Preparation of novel UV-curable methacrylated urethane resins from a modified epoxy resin and isocyanatoethylmethacrylate (IEM)

Summary New UV curable methacrylated urethanes (PAPHEN-XIEM) were synthesized by substituting X percent (e.g., 10, 20, 30 %) of the total OH content of the PAPHEN-301 (Scheme 1) with isocyanatoethyl methacrylate (IEM). These resins were used alone (neat resin formulation) or as a mixture of 5, 10 and 13 % (w/w) respectively with methacrylated urethane prepolymer (PTHFUMA) in UV systems. For neat resin formulations, tensile strength and modulus values were observed to be inversely proportional with the modification degree of PAPHEN-301 as opposed to what is normally expected. This may be explained as a result of screening effect of increasing unsaturation. The water absorption capacities for neat resins and PTHFUMA-included formulations were decreased as the modification degree increased due to the replacement of hydrophilic OH groups of PAPHEN-301 by the hydrophobic methacrylate groups. TGA thermograms of neat resin formulation show that, initial weight loss temperatures are lower; possibly owing to the higher methacrylate content in the formulations. Received: 26 June 2001/Revised version: 5 April 2001/Accepted: 5 April 2001     

脱水蓖麻油酸环氧UV固化阴极电泳涂料的研制

脱水蓖麻油酸酯化改性环氧树脂,将其与二乙醇胺反应,而后产物在光引发剂和活性单体作用下制得UV固化阴极电泳涂料。研究了环氧树脂分子质量、催化剂种类及用量、反应温度对酯化反应的影响,探讨了酯化程度、胺开环率、活性单体的种类及用量对涂料稳定性及涂膜性能的影响。结果表明,选取环氧树脂E-44,酯化温度110℃,催化剂N,N-二甲基苄胺,添加质量分数0.8%～1%,酯化程度35%～40%,胺开环率≥60%,活性单体季戊四醇三丙烯酸酯质量分数15%～20%时,所制备的UV固化阴极电泳涂料涂膜固化快速完全,表面均匀丰满光亮,附着力好,耐溶剂性优。     

静电纺PU纳米纤维膜及其固定化酶的研究

采用静电纺丝技术制备聚氨酯纳米纤维膜,用壳聚糖进行亲水改性后固定柚苷酶,测定不同浓度的壳聚糖对纤维膜亲水改性下的载酶量和酶活力以及固定化柚苷酶在不同酶解温度、时间和pH条件下的酶活力。结果表明,当聚氨酯纺丝液质量分数为12%,接收距离为22 cm,纺丝电压为22 kV,注射的速率为0.5 mL/h,接收器滚轮转速为300 r/h的条件下,能够得到纤维样貌良好的纳米纤维膜;通过亲水改性,聚氨酯膜由疏水性变为亲水性,膜上接枝了作为亲水基团的羟基;壳聚糖浓度为0.5%时,聚氨酯膜上有最大的载酶量,为83.2 mg/g;同时固定化柚苷酶具有最高的相对酶活性,且固定化酶相较于游离酶在一定的温度、反应时间和pH下表现出更高的酶活性。     

Copper adsorption and enzyme immobilization on organosilane-glutaraldehyde hybrids as support

Summary New hybrids SiglutX (X=l to 3) were synthesized from silylant agents: (CH₃O)₃Si-R-NH₂ [R = −(CH₂)₂₋, −(CH₂)₂NH(CH₂)₂₋ and −(CH₂)₂NH(CH₂NH(CH₂)₂₋]. The primary amine groups crosslinked with linear glutaraldehyde in two stages: crosslinking and sol-gel processes. The resulting polymers are amorphous, insoluble in organic as well as in acidic or alkaline aqueous media. The hybrids have a large capacity for copper adsorption with very similar kinetic behaviors, defining a plateau after 1 h. The adsorption increases with the increase of nitrogen atoms attached to the organic chain length of the precursor silylant, being 0.25±0.01, 0.37±0.01 and 0.50±0.01 mmol g⁻¹ for X = 1 to 3, respectively. These hybrids also presented a good ability for immobilizing enzymes with distinguishable affinities. The amount of catalase and urease immobilization increased significantly from Sight1 to Siglut2, while the amount of glucose oxidase and invertase anchored decreased from Siglutl to Siglut2. Undefined amounts of enzyme immobilized for Sight3 could be related to possible difficulties arising from its degradation during the interactive process. Received: 30 October 2002/Revised version: 26 February 2003/ Accepted: 26 February 2003 Correspondence to Claudio Airoldi     

