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1.
Eugene Arthur-Baidoo Joao Ameixa Milan On
k Stephan Denifl 《International journal of molecular sciences》2021,22(6)
We investigate dissociative electron attachment to tirapazamine through a crossed electron–molecule beam experiment and quantum chemical calculations. After the electron is attached and the resulting anion reaches the first excited state, D1, we suggest a fast transition into the ground electronic state through a conical intersection with a distorted triazine ring that almost coincides with the minimum in the D1 state. Through analysis of all observed dissociative pathways producing heavier ions (90–161 u), we consider the predissociation of an OH radical with possible roaming mechanism to be the common first step. This destabilizes the triazine ring and leads to dissociation of highly stable nitrogen-containing species. The benzene ring is not altered during the process. Dissociation of small anionic fragments (NO2−, CN2−, CN−, NH2−, O−) cannot be conclusively linked to the OH predissociation mechanism; however, they again do not require dissociation of the benzene ring. 相似文献
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The complex physical and chemical reactions between the large number of low-energy (0–30 eV) electrons (LEEs) released by high energy radiation interacting with genetic material can lead to the formation of various DNA lesions such as crosslinks, single strand breaks, base modifications, and cleavage, as well as double strand breaks and other cluster damages. When crosslinks and cluster damages cannot be repaired by the cell, they can cause genetic loss of information, mutations, apoptosis, and promote genomic instability. Through the efforts of many research groups in the past two decades, the study of the interaction between LEEs and DNA under different experimental conditions has unveiled some of the main mechanisms responsible for these damages. In the present review, we focus on experimental investigations in the condensed phase that range from fundamental DNA constituents to oligonucleotides, synthetic duplex DNA, and bacterial (i.e., plasmid) DNA. These targets were irradiated either with LEEs from a monoenergetic-electron or photoelectron source, as sub-monolayer, monolayer, or multilayer films and within clusters or water solutions. Each type of experiment is briefly described, and the observed DNA damages are reported, along with the proposed mechanisms. Defining the role of LEEs within the sequence of events leading to radiobiological lesions contributes to our understanding of the action of radiation on living organisms, over a wide range of initial radiation energies. Applications of the interaction of LEEs with DNA to radiotherapy are briefly summarized. 相似文献
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Maicol Cipriani Styrmir Svavarsson Filipe Ferreira da Silva Hang Lu Lisa McElwee-White Oddur Inglfsson 《International journal of molecular sciences》2021,22(16)
Platinum coordination complexes have found wide applications as chemotherapeutic anticancer drugs in synchronous combination with radiation (chemoradiation) as well as precursors in focused electron beam induced deposition (FEBID) for nano-scale fabrication. In both applications, low-energy electrons (LEE) play an important role with regard to the fragmentation pathways. In the former case, the high-energy radiation applied creates an abundance of reactive photo- and secondary electrons that determine the reaction paths of the respective radiation sensitizers. In the latter case, low-energy secondary electrons determine the deposition chemistry. In this contribution, we present a combined experimental and theoretical study on the role of LEE interactions in the fragmentation of the Pt(II) coordination compound cis-PtBr2(CO)2. We discuss our results in conjunction with the widely used cancer therapeutic Pt(II) coordination compound cis-Pt(NH3)2Cl2 (cisplatin) and the carbonyl analog Pt(CO)2Cl2, and we show that efficient CO loss through dissociative electron attachment dominates the reactivity of these carbonyl complexes with low-energy electrons, while halogen loss through DEA dominates the reactivity of cis-Pt(NH3)2Cl2. 相似文献
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Srinath Chamarthy Chung W Seo Wayne E Marshall 《Journal of chemical technology and biotechnology (Oxford, Oxfordshire : 1986)》2001,76(6):593-597
