The correlation between molecular polarizability of PAHs and their retention data on various stationary phases in reversed-phase HPLC

Summary The equation for the potential energy of interactions established for gas-liquid chromatography has been confirmed in reversed phase liquid chromatography. Equations derived for molecular polarizabilities of PAHs and their retention data have very high correlation coefficients. The results indicate that the inductive effect between solute and stationary phase is the main one and the dispersive effect is very small compared with the inductive effect but its contribution increases with the carbon chain length of the stationary phase.     

反相高效液相色谱法测定3种中成药中的葛根素

 建立了测定小儿清感灵片、步长新脑心通胶囊和感冒清热颗粒 3种中成药中葛根素含量的反相高效液相色谱方法。采用APEXODS色谱柱 ,以醋酸铵缓冲液 (10 0mmol/L ,pH 5 0 ) 甲醇 (体积比为 75∶2 5 )的混合溶液为流动相 ,检测波长为 2 5 0nm ,流速为 0 8mL/min。葛根素在 2mg/L～ 2 0mg/L时其色谱峰面积与质量浓度的线性关系良好 (r =0 9999) ;上述 3种中成药中的葛根素含量分别为 3 48mg/g ,1 0 8mg/ g及 1 5 2mg/ g(蔗糖型 ) ;其加样回收率分别为 99 0 % ,93 4%和 97 5 %。该法简便、快速、专属性强 ,可以作为多种中药制剂中葛根素含量的测定方法。     

Rearrangement Free Method for Hardy-Littlewood-Sobolev Inequalities on $\mathbb{S}^n$

For conformal Hardy-Littlewood-Sobolev(HLS) inequalities [22] and reversed conformal HLS inequalities [8] on $\mathbb{S}^n,$ a new proof is given for the attainability of their sharp constants. Classical methods used in [22] and [8] depends on rearrangement inequalities. Here, we use the subcritical approach to construct the extremal sequence and circumvent the blow-up phenomenon by renormalization method. The merit of the method is that it does not rely on rearrangement inequalities.     

High performance liquid chromatographic studies on lanthanides, uranium and thorium on amide modified reversed phase supports

The retention behavior of uranium, thorium and lanthanides has been investigated with amide modified reversed phase C₁₈ supports using α-hydroxy isobutyric acid (α-HIBA) as the mobile phase. Four structurally different amide moieties namely, 4-hydroxy-N,N-dihexyl butyramide (4HHBA), 4-hydroxy-N,N-di-2-ethylhexylhexanamide (4HEHHA), bis(N,N,N′,N′-2-ethylhexyl)malonamide (B2EHM) and N-methyl-tris(dihexylcarbamoyl-3-methoxy)pivolamide (MTDCMPA) have been synthesized and studied. Among the various amide coated columns, the supports modified with 4HHBA, B2EHM and MTDCMPA exhibit an interesting retention for uranium and thorium, which is different from 4HEHHA modified support. The retention time for uranium and thorium increases with increasing amide concentration for 4HHBA, B2EHM and MTDCMPA supports, while the same decreases with increasing 4HEHHA content. However, the separation factor for uranium and thorium is greater on a 4HEHHA support, compared to an unmodified C₁₈ column, reflecting the amide's preferential complexation of uranium over thorium.Columns modified with 4HHBA, B2EHM and MTDCMPA exhibit relatively higher retentions for lanthanides. However, MTDCMPA modified support shows a different elution profile for lanthanides compared to 4HHBA, and B2EHM modified columns. Individual separations of heavier lanthanides, i.e., from gadolinium to lutetium also have been achieved using 4HHBA and B2EHM modified supports.The influence of modifier content, mobile phase concentration and its pH on the retention of metal ions has also been studied. Based on these investigations, an efficient high performance liquid chromatographic method (HPLC) has been developed for the rapid separation of uranium from thorium as well as for the individual separation of heavier lanthanides.     

反相离子对高效液相色谱法测定母粉及母液中的杀鼠新

用反相离子对高效液相色谱法测定了杀鼠新母粉及母液中有效成份含量。采用Partisil-10ODS色谱柱，以甲醇：离子对溶液＝80：20（体积比）为流动相，离子对溶液为0.005mol/L四丁基铵磷酸盐（pH为7.5)的缓冲溶液，测定波长285nm。方法在0.025-0.15g/L范围内有很好的线性关系。杀鼠新母粉和母液的相对标准偏差分别为1.24%、0.77%(n=7)，回收率分别为：母粉,97.7%-99.8%；母液，98.5%-100.4%。     

One-Step Synthesis of Monolithic Silica Nanocomposites in Fused Silica Capillaries

