硫二甘醇 | 111-48-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 中文名称: 硫二甘醇
• 中文别名: 硫双乙醇；2,2'-硫代二乙醇；二羟乙基硫醚；硫化双乙醇；二(2-羟乙基)硫醚；2,2-硫代双乙醇；硫代二甘醇；2,2'-硫基二乙醇；硫代双乙醇；2,2`-硫代二乙醇；二(2－羟乙基)硫醚
• 英文名称: 2,2'-thiobis-ethanol
• 英文别名: 2,2'-Thiodiethanol；Thiodiglycol；2-(2-hydroxyethylsulfanyl)ethanol
• CAS: 111-48-8
• 化学式: C₄H₁₀O₂S
• mdl: MFCD00002910
• 分子量: 122.188
• InChiKey: YODZTKMDCQEPHD-UHFFFAOYSA-N

物化性质

• 稳定性/保质期：
  1. 避免与氧化物接触。与氯化钙能形成加合物。 2. 生产过程中会产生硫化氢气体，因此应按照有毒硫化氢气体的防护要求采取措施。

计算性质

• 辛醇/水分配系数(LogP)：
  -0.6
• 重原子数：
  7
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  65.8
• 氢给体数：
  2
• 氢受体数：
  3

ADMET

代谢

亚硫二甘醇被氧化成四种代谢物。在这四种代谢物中有三种硫发生了氧化，其中两种形成了醋酸。没有记录代谢物的毒性影响信息...在啮齿动物中，亚硫二甘醇可以与葡萄糖醛酸和硫酸盐结合，或者它可以转化为亚硫二甘醇酸，后者可以与甘氨酸和葡萄糖醛酸结合...主要代谢物是亚硫二甘醇亚砜，次要代谢物是亚硫二甘醇砜、S-(2-羟基乙基亚硫酰)醋酸和S-(2-羟基乙硫基)醋酸。只有大约0.5到1%的亚硫二甘醇以原形排出。

Thiodiglycol is oxidized to four metabolites. In three of the four metabolites sulfur undergoes oxidation and in two of them acetic acid is formed. No information of toxic effects of the metabolites is recorded ... In rodents thiodiglycol can conjugate with glucuronic acid and sulfate or it can be converted to thiodiglycolic acid which can conjugate with glycine and glucuronic acid ... The major metabolite was thiodiglycol sulfoxide, minor metabolites were thiodiglycol sulfone, S-(2-hydroxyethylsulfinyl)acetic acid and S-(2-hydroxyethylthio)acetic acid. Only around 0.5 to 1% of thiodiglycol was excreted unchanged.

来源:Hazardous Substances Data Bank (HSDB)

代谢

皮肤水疱/由于芥子气暴露/可以进行抽吸，并分析获得的液体中的硫二甘醇。同样的估计也可以在血液和尿液中进行，以便区分由...其他剂如路易斯剂...产生的疱性反应。

Skin blisters /from mustard gas exposure/ may be aspirated and the fluid obtained analyzed for thiodiglycol. The same estimation may be performed in blood and urine in order to differentiate blistering produced by ... other agents such as Lewisite ...

来源:Hazardous Substances Data Bank (HSDB)

代谢

代谢研究使用了带有放射性标记的芥子气，在啮齿类动物中进行了实验...提出了以下代谢途径：水解为硫代双甘醇和S-氧化为亚砜和砜，随后进行结合。大鼠尿液中的代谢物包括硫代双甘醇和结合物（15%）、谷胱甘肽-双(β-氯乙基)硫醚结合物（45%）、谷胱甘肽-双(β-氯乙基)砜（7%）、双(β-氯乙基)砜和结合物（8%）以及少量的半胱氨酸结合物。大鼠经腹膜内注射形成的尿液代谢物是双半胱氨酰乙基砜和硫代双甘醇。

Metabolic studies with radioactively labelled mustard gas were performed in rodents ... The following metabolic pathways were proposed: hydrolyses to thiodiglycol and S-oxidation to sulfoxide and sulfone, followed by conjugation. Urinary metabolites in rats consisted of thiodiglycol and conjugates (15%), glutathione-bis-beta-chloroethylsulfide conjugates (45%), glutathione-bis-beta chloroethylsulfone (7%), bis-beta-chloroethylsulfone and conjugates (8%), and small amounts of cysteine conjugates. Urinary metabolites formed from intraperitoneal injection in rats were bis-cysteinylethylsulfone and thiodiglycol.

