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1.
Interpenetrating polymer networks (IPN), either semi‐IPN (s‐IPN) or full IPN, based on a natural polymer tannic acid (TA) and synthetic poly(acrylamide) (p(AAm)) were prepared by incorporation of TA during p(AAm) hydrogel film preparation with and without crosslinking of TA simultaneously. The synthesis of p(AAm/TA) s‐IPN and IPN hydrogels with different amounts of TA were prepared by concurrent use of redox polymerization and epoxy crosslinking. The p(AAm)‐based hydrogels were completely degraded at 37.5°C within 9 and 2 days at pHs 7.4 and 9, respectively. Biocompatibility of p(AAm), s‐IPN, and IPN were tested with WST assay and double staining, they had 75% cell viability up to almost 20 μg mL?1 concentration against L929 fibroblast cell. Antioxidant properties of IPN and s‐IPN hydrogels were investigated with FC and ABTS? methods. Antimicrobial properties of TA‐containing s‐IPN, and IPN hydrogels were determined against three common bacterial strains, Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 6538, and Bacillus subtilis ATCC 6633, and it was found that p(AAm/TA)‐based s‐IPN and IPN hydrogels are effective antimicrobial and antioxidant materials. Moreover, almost up to day‐long linear TA release profiles were obtained from IPN and s‐IPN hydrogels in phosphate buffer solution at pH 7.4 at 37.5°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41876.  相似文献   

2.
Thermogravimetric analysis (TGA) and devolatilization kinetics of melon seed shell (MSS) at different particle sizes (150?µm and 500?µm) and at different heating rates (10, 15, 20, and 25?°C/min) were investigated with the aid of TGA. The results of the TGA analysis show that the TGA curves corresponding to the first and third stages for 150?µm particle sizes exhibited some bumps that developed at the first and third stages of pyrolysis. It was also observed that at constant heating rate, the maximum peak temperature increases as the particle sizes increase from 150 to 500?µm, whereas 500?µm particle sizes exhibited higher peak temperatures compared to 150?µm particle sizes. The resulting TGA data were applied to the Kissinger (K), Kissinger–Akahira–Sunose (KAS) and Flynn–Wall–Ozawa (FWO) methods and kinetic parameters (activation energy, E and frequency factor, A) were determined. The E and A obtained using K method were 74.27?kJ mol?1 and 3.84?×?105?min?1 for 150?µm particle size, whereas for 500?µm particle size were 97.12?kJ mol?1 and 3.74?×?107?min?1, respectively. However, the average E and A obtained using KAS and FWO methods were 82.35?kJ mol?1, 1.29?×?107?min?1, and 88.50?kJ mol?1, 1.32?×?107?min?1 for 150?µm particle sizes. While for 500?µm particle sizes, the E and A were 108.46?kJ mol?1, 3.14?×?109?min?1, and 113.05?kJ mol?1, 7.56?×?109?min?1, respectively. It was observed that E and A calculated from FWO and KAS methods were very close and higher than that obtained by K method. It was observed that the minimum heat required for the cracking of MSS particles into products is reached later at higher peak temperatures since the heat transfer is less effective as they are at lower peak temperatures.  相似文献   

3.
Enhancing thermal conductivity of polymeric nanocomposites remains a great challenge because of the poor compatibility between nanofillers and the polymeric matrix and the aggregation effect of nanofillers. We report the enhanced thermal conductivity of poly(lactic acid) (PLA)‐based nanocomposites by incorporation of graphite nanoplatelets functionalized by tannic acid. Graphite nanoplatelets (GNPs) were noncovalently functionalized with tannic acid (TA) by van der Waals forces and π–π interaction without perturbing the conjugated sp2 network, thus preserving the high thermal conductivity of GNPs. PLA‐based nanocomposites with different contents of TA‐functionalized GNPs (TA‐GNPs) were prepared and characterized, and the influences of TA‐GNPs content on the morphologies, mechanical properties, and thermal properties of the composites were investigated in detail. TA‐GNPs remarkably improved the thermal conductivity of PLA up to 0.77 W/(m K), showing its high potential as a thermally conductive filler for polymer‐based nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46397.  相似文献   

