconstructed block copolymer film, and heating the metal-coated block copolymer film to redistribute at least some of the metal into the cylindrical voids. When very thin metal layers and low heating temperatures are used, metal nanodots can be formed. When thicker metal layers and higher heating temperatures are used, the resulting metal structure includes nanoring-shaped voids. The nanopatterned surfaces can be transferred to the underlying substrates via etching, or used to prepare nanodot- or nanoring-decorated substrate surfaces.

  20. Comment on "Tropospheric temperature response to stratospheric ozone recovery in the 21st century" by Hu et al. (2011

    C. McLandress

    2011-12-01

    Full Text Available In a recent paper Hu et al. (2011 suggest that the recovery of stratospheric ozone during the first half of this century will significantly enhance free tropospheric and surface warming caused by the anthropogenic increase of greenhouse gases, with the effects being most pronounced in Northern Hemisphere middle and high latitudes. These surprising results are based on a multi-model analysis of IPCC AR4 model simulations with and without prescribed stratospheric ozone recovery. Hu et al. suggest that in order to properly quantify the tropospheric and surface temperature response to stratospheric ozone recovery, it is necessary to run coupled atmosphere-ocean climate models with stratospheric ozone chemistry. The results of such an experiment are presented here, using a state-of-the-art chemistry-climate model coupled to a three-dimensional ocean model. In contrast to Hu et al., we find a much smaller Northern Hemisphere tropospheric temperature response to ozone recovery, which is of opposite sign. We argue that their result is an artifact of the incomplete removal of the large effect of greenhouse gas warming between the two different sets of models.

  1. Comment on "Tropospheric temperature response to stratospheric ozone recovery in the 21st century" by Hu et al. (2011

    C. McLandress

    2012-03-01

    Full Text Available In a recent paper Hu et al. (2011 suggest that the recovery of stratospheric ozone during the first half of this century will significantly enhance free tropospheric and surface warming caused by the anthropogenic increase of greenhouse gases, with the effects being most pronounced in Northern Hemisphere middle and high latitudes. These surprising results are based on a multi-model analysis of CMIP3 model simulations with and without prescribed stratospheric ozone recovery. Hu et al. suggest that in order to properly quantify the tropospheric and surface temperature response to stratospheric ozone recovery, it is necessary to run coupled atmosphere-ocean climate models with stratospheric ozone chemistry. The results of such an experiment are presented here, using a state-of-the-art chemistry-climate model coupled to a three-dimensional ocean model. In contrast to Hu et al., we find a much smaller Northern Hemisphere tropospheric temperature response to ozone recovery, which is of opposite sign. We suggest that their result is an artifact of the incomplete removal of the large effect of greenhouse gas warming between the two different sets of models.

  2. An imaging-guided platform for synergistic photodynamic/photothermal/chemo-therapy with pH/temperature-responsive drug release.

    Lv, Ruichan; Yang, Piaoping; He, Fei; Gai, Shili; Yang, Guixin; Dai, Yunlu; Hou, Zhiyao; Lin, Jun

    2015-09-01

    To integrate biological imaging and multimodal therapies into one platform for enhanced anti-cancer efficacy, we have designed a novel core/shell structured nano-theranostic by conjugating photosensitive Au25(SR)18 - (SR refers to thiolate) clusters, pH/temperature-responsive polymer P(NIPAm-MAA), and anti-cancer drug (doxorubicin, DOX) onto the surface of mesoporous silica coated core-shell up-conversion nanoparticles (UCNPs). It is found that the photodynamic therapy (PDT) derived from the generated reactive oxygen species and the photothermal therapy (PTT) arising from the photothermal effect can be simultaneously triggered by a single 980 nm near infrared (NIR) light. Furthermore, the thermal effect can also stimulate the pH/temperature sensitive polymer in the cancer sites, thus realizing the targeted and controllable DOX release. The combined PDT, PTT and pH/temperature responsive chemo-therapy can markedly improve the therapeutic efficacy, which has been confirmed by both in intro and in vivo assays. Moreover, the doped rare earths endow the platform with dual-modal up-conversion luminescent (UCL) and computer tomography (CT) imaging properties, thus achieving the target of imaging-guided synergistic therapy under by a single NIR light. PMID:26093792

