Synthesis and characterization of copper(II) complexes of sulfadiazine with amino acids: catalytic activity toward oxidation of phenol and catechol

New copper complexes of DL-methioninoylsulfadiazine (MTS) and L-cystinoylsulfadiazine (CYS) were prepared and characterized using elemental analysis, IR, electronic spectroscopy, EPR spectroscopy, and thermal analysis. The mode of binding indicates that copper binds to MTS through carbonyl oxygen with the amino group nitrogen while for Cu^II–CYS the copper binds through carbonyl oxygen and SH with removal of its proton. The proposed structures were supported by conformational analysis which showed predominance of the trans form of copper(II)-L-cystinoylsulfadiazine. The two complexes enhanced oxidation of phenol and catechol in the presence of H₂O₂ under mild conditions. The catalyst shows proficiency toward oxidation of phenol and catechol compared to the auto-catalytic oxidation. Cu^II–MTS exhibited higher catalytic activity than Cu^II–CYS. The phenol and catechol oxidation is inhibited by Kojic acid.     

Kinetics of oxidation of butene-1 to butanone in aqueous solution in the presence of ions Pd2+ and Mo-V-phosphoric heteropoly acid

Oxidation of butene-1 to butanone in the presence of homogeneous catalysts (PdSO₄ + HPA-x), where HPA-x = H_3+xPV_xMo_12-xO₄₀, 1 ￡ x ￡ 4, was investigated. This reaction is found to be of the 1st order with respect to C₄H₈, and of the 0.64th order with respect to Pd. The reaction rate does not depend on the HPA-x concentration and pH of the solution. The activation energy of the reaction is variable. A kinetic expression of the reaction is obtained for 303-343 K. This revised version was published online in June 2006 with corrections to the Cover Date.     

Molecular properties of hemicelluloses located in the surface and inner layers of hardwood and softwood pulps

The molecular properties of hemicelluloses located in the surface and inner layers of fibers present in hardwood and softwood pulps, together with the effects of different bleaching processes on these properties, have been investigated in this study. In order to separate the hemicelluloses located in these two layers, fibers were subjected to mechanical peeling and then separated by filtration into surface (filtrate) and inner layer materials. The materials thus obtained were characterized with respect to their polysaccharide compositions and uronic acid contents. The molar mass parameters of the hemicelluloses (extracted by alkali) were determined by employing size-exclusion chromatography in combination with off-line MALDI mass spectrometry. For all of the pulps examined, the relative content of xylan was found to be greater in the surface layer of the fiber than in the corresponding inner layer. The xylan polymers of the surface layer exhibited higher molar masses and lower frequencies of uronic acid side groups than did the xylans in the inner fiber layer. In connection with ozone treatment, hexenuronic acid residues in the surface layer xylan were removed to a greater extent than in the case of the inner layers, indicating a gradient for the reaction with ozone across the fiber wall. The xylan polymer remaining on the surface of the softwood pulps after completion of the chlorine dioxide bleaching process was predominantly uncharged.     

Partial Molar Volumes of Amino Acids and Peptides in Aqueous Salt Solutions at 25°C and a Correlation with Stability of Proteins in the Presence of Salts

Partial molar volumes for a homologous series of amino acids and peptides have been measured in aqueous 1M sodium acetate, sodium thiocyanate, and sodium sulfate at 25^°C. These data have been utilized in conjunction with the data in water to deduce partial molar volumes of transfer V _2,m ⁰(tr) from water to these aqueous salt solutions. The volumes of transfer for the amino acids and peptides are found to be positive. The interpretation is that this result arises from the dominant interaction of the sodium salts with the charged centers of amino acids and peptides. Thermal denaturation of the structurally homologous proteins lysozyme and -lactalbumin has been studied in the presence of these salts. Significant thermal stabilization of hen egg-white lysozyme has been observed in the presence of sodium acetate and sodium sulfate. However, the thermal stabilization observed for -lactalbumin is very small in the presence of these salts and sodium thiocyanate leads to a lowering of its thermal denaturation temperature. The rise in the surface tension of aqueous salt solutions with salt concentration has been correlated with the calorimetric and volumetric measurements. The results show that V _2,m ⁰(tr) depends less on the type of electrolyte than on the ionic strength of the solution. The V _2,m ⁰(tr) values correlate very well with the increase in the surface tension of aqueous salt solutions, indicating significant role of surface tension in interactions of amino acids, peptides, or protein with the salts.     