来源:Hazardous Substances Data Bank (HSDB)

代谢

尿液中来自未接触过硫磺芥子气的志愿者的样本中，检测到了含量非常低的硫二甘醇（小于0.2ng/mL），这与之前使用不同方法的研究结果一致。在将硫二甘醇亚砜还原为钛三氯化物之后，确定了硫二甘醇和硫二甘醇亚砜的复合浓度。在这种情况下，观察到了更高的背景水平（高达3ng/mL），这与亚砜是这两种代谢物的主要排泄产物的观点一致。该方法应用于储存了13年的两个意外芥子气中毒受害者的尿液样本。硫二甘醇的水平为1和3 ng/mL，在使用钛三氯化物处理尿液后增加到了78和104 ng/mL。

Urine, from human volunteers with no known exposure to sulfur mustard, contained detectable but very low concentrations (<0.2ng/mL) of thiodiglycol, consistent with previous observations using different methodologies. Combined concentrations of thiodiglycol and thiodiglycol sulfoxide were determined after reduction of the latter with titanium trichloride. In this case higher background levels (up to 3ng/mL) were observed, consistent with the sulfoxide being the major excretion product of the two metabolites. The method was applied to urine samples, stored frozen for 13 years, from two casualties of accidental mustard poisoning. Levels of thiodiglycol were 1 and 3 ng/mL, which increased to 78 and 104 ng/mL after treatment of the urine with titanium trichloride.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

识别和使用：硫二甘醇是一种粘稠的无色液体。它被用作化学中间体，纺织印花添加剂。它也是芥子气、倍半芥子气、HT、T和Q的2B类前体（具有低到中等商业用途和高风险前体）。它用于制造圆珠笔墨水。人体研究：据报道，芥子气的水解产物具有毒性。然而，主要分解产物硫二甘醇的毒性较低。因此，水解产物的大部分毒性效应可能归因于原始材料中未反应的芥子和二（氯乙基）多硫化物。动物研究：在兔子上测试了急性皮肤刺激性。在处理1小时后有1只兔子出现非常轻微的红斑，持续到第4天。这种效果在5天内完全可逆。其他2只动物没有观察到皮肤反应。在豚鼠最大量测试中，挑战没有在硫二甘醇处理的动物身上引起皮肤反应。在大鼠吸入危害测试中，报告在室温下饱和气氛中暴露8小时后没有死亡。在开始暴露后，动物表现出试图逃跑的行为。在暴露开始后1小时观察到粘膜的刺激。在大鼠的产前发育毒性研究中，胸椎体的哑铃状骨化显著增加（12%对对照组的5.2%）。还观察到其他显著的骨骼变异增加，如原始颈肋（7.1%对对照组的1.2%）以及总变异的一般增加（涉及受影响的胎儿/窝：52.9%对对照组的38.6%）。硫二甘醇在存在或不存在代谢激活的情况下，在高达5 mg/板的浓度下未在沙门氏菌typhimurium TA98、TA100、TA1535、TA1537和E. coli WP2uvrA中诱导逆向基因突变。硫二甘醇在鼠淋巴瘤和体内鼠微核试验中不是致突变剂，但在中国仓鼠卵巢（CHO）细胞中诱导了染色体畸变。尽管经过80年的研究，芥子酸的疱形成机制仍然未知。据报道，体外组织中芥子酸相关抑制一种或多种蛋白（丝氨酸/苏氨酸）磷酸酶可能是其他疱形成剂如斑蟊素和路易斯剂的共同机制。这种抑制作用与硫二甘醇的浓度有关，而不是芥子本身的浓度。生态毒性研究：对蓝鳃太阳鱼在1,000 mg/L的浓度下没有毒性。

