Optimization of the mass spectrometric analysis of triacylglycerols using negative-ion chemical ionization with ammonia

Conditions for the mass spectrometric analysis of triacylglycerols,via direct exposure probe, with ammonia negative-ion chemical ionization were optimized. Triacylglycerols were most favorably ionized, using the reactant gas pressure of approximately 8500 mtorr at the ion source temperature of 200°C with the instrumentation used. Abundant [M-H]⁻ ions were produced under these conditions without the formation of [M+35]⁻ cluster ions, which would interfere with the molecular weight region of triacylglycerols in the spectra. A rapid desorption of the sample from the probe wire is recommended, using a relatively high heating rate (approximately 40 mA s⁻¹), to minimize thermal degradation of unsaturated molecules and the reducing effect of double bonds on the mass spectrometric response of triacylglycerols. Furthermore, the abundance of [M-H]⁻ ion was enhanced by rapid heating, which we found to be important to improve the sensitivity. The appropriate amount of sample applied to the rhenium wire was in the region of 50–300 ng for one determination, i.e., only a few nanograms of a single triacylglycerol is required for production of a reliable spectrum. The reproducibility of the method was good as demonstrated with standards and a raspberry seed oil sample. The described mass spectrometric method is a fast and potentially useful tool for semiquantitative determination of triacylglycerol mixtures of various fats and oils. The discrimination, caused by differences in molecular size and unsaturation of triacylglycerols with 50 to 56 acyl carbons, was negligible under our optimized ionization conditions, thus, no correction factors were needed. These findings have not yet been verified with instruments in other laboratories. However, the present study shows how the analysis of triacylglycerols can be improved, regardless of the instrument, by optimization of the analytical conditions.     

Electrospray ionization mass spectrometric end-group analysis of PMMA produced by radical polymerization using diacyl peroxide initiators

The type and number of end groups of poly(methyl methacrylates) from free-radical polymerization with six diacyl peroxides, R-(CO)O-O(CO)-R, acting as initiators have been analyzed via electrospray ionization mass spectrometry using an ion trap and additionally Fourier transform ion cyclotron resonance for mass detection. The polymerizations were carried out in benzene solution at high initiator concentration to yield low molecular weight polymer. With R being an alkyl group, only R moieties are observed as end groups. For each oligomer size, molecules with one or two such end groups are formed, depending on whether termination occurs via disproportionation or combination. With R being an aryl type, as in di-benzoyl and di-naphthoyl peroxides, both R and R-(CO)O moieties are detected as polymeric end groups. Because of aromatic delocalization, fractions of the arylic R-(CO)O radicals are sufficiently long living at 95 °C to add to a monomer molecule prior to undergo decarboxylation.     

Probing mechanistic features of conventional, catalytic and living free radical polymerizations using soft ionization mass spectrometric techniques

The present feature article provides an overview on the use of state-of-the-art mass spectrometry techniques such as matrix assisted laser desorption and ionization time of flight (MALDI-TOF) mass spectrometry as well as electrospray ionization mass spectrometry (ESI-MS) for probing the mechanism of free radical polymerization processes. The article features representative examples of the application of mass spectrometry techniques to conventional free radical polymerization, nitroxide mediated polymerization (NMP), atom transfer radical polymerization (ATRP), reversible addition fragmentation chain transfer (RAFT) as well as catalytic chain transfer (CCT) processes.     

Equilibrium and crystallographic measurements of the binary tetrahydrofuran and helium clathrate hydrates

Clathrate compounds are crystalline materials formed by a physical interaction between host and relatively light guest molecules. Various types of nano-sized cages surrounded by host frameworks exist in the highly unique crystalline structures and free guest molecules are entrapped in an open host-guest network. Recently, we reported two peculiar phenomena, swapping and tuning, naturally occurring in the hydrate cages. Helium, one of the smallest light guest molecules, must be the challengeable material in the sense of physics and moreover possesses versatile applications in the field of superconductivity technology and thermonuclear industry. In this regard, we attempted for the first time to synthesize helium hydrates at moderate temperature and pressure conditions. According to inclusion phenomena, helium itself normally cannot form clathrate hydrates due to being too small molecularly without the help of hydrate former molecules (sI, sII, and sH formers). In this study, the hydrate equilibria of the binary clathrate hydrate containing tetrahydrofuran, helium, and water were determined at 2, 3, 5.56 THF mol%. Direct volumetric measurements were also carried out to confirm the exact amount of helium captured in the hydrate cages. Finally, the crystalline structure of the formed mixed hydrates was identified by powder X-ray diffraction, resulting in structure II.     

