镍离子(Ⅱ)印迹聚合物的制备及性能研究

以镍(Ⅱ)离子为模板,丙烯酰胺为功能单体,二乙烯基苯为交联剂,偶氮二异丁腈为引发剂,甲醇为溶剂,采用本体聚合法制备了镍离子(Ⅱ)印迹聚合物.用红外光谱对镍离子印迹聚合物的结构进行表征,红外光谱研究表明聚合物中存在与模板分子相互作用的特征基团.通过研究Ni2+与单体的物质的量之比、单体与交联剂的物质的量之比、溶剂量对镍离...     

红外光谱法研究氯化钙甲醇溶液的溶剂化性质

利用红外光谱研究了不同浓度氯化钙甲醇溶液中离子-溶剂和离子-离子的相互作用.溶剂分子谱带的变化说明了钙离子与甲醇分子发生了强烈的相互作用,这种作用主要是通过C-O中的氧原子实现,而溶剂甲醇分子的O-H谱带的偏移主要是离子(浓度)促使氢键发生改变.通过对光谱曲线的拟合,可定量计算阳离子溶剂化数,进一步揭示了溶剂化过程的微观性质.     

高浓度LiClO4/丙酮溶液中离子-溶剂和离子-离子的相互作用

利用红外和拉曼光谱技术研究了不同浓度LiClO₄/丙酮溶液中离子-溶剂和离子-离子的相互作用. 红外和拉曼光谱的分析表明, Li^＋与丙酮分子发生了强烈的相互作用, 导致丙酮C—C伸缩振动谱带、C＝O伸缩振动谱带等发生了分裂. Li^＋的溶剂化数随溶液浓度的增加逐渐降低, 在所研究的LiClO₄浓度范围(0.31～3.98 mol•kg^－1)内由3.4减小到1.9. 此外, 根据的谱带变化确定了溶液中存在的多种离子对的形式, 计算了缔合平衡常数, 并与电导实验结果进行了比较, 解释了这两种方法测定的离子缔合常数存在差异的主要原因.     

高浓度LiClO4/丙酮溶液中离子-溶剂和离子-离子的相互作用

利用红外和拉曼光谱技术研究了不同浓度LiClO₄/丙酮溶液中离子-溶剂和离子-离子的相互作用. 红外和拉曼光谱的分析表明, Li^＋与丙酮分子发生了强烈的相互作用, 导致丙酮C—C伸缩振动谱带、C＝O伸缩振动谱带等发生了分裂. Li^＋的溶剂化数随溶液浓度的增加逐渐降低, 在所研究的LiClO₄浓度范围(0.31～3.98 mol•kg^－1)内由3.4减小到1.9. 此外, 根据的谱带变化确定了溶液中存在的多种离子对的形式, 计算了缔合平衡常数, 并与电导实验结果进行了比较, 解释了这两种方法测定的离子缔合常数存在差异的主要原因.     

LiNO3在DMF中的离子溶剂化和离子缔合的红外光谱

LiNO3在DMF中的离子溶剂化和离子缔合的红外光谱;硝酸锂;N;N-二甲基甲酰胺;离子溶剂化;离子缔合;红外光谱法     

NaNO3和NaClO4在N,N-二甲基甲酰胺中的离子溶剂化

利用红外光谱研究了NaNO₃和NaClO₄在N,N-二甲基甲酰胺(DMF)溶剂中发生离子-溶剂和离子-离子的相互作用, 分析结果表明, DMF的OC-N谱带发生了明显的变化. 定量计算了在Na⁺浓度为0.22~1.24 mol/kg范围内的溶剂化数为1~4. 对谱图中酰胺基上C-N和CO的特征峰强度随Na⁺浓度变化的对比, 推测离子溶剂化作用导致DMF的酰胺基内部形成共轭键. 利用量子化学方法进行优化及热力学性质计算, 得到C-N键伸缩振动频率及红外光谱强度变化规律. 优化结构与实验结论相符合. 由NaNO₃的ν₂谱带及NaClO₄的ν₁谱带的解析得到溶液中阴离子缔合效应的一般规律, 并通过阴离子缔合特征峰与酰胺基上的N-C-N面外振动峰(865 cm^-1)的变化情况, 讨论了溶液中的离子溶剂化作用.     