4.
BACKGROUND: Hexyl laurate has been applied widely in cosmetic industries and is synthesized by chemical methods with problems of cost, environmental pollution, and by‐products. In this study, Lipozyme® IM77 (from Rhizomucor miehei) was used to catalyze the direct‐esterification of hexanol and lauric acid in a solvent‐free system by utilizing a continuous packed‐bed reactor, wherein the aforementioned difficulties could be overcome. Response surface methodology (RSM) and three‐level‐three‐factor Box‐Behnken design were employed to evaluate the effects of synthesis parameters, such as reaction temperature (45–65 °C), mixture flow rate (0.25–0.75 mL min?1) and concentration of lauric acid (100–300 mmol L?1) on the production rate (µmol min?1) of hexyl laurate by direct esterification. RESULTS: The production rate was affected significantly by the mixture flow rate and lauric acid concentration. On the basis of ridge‐max analysis, the optimum synthesis conditions for hexyl laurate were as follows: 81.58 ± 1.76 µmol min?1 at 55 °C, 0.5 mL min?1 flow rate and 0.3 mol L?1 lauric acid. CONCLUSION: The lipase‐catalyzed synthesis of hexyl laurate by Lipozyme® IM‐77 in a continuous packed‐bed bioreactor and solvent‐free system was successfully developed; optimization of the reaction parameters was obtained by Box–Behnken design and RSM. Copyright © 2008 Society of Chemical Industry  相似文献   

5.
A novel polymer bearing coumarin pendants of 4‐allyloxy‐2H‐chromen‐2‐one (ACO) was synthesized by atom transfer radical polymerization (ATRP) in toluene at 110°C using 2‐Bromoisobutyryl bromide (BIBB), Cu (I) Br, and 2,2′‐bipyridyl (bpy) as initiator, catalyst, and ligand, respectively. The most appropriate molar concentration ratio of [ACO] : [BIBB] : [Cu (I) Br] : [bpy] was found to be 40 : 1 : 1 : 2 for controlled polymerization. Successful chain extension polymerization of poly (4‐allyloxy‐2H‐chromen‐2‐one) (PACO) confirms the livingness of the process. The activation energy (Ea) (76.26 kJ mol?1) and enthalpy of activation (ΔH?) (73.07 kJ mol?1) were in good agreement to each other proving the feasibility of the reaction and negative value of entropy of activation (ΔS?) (?320 J mol?1 K?1) supported the highly restricted movement of reacting species in transition state during polymerization. Initial polymer decomposition temperature of PACO was found to be 130°C. SEM analysis revealed that polymer surface is not smooth with pointed rod like shapes. The polymer/Ag nanocomposite was synthesized and examined in view of antibacterial effect against Enterococcus faecalis, Staphylococcus aureus, Escherichia coli, Proteus mirabilis, and Klebsiella pneumonae. PACO and its Ag nanocomposite (PACON) have been found to be active selectively against bacterial pathogen E. fecalis with minimum inhibitory concentration of 50 and 32 μg mL?1, respectively. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

6.
A one‐phase synthesis of AuNPs‐polymer nanocomposites using HAuCl4 as the precursor is reported in this article. A flexible polymer, poly(2‐(4‐(di(1H‐indol‐3‐yl)methyl)phenoxy) ethyl methacrylate) (PMPEM), containing indole groups on the side chain was utilized as both a reducing reagent and soft template in the system. The PMPEM‐Au nanocomposites with three different sizes of AuNPs (25–50, 2, and 5 nm) were obtained just through choosing different solvents such as toluene, tetrahydrofuran (THF), and N,N‐dimethylformamide, respectively. Nanocomposites including the size of 25–50 and 2 nm AuNPs showed strong NLO absorption and refraction behaviors. The nonlinear refractive index n2 of PMPEM‐Au nanocomposites prepared in toluene and THF were 9.35 × 10?11 and 1.85 × 10?10 m2/W, third‐order susceptibility χ(3) were 2.55 × 10?11 and 4.26 × 10?11 esu, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