New oxidation pathway of 3,5-di-tert-butyl-4-hydroxytoluene: An ionspray tandem mass spectrometric and gas chromatographic/mass spectrometric study

The autoxidation of 3,5-di-tert-butyl-4-hydroxytoluene (BHT, 1) in bar soap was investigated with ionspray tandem mass spectrometric and on-line gas chromatographic/mass spectrometric methods. The oxidation products of BHT were extracted from the bar soap surface, concentrated, and fractionated with open-column chromatography to remove the impurities. New oxidation products of BHT (BHT phenol-type dimer 7 and others) were identified with the two mass spectrometric methods. The results suggested that oxidation of BHT in bar soap occurred in a way different from that in the previous studies. In the new pathway, oxidation of BHT first generates an excited state of phenol-type dimer 4, and then this species decomposes, due to its high energy, to form dimer 7. The mechanism of oxidation is discussed.     

X射线荧光分析技术及相关标准介绍

1X射线荧光分析简介X射线荧光分析是以化学元素受到适当激发时放射出特征辐射的事实为依据的。根据荧光X射线的激发方式和分光方式的不同,相应的仪器被称为光谱仪和能谱仪。光谱仪采用X射线管激发,分光晶体分光,可对氟到铀之间的所有元素进行分析,仪器构造复杂,国内尚无法生产。能谱仪采用小功率X射线管、同位素源等激发,采用波高分析器分光,一般仅能对设定的10种左右的元素进行分析,国内已可进行批量生产,在水泥行业应用较广的有钙铁分析仪、硅铁铝钙四元素分析仪和硅铁铝钙镁硫钛钾钠多元素分析仪等。X射线荧光分析除具有一般的仪器分…     

A mass spectrometric investigation of native and oxidatively inactivated chloroperoxidase

The enzyme chloroperoxidase (CPO) found in Caldariomyces fumago is able to catalyze several stereoselective oxidation reactions by using a clean oxidant, usually hydrogen peroxide (H(2)O(2)), without the need for expensive cofactor generation. CPO's lack of operational stability, however, is a major limitation for its commercial use. In the present study, a capillary-LC on-line trypsin-digestion system combined with reversed-phase chromatography and mass spectrometric detection was optimized for studying the primary sequence of CPO. Samples containing native CPO, CPO treated with H(2)O(2), and CPO oxidatively inactivated by the use of indole and H(2)O(2) were analyzed and compared. Three oxidized peptides were found in the samples treated with H(2)O(2). Two additional oxidized peptides were found in the CPO samples that were completely inactivated, one of which contained an oxidized cysteine residue, Cys50, which is an essential amino acid due to its function as the axial ligand to the iron in the heme--the prosthetic group in CPO. In addition, the heme group was absent in the inactivated samples but was readily detected in other samples.     

Electrospray ionization mass spectrometric analyses of changes in tissue phospholipid molecular species during the evolution of hyperlipidemia and hyperglycemia in Zucker diabetic fatty rats