IDENTIFICATION AND USE: Thiodiglycol is a syrupy, colorless, liquid. It is used as chemical intermediate, additive for textile printing. It is also a Schedule 2B precursor (dual-use chemicals with low to moderate commercial use and high-risk precursors) to mustard gas, sesquimustard, HT, T, and Q. It is used to manufacture ball-point pen ink. HUMAN STUDIES: The hydrolysis products of mustard gas are reported to exhibit toxicity. However, thiodiglycol, the major breakdown product, exhibits low toxicity. Therefore, it is likely that the majority of the toxic effects attributed to the hydrolysis products are due to unreacted mustard and bis(chloroethyl)polysulfides present in the original material. ANIMAL STUDIES: Acute dermal irritation was tested on rabbits. A very slight erythema was noted in 1 out of 3 animals 1 hour after treatment until day 4. The effect was completely reversible within 5 days. No cutaneous reactions were observed in the other 2 animals. In a guinea pig maximization test the challenge resulted in no skin reaction in thiodiglycol treated animals. In the Rat Inhalation Hazard Test, no mortality was reported after 8 hr exposure to a saturated atmosphere at room temperature. Immediately after the start of exposure, the animals showed attempts to escape. Irritation of the mucous membranes was observed 1 hr after start of exposure. In a prenatal developmental toxicity study in rats a significant increase in dumbbell ossifications of thoracic vertebral bodies was noted (12% versus 5.2% in control). Other significant increases in skeletal variations, such as rudimentary cervical ribs were also observed (7.1% versus 1.2% in control) as well as a general increase in total variations (concerning affected fetuses/litter: 52.9% versus 38.6% in control). Thiodiglycol did not induce reverse gene mutations in Salmonella typhimurium strains TA98, TA100, TA1535, TA1537, and E. coli WP2uvrA at concentrations up to 5 mg/plate in the presence or absence of metabolic activation. Thiodiglycol was not mutagenic in mouse lymphoma, and in vivo mouse micronucleus assays, but it induced chromosomal aberrations in Chinese hamster ovarian (CHO) cells. The mechanism of vesication from sulfur mustard remains unknown in spite of 80 years of investigation. It was reported that sulfur mustard-related inhibition of one or more protein (serine/threonine) phosphatases in tissue cytosol in vitro, could be a mechanism common to other vesicants such as cantharidin and Lewisite. This inhibition was related to the concentration of thiodiglycol, the hydrolysis product of sulfur mustard, rather than to the concentration of mustard itself. ECOTOXICITY STUDIES: It was not toxic to bluegill sunfish at 1,000 mg/L.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 吸入症状

咳嗽。恶心。

Cough. Nausea.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

毒理性

• 眼睛症状

红斑。疼痛。

Redness. Pain.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

毒理性

• 摄入症状

泻肚子。恶心。呕吐。

Diarrhoea. Nausea. Vomiting.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

毒理性

• 副作用

职业性肝毒素 - 第二性肝毒素：在职业环境中的毒性效应潜力是基于人类摄入或动物实验的中毒案例。

Occupational hepatotoxin - Secondary hepatotoxins: the potential for toxic effect in the occupational setting is based on cases of poisoning by human ingestion or animal experimentation.

来源:Haz-Map, Information on Hazardous Chemicals and Occupational Diseases

吸收、分配和排泄

该程序应用于从伊朗患者获得的尿样，这些患者据称是化学战剂（可能是芥子气）袭击的受害者。还调查了一些对照样本。在伊朗患者的尿液中发现了硫二甘醇，浓度在3至140 ng/mL之间变化。然而，在对照样本中检测到高达55 ng/mL的硫二甘醇，这排除了对伊朗患者使用芥子气的明确验证。

The procedure was applied to urine samples obtained from Iranian patients who were the alleged victims of an attack by chemical warfare agents (probably mustard gas). A number of control samples were investigated as well. Thiodiglycol was found in the urine of the Iranian patients in concentrations varying between 3 and 140 ng/mL. However, the detection of thiodiglycol in concentrations up to 55 ng/mL in control samples excluded the unambiguous verification of the use of mustard gas against the Iranian patients.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

