低功率超声增强碘帕醇氯氧化的效果和路径

研究了低功率超声(US, <38 W)对NaClO氧化非离子型碘代X射线造影剂—碘帕醇(IPM)的增强作用及机理, 考察了NaClO添加浓度和超声功率的影响, 分析并计算了体系中的主要活性物种及其贡献. 采用高效液相色谱/串联质谱(HPLC/MS/MS)对降解产物进行分析, 推测IPM的降解路径. 结果表明, 低功率US显著增强了NaClO对IPM的氧化效果, 在25 ℃, pH=5.8, NaClO浓度为0.12 mmol/L条件下, 10 mg/L IPM在60 min的降解率达到85.8%. 其中NaClO氧化、 HO·和活性氯自由基(RCSs)是US/NaClO增强IPM降解的主要原因, 自由基分析计算它们的贡献率分别为15.82%, 4.65%和79.53%. NaClO浓度在0~0.24 mmol/L范围内, IPM的降解率随NaClO浓度升高而增加, 60 min后降解率由4.75%增加到91.12%; 超声功率为28.5 W, 降解率达到最高. 在 15~45 ℃温度范围内, IPM的降解过程符合表观一级反应动力学, 反应活化能(E_a)为59.03 kJ/mol. HPLC/MS/MS共检测出5种中间产物, 结合密度泛函理论(DFT)计算结果, 初步推测了IPM在US/NaClO体系中的降解途径和机理.     

Reactivity of Binary and Ternary Sulfur Halides towards Transition-Metal Compounds

Binary sulfur fluorides exhibit an interesting reactivity towards transition metal complexes. They open up routes for the generation of sulfur-containing building blocks. Often ligands with particular properties can be constructed. This includes their ability to transfer sulfur atoms or polysulfide units as well as fluorination reactions. This Minireview provides an insight into the reactivity of the binary and ternary sulfur halides S₂Cl₂, SCl₂, SF₄, SF₆ and SF₅Cl towards transition-metal compounds.     

硝酰氯的大气化学

硝酰氯(nitryl chloride,ClNO₂)是大气中一种重要的气态污染物,对大气氧化性、一次污染物的降解和二次污染物的生成具有重要影响,并在全球氮循环和氯循环中扮演着不可忽视的角色。本文归纳了ClNO₂的基本物理化学性质及其在大气中的生成和去除机制,并介绍了实验室研究和外场观测中ClNO₂的主要测量方法。在此基础上,本文总结了过去十几年报道的ClNO₂在实际大气中的时空分布特征,通过分析实验室模拟和外场观测的研究结果系统讨论了ClNO₂非均相生成的机制、产率及其影响因素,探讨了ClNO₂对氯自由基、大气氧化性以及臭氧和硝酸盐形成的影响。我们指出,ClNO₂既耦合了气相化学和非均相化学,又耦合了夜间大气化学和日间光化学,在我国大气复合污染中可能起着非常重要的作用。最后,本文提出了ClNO₂大气化学研究中尚待解决的关键科学问题,并简要讨论了该领域的未来发展方向。     

高氯废水化学需氧量分析方法综述

对高氯废水化学需氧量分析方法进行归纳和综述。常用的高氯废水化学需氧量分析方法有氯气校正容量法、降氯密闭消解分光光度法以及高温氧化总有机碳系数换算法等。其中氯气校正容量法操控要求较高,分析耗时较长,不适用于大批量样品同步分析;降氯密闭消解分光光度法灵敏度高,但在降氯过程中增加了重金属盐硫酸汞的用量,分析成本较高,易产生二次污染,且对样品的均质性要求较高;高温氧化总有机碳系数换算法操作便捷、抗干扰能力强,但是换算系数易随不同来源、不同组分的样品发生波动,数据可比性需要通过实验验证。经过梳理归纳,明确各种分析方法的特点和适用范围,为研究人员选择合适的分析方法或进一步开展相关的方法研究提供参考。     

Energy‐dependent normal and unusually large inverse chlorine kinetic isotope effects of simple chlorohydrocarbons in collision‐induced dissociation by gas chromatography‐electron ionization‐tandem mass spectrometry

