Synthesis and spectral investigation of alkyl methacrylates with halogenated carbazolyl pendant groups for photonics applications

The alkyl methacrylates with halogenated carbazolyl pendant groups were prepared, and the analysis of their absorption and emission spectra showed that the polymers containing monohalogenatged carbazole rings were capable of exhibiting a high singlet‐triplet (S‐T) conversion. The reasons that mainly triplet excitons could be observed in such polymers and additional bands appearance in the spectra of the polymers with dihalogenated carbazole rings are discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1650–1656, 2002; DOI 10.1002/app.10469     

Mask‐free Localized Grafting of Organic Polymers at the Micrometer or Submicrometer Scale on Composite Conductors or Semiconductor Substrates

This work presents a new one‐step process enabling the mask‐free localized functionalization by organic polymers of the conducting or semiconducting parts of composite surfaces at the micrometer and submicrometer scale. The functionalization is carried out via cathodic electrografting of suitable precursors of composite cathodes, which gives an insulating polymer film strongly grafted to selected parts of the composite electrodes and guarantees that the resolution is that of the pre‐existing pattern, even when the whole surface is dipped into the reaction medium. The presumed mechanism is based on a regioselective extraction of electrons from the composite surface according to its apparent local work function in solution.     

Potentiometric studies of oxidation–reduction reactions with redox copolymers

Polymeric oxidants in the bead form that were macroporous styrene/divinylbenzene copolymers containing N‐chlorosulfonamide functional groups (in sodium or hydrogen form) or N‐bromosulfonamide groups (in sodium form) were synthesized and investigated to determine their oxidizing powers. The redox potentials of the N‐chlorosulfonamide/sulfonamide and N‐bromosulfonamide/sulfonamide systems were determined by potentiometric studies at different pH values with aqueous solutions of Na₂SO₃, KCN, and KSCN as reducers. The formal redox potentials of the N‐chlorosulfonamide copolymers were 0.79, 0.44, and ?0.12 V at pH's of 1.8, 8.45, and 13.6, respectively. The formal redox potential of the N‐bromosulfonamide copolymer was about 100 mV higher in comparable conditions and in solutions over pH = 5 (e.g., 0.56 V at pH = 8.56). The comparatively higher oxidizing power of the N‐bromosulfonamide copolymer was particularly evident in a strong alkaline medium (in which the N‐chlorosulfonamide copolymer was not reactive). In contrast, the N‐chlorosulfonamide copolymer showed strong oxidative properties in acidic media (in which the N‐bromosulfonamide copolymer decomposed itself). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Preparation and adsorption behavior of a cellulose‐based,mixed‐mode adsorbent with a benzylamine ligand for expanded bed applications

A novel mixed‐mode expanded bed adsorbent with anion‐exchange properties was explored with benzylamine as the functional ligand. The cellulose composite matrix, densified with stainless steel powder, was prepared with the method of water‐in‐oil suspension thermal regeneration. High activation levels of the cellulose matrix were obtained with allyl bromide because of the relative inertness of the allyl group under the conditions of the activation reaction. After the formation of the bromohydrin with N‐bromosuccinimide and coupling with benzylamine, the activated matrix was derived to function as a mixed‐mode adsorbent containing both hydrophobic and ionic groups. The protein adsorption capacity was investigated with bovine serum albumin as a model protein. The results indicated that the prepared adsorbent could bind bovine serum albumin with a high adsorption capacity, and it showed salt tolerance. Effective desorption was achieved by a pH adjustment across the isoelectric point of the protein. The interactions between the cell and adsorbent were studied, and the bioadhesion was shielded by the adjustment of the salt concentration above 0.1M. Stable fluidization in the expanded bed was obtained even in a 2% (dry weight) yeast suspension. The direct capture of target proteins from a biomass‐containing feedstock without extra dilution steps could be expected with the mixed‐mode adsorbent prepared in this work, and this would be especially appropriate for expanded bed adsorption applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of functionalization and boron and nitrogen substitution on some properties of carbon nanotubes

Molecular orbital calculations of the ionization potential of single wall carbon nanotubes having donor NH₂ and acceptor NO₂ groups bonded to the side walls and ends and boron and nitrogen substituted for carbon show substantial increases in ionization potential compared to carbon nanotubes with no functional groups and no carbon substitutions. The presence of a carbon vacancy on the side wall also causes a substantial increase in the ionization potential. The effect of tube length on the ionization energy is also calculated. The calculations also suggest that at appropriate levels of boron and nitrogen doping the armchair carbon nanotubes could be high temperature organic ferromagnetic materials.     