UV混杂固化硅氧烷改性水性PUA/邻甲酚醛环氧树脂的制备

制备了水性邻甲酚醛环氧树脂(o-CFER)和聚氨酯丙烯酸酯(PUA),研究了γ-缩水甘油醚氧丙基三甲氧基硅烷偶联剂KH560对紫外光-阳离子混杂固化PUA/o-CFER热固性树脂热性能的影响,并用动态力学谱仪和热重分析仪进行了表征。结果表明:PUA/o-CFER体系相容性很好,KH560用量占总质量的6%时,PUA/o-CFER热固性树脂的玻璃化转变温度达125.9℃;当KH560用量占总质量的8%时,PUA/o-CFER热固性树脂热降解所需活化能最高为41.41 kJ/mol,反应级数为1.54;固化后树脂涂膜的硬度达4 H,冲击强度达50 kg·cm,并具有良好的附着力。     

Evaluation of nanogels as supports for enzyme immobilization

Nanogels are hydrophilic polymers made up of crosslinked nano‐sized particles. These nanogels have large surface area that offers several functional groups as reserves for binding drugs, generating biosensors and as supports for enzyme immobilization. This mini‐review is an attempt to evaluate the recent developments in the use of nanogels as supports in enzyme immobilization. Emphasis is laid on the effect of nanogel structure and immobilization protocol on the property profile of the immobilized enzymes as compared with their free counterparts. The prospective applications of the nanogel‐immobilized enzymes are also evaluated. © 2014 Society of Chemical Industry     

Enzyme@bismuth-ellagic acid: a versatile platform for enzyme immobilization with enhanced acid-base stability

In situ encapsulation is an effective way to synthesize enzyme@metal–organic framework biocatalysts; however, it is limited by the conditions of metal–organic framework synthesis and its acid-base stability. Herein, a biocatalytic platform with improved acid-base stability was constructed via a one-pot method using bismuth-ellagic acid as the carrier. Bismuth-ellagic acid is a green phenol-based metal–organic framework whose organic precursor is extracted from natural plants. After encapsulation, the stability, especially the acid-base stability, of amyloglucosidases@bismuth-ellagic acid was enhanced, which remained stable over a wide pH range (2–12) and achieved multiple recycling. By selecting a suitable buffer, bismuth-ellagic acid can encapsulate different types of enzymes and enable interactions between the encapsulated enzymes and cofactors, as well as between multiple enzymes. The green precursor, simple and convenient preparation process provided a versatile strategy for enzymes encapsulation.     

Enzyme immobilization: Part 1. Modified bentonite as a new and efficient support for immobilization of Candida rugosa lipase

Immobilization of Candida rugosa lipase onto modified and unmodified bentonites is described. The effect of hydrophilic or hydrophobic nature of the support, the reuse efficiency, and kinetic behavior of immobilized lipase were studied. The modified bentonite with monolayer surfactant (BMS), was the best support, for immobilization. The activity of the immobilized enzyme was examined under varying experimental conditions. The effect of various factors such as concentration of enzyme solution, pH and temperature, stirring and various thermodynamic parameters were also evaluated. The activity of lipase on Na-bentonite, on BMS and on bentonite with bilayer surfactant (BBS) at the optimum pH was 7.2%, 56.6% and 3.6%, respectively. The adsorption isotherm was modelled by the Langmuir equation. The amounts of immobilized lipase on Na-bentonite, BMS and BBS at the highest activity were 42.6%, 61.2% and 28.3%, respectively. The effect of substrate concentration on enzymatic activity of the free and immobilized enzymes showed a good fit to the Michaelis–Menten plots. The immobilized enzyme exhibited an activity comparable to the free enzyme after storage at 30 °C. The thermal stability of free and immobilized lipase were also studied.     