修改后的程序应用于1986年在欧洲医院接受治疗的几名伊朗患者的尿样，这些患者据称是芥子气袭击的受害者。除了一位相对较高的值（330 ng/mL）外，硫二甘醇的浓度与1984年调查中发现的浓度范围相同（10至100 ng/mL）。20名男性对照的尿液中硫二甘醇含量不超过20 ng/mL。1984年和1986年获得的数据（25名伊朗患者和25名对照）显示出统计学上的显著差异。大约80%的伊朗患者的水平高于从对照组计算出的95%置信限。

The modified procedure was applied to urine samples of several Iranian patients who were victims of an alleged attack with mustard gas and who were treated in European hospitals in 1986. With the exception of one relatively high value (330 ng/mL), the thiodiglycol concentrations were in the same range (10 to 100 ng/mL) as those found during an investigation in 1984. The urine of 20 male controls contained thiodiglycol amounts not above 20 ng/mL. The combined data obtained in 1984 and 1986 (25 Iranian patients and 25 controls) show statistically significant differences. Approximately 80% of the Iranian patients had levels above the 95% confidence limit calculated from the control group.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

该研究的目的是开发一种检测方法，以研究硫芥（HD）通过皮肤的流量，并确定是否由于表皮对HD的代谢而在隔离灌注的猪皮瓣（IPPSF）局部暴露于14C-HD后形成了代谢物。四个IPPSF局部给药2.85毫克的14C-HD乙醇溶液。收集静脉灌注液样本，并加入34%的NaCl溶液中，迅速冷冻以抑制HD的代谢，直到进行检测。使用固相萃取柱和乙酸乙酯提取灌注液样本，然后使用气相色谱进行检测。在给药后15分钟，4个IPPSF中有2个在静脉灌注液中检测到HD的水平，其中1个在给药后2小时仍能在灌注液中检测到HD。在2小时的实验过程中，所有4个IPPSF的灌注液中HD的代谢物不超过3种，其中一种代谢物被鉴定为硫二甘醇。这些实验表明，经皮吸收后，HD几乎不会完整地出现在静脉灌注液中，并且IPPSF中HD的表皮代谢确实达到了相当的程度。

The purpose of this study was to develop an assay to study the flux of sulfur mustard (HD) through the skin and determine if metabolites are formed due to the epidermal metabolism of HD after topical exposure of the isolated perfused porcine skin flap (IPPSF) to 14C-HD. Four IPPSFs were topically dosed with 2.85 mg of 14C-HD in ethanol. Venous perfusate samples were collected and added to a 34% solution of NaCl and snap-frozen to inhibit the metabolism of HD until time for assay. Perfusate samples were extracted using a solid-phase extraction cartridge with ethyl acetate and then assayed using gas chromatography. Two of the 4 IPPSFs showed detectable levels of HD in the venous perfusate 15 min after dosing, with 1 of these 2 IPPSFs showing detectable levels of HD in the perfusate 2 hours after dosing. All 4 IPPSFS had no more than 3 metabolites of HD appearing in the perfusate throughout the 2 hr experiment, with one of the these metabolites identified as thiodiglycol. These experiments showed that little, if any, HD appears in the venous perfusate intact after percutaneous absorption and that epidermal metabolism of HD does occur to a significant degree in the IPPSF.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

在大鼠中，腹腔内给药的90%的硫代二甘醇在24小时内通过尿液排出，到8天时几乎全部排出。在粪便中没有显著排出...仅有大约0.5%到1%的硫代二甘醇以原形排出。

90% of an intraperitoneal dose of thiodiglycol in rats was excreted in the urine within 24 hr and by 8 days virtually all of the dose had been excreted. There was no significant excretion in the feces ... Only around 0.5 to 1% of thiodiglycol was excreted unchanged.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