  3. Temperature-responsiveness and biocompatibility of DEGMA/OEGMA radiation-grafted onto PP and LDPE films

    Polypropylene (PP) and low density polyethylene (LDPE) were modified by γ-ray grafting of di(ethylene glycol) methyl ether methacrylate (DEGMA) and oligo (ethylene glycol) methyl ether methacrylate (OEGMA300 or OEGMA475 with Mn 300 and 475 respectively) with different monomer concentrations and mol ratios. The grafting percentage was evaluated as a function of the solvent, irradiation dose, reaction time, temperature, and monomers concentration. The grafted materials were more hydrophilic than the pristine polymers, as observed by contact angle and swelling in water. Temperature-responsive behavior was evaluated using DSC showing transitions between 34 and 48 °C. In vitro hemocompatibility, protein adsorption, cytotoxicity and bacteria adhesion tests were also carried out. Overall, the DEGMA/OEGMA grafting provides hemo and cytocompatible materials that exhibit temperature-responsive hydrophilic features and decreased protein adsorption. - Highlights: • Simultaneous grafting of DEGMA/OEGMA from PP and LDPE achieved via γ-ray pre-irradiation. • Grafting yield depends on solvent, feed ratio, inhibitors, temperature and time of reaction. • DEGMA/OEGMA grafting determines LCST, swelling and protein adsorption

  4. Characterization of chondrocyte sheets prepared using a co-culture method with temperature-responsive culture inserts.

    Kokubo, Mami; Sato, Masato; Yamato, Masayuki; Mitani, Genya; Kutsuna, Toshiharu; Ebihara, Goro; Okano, Teruo; Mochida, Joji

    2016-06-01

    Conventional culture methods using temperature-responsive culture dishes require 4-5 weeks to prepare layered chondrocyte sheets that can be used in articular cartilage repair and regeneration. This study investigated whether the use of synovial tissue obtained from the same joint as the chondrocyte nutritive supply source could more quickly facilitate the preparation of chondrocyte sheets. After culturing derived synoviocytes and chondrocytes together (i.e. combined culture or co-culture) on temperature-responsive inserts, chondrocyte growth was assessed and a molecular analysis of the chondrocyte sheets was performed. Transplantable tissue could be obtained more quickly using this method (average 10.5 days). Real-time polymerase chain reaction and immunostaining of the three-layer chondrocyte sheets confirmed the significant expression of genes critical to cartilage maintenance, including type II collagen (COL2), aggrecan-1 and tissue metallopeptidase inhibitor 1. However, the expression of COL1, matrix metalloproteinase 3 (MMP3), MMP13 and A-disintegrin and metalloproteinase with thrombospondin motifs 5 was suppressed. The adhesive factor fibronectin-1 (FN1) was observed in all sheet layers, whereas in sheets generated using conventional preparation methods positive FN1 immunostaining was observed only on the surface of the sheets. The results indicate that synoviocyte co-cultures provide an optimal environment for the preparation of chondrocyte sheets for tissue transplantation and are particularly beneficial for shortening the required culture period. Copyright © 2013 John Wiley & Sons, Ltd. PMID:23868865

  5. Fabrication and evaluation of temperature responsive molecularly imprinted sorbents based on surface of yeast via surface-initiated AGET ATRP

    Pan, Jianming, E-mail: pjm@ujs.edu.cn; Hang, Hui; Li, Xiuxiu; Zhu, Wenjing; Meng, Minjia; Dai, Xiaohui; Dai, Jiangdong; Yan, Yongsheng

    2013-12-15

    Temperature responsive molecularly imprinted polymers (T-MIPs) were prepared based on the surface of yeast by electron transfer atom transfer radical polymerization (AGET ATRP). The as-prepared T-MIPs were charcterized by FT-IR, SEM, TGA and elemental analysis, which indicated that T-MIPs exhibited thermal stability and composed of temperature responsive imprinted layer. Then T-MIPs were evaluated as sorbents to selectively recognise and release cefalexin (CFX) molecules. The results suggested binding properties of T-MIPs were related to the testing temperature. The maximum adsorption capacity of T-MIPs at 303 K was 59.4 mg g{sup −1}, and the maximum release proportion for T-MIPs at 293 K in water for 24 h was 71.08%. The selective recognition experiments demonstrated high affinity and selectivity of T-MIPs towards CFX over competitive compounds, and the specific recognition of binding sites may be based on the distinct size, structure and functional group to the template molecules.

