Effect of p-tert-Butylcalix[4]arene Fitted with Phosphinoyl Pendant Arms as Synergistic Agent in the Solvent Extraction and Separation of Some Trivalent Lanthanoids with 4-Benzoyl-3-methyl-1-phenyl-5-pyrazolone

The synergistic solvent extraction of five selected lanthanoid ions (La³⁺, Nd³⁺, Eu³⁺, Ho³⁺ and Lu³⁺) with a 4-benzoyl-3-methyl-1-phenyl-5-pyrazolone(HP) and the 5,11,17,23-tert-butyl-25,26,27,28-tetrakis(dimethylphosphinoylmethoxy)calix[4]arene, (S) in CHCl₃ has been studied. It was found that in presence of this phosphorus-containing calix[4]arene the lanthanoids have been extracted as LnP₃ · S. On the basis of the experimental data, the values of the equilibrium constants have been calculated. The influence of the synergistic agent on the extraction process has been discussed. A synergistic effect of almost three orders of magnitude occurs in the extraction of Ln(III) with mixture of HP and S. The values of the separation factors (S.F.) between the adjacent elements have been evaluated. On the basis of the IR and NMR spectra the stoichiometry and the structure of the solid complexes of Eu(III) with HP and Eu(III) with HP and S were proposed.     

Zur Totalsynthese von Human-Sekretin

Summary The synthesis of the heptacosapeptide amide with the primary structure of Human-secretin is described. For this purpose 7 fragments were designed, i.e. H-Gly-Leu-Val-NH₂ 25–27b,Z-Arg(Z ₂)-Leu-Leu-Gln-OH 21–24,Z-Arg(Z ₂)-Leu-Gln-OH 18–20,Z-Arg(Z ₂)-Glu(OtBu)-Gly-Ala-OH 14–17,Z-Arg(Z ₂)-Leu-OH 12–13,Z-Thr(tBu)-Ser(tBu)-Glu(OtBu)-Leu-Ser(tBu)-OH 7–11,Adoc-His(Adoc)-Ser(tBu)-Asp(OtBu)-Gly-Thr(tBu)-Phe-OH 1–6 these fragments were consequently assembled to the overall protected total sequence using the Wünsch/Weygand-method with dicyclohexylcarbodiimide. After deprotection by exposure to trifluoroacetic acid in presence of 1,2-ethanedithiol and water as scavenger, the isolated crude product was purified by column chromatography on CM-Sepharose, fast flow. This synthetized Human-secretin showed the full biological activity in comparison to Porcine-secretin.

Herrn Prof. Dr. E. Bayer zum 65. Geburtstag gewidmet.     

Optimization strategies in micellar electrokinetic capillary chromatography

Summary Computer-assisted procedures for the one-parameter optimization of the surfactant concentration and the concentration of urea or D-glucose as modifiers in micellar electrokinetic capillary chromatography have been developed. These procedures permit a rapid optimization of one parameter on the basis of only two experiments. Predicted values are compared to empirically obtained optimum values. The influence of the modifier concentration on the critical micelle concentration of sodium dodecyl sulfate was experimentally determined in buffers commonly employed in micellar electrokinetic chromatography. The alteration of retention factors of solutes caused by the influence of urea addition on the critical micelle concentration of sodium dodecyl sulfate was calculated under the assumption of constant distribution coefficients and compared to experimentally obtained values. It was demonstrated that the addition of urea or of D-glucose does not alter the phase ratio substantially.     

Pretreatment of swine wastewater using anaerobic filter

Efforts were made to assess the efficiency of an anaerobic filter packed with porous floating ceramic media and to identify the optimum operational condition of anaerobic filter as a pretreatment of swine wastewater for the subsequent biological removal of nitrogen and phosphorus. A stepwise decrease in hydraulic retention time (HRT) and an increase in organic loading rate (OLR) were utilized in an anaerobic filter reactor at mesophilic temperature (35°C). The optimum operating condition of the anaerobic filter was found to be at an HRT of 1 d. A soluble chemical oxygen demand (COD) removal efficiency of 62% and a total suspended solids removal efficiency of 39% at an HRT of 1 d were achieved with an OLR of 16.0 kg total COD/(m³·d), respectively. The maximum methane production rate approached 1.70 vol of biogas produced per volume of reactor per day at an HRT of 1 d. It was likely that the effluent COD/total Kjeldahl nitrogen ratio, of 22, the COD/total phosphorous ratio of 47, and the high effluent alkalinity >2500 mg/L as CaCO₃ of the anaerobic filter operated at an HRT of 1 d was adequate for the subsequent biological removal of nitrogen and phosphorus.     

