首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
A thermoplastic hydrogel based on a pentablock copolymer composed of poly(γ‐benzyl L ‐glutamate) (PBLG) and poloxamer was synthesized by polymerization of BLG N‐carboxyanhydride, which was initiated by diamine‐terminated groups located at the ends of poly(ethylene oxide) (PEO) chains of the poloxamer, to attain a new pH‐ and temperature‐sensitive hydrogel for drug delivery systems. Circular dichroism measurements in solution and IR measurements in the solid state revealed that the polypeptide block existed in the α‐helical conformation, as in the PBLG homopolymer. The intensity of the wide‐angle X‐ray diffraction patterns of the polymers depended on the poloxamer content in the copolymer and showed basically similar reflections to the PBLG homopolymer. The melting temperature (Tm) of the poloxamer in the copolymer was reduced with an increase of the PBLG block in comparison with the Tm of the poloxamer, which is indicative of a thermoplastic property. The water contents of the copolymers were dependent on the poloxamer content in the copolymers, for example, those for the GPG‐2 (48.7 mol % poloxamer) and GPG‐1 (57.5 mol % poloxamer) copolymers were 31 and 41 wt %, respectively, indicating characteristics of a polymeric hydrogel. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2649–2656, 2003  相似文献   

2.
Poly(γ‐benzyl L ‐glutamate) (PBLG) gels with highly oriented α‐helix chains were prepared by the crosslinking of PBLG chains through changes in the concentration of ethylenediamine, used as a crosslinker, in 1,4‐dioxane in the presence of the strong magnetic field of an NMR magnet with a strength of 10.5 T. The experimental results showed that in one of these gels, long channels with an average diameter of about 100 μm were formed by phase separation between crosslinked PBLG and the solvent. Furthermore, three‐dimensional 1H‐NMR imaging patterns showed that the long channels were aligned in the direction parallel to the α‐helix axis. The PBLG gel was swollen in the direction perpendicular to the α‐helix axis, but it was not swollen in the direction parallel to the α‐helix axis. The X‐ray diffraction patterns of the gel showed that the interchain distance between the two nearest neighboring PBLG chains changed from 13.4 to 18.1 Å with a change in the swelling degree. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1053–1060, 2004  相似文献   

3.
Water‐soluble poly(γ‐glutamic acid) (PGGA) esters were prepared by transesterification of poly(α‐methyl‐γ‐glutamate) with mono‐, di‐, and triethylene glycols with one hydroxyl end group blocked as methyl ether. Only the monoglycol appeared to be crystalline with melting at 160°C, and glass‐transition temperatures were found to increase from 10 to 60°C with the length of the oxyethylene side chain. All these poly(γ‐glutamate)s are stable up to temperatures near 250°C. Moisture sorption, surface wettability, and hydrodegradability were evaluated as a function of time. It was found that in overall sensitivity to water increased with the glycol chain length but the behavior at short contact times was critically affected by conformational factors. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2027–2036, 2001  相似文献   

4.
One of the latest developments in the field of piezoelectric polymers is the use of poly(γ‐benzyl‐α,L‐glutamate) (PBLG), a poly(amino acid) that can be poled along its α‐helical axis and fabricated into thermally stable piezoelectric microfibers via electrospinning. This study demonstrates a method for improving the piezoelectricity of electrospun PBLG microfibers by controlling the orientation of fibers using a method based on a concentrated electric field. The piezoelectricity is verified via customized quasi‐static and dynamic measurement methods, while the correlation between fiber alignment and the piezoelectric constant, d33, in the longitudinal mode of the electrospun PBLG fibers is investigated. When the level of alignment was varied from 50% to 90%, the piezoelectric constant increased linearly, showing a maximum d33 of 27 pC N?1 and a maximum force sensitivity of 65 mV N?1 at peak alignment. A fabricated flexible prototype based on electrospun PBLG fibers provides a new solution for the use of PBLG fibers in wearable energy harvesters or composites based on piezoelectric polymer fibers. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46440.  相似文献   