Vibrational Spectroscopic Study on Ion Solvation and Ion Association of Lithium Tetrafluoroborate in 4‐Ethoxymethyl‐ethylene Carbonate

应用红外及拉曼光谱研究了不同浓度的四氟硼酸锂在4-乙氧甲基-碳酸乙烯酯溶剂中的离子溶剂化和离子缔合现象。环形变谱带和羰基伸缩振动谱带的分裂,以及骨架环振动谱带的迁移和分裂表明,锂离子与溶剂分子间存在着较强的相互作用,这种相互作用是通过溶剂羰基氧原子实现的。利用光谱拟合技术定量计算了表观溶剂化数。随着电解质锂盐浓度的增加,溶剂化数逐渐由4.32降至1.26。此外,四氟硼酸根v1谱带的分裂表明在高浓度溶液中存在着光谱自由的四氟硼酸根、直接接触离子对和离子对二聚体。     

NaBF4/DMSO溶液微观结构的研究

利用红外、拉曼光谱技术和密度泛函理论研究了高浓度四氟硼酸钠／二甲基亚砜(DMSO)溶液中的离子溶剂化和离子缔合现象。红外和拉曼光谱分析表明,Na^ 与DMSO分子间有较强的相互作用．这种相互作用破坏了DMSO分子间的缔合,改变了DMSO分子的微观结构,使DMSO分子的谱带发生了明显的变化．对Na^ 与DMSO分子相互作用的溶剂化构型的量子化学计算表明,Na^ 与DMSO分子的相互作用是通过S-O基团上的氧原子进行的,钠离子的溶剂化数为4．另外,BF4^-离子的v1谱带的分裂表明,溶液中存在着直接接触离子对,形成的Na^ BF4^-离子对具有Cs构型．     

利用红外光谱分析固溶体中离子对间相对排布和相互作用

振动光谱已被推广用来探讨熔盐以及晶体中离子对间的相对排布和相互作用。本文利用红外光谱对固溶体中某些离子对间的相互作用及它们在溶剂品格内的配置方式进行一些分析。该分析方法主要基于:利用振动光谱选择定则确定特定“离子对”的各种简正振动方式的对称性,通过把上述预计的振动方式与实际记录到的红外吸收峰的数目相比较,进而确定特定离子对的相对排布。通过吸收峰位置变化的大小,则可推测到离子间相互作用的强弱。     

利用红外光谱和拉曼光谱研究离子液体结构与相互作用的进展

热力学实验、理论计算以及计算机模拟是离子液体微观结构与相互作用研究中常用的三种手段,但是目前采用这些手段对离子液体结构的认识尚处于初步探索阶段,还没有完全找到离子液体性质随结构变化的规律,尚未完全能够对离子液体进行"设计",这也使得对离子液体的进一步开发和应用受到极大的限制.近年来,谱学方法成为研究溶液结构的重要手段.其中,红外光谱(IR)和拉曼光谱(Raman)等谱学手段在离子液体的结构与相互作用研究中发挥着越来越重要的作用.本文着重概述了红外光谱和拉曼光谱在纯离子液体及离子液体混合溶液结构与相互作用方面的研究进展、挑战以及发展方向.     

Ion/molecule reactions in the orifice-skimmer region of an atmospheric pressure Penning ionization mass spectrometer

Atmospheric pressure Penning ionization mass spectra of methanol were measured as functions of Ar or He gas pressure in the first vacuum chamber, the position of the skimmer, and the voltage applied between the orifice and the skimmer. When the orifice and the skimmer were coaxial with a distance of 4 mm, the distribution of CH3OH2+(CH3OH)n clusters was only weakly dependent on both Ar pressure (in the range of 19-220 Pa) and orifice-skimmer voltage (in the range of 1-45 V). The ion/molecule reaction CH3OH2+ + CH3OH --> CH3+(CH3OH) + H2O was observed in the free jet expansion, especially at high orifice-skimmer voltage values. When the orifice and the skimmer were off-centered and the distance between them was increased to 18 mm, the formation of large CH3OH2+(CH3OH)n clusters, as well as their dissociation, were seen. The endothermic proton transfer reaction, CH3+(CH3OH) + CH3OH --> CH3OH2+ + CH3OCH3, occurred at high orifice-skimmer voltage. The collision-induced dissociation of cluster ions by He gas in the first vacuum chamber was much more efficient than by Ar. These results demonstrated that the mass spectra are highly dependent on skimmer position and on orifice-skimmer voltage and that ions observed by mass spectrometry do not necessarily reflect the abundance of ions produced in the atmospheric pressure ion source.     