人体尿液中硫二甘醇的背景水平通常小于1 ng/mL ... 其他报告指出硫二甘醇的背景水平在1到55 ng/mL之间 ... 这些背景水平的来源尚不清楚。

Background levels of thiodiglycol in human urine are normally <1 ng/mL ... Others have reported background levels of thiodiglycol to be from 1 to 55 ng/mL ... The source of these background levels is unknown.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 储存条件：
  1. 密封保存于阴凉、干燥处，并确保工作间有良好的通风设施。远离火源，避免与氧化剂接触。 2. 本品采用塑料桶包装，每桶重25公斤。由于易燃，请注意防火，在贮存和运输过程中远离火源和热源。应储存在阴凉、通风且干燥的地方。

制备方法与用途

制备方法： 将氯乙醇和硫化钠依次加入反应釜中，边搅拌边升温至90～95℃。反应完毕后，冷却物料并用硫酸中和至pH值呈中性。经过滤、减压蒸馏收集硫代双乙醇馏分。

合成制备方法： 将氯乙醇和硫化钠依次加入反应釜中，边搅拌边升温至90～95℃。反应完毕后，冷却物料并用硫酸中和至pH值呈中性。经过滤、减压蒸馏收集硫代双乙醇馏分。

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  2-羟基乙基 2-氯乙基硫醚	mustard chlorohydrin	693-30-1	C4H9ClOS	140.634

• 下游产品

  中文名称	英文名称	CAS号	化学式	分子量
  ——	bis(2-methoxyethyl)sulfide	22428-72-4	C6H14O2S	150.242
  1,4-噻烷	1,4-Oxathiane	15980-15-1	C4H8OS	104.173
  2-羟基乙基 2-氯乙基硫醚	mustard chlorohydrin	693-30-1	C4H9ClOS	140.634
  1-乙烯基硫基乙醇	2-hydroxyethyl vinyl sulfide	3090-56-0	C4H8OS	104.173
  ——	2.2'-Diaethoxy-diaethylsulfid	41719-25-9	C8H18O2S	178.296
  硫代二乙二醇亚砜	bis(2-hydroxyethyl)sulfoxide	3085-45-8	C4H10O3S	138.188
  ——	S,S-bis-(2-hydroxy-ethyl)-sulfimide	——	C4H11NO2S	137.203
  2-羟基乙基硫代乙酸酯	<(2-hydroxyethyl)thio>acetic acid	5512-65-2	C4H8O3S	136.172

反应信息

• 作为反应物：
  描述：

  硫二甘醇 在 copper(ll) bromide 作用下， 反应 4.0h， 以99%的产率得到1,4-噻烷
  参考文献：
  名称：

  铜催化剂存在下由二醇合成环醚

  摘要：

  在铜的存在下，通过二醇的分子内脱水，以高收率合成了许多环醚，即四氢呋喃，2,5-二甲基四氢呋喃，四氢吡喃，1,4-二恶烷，氧杂环丁烷，氧杂环丁烷和1,4-氧杂蒽。基催化剂。

  DOI：

  10.1134/s1070428017120090
• 作为产物：
  描述：

  芥子气 生成 硫二甘醇
  参考文献：
  名称：

  Ktrordagul Hosny, Al-Ajmi Dhari, J. Environ. Sci. and Health. A, 29 (1994) N 4, S 687-700

  摘要：

  DOI：
• 作为试剂：
  描述：

  bis (2-chloroethyl) sulphide 在 硫二甘醇 作用下， 生成 2-[2-hydroxyethyl-[2-[2-(2-hydroxyethylsulfanyl)ethylsulfanyl]ethyl]-(2-oxidoethyl)-λ⁴-sulfanyl]ethanolate,dichloride
  参考文献：
  名称：

  Truhaut, Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1948, vol. 227, p. 919

  摘要：

  DOI：

文献信息

• Production of Hydroxy Acids: Selective Double Oxidation of Diols by Flavoprotein Alcohol Oxidase
  作者：Caterina Martin、Milos Trajkovic、Marco W. Fraaije

