X射线荧光光谱法测定重整铂催化剂中氯

建立重整铂催化剂中氯的X射线荧光光谱测定方法。通过研磨机将铂催化剂研磨至粒径小于75 μm的颗粒,采用仪器压片制样,通过测量不同氯含量样品的计数率,建立铂催化剂中氯含量与计数率的线性关系。氯的质量分数在0.85%~1.04%范围内与计数率成良好的线性关系,相关系数为0.9995,检出限为0.0076%。样品加标回收率为96.2%~104.2%,测定结果的相对标准偏差小于2%(n=6)。该法测定结果与电位滴定法相吻合。该方法精密度高,分析速度快,满足重整装置生产调整的要求。     

气相色谱–质谱法快速分析化妆品中3种香精香料

建立气相色谱-质谱法快速测定化妆品中甲基柏木酮、甲基柏木醚、壬酸3种香精香料的方法。样品用甲醇超声提取,经高速冷冻离心,上清液干燥脱水后经0.45 μm滤膜过滤,直接注入气相色谱-质谱仪进行测定,用选择离子和保留时间定性,外标法定量。甲基柏木酮、甲基柏木醚、壬酸在各自的质量浓度范围内与色谱峰面积成良好的线性关系,相关系数分别为0.9992,0.9991,0.9994,检出限分别为0.05,0.1,0.1 mg/kg。测定结果的相对标准偏差为2.1%~6.6%(n=5),样品加标回收率为91.5%~97.7%。该方法准确度和灵敏度高,样品用量少,前处理简单,可同时测定化妆品中3种香精香料。     

Adsorption of a cationic water-soluble dye onto cationic Langmuir–Blodgett films via nano clay platelets: An efficient approach to control the H-dimer

This communication reports the successful adsorption of a water-soluble cationic fluorescent dye Acridine Orange (AO) onto Langmuir–Blodgett (LB) films of a cationic amphiphile octadecylamine (ODA) in the presence of nano-clay platelets hectorite. Acridine orange (AO) has been widely used as a stainer for the characterization of biopolymers. But AO has a tendency to form non-florescent H-dimer even in the aqueous solution. Anionic nano-clay platelets hectorite played an important role in controlling the H-dimer formation of AO in the hybrid film. Effects of various parameters in the adsorption process were investigated in detail.     

New insights into the extraction of uranium(VI) by an N,N-dialkylamide

This paper presents the methodology developed in order to thoroughly characterise a solvent extraction system containing high solute concentrations. The chemical system selected is N,N-(2-ethylhexyl)isobutyramide (DEHiBA) diluted in one alkane with increasing concentration of uranium(VI). Combining experiments with theoretical calculations allowed a deeper understanding of the extraction mechanism. A thermodynamic study was performed by the classical van't Hoff method and also by direct calorimetry to provide the enthalpies of extraction and specific heats. Dedicated methods like vapour pressure osmometry and electrospray ionisation mass spectrometry analysis provide information about the stoichiometry of the extracted species. Spectroscopic investigations with ultraviolet–visible and Fourier transform infrared probed the uranium coordination. Finally, a combination of molecular dynamics simulations, and small and wide-angle X-ray scattering experiments investigated the organisation in the organic phase beyond the molecular scale. It was shown that the high concentrations of uranium extracted have no influence on the stoichiometry of the complexes and the coordination of uranium in the inner sphere. The thermodynamic properties related to the extraction process and obtained with a fine consideration of the activity coefficients showed to be the same as those found with trace concentration. However, an unexpected organisation beyond the molecular scale was observed with an important role of nitrates as bridging ligands which could explain some physico-chemical properties. This approach could be applied to other chemical systems (other N,N-dialkylamides or other cations) to identify the origin of the different affinities between ligands and the difference of selectivity between cations.     

Strategies for differentiation of isobaric flavonoids using liquid chromatography coupled to electrospray ionization mass spectrometry

Flavonoids are a class of secondary plant metabolites existing in great variety in nature. Due to this variety, identification can be difficult, especially as overlapping compounds in both chromatographic separations and mass spectrometric detection are common. Methods for distinguishing isobaric flavonoids using MS² and MS³ have been developed. Chromatographic separation of various plant extracts was done with RP‐HPLC and detected with positive ESI‐MS operated in information‐dependent acquisition (IDA) mode. Two methods for the determination of flavonoid identity and substitution pattern, both featuring IDA criteria, were used together with the HPLC equipment. A third method where the collision energy was ramped utilized direct infusion. With the developed strategies, it is possible to differentiate between many isobaric flavonoids. Various classes of flavonoids were found in all of the plant extracts, in the red onion extract 45 components were detected and for 29 of them the aglycone was characterized, while the substituents were tentatively identified for 31 of them. For the strawberry extract, those numbers were 66, 30 and 60, and for the cherry extract 99, 56 and 71. The great variety of flavonoids, several of them isobaric, found in each of the extracts highlights the need for reliable methods for flavonoid characterization. Methods capable of differentiating between most of the isobars analyzed have been developed. Copyright © 2014 John Wiley & Sons, Ltd.     

