Fragmentation patterns of novel dithiocarbamate derivatives with pharmaceutical activity under electrospray ionization tandem mass spectrometry conditions

The fragmentation patterns of a novel series of dithiocarbamate derivatives with pharmaceutical activity were investigated by positive ion electrospray ionization mass spectrometry in conjunction with tandem mass spectrometry (ESI-MS(n)). In the gas phase, the dithiocarbamate protonated molecules containing the piperazinium moiety undergo losses of bromide to form the piperazinium cation by ionization, followed by subsequent losses of methyl bromide, ring opening and rearrangement of piperazinium. Furthermore, the dithiocarbamate derivatives and their intermediates both undergo cleavage of the C-S bond to produce two common fragment ions. The different fragmentation observed for these compounds facilitated their identification and could be valuable in the further study of their metabolic pathways as prodrugs.     

Aggregation-induced emission of tetraphenylethene derivative as a fluorescence method for probing the assembling/disassembling of amphiphilic molecules

The aggregation-induced emission (AIE) of a 1,2-diphenyl-1,2-di(p-tolyl)ethene (TPE) was explored as a novel fluorescence method for probing the assembling/disassembling of amphiphilic molecules. The fluorescence intensity was able to monitor the formation of micelles and determine the critical micelle concentration (CMC) of surfactants. The temperature-dependent micellization of the pharmaceutically important PEO-PPO-PEO copolymer, Pluronic F127, was further studied by using the TPE fluorescence spectrum intensity. Our results showed good agreement with those reported in the literature by using other methods. The special advantage of the AIE probe method was further explored to determine the assembling/disassembling process of the colored amphiphilic molecule, 1-[4-(3-phenylazophenoxy)butyl]triethylamine bromide (AzoC4), whose CMC value has not previously been described. Since the TPE fluorescence signal mainly comes from the aqueous phase, not from the inside of hydrophobic core, it provides a possible platform to study the CMC of those colored surfactants. Based on the novel fluorescence properties of TPE in the aggregated and dispersed states, one can conclude that the TPE method is a promising method for the determination of the CMC and critical micellization temperature (CMT), particularly having a special advantage to determine the assembling/disassembling process of colored amphiphilic molecules.     

Dynamic pH junction-sweeping for on-line focusing of dipeptides in capillary electrophoresis with laser-induced fluorescence detection

In this paper, we developed a simple and effective on-line focusing technique combining dynamic pH junction and sweeping by capillary electrophoresis (CE) with laser-induced fluorescence (LIF) detection. Dynamic pH junction-sweeping is defined when the sample has a different buffer pH (dynamic pH junction condition) and is devoid of micelles (sweeping condition) relative to the background electrolyte (BGE). This hyphenated focusing mode was applied to the sensitive and selective focusing of four dipeptides: Tyr-Phe, Tyr-Leu, Trp-Gly, and Ala-Gln. Picomolar detectability of these dipeptides by CE-LIF detection was demonstrated through effective focusing of large sample volumes (up to 39% capillary length) using the dual pH junction-sweeping focusing mode. 25 mmol L(-1) sodium dihydrogen phosphate, pH 2.5 was used as the sample matrix, and 100 mmol L(-1) borate, 21 mmol L(-1) sodium dodecylsulfate (SDS), 16 mmol L(-1) Brij35, pH 9.0 as the background solution (BGS). The concentration detection limits (S/N = 3) of the four dipeptides were in the range of 1.0-5.0 pmol L(-1). The developed method has been successfully used for the determination of dipeptides in human serum samples.     

Bifunctionalized SBA-15 as a novel micropipette tip sorbent for selective removal and enrichment of biomolecules

Selective enrichment or removal of specific proteins prior to analysis can minimize nonspecific interferences as well as information loss, which has been an important issue in current proteomics fields. In this work, two kinds of mesoporous silica SBA-15 (mean pore diameter of 5 nm and 7 nm), bifunctionalized with quaternary ammonium and C18 groups via silylanization reaction, was used to investigate the adsorption behavior for different proteins (bovine serum albumin (BSA), ovalbumin (OVA), hemoglobin (Hb), lysozyme (Lys) and cytochrome c (cyt c)). As possessing anion exchange (quaternary ammonium) groups, the bifunctionalized SBA-15 showed selective adsorption of the negative charged proteins, BSA and OVA. Based on these properties, sequential fractionation based on different SBA-15 materials as micropipette tip sorbents was developed for sample preparation prior to protein analysis. As expected, after the sequential treatment of the sample, the detection signal of the high abundant BSA was significantly decreased and that of the low abundant cyt c was obviously enlarged, which solved the problem that low abundant protein was suppressed by adjacent high abundant protein. The sample preparation technique significantly improved protein identification and this sequential fractionation approach could be potentially applied to extend information on the protein identification for biological samples with a wide dynamic range.     

Spectroscopic investigation of fluoroiodomethane, CH2FI: Fourier-transform microwave and millimeter-/submillimeter-wave spectroscopy and quantum-chemical calculations

Guided by theoretical predictions, the rotational spectrum of fluoroiodomethane, CH(2)FI, has been recorded and assigned. Accurate values are reported for the ground-state rotational constants, all quartic, sextic, and two octic centrifugal-distortion constants. The hyperfine structure of the rotational spectrum was thoroughly investigated using a Fourier-transform microwave spectrometer and the Lamb-dip technique in the millimeter-/submillimeter-wave region, thus allowing the accurate determination of the complete iodine quadrupole-coupling tensor and of the diagonal elements of the iodine spin-rotation tensor. Relativistic effects turned out to be essential for the accurate theoretical prediction of the dipole moment and quadrupole-coupling constants and were accounted for by direct perturbation theory and a spin-free four-component treatment based on the Dirac-Coulomb Hamiltonian. The relativistic corrections to the dipole moment amount to up to 34% and to the iodine quadrupole-coupling tensor to about 15-16% of the total values.     