  DOI：10.1002/anie.201914877

  日期：2020.3.16

  oxidases can catalyze oxidations of alcohols and amines by merely using molecular oxygen as the oxidant, making this class of enzymes appealing for biocatalysis. The FAD-containing (FAD=flavin adenine dinucleotide) alcohol oxidase from P. chrysosporium facilitated double and triple oxidations for a range of aliphatic diols. Interestingly, depending on the diol substrate, these reactions result in formation

  黄素蛋白氧化酶仅使用分子氧作为氧化剂即可催化醇和胺的氧化，使得此类酶在生物催化方面具有吸引力。来自 P. chrysosporium 的含有 FAD（FAD=黄素腺嘌呤二核苷酸）的醇氧化酶促进了一系列脂肪族二醇的双重和三重氧化。有趣的是，根据二醇底物，这些反应会导致内酯或羟基酸的形成。例如，二甘醇可以选择性地完全转化为2-(2-羟基乙氧基)乙酸。这种简单的、不依赖辅因子的羟基酸生物催化途径为聚酯结构单元的制备开辟了新途径。
• Mass Spectral Studies on Vinylic Degradation Products of Sulfur Mustards under Gas Chromatography/Mass Spectrometry Conditions
  作者：L. Sai Sachin、R. Karthikraj、K. Kalyan Kumar、T. Sony、N. Prasada Raju、S. Prabhakar

  DOI：10.1255/ejms.1398

  日期：2015.12

  Sulfur mustards are a class of vesicant chemical warfare agents that rapidly degrade in environmental samples. The most feasible degradation products of sulfur mustards are chloroethyl vinylic compounds and divinylic compounds, which are formed by the elimination of one and two HCl molecules from sulfur mustards, respectively. The detection and characterization of these degradation products in environmental samples are an important proof for the verification of sulfur mustard usage. In this study, we synthesized a set of sulfur mustard degradation products, i.e., divinylic compounds (1–7) and chloroethyl vinylic compounds (8–14), and characterized using gas chromatography/mass spectrometry (GC/MS) under electron ionization (EI) and chemical ionization (CI) (methane) conditions. The EI mass spectra of the studied compounds mainly included the fragment ions that resulted from homolytic cleavages with or without hydrogen migrations. The divinylic compounds (1–7) showed [M – SH]⁺ ions, whereas the chloroethylvinyl compounds (8–14) showed [M – Cl]⁺ and [M – CH₂CH₂Cl]⁺ ions. Methane/CI mass spectra showed [M + H]⁺ ions and provided molecular weight information. The GC retention index (RI) values were also calculated for the studied compounds. The EI and CI mass spectral data together with RI values are extremely useful for off-site analysis for the verification of the chemical weapons convention and also to participate in official Organization for the Prohibition of Chemical Weapons proficiency tests.

  硫芥子是一类气泡剂化学战剂，它们在环境样品中迅速降解。硫芥子最可行的降解产物是氯乙基乙烯化合物和二乙烯化合物，它们分别通过从硫芥子中消除一个和两个HCl分子形成。在环境样品中检测和表征这些降解产物对于验证硫芥子的使用是重要的证据。在这项研究中，我们合成了一组硫芥子降解产物，即二乙烯化合物（1-7）和氯乙基乙烯化合物（8-14），并使用气相色谱/质谱联用（GC/MS）在电子电离（EI）和化学电离（CI）（甲烷）条件下进行表征。研究化合物的EI质谱主要包括由于有或无氢迁移而导致的自由裂解的碎片离子。二乙烯化合物（1-7）显示[M - SH]⁺离子，而氯乙基乙烯化合物（8-14）显示[M - Cl]⁺和[M - CH₂CH₂Cl]⁺离子。甲烷/CI质谱显示[M + H]⁺离子并提供分子量信息。还计算了研究化合物的GC保留指数（RI）值。EI和CI质谱数据以及RI值对于离线分析以验证化学武器公约以及参加官方禁化武组织的熟练测试非常有用。
• A dual-function all-inorganic intercluster salt comprising the polycation ε-[Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺ and polyanion α-[PMo₁₀V₂O₄₀]⁵⁻ for detoxifying sulfur mustard and soman
  作者：Jialin Yu、Qi Gao、Lijuan Zhang、Yunshan Zhou、Yuxu Zhong、Jianbo Yin、Yuanyuan Zhou、Fangsheng Tao、Yong'an Wang

  DOI：10.1039/d0dt01307b

  日期：——

  The specially designed intercluster compound can catalytically decontaminate both HD and GD at ambient conditions with high efficiency.