7.
A novel lead compound for inhibition of the antibacterial drug target, glutamate racemase (GR), was optimized for both ligand efficiency and lipophilic efficiency. A previously developed hybrid molecular dynamics–docking and scoring scheme, FERM‐SMD, was used to predict relative potencies of potential derivatives prior to chemical synthesis. This scheme was successful in distinguishing between high‐ and low‐affinity binders with minimal experimental structural information, saving time and resources in the process. In vitro potency was increased approximately fourfold against GR from the model organism, B. subtilis. Lead derivatives show two‐ to fourfold increased antimicrobial potency over the parent scaffold. In addition, specificity toward B. subtilis over E. coli and S. aureus depends on the substituent added to the parent scaffold. Finally, insight was gained into the capacity for these compounds to reach the target enzyme in vivo using a bacterial cell wall lysis assay. The outcome of this study is a novel small‐molecule inhibitor of GR with the following characteristics: Ki=2.5 μM , LE=0.45 kcal mol?1 atom?1, LiPE=6.0, MIC50=260 μg mL?1 against B. subtilis, EC50, lysis=520 μg mL?1 against B. subtilis.  相似文献   

8.
This study presents an automatic batch mode (i.e., off‐line) multi‐angle light scattering (MALS) method for the molecular weight (MW) determination of ultra‐high MW (UHMW) polyacrylamide (PAM) homopolymer and acrylamide copolymers. This method combines a MALS detector with a sample dilution and injection device that automatically delivers a concentration gradient from a stock solution. The automation makes it practical to use the batch MALS method for routine MW analysis of UHMW polymers. The automatic batch MALS analyses of a series of poly(sodium acrylate‐co‐acrylamide) (30:70 mol %) in 1.0M NaCl show a non‐linear Mark‐Houwink relation in the MW range of 1.2 × 106 to 12.6 × 106 g mol?1. The entire molecular weight range can be fit with a quadratic relation or two linear equations, one for molecular weight up to 5.3 × 106 g mol?1 and the other from 5.3 × 106 to 12.6 × 106 g mol?1. The non‐linear Mark‐Houwink relation suggests that the extrapolation of the Mark‐Houwink equation beyond the measured MW range into the UHMW regions can significantly overestimate the MW of the UHMW polymers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43748.  相似文献   

9.
A series of novel multi‐arm azide copolymers (POGs) with the same hyperbranched poly[3‐ethyl‐3‐(hydroxymethyl)oxetane] core (PEHO‐c) and different content of linear glycidyl azide polymer shell (GAP‐s) have been synthesized by sequential cationic ring‐opening polymerization and azidation. Detailed structural information of these copolyethers was deduced from Fourier transform infrared, 1H NMR and inverse gated decoupled 13C NMR spectroscopies, matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry, gel permeation chromatography and elemental analysis. The molecular weight of POG having GAP‐s and PEHO‐c with a molar ratio 14.95:1 (Rs/c) was around 31 000 g mol?1, far above that of linear GAP (around 4000 g mol?1). The apparent viscosity and glass transition temperature (?51 to ?23 °C) decreased first and then slightly increased with increasing molecular weight. Thermal analysis revealed that all the obtained POGs exhibited excellent resistance to thermal decomposition up to 220 °C. Moreover, the energetic properties, investigated using oxygen bomb calorimetric measurements, indicated that the enthalpy of formation of the POGs was higher than that of general linear GAP, but similar to that of branched GAP under reasonable Rs/c. The compatibilities of the POGs with common materials used in solid propellants were studied using differential scanning calorimetry and the results indicated that the POGs had good compatibility with these materials. © 2017 Society of Chemical Industry  相似文献   