  6. Fabrication and evaluation of temperature responsive molecularly imprinted sorbents based on surface of yeast via surface-initiated AGET ATRP

    Pan, Jianming; Hang, Hui; Li, Xiuxiu; Zhu, Wenjing; Meng, Minjia; Dai, Xiaohui; Dai, Jiangdong; Yan, Yongsheng

    2013-12-01

    Temperature responsive molecularly imprinted polymers (T-MIPs) were prepared based on the surface of yeast by electron transfer atom transfer radical polymerization (AGET ATRP). The as-prepared T-MIPs were charcterized by FT-IR, SEM, TGA and elemental analysis, which indicated that T-MIPs exhibited thermal stability and composed of temperature responsive imprinted layer. Then T-MIPs were evaluated as sorbents to selectively recognise and release cefalexin (CFX) molecules. The results suggested binding properties of T-MIPs were related to the testing temperature. The maximum adsorption capacity of T-MIPs at 303 K was 59.4 mg g-1, and the maximum release proportion for T-MIPs at 293 K in water for 24 h was 71.08%. The selective recognition experiments demonstrated high affinity and selectivity of T-MIPs towards CFX over competitive compounds, and the specific recognition of binding sites may be based on the distinct size, structure and functional group to the template molecules.

  7. A noninvasive transfer system for polarized renal tubule epithelial cell sheets using temperature-responsive culture dishes

    Kushida A.

    2005-08-01

    Full Text Available We used temperature-responsive culture dishes onto which the temperature-responsive polymer, poly(Nisopropylacrylamide, was covalently grafted for tissue engineering. Confluent cells harvested as intact sheets from these surfaces by simple temperature reduction can be transferred to various surfaces including additional culture dishes, other cell sheets, and tissues. In order to examine the maintenance of cell polarity, Madin-Darby canine kidney cells and human primary renal proximal tubule epithelial cells which had developed apical-basal cell polarity in culture, were subjected to cell sheet transfer. This functional and structural cell polarity, which is susceptible to treatment with trypsin, was examined by immunohistochemistry and transmission electron microscopy. Using our cell-sheet method, the noninvasive transfer of these cell sheets retaining typical distributions of Na+/K+-ATPase, GLUT-1, SGLT-1, aquaporin-1, neutral endopeptidase and dipeptidylendopeptidase IV, could be achieved. The transferred cell sheets also developed numerous microvilli and tight junctions at the apical and lateral membranes, respectively. For biochemical analysis, immunoblotting of occludin, a transmembrane protein that composes tight junctions, was conducted and results confirmed that occludin remained intact after cell sheet transfer. This two-dimensional cell sheet manipulation method promises to be useful for tissue engineering as well as in the investigation of epithelial cell polarity.

  8. Viscometric Studies of Graft Copolymers of Methylcellulose and Polyacrylamide

    Krishna Kohli (Bardhan); Sailes Mukhopadhyay; Satya R. Chatterjee

    1985-01-01

    Viscometric studies of graft copolymers (methyl cellulose g polyacrylamide) were made at four temperatures. The values of intrinsic viscosity of the graft copolymers were found to be much less than the linear methyl cellulose which was used as a backbone polymer. Intrinsic viscosity also decreased with the increase in the number and length of the branches.Huggin's slope constant k' was found to be much higher than the linear methyl cellulose. k' values also increased with increase in the numb...

  9. Adsorption of semiflexible block copolymers on homogeneous surfaces

    Cerdà, Joan J.; Sintes, Tomàs; Sumithra, K.

    2005-01-01

    We present the results of extensive numerical off-lattice Monte Carlo simulations of semiflexible block-copolymer chains adsorbed onto flat homogeneous surfaces. We have compared the behavior of several chain structures, such as homopolymers, diblocks, (AαBα) block copolymers, and random heteropolymers. In all the cases studied, we have found the adsorption process to be favored with an increase of the chain rigidity. Particularly, the adsorption of diblock structures becomes a two-step proce...