潮湿空气微波放电离子形成动力学

利用微波放电电离质谱装置，通过水蒸气与空气混合气体（潮湿空气）的微波放电，同时获得了化学电离质谱探测技术中常用的三种重要母体离子H3O＋、NO＋和.结合潮湿空气中主要成分N2、O2以及水蒸气各自微波放电后的质谱探测结果，对潮湿空气微波放电后上述三种离子产生的动力学过程进行了分析，并给出了各种离子的形成机制.这些离子 分子反应过程在计算机模拟中得到了进一步的证实.     

Detection of OH stretching mode of CH3OH chemisorbed on Ni3+ and Ni4+ by infrared photodissociation spectroscopy

Structures of nickel cluster ions adsorbed with methanol, Ni3+ (CH3OH)m (m = 1-3) and Ni4+ (CH3OH)m (m = 1-4) were investigated by using infrared photodissociation (IR-PD) spectroscopy based on a tandem-type mass spectrometer, where they were produced by passing Ni3,4+ through methanol vapor under a multiple collision condition. The IR-PD spectra were measured in the wavenumber region between 3100 and 3900 cm-1. In each IR-PD spectrum, a single peak was observed at a wavenumber lower by approximately 40 cm-1 than that of the OH stretching vibration of a free methanol molecule and was assigned to the OH stretching vibrations of the methanol molecules in Ni3,4+ (CH3OH)m. The photodissociation was analyzed by assuming that Ni3,4+ (CH3OH)m dissociate unimolecularly after the photon energy absorbed by them is statistically distributed among the accessible modes of Ni3,4+ (CH3OH)m. In comparison with the calculations performed by the density functional theory, it is concluded that (1) the oxygen atom of each methanol molecule is bound to one of the nickel atoms in Ni3,4+ (defined as molecular chemisorption), (2) the methanol molecules in Ni3,4+ (CH3OH)m do not form any hydrogen bonds, and (3) the cross section for demethanation [CH4 detachment from Nin+ (CH3OH)] is related to the electron density distribution inside the methanol molecule.     

非抑制型离子色谱法测定碱金属、铵离子和烷基胺

 采用非抑制型离子色谱法、以氨磺酸作流动相分离测定了Li+ 、Na+ 、NH+ 4、K+ 、甲胺、乙胺和正丙胺等 7种物质 ,研究了氨磺酸流动相浓度对溶质保留值的影响。结果发现 ,随着流动相浓度的增大 ,溶质保留值减小 ;适宜的流动相浓度为 4 0mmol/L。以 4 0mmol/L氨磺酸为流动相测得上述 7种物质的检出限及工作曲线的线性回归方程。方法应用于自来水试样的分析 ,结果良好。     

芳香酸淋洗液的单柱阳离子色谱法测定碱金属,铵离子和烷基胺

研究了邻苯二甲酸、苯甲酸和对羟基苯甲酸３种芳香酸分别做淋洗液的单柱阳离子色谱法分离测定Ｌｉ＋、Ｎａ＋、ＮＨ４＋、Ｋ＋、甲胺、乙胺和正丙胺７种物质。３种芳香酸做淋洗液均可将７种物质分离开，且分离结果差异不大。在淋洗液浓度相同的条件下，邻苯二甲酸做淋洗液测定的检出限较低。选择３．０ ｍｍｏｌ／Ｌ邻苯二甲酸做淋洗液测得了上述７种物质的检出限和线性范围，并进行了叶面肥试样分析，７种物质的加标回收率在９６．４％～９８．６％之间。     

Variable-temperature ion mobility time-of-flight mass spectrometry studies of electronic isomers of Kr2+ and CH3OH*+ radical cations

Preliminary results from a liquid nitrogen-cooled ion mobility (IM) orthogonal-time-of-flight (o-ToF) mass spectrometer applied to the separation of electronic isomers of Kr2+ and methanol radical cations (conventional and distonic) are presented. Ab initio calculations were used to estimate the energies and energy barriers to interconversion between conventional (CH3OH*+) and distonic (CH2*OH2+) radical cations. In addition, computations and experiments are used to compare ion-neutral collision cross-sections for CH3OH*+ and CH2*OH2+ radical cations and suggest that the mobility separation is achieved by ion-neutral interactions between ions and neutral buffer gas.     

