Preparation, characterization, resistance to protein adsorption, and specific avidin-biotin binding of poly(amidoamine) dendrimers functionalized with oligo(ethylene glycol) on gold

Protein-resistant films derived from the fifth-generation poly(amidoamine) dendrimers (PAMAM G5) functionalized with oligo(ethylene glycol) (OEG) derivatives consisting of various ethylene glycol units (EG(n), n = 3, 4, and 6) were prepared on the self-assembled monolayers (SAMs) of 11-mercaptoundecanoic acid (MUA) on gold substrates. The resulting films were characterized by ellipsometry, contact angle goniometry, and X-ray photoelectron spectroscopy (XPS). About 35% of the peripheral amines of the dendrimers were reacted with N-hydroxysuccinimide-terminated EG(n) derivatives (NHS-EG(n)). The dendrimer films showed improved stability over octadecanethiolate SAMs on gold in hot solvents, attributed to the formation of multiple amide bonds per PAMAM unit with underlying NHS-activated MUA monolayer. The EG(n)-attached PAMAM surfaces with n = 3 reduced the adsorption of fibrinogen to approximately 20% monolayer, whereas 2-3% for n = 4 or 6. The dendrimer films with various densities of EG(n) molecules on PAMAM surfaces were prepared by immersion of the NHS-terminated MUA-functionalized gold substrates in ethanolic solutions containing PAMAM and NHS-EG(n) of various mole ratios. The density (r) of the EG(n) molecules on the PAMAM surfaces is consistent with the mole ratio (r') of NHS-EG(n)/free amine of PAMAM in solutions. The resistance to protein adsorption of the resulting surfaces is correlated with the surface density and the length of the EG chains. At their respective r, the EG(n)-modified dendrimer films resisted approximately 95% adsorption of fibrinogen on gold surfaces. Finally, the specific binding of avidin to the approximately 5% and approximately 40% biotinylated EG3 dendrimers (surface density of biotin with respect to the total number of terminal amino groups on PAMAM G5) gave rise to about 50% and 100% surface coverage by avidin, respectively.     

ε-己内酯改性聚氨酯丙烯酸酯的制备及电子束固化涂料性能研究

本文以甲基丙烯酸羟乙酯、ε-己内酯及异氟尔酮二异氰酸酯为原料制备了己内酯改性聚氨酯丙烯酸酯。使用傅里叶变换红外光谱(FT-IR)和核磁共振氢谱(~1HNMR)表征了产物结构。探究了ε-己内酯链段含量对改性聚氨酯丙烯酸酯树脂黏度的影响,并进一步对比研究了其电子束(EB)固化膜和紫外光(UV)固化膜的热机械性能、拉伸性能和涂层基本性能的差异。     

Electrically conducting,transparent, graphene based nanocomposite coatings on flexible film substrate

Transparent, electrically conducting nanocomposite coated polyethylene terephthalate (PET) films are prepared using two types of bulk synthesized few layered graphene; namely reduced graphene oxide (rGO) and liquid exfoliated graphite (EG) dispersed in ultra high molecular weight polyethylene (UHMWPE). This study focuses on application of high concentration of such nanofillers (1: 1 to 2.5: 1 ratios with polymer) in order to develop a highly conducting but ultrathin coating for better transparency. The coated PET films are characterized for their surface morphology, electrical and optical properties. High resolution transmission electron microscopic (HRTEM) images and corresponding selected area electron diffraction (SAED) patterns confirm that the graphite has been exfoliated to few layer graphene using both the synthesis routes. Transmittance values of these coated films are measured in UV visible spectrum. The rGO based samples have high transmittance (~90–95%) compared to EG based samples (~40–50%). From current-voltage (I?V) graph and surface resistivity studies, it has been observed that rGO based samples are dielectric in nature similar to UHMWPE while EG based samples are electrically conducting and its conductivity increases with its concentration. EG based nanocomposite coated samples show much better electrical conductivities (resistance 338 to 66 kΩ at different concentrations of EG) than rGO based samples.     