5.
α‐Tocopherol (α‐TC) and α‐TC/cyclodextrin (CD)–inclusion complex (IC) incorporated electrospun poly(lactic acid) (PLA) nanofibers (NF) were developed via electrospinning (PLA/α‐TC–NF and PLA/α‐TC/γ‐CD–IC–NF). The release of α‐TC into 95% ethanol (fatty food simulant) was much greater from PLA/α‐TC/γ‐CD–IC–NF than from PLA/α‐TC–NF because of the solubility increase in α‐TC; this was confirmed by a phase‐solubility diagram. 2,2‐Diphenyl‐1‐picrylhydrazyl radical‐scavenging assay shows that PLA/α‐TC–NF and PLA/α‐TC/γ‐CD–IC–NF had 97% antioxidant activities; this value was expected to be high enough to inhibit lipid oxidation. PLA/α‐TC–NF and PLA/α‐TC/γ‐CD–IC–NF were tested directly on beef with the thiobarbituric acid reactive substance (TBARS) method, and the nanofibers displayed a lower TBARS content than the unpackaged meat sample. Thus, active packaging significantly enhanced the oxidative stability of the meat samples at 4 °C. In conclusion, PLA/α‐TC/γ‐CD–IC–NF was shown to be promising as an active food‐packaging material for prolonging the shelf life of foods. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44858.  相似文献   

6.
Multi‐responsive hydrogels have recently received considerable attention for bioapplications. Here, novel temperature‐ and redox‐responsive polypetide hydrogels have been developed. Thermo‐sensitive hydrogels based on poly(ethyleneglycol)‐block ‐poly(γ‐propargyl‐l ‐glutamate) (PEG‐PPLG ) were first synthesized by the ring opening polymerization of γ‐propargyl‐l ‐glutamate N ‐carboxyanhydride (PLG‐NCA ) with amino group terminated PEG monomethyl ether (mPEG‐NH2 ) as macroinitiator and were then functionalized via the ‘thiol‐yne’ click reaction between the propargyl pendents and the thiol‐containing 1‐propanethiol. The sol ? gel phase transition of the obtained copolymer aqueous solution in response to temperature change was studied. The mass loss of the hydrogel in vitro was accelerated in the presence of H2O2 , exhibiting a redox‐responsive property. Further, the methyl thiazolyl tetrazolium viability results revealed that this polypetide hydrogel has excellent biocompatibility, presenting potential applications in the biomedical field. © 2016 Society of Chemical Industry  相似文献   

7.
The miscibility, melting and crystallization behaviour of poly[(R)‐3‐hydroxybutyrate], PHB, and oligo[(R,S)‐3‐hydroxybutyrate]‐diol, oligo‐HB, blends have been investigated by differential scanning calorimetry: thermograms of blends containing up to 60 wt% oligo‐HB showed behaviour characteristic of single‐phase amorphous glasses with a composition dependent glass transition, Tg, and a depression in the equilibrium melting temperature of PHB. The negative value of the interaction parameter, determined from the equilibrium melting depression, confirms miscibility between blend components. In parallel studies, glass transition relaxations of different melt‐crystallized polymer blends containing 0–20 wt% oligo‐HB were dielectrically investigated between ?70 °C and 120 °C in the 100 Hz to 50 kHz range. The results revealed the existence of a single α‐relaxation process for blends, indicating the miscibility between amorphous fractions of PHB and oligo‐HB. © 2002 Society of Chemical Industry  相似文献   

8.
Charged polypeptides containing sulfonate groups were prepared by transesterification of poly(γ‐methyl L ‐glutamate) with isethionic acid. The coil–helix transition of the sulfonated polypeptides was investigated in aqueous alcohols. Marked counter‐ion specificity was observed for helix formation: Li+ < Na+ < Cs+ ≦ Rb+ ≦ K+; this was different to that for poly(L ‐glutamate) (PLG): Cs+ ? K+ < Li+ < Na+. Specific helix stabilization by counter‐ion mixing, which has been found for the PLG system, was not observed for the sulfonated polypeptides. The counter‐ion‐ and solvent‐specific helix formation is discussed and compared with that in PLG. © 2001 Society of Chemical Industry  相似文献   

9.
Ethylene homopolymerization and ethylene/α‐olefin copolymerization were carried out using unbridged and 2‐alkyl substituted bis(indenyl)zirconium dichloride complexes such as (2‐MeInd)2ZrCl2 and (2‐BzInd)2ZrCl2. Various concentrations of 1‐hexene, 1‐dodecene, and 1‐octadecene were used in order to find the effect of chain length of α‐olefins on the copolymerization behavior. In ethylene homopolymerization, catalytic activity increased at higher polymerization temperature, and (2‐MeInd)2ZrCl2 showed higher activity than (2‐BzInd)2ZrCl2. The increase of catalytic activity with addition of comonomer (the synergistic effect) was not observed except in the case of ethylene/1‐hexene copolymerization at 40°C. The monomer reactivity ratios of ethylene increased with the decrease of polymerization temperature, while those of α‐olefin showed the reverse trend. The two catalysts showed similar copolymerization reactivity ratios. (2‐MeInd)2ZrCl2 produced the copolymer with higher Mw than (2‐BzInd)2ZrCl2. The melting temperature and the crystallinity decreased drastically with the increase of the α‐olefin content but Tm as a function of weight fraction of the α‐olefins showed similar decreasing behavior. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 928–937, 2000  相似文献   