The objective of this study was to modify peanut shells to enhance their adsorptive properties toward the metal ions cadmium (Cd2+), copper (Cu2+), nickel (Ni2+), lead (Pb2+) and zinc (Zn2+). Milled peanut shells were initially washed with water or 0.1 N NaOH or left unwashed. Following these treatments or lack of treatment, the shells were either left unmodified or modified by a heat treatment in the presence of either 1.0 M phosphoric acid or 0.6 M citric acid. Modified peanut shells were evaluated either for adsorption efficiency or for adsorption capacity using the five metal ions listed above. Adsorption efficiencies and capacities were compared with efficiencies and/or capacities for the commercial chelating or cation exchange resins Amberlite 200, Amberlite IRC‐718, Duolite GT‐73, and carboxymethylcellulose. For the adsorption efficiencies of individual metal ions, modified peanut shells met or exceeded the adsorption values for cadmium, copper, nickel or zinc ions compared with the commercial resins Duolite GT‐73 and carboxymethylcellulose. In a solution containing all five metal ions, modified peanut shells met or exceeded the adsorption efficiencies for cadmium, copper and lead ions compared with Duolite GT‐73, Amberlite IRC‐718 and carboxymethylcellulose. Adsorption capacities of modified peanut shells met or exceeded the adsorption capacity of Duolite GT‐73 for lead ions only. Citric or phosphoric acid‐modified peanut shells showed a preference for Cu2+ and Pb2+ and appear promising as potentially inexpensive adsorbents for selected metal ions. © 2001 Society of Chemical Industry 相似文献
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In chemoradiation therapy, dissociative electron attachment (DEA) may play an important role with respect to the efficiency of the radiosensitizers used. The rational tailoring of such radiosensitizers to be more susceptive to DEA may thus offer a path to increase their efficiency. Potentially, this may be achieved by tailoring rearrangement reactions into the DEA process such that these may proceed at low incident electron energies, where DEA is most effective. Favorably altering the orbital structure of the respective molecules through substitution is another path that may be taken to promote dissociation up on electron capture. Here we present a combined experimental and theoretical study on DEA in relation to pentafluorothiophenol (PFTP) and 2-fluorothiophenol (2-FTP). We investigate the thermochemistry and dynamics of neutral HF formation through DEA as means to lower the threshold for dissociation up on electron capture to these compounds, and we explore the influence of perfluorination on their orbital structure. Fragment ion yield curves are presented, and the thermochemical thresholds for the respective DEA processes are computed as well as the minimum energy paths for HF formation up on electron capture and the underlying orbital structure of the respective molecular anions. We show that perfluorination of the aromatic ring in these compounds plays an important role in enabling HF formation by further lowering the threshold for this process and through favorable influence on the orbital structure, such that DEA is promoted. We argue that this approach may offer a path for tailoring new and efficient radiosensitizers. 相似文献
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矿浆中金属离子对硅线石与石英浮选分离的影响 总被引：5，自引：0，他引：5
系统研究了Fe^3 和Al^3 等金属离子对硅线石和石英可浮性的影响,结果表明：采用油酸钠为捕收剂,Fe^3 和Al^3 在中性或弱碱性介质中对石英浮选有很强活化作用,从而使硅线石和石英浮选分离困难,柠檬酸对金属离子活化石英有很强抑制作用,而对硅线石抑制作用较弱,是浮选分离硅线石和石英较好的的选择性抑制剂,Auger电子能谱仪测试表明：柠檬酸在硅线石表面作用前后Al峰的化学位移为-0.1eV,化学作用很弱,而在Fe^3 和Al^3 离子活化的石英表面,加入柠檬酸前有明显Al Auger电子能峰,加入后,石英表面Al Auger电子能峰消失,表明柠檬酸加入促使吸附在石英表面Al^3 离子溶解,使石英表面阴离子捕收剂吸附活性点降低。 相似文献
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M. M. Mossoba P. M. Yurawecz J. A. G. Roach R. E. McDonald E. G. Perkins 《Journal of the American Oil Chemists' Society》1996,73(10):1317-1321
Cyclic fatty acid monomers (CFAM) are degradation products found in heat-abused edible oils. This study confirms previously
published data and reports the structural elucidation of hydrogenated and deuterated monocyclic and bicyclic CFAM prepared
from the corresponding unsaturated species that were previously isolated from heated flaxseed (linseed) oil. CFAM structures
were determined as 2-alkyl-4,4-dimethyloxazoline derivatives by using gas chromatography-electron ionization mass spectrometry.
The observed retention times for the deuterated CFAM were about 0.1 min shorter than those of the corresponding hydrogenated
species. For two minor six-membered ring CFAM components, an increase in the mass of the unsaturated ring by eight mass units
upon deuteration indicated the addition of four deuterium atoms to two double bonds in that ring. These data unequivocally
confirmed the identity of cyclohexadienyl CFAM species in the original CFAM mixture that was isolated from heated linseed
oil. The observed electron ionization mass spectrometic data for minor hydrogenated and deuterated CFAM species, which correspond
to the last two eluting monounsaturated species, were consistent with CFAM having bicyclic (fused 5- and 6-membered rings)
structures. The location of the ring along the fatty acid chain was also confirmed for all saturated CFAM mixture components.
The presence of a pair of deuterium atoms on two adjacent carbon atoms further confirmed the previously determined double-bond
position along the fatty acid chain of the corresponding parent (unsaturated) compound.