  这种特别设计的簇间化合物可以在常温下高效催化去污剂HD和GD。
• Synthesis of macroscopic monolithic metal–organic gels for ultra-fast destruction of chemical warfare agents
  作者：Chuan Zhou、Shouxin Zhang、Hongjie Pan、Guang Yang、Lingyun Wang、Cheng-an Tao、Heguo Li

  DOI：10.1039/d1ra01703a

  日期：——

  for the destruction of CWAs. We found that the UiO-66-NH2 xerogel with a larger pore size and a higher surface area than the UiO-66-NH2 powder possessed better degradability of 2-chloroethyl ethyl sulfide (2-CEES), which is a sulfur mustard simulant. These UiO-66-X xerogels exhibit outstanding performance for decomposing CWAs. The half-lives of vesicant agent sulfur mustard (HD) and nerve agent O-ethyl

  源自化学战剂 (CWA) 的潜在威胁促进了先进材料的发展，以加强对平民和军事人员的保护。Zr 基金属有机骨架（Zr-MOFs）最近已被证明是分解 CWAs 的优良催化剂，但将 Zr-MOFs 的微晶粉末整合到整体中的挑战仍然存在。在此，我们报告了用于破坏 CWA 的分级多孔单片 UiO-66-X 干凝胶。我们发现UiO-66-NH 2干凝胶比UiO-66-NH 2具有更大的孔径和更高的表面积。粉末对硫芥模拟物2-氯乙基乙基硫醚（2-CEES）具有更好的降解性。这些 UiO-66-X 干凝胶在分解 CWA 方面表现出出色的性能。发泡剂硫芥 (HD) 和神经毒剂O-乙基S- [2-(二异丙基氨基)乙基] 甲基硫代磷酸酯 (VX)的半衰期分别短至 14.4 分钟和 1.5 分钟。据我们所知，这项工作是关于用于超快分解 CWA 的宏观整体 UiO-66-X 干凝胶的第一份报告。
• Facile Hydrolysis-Based Chemical Destruction of the Warfare Agents VX, GB, and HD by Alumina-Supported Fluoride Reagents
  作者：E. Gershonov、I. Columbus、Y. Zafrani

  DOI：10.1021/jo8019972

  日期：2009.1.2

  A facile solvent-free hydrolysis (chemical destruction) of the warfare agents VX (O-ethyl S-2-(diisopropylamino)ethyl methylphosphonothioate), GB (O-isopropyl methylphosphonofluoridate or sarin), and HD (2,2′-dichloroethyl sulfide or sulfur mustard) upon reaction with various solid-supported fluoride reagents is described. These solid reagents include different alumina-based powders such as KF/Al2O3

  简便的无溶剂水解剂（战争破坏剂VX（O-乙基S -2-（二异丙氨基氨基）乙基甲基硫代磷酸酯），GB（O-异丙基甲基氟代磷酸酯或沙林）和HD（2,2'-二氯乙基硫醚）描述了在与各种固体负载的氟化物试剂反应后产生的硫芥末或硫芥末）。这些固体试剂包括不同的氧化铝基粉末，例如KF / Al 2 O 3，AgF / KF / Al 2 O 3和KF / Al 2 O 3，它们富含所谓的配位不饱和氟化物离子（我们称其为ECUF- KF / Al 2 O 3）。当吸附在这些吸附剂上时，神经毒剂VX迅速水解（t 1/2范围在0.1-6.3 h之间）水解成相应的无毒膦酸主要成分EMPA（> 90％）和相对毒性的脱乙基VX（< 10％）。后者的副产物进一步水解为无毒的MPA产物（t 1/2范围为2.2-161 h）。发现反应速率和产物分布强烈地取决于KF / Al 2 O 3基质中氟离子的性质及其含水量。所研

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