细菌纤维素的功能化改性研究进展

细菌纤维素(BC)是微生物生长过程中产生的以葡萄糖为基本骨架的结构性碳水化合物,具有高纯度、高聚合度、高结晶度、高持水性、高抗张强度和良好的机械强度,在功能材料领域显示了巨大的应用潜力.综述了近年来BC合成菌种筛选的研究现状;分析了BC在透气、吸湿排汗、力学性能和染色与脱色性能调控方面的进展情况;重点总结了BC基材料在抗菌、防紫外线、防辐射、防静电、拒水拒油、导电和传感等功能化改性方面的研究进展;最后,指出BC大规模高效成模和成型技术、差异化高功能BC材料制备技术是未来的重点研发方向.     

Fabrication of poly(PEGMA) surface with controllable thickness gradient and its mediation on the gradient adhesion of cells

The gradient surface shows enormous potential in the development of tissue engineering, biosensor, microfluidic control, and particle sorting. In this work, a poly(polyethyleneglycol methacrylate) (poly(PEGMA)) gradient surface was prepared through surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-AGRET ATRP). The effect of various parameters on the thickness growth of poly(PEGMA) film were analyzed, among which the excessive reducing agent was utmost important. The reducing agents supported the regeneration of Cu^I and eliminated the disturbance of air, maintaining the "living polymerization" of poly(PEGMA) up to 73.1 nm under tested conditions. The physicochemical properties of the fabricated surfaces were characterized by ellipsometry, X-ray photoelectron spectroscopy, water contact angle. The thickness slope of gradient poly(PEGMA) was controllable in a nanoscale range. The gradient surface was further grafted with CRGD (Cys-Arg-Gly-Asp) peptides onto the poly(PEGMA-co-[glycidyl methacrylate]) blocks via the ring-opening reaction between epoxy and amino groups, which showed a gradient change in water contact angle and adhesion of endothelial cells.     

7-取代吲哚类化合物合成及官能团化研究进展

7-取代吲哚化合物是合成药物及精细化学品的重要中间体.本文综述了近15年金属Pd催化的7-取代吲哚化合物的制备方法,将其分成直接合成法和吲哚7位官能团化法两类,对每一类的反应过程和机理进行了详细介绍和评述.     

Vitamin A microencapsulation within poly(methyl methacrylate)‐g‐polyethylenimine microspheres: Localized proton buffering effect on vitamin A stability

To stabilize vitamin A in a cosmetic/dermatological formulation, we present here a new encapsulation method based on polymer microspheres having a localized “proton‐buffering” capacity. Poly(methyl methacrylate)‐g‐polyethylenimine (PMMA‐g‐PEI) was prepared by direct condensation grafting of PEI onto poly(methyl methacrylate‐co‐methyl acrylic acid). The reaction was confirmed by FT‐IR analysis showing the amide vibration at 1,550 cm^?1. Elemental analysis indicated that the weight content of the grafted PEI was 1.6% (w/w). Vitamin A was encapsulated into PMMA‐g‐PEI microspheres by using an oil‐in‐water (O/W) single emulsion method. The presence of PEI moiety dramatically improved the chemical stability of vitamin A in microspheres. Vitamin A encapsulated within PMMA‐g‐PEI microspheres maintained 91% of its initial activity after 30‐day incubation at 40°C, while only maintaining 60% within plain PMMA microspheres. This study demonstrates that proton‐buffering within hydrophobic polymer matrix is a useful strategy for stabilizing “acid‐labile” active ingredients. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 517–522, 2004     

Kinetics of hydroformylation of 1-decene using homogeneous HRh(CO)(PPh3)3 catalyst: a molecular level approach

The kinetics of hydroformylation of 1-decene using homogenous HRh(CO)(PPh₃)₃ catalyst has been reported in the temperature range of 50–70 °C. The effect of catalyst,P _{H 2},P _CO, and 1-decene concentration on the rate of hydroformylation has been studied. Based on the analysis of initial rate data, a rate equation has been proposed and kinetic parameters evaluated. The activation energy was found to be 11.76 kcal/mol. A molecular level approach to kinetic modelling has also been illustrated. The rate equation derived assuming oxidative addition of H₂ as a rate determining step, has been found to represent the data satisfactorily. The rate parameters for the mechanistic model have been evaluated for the data at 60 °C.NCL Communication No. 5735.