Cu/SiO2催化剂制备方法对其草酸二甲酯催化氢解性能的影响

以化学吸附水解法、蒸氨法和浸渍法制备了Cu/SiO2催化剂, 并用于草酸二甲酯氢解制备乙二醇的反应. 发现用化学吸附水解法制备的催化剂具有最高的催化活性和乙二醇选择性, 乙二醇得率可达92.6%. 对还原前后不同方法制备的催化剂进行表征发现, 浸渍法制备的催化剂中Cu物种不能很好地得到分散, 因此活性较差. 蒸氨法和化学吸附水解法能较好地分散Cu物种. 由于化学吸附水解法制备的催化剂的Cu0表面积较蒸氨法的大, 且Cu＋表面积相当, 故活性高于蒸氨法制备的催化剂.     

Studies on the photo-oxidative degradation of LDPE films in the presence of oxidised polyethylene

This paper reports the results of photo-oxidative degradation studies of LDPE in the presence of varying amounts of oxidised polyethylene (OPE), which was prepared by heating LDPE films containing 0.1% cobalt stearate in oxygen atmosphere at 100 °C. OPE, with a CI of 12 was used as an additive for LDPE. Varying amounts of OPE (0.5-5%) were blended with polyethylene in an extruder and films of 70 μm thickness were prepared by film blowing process. The physico-chemical properties of the films were evaluated and these were found to be proportional to the amount of OPE. The films thus obtained were subjected to UV-B exposure at 30 °C for extended time periods. The chemical and physical changes induced by UV exposure were followed by monitoring the changes in mechanical properties (tensile strength and elongation at break), carbonyl index (CI), morphology, molecular weight, MFI and DSC crystallinity. Incorporation of OPE was found to be effective in initiating the photo-degradation of LDPE in relatively short span of time and the degradation was found to be proportional to the amount of OPE in the formulation.     

马来酸酐接枝聚丙烯/石墨导电纳米复合材料的研究

用溶液插层 (SI)法制备了马来酸酐接枝聚丙烯 (gPP) 膨胀石墨 (EG)导电纳米复合材料 ,以熔体混合(MM)法作对照 ,通过室温体积电导率 (σ)测试和OM、SEM、TEM观察 ,研究了复合材料的制备方法、微观结构和导电性能关系 .结果表明 ,SI法制得纳米复合材料的室温逾渗阈值c=0 6 7vol% ,远低于MM法制得复合材料的c=2 96vol% ;3 90vol%EG含量下 ,前者的σ达 2 4 9× 10 - 3S cm ,而后者的σ仅 6 85× 10 - 9S cm .产生上述差异的原因 ,与两种方法制得复合材料中EG分散相的形态及其内部微结构直接相关 .     

Mixed self-assembled monolayers (SAMs) consisting of methoxy-tri(ethylene glycol)-terminated and alkyl-terminated dimethylchlorosilanes control the non-specific adsorption of proteins at oxidic surfaces

Monolayers from the newly synthesized compound methoxy-tri(ethylene glycol)-undecenyldimethylchlorosilane (CH3O(CH2CH2O)3(CH2)11Si(CH3)2Cl, MeO(EG)3C11DMS) and dodecyldimethylchlorosilane (DDMS), both pure and mixed, were prepared by self-assembly from organic solution in the presence of an organic base. The films obtained were characterized by advancing and receding contact angle measurements and ellipsometry to confirm the formation of self-assembled monolayers (SAMs). The resulting data on the covalently attached dimethylsilanes were compared to known oligo(ethylene glycol) (OEG)-terminated SAM systems based on terminal alkenes, thiolates or trihydrolyzable silanes. The composition of the mixed SAMs was found to depend directly and linearly on the composition of the silanization solution. Enhanced protein repellent properties were found for the SAMs using a variety of proteins, including the Ras Binding Domain (RBD), a protein with high relevance for cancer diagnostics. Roughly a RBD protein monolayer amount was adsorbed to silicon oxide surfaces silanized with DDMS or non-silanized silicon wafers, and in contrast, no RBD was adsorbed to surfaces silanized with MeO(EG)3C11DMS or to mixed monolayers consisting of DDMS and MeO(EG)3C11DMS if the content of OEG-silane overcame a critical content of X(EG) approximately 0.9.     