A polyacrylic acid as a carrier for immobilization of penicillin acylase

A copolymer of acrylic acid with divinylbenzene was synthesized by suspension polymerization. This polymer is an effective carrier. Penicillin acylase was immobilized on this carrier to convert benzylpenicillin to 6‐aminopenicillanic acid, which may be employed in the manufacture of semisynthetic penicillins. Factors that affect the activity of immobilized penicillin acrylase, such as temperature, pH, and amount of native enzyme, were studied. Under suitable conditions, the activity and activity recovery of the immobilized enzyme were 3100 U/g (dry carrier, p‐dimethylaminobenzaldehyde method) and 59.7%, respectively. The immobilized penicillin acylase shows a remarkable increase in stability. At 40°C and pH 8.0 the value of the kinetic Michaelis–Menten constant (K_m) of the immobilized enzyme is 2.8 × 10^?3 mol/L, and the value of activation energy of enzyme catalysis is 71.5 kJ/mol. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2067–2069, 2002     

Bisacryloylpiperazine as vinylating agent for enzyme immobilization by graft-copolymerization onto polysaccharides

A method of enzyme immobilization by graft-copolymerization onto polysaccharides is reported. Bisacryloylpiperazine has been used as a vinylating reagent and the reaction product with several enzymes (HRP, GOD, Am, ChT, Cel) was copolymerized onto different matrices (cellulose, Sepharose, Sephadex, starch). Immobilization parameters which influence the copolymer activity have been studied for the insolubilization of horseradish peroxidase onto cellulose. These parameters are pH, time, and temperature of bisacryloylpiperazine enzyme activation reaction. Under the best immobilization conditions copolymer activity linearly depends on enzyme concentration. Enzyme coupling efficiency depends on the type of enzyme and it ranges from 7 to 20%. The most important characteristics of these immobilized enzyme systems were tested and compared with those of similar systems obtained by glycidylmethacrylate enzyme activation (stability in continuous washing, kinetic characteristics, and storage, thermal, and operational stability). Immobilized enzyme graft copolymers have kinetic behaviour very close to that of the free enzymes. Diffusion is not seriously limited because immobilization reaction does not alter the enzymatic activity. By means of bisacryloylpiperazine it was possible to immobilize chymotrypsin with better results than those previously obtained, particularly coupling efficiency and long term continuous working.     

Chitosan‐treated polypropylene matrix as immobilization support for lactic acid production using Lactobacillus plantarum NCIM 2084

Adsorption coupled with electrostatic interaction as an immobilization technique is an important microbial cell immobilization technique. Treatment of the polymer matrix with the cationic surface treating agent chitosan for lactic acid production has been studied. Cells of Lactobacillus plantarum NCIM 2084 were immobilized on a polypropylene (PP) matrix treated with different concentrations of chitosan. The biocatalyst adsorbed on the 1.0 g dm^?3 chitosan‐treated PP matrix proved to be most effective. Repeated batch fermentation experiments showed that the immobilized biocatalyst could be recycled effectively 11 times. Studies were also carried out in a packed bed reactor with media recirculation. A high productivity of 7.66 g dm^?3 h^?1 could be obtained with a conversion of 94% and a yield of 97% at an average residence time of 30 h. © 2001 Society of Chemical Industry     

Utilization of rice hull ash as a support material for immobilization of Candida cylindracea lipase

Rice hull ash was heated in a muffle furnace at 700°C for 2 h and metallic oxides were leached with 10% sulfuric acid. The acid-activated ash was then examined for immobilization of Candida cylindracea lipase. Immobilization was carried out by direct addition of the enzyme solution to the activated ash suspended in hexane. The immobilized lipase retained 30% of its hydrolytic activity, but thermal stability was greatly increased. Half-lives of the immobilized enzyme at 50, 60, and 70°C were 45, 17, and 4 min, respectively. Optimal pH of the immobilized enzyme was 7.2. The apparent K_m and V_max for olive oil were 41 mM and 99.5 μmol/h-mg solid, respectively.     

