甘油的催化选择氧化

综述了近年来生物柴油主要副产物甘油的催化选择氧化的研究进展。分析了甘油的化学催化选择氧化的反应网络;介绍了催化甘油选择氧化反应主要的催化剂如负载型金属催化剂、多孔催化剂以及有机酰基-TEMPO催化剂的催化性能及其催化机理;评述了甘油催化氧化过程中各反应条件等对产物选择性和反应物转化率的影响;概括了甘油的电催化氧化、甘油催化氧化聚合生成新型聚合物-聚丙酮二酸盐（Polyketomalonate）等新催化反应及其机理,总结了甘油生物催化氧化的产物二羟基丙酮（DHA）的新进展。最后提出了甘油的催化氧化存在的一些问题,并展望了甘油催化氧化的研究和发展方向。     

Hydrogels based on physiologically clotted fibrin–gelatin composites

Fibrin–gelatin composite (PFG) films were prepared and crosslinked with glutaraldehyde as reported by us previously. These composites were graft‐copolymerized with poly(2‐hydroxyethyl methacrylate) (PHEMA) and poly(2‐hydroxypropyl methacrylate) (PHPMA) with a potassium persulfate and sodium metabisulfite redox initiation system. The graft copolymers (PFG‐HEMA and PFG‐HPMA) were characterized for their percentage of grafting, percentage of equilibrium water content, and percentages of free water and bound water. The chemical composition and thermal, mechanical, morphological, and surface characteristics were also evaluated. The optimum conditions for obtaining a maximum percentage of grafting were standardized. PFG and its graft copolymers exhibited higher equilibrium water contents ranging from 60 to 77% when compared with those of HEMA and HPMA homopolymers. DSC studies revealed increased freezing water contents and decreased bound‐water contents for the graft copolymers when compared with those of PFG alone. These properties improved the efficacy of hydrogels. PFG demonstrated better mechanical properties as compared with its graft copolymers. This may be attributed to the alkaline reaction conditions wherein protein hydrolysis of PFG would have occurred thereby reducing the overall strength of the graft copolymers. IR and scanning electron microscopic studies confirmed the grafting of PHEMA and PHPMA onto PFG. Contact‐angle studies revealed increased polarity for graft copolymers, which is a symbol for increased hydrophilicity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2241–2252, 2004     

Functionalization of three‐dimensionally ordered macroporous cross‐linked polystyrene by atom‐transfer radical polymerization of hydroxyethyl methacrylate and subsequent derivatization

The surface‐initiated atom‐transfer radical polymerization (ATRP) technique was applied to the graft polymerization of 2‐hydroxyethyl methacrylate (HEMA) from three‐dimensionally ordered macroporous crosslinked polystyrene (3DOM CLPS) on which the initiator (benzyl chloride) was immobilized onto the pore wall of 3DOM CLPS by chloromethylation of benzene ring. By the adjustment of the monomer concentration or graft polymerization time, the thickness of grafted polymer layers can be controlled. FTIR analysis confirms that the graft polymerization of HEMA via ATRP had been taken place at the pore wall of 3DOM CLPS. SEM images of PHEMA‐grafted 3DOM CLPS show that the ordered structure is well preserved after graft polymerization and the grafted layers are dense and homogeneous. The maximum thickness of grafted layer is up to 35 nm and the corresponding percent weight increase is 102.8% in this study. Moreover, the PHEMA layers were further functionalized in high yield via their reactive hydroxyl groups under gentle condition. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7950–7959, 2008     

Synthesis and Structure of a New Bicadmium （Ⅱ） Complex with Macrocyclic Hexaaza Bearing Hydroxyethyl Pendants

1 INTRODUCTION The cadmium(??) complexes have been exten-sively studied because of their potentially usefulproperties, such as toxicity research[1], catalysis[2],magnetism[3] and nonlinear optics[4]. A lot of studieson binuclear cadmium(??) pendant-ar…     

壳聚糖改性及用其整理纺织品抗菌性能的研究

用羟甲基化和醚化等方法制备了改性壳聚糖羟甲基壳聚糖和羟乙基乙基醚壳聚糖。在中性条件下它们溶解于水。实验显示，改性壳聚糖具有较好的抑菌作用和吸湿保湿性能。对织物进行的后整理实验发现，羟乙基乙基醚壳聚糖适用于对棉布的整理加工，羟甲基壳聚糖适用于对真丝绸的整理加工。经整理后的织物具有较好的抗菌性，且吸湿、透湿、染色性能较优。研究表明改性壳聚糖可作为优良的功能性天然“绿色”纺织品整理剂。     

Improved mechanical properties of poly (vinyl alcohol) films with glycerol plasticizer by uniaxial drawing

In this work, the uniaxial stretching poly (vinyl alcohol) (PVA) films with glycerol as plasticizer were prepared to explore the influence of drawing temperature and drawing ratio. The structure and property were investigated with scanning electron microscope, wide‐angle X‐ray diffraction, X‐ray diffraction, differential scanning calorimetry, mechanical tests, etc. With the increase of stretching temperature, the melting and crystallization temperatures increased. The tensile strength and Young modulus of glycerol/PVA films increased first and then decreased; when the temperature was 80°C, the tensile strength and Young modulus reached to maximum values of 197.2 and 470 MPa, respectively. In addition, with the increase of draw ratio, the orientation degree of the PVA molecular chains increased, indicating the improved regularity of molecular chains. When the PVA films were stretched to 4 times, the tensile strength and Young modulus of the films reached 162 and 143 MPa, respectively, which were 4 and 1.3 times compared with those of unoriented films. These environmentally friendly PVA films with excellent mechanical properties would find wide applications in the industry such as packaging, coating, etc.     