10.
A series of poly(γ‐alkyl α L ‐glutamate)s with different alkyl groups were synthesized by the ring opening polymerization of corresponding α‐amino acid N‐carboxyanhydrides. The characteristics of these polyglutamate surfaces were evaluated by attenuated total reflectance Fourier transform infrared spectroscopy spectra, water contact angle, water absorption, protein adsorption, and platelet adhesion measurements. Changing the length of the alkyl side chain provides a unique opportunity to study the influence of carbon number in the alkyl group on the surface properties of the polyglutamates. Water contact angle and water absorption data show that the hydrophilicity of these polyglutamate surfaces decreases with the increasing of methylene in the alkyl group. Protein adsorption on these polyglutamate surfaces increases with the enhancing of surface hydrophobicity. However, the changes in platelets adhesion could be attributed to the hydrophilicity/hydrophobicity of the polyglutamates and the specific effect of alkyl group. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

11.
The quantitative syntheses of α‐bis and α,ω‐tetrakis tertiary diamine functionalized polymers by atom transfer radical polymerization (ATRP) methods are described. A tertiary diamine functionalized 1,1‐diphenylethylene derivative, 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1), was evaluated as a unimolecular tertiary diamine functionalized initiator precursor as well as a functionalizing agent in ATRP reactions. The ATRP of styrene, initiated by a new tertiary diamine functionalized initiator adduct (2), affords the corresponding α‐bis(4‐dimethylaminophenyl) functionalized polystyrene (3). The tertiary diamine functionalized initiator adduct (2) was prepared in situ by the reaction of (1‐bromoethyl)benzene with 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1) in the presence of a copper (I) bromide/2,2′‐bipyridyl catalyst system. The ATRP of styrene proceeded via a controlled free radical polymerization process to afford quantitative yields of the corresponding α‐bis(4‐dimethylaminophenyl) functionalized polystyrene derivative (3) with predictable number‐average molecular weight (Mn) and narrow molecular weight distribution (Mw/Mn) in a high initiator efficiency reaction. The polymerization process was monitored by gas chromatography analysis. Quantitative yields of α,ω‐tetrakis(4‐dimethylaminophenyl) functionalized polystyrene (4) were obtained by a new post ATRP chain end modification reaction of α‐bis(4‐dimethylaminophenyl) functionalized polystyrene (3) with excess 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1). The tertiary diamine functionalized initiator precursor 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1) and the different tertiary amine functionalized polymers were characterized by chromatography, spectroscopy and non‐aqueous titration measurements. Copyright © 2012 Society of Chemical Industry  相似文献   

12.
pH‐sensitive anionic hydrogels composed of poly(vinyl alcohol) (PVA) and poly(γ‐glutamic acid) (γ‐PGA) were prepared by the freeze drying method and thermally crosslinked to suppress hydrogel deformation in water. The physical properties, swelling, and drug‐diffusion behaviors were characterized for the hydrogels. In the equilibrium swelling study, PVA/γ‐PGA hydrogels shrunk in pH regions below the pKa (2.27) of γ‐PGA, whereas they swelled above the pKa. In the drug‐diffusion study, the drug permeation rates of the PVA/γ‐PGA hydrogels were directly proportional to their swelling behaviors. The cytocompatibility test showed no cytotoxicity of the PVA/γ‐PGA hydrogels for the 3T3 fibroblast cell lines. The results of these studies suggest that hydrogels prepared from PVA and γ‐PGA could be used as orally administrable drug‐delivery systems. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

13.
A novel acetylated anhydroglucose oligomer (AGU‐oligomer), prepared by acid catalyzed transglycosidation of potato starch triacetate and ethylene glycol, was used as a multifunctional coinitiator for the ring‐opening polymerization of ε‐caprolactone (ε‐CL). The polymers were synthesized using different weight ratios of the starting materials and were characterized by NMR, SEC, and MALLS. The results confirmed the expected P(AGU/CL) polymer structure, namely a ‘comb‐like’ graft‐copolymer having the AGU oligomer as backbone with PCL grafts of variable chain lengths (LCL = 4–21). Thermal and mechanical properties of graft‐copolymers with different ε‐CL block lengths were examined. By changing the graft length, crystallinity was controlled and amorphous polymers were obtained with AGU‐oligomer contents higher than 50 wt %. The tensile properties varied with the composition and a copolymer having 40 wt % of AGU‐oligomer behaved like soft elastomer, showing high elongation at break. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1633–1641, 2006  相似文献   