Experimental assessment on potential for processiblity of carbon nanotubes/epoxy system used as nanocomposites

In this study, carboxylic acid functionalized carbon nanotubes (CNTs) were used to modify epoxy with intent to develop a nanocomposite matrix for hybrid multiscale composites combining benefits of nanoscale reinforcement with well‐established fibrous composites. CNTs were dispersed in epoxy by using high energy sonication, followed by the fabrication of epoxy/CNTs composites. The processibility of CNTs/epoxy systems was explored with respect to their dispersion state and viscosity. The dependences of viscosity, mechanical and thermomechanical properties of nanocomposite system on CNTs content were investigated. The dispersion quality and reagglomeration behavior of CNTs in epoxy and the capillary infiltration of continuous fiber with the epoxy/CNTs dispersion were characterized using optical microscope and capillary experiment. As compared with neat epoxy sample, the CNTs nanocomposites exhibit flexural strength of 126.5 MPa for 1 wt% CNTs content and impact strength of 28.9 kJ m^?2 for 0.1 wt% CNTs content, respectively. A CNTs loading of 0.1 wt% significantly improved the glass transition temperatures, T_g, of the nanocomposites. Scanning electron microscopy (SEM) was used to examine the fracture surface of the failed specimens. It is demonstrated that the properties of CNTs/epoxy system are dispersion‐dominated and interface sensitive. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Fabrication and characterization of epoxylated zwitterionic copolymergrafted silica nanoparticle as a new support for lipase immobilization

Our previous work proved that the thermal stability of Candida rugosa lipase (CRL) immobilized on zwitterionic polymer (poly(carboxybetaine methacrylate)) grafted silica nanoparticle (SNP) was much higher than that on poly(glycidyl methecrylate) (pGMA) grafted SNP, while the latter showed significantly increased activity. Inspired by the research, we have herein proposed to synthesize copolymers of zwitterionic sulfobetaine methacrylate (SBMA) and GMA for CRL immobilization. The copolymers were grafted onto SNP surface at three GMA/ SBMA (G/S) molar ratios (G100/S0, G50/S50, G10/S90), followed by the covalent coupling of CRL to the surface copolymers. The immobilized CRLs on the corresponding supports were denoted as p(G100-S0)-CRL, p(G50-S50)-CRL and p(G10-S90)-CRL. The enzyme loading increased with the increase of GMA content in the copolymer, while the activity varied with the grafted copolymer composition. Kinetic study proved the improvement of enzyme-substrate affinity after immobilization. In comparison to p(G100-S0)-CRL, p(G50-S50)-CRL and p (G10-S90)-CRL presented remarkably enhanced thermal stability and pH tolerance, and p(G10-S90)-CRL showed the highest stability. These results suggest that the copolymer design is promising for development as a versatile platform for enzyme immobilization.     

TiO2/modified natural clay semiconductor as a potential electrode for natural dye-sensitized solar cell

TiO₂/modified natural bentonite clay semiconductor, as a potential electrode of dye-sensitized solar cell, having a Ti:Si molar ratio of 85:15 was, for the first time, compared with pure TiO₂ (commercial P25) electrode in terms of solar cell efficiency and characteristics. 4-Chloro-2,5-difluorobenzoic acid and 4-(chloromethyl)benzoyl chloride were added to the electrodes to increase light harvesting ability of natural dyes extracted from red cabbage, rosella, and blue pea. The results showed that the TiO₂/clay semiconductor provided a higher surface area but a slightly lower efficiency than the pure TiO₂. The best natural sensitizer was found to be the dye extracted from red cabbage. Besides, the 4-(chloromethyl)benzoyl chloride provided a higher short circuit current for the TiO₂/clay semiconductor.     

Synthesis of N-acetylmuramic acid derivatives as potential inhibitors of the D-glutamic acid-adding enzyme

Compounds containing N-acetyl-D-muramic acid and (L-1-aminoethyl)phosphonic acid were designed as potential inhibitors of the D-glutamic acid-adding enzyme of the biosynthesis of bacterial peptidoglycan. 2-Acetamido-2-deoxy-3-O-[(R)-2-propionyl-(L-1-aminoethyl)phosphonic acid]-D-glucopyranose ( 3 ) was synthesized. 2-Acetamido-1,4,6-tri-O-acetyl-2-deoxy-3-O[(R)-2-propionyl-(L-1-aminoethyl)phosphonic acid dimethyl ester]-α,β-D-glucopyranose ( 9 ) was also prepared and was submitted to the MacDonald reaction in order to introduce a phosphate group on the anomeric position. A complex mixture of phosphorylated or/and methylated derivatives of 3 was obtained. They were purified by h.p.l.c. and characterized by analyses of hexosamine, amino acid and labile phosphate, and by plasma desorption mass spectrometry. Neither 3 nor its derivatives inhibited the D-glutamic acid-adding enzyme from Escherichia coli.     