Development of simultaneous analysis of tryptophan metabolites in serum and gastric juice – an investigation towards establishing a biomarker test for gastric cancer diagnosis

To evaluate changes in tryptophan metabolism and discover diagnostic biomarkers for gastric cancer, a quantitative method was developed for tryptophan and its seven metabolites (indole‐3‐lactic acid, anthranilic acid, serotonin, nicotinic acid, kynurenic acid, kynurenine and 3‐indoxyl sulfate) in both human serum and gastric juice using liquid chromatography–tandem mass spectrometry (LC–MS/MS). Serum and gastric juice were prepared with a simple protein precipitation using aqueous 0.1% formic acid and acetonitrile. As a result, it was found that the kynurenine pathway of tryptophan metabolism was activated in gastric cancer and that the metabolic ratio of kynurenine/tryptophan, which reflects the enzyme activity of indoleamine‐2,3‐dioxygenase, was associated with the observed metabolic changes. Finally, the investigation of tryptophan metabolites, especially kynurenic acid, in serum and gastric juice might serve as biomarkers for gastric cancer. The findings in this study provide critical information of tryptophan metabolism which can be applied to a serum‐based diagnostic test for gastric cancer.     

Mechanism of Disulfide–Disulfide Interchange in Polysulfide Polymer Melt Blend by Electron Ionization Mass Spectrometry. II

Abstract

The degree of randomization, q, of structural units in melt blends of the polysulfide homopolymers A(PS1) and B(PS2), wherein the disulfide equivalents D _A/D _B = 1, were studied by electron ionization mass spectrometry. Over the temperature range of 207–219°C, the relaxation process, due to the dominant disulfide–disulfide interchange reactions, is postulated to follow an associative reaction mechanism. These intermolecular disulfide–disulfide interactions promote a transient enhancement of the sulfur rank in the activated complex resulting in formation of the randomized co‐polymer AB. The mass spectrometric experimental design enabled measurement of concentrations of reactants A(PS1) and B(PS2), as well as the randomized copolymer AB, by monitoring the abundance of dimer units a₂, b₂, and ab, respectively as a function of time. The degree of randomization, q, was observed in the absence of catalysts or solvents, notwithstanding the solvent/solute and solute/solvent characteristics of the polymer melt blend. The mechanism of this randomization process, was rationalized on the basis of the properties of sulfur, aided by the observation of macrocyclic monomeric and dimeric units during the retro‐polymerization reactions under the EI/MS conditions employed. The model polysulfide polymers A(PS1) and B(P52), used in this study were synthesized from bis(2‐chloroethyl)ether and bis(2‐chloro ethoxy)methane, respectively.     

Actuation design for high‐performance shape memory polyurethanes

A series of shape memory polyurethanes were synthesized from poly(tetramethylene glycol), 4,4‐methylene diphenyl diisocyanate, and 1,3‐butanediol. The prepolymers with different molecular weights (M_c) were capped with 2‐hydroxyl ethylacrylate or 3‐aminopropyltriethoxysilane (APTES) and crosslinked by UV curing or a sol–gel reaction. Variations of the crosslinker functionality (f), subchain density (N), and hard segment content (HSC) produced systematic variations of the glass transition temperature (6–45 °C), accompanied by changes in the mechanical, dynamic mechanical and shape memory properties. More than 95% of shape fixity and 98% of shape recovery up to the fourth cycles were obtained with APTES crosslinked 3000M_c with 30% of HSC. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1473–1479     

Differential isotope dansylation labeling combined with liquid chromatography mass spectrometry for quantification of intact and N-terminal truncated proteins

The N-terminal amino acids of proteins are important structure units for maintaining the biological function, localization, and interaction networks of proteins. Under different biological conditions, one or several N-terminal amino acids could be cleaved from an intact protein due to processes, such as proteolysis, resulting in the change of protein properties. Thus, the ability to quantify the N-terminal truncated forms of proteins is of great importance, particularly in the area of development and production of protein-based drugs where the relative quantity of the intact protein and its truncated form needs to be monitored. In this work, we describe a rapid method for absolute quantification of protein mixtures containing intact and N-terminal truncated proteins. This method is based on dansylation labeling of the N-terminal amino acids of proteins, followed by microwave-assisted acid hydrolysis of the proteins into amino acids. It is shown that dansyl labeled amino acids are stable in acidic conditions and can be quantified by liquid chromatography mass spectrometry (LC–MS) with the use of isotope analog standards.     

Zur Anreicherung der stabilen Isotope des Schwefels durch Fest-Flüissig-Austausch unter Verwendung von Ionenaustauschern

An verschiedenen Systemen chemischer Verbindungen wurden Versuche zur Anreicherung des stabilen Isotopes ³⁴S unter Verwendung der Ionenaustauscher Wofatit L 150, SBW und SBK nach den Methoden der Frontalchromatographie und der Bandenverdrāngungschromatographie ausgeführt. Beim Isotopenaustauschsystem Hydrogensulfit (am Ionenaustauscher)/Schwefeldioxid (in wäβriger Lösung) wurden Verfahrensweise und Betriebsparameter hinsichtlich des Anreicherungsgrades optimiert. Mit Hilfe einer einfachen Methode gelang es, aus den Versuchsergebnissen Werle für den elementaren Trennfaktor und die Trennstufenhöhe zu berechnen.