10.
RAFT polymerization of N‐vinyl pyrrolidone (NVP) has been investigated in the presence of chain transfer agent (CTA), i.e., prop‐2‐ynyl morpholine‐4‐carbodithioate (PMDC). The influence of reaction parameters such as monomer concentration [NVP], molar ratio of [CTA]/[AIBN, i.e., 2,2′‐azobis (2‐methylpropionitrile)] and [NVP]/[CTA], and temperature have been studied with regard to time and conversion limit. This study evidences the parameters leading to an excellent control of molecular weight and molar mass dispersity. NVP has been polymerized by maintaining molar ratio [NVP]: [PMDC]: [AIBN] = 100 : 1 : 0.2. Kinetics of the reaction was strongly influenced by both temperature and [CTA]/[AIBN] ratio and to a lesser extent by monomer concentration. The activation energy (Ea = 31.02 kJ mol?1) and enthalpy of activation (ΔH?= 28.29 kJ mol?1) was in a good agreement to each other. The negative entropy of activation (ΔS? = ?210.16 J mol‐1K‐1) shows that the movement of reactants are highly restricted at transition state during polymerization. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

11.
The present contribution describes an innovation in the copolymerization of cyclic monomers, ε‐caprolactam (ε‐CL) and 2,2‐dimethyltrimethylene carbonate (DTC), with ethyl diazoacetate (EDA). The characterizations of the obtained copolymers, poly(EA‐ran‐EDA‐ran‐ε‐CL) and poly(EA‐ran‐EDA‐ran‐DTC) (where EA refers to the ethyl acetate group from EDA after nitrogen release), were performed using 1H NMR and 13C NMR spectroscopies and size exclusion chromatography. Under optimized conditions, the copolymer of ε‐CL with EDA possessing a number‐average molar mass (Mn) of 1300 g mol?1 and dispersity of 2.12 as well as that of DTC with EDA with Mn of 8000 g mol?1 and dispersity of 1.47 were obtained. The incorporation of the azo group in the obtained copolymers was determined from the results of elemental analysis (3.30–10.22% nitrogen) and Fourier transform infrared spectroscopy. Furthermore, the thermal properties of the obtained copolymers were examined using differential scanning calorimetry. X‐ray diffraction results showed that the synthesized copolymers were amorphous. © 2014 Society of Chemical Industry  相似文献   

12.
Limited amount of isotactic polypropylene (iPP) is added to high‐density polyethylene (HDPE) containing 1% w/w an oxo‐biodegradable additive and extruded and converted to films. The films are put under UV irradiation for different periods of time. Irradiation of the films for 6 weeks imposes remarkable effects on viscosity average molecular weight (Mv) and carbonyl index (CI) of them. Mv decreases from 3.4 × 105 to 4.7 × 104 g mol?1 for neat HDPE films; from 3.1 × 105 to 3.3 × 104 g mol?1 for the films containing oxo compound, and from 1.5 × 105 to 2.6 × 104 g mol?1 for the films containing oxo compound and 1% w/w iPP. Carbonyl index of the neat HDPE films increases from 4 to 8.7 while for the sample containing only the oxo compound it increases from 4.5 to 7.3 and for the sample containing both oxo compound and iPP it decreases from 12.0 to 8.8. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) indicate more cracks and uniform degradation in the samples containing iPP and oxo compound. Thermogravimetric analysis (TGA/DTG) of the samples shows that the samples containing iPP and oxo compound have lower decomposition temperature after UV irradiation. Finally, it can be said that the presence of iPP in HDPE matrix containing oxo compound can improve HDPE oxo‐biodegradablity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45843.  相似文献   

13.
The effects of the extrusion rate on the morphological changes of poly(lactic acid) (PLA)/poly(vinyl alcohol) (PVA) blend through a capillary die were investigated. In this study, the extrusion rate or mass flow rate is altered from 0.5 g min?1 to 2 g min?1 with an increment of 0.5 g min?1. The PLA/PVA blend with a composition of 30/70 (wt %) exhibits a particle matrix morphology with dispersed PLA droplets within the PVA matrix. It is found that, the spherical or ellipsoidal dispersed PLA droplets are elongated and coalesced into rod‐like or longer ellipsoidal droplets when they pass through the capillary die. When the extrusion rate increases, the coalescence between the large PLA droplets occurs more intense. However, the changes of the extrusion rate have no strong effect on the coalescence of small droplets having diameter less than about 150 nm. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44257.  相似文献   

