The decisive role of calorimetric measurements in equilibrium phase diagram calculations

In this paper, examples are given of how calorimetric values can give greater certainty to phase equilibria calculated from thermodynamic data. Errors that may arise when phase diagram evaluations are carried out largely from the basis of Gibbs energy information only are illustrated by reference to recent evaluations of the Ti?Si system and the resulting calculated oxidation behaviour of titanium silicides. The importance of calorimetric values for calculation of metastable phase equilibria is demonstrated by results of work on the AlN?TiN hard-metal coating system. Finally, suggestions are made with regard to areas of work where calorimetric data are urgently needed.     

Modeling of drug molecule orientation within a receptor cavity in the BiS algorithm framework

The BiS algorithm is suggested for modeling the drug molecule orientation within a receptor cavity. It is based on the assumption of complementarity of the field created by biologically active compounds and the field of the responsive receptor. The comparison of predicted orientations of various biologically active compounds on the relevant receptors with the data of X-ray structural studies (Protein Data Bank) reveals that the results obtained with this approach surpasses those reported in the literature. The suggested technique made it possible to elucidate the details of the action mechanism of DNA antimetabolites, dihydrofolate reductase inhibitors. The dependence of the activity on the structural parameters of “ligand-receptor” complexes is determined.     

Unexpected end‐groups of poly(acrylic acid) prepared by RAFT polymerization

Low‐molecular‐weight poly(acrylic acid) (PAA) was synthesized by reversible addition fragmentation chain transfer polymerization with a trithiocarbonate as chain‐transfer agent (CTA). With a combination of NMR spectroscopy and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, the PAA end‐groups of the polymer were analyzed before and after neutralization by sodium hydroxide. The polymer prior to neutralization is made up of the expected trithiocarbonate chain‐ends and of the H‐terminated chains issued from a reaction of transfer to solvent. After neutralization, the trithiocarbonates are transformed into thiols, disulfides, thiolactones, and additional H‐terminated chains. By quantifying the different end‐groups, it was possible to demonstrate that fragmentation is the rate limiting step in the transfer reaction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5439–5462, 2004     

示差半微分循环伏安法研究琥珀酰胆碱在水/硝基苯界面的传递行为

研究了油/水界面电解的示差半微分循环伏安行为。在0.01mol/L LiCl(w)-0.01mol/L TBATCIPB(nb)体系“电位窗”比TBATPB(nb)向正方向扩展约50mV,残余电流基本消除,使“电位窗”内的平台向左右拓宽约50mV。算得界面电容约为16μF/cm~2。考察了琥珀酰胆碱离子在w/nb界面的传递伏安特性,结果与一般半微分循环伏安法相似。但峰形改善,检测限降低一个数量级(1×10~(-6)mol/L),相对标准偏差在5％以内,可用于定量测定琥珀酰胆碱。     

Synthesis and herbicidal activity of O,O-dialkyl phenoxyacetoxyalkylphosphonates containing fluorine

A series of substituted phenoxyacetoxyalkylphosphonates bearing fluorine were designed and synthesized. All the new compounds were identified by elemental analysis, IR, ¹H NMR and MS and were tested for herbicidal activity in greenhouse at a rate of 1.5 kg/ha. The results of preliminary bioassay showed that fluorine moiety introduced to the core structure could help to improve the herbicidal activity, and compounds with a 3-trifluoromethyl in benzene ring exhibited higher inhibitory activity.     

Synthesis and studies of antibacterial activity of pongaglabol

Pongaglabol [8-hydroxy-5-phenyl-furo[2,3-h]benzo(b)pyran-7-one] was synthesized and tested for antibacterial effects againstShigella dysenteriae, Salmonella typhi, Streptococcus β-haemolyticus andStaphylococcus aureus. The synthesized compounds were characterized using UV, IR and¹H NMR spectral data     

Succinic acid adsorption from fermentation broth and regeneration

More than 25 sorbents were tested for uptake of succinic acid from aqueous solutions. The best resins were then tested for successive loading and regeneration using hotwater. The key desired properties for an ideal sorbent are high capacity, complete stable regenerability, and specificity for the product. The best resins have a stable capacity of about 0.06 g of succinic acid/g of resin at moderate concentrations (1–5 g/L) of succinic acid. Several sorbents were tested more exhaustively for uptake of succinic acid and for successive loading and regeneration using hot water. One resin, XUS 40285, has a good stable isotherm capacity, prefers succinate over glucose, and has good capacities at both acidic and neutral pH. Succinic acid was removed from simulated media containing salts, succinic acid, acetic acid, and sugar using a packed column of sorbent resin, XUS 40285. The fermentation byproduct, acetate, was completely separated from succinate. A simple hot water regeneration successfully concentrated succinate from 10 g/L (inlet) to 40–110 g/L in the effluent. If successful, this would lower separation costs by reducing the need for chemicals for the initial purification step. Despie promising initial results of good capacity (0.06 g of succinic/g of sorbent), 70% recovery using hot water, and a recovered concentration of >100 g/L, this regeneration was not stable over 10 cycles in the column. Alternative regeneration schemes using acid and base were examined. Two (XUS 40285 and XFS-40422) showed both good stable capacities for succinic acid over 10 cycles and >95% recovery in a batch operation using a modified extraction procedure combining acid and hot water washes. These resins showed comparable results with actual broth.     

3-乙氧基-6-取代苯氧基哒嗪除草活性的相关性研究

在分子拓扑理论的基础上,构建了新的结构信息价连接性指数mχY和取代基染色指数I,并用它们研究了3 乙氧基 6 取代苯氧基哒嗪的除草活性pI50与其结构之间的定量关系,给出了相关方程,相关性良好,复相关系数分别为R1=0.9807、R2=0.9926、R3=0.9881,并预测了几个化合物的pI50值,预测值pI50(cal.)与测定值pI50(exp.)相当吻合.新方法计算方便、结果可靠.