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1.
A triple‐helix‐forming collagen model peptide, (prolyl‐trans‐4‐hydroxyprolyl‐glycyl)10 [(Pro‐Hyp‐Gly)10], and a thermosensitive elastin‐derived pentapeptide, valyl‐prolyl‐glycyl‐valyl‐glycyl (Val‐Pro‐Gly‐Val‐Gly), were copolymerized in various mole ratios using 1‐ethyl‐3‐(3‐dimethylaminopropyl)‐carbodiimide hydrochloride and 1‐hydroxybenzotriazole in dimethyl sulfoxide at 20 °C. All of the obtained polypeptides have molecular weight higher than 103 and contain a triple‐helical structure, and showed an inverse phase transition from transparent solution to turbid suspension in response to a rise in temperature. The lower critical solution temperature of the polypeptide solution decreased upon increasing the content of Val‐Pro‐Gly‐Val‐Gly. Furthermore, polypeptides containing 82–86 mol % of Val‐Pro‐Gly‐Val‐Gly in composition showed reversible gel formation, suggesting that (Pro‐Hyp‐Gly)10 acts as a hydrated unit and Val‐Pro‐Gly‐Val‐Gly acts as a thermosensitive crosslinking point. These biodegradable thermosensitive polypeptides may be useful for biomedical applications, including, as a scaffold for tissue regeneration. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6048–6056, 2005  相似文献   

2.
The four ternary limiting isotherms of the system K+− NH4+ CrO4−− SO4−− H2O are given for 25° C. In the systems K2SO4 (NH4)2SO4 H2O and K2SO4 K2CrO4 H2O only one solid phase has been encountered; both systems belong to the type I of the ROOZEBOOM classification. A miscibility gap is present in the systems (NH4)2CrO4 K2CrO4 H2O and (NH4)2CrO4 (NH4)2SO4 H2O; they belong to ROOZEBOOM'S type V.  相似文献   

3.
The molecular structure of the phase—stable at room temperature—for the polymer with formula [ p C6H4 COO p C6H3(R) p C6H3(R) OOC p C6H4 O (CH2)10O ]x, with R =  CH2 CHCH2, is reported. The cell is hexagonal (a = b = 13.43 Å, c = 33.3 Å, γ = 120°), space group P63, six chains per unit cell (dcalcd = 1.23 g cm−3). The six chains are packed together to give a bundle with the center of mass set at the origin of the unit cell. The allyl groups are placed inside the bundle, thus explaining the unexpected reactivity of the double bonds to give crosslinking when fiber samples are annealed in the solid state. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1601–1607, 1999  相似文献   

4.
Tuning the secondary structure of polypeptide is an effective strategy to modulate the assembly behaviors of polypeptide‐based copolymers. In this study, ring‐opening polymerization of l ‐alanine (Ala) and γ‐benzyl‐l ‐glutamate (BLG) N‐carboxyanhydrides was adopted using mPEG‐NH2 as the initiator to prepare mPEG‐poly(l ‐alanine‐co‐γ‐benzyl‐l ‐glutamate) (PEAB) copolymers with various Ala to BLG ratios. 1H NMR spectra and GPC test confirmed their well‐defined chemical structures. FT‐IR spectra indicated that at the powder state, all copolymers adopted both β‐sheet and αhelical conformations. With the content of PBLG increased, the crystallization temperature and melting points of PEAB copolymers first rose then fell indicated by DSC curves. The self‐assembly of PEAB copolymers in dilute aqueous solution studied by DLS, TEM and circular dichroism spectra showed that PEAB copolymers self‐assembled into nanostructures with diverse morphologies and sizes due to distinct polypeptide conformations. Rheological analysis indicated that the alteration of the polypeptide composition can effectively modulate the modulus of PEAB assemblies in concentrated solutions. In all, copolymerization of two hydrophobic amino acid N‐carboxyanhydrides into the polypeptide block maybe an effective approach for modulating the assembly properties of PEGylated polypeptide. Besides, nanosilver‐encapsulated PEA or PEAB hydrogel showed promising antibacterial effect against Staphylococcus aureus and Bacillus subtillis. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1512–1523  相似文献   