Variable low-mass filtering using an electrodynamic ion funnel

An adjustable low-mass filter has been developed for an electrospray ionization (ESI) source to block ions associated with unwanted background species from entering the mass spectrometer. The low-mass filter is made by using an adjustable potential energy barrier from the conductance-limiting plate of an electrodynamic ion funnel, which prohibits species with higher ion mobilities from exiting the ESI source. We show that this arrangement provides a linear voltage adjustment for low-mass filtering from m/z 0 to 500. Mass filtering above m/z 500 is also performed; however, higher-mass species are attenuated. The mass filter was tested with a liquid chromatography/mass spectrometry (LC/MS) analysis of a bovine serum albumin (BSA) tryptic digest and resulted in the ability to block low-mass, background species, which accounted for 40-70% of the total ion current immediately behind the ESI source during peak elution and detection.     

Effect of pressure on retention factors in HPLC using a non-porous stationary phase

Summary Pressure and temperature have significant influence on retention in HPLC. This study investigates the effect of pressure and temperature on the retention behavior of aromatic hydrocarbons (toluene, ethyl benzene, butyl benzene, pentyl benzene) and polar, acidic and basic samples (phenol, acetophenone, N,N-dimethyl aniline, benzophenone) on a reversed phase column. The effect has been studied on non-porous, tetradecyl (C₁₄) coated silica particles. We found that the adsorption-induced decrease of the partial molar volume of the solutes investigated was between ΔV _m =5–15 cm³ mol⁻¹. The increment of the decrease of the partial molar volume due to the addition of one CH₂ group, for the homologous series of the aromatic hydrocarbons is approximately ΔV _CH2 =2.3 cm³mol⁻¹. Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001.     

Evaluation of behaviour of linear monoamines CH3-(CH2)n−1-NH2 (n=1-6) in ion chromatography

This paper reports the results on a study of ion chromatography (IC) behaviour on strong cationic exchange column of CH₃-(CH₂)_n−1-NH₂ (n=1-6) type linear monoamines. The eluents were mixtures of HCl-NaCl, HNO₃-NaNO₃, HClO₄-NaClO₄, H₂SO₄-Na₂SO₄, HClO₄-NaClO₄-CH₃CN. Amines were revealed with an amperometric detector. The influence of different counter-ions on retention factors, k′, is discussed. Relationships between k′ and pE (E=sum of Na⁺ and H⁺ concentrations), and length of alkylic chain, and sensitivity coefficient S, are reported and discussed. The addition of acetonitrile (ACN) in the eluent was also taken into account. Suitable considerations are derived from these data. An example of monoamines separation is given.     

基于碘乙酸功能化树枝状聚合物的硫巯化肽段选择性富集新方法

蛋白质的硫巯化是一种重要的氧化翻译后修饰，在细胞衰老、内质网应激、血管舒张、细胞凋亡等过程中扮演重要角色。利用蛋白质组学技术表征硫巯化修饰具有十分重要的意义。该文发展了一种基于碘乙酸功能化的聚酰胺-胺树枝状聚合物（PAMAM-INS），并结合滤膜辅助的样品预处理技术用于硫巯化肽段的富集（简称FADE策略），利用FADE策略能从100倍质量干扰的牛血清白蛋白酶解产物中选择性地富集出硫巯化标准肽段。将细胞培养稳定同位素标记技术引入到FADE策略中，并将其应用于不同浓度梯度硫氢化钠刺激的SHSY5Y细胞硫巯化蛋白质组分析，共鉴定到163条硫巯化肽段。生物信息学的结果表明，硫巯化修饰可能在中枢神经系统中扮演着重要角色。     

基于5-芳基乙内酰脲类化合物的CoMFA和HQSAR研究

用CoMFA和HQSAR两种QSAR方法研究了50个乙内酰脲类分子的定量构效关系.本研究从构象搜索所得的低能结构出发构建化合物分子的构象, 建立CoMFA模型,并进行了全空间搜索. HQSAR本质上是一种二维的QSAR方法,与CoMFA方法相比,该方法在数据处理方面,比CoMFA方法快捷,并且可重复性好.两种方法均得到了较好分析结果, CoMFA的交叉验证相关系数q2 值为0.815, HQSAR的q2值为0.893.这些方程有力地说明了该类分子在(R,R)-N-3,5-dinitrobenzoyl-1,2-diamine型手性固定相上拆分过程中的影响因素,对今后类似拆分的实验研究提供了理论支持.     

MEASUREMENTS OF CHAIN INTERPENETRATION OF POLYMER GLASSES

The concept of entanglement provides the basis of our current understanding of the flow behavior of polymer melts, Current techniques developed to investigate the degree of interpenetration of polymer chains only provide indirectly the information of the degree of entanglement in a relatively large scale （several to tens of nanometer）. In this article, we report ^1H-NMR spectroscopy with dipolar filters under fast magic angle spinning for probing chain interpenetration of polymer glasses at the molecular level.