The Zucker diabetic fatty (ZDF) rat is a genetic model of type II diabetes mellitus in which males homozygous for nonfunctional leptin receptors (fa/fa) develop obesity, hyperlipidemia, and hyperglycemia, but rats homozygous for normal receptors (+/+) remain lean and normoglycemic. Insulin resistance develops in young fa/fa rats and is followed by evolution of an insulin secretory defect that triggers hyperglycemia. Because insulin secretion and insulin sensitivity are affected by membrane phospholipid fatty acid composition, we have determined whether metabolic abnormalities in fa/fa rats are associated with changes in tissue phospholipids. Electrospray ionization mass spectrometric analyses of glycerophosphocholine (GPC) and glycerophosphoethanolamine (GPE) molecular species from tissues of prediabetic (6 wk of age) and overtly diabetic (12 wk) fa/fa rats and from +/+ rats of the same ages indicate that arachidonate-containing species from heart, aorta, and liver of prediabetic fa/fa rats made a smaller contribution to GPC total ion current than was the case for +/+ rats. There was a correspondingly larger contribution from species with sn-2 oleate or linoleate substituents in fa/fa heart and aorta. The relative contributions of arachidonate-containing GPC species increased in these tissues as fa/fa rats aged and were equal to or greater than those for +/+ rats by 12 wk. For heart and aorta, relative contributions from GPE species with sn-2 arachidonate or docosahexaenoate substituents to the total ion current increased and those from species with sn-2 oleate or linoleate substituents fell as fa/fa rats aged, but these tissue lipid profiles changed little with age in +/+ rats. GPC and GPE profiles for brain, kidney, sciatic nerve, and red blood cells were similar among fa/fa and +/+ rats at 6 and 12 wk or age, and pancreatic islets from fa/fa and +/+ rats exhibited similar GPC and GPE profiles at 12 wk of age. Under-representation of arachidonate-containing GPC and GPE species in some fa/fa rat tissues at 6 wk could contribute to insulin resistance, but depletion of islet arachidonate-containing GPC and GPE species is unlikely to explain the evolution of the insulin secretory defect that is well-developed by 12 wk of age.     

Pyrolysis-field ionization mass spectrometry of polyamide copolymers and blends

Nylon foils of PA 6, PA 66, PA 69, PA 12, the copolymer PA 666, and nine blends based on these polymides have been investigated by in-source pyrolysis (Py)–field ionization mass spectrometry (FIMS). These polymers and blends can be distinguished by characteristic molecular ions of oligomers, protonated amines and nitriles, and products terminated by olefinic end groups. Series of ions are formed differing in the number of additional monomeric units. Thus, polymers containing different chemical subunits were easily distinguished from each other in the spectra of the blends. Mass signals, only expected for copolymers, were found in the integrated blend spectra, indicating that amide exchange reactions occur under the experimental conditions employed. This observation was confirmed by pyrolysis of mixtures of pure polymers in the same crucible and under the same experimental conditions. Hence, the distinction by Py–MS alone between blends and copolymers with an identical averaged number of identical chemical subunits is not possible.     

Direct measurement of formation and dissociation rate and storage capacity of dry water methane hydrates

Dry water (DW) has been recently demonstrated to be an effective medium for methane storage in a hydrated form. Here, a series of experiments have been carried out on dry water methane hydrates (DW-MH) to investigate their formation and dissociation rates, storage capacity and structural characteristics. The result shows that the storage capacity of MH increases at least 10% by using DW relative to using surfactants like sodium dodecyl sulfate (SDS) solution. Also, it is found that controls on pressure-temperature (P-T) condition have influences on the induction and reaction time of DW-MH formation, i. e. the induction and reaction time are much shorter when the reaction cell is cooled to ~ 3 °C first. On the basis of Raman spectra, the hydration number is calculated as 5.934 ± 0.06 at different positions of the DW-MH, which suggests that the sample is very homogeneous. The dissociation process of the DW-MH sample exhibits a rapid release of methane gas at the first stage of dissociation. Although hydrate dissociation is prevented by the effect of self preservation, most methane gas has released from the hydrate, however, before the self preservation occur.     

A mass spectrometric and molecular modelling study of cisplatin binding to transferrin

A combination of mass spectrometry, UV/Vis spectroscopy and molecular modelling techniques have been used to characterise the interaction of cisplatin with human serum transferrin (Tf). Mass spectrometry indicates that cisplatin binds to the hydroxy functional group of threonine 457, which is located in the iron(III)-binding site on the C-terminal lobe of the protein. UV/Vis spectroscopy confirms the stoichiometry of binding and shows that cisplatin and iron(III) binding are competitive. The binding of cisplatin has been modelled by using molecular dynamic simulations and the results suggest that cisplatin can occupy part of both the iron(III)- and carbonate-binding sites in the C-terminal lobe of the protein. Combined, the studies suggest that cisplatin binding sterically restricts iron(III) binding to the C-terminal lobe binding site, whereas the N-terminal lobe binding site appears to be unaffected by the cisplatin interaction, possibly allowing the iron(III)-induced conformational change necessary for binding to a Tf receptor.     