14.
Ultrafast preparation of branched poly(methyl acrylate) (BPMA) with high‐molecular weight through single electron transfer living radical polymerization (SET‐LRP) of inimer at 25°C has been attempted, atom transfer radical polymerization (ATRP) at 60°C was also carried out for comparison. Gas chromatography, proton nuclear magnetic resonance, and triple detection size exclusion chromatography were used to analyze these polymerizations. As expected, SET‐LRP system showed much faster polymerization rate than ATRP system, the calculated apparent propagation rate constants (kpapp) are 3.69 × 10?2 min?1 and 6.23 × 10?3 min?1 for SET‐LRP and ATRP system, respectively. BPMA with high‐molecular weight (Mw.MALLS = 86,400 g mol?1) compared with that in ATRP (Mw.MALLS = 61,400 g mol?1) has been prepared. POLYM. ENG. SCI., 54:1579–1584, 2014. © 2013 Society of Plastics Engineers  相似文献   

15.
The triblock energetic copolymer poly(lactic acid)‐block‐(glycidylazide polymer)‐block‐polystyrene (PLA‐b‐GAP‐b‐PS) was synthesized successfully through atom‐transfer radical polymerization (ATRP) of styrene and ring‐opening polymerization of d,l ‐lactide. The energetic macroinitiator GAP‐Br, which was made from reacting equimolar GAP with α‐bromoisobutyryl bromide, firstly triggered the ATRP of styrene with its bromide group, and then the hydroxyl group on the GAP end of the resulting diblock copolymer participated in the polymerization of lactide in the presence of stannous octoate. The triblock copolymer PLA‐b‐GAP‐b‐PS had a narrow distribution of molecular weight. In the copolymer, the PS block was solvophilic in toluene and improved the stability of the structure, the PLA block was solvophobic in toluene and served as the sacrificial component for the preparation of porous materials, and GAP was the basic and energetic material. The three blocks of the copolymer were fundamentally thermodynamically immiscible, which led to the self‐assembly of the block copolymer in solution. Further studies showed that the concentration and solubility of the copolymer and the polarity of the solvent affected the morphology and size of the micelles generated from the self‐assembly of PLA‐b‐GAP‐b‐PS. The micelles generated in organic solvents at 10 mg mL?1 copolymer concentration were spherical but became irregular when water was used as a co‐solvent. The spherical micelles self‐assembled in toluene had three distinct layers, with the diameter of the micelles increasing from 60 to 250 nm as the concentration of the copolymer increased from 5 to 15 mg L?1. © 2017 Society of Chemical Industry  相似文献   

16.
The isothermal kinetics of in vitro nicotinamide release from poly(acrylic‐co‐methacrylic acid) loaded xerogel into water was evaluated. The isothermal kinetics curves of nicotinamide release from poly(acrylic‐co‐methacrylic acid) xerogel were measured at different temperatures ranging from 296 K to 315 K. It was proven that the kinetics of nicotinamide release from poly(acrylic‐co‐methacrylic acid) xerogel was a kinetically complex process which was neither controlled by the processes of drug diffusion nor with the relaxation of the xerogel. The kinetic of nicotinamide release from poly(acrylic‐co‐methacrylic acid) may be described by the kinetics model of reversible first order chemical reaction and the apparent activation energy have value of Ea,M = 14.1 kJ mol?1 and preexponential factor ln(AM min?1) = 2.3. The rate constants of nicotinamide release ( ) and the rate constants of its reversible absorption reaction ( ) were calculated and found to fall within the range 0.019 min?1?0.033 min?1 for and 0.014 min?1?0.016 min?1 for . The value of activation energy for the nicotinamide releas, Ea.R =21.25 kJ mol?1, is significantly higher than the value for the process of nicotinamide absorption (Ea,A = 2.6 kJ mol?1). The rate of nicotinamide release was predetermined with the rate of nicotinamide molecules distribution between the hydrogel and surrounding solution. POLYM. ENG. SCI., 55:60–69, 2015. © 2014 Society of Plastics Engineers  相似文献   