  10. Synthesis and Morphological Characterization of Block Copolymers for Improved Biomaterials

    Schricker, Scott; Palacio, Manuel; Thirumamagal, B.T.S.; Bhushan, Bharat

    2010-01-01

    Biocompatible polymers are known to act as scaffolds for the regeneration and growth of bone. Block copolymers are of interest as scaffold materials because a number of the blocks are biocompatible, and their nanostructure is easily tunable with synthetic techniques. In this paper, we report the synthesis of a novel class of biomaterials from block copolymers containing a hydrophobic block of methyl methacrylate and a hydrophilic block of either acrylic acid, dimethyl acrylamide, or 2-hydroxy...

  11. Aggregation behavior of water-soluble amphiphilic block copolymers

    Bonné, Tune Bjarke

    2007-01-01

    Polymers and block copolymers based on 2-alkyl-2-oxazoline have the advantage that their hydrophobicity can be varied by changing the length of the alkyl side chain and that fluorescence groups can be attached to the block ends. We have studied the aggregation behavior of 2-alkyl-2-oxazoline based diblock, triblock and random copolymers in aqueous solutions, using fluorescence correlation spectroscopy (FCS), where fluorescence labeled polymers were used as tracers. FCS experiments in combinat...

  12. Synthesis and Characterization of Novel Magnetite Nanoparticle Block Copolymer Complexes

    Zhang, Qian

    2007-01-01

    Superparamagnetic Magnetite (Fe3O4) nanoparticles were synthesized and complexed with carboxylate-functionalized block copolymers, and aqueous dispersions of the complexes were investigated as functions of their chemical and morphological structures. The block copolymer dispersants possessed either poly(ethylene oxide), poly(ethylene oxide-co-propylene oxide), or poly(ethylene oxide-b-propylene oxide) outer blocks, and all contained a polyurethane center block with pendant carboxylate functi...

  13. SYNTHESIS OF A NEW SILICONE-CONTAINING BISMALEIMIDE COPOLYMER RESIN

    KUANG Wenfeng; CAI Xingxian; JIANG Luxia

    1997-01-01

    A copolymer of bismaleimide-diallylbisphenol A-diphenylsilandiol was synthesized and the copolymerization was studied by using N-phenylmaleimide, bisphenol A and diphenylsilandiol as model compounds. The copolymer could be well cured around 200 ℃, and the cured resins had good thermal stability. In the range of 170-210 ℃, a higher curing temperature was favorable to obtain more thermal stable resin by reducing the content of diphenylsilandiol cyclo-homopolymer in resin which would spoil its thermal stability.

  14. Phase diagram for a copolymer in a micro-emulsion

    den Hollander, F.; Petrelis, N.

    2013-01-01

    In this paper we study a model describing a copolymer in a micro-emulsion. The copolymer consists of a random concatenation of hydrophobic and hydrophilic monomers, the micro-emulsion consists of large blocks of oil and water arranged in a percolation-type fashion. The interaction Hamiltonian assigns energy $-\\alpha$ to hydrophobic monomers in oil and energy &-\\beta$ to hydrophilic monomers in water, where $\\alpha,\\beta$ are parameters that without loss of generality are taken to lie in the c...

  15. Biodegradable copolymers carrying cell-adhesion peptide sequences.

    Proks, Vladimír; Machová, Lud'ka; Popelka, Stepán; Rypácek, Frantisek

    2003-01-01

    Amphiphilic block copolymers are used to create bioactive surfaces on biodegradable polymer scaffolds for tissue engineering. Cell-selective biomaterials can be prepared using copolymers containing peptide sequences derived from extracellular-matrix proteins (ECM). Here we discuss alternative ways for preparation of amphiphilic block copolymers composed of hydrophobic polylactide (PLA) and hydrophilic poly(ethylene oxide) (PEO) blocks with cell-adhesion peptide sequences. Copolymers PLA-b-PEO were prepared by a living polymerisation of lactide in dioxane with tin(II)2-ethylhexanoate as a catalyst. The following approaches for incorporation of peptides into copolymers were elaborated. (a) First, a side-chain protected Gly-Arg-Gly-Asp-Ser-Gly (GRGDSG) peptide was prepared by solid-phase peptide synthesis (SPPS) and then coupled with delta-hydroxy-Z-amino-PEO in solution. In the second step, the PLA block was grafted to it via a controlled polymerisation of lactide initiated by the hydroxy end-groups of PEO in the side-chain-protected GRGDSG-PEO. Deprotection of the peptide yielded a GRGDSG-b-PEO-b-PLA copolymer, with the peptide attached through its C-end. (b) A protected GRGDSG peptide was built up on a polymer resin and coupled with Z-carboxy-PEO using a solid-phase approach. After cleavage of the delta-hydroxy-PEO-GRGDSG copolymer from the resin, polymerisation of lactide followed by deprotection of the peptide yielded a PLA-b-PEO-b-GRGDSG block copolymer, in which the peptide is linked through its N-terminus. PMID:12903721