Studies on copolymerization of N-isopropylacrylamide with poly(ethylene glycol) methacrylate

The paper describes the preparation and characterization of cross-linked homopolymers and copolymers of N-isopropyl acrylamide (NIPAAm) with poly(ethylene glycol) methacrylate (PEGMA, M_n = 526 g/mol). Several copolymer samples were prepared by taking varying amounts of monomers i.e. NIPAAm and PEGMA in the initial feed using hydrophilic (IRGACURE-2959) and hydrophobic (DURACURE-1173) photoinitiator. In order to investigate the effect of reaction conditions, copolymers were prepared below or above the lower critical solution temperature (LCST) using water or water:ethanol (50:50) as solvent and by varying the amounts of cross-linker. Hydrogels prepared under varying reaction conditions were characterized for its swelling behaviour (using optical microscope), phase transition temperature (using DSC) and morphology (using SEM). As expected LCST increased from 35 to 39 °C as PEGMA content in copolymers increased from 1 to 20% (w/w). However, the morphology of hydrogels was found to be independent on the reaction conditions.Copolymer films having an optimum combination of swelling and performance properties were evaluated as switchable cell culture membranes. Hepatic cancer cell lines (Hep G-2) was used to study the cell growth and detachment. Cell growth and detachment were found to be dependent on the copolymer composition. Cell viability was found comparable to trypsin which also supports application of these films as cell culture membrane.     

Measurement of the azimuthal anchoring energy of liquid crystals in contact with oligo(ethylene glycol)-terminated self-assembled monolayers supported on obliquely deposited gold films

We report measurements of the orientations and azimuthal anchoring energies of the nematic liquid crystal 4-cyano-4'-pentylbiphenyl (5CB) on polycrystalline gold films that are deposited from a vapor at an oblique angle of incidence and subsequently decorated with organized monolayers of oligomers of ethylene glycol. Whereas the gold films covered with monolayers presenting tetra(ethylene glycol) (EG4) lead to orientations of 5CB that are perpendicular to the plane of incidence of the gold, monolayers presenting tri(ethylene glycol) (EG3) direct 5CB to orient parallel to the plane of incidence of the gold during deposition of the gold film. We also measure the azimuthal anchoring energy of the 5CB to be smaller on the surfaces presenting EG3 (3.2 +/- 0.8 microJ/m2) as compared to EG4 (5.5 +/- 0.9 microJ/m2). These measurements, when combined with other results presented in this paper, are consistent with a physical model in which the orientation and anchoring energies of LCs on these surfaces are influenced by both (i) short-range interactions of 5CB with organized oligomers of ethylene glycol at these surfaces and (ii) long-range interactions of 5CB with the nanometer-scale topography of the obliquely deposited films. For surfaces presenting EG3, these short- and long-range interactions oppose each other, leading to small net values of anchoring energies that we predict are dependent on the level of order in the EG3 SAM. These measurements provide insights into the balance of interactions that control the orientational response of LCs to biological species (proteins, viruses, cells) on these surfaces.     

Waterborne anionic polyurethanes and poly(urethane-urea)s: influence of the chain extender on mechanical and adhesive properties

Polyurethane and poly(urethane-urea) aqueous dispersions based on 4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI), poly(propylene glycol) (PPG) and dimethylolpropionic acid (DMPA) were synthesized. Three types of chain extenders were used, hydrazine (HYD) and ethylenediamine (EDA), producing poly(urethane-urea)s and ethylene glycol (EG), polyurethanes. The dispersion was performed before or after the chain extension reaction, depending on the extender employed. The dispersions were prepared with and without the addition of acetone after the prepolymer synthesis and neutralization steps. The length of soft segment and NCO/OH ratio were varied. Some mechanical properties of cast films obtained from the aqueous dispersions, the characteristics of coating application on a wood surface and their adhesive properties were evaluated.     