Does electrospray ionization produce gas-phase or liquid-phase structures?

Electrospray ionization of tyrosine from a 3:1 (v:v) CH3OH/H2O solution is found to afford an M - H ion which is a 70:30 mixture of phenoxide and carboxylate ions. This corresponds to the gas-phase equilibrium composition and not the liquid-phase proportions. In contrast, the carboxylate is produced as the dominant ion (approximately 95%) from anhydrous CH3CN and CH3CN/H2O mixtures. The addition of small amounts of CH3OH to the solvent, however, convert the M - H ion back into the gas-phase isomeric ratio. The isomeric structure therefore depends on the solvent system from which an ion is sprayed.     

Electrospray and chemical ionization mass spectrometry of di-n-butyl sulfate. Unimolecular chemistry of its protonated form and quantification method by liquid chromatography/electrospray ionization tandem mass spectrometry

Di-n-butyl sulfate (DNBS) has been studied by electrospray (ESI) and chemical (CI) ionization mass spectrometry. The use of methanol as solvent in electrospray ionization allows observation of relatively abundant [DNBS + CH(3)OH + H](+) ions (m/z 243) which upon collision dissociate to [DNBS + H](+) ions (m/z 211). In both ESI and CI experiments, it is found that [DNBS + H](+) ions lead to m/z 113 daughter ions. The composition of this m/z 113 fragment ion and its mechanism of formation have been established by high resolution measurements and CID-MIKE experiments. An 'internal substitution' reaction involving an ion-neutral intermediate is proposed to explain the formation of a [C(8)H(17)](+) ion (m/z 113) by loss of a H(2)SO(4) molecule. Finally, a LC/ESI-MS/MS quantification method is proposed in which a detection limit of di-n-butyl sulfate in the ppm range is obtained. It is suggested that the quantification method might be extended to higher dialkyl sulfates. Copyright 2000 John Wiley & Sons, Ltd.     

Properties and Applications of Cryptand‐22 Surfactant for Ion Transport and Ion Extraction

A non‐ionic cryptand‐22 surfactant consisting of a macrocyclic cryptand‐22 polar head and a long paraffinic chain (C₁₀H₂₁‐Cryptand‐22) was synthesized and characterized. The critical micellar concentration (CMC) of the cryptand surfactant in ROH/H₂O mixed solvent was determined by the pyrene fluorescence probe method. In general, the cmc of the cryptand surfactant increased upon decreasing the polarity of the surfactant solution. The cryptand surfactant also can behave as a pseudo cationic surfactant by protonation of cryptand‐22 or complexation with metal ions. Effects of protonation and metal ions on the cmc of the cryptand surfactant were investigated. A preliminary application of the cryptand surfactant as an ion‐transport carrier for metal ions, e.g., Li⁺, Na⁺, K⁺ and Sr²⁺, through an organic liquid‐membrane was studied. The transport ability of the cryptand surfactant for these metal ions was in the order: K⁺ ≥ Na⁺ < Li⁺ < Sr²⁺. A comparison of the ion‐transport ability of the cryptand surfactant with other macrocyclic polyethers, e.g., dibenzo‐18‐crown‐6, 18‐crown‐6 and benzo‐15‐crown‐5, was studied and discussed. Among these macrocyclic polyethers, the cryptand surfactant was the best ion‐transport carrier for Na⁺, Li⁺ and Sr²⁺ ions. Furthermore, a foam extraction system using the cryptand surfactant to extract the cupric ion was also investigated.     

C60与甲基醚CH3OCnH2n+1的气相离子分子反应研究

自宏观量合成和分离C₆₀以来,人们不断地合成各种功能化的C₆₀衍生物.在对C₆₀化学性质的认识过程中,气相离子化学一直起着十分重要的作用。