  16. Unexpected phase behavior of an asymmetric diblock copolymer

    Papadakis, Christine Maria; Almdal, Kristoffer; Mortensen, Kell; Vigild, Martin Etchells; Stepanek, Petr

    1999-01-01

    We report on measurements of the transmitted depolarized light intensity and on small-angle neutron scattering (SANS) measurements on a compositionally asymmetric poly(ethylene propylene)-poly(dimethylsiloxane) diblock copolymer studied in the bulk. SANS measurements were made both on isotropic and...... which may be body-centered cubic. The available data cannot, however, finally prove this. These findings are in contrast to both available theories and to expectations based on analogous experiments on related diblock copolymer systems....

  17. Blends of caprolactam/caprolactone copolymers and chlorinated polymers

    Alberda van Ekenstein, G.O.R.; Deuring, H.; ten Brinke, G.; Ellis, T. S.

    1997-01-01

    The phase behaviour of blends of chlorinated polyethylene, polyvinyl chloride (PVC) and chlorinated PVC with random copolymers of caprolactone and caprolactam has been investigated and the results correlated with a binary interaction model. The known miscibility of polycaprolactone in the chlorinated polymers is not compromised until a relatively high lactam content in the copolymer is attained. The incorporation of segmental interaction parameters, derived from separate studies involving pol...

  18. Self-assembled materials from thermosensitive and biohybrid block copolymers

    De Graaf, A.J.

    2012-01-01

    In this research, several block copolymers were synthesized and characterized with regard to possible pharmaceutical applications. All block copolymers were thermosensitive and self-assembled at 37 °C into structures like micelles and hydrogels, which can be used for innovative drug delivery purposes. Some of the synthesized polymers were biohybrid, in the sense that they contained peptide segments which enabled their cleavage by enzymes that are upregulated in diseased tissues. First, method...

  19. Electrosynthesis and characterization of viologen cross linked thiophene copolymer

    Highlights: • Electrochemical copolymerization of OOT and HOT-CNP. • Further reductive coupling of cyanopyridine from HOT-CNP into viologen during cathodic scan. • Redox response of copolymer along with spectral studies confirms formation of viologen. • Spectroelectrochemical analysis of copolymer film indicates its future incorporation into practically usable electrochromic devices. -- Abstract: Electrochemical copolymerization of 3-octyloxy-4-methylthiophene (OOT) and 1-[6-[(4-methyl-3-thienyl) oxy] hexyl]-4-cyanopyridinium bromide (HOT-CNP) was carried out using tetrabutylammonium hexafluorophosphate and acetonitrile (TBAPF6/ACN) as electrolyte. The cyanopyridine functionalized HOT-CNP undergoes further electrochemical reductive coupling to viologen. Both polymer (POOT) and copolymer P(OOT-co-HOT-CNP) were characterized by cyclic voltammetry (CV), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and in situ UV–vis spectroscopy. The effect of the monomer concentration ratio and the scan rate on the electrochemical properties of the copolymer was studied by the CV technique. The electrochemical redox response of the copolymer together with FTIR analysis further confirms the formation of viologen. The surface morphology was studied using SEM analysis. The polymer POOT revealed color changes between violet and bright blue, whereas the copolymer showed the most vivid change of color between purple and greenish blue in its fully reduced and oxidized states respectively. The results showed that copolymerization is a valuable approach in order to achieve desired electrochromic and redox properties

