MALDI Q-TOF CID MS for Diagnostic Ion Screening of Human Milk Oligosaccharide Samples

Human milk oligosaccharides (HMO) represent the bioactive components of human milk, influencing the infant’s gastrointestinal microflora and immune system. Structurally, they represent a highly complex class of analyte, where the main core oligosaccharide structures are built from galactose and N-acetylglucosamine, linked by 1–3 or 1–4 glycosidic linkages and potentially modified with fucose and sialic acid residues. The core structures can be linear or branched. Additional structural complexity in samples can be induced by endogenous exoglycosidase activity or chemical procedures during the sample preparation. Here, we show that using matrix-assisted laser desorption/ionization (MALDI) quadrupole-time-of-flight (Q-TOF) collision-induced dissociation (CID) as a fast screening method, diagnostic structural information about single oligosaccharide components present in a complex mixture can be obtained. According to sequencing data on 14 out of 22 parent ions detected in a single high molecular weight oligosaccharide chromatographic fraction, 20 different oligosaccharide structure types, corresponding to over 30 isomeric oligosaccharide structures and over 100 possible HMO isomers when biosynthetic linkage variations were taken into account, were postulated. For MS/MS data analysis, we used the de novo sequencing approach using diagnostic ion analysis on reduced oligosaccharides by following known biosynthetic rules. Using this approach, de novo characterization has been achieved also for the structures, which could not have been predicted.     

Radiation- and Photo-Induced Oxidation Pathways of Methionine in Model Peptide Backbone under Anoxic Conditions

Within the reactive oxygen species (ROS) generated by cellular metabolisms, hydroxyl radicals (HO^•) play an important role, being the most aggressive towards biomolecules. The reactions of HO^• with methionine residues (Met) in peptides and proteins have been intensively studied, but some fundamental aspects remain unsolved. In the present study we examined the biomimetic model made of Ac-Met-OMe, as the simplest model peptide backbone, and of HO^• generated by ionizing radiation in aqueous solutions under anoxic conditions. We performed the identification and quantification of transient species by pulse radiolysis and of final products by LC-MS and high-resolution MS/MS after γ-radiolysis. By parallel photochemical experiments, using 3-carboxybenzophenone (CB) triplet with the model peptide, we compared the outcomes in terms of short-lived intermediates and stable product identification. The result is a detailed mechanistic scheme of Met oxidation by HO^•, and by CB triplets allowed for assigning transient species to the pathways of products formation.     

裂解气相色谱-质谱法鉴别双组分丙烯酸汽车清漆

为了提高微量物证鉴定中对双组分丙烯酸汽车清漆的鉴别能力，采用裂解气相色谱-质谱法(Py-GC/MS)检测该类清漆，并考察该方法在鉴定实践中的适用性。该方法的重现性好，丙烯酸聚氨酯清漆3个裂解单体的相对峰面积的日内RSD不大于5.3%，日间RSD不大于10.6%。应用该方法对6种丙烯酸氨基树脂汽车清漆样品及一例微量物证案件送检样品进行检测，结果表明，裂解气相色谱-质谱法对双组分丙烯酸汽车清漆的鉴别能力优于红外光谱法。在微量物证鉴定实践中，需要根据检材量酌情使用此方法，并注意“先无损后有损”的检验顺序。     

Corrosion inhibition of mild steel using Novel Bis Schiff’s Bases as corrosion inhibitors: Electrochemical and Surface measurement

Purpose: The aim of the present investigation is to evaluate the corrosion inhibiting properties of four novel synthesize compounds namely N¹,N^1′-(1,4-phenylene)bis(N⁴-(4-nitrobenzylidene)benzene-1,4-diamine) SB-I, N¹,N^1′-(1,4-phenylene)bis(N⁴-benzylidenebenzene-1,4-diamine) SB-II, N¹,N^1′-(1,4-phenylene)bis(N⁴-(4-methylbenzylidene)benzene-1,4-diamine) SB-III, N¹,N^1′-(1,4-phenylene)bis(N⁴-(4-methoxybenzylidene)benzene-1,4-diamine) SB-IV for mild steel in 1 M HCl. Corrosion inhibitors find wide application in industries during pickling of steel, descaling and oil well acidization. Inhibitors have attracted great attention due to cost effectiveness and simplicity of the methods. Method: Different experimental techniques such as weight loss, open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization were used to evaluate the corrosion inhibition performance of SBs for mild steel in acid solution. After the corrosion experiments, the surface morphology of metal surface in the absence and presence of SBs were studied by scanning electron microscopy (SEM) and Atomic force microscopy (AFM). Findings: The corrosion inhibition efficiency of SBs for mild steel are 71.42% (SB-I), 89.52 (SB-II), 92.85 (SB-III), 96.19 (SB-IV). Tafel polarization revealed that all the SBs behaved as mixed-type inhibitor but predominantly of cathodic type. The inhibition actions of these Schiff base molecules blocked the electrode surface by means of adsorption of the inhibitor molecule on metal surface, obeying the Langmuir adsorption isotherm. SEM/AFM studies of the metal surfaces confirm the protection of metal surface in presence of inhibitor as compared to the damaged surface in blank acid solution.     