The ideal way to prepare efficient, yet robust stationary phases for microanalytical high-resolution methods such as capillary chromatography and electrochromatography remains to be defined. In this contribution a one step sol-gel process is proposed for the production of monolithic, macroporous nanocomposite phases in fused silica capillaries, which require no additional derivatization, since they already bear the interactive (C8) moieties. The effect of the catalyst, the water content, the pH, as well as that of certain additives on monolith formation and porosity is investigated. Volume shrinkage and a tendency to crack were the major obstacles to overcome. Homogeneous stationary phases could be produced by applying a pH gradient during sol formation, thereby changing the catalytic principle from acidic (0.1 M HCl) to basic (gradual formation of OH^– as a consequence of the hydrolysis of N-methylformamide). Gelation/coacervation of suchgels could be induced by the addition of N,N-diethylamine. The water content during sol formation was determined as decisive for pore formation, with 250% of the amount theoretically needed for complete hydrolysis of all precursors giving optimal results. The volume shrinkage problem during xerogel formation was resolved by integrating dialkyldialkoxysilane units (dimethyldiethoxysilane 35 mol%) into the silica network.     

The identification of tricyclic neuroleptics and sulphonamides by high-performance thin-layer chromatography

Circular high-performance thin-layer chromatography (HPTLC) has been used to differentiate a series of twelve tricyclic neuroleptics, using both normal phase and reverse phase procedures. The use of normal phase systems also allows the resolution of geometric isomers of chlorprothixene, clopenthixol and flupenthixol. Thirteen sulphonamides and Trirnethoprim may also be distinguished using HPTLC.     

Gas Hydrate Formation in Reversed Micelles

We describe a technique to modify protein solubility and optimize enzyme activity in reversed micellar solutions. The technique is based on the ability of hydrates of natural gas to form in the micro-aqueous phase. Clathrate hydrates are crystalline inclusions of water and gas, and their formation in bulk water has traditionally been studied with relevance to natural gas recovery. We have found that hydrates can form in the environment of the microaqueous pools of reversed micelles, and that their extent of formation can be well controlled through the thermodynamic variables of temperature and pressure. Additionally, formation of hydrates affects the size and aggregation number of the micelles, and thus influences the solubility and conformation of encapsulated proteins. We demonstrate how the concept can be used in two applications: (i) protein extraction into reversed micelles and subsequent recovery, and (ii) optimization of enzyme activity in reversed micelles.     

Kinetic and stability characterization ofChromobacterium viscosum lipase and its comparison withPseudomonas glumae lipase

A kinetic study ofChromobacterium viscosum lipase was undertaken, and compared withPseudomonas glumae lipase. Optimum operation conditions were pH 9.0 and 50°C for both enzymes. A substrate specificity study was also developed. Both enzymes showed higher activity on triglycerides with a long chain of fatty acid; the specific activity was always higher for C.viscosum lipase. Stability of both enzymes in aqueous medium at 60°C and pH 9.0 was evaluated. C.viscosum lipase was three times more stable than P.glumae lipase, with at _1/2 value of 0.75 h. In addition, the activity of C.viscosum lipase with substrate concentration was studied with a triolein emulsion. A dependence of the intrinsic characteristics of the emulsion was observed. Therefore, stability ofC. viscosum lipase B with reaction products was assayed in a micellar system. Acid products reduced the specific activity of the enzyme. Glycerol and high buffer concentration were stabilizers of enzyme deactivation. Finally, substrate specificity ofC. viscosum lipase B in a micellar system was developed with tributyrin, tricaprylin, and triolein. Only tributyrin showed an apparent Michaelis-Menten kinetic with V_max ^app = 958 U/mg and K_ma ^app = 75.5 mM. Tricaprylin and triolein showed diffusion limitations at low substrate concentration and substrate inhibition at high substrate concentration. Diffusion parameters were calculated for both these substrates. Mass transfer coefficients (k₁) were 0.314 Å/min and 1.53 Å/min for tricaprylin and triolein, respectively. Effectiveness factors (η) were 0.536 and 0.768 for tricaprylin and triolein, respectively.     

N，N-二丁基癸酰胺萃取硝酸有机相结构研究

利用界面张力、电导、FT-IR等研究了不同硝酸浓度下萃取有机相的微结构。利用Gaussian曲线拟合处理N，N-二丁基癸酰胺(DBDEA)的羰基吸收峰，结果表明体系中存在多种以氢键结合的物种如DBDEA·HNO₃、(DBDEA)₂·HNO₃等。在较高酸度下有机相中萃取剂分子自组装成小的聚集体-反相胶团，极性核由水、硝酸和萃取剂高电荷密度的极性部分构成。