Theory and kinematic measurements of the mechanics of stable electrospun polymer jets

We present a simplified approach to understanding the mechanics of stable electrospinning jets based on electrohydrodynamic theory that explicitly incorporates the extensional rheology of polymeric fluids. Flow regimes of electrospun jets are identified by analogy to uniaxial extension of a fluid jet. These flow regimes predict the limiting kinematics of electrospinning jets and identify dimensionless parameters important to the control and operation of electrospinning processes. In situ kinematic measurements validate model assumptions and scaling predictions, and allow the reduction of entire jet radius and velocity profiles to several key parameters. The model predictions are shown to hold both above and below the entanglement concentration, as well as for solutions with added electrolyte and increased conductivity. The analysis also enables direct measurement of the apparent extensional viscosity of solutions at the high extension rates experienced during electrospinning. Finally, dimensional analysis of the model yields a correlation for electrospun fiber diameter in terms of measurable fluid properties, controlled process parameters, and measured jet variables, demonstrating the influence of mechanics in the straight portion of the jet on ultimate fiber morphology.     

Applications of electrospray ionization mass spectrometry in mechanistic studies and catalysis research

Mechanistic studies form the basis for a better understanding of chemical processes, helping researchers develop more sustainable reactions by increasing the yields of the desired products, reducing waste production, and lowering the consumption of resources and energy overall. Conventional methods for the investigation of reaction mechanisms in solution include kinetic studies, isotope labeling, trapping of reactive intermediates, and advanced spectroscopic techniques. Within the past decade, electrospray ionization mass spectrometry (ESI-MS) has provided an additional tool for mechanistic studies because researchers can directly probe liquid samples by mass spectrometry under gentle conditions. Specifically, ESI-MS allows researchers to identify the molecular entities present in solution over the course of a chemical transformation. ESI-MS is particularly useful for investigations of organic reactions or metal catalysis that involve ionic intermediates. Accordingly, researchers are increasingly using ESI-MS in mechanistic studies and catalyst development. However, a further understanding of the ESI process and how it can facilitate mechanistic studies has not accompanied this increased use of the technique. Therefore, at least in part the ESI-MS method not only has offered great promise for the elucidation of reaction mechanisms but also became a black box with the occasional risk of misinterpretation. In this Account, we summarize applications of ESI-MS for synthetic and mechanistic research. Recently researchers have established direct linkages between gas-phase data obtained via ESI-MS and processes occurring in solution, and these results reveal qualitative and quantitative correlations between ESI-MS measurements and solution properties. In this context, time dependences, concentration series, and counterion effects can serve as criteria that allow researchers assess if the gas-phase measurements correlate with the situation in the solution. Furthermore, we report developments that bridge the gap between gas-phase and solution-phase studies. We also describe predictions derived from ESI-MS that have been verified with solution-phase chemistry experiments.     

GPC法测定PAN的平均相对分子质量及其分布

用凝胶渗透色谱 (GPC)测定PAN的平均相对分子质量及其分布。采用宽分布的PAN标准试样 ,在溶剂二甲基甲酰胺中加入 0 .0 4～ 0 .0 8mol/L的NaNO3替代LiBr ,提高了色谱柱的分离效果。用计算机模拟出PAN的GPC校正曲线方程 ,对宽分布的标准试样进行重复测定 ,结果相对标准偏差均小于 3 .5 %。     

Determination of the structure and composition of clinically important polyurethanes by mass spectrometric techniques