Preparation and physicochemical and electrochemical characterization of exfoliated graphite oxide

Exfoliated graphite oxide (EGO) is prepared by oxidizing exfoliated graphite (EG) using a mixture of KMnO(4)/H(2)SO(4). The physicochemical characterization of the EGO has been carried out using FT-Raman, FT-IR, XPS, NMR, and diffraction techniques. Colloidal form of EGO is subsequently prepared by ultrasonicating EGO in water. Thin films of EGO on a glassy carbon/gold surface are formed and the electrochemical and ion exchange properties have been studied using various redox systems such as K(4)[Fe(CN)(6)], ascorbic acid, and dopamine. The charge-based adsorption properties can be made use of, to either suppress or catalyze ascorbic acid oxidation. Adsorption and preconcentration of dopamine on the EGO film has been shown to electrocatalyze the oxidation of NADH.     

Fabrication and characterization of composites composed of a bioresorbable polyester matrix and surface modified calcium carbonate whisker for bone regeneration

This work aims to evaluate the potential of a bioresorbable composite as material for bone regeneration. Surface‐modified calcium carbonate whiskers (CCWs) were prepared by grafting of ethylene glycol (EG) using 1,6‐hexamethylene diisocyanate as coupling agent, followed by ring‐opening polymerization of l ‐lactide initiated by the hydroxyl group of EG. The resulting PLLA‐EG‐g‐CCW was used as filler to reinforce a bioresorbable terpolymer, poly(l ‐lactide‐co‐trimethylene carbonate‐co‐glycolide) (PLTG). The mechanical properties and thermal stability of the PLTG/PLLA‐EG‐g‐CCW composites were greatly improved. Compared with neat PLTG, a 39.3% increase in tensile strength and 26.7% increase in elongation at break were obtained for the composite with 2 wt% PLLA‐EG‐g‐CCW filler. This was assigned to the reinforcement effect of evenly dispersed PLLA‐EG‐g‐CCW in the polymeric matrix. In fact, entanglement of PLLA grafts at the surface of PLLA‐EG‐g‐CCW with PLTG chains results in a homogeneous distribution of the filler in the matrix. Thus, the composites are simultaneously strengthened and toughened. The cytocompatibility of the materials was evaluated from cell morphology and 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay using L929 mouse fibroblast cell line. The results indicate that the composite presents very low cytotoxicity. Copyright © 2017 John Wiley & Sons, Ltd.     

Tuning the physical properties of a nematic liquid crystal elastomer actuator

In this report we demonstrate the ability to tune the physical properties of a liquid crystal elastomer (LCE) by varying the amount and type of crosslinking within the elastomer network. LCE films composed of a single mesogenic compound were capable of uniaxial contraction when thermally actuated through the nematic to isotropic phase of the material. We probed the physical properties of the LCE films while varying the amount and concentration of two crosslinking agents and measured actuation strains of 10-35%, elastic moduli of 3-14 MPa, and transition temperatures ranging between 75 and 60°C. The viscous losses of the elastomers and the estimated work capable of being produced by the films were also evaluated. The ability to tune the physical properties of the LCE films allows for a wide range of applications including robotics, microelectromechanical systems (MEMS), shape-changing membranes, and/or microfluidics.     