5.
RuH2(PPh3)4 catalyzed Tishchenko type polyaddition of terephthal-aldehyde gives aromatic polyester ( 1 ), which contains three structural units, [OCH2 C6H4 CH2O] ( 1a ), [OCH2 C6H4 CO] ( 1b ), and [CO C6H4 CO] ( 1c ). 1H-NMR spectrum shows the presence of the three units in a 1 : 2 : 1 ratio. Isophthalaldehyde also undergoes similar polyaddition to give another aromatic polyester ( 2 ), while 1,12-dodecanedial gives an aliphatic polyester ( 3 ) containing the following structural units: [OCH2 (CH2)10 CH2O] ( 3a ), [OCH2 (CH2)10 CO] ( 3b ), and [CO (CH2)10 CO] ( 3c ). The above polymers have Mn of 2.7 × 103−5.4 × 103 and Mw of 4.3 × 103 − 9.7 × 103, respectively. Mixtures of terephthalaldehyde and 1,12-dodecanedial produce copolymers, which contain the units 1a–1c and 3a–3c in a random sequence. In the copolymerization, terephthalaldehyde shows a strong tendency to give 1c units, whereas 1,12-dodecanedial predominantly affords 3a units. SmI2 also catalyzes polyaddition of terephthalaldehyde to give the corresponding polyester with Mn of 1.7 × 103 and Mw of 3.7 × 103, respectively. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1265–1273, 1997  相似文献   

6.
In this study, the seGVB method was implemented for the N H bonding system, specifically for hydrogen‐bonded ammonia complexes, and the model well reproduces the MP2 geometries and energetics. A comparison between the ammonia dimer and water dimer is given from the viewpoint of valance‐bond structures in terms of the calculated bond energies and pair–pair interactions. The linear hydrogen bond is found to be stronger than the bent bonds in both cases, with the difference in energy between the linear and cyclic structures being comparable in both cases although the NH bonds are generally weaker. The energy decomposition clearly demonstrates that the changes in electronic energy are quite different in the two cases due to the presence of an additional lone pair on the water molecule, and it is this effect which leads to the net stabilization of the cyclic structure for the ammonia dimer. Proton‐transfer profiles for hydrogen‐bonded ammonia complexes [NH2 H NH2] and [NH3 H NH3]+ were calculated. The barrier for proton transfer in [NH3 H NH3]+ is larger than that in [NH2 H NH2], but smaller than that in the protonated water dimer. The different bonding structures substantially affect the barrier to proton transfer, even though they are isoelectronic systems. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 73: 357–367, 1999  相似文献   

7.
A new polymer (polyalcohol) was synthesized by hydrogenation of an ethylene carbon monoxide (CO) copolymer produced by a radical method with a catalyst and H2. The Ru/α-alumina catalyst systems showed an excellent activity for hydrogenation of the radical copolymer of CH2CH2 and CO. Films prepared by melting and pressing the synthesized polyalcohol had a high gas barrier property and high tensile modulus. This new polymer has hydroxymethylenic units [ CH(OH) ] and ethylenic units [ CH2CH2 ] in its molecular structure. The new functional polymer poly(hydroxymethylene-co-ethylene),  [ CH(OH) ]n[ CH2CH2 ]m , is amorphous and has excellent and important properties as a high oxygen gas barrier film for wrapping and storage. This may be attributed to the new structure of poly(hydroxymethylene-co-ethylene) (PHME as an IUPAC name), or ethylene methine alcohol copolymer (EMOH as a generic name), compared to the other ethylene vinyl alcohol copolymer (EVOH as a generic name),  [ CH2CH2 ]m [ CH2CH(OH) ]n , which is used as one of the highest gas barrier polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 889–900, 1998  相似文献   

8.
Poly(γ‐methyl L ‐glutamate)s with Ser, His, Asp, and Glu residues at the amino terminal as the serine protease catalytic site were prepared. The number‐average degree of polymerization of the polypeptides was 51. A dipalmitoylphosphatidylcholine monolayer containing the polypeptides was formed at the air–water interface and was transferred onto gold‐deposited glass plates. The binding of N‐acetyltyrosine ethyl ester, a typical substrate of the serine protease, to the monolayer was characterized by surface plasmon resonance measurements. The four‐polypeptide–lipid monolayer system conditioned on an aqueous solution containing the substrate N‐acetyltyrosine ethyl ester exhibited Langmuir‐type binding of the substrate. Its binding constant of 6.1 × 104 M−1 was about 20 times larger than that observed for a monolayer prepared on pure water. The behavior may have arisen from a substrate‐induced rearrangement of the four kinds of polypeptides in the monolayer, forming a substrate‐binding structure similar to that found in serine protease. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2186–2191, 2000  相似文献   