  20. Influence of copolymer composition on the transport properties of conducting copolymers: poly(aniline-co-o-anisidine)

    S S Umare; A D Borkar; M C Gupta

    2002-06-01

    The effect of different compositions of monomers on the transport properties of copolymers by various techniques such as optical, electrical and magnetic has been investigated and compared with the homopolymers. The UV-visible absorption spectra show a hypsochromic shift with an increase in the o-anisidine content in copolymers indicating a decrease in the extent for conjugation (i.e. an increase in the bandgap). From temperature dependence of electrical conductivity the transport parameters such as charge localization length and average hopping distance are calculated and also the effect of the monomeric composition on the coherence length has been discussed. The magnetic studies show the paramagnetic and diamagnetic nature of homopolymers and copolymers. The X-ray diffraction pattern indicates that the copolymers are of amorphous nature.

  1. LOW DENSITY POLYETHYLENE/CLAY NANOCOMPOSITES MODIFIED BY ETHYLENE COPOLYMERS: EFFECTS OF FUNCTIONALIZED SEGMENTS ON MORPHOLOGY

    Bo Xu; Yi-hu Song; Yong-gang ShangGuan; Qiang Zheng

    2006-01-01

    Melt extrusion was used to prepare binary nanocomposites of ethylene copolymers and organoclay and trinary nanocomposites of low-density polyethylene (LDPE), ethylene copolymer and organoclay. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to analyze the structure of the clay phase and the morphology of the nanocomposites. Influences of the comonomer in the copolymer and the content of the copolymer on the morphology of the resulting nanocomposites were discussed. The binary and the trinary composites may form intercalated or exfoliated structures depending on the interaction between the copolymer and the clay layers and the content of the copolymer.

  2. Method of forming oriented block copolymer line patterns, block copolymer line patterns formed thereby, and their use to form patterned articles

    Russell, Thomas P.; Hong, Sung Woo; Lee, Doug Hyun; Park, Soojin; Xu, Ting

    2015-10-13

    A block copolymer film having a line pattern with a high degree of long-range order is formed by a method that includes forming a block copolymer film on a substrate surface with parallel facets, and annealing the block copolymer film to form an annealed block copolymer film having linear microdomains parallel to the substrate surface and orthogonal to the parallel facets of the substrate. The line-patterned block copolymer films are useful for the fabrication of magnetic storage media, polarizing devices, and arrays of nanowires.

  3. Synthesis, morphologies and applications of polyoxometalate-containing diblock copolymers

    Chakraborty, Sanjiban

    Block copolymers by virtue of their ability to self assemble and microphase-separation due to the contrast in chemical and physical properties of the covalently linked blocks constitute the essential building blocks towards various nano or micro sized architectures. Polyoxometalates (POM), on the other hand, being an interesting class of metal-oxygen nanometer-sized anionic clusters, are regarded highly due to their excellent electron accepting capability. Combining POM clusters with diblock copolymers can lead to a fascinating class of hybrid materials where the POM cluster not only affect the self-assembly process of various diblock copolymers but also brings its unique electronic properties into the hybrid system. Herein we report the detailed synthesis and characterizations of two hybrid coil-coil diblock copolymers along with two hybrid rod-coil diblock copolymers through polymerization-hybridization approach. The coil-coil diblocks were synthesized via atom transfer radial polymerization (ATRP) of styryl-type monomers and 4-vinylpyridine in sequence. For rod-coil diblock copolymers, the coil block was synthesized through ATRP, followed by the conversion of the terminal bromide to an azide. Ethynyl terminated poly (p-phenylenevinylene) (PPV) and poly (3-hexylthiophene) (P3HT) were prepared separately as the rod blocks. The rod block and the coil block were connected through click chemistry to yield rod-coil diblock copolymers. After removing the phthalimide protecting groups to regenerate aryl amines, POM clusters were finally linked to the coil block of all diblock copolymers to yield the targeted hybrid diblock copolymers. The covalent cluster attachment was confirmed by UV-Vis spectroscopy, FTIR and cyclovoltammetry measurements. The structures, solution and film optical properties, self-assembled morphologies and solar cell performances of these hybrids have been studied. It has been found that solar cell devices based on hybrid P3HT exhibited rather poor