Development and in vitro evaluation of ketoprofen extended release pellets using powder layering technique in a rotary centrifugal granulator

Powder layering technique was evaluated using laboratory scale centrifugal granulator instrument to prepare extended release pellet dosage form of ketoprofen. Ethyl cellulose and shellac polymers were used for drug layering and extended release coating in the same apparatus. Inert sugar spheres were intermittently treated with drug powder and binding solution. Combination of ethyl cellulose (45cps) and shellac was evaluated as binders at different levels (1:3 ratio, at 6%, 12%, 16% and 21%w/w polymer) for drug loading and for extended release coating (1:3 ratio at 2%, 4% and 7% w/w polymer). Pellets were evaluated for drug release study using paddle apparatus in pH 6.8 Phosphate buffer, 900ml at 100 rpm. Ethyl cellulose and shellac when used as binder during drug layering did not extend the ketoprofen release beyond 4h. However, coating of drug loaded pellets using ethyl cellulose and shellac resulted in extended release profile of ketoprofen for about 10h. Ethyl cellulose coating alone at a level of 3% w/w resulted in extended release profile. Coated pellets were evaluated for sphericity, Hardness-Friability Index and scanning electron microscopy. Scanning electron micrographs of the pellets showed a uniform coating of polymer on the core pellets substantiating the use of centrifugal granulator for extended release coating. Release pattern from the optimized batch was best explained by Higuchi's model. The drug release pattern from the pellets was found to be Non-Fickian anomalous type, involving both diffusion and erosion mechanism. Accelerated stability study of the coated pellets filled in hard gelatin capsule was conducted for 3-month period and observed for the effect on drug release profile.     

Efficient approach to high barrier packaging using microfibrillar cellulose and shellac

This paper presents an investigation on the enhancement of the barrier properties of paperboard and paper. Microfibrillar cellulose (MFC) and shellac were deposited on the fibre based substrates using a bar coater or a spray coating technique. The air, oxygen and water vapour permeability properties were measured to quantify the barrier effect of the applied coatings. In addition, the mechanical properties were determined and image analysis of the structure was performed to examine the coating adhesion. The air permeance of the paperboard and papers was substantially decreased with a multilayer coating of MFC and shellac. Furthermore, for the MFC and shellac coated papers, the oxygen transmission rate decreased several logarithmic units and the water vapour transmission rate reached values considered as high barrier in food packaging (6.5 g/m² 24 h). The analysis of mechanical and morphological properties indicated good adhesion between the coating and the base substrate.     

Monomer and Radiation-Mediated Sago Starch Blend Film: Mechanical and Thermal Property Optimization

Bio-blend films were prepared with sago starch and N-vinyl-2-pyrrolidone (NVP) by the casting method, varying the concentrations of sago starch (100 to 93%) and NVP (0 to 7%). The formulations were designated as F1 (starch 100%), F2 (starch 97%), F3 (starch 95%), and F4 (starch 97%). The highest tensile strength (TS), tensile modulus (TM), and elongation at break (Eb%) were found correspondingly to be 30.47 MPa, 407.74 MPa, and 8.25% for the F3 formulation. Gamma radiation was applied to films to modify their performance through grafting and cross-linking. The highest TS, TM, and Eb% were found at 500 krad dose and they were 38.12 MPa, 481.00 MPa, and 9.78%, respectively for F3 formulation. The water uptake nature and thermal properties of the treated and untreated films were also investigated.     

Modification and Characterization of Chitosan Films Using 3-trimethoxyl Silyl Propylmethacrylate

The biodegradable flexible chitosan film was prepared by solution casting. The physico-mechanical properties, polymer loading (PL), gel content and water uptake of the chitosan film were studied. The tensile strength (TS) and % elongation at break (Eb) of the uncured chitosan film were 7.0 (MPa) and 8%, respectively. Four formulations were developed using 3-trimethoxyl silyl propylmethacrylate (TSPMA) (varied from 10–80% by weight) in methanol along with photoinitator (Darocur-1664). The raw chitosan films were then soaked in the prepared formulations and cured under UV radiation at different intensities to improve the physico-mechanical properties of the films. TS for the photocured chitosan film was 28.0 (MPa) which was 4 times higher compared to the uncured chitosan film. This TS was obtained for the formulation containing 30% silane (TSPMA) at 24th UV pass for 4 min soaking time. The maximum PL of 45.1% was obtained for the same formulation at 24th UV pass for 4 min soaking time. The water uptake and gel content of the photocured chitosan films were also studied. The scanning electron micrographs of the photocured chitosan film showed smooth surface, compact and homogeneous structure.     