9.
Stimuli‐responsive polypeptides are receiving much attention for drug delivery systems and tissue engineering scaffolds; however, it is challenging to construct multiple‐responsive polypeptides and one‐component polymeric hydrogels. Herein, a novel type of triple redox/temperature‐responsive diselenide‐containing poly(methoxydiethylene glycol‐l ‐glutamate) homopolypeptide was facilely synthesized by selenocystamine‐initiated ring‐opening polymerization in DMF at 30 °C, and their chemical structures and physical properties were fully characterized by means of 1H NMR, GPC, FT‐IR, WAXD, and CD. They self‐assembled into spherical micelles in aqueous solution, which possess a lower critical solution temperature, redox‐responsiveness inherited from diselenide bond, and the triple stimuli‐sensitive self‐assembly behaviors, as characterized by means of turbidity, DLS, TEM, and zeta potential measurements. The diselenide‐containing homopolypeptides formed supramolecular hydrogels at room temperature, exhibiting a thermal gel–sol transition. The rheological tests evidence that the mechanical modulus of the hydrogel is independent of angular frequency within 100 rad/s and at 25 °C, in which the storage modulus of G′ is order of magnitude greater than the loss modulus of G″, displaying a solid‐like elastic behavior. Moreover, the mechanical modulus of the hydrogel can be tuned by changing the chain length of the homopolypeptide, the 10‐mM 1,4‐dithiothreitol (DTT) reduction, and 1 mM H2O2 oxidation, respectively. Consequently, this work provides a simple strategy to fabricate triple‐stimuli responsive polypeptide micelles and one‐component hydrogels. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1067–1077  相似文献   

10.
A study of gas transport properties of novel polynorbornenes with increasing length of an aliphatic pendant group R (CH3 , CH3(CH2)3 , CH3(CH2)5 , CH3(CH2)9 ) has been performed. These polymers were synthesized using novel organometallic complex catalysts via an addition polymerization route. This reaction route maintained the bridged norbornene ring structure in the final polymer backbone. Gas permeability and glass transition temperature were found to be higher than those for polynorbornenes prepared by ring-opening metathesis and reported in the literature. It was shown that for noncondensable gases such as H2 and He the selectivity over N2 decreased when the length of the pendant group increased, but remained relatively stable for the more condensable gases (O2 and CO2). The permeability coefficient is correlated well to the inverse of the fractional free volume of the polymers. The more condensable gases showed a deviation from this correlation for the longest pendant group, probably due to an increase of the solubility effect. This polymer series demonstrated a simultaneous increase in permeability and selectivity, uncommon for polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 797–803, 1998  相似文献   

11.
The reactions of 3,3′‐diaminobenzidine with 1,12‐dodecanediol in 1 : 1–1:3 molar ratios in the presence of RuCl2(PPh3)3 catalyst give poly(alkylenebenzimidazole), [ (CH2)11 O (CH2)11 Im / (CH2)10 Im ]n (Im: 5,5′‐dibenzimidazole‐2,2′‐diyl) (Ia‐Id) in 71–92% yields. The relative ratio between the [(CH2)11 O (CH2)11 Im ] unit (A) and the [‐ (CH2)10 Im ] unit (B) in the polymer chain varies depending on the ratio of the substrates used. The polymer Ia obtained from the 1 : 3 reaction contains these structural units in a 98 : 2 ratio. The polymers are soluble in polar solvents such as DMF (N,N‐dimethylformamide), DMSO (dimethyl sulfoxide), and NMP (N‐methyl‐2‐pyrrolidone) and have molecular weights Mn (Mw) of 4,200–4,800 (4,800–6,500) by GPC (polystyrene standard). The polymerization of the diol and 3,3′‐diaminobenzidine in higher molar ratios leads to partial cross‐linking of the resulting polymers Ie and If via condensation of imidazole NH group with CH2OH group. Similar reactions of 3,3′‐diaminobenzidine with α,ω‐diols, HO(CH2)mOH (m = 4–10), in a 1 : 3 molar ratio give the polymers containing [ (CH2)m−1 O (CH2) m−1 Im ] and [ (CH2) m−2 Im ] units with partial cross‐linked structures. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1383–1392, 1999  相似文献   