Molecular dynamics simulations of shock waves in oriented nitromethane single crystals

The structural relaxation of crystalline nitromethane initially at T = 200 K subjected to moderate (~15 GPa) supported shocks on the (100), (010), and (001) crystal planes has been studied using microcanonical molecular dynamics with the nonreactive Sorescu-Rice-Thompson force field [D. C. Sorescu, B. M. Rice, and D. L. Thompson, J. Phys. Chem. B 104, 8406 (2000)]. The responses to the shocks were determined by monitoring the mass density, the intermolecular, intramolecular, and total temperatures (average kinetic energies), the partitioning of total kinetic energy among Cartesian directions, the radial distribution functions for directions perpendicular to those of shock propagation, the mean-square displacements in directions perpendicular to those of shock propagation, and the time dependence of molecular rotational relaxation as a function of time. The results show that the mechanical response of crystalline nitromethane strongly depends on the orientation of the shock wave. Shocks propagating along [100] and [001] result in translational disordering in some crystal planes but not in others, a phenomenon that we refer to as plane-specific disordering; whereas for [010] the shock-induced stresses are relieved by a complicated structural rearrangement that leads to a paracrystalline structure. The plane-specific translational disordering is more complete by the end of the simulations (~6 ps) for shock propagation along [001] than along [100]. Transient excitation of the intermolecular degrees of freedom occurs in the immediate vicinity of the shock front for all three orientations; the effect is most pronounced for the [010] shock. In all three cases excitation of molecular vibrations occurs more slowly than the intermolecular excitation. The intermolecular and intramolecular temperatures are nearly equal by the end of the simulations, with 400-500 K of net shock heating. Results for two-dimensional mean-square molecular center-of-mass displacements, calculated as a function of time since shock wave passage in planes perpendicular to the direction of shock propagation, show that the molecular translational mobility in the picoseconds following shock wave passage is greatest for [001] and least for the [010] case. In all cases the root-mean-square center-of-mass displacement is small compared to the molecular diameter of nitromethane on the time scale of the simulations. The calculated time scales for the approach to thermal equilibrium are generally consistent with the predictions of a recent theoretical analysis due to Hooper [J. Chem. Phys. 132, 014507 (2010)].     

免疫亲和柱净化-液相色谱-串联质谱法测定中药材中的14种真菌毒素

依次采用磷酸盐缓冲液(PBS)和甲醇-PBS溶液提取样品,以多功能免疫亲和柱净化,采用液相色谱-串联四极杆质谱检测,可同时测定中药材中的黄曲霉毒素B1、黄曲霉毒素B2、黄曲霉毒素G1、黄曲霉毒素G2、伏马毒素B1、伏马毒素B2、T-2毒素、HT-2毒素、赭曲霉毒素A(OTA)、玉米赤霉烯酮等14种真菌毒素。优化条件下,真菌毒素的定量限(LOQ)为1～5 μg/kg, 4种中药材基质(人参、桔梗、板蓝根、麦门冬)中3个不同添加水平的平均回收率(n=6)为71.9%～99.7%,相对标准偏差(RSD)为4.8%～15.8%。该方法的检测速度快,中药材复杂基质的干扰较少,结果准确、可靠,定量限可满足国内外中药材真菌毒素相关限量的要求。     

高效液相色谱法测定乳及乳制品中4种人工合成甜味剂

提出了高效液相色谱法测定乳及乳制品中4种人工合成甜味剂安赛蜜、糖精钠、阿斯巴甜和纽甜含量的方法。样品加入亚铁氰化钾和乙酸锌使蛋白质沉淀析出后,以Diamonsil-C18色谱柱(250 mm×4.6 mm,5μm)为固定相,0.05 mol.L-1磷酸二氢钾溶液和乙腈为流动相梯度洗脱,用二极管阵列检测器于230 nm波长处检测安赛蜜,210 nm波长处检测糖精钠、阿斯巴甜和纽甜。安赛蜜、糖精钠、阿斯巴甜和纽甜的方法检出限(3S/N)分别为1.0,0.5,1.5,2.5μg.g-1。以空白乳粉样品为基体作加标回收试验,测得回收率在90.0%～103.3%之间,相对标准偏差(n=8)在2.1%～5.8%之间。     

基于分子内电荷转移的阴离子比率荧光分子探针

设计合成了一种基于4-甲基-1-羟基二苯甲酮对硝基苯腙的比色和比率荧光阴离子受体1。此类受体以羟基和腙单元为识别位点,以硝基苯基为信号报告基团。向受体1的DMSO溶液中加入AcO-、H2PO4-、F-后,溶液颜色由黄色变为紫红色,而加入所研究的其它阴离子则无变化,从而实现对AcO-、H2PO4-、F-这三种离子的裸眼识别。利用紫外-可见吸收光谱、荧光光谱考察了其与AcO-,H2PO4-,F-,Cl-,Br-,I-等阴离子的识别作用。1H NMR滴定为受体分子与阴离子之间氢键作用本质提供了有力证据。