17.
A generally applicable stoichiometric and kinetic model was developed for the polymerization of dimer fatty acids with ethylenediamine. The rate equations were second‐order before 90% conversion and were used between 405 and 475 K. The parameters of the rate equations were determined with nonlinear regression analysis. A comparison of the model predictions and the experimental data showed that the approach was useful in predicting the polymerization kinetics. The equilibrium constant changed from 3.175 to 7.311. The frequency factor and activation energy for the forward rate constant before 90% conversion were 2,716,894 kg mol?1 min?1 and 66.7 kJ mol?1, respectively. The equilibrium constant was independent of the temperature at frequency factor and activation energy values of 74.4 and 9.7 kJ mol?1, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2504–2513, 2004  相似文献   

18.
This article deals with the synthesis of an organic?inorganic hybrid molecularly imprinted poly(methacrylic acid‐trimethylolpropane trimethacrylate)/SiO2 combined with restricted access. Fourier Transform Infrared Spectroscopy, Transmission Electron Microscopy, Thermogravimetric Analysis, and textural data were used to characterize the structure of material. Higher selectivity was obtained for the molecularly imprinted polymer with restricted access when compared to nonimprinted polymer with restricted access, confirming the imprinting effect. The folic acid sorption for the polymers molecularly imprinted with restricted access, nonimprinted with restricted access, and molecularly imprinted, exhibited the following values of 5.6, 4.5, and 4.8 mg g?1, respectively. Kinetic experimental data were very well adjusted to Elovich and pseudo‐second‐order models, which suggest that the sorption of folic acid takes place in binding sites with different energies. The obtained values of enthalpy, entropy and Gibbs free energy of ?12.79 kJ mol?1, ?36.38 K?1 J mol?1, and ?1.76 kJ mol?1, respectively, showed that the sorption of folic acid onto molecularly imprinted polymer combined with restricted access occurs spontaneously, is of both exothermic and of physical nature with an increase of ordering at the solid?solution interface. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43463.  相似文献   

19.
Site‐specific incorporation of non‐standard amino acids (NSAAs) into proteins opens the way to novel biological insights and applications in biotechnology. Here, we describe the development of a high yielding cell‐free protein synthesis (CFPS) platform for NSAA incorporation from crude extracts of genomically recoded Escherichia coli lacking release factor 1. We used genome engineering to construct synthetic organisms that, upon cell lysis, lead to improved extract performance. We targeted five potential negative effectors to be disabled: the nuclease genes rna, rnb, csdA, mazF, and endA. Using our most productive extract from strain MCJ.559 (csdA? endA?), we synthesized 550±40 μg mL?1 of modified superfolder green fluorescent protein containing p‐acetyl‐L ‐phenylalanine. This yield was increased to ~1300 μg mL?1 when using a semicontinuous method. Our work has implications for using whole genome editing for CFPS strain development, expanding the chemistry of biological systems, and cell‐free synthetic biology.  相似文献   

20.
In this study, microcapsules containing fragrance oils as active agent were synthesized by interfacial thiol‐ene polymerization in oil‐in‐water emulsion. One water‐soluble dithiol and four oil‐soluble acrylates were used as “click”able monomers. The polymerization kinetics was studied by HPLC and 1H‐NMR. The size and morphology of the microcapsules were characterized by means of light scattering, optical microscope, and scanning electron microscope, and their thermal property was examined by TGA. The encapsulation efficiency and stability of the microcapsules were monitored at room temperature and 45 °C for 1 month. In general, this interfacial thiol‐ene polymerization was demonstrated to be a facile and efficient approach for fragrance microencapsulation with new and stable shell materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43905.  相似文献   

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