Rauvolfianine,a new antimycobacterial glyceroglycolipid and other constituents from Rauvolfia caffra. Sond (Apocynaceae)

The chemical investigation of the extract of the dried leaves of Rauvolfia caffra (Sond) (synonym Rauvolfia macrophylla) (Apocynaceae) led to isolation of a new glycoside derivative, rauvolfianine (1) as well as six known compounds: oleanolic acid (2), sitosterol-3-O-β-D-glucopyranoside (3), betulinic acid (4), vellosimine (5), sarpagine (6) and D-fructofuranosyl-β-(2→1)-α-D-glucopyranoside (7). Compounds 1, 2, 3, 4 and 7 were evaluated for antitubercular activity. Compounds 1 and 2 were the most active (MIC = 7.8125 and 31.25 μg/mL) towards the Isoniazid resistant strain of Mycobacterium tuberculosis AC45. Their structures and relative stereochemistry were elucidated by spectroscopic methods.     

Novel Biotreatment Process for Glycol Waters

Propylene oxide (PO), propylene glycol (PG), and polyols are produced from propylene via propylene chlorohydrin. Effluents from these plants contain biological oxygen demand/chemical oxygen demand (BOD/COD) loads besides high chloride concentrations. The high salinity poses severe problem to adopt conventional methods like activated sludge processes. Presently, a simple, economically viable and versatile microbiological process has been developed to get more than 90% biodegradation in terms of BOD/COD, utilizing specially developedPseudomonas andAerobacter. The process can tolerate high salinity up to 10 wt% NaCl or 5 wt% CaCl₂ and can withstand wide variations in_pH (5.5–11.0) and temperature (15–45°C). The biodegradation of glycols involves two steps. The enzymatic conversion of glycols to carboxylic and hydroxycarboxylic acids is aided byPseudo- omonas. Further degradation to CO₂ and H₂O by carboxylic acid utilizingAerobacter, and possible metabolic degradative pathway of glycols are discussed. Various process parameters obtained in the lab scale (50 L bioreactor) and pilot scale (20 m³ bioreactor), and unique features of our process are also discussed.     

Biologically active polymers. V. Synthesis and antimicrobial activity of modified poly(glycidyl methacrylate‐co‐2‐hydroxyethyl methacrylate) derivatives with quaternary ammonium and phosphonium salts

Antimicrobial copolymers bearing quaternary ammonium and phosphonium salts based on a copolymer of glycidyl methacrylate and 2‐hydroxyethyl methacrylate were synthesized. Poly(glycidyl methacrylate‐co‐2‐hydroxyethyl methacrylate) was modified for the introduction of chloromethyl groups by its reaction with chloroacetyl chloride. The chloroacetylated copolymer was modified for the production of quaternary ammonium or phosphonium salts. The antimicrobial activity of the obtained copolymers was studied against gram‐negative bacteria (Escherichia coli, Pseudomonas aeruginosa, Shigella sp., and Salmonella typhae), gram‐positive bacteria (Bacillus subtilus and B. cereus), and the fungus Trichophyton rubrum by the cut‐plug method. The results showed that the three copolymers had high antimicrobial activity. A control experiment was carried out on the main polymer without ammonium or phosphonium groups. The copolymer bearing quaternary salt made from tributyl phosphine was the most effective copolymer against both gram‐negative and gram‐positive bacteria and the fungus T. rubrum. The diameters of the inhibition zones ranged between 20 and 60 mm after 24 h. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2384–2393, 2002     

Rheological and electron microscopic characterization of aqueous carboxymethyl cellulose gels Part II: Visualization of the gel structure by freeze-fracturing

The spatial structure of gels of sodium carboxymethyl cellulose (NaCMC-gel) and carboxymethyl cellulose in the free acid form can be imaged in the transmission electron microscope (TEM). The freeze-fracturing technique is suitable for this. Experiments with test preparations (10 % aqueous glycerol solution) show that cooling rates during freeze-fixing are decisive for visualization, and that cooling rates can be improved substantially by using a cryojet. The increase of the cooling rate to more than 15 000 K/s makes it possible to obtain extremely fine network structures with a mesh width of 5–25 nm and with a filament thickness of 2–3 nm. The results obtained after jet-freezing show differences in the structure of the two gels: quasi-crystalline microaggregates in the HCMC-gel can be seen, and they cause an increased elasticity and opalescence of the aged HCMC-gels.