Curie-point pyrolysis mass spectrometry (Py-MS) and direct probe pyrolysis high resolution mass spectrometry (Py-HRMS) were used to identify the components and additives used in the synthesis and compounding of Biomer, Lycra Spandex, Tecoflex, and Pellethane. Two types of Biomer were identified (P and Q, our notation) which are composed of poly(tetramethylene glycol) (PTMG) capped with 4,4′-methylenebis(phenylisocyanate) (MDI) and chain-extended with ethylenediamine (EDA). Both forms contain 4,4′-butylidene-bis-(6-t-butyl-m-cresol) antioxidant, and Biomer Q also contains an additive which appears to be a quaternary ammonium chloride salt. Lycra Spandex was found to be identical to Biomer Q, with the exception that a low molecular weight polydimethylsiloxane oil is also present. This silicone oil can be removed by solvent extraction. Tecoflex (type SG80A) is composed of PTMG capped with 4,4′-diisocyanatodicyclohexylmethane and extended with 1,4-butanediol (BD). An industrial grade and a medical grade of Pellethane were analyzed. Both were composed of PTMG capped with MDI and extended with 1,4-butanediol. the industrial grade also contains an antioxidant, possibly butylated diphenylamine.     

Characterization of triacylglycerols in the seeds ofAquilegia vulgaris by chromatographic and mass spectrometric methods

A combination of analytical techniques is generally necessary to properly characterize complex lipid materials. Chromatographic separation in conjunction with spectroscopic characterization was utilized for the analysis of the triacylglycerols in the seeds ofAquilegia vulgaris. Reversed-phase high-performance liquid chromatography (HPLC), micropacked argentation supercritical fluid chromatography (SFC), and combinations of the two techniques were used. The fatty acid profile was determined by gas chromatography/mass spectrometry of the picolinyl esters and by gas chromatography/flame-ionization detection of the methyl esters. The major components were also identified by direct inlet mass spectrometry. The excellent selectivity of packed fused silica argentation SFC for the separation of triacylglycerols was demonstrated.     

PPTA分子构象模拟及相对分子质量及其分布研究

利用Material Studio软件对聚对苯二甲酰对苯二胺(PPTA)的模型分子对苯二甲酰对苯二胺的单键内旋转势能进行计算,在最小能量假设条件下推算出一定聚合度PPTA大分子的末端距,以此与PPTA稀溶液(PPTA质量分数为0.8%的浓硫酸溶液)的光散射图谱得到的均方回转径分布进行关联,可得到其相对分子质量及其分布。结果表明:PPTA的链节长为1.328 nm,数均相对分子质量和重均相对分子质量分别为32 405,38 862;根据Mark-Houwink方程测得的PPTA的特性黏数为5.79 dL/g,与用乌氏黏度计测得的PPTA比浓对数黏度值5.58 dL/g的结果一致。     

Biodesulphurization of a coal by packed-column leaching. Simultaneous thermogravimetric and mass spectrometric analyses

This study has two aims: to improve the biodesulphurization of a semi-anthracite by packed-column leaching by reducing the insoluble sulphate on the coal surface, and to determine whether after the combustion of treated and untreated coal, sulphate sulphur is transformed completely into sulphur dioxide or part remains in the ashes without reacting. Combustion tests were analysed by TG-MS. To reduce the precipitation of salts, two parameters are worked on: solution pH, which is reduced to 1.3, and the idle time between washes (ITBW), which is altered. After 125 days of treatment, comparison with the results of previous studies showed that the precipitated salt content was reduced pyritic desulphurization was increased up to 43%, and total desulphurization to 24%.     

APC-MALLS法测定聚酰胺相对分子质量及其分布

以5 mmol/L的三氟乙酸钠的六氟异丙醇溶液为溶剂及流动相,采用超高效聚合物色谱-多角度激光光散射仪-示差折光仪检测器,在色谱柱为ACQUITY APC XT 450,200,125,柱温55℃,检测器温度25℃,流动相流速0.5 m L/min,进样量为50μL的条件下,测定聚酰胺6(PA 6)、聚酰胺66(PA 66)的相对分子质量及其分布,探讨了折光指数增量(dn/dc),试样浓度对测试结果的影响。结果表明:PA 6,PA 66的dn/dc分别为(0.260 3±0.009 3)m L/g,(0.243 9±0.003 8)m L/g,质量浓度均为2×10-3g/m L时,在色谱操作条件下,测得PA 6,PA 66数均相对分子质量分别为20 100,19 100,重均相对分子质量分别为31 400,27 800,相对分子质量分布宽度平均值为1.56,1.46,6次测量的变异系数分别为1.96%,2.26%,试样洗脱峰出现时间均为4.5~9 min;该方法重复性和准确性较好,可大幅度缩短测试时间。