This work was presented in part at the 85th AOCS Annual Meeting in Atlanta, Georgia, May 8–12, 1994. 相似文献
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Acrylamide was grafted to an xanthate mixture of carboxymethylcellulose with a sodium bisulfate/ammonium persulfate redox initiator system in water, sodium hydroxide, potassium hydroxide, and dioxane at 40, 50, 60, 70, and 80°C during a reaction period of 2 h. The grafted polymer and homopolymer were isolated with diethyl ether from the reaction mixture, dried, and weighed. The grafted polymer was characterized with IR and mass spectrometry methods, and the microscopic morphology was detected with electron scanning microscopy. The graft level percentage distinctly increased with the use of sodium hydroxide, potassium hydroxide, and dioxane over that of a reaction carried out completely in an aqueous medium. Also, the graft level decreased as the reaction temperature increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 271–278, 2004 相似文献
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采用气相色谱/串联三重四级杆质谱法(GC/MS/MS)建立了分析葱、蒜、洋葱及其制品中25种有机磷的分析方法。葱、蒜、洋葱及其制品经提取、净化处理后,采用气相色谱/串联三重四级杆质谱法检测,25种有机磷农药在线性范围内均呈现良好的线性关系,线性系数0.99。该方法的检出限(LOD)为0.001~0.005 mg/kg。三水平六平行的实验结果表明,该类化合物的回收率为63%~115%,相对标准偏差(RSD)为0.67%~13.5%。方法重现性好、精密度高、操作简单,适用于对葱、蒜、洋葱及其制品中多种有机磷的检测。 相似文献
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《云南化工》2017,(7):31-35
研究苹果酸和柠檬酸热裂解产物对卷烟品质的影响。利用热裂解-气相色谱/质谱法模拟苹果酸和柠檬酸在卷烟燃吸过程中产物的变化,研究不同裂解温度(300℃,600℃,900℃)条件下苹果酸和柠檬酸的裂解产物和对卷烟品质的影响,并对机理进行了初步的探讨。在不同温度热裂解时,苹果酸的热裂解产物,主要是乙酸,丙烯酸和2,5-呋喃二酮,柠檬酸热裂解产物主要是丙酮和柠康酸酐。苹果酸和柠檬酸的热裂解产物都产生了大量的酸性物质。相比柠檬酸,苹果酸更利于改善吸味,平衡烟气,增加烟气浓度。根据苹果酸和柠檬酸裂解生成的主要产物,对裂解原理进行了探讨,认为苹果酸可能按照三种途径发生裂解,柠檬酸可能按照两种途径发生裂解。 相似文献
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电站锅炉的柠檬酸清洗 总被引：1，自引：3，他引：1
大港电厂采用柠檬酸作清洗剂对锅炉进行了化学清洗,清洗效果不错,设备表面清洗干净,形成了钢灰色的钝化膜,监视片腐蚀速率低,圆满完成了清洗任务。 相似文献
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以乙二胺四乙酸或柠檬酸作配位剂,在无氰的硫代硫酸盐–亚硫酸盐体系中研究了金在镀镍铜基底上的电沉积。在温度为60°C,pH为6和电流密度为2A/dm2的条件下,研究了不同配位剂对电流效率、镀速、镀层硬度及镀液分散能力的影响。最佳的镀液组成为0.5mol/L硫代硫酸钠–亚硫酸钠 0.2mol/L乙二胺四乙酸(或0.3mol/L柠檬酸)。该镀液具有良好的分散能力及高达98%的电流效率。采用扫描电镜、原子力显微镜及X射线衍射分析了镀态金镀层的表面形貌和晶体结构。所得的金镀层几乎无孔(孔隙率<2~4个/cm2),结合力良好,硬度适中(80~130HV)。 相似文献
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Maillard reactions generate a wide array of amino acid- and sugar-derived intermediates; the isomeric mixtures of glycated amino acids are of particular interest. Excluding stereoisomers, regioisomers, and various anomers, most amino acids can form two monoglycated and three N,N-diglycated isomers when reacted with sugars during the Maillard reaction. Using synthetic Schiff bases and Amadori compounds as standards, we have demonstrated that diagnostic ions obtained from MS/MS fragmentations in negative ionization mode can be used effectively for the discrimination between glucose-derived Schiff bases and their corresponding Amadori compounds in both mono- and diglycated forms. The utilization of these diagnostic ions and isotopic labeling in the glycine/glucose model system revealed that milling glucose/glycine mixtures for 30 min/30 Hz at ambient temperature produced monoglycated glycine in equal proportions of Amadori and Schiff base forms, whereas diglycated glycine was a mixture of the three isomers: Schiff-Schiff, Schiff-Amadori, or Amadori-Amadori in approximately equal molar proportions. The above results were further corroborated using a synthetic histidine Amadori product, N,N-difructosyl-β-alanine, dipeptides, and ribose. Using mechanochemistry as a convenient synthetic tool in combination with MS/MS diagnostic ions, the isomeric diversity of the early stages of the Maillard reaction can be revealed. 相似文献
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