  4. Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

    Hoarfrost, Megan Lane

    Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there is incredible freedom in designing the block copolymer architecture

  5. Investigation on the structure of temperature-responsive N-isopropylacrylamide microgels containing a new hydrophobic crosslinker

    G. Roshan Deen

    2015-12-01

    Full Text Available Temperature-responsive poly(N-isopropylacrylamide microgels crosslinked with a new hydrophobic chemical crosslinker was prepared by surfactant-mediated precipitation emulsion polymerization. The temperature-responsive property of the microgel and the influence of the crosslinker on the swelling behaviour was studied systematically by light scattering and small-angle X-ray scattering (SAXS. The radius of gyration (Rg and the hydrodynamic radius (Rh of the microgels decreased with increase in temperature due to the volume-phase transition from a swollen to a collapsed state. The ratio of Rg/Rh below the transition temperature was lower than that of hard-spheres due to the lower crosslinking density of the microgels. The SAXS data were analysed by a model in which the microgels were modelled as core-shell particles with a graded interface. The model at intermediate temperatures included a central core and a more diffuse outer layer describing pending polymer chains with a low crosslinking density. In the fully swollen state, the microgels were modelled with a single component with a broad graded surface. In the collapsed state, they were modelled as homogeneous and relatively compact particles. The polymer volume fraction inside the microgel was also derived based on the model and was found to increase with increase in the temperature as a result of collapse of the microgel to compact particles. The polymer volume fraction in the core of the microgel in the collapsed state was about 60% which is higher than that of similar microgels crosslinked with hydrophilic and flexible crosslinkers.

  6. Disulfide-Functionalized Diblock Copolymer Worm Gels.

    Warren, Nicholas J; Rosselgong, Julien; Madsen, Jeppe; Armes, Steven P

    2015-08-10

    Two strategies for introducing disulfide groups at the outer surface of RAFT-synthesized poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) (PGMA-PHPMA, or Gx-Hy for brevity) diblock copolymer worms are investigated. The first approach involved statistical copolymerization of GMA with a small amount of disulfide dimethacrylate (DSDMA, or D) comonomer to afford a G54-D0.50 macromolecular chain transfer agent (macro-CTA); this synthesis was conducted in relatively dilute solution in order to ensure mainly intramolecular cyclization and hence the formation of linear chains. Alternatively, a new disulfide-based bifunctional RAFT agent (DSDB) was used to prepare a G45-S-S-G45 (or (G45-S)2) macro-CTA. A binary mixture of a non-functionalized G55 macro-CTA was utilized with each of these two disulfide-based macro-CTAs in turn for the RAFT aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA). By targeting a PHPMA DP of 130 and systematically varying the molar ratio of the two macro-CTAs, a series of disulfide-functionalized diblock copolymer worm gels were obtained. For both formulations, oscillatory rheology studies confirmed that higher disulfide contents led to stronger gels, presumably as a result of inter-worm covalent bond formation via disulfide/thiol exchange. Using the DSDB-based macro-CTA led to the strongest worm gels, and this formulation also proved to be more effective in suppressing the thermosensitive behavior that is observed for the nondisulfide-functionalized control worm gel. However, macroscopic precipitation occurred when the proportion of DSDB-based macro-CTA was increased to 50 mol %, whereas the DSDMA-based macro-CTA could be utilized at up to 80 mol %. Finally, the worm gel modulus could be reduced to that of a nondisulfide-containing worm gel by reductive cleavage of the inter-worm disulfide bonds using excess tris(2-carboxyethyl)phosphine (TCEP) to yield thiol groups. These new biomimetic worm gels are

  7. New adhesive systems based on functionalized block copolymers

    Kent, M.; Saunders, R.; Hurst, M.; Small, J.; Emerson, J.; Zamora, D.