14.
Enzymatic crosslinking was developed to prepare in situ forming poly(γ‐glutamic acid) (γ‐PGA) based hydrogel in this study. First, the precursor of poly(γ‐glutamic acid)–tyramine (γ‐PGA–Ty) was synthesized through the reaction of carboxyl groups from a γ‐PGA backbone with tyramine. The structure of the grafted precursor was confirmed by 1H‐NMR and Fourier transform infrared spectroscopy. After that, the crosslinking of the phenol‐containing γ‐PGA–Ty precursor was triggered by horseradish peroxidase in the presence of H2O2; this resulted in the formation of the γ‐PGA–Ty hydrogels. The equilibrium water content, morphology, enzymatic degradation rate, and mechanical properties of the hydrogels were characterized in detail. The data revealed that the well‐interconnected hydrogels had tunable water contents, mechanical properties, and degradability through adjustments of the composition. Furthermore, cell experiments proved the biocompatibility of the hydrogels by 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay. These characteristics provide an opportunity for the in situ formation of injectable biohydrogels as potential candidates in cell encapsulation and drug delivery. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42301.  相似文献   

15.
A novel soluble conjugated polymer, poly[(2,5‐diphenylene‐1,3,4‐oxadiazole)‐4,4′‐vinylene] (O‐PPV), containing an electron‐transporting group on the main chain of PPV, was synthesized according to HORNER mechanism. The oligo‐polymer with Mw = 1000 and Td = 270°C is soluble in chloroform and tetrahydrofuran. The photoluminescent (PL) properties were investigated using different concentrations of solid‐state O‐PPV/PEO blends absorption and selective excitation measurements. The results show that PL arises from interchain charge‐transfer states in solid‐state O‐PPV. Compared with the analogous single‐layer device constructed with PPV (ITO/PPV/Al), which emits two peaks at λ = 520 nm and 550 nm (shoulder), the electroluminescence (EL) spectrum of the device [ITO/O‐PPV (80 nm)/Al] is a broad peak at λmax = 509 nm. The quantum efficiency (0.13%) of the device ITO/O‐PPV/Al is much higher than that of the device ITO/PPV/Al, due to the introduction of the electron‐transporting group–oxadiazole units in the main chain of PPV. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3535–3540, 1999  相似文献   

16.
A double‐network (DN) hydrogel was prepared through the sequential photopolymerization of oligo(trimethylene carbonate) (TPT)‐block‐poly(ethylene glycol)‐block‐oligo(trimethylene carbonate) diarylate and methacrylated chitosan (CS–MA). The swelling behavior and mechanical properties of the hydrogels were tunable via the control of the concentration of CS–MA. Under physiological conditions, the fracture stress of the DN hydrogel reached 3.4 MPa; this was more than twice that of the corresponding TPT‐block‐poly(ethylene glycol)‐block‐TPT single network (1.6 MPa). At high ionic strength, the fracture stress of the DN hydrogel reached 6.4 MPa. The DN hydrogel exhibited good cytocompatibility, as revealed by a live–dead assay. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42459.  相似文献   