12.
《Electroanalysis》2004,16(17):1407-1412
A three‐step sequential self‐assembly procedure was applied in preparing gold electrodes modified in a stable and controlled way by a monolayer of thiolated β‐cyclodextrin (β‐CD), with methylene blue (MB) included in its cavity as the active component of the monolayer, and octanethiol as the nonelectroactive spacer blocking the electrode surface not occupied by β‐CD. MB acted as a mediator of electrons with respect to a solution soluble analyte, H2O2, and provided electrical contact between the electrode and solution resident enzyme, laccase, catalyzing reduction of oxygen to water.  相似文献   

13.
Water‐soluble supramolecular polymers, especially made up of biomolecules, are ideally suited to build new biomaterials that can mimic or interact with dynamic, biological environments. Here, two derivatives from thymine (T), that is N‐[2‐(3,4‐Dihydro‐5‐methyl‐2,4‐dioxo‐1(2H)‐pyrimidinyl)acetyl]‐L‐phenylalanine (T‐phe) and N‐(2‐Aminoethyl)‐3,4‐dihydro‐5‐methyl‐2,4‐dioxo‐1(2H)‐pyrimidineacetamide (T‐NH2) were synthesized. Then the optimal condition for self‐assembly of T‐phe and T‐NH2 driven by melamine (M) was explored. It was observed that M/T kept at 1:3 with equivalent T‐phe and T‐NH2 under neutral environment resulted in long fibers (>1 μm) with extremely high aspect ratios, which suggested that electrostatic and π‐stacking interactions could be effectively orchestrated by hydrogen bonds to direct the hierarchical assembly. Furthermore, hydrogels were spontaneously generated with a concentrated solution of T‐phe, T‐NH2, and M due to the fibril entanglement. Given its biomimetic nature and efficient self‐assembly process, this newly developed supramolecular polymer stacked by tetrameric structures represented an innovative concept and pathway for novel bio‐inspired materials. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 789–796  相似文献   

14.
A very cheap catalyst, a silica-supported polystannazane-copper complex (abbreviated as SiO2 Sn N Cu) was prepared by the reaction of the silica-supported polystannazane ligand with CuCl2 in ethanol. The results showed that SiO2 Sn N Cu can catalyze the oxidation of methanol to formaldehyde in high yield at mild conditions, i.e. at 40°C and 1 atm of oxygen. The catalyst could be recovered and could catalyze the reaction repeatedly.  相似文献   

15.
Ethylene polymerization reactions with many Ziegler–Natta catalysts exhibit several features which differentiate them from polymerization reactions of α-olefins: a relatively low ethylene reactivity, higher polymerization rates in the presence of α-olefins, a high reaction order with respect to ethylene concentration, and strong reversible rate depression in the presence of hydrogen. A detailed kinetic analysis of ethylene polymerization reactions (see ref. 1 ) provided the basis for a new reaction scheme which explains all these features by postulating the equilibrium formation of a Ti C2H5 species with the H atom in the methyl group β-agostically coordinated to the Ti atom in an active center. This mechanism predicts that the β-agostically stabilized Ti C2H5 groups can decompose in the β-hydride elimination reaction with expulsion of ethylene and the formation of a Ti H bond even in the absence of hydrogen in the reaction medium. If D2 is used as a chain transfer agent instead of H2, the mechanism predicts the formation of deuterated ethylene molecules, which copolymerize with protioethylene. To prove this prediction, several ethylene homopolymerization reactions were carried out with a supported Ziegler–Natta titanium-based catalyst in the presence of large amounts of D2. Analysis of gaseous reaction products and polymers confirmed the formation of several types of deuterated ethylene molecules and protio/deuterioethylene copolymers, respectively. In contrast, a metallocene catalyst, Cp2ZrCl2 MAO, does not exhibit these kinetic features. In the presence of deuterium, it produces only DCH2 CH2 (CH2 CH2)x CH2 CH2D molecules. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4273–4280, 1999  相似文献   

