Sensitive CE-MS method for monitoring of riociguat and desmethylriociguat levels in human serum

Riociguat is novel antihypertensive drug for treatment of pulmonary hypertension. As such, it is still being tested in many clinical and pharmacokinetic trials. Existing methods that determine serum riociguat and desmethylriociguat (DMR) are based solely on liquid chromatography with mass spectrometry. Therefore, we present a novel capillary electrophoresis with mass spectrometry method (CE-MS) for their determination in human serum as alternative method for ongoing trials. Complete resolution of both analytes was achieved by means of pH optimization of ammonium formate background electrolytes that are fully compatible with ESI/MS detection. Simple liquid-liquid extraction was used as sample pretreatment. The calibration dependence of the method was linear (in the range of 10–1000 ng/mL), with adequate accuracy (90.1–114.9%) and precision (13.4%). LOD and LOQ were arbitrarily set at 10 ng/mL for both analytes. Clinical applicability was validated using serum samples from patients treated with riociguat in pharmacokinetic study and the results corresponded with reference HPLC-MS/MS values. Capillary electrophoresis proved to be sensitive and selective tool for the analysis of riociguat and DMR.     

Metabolomics techniques applied in the investigation of phenolic acids from the agro-industrial by-product of Carapa guianensis Aubl

Processing of Carapa guianensis seeds to obtain oil on an industrial scale generates a significant amount of by-product, approximately 66% w/w, which is called cake and is a potential source of biomolecules, including simple phenolic structures. For this reason, studies were carried out on the chemical profiles of hydrolyzed extract from this agro-industrial by-product through High Performance Thin-Layer Chromatography (HPTLC) and Gas Chromatography coupled to Mass Spectrometry (GC–MS). These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product. The sample antioxidant capacity was determined by methods of 2,2-diphenyl-1-picrylhydrazyl (DPPH)and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS⁺) radicals direct sequestration. The hydrolyzed fraction showed a total of 63.47% in the relative abundance of the total of compounds, standing out: p-hydroxybenzoic acid (39.19%) and protocatechuic acid (3,4-dihydroxybenzoic acid) (5.62%), both from hydroxybenzoic acids and 3-(3,4-dihydroxyphenyl)lactic acid, (7.76%) hydroxycinnamic acids derivatives. In these results, the fraction rich in simple phenolic acids was obtained, attributing the prominent behavior of this matrix antioxidant activity, expressed by (IC₅₀: of 16.42 µg/mL and 6.52 µg/mL for DPPH and ABTS⁺ radicals, respectively). The research demonstrated an alternative to applicability that involves sustainability from agro-industrial. These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product, generating a process capable of converting biomass into a bioproduct, consisting of bioactive compounds, in addition to adding value to the industrial chain.     

焦炉上升管内壁结焦炭层的光谱学分析及结焦机理研究

以焦炉上升管内壁结焦炭层块为研究对象，采用X射线荧光光谱仪（XRF）、X射线衍射仪（XRD）、傅里叶红外光谱仪（FTIR）和激光共聚焦拉曼光谱仪（Raman）对结焦炭层的元素组成，以及各结焦炭层的矿物组成、组成结构和分子结构进行测试。分析从结焦炭层块外表面向内表面过渡的各结焦炭层的差异性，揭示焦炉上升管内壁结焦机理。结果表明焦炉上升管内粉尘中Fe，S和Cr极易催化荒煤气中蒽、萘等稠环芳烃化合物成炭，在焦炉上升管内壁形成炭颗粒沉积，为焦油凝结挂壁提供载体，在荒煤气温度降至结焦温度时易结焦积碳。结焦炭层均含有芳香层结构，随着结焦炭层从外表面向内表面过渡，各结焦炭层的面层间距(d₀₀₂)逐渐降低、层片直径(L_a)先降低后增加、层片堆砌高度(Lc)和芳香层数(N)先稳定后增加。结焦炭层石墨化过程是由结焦炭层内表面向外表面进行，主要包括其片层外缘的羧基和部分C-O结构的降解剥离，从而形成高度规整的共轭结构。结焦炭层块中C元素是以结晶碳与无定型碳的混合物形式存在。以上研究为解决焦炉上升管内壁结焦及腐蚀问题，提高换热器换热效率，有效回收焦炉荒煤气显热，降低焦化企业能耗提供实验基础和理论依据。     

Mass transport in metals under intensive impulse reactions

An unusually high mobility of atoms under intensive impulse reactions is explained by the behavior of point defects at the shock wave front. It is shown that either a shock wave front or moving dislocations can capture the interstitials, or they can be thermally activated in the direction of the shock wave propagation.     