17.
A series of hydrolysis‐improved thermosensitive polyorganophosphazenes with α‐amino‐ω‐methoxy‐poly(ethylene glycol) (AMPEG) and amino acid esters (AAEs) of ‘N,N‐systems’ was synthesized, and their properties were evaluated in comparison with the thermosensitive polyorganophosphazenes with methoxy‐poly(ethylene glycol) (MPEG) and AAEs of ‘O,N‐systems’, by means of 31P NMR spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). Most of the present polymers showed a lower critical solution temperature (LCST) in the range 32.0–79.0 °C, depending on the kinds of AAE, length of AMPEG and the mol ratio of the two substituents. These polymers exhibited higher LCSTs and faster degradation rates than the MPEG‐based polymers. The aqueous solution of poly(ethyl glycinate phosphazene)‐graft‐poly(ethylene glycol) [NP(GlyEt)0.94(AMPEG350)1.06]n did not show an LCST, which is presumed to be due to its high hydrophilicity, in contrast to [NP(GlyEt)1.01(MPEG350)0.99]n which showing an LCST at 77.5 °C. On the other hand, the polymers with a high content of AAE or with hydrophobic amino acids such as L ‐aspartic acid and L ‐glutamic acid, have shown a similar LCST to those of the MPEG‐based polymers. The half‐lives (t1/2) for hydrolysis of [NP(AMPEG350)1.06(GlyEt)0.94]n at pH 5, 7.4 and 10 were 9, 16, and 5 days, respectively, which are almost 2.5 to 4 times faster than that of the MPEG‐based polymers. The LCST of the present N,N‐polymers has been shown to be more influenced by salts such as NaCl (‘salting‐out’ effect) and tetrapropylammonium bromide (TPAB) (‘salting‐in’ effect) compared with the ‘O,N‐system’. Such differences of the ‘N,N‐systems’ from the ‘O,N‐systems’ in thermosensitivity, hydrolysis behavior and salt effect seem to be due to the higher hydrophilicity of the amino group in AMPEG. Copyright © 2005 Society of Chemical Industry  相似文献   

18.
Hybrid block copolymers find applications in drug delivery, tissue engineering, biomimetics and bioimaging, amongst others, mainly due to their propensity to form phase‐separated microdomains as well as to the aggregation of their polypeptide segments. They not only enhance control over structure at the nanometre scale but also yield materials that can interface with various biosystems for different utilities. α‐Methoxy‐poly(ethylene glycol)‐block‐poly[?‐(benzyloxycarbonyl)‐l ‐lysine] hybrid block copolymers of varying degrees of polymerization, MPEGn‐b‐PLL(Z)m, were synthesized by N‐carboxyanhydride ring‐opening polymerization and characterized using infrared and NMR spectroscopy and gel permeation chromatography. Their secondary structures and bulk conformations were investigated using circular dichroism spectroscopy and wide‐angle X‐ray diffraction, respectively, whereas thermogravimetric analysis (TGA), derivative TGA and differential scanning calorimetry were employed for thermal analyses. The resulting block copolymers exhibited microphase separation and suppressed degrees of crystallinity with increasing l ‐lysine content and adopted α‐helix and β‐sheet secondary structures in aqueous milieu. The copolymers were also more thermally stable than their constituent homopolymers. Interestingly, the effects of the retention of the N?‐benzyloxycarbonyl moiety on polymer properties proved considerable. The hybrid block copolymers herein afforded hierarchical structures of potential utility in the biomedical and pharmaceutical fields. © 2012 Society of Chemical Industry  相似文献   

19.
The purpose of this study was to develop a poly(γ‐glutamic acid) (γ‐PGA)‐based hydrogel loaded with superoxide dismutase (SOD) to accelerate wound healing. First, γ‐PGA was modified with taurine (γ‐PGAS), and then the SOD‐loaded γ‐PGAS/γ‐PGA hydrogel (SOD‐PGAS/PGA‐H) was prepared by cross‐linking of ethylene glycol diglycidyl ether. The swelling behavior and water vapor transmission rate revealed that PGAS/PGA‐H could create a moist environment for wound surface. In vitro kinetics of SOD release showed that SOD released from PGAS/PGA‐H maintained high activity and SOD‐PGAS/PGA‐H effectively scavenged the superoxide anion. The results of our fibroblast proliferation experiments showed that PGAS/PGA‐H had good cytocompatibility. The effects of SOD‐PGAS/PGA‐H on wound healing were examined in a Type I diabetic rat model with full‐thickness wounds. Twenty‐one days after grafted to wounds, SOD‐PGAS/PGA‐H exhibited a higher rate of wound healing than control group and showed increased collagen deposition and epithelialization. SOD‐PGAS/PGA‐H seems to promote better wound healing and thus might be a promising candidate for wound healing management. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42033.  相似文献   

20.
The fabrication of honeycomb‐patterned films from amphiphilic poly(L ‐lactide)‐block‐poly(ethylene glycol) (PLEG) in a high‐humidity atmosphere is reported. The influence of the solution concentration on pattern formation was investigated. Moreover, by comparing the different conditions of fabricating regular structures between PLEG and poly(phenylene oxide), the mechanism of the regular pattern formation was studied. Finally, by adding sodium dodecylsulfate to a concentrated solution of 1 g L?1 PLEG? CHCl3 which otherwise could not form regular pores, we found that regular pores could be obtained. The PLEG honeycomb films are expected to be of use in cell culture, tissue engineering and many other areas. Copyright © 2007 Society of Chemical Industry  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号