The bark biorefinery: a side-stream of the forest industry converted into nanocomposites with high oxygen-barrier properties

The purpose of the bark biorefinery concept is to upgrade the different constituents present in bark to multiple value-added bio-based products. Non-cellulosic polysaccharides (NCP) and cellulose nanocrystals (CNC) sequentially isolated from the inner bark of Norway spruce were used as raw materials for the formulation of renewable nanocomposites. The film formation abilities of NCP/CNC formulations prepared with different proportions of CNC were studied. Homogeneous transparent films with a glossy appearance were obtained when more than 30 wt% CNC was incorporated. The influence of the CNC content on the NCP/CNC films was assessed in terms of structural, thermal, mechanical and oxygen-barrier properties. All the films showed better performances with increasing CNC content, which was explained by the strong interactions between the two components. The effect on the film performances of adding sorbitol as a plasticizer was also evaluated. The presence of sorbitol decreased the thermal stability, the stiffness and the oxygen permeability of the films at 80 % RH. However, the addition of sorbitol enhanced the elongation of the films and further improved their oxygen-barrier properties at 50 % RH. The composite properties could thus be tailored by adding different amounts of sorbitol and CNC, resulting in all-carbohydrate materials with performances similar to or even better than the conventional barrier materials used in packaging.     

Nanoparticle formation and ultrathin film electrodeposition of carbazole dendronized polynorbornenes prepared by ring-opening metathesis polymerization

We report on the synthesis, electropolymerization, and nanoparticle formation of a series of electroactive carbazole-terminated dendronized linear polynorbornenes prepared by living ring-opening metathesis polymerization (ROMP). The molecular weight (MW) of the dendronized polymers was controlled by varying the feed ratio between the dendronized monomer and first-generation Grubbs' catalyst. Ultrathin films were prepared by electrodeposition. The electrochemical behavior and viscoelastic properties of such films were found to be highly dependent on the dendron generation and linear polymer MW as studied by electrochemical quartz crystal microbalance (E-QCM). Moreover, nanoparticle formation and size/shape control were observed by tuning the surface wetting properties of the substrate during adsorption and by intramolecular cross-linking via chemical oxidation in solution.     

Cathodic electrodeposition of mixed molybdenum tungsten oxides from peroxo-polymolybdotungstate solutions

Mixed molybdenum tungsten trioxide films of varying stoichiometry (MoxW1 - xO3, 0 < x < 1) were prepared by cathodic electrodeposition on indium tin oxide (ITO)-coated glass substrates from aqueous peroxo-polymolybdotungstate solutions. Electrochemical quartz crystal microbalance (EQCM), cyclic voltammetry, and chronocoulometry were used to gain insight into the electrodeposition mechanism. The compositional and structural properties were characterized for MoxW1 - xO3 films deposited at intermediate potentials (-0.35 V vs Ag/AgCl) and sintered at 250 degrees C using energy-dispersive spectroscopy, X-ray diffraction, and Raman spectroscopy. These studies reveal that films consist of homogeneously mixed MoxW1 - xO3, with an enriched Mo content ranging in composition from 0.4 < x < 0.7 depending upon the mol % Mo present in the deposition solution. Chronoamperometry and spectroelectrochemical measurements were conducted to estimate lithium ion diffusion coefficients and coloration efficiencies for the mixed metal oxide films in 1 M LiClO4/propylene carbonate. The subtle interplay between structural and compositional properties due to the uniform mixing of Mo and W oxide components shows that electrochromic and lithium ion transport properties are moderately enhanced relative to those of single-component WO3 and MoO3 and demonstrate improved structural stability over pure MoO3 polymorphs during electrochemical cycling.