Selective double Suzuki cross-coupling reactions. Synthesis of unsymmetrical diaryl (or heteroaryl) methanes

Using a double Suzuki cross-coupling reaction ortho- or para-bromobenzyl bromides are easily transformed into unsymmetrical diaryl (or heteroaryl) methanes     

Conversion of sugarcane bagasse to carboxylic acids using a mixed culture of mesophilic microorganisms

Using the MixAlco process, biomass can be converted into carboxylic acids, which can be chemically converted into mixed alcohol fuels. This study focused on the use of countercurrent fermentation to anaerobically convert sugarcane bagasse and chicken manure to mixed carboxylic acids using a mixed culture of mesophilic microorganisms from terrestrial and marine sources. Bagasse was pretreated with lime to increase digestibility. The continuum particle distribution model (CPDM) simulated continuous fermentors based on data collected from batch experiments. This model saves considerable time in determining optimum operating conditions. For an 80% bagasse/20% chicken manure fermentation with terrestrial inoculum at a volatile solids loading rate (VSLR) of 7.36 g/(L of liquid·d) and a liquid residence time (LRT) of 8.88 d, total carboxylic acid productivity, total acid selectivity, and yield were 2.49 g/(L of liquid·d), 0.581 g of total acid/g of VS digested, and 0.338 g of total acid/g of VS fed, respectively, at a concentration of 18.7 g of total acid/L. At the same VSLR and LRT, fermentation with marine inoculum gave higher total acid productivity, total acid selectivity, and yield than fermentation with terrestrial inoculum. For an 80% bagasse/20% chicken manure fermentation with marine inoculum at a VSLR of 3.83 g/(L of liquid·d) and an LRT of 12.1 d, total carboxylic acid productivity, total acid selectivity, and yield were 1.38 g/(L of liquid·d), 0.667 g of total acid/g of VS digested, and 0.359 g of total acid/g of VS fed, respectively, at a concentration of 16.2 g of total acid/L.     

凝胶体系中羧酸对草酸钙结晶的影响

羧酸是泌尿系结石形成的抑制剂。本文采用双扩散法考察凝胶体系中一元羧酸HAc、二元羧酸酒石酸、三元羧酸柠檬酸和四元羧酸EDTA对草酸钙(CaOx)结晶的影响。HAc没有抑制作用。酒石酸和柠檬酸能够改变一水草酸钙(COM)晶体的形貌，并抑制草酸钙晶体二维生长，这种抑制作用随时间的增加而增强。EDTA使COM晶体在长度方向生长更快，而在宽度和厚度上生长更慢。随着结晶温度的降低，形成草酸钙晶体的时间增加，且二水草酸钙(COD)的比例增加。在5℃的低温条件下，添加有二元、三元和四元羧酸的CaOx结晶中，COD成为主要的物相。     

邻苯二甲醛柱前衍生反相高效液相色谱法测定氨基酸类神经递质

以邻苯二甲醛柱前衍生,ODS(C_(18))柱分离,pH 6.0乙酸盐缓冲溶液与甲醇二元梯度洗脱,荧光检测,仅9min内分离测定了大鼠脑中5种氨基酸递质的含量。在1～10μmol·L~(-1)浓度范围内,氨基酸的峰面积与其浓度呈现良好的线性关系,相关系数在0.9978～0.9999之间。     

工业氨基三甲叉膦酸中副产物的核磁共振分析

采用多种核磁共振(NMR)技术测定了工业氨基三甲叉膦酸(ATMP)产品中副产物的分子结构，发现该物质为甲氨基二甲叉膦酸(MADMP)，它是甲醛歧化反应导致的副产物；给出了可能的反应方程式；测出了MADMP的相对含量，MADMP与ATMP摩尔比约为2。