    1997-05-01

    The goal of this work was to evaluate chemically-functionalized block copolymers as adhesion promoters for metal/thermoset resin interfaces. Novel block copolymers were synthesized which contain pendant functional groups reactive toward copper and epoxy resins. In particular, imidazole and triazole functionalities that chelate with copper were incorporated onto one block, while secondary amines were incorporated onto the second block. These copolymers were found to self-assemble from solution onto copper surfaces to form monolayers. The structure of the adsorbed monolayers were studied in detail by neutron reflection and time-of-flight secondary ion mass spectrometry. The monolayer structure was found to vary markedly with the solution conditions and adsorption protocol. Appropriate conditions were found for which the two blocks form separate layers on the surface with the amine functionalized block exposed at the air surface. Adhesion testing of block copolymer-coated copper with epoxy resins was performed in both lap shear and peel modes. Modest enhancements in bond strengths were observed with the block copolymer applied to the native oxide. However, it was discovered that the native oxide is the weak link, and that by simply removing the native oxide, and then applying an epoxy resin before the native oxide can reform, excellent bond strength in the as-prepared state as well as excellent retention of bond strength after exposure to solder in ambient conditions are obtained. It is recommended that long term aging studies be performed with and without the block copolymer. In addition, the functionalized block copolymer method should be evaluated for another system that has inherently poor bonding, such as the nickel/silicone interface, and for systems involving metals and alloys which form oxides very rapidly, such as aluminum and stainless steel, where bonding strategies involve stabilizing the native oxide.

  8. Monte Carlo simulations of the phase separation of a copolymer blend in a thin film

    Wang, Zhexiao

    2014-12-11

    Monte Carlo simulations were carried out to study the phase separation of a copolymer blend comprising an alternating copolymer and/or block copolymer in a thin film, and a phase diagram was constructed with a series of composed recipes. The effects of composition and segregation strength on phase separation were discussed in detail. The chain conformation of the block copolymer and alternating copolymer were investigated with changes of the segregation strength. Our simulations revealed that the segment distribution along the copolymer chain and the segregation strength between coarse-grained beads are two important parameters controlling phase separation and chain conformation in thin films of a copolymer blend. A well-controlled phase separation in the copolymer blend can be used to fabricate novel nanostructures.

  9. Ionic Block Copolymers for Anion Exchange Membranes

    Tsai, Tsung-Han; Herbst, Dan; Giffin, Guinevere A.; di Noto, Vito; Witten, Tom; Coughlin, E. Bryan

    2013-03-01

    Anion exchange membrane (AEM) fuel cells have regained interest because it allows the use of non-noble metal catalysts. Until now, most of the studies on AEM were based on random polyelectrolytes. In this work, Poly(vinylbenzyltrimethylammonium bromide)-b- (methylbutylene) ([PVBTMA][Br]-b-PMB) was studied by SAXS, TEM and dielectric spectroscopy to understand the fundamental structure-conductivity relationship of ion transport mechanisms within well-ordered block copolymers. The ionic conductivity and the formation of order structure were dependent on the casting solvent. Higher ion exchange capacity (IEC) of the membranes showed higher conductivity at as IEC values below 1.8mmol/g, as above this, the ionic conductivity decreases due to more water uptake leading to dilution of charge density. The humidity dependence of morphology exhibited the shifting of d-spacing to higher value and the alteration in higher characteristic peak of SAXS plot as the humidity increase from the dry to wet state. This phenomenon can be further explained by a newly developed polymer brush theory. Three ionic conduction pathways with different conduction mechanism within the membranes can be confirmed by broadband electric spectroscopy. US Army MURI (W911NF1010520)

  10. Molecular Transfer Printing Using Block Copolymers

    Ji, Shengxiang; Liu, Chi-Chun; Liu, Guoliang; Nealey, Paul

    2009-03-01

    We report a new parallel patterning technique, molecular transfer printing (MTP), for replicating geometrically complex patterns over macroscopic areas with sub-15 nm feature dimensions, and the ability to replicate the same pattern multiple times. In MTP, inks are mixed with block copolymers (BCPs) and deposited as films on a substrate. The inks are compatible with only one block of the BCP, and sequestered into domains of nanometer scale dimensions after microphase separation. A second substrate is then placed in contact with the surface of the film. By designing the inks to react, adsorb, or otherwise interact with the second substrate, inks are transferred to the second substrate in the exact pattern of domains present at the surface of the ``master'' BCP film. Here we demonstrate high degrees of perfection on both line and dot patterns. We also show that 1) the master template can be regenerated, 2) the resultant replica can be used to direct the assembly of BCPs and as a daughter master for MTP, and 3) the master and daughter templates can be reused tens of times.