Kinetic isotope effects (KIEs) occurring in mass spectrometry (MS) can provide in‐depth insights into the fragmentation behaviors of compounds of interest in MS. Yet, the fundamentals of KIEs in collision‐induced dissociation (CID) in tandem mass spectrometry (MS/MS) are unclear, and information about chlorine KIEs (Cl‐KIEs) of organochlorines in MS is particularly scarce. This study investigated the Cl‐KIEs of dichloromethane, trichloroethylene, and tetrachloroethylene during CID using gas chromatography‐electron ionization triple‐quadrupole MS/MS. Cl‐KIEs were evaluated with MS signal intensities. All the organochlorines presented large inverse Cl‐KIEs (<1, the departures of Cl‐KIEs from 1 denote the magnitudes of Cl‐KIEs), showing the largest magnitudes of 0.797, 0.910, and 0.892 at the highest collision energy (60 eV) for dichloromethane, trichloroethylene, and tetrachloroethylene, respectively. For dichloromethane, both intra‐ion and inter‐ion Cl‐KIEs were studied, within the ranges of 0.820–1.020 and 0.797–1.016, respectively, showing both normal and inverse Cl‐KIEs depending on collision energies. The observed Cl‐KIEs generally declined from large normal to extremely large inverse values with increasing collision energies from 0 to 60 eV but were inferred to be independent of MS signal intensities. The Cl‐KIEs are dominated by critical energies at low internal energies of precursor ions, resulting in normal Cl‐KIEs; while at high internal energies, the Cl‐KIEs are controlled by rotational barriers (or looseness/tightness of transition states), which lead to isotope‐competitive reactions in dechlorination and thereby inverse Cl‐KIEs. It is concluded that the Cl‐KIEs may depend on critical energies, bond strengths, available internal energies, and transition state looseness/tightness. The findings of this study yield new insights into the fundamentals of Cl‐KIEs of organochlorines during CID and may be conducive to elucidating the underlying mechanisms of KIEs in collision‐induced and photo‐induced reactions in the actual world.     

Synthesis and Crystal Structure of [Mn(DPMT)2Cl2(H20)2]

The title compound [Mn(DPMT)2Cl2(H2O)2] (DPMT = 1 -[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole) was synthesized by the reaction of MnCl2-4H2O and DPMT in ethanol solution and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P2/c with a=23.913(4), b=7.8883(13), c=8.6291(14) (A),β=95.816(3)°,V=1619.4(5)(A)3,Z=2,C24H26Cl6MnN6O6 Mr=762.15, Dc=1.563 g/cm3, μ=0.950 mm'1, S=1.045, F(000)=774, R=0.0462 and wR=0.0981. The molecular structure is a centrosymmetric conformation, and two ligands are symmetrically located on both sides of the Mn atom. The manganese atom is surrounded by two nitrogen atoms from ligands, two chlorine atoms and two oxygen atoms from water molecules to form a slightly distorted octahedral geometry.     

Synthesis and Crystal Structure of 2-Amino-4- chloro-5-（4-methylbenzyl）-6-methylpyrimidine

The title compound 2-amino-4-chloro-5-(4-methylbenzyl)-6-methylpyrimidine (C26H28Cl2N6, Mr = 495.44) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. The crystal belongs to monoclinic, space group P21/c with a = 14.892(7), b = 6.129(3), c = 14.889(7) , β = 109.795(8)°, V = 1278.7(10) 3, Z = 2, F(000) = 520, Dc = 1.287 g/cm3, μ = 0.280 mm-1, the final R = 0.0577 and wR = 0.1589 for 1357 observed reflections with I > 2σ(I). A total of 6091 reflections were collected, of which 2257 were independent (Rint = 0.033). The X-ray analysis reveals that the chlorine atom and methyl of the title compound are disordered.     

用离子色谱法测定水中的二氧化氯、氯、亚氯酸根及氯酸根

建立了一种测定水中的ClO2、Cl2、ClO2^-、ClO3^-离子色谱法,在含有碳酸氢钠缓冲溶液的中性条件下,用NaNO2将ClO2、Cl2还原为ClO2^-、Cl^-,通过测定ClO^-和NO3^-的变化值,间接测定ClO2和Cl2。加入硫代乙酰胺(TAA)作掩蔽剂测定ClO2^-。     

纳米金催化剂的抗水性能和抗硫中毒性能

与Au/Al2O3相比,复合载体负载的Au/FeOx/Al2O3具有更高的催化CO氧化的低温活性和稳定性,且表现出湿度增强效果,水分压为550~1 600 Pa时催化剂活性较高.在完全无水的环境中,催化剂发生快速不可逆失活;在饱和水汽的环境中,催化剂发生缓慢可逆失活.在水汽作用下的失活与纳米金粒子的粒径长大有关.助剂对催化剂抗水性能影响不大,但对抗硫中毒性能的影响较大.Au/CeO2/Al2O3催化剂显示有最佳的抗硫中毒性能.催化剂表面硫化物和硫酸盐的生成是导致催化剂不可逆硫中毒失活的主要原因.     

流动注射-分光光度法测定自来水中游离氯的研究

设计了游离氯流动注射自动在线检测仪,并研究了仪器的最佳测试条件.该仪器采用改进的N,N-二乙基-1,4-苯二胺(DPD)比色原理,通过流动注射进样技术,结合光电转化、数字信号处理及自动化控制技术,克服了DPD分光光度法中手工操作的缺陷,实现了样品分析的自动化.结果证明,此系统的试剂用量少、测定范围宽(0.05～6.00...