Laccase immobilization on radiation synthesized epoxy functionalized polyethersulfone beads and their application for degradation of acid dye

The enzymatic degradation of textile dyes offers an alternative approach over the conventional waste water treatment processes. Covalent immobilization of the enzymes onto insoluble supports not only permits their reusability and easy separation of enzymes from the product but also, if properly performed, may improve their activities, stability and hence reduces the cost of process. In the present work, epoxy functionalized polyethersulfone (PES) was synthesized via radiation induced polymerization of poly(2,3-epoxypropyl methacrylate) [poly(EPMA)] in PES-NMP (N-methyl-2-pyrrolidone) solution using ⁶⁰Co-gamma radiation source. Poly(EPMA)-functionalized-PES [poly(EPMA)-f-PES] beads were fabricated via phase inversion route using water as the anti solvent. Laccase was covalently immobilized on to the beads via one step-room temperature coupling reaction of amine group of enzyme with the epoxy group of poly(EPMA). Enzyme activity was assayed using 2,2′-azino-bis(3-ethylthiazoline-6-sulfonate) (ABTS) as the substrate. Effect of temperature and pH on the free and immobilized enzyme activity was studied. The immobilized laccase was successfully employed to degrade Acid Red 1 (AR1) dye in aqueous solution. Room temperature incubation of the laccase immobilized poly(EPMA)-f-PES beads with AR1 dye (∼10 ppm) resulted in ∼88% degradation of the dye over a period of 15 days.     

Preparation and characterization of superparamagnetic chitosan microspheres: Application as a support for the immobilization of tyrosinase

Superparamagnetic chitosan microspheres were prepared by a water‐in‐oil suspension‐crosslinking technique. To this end, magnetite particles were dispersed in a chitosan solution in acetic acid. The dispersion was added to toluene containing Span 20 as a surfactant with stirring. Chitosan solution droplets were hardened with glutaraldehyde. The magnetic chitosan microspheres obtained were characterized with scanning electron microscopy, differential thermal analysis, and vibrational magnetometry. The microspheres had a wide size distribution, ranging from 43 ± 25 to 255 ± 55 μm, that depended on the reaction conditions. The mean particle size decreased with an increase in the concentration of Span 20 or the amount of glutaraldehyde and with the addition of NaCl. However, a major size reduction was achieved by an increase in the stirring rate. Tyrosinase was immobilized on the microspheres. The immobilized enzyme retained 70% of its activity, as determined by the capacity to degrade phenolic compounds. The immobilized tyrosinase resulted in greater stability than the free enzyme. In addition, the enzyme maintained 65% of its phenol oxidation activity after 10 cycles of reuse. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 651–657, 2005     

Multifunctional epoxy composites modified with a graphene nanoplatelet/carbon nanotube hybrid

Epoxies are a class of thermoset polymers which find use in high performance applications. However, epoxies are inherently brittle and are poor conductors of electricity, which limits their ability to be employed in functional applications. Carbon nanomaterials have attracted considerable attention as filler materials, due to their combination of outstanding properties. In the present work, an epoxy polymer was modified with a hybrid nanofiller, consisting of graphene nanoplatelets (GNPs) and carbon nanotubes (CNTs) at a mass ratio of 9:1, using three-roll milling. Addition of 1 wt% resulted in an increase of eight orders of magnitude in the electrical conductivity and a 182% increase in the fracture energy, G_IC, of the epoxy. CNTs contributed greatly in the reduction of the percolation threshold, which was 10 times lower than that of conventional GNP/epoxy composites, while the increase in toughness was entirely attributed to the GNPs, predominantly through the mechanism of crack deflection. The toughening contribution of the hybrid nanofiller was theoretically calculated using analytical modeling, which showed excellent agreement between the predicted and experimental values of G_IC.