BP神经网络-FTIR方法测定苯乙烯-丙烯酸丁酯共聚物中单体含量

利用红外特征峰波数偏移值与单体含量间的非线性定量关系,BP人工神经网络-FTIR法在较宽的含量范围(10%-90%之间)之内,准确测定了苯乙烯-丙烯酸丁酯共聚物中丙烯酸丁酯单体含量,回收率在97.3%-101.8%之间.     

一种高信噪比的双光束激光光声光谱仪原理及应用

作为一种新兴的检测手段 ,激光光声光谱技术与其他检测技术相比具有很多优点。本文设计的光声光谱仪用激光做光源 ,有两个光声池 ,分别用来放置参考样品和待测样品 ,输出结果为二者光声信号的比值。利用这一比值 ,可以由参考样品的性能参数方便地求出待测样品的相关性能参数。该光声光谱仪有效地减小了本底吸收噪声的影响 ,提高了信噪比 ,扩大了固体光声理论的应用范围。本文还阐述了该光声光谱仪在定性定量分析中的一些应用     

CdSe和ZnO量子点的拉曼光谱研究

本文介绍了用拉曼光谱研究CdSe和ZnO两种Ⅱ Ⅳ族量子点材料的结果,对拉曼峰进行了指认。观察到的光学声子峰位的移动被认为是由量子限制效应引起。     

Improvements in Depth Selective Electron Mössbauer Spectroscopy

The conditions for achievement of high resolving power of depth selective conversion electron Mössbauer spectroscopy method at a combined installation ‘electron spectrometer–nuclear gamma-resonance spectrometer’ have been obtained. There has been made a considerable step in development of the method at its realization at a magnetic sector electron spectrometer with double focusing, equipped with electron source (a sample under investigation) of large-area and position-sensitive detector. The paper presents a prospective symmetrical version of a magnetic sector electron spectrometer that allows realizing more completely possibilities of the method. It is noted that the proposed method is particularly valuable for investigations of nanosystems, nanostrutures that contain Mössbauer nuclei.     

原子光谱线增宽的原因

本文从理论上给出了原子光谱线增宽的几种原因 ,即 :①自然线宽 ,它是原子的内禀特性 (即在跃迁中所涉及到的能级的特性 ) ;②多普勒增宽 ,它是原子无规则热运动的结果 ;③碰撞增宽 ,它是原子间相互作用的结果。并对这几种原因分别给出了数量级上的估算。对原子光谱的测定具有参考意义。     

On-line cysteine modification for protein analysis: new probes for electrochemical tagging nanospray mass spectrometry

A series of electrogenerated selective electrophiles based on substituted benzoquinones has been characterized as tags for l-cysteine and cysteine residues in proteins. The electrophiles are generated electrochemically from the corresponding hydroquinones. It is shown from mass spectrometry analysis that the electrogenerated benzoquinone can tag the biomolecules. The rate constants pertaining to the addition of l-cysteine onto the electrogenerated benzoquinones have been determined using electrochemical techniques. The substitution patterns have been unraveled leading to the assessment of site-specific rate constants. It is shown that the rate constants are primarily dependent on the electronic nature of the substituents as expressed by the Hammett substitution constant. The apparent tagging yields observed for l-cysteine in nanospray mass spectrometry experiments do not correspond to the yields expected from the electrochemical study, as the ionisation efficiencies are highly dependent on the tag. Finally, the on-line tagging has been tested using β-lactoglobulin A and myoglobin. Based on these results, it is concluded that the tagging reaction is selective towards cysteine when it takes place in the nanospray interface. The results show that the methodology presented can be used for a rapid characterization and identification of reactive sites in biomolecules.