16.
Polymer dielectrics generally have comparatively low dielectric constant, operating temperatures, and/or high dielectric loss, which limits their uses especially in harsh environment. In this article, a novel trilayered nanocomposite film (TNF) was constructed via solution‐casting and, subsequently, hot‐pressing process, which was composed of two outer layers of polyvinylidene fluoride (PVDF, high dielectric constant) and a middle layer of polymethyl methacrylate (PMMA, high glass transition temperature, Tg). The two outer layers of TNF were filled with barium strontium titanate nanoparticles to further increase the dielectric constant of PVDF. The PMMA in the middle layer was used to largely suppress the dielectric loss and simultaneously improve the temperature tolerance of TNF. Results show that the introduction of PMMA induced oriented crystal formation in the interface regions between PVDF and PMMA components. Moreover, most of the impurity ions were dramatically immobilized by partly oriented α crystals and high Tg PMMA layer until the temperature exceeded 120 °C. Therefore, the TNFs showed a high‐temperature tolerance and notably decreased loss, which are promising for widespread energy storage applications where harsh working conditions are present. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1043–1052  相似文献   

17.
Cu doped MoSi2N4 monolayer (Cu-MoSi2N4) was firstly proposed to analyze adsorption performances of common gas molecules including O2, N2, CO, NO, NO2, CO2, SO2, H2O, NH3 and CH4 via density functional theory (DFT) combining with non-equilibrium Green's function (NEGF). The electronic transport calculations indicate that Cu-MoSi2N4 monolayer has high sensitivity for CO, NO, NO2 and NH3 molecules. However, only NH3 molecule adsorbs on the Cu-MoSi2N4 monolayer with moderate strength (−0.55 eV) and desorbs at room temperature (2.36×10−3 s). Thus, Cu-MoSi2N4 monolayer is demonstrated as a potential NH3 sensor.  相似文献   

18.
Oxidative polymerization of pyrrole has been studied using FeCl3 or (NH4)2S2O8 (APS) as oxidant, ethylhydroxyethylcellulose (EHEC) as a steric stabilizer and water or aqueous ethanol as the dispersion medium. Transmission electron micrographic images of the particles from the as-prepared dialysed dispersions in aqueous ethanol show small as well as large particles (about a decade larger) when FeCl3 is used as the oxidant but only large particles when APS is used as the oxidant. Small particles are not found when the dispersions are prepared in water, irrespective of the oxidant used. The particle size decreases with an increase in molecular weight of the stabilizer for the same stabilizer concentration. The minimum amount of stabilizer required to support dispersion polymerization decreases upon increasing the alcohol content of the medium. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3723–3729, 1999  相似文献   

19.
Polymer electrolytes, (PEO:LiClO4)+x IL (1‐Buty‐3‐methylimidazolium hexafluorophosphate) with varying concentration of IL; x = 0,5,10,15,20 wt % have been prepared by solution cast technique and characterized by X‐Ray diffraction, differential scanning calorimetery, FTIR, conductivity and dielectric relaxation measurements in the frequency range of 100 Hz–5 MHz. Temperature dependence of relaxation frequency and conductivity were found to be typical of thermally activated process both at T > Tm and T < Tm. Composition dependence of conductivity, dielectric relaxation, and degree of crystallinity has also been studied. On addition of IL, the degree of crystallinity after a decrease at 5 wt % IL increases slightly at 10 wt % and then finally decreasing. Variation of conductivity and relaxation frequency with composition could only be partly explained on the basis of variation of degree of crystallinity. An additional feature of ion–ion interaction (contact ion pair formation between IL or salt cations and their associated anions) has been invoked which was supported by FTIR studies. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011  相似文献   

20.
This present work discusses dual-blend green polymer electrolyte (GPE)–based natural polymers, composed of carboxyl methylcellulose (CMC) and chitosan (CS), created by introducing various compositions of ammonium bromide (NH4Br) as a dopant in the system. These GPEs were successfully prepared by the solution casting technique and characterized using electrical impedance spectroscopy (EIS). From EIS measurement, the highest room-temperature conductivity is 1.21 × 10?5 Scm?1 for the sample containing 20 wt.% of NH4Br. Plot of the temperature dependence of the GPEs revealed that the system obeys the Arrhenius rule and was thermally assisted. Besides that, dielectric studies were also conducted and the data were analyzed using complex permittivity, ?*, and complex electrical modulus, M*, to determine the sample with the highest conductivity value. Thus, this study confirmed non-Debye behavior in the sample.  相似文献   

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