PTA尾气组成及浓度分布的研究

通过典型炼厂PTA装置尾气来源及去向分析,对装置排放点尾气组成及浓度分布进行了研究,采用气相色谱/质谱法研究了PTA尾气组成,采用直接进样大口径毛细管柱气相色谱法,测定了PTA尾气中溴甲烷、乙酸甲酯、苯、甲苯、对二甲苯、乙酸。进样量为1 m L时,方法对溴甲烷、乙酸甲酯、苯、甲苯、对二甲苯、乙酸的最低检出浓度分别为0.5、0.5、0.5、0.5、1.5,20 mg/m~3,加标回收率为95.2%~99.4%,相对标准偏差为1.8%~3.9%。采用总烃测定仪和烟气分析仪对总烃、一氧化碳、二氧化碳、氧气等进行了分析。同时采用本法对PTA尾气治理设施处理效率进行了评价,证明方法具有较好的适应性。     

Determination of organochlorine pesticides in shrimp by gas chromatography–mass spectrometry using a modified QuEChERS approach

Pacific white shrimp (Litopenaeus vannamei) collected during dry and rainy seasons from three different states in Malaysia were analyzed for nine organochlorine pesticides (OCPs) (α-HCH, β-HCH, γ-HCH, δ-HCH, trans-chlordane, cis-chlordane, p,p′-DDE, p,p′-DDD and p,p′-DDT) using QuEChERS sample preparation method and GC–MS SIM with split/splitless injection mode. The efficiency of combination of primary and secondary amine (PSA) and octadecyl (C18) at 25 mg of PSA and 25 mg of C18 per mL of shrimp extract as the clean-up sorbent to remove matrix interferences was evaluated. By combining PSA and C18, matrix interferences such as gamma-tocopherol and cholesterol were not able to be eliminated. Good separation and high recoveries which ranged from 90 to 105% with associated RSD < 15% were obtained for all OCPs at 3–75 ng/g. No significant difference in recoveries due to seasonal variation for studied OCPs, except for α-HCH, β-HCH, δ-HCH and p,p′-DDT were obtained. The limits of detection and quantification ranged from 0.3 to 4.5 ng/g and 3 to 15 ng/g, respectively. The linearity for matrix matched standard calibrations was >0.99.     

The rapid selecting of precursor ions and product ions of thirty-four kinds of pesticide for content determination by GC–EI/MS/MS

Pesticide residues caused great threat to human body health, and all countries protected the health of human body by specifying its upper limit. However, pesticide residues were generally very low, similar to trace analysis and as low as millionth or less, the content determination of pesticide residues was a troublesome problem. With the application and promotion of tandem mass spectrometry, it was able to do trace analysis. GC–EI/MS/MS was a common method for the determination of pesticide residues. The multiple reaction monitoring (MRM) mode was the most common quantitative method used in GC–EI/MS/MS. It has the characteristics of high sensitivity, good reproducibility, high accuracy, strong anti-interference and high ion flux. Multiple-twin precursor ions, product ions and collision energy of thirty-four pesticides were provided for MRM. It could play an important role in developing MRM method for the quantifying of 34 kinds of pesticide. Meanwhile, the development of MRM method for the quantifying of other compounds could also refer to this paper.     

The water–gas shift reaction over CeO2/CuO: Operando SSITKA–DRIFTS–mass spectrometry study of low temperature mechanism

An inverse CeO₂/CuO catalyst has been investigated by operando steady-state isotopic transient kinetic analysis (SSITKA) in combination with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) under 3% CO + 3% H₂O reactant mixture at 473 K with the aim of determining intermediates involved in the water–gas shift reaction at relatively low temperatures. Among the various species detected in the infrared spectra which may be involved in the reaction, i.e. formates, copper carbonyls and carbonates, a particular type of carbonate species is identified as a reaction intermediate on the basis of detailed analysis of the spectra during isotopic exchange in comparison with the change in the corresponding isotopically labelled CO₂ product.     

Detection of the residues of nineteen pesticides in fresh vegetable samples using gas chromatography–mass spectrometry

In this study, we investigated the presence of 19 different agricultural pesticides in 210 samples of eight types of domestic vegetables collected from several vegetable-growing regions in Bangladesh. A multiresidue method was developed to detect the pesticide levels in the collected samples using gas chromatography with mass spectrophotometry (GC–MS). Pesticide residues were detected in 51.30% of the total samples, and among the positive samples, 38.89% contained levels above the maximum residue levels (MRLs). The most frequently detected pesticides were chlorpyrifos (34) followed by carbofuran (17), diazinon (16), carbaryl (14), malathion (11), endosulfan (8), cypermethrin (7) and dimethoate (6). Some (10.47%) of the samples contained multiple residues. It is concluded that the continuous monitoring and strict regulation of pesticide use on food crops, especially vegetables, are necessary.