Synthesis and ion-binding studies of platinum(II) phenanthroline complexes containing crown ether moiety

Square-planar platinum(II) polypyridyl complexes represent an important class of compounds that possess a rich range of spectroscopic and photophysical proper- ties[1―17]. Some of them have demonstrated promise in wide-ranging applications including opti…     

特殊环境条件下复合重金属污染固化土中离子迁移特性分析

运用有限元软件建立二维轴对称分析模型,研究了重金属离子(Cu2+,Cd2+)在土壤中的迁移扩散规律,对比了单一重金属离子(Cu2+)和复合重金属(Cu-Cd)的迁移特性,分析了固化前后重金属的扩散规律,并考虑了温度和干湿作用的影响。结果表明:复合重金属在渗透过程中的迁移半径大于单一重金属离子的迁移半径;固化后的污染土对于重金属离子的扩散速率有着良好的控制作用,固化作用对单一重金属离子扩散的影响更为明显。环境温度对于重金属离子的扩散速率和范围呈现出正相关的影响;干湿循环作用下重金属离子的扩散范围明显增大。     

Electromigration in eutectic SnAg solder reaction couples with various ambient temperatures and current densities

The electromigration behavior of eutectic SnAg solder reaction couples was studied at various temperature (25 and 120℃ when the current density was held constant at 104 A/cm2 or 5×103 A/cm2. Under the current density of 104 A/cm2, scallop type Cu₆Sn₅ spalls and migrates towards the direction of electron flow at room ambient temperature (25℃), but transforms to layer type Cu₃Sn and leaves Kirkendall voids in it at high ambient temperature (120℃). Under the current density of 5×103 A/cm2 plus room ambient temperature, no obvious directional migration of metal atoms/ions is found. Instead, the thermal stress induced by mismatch of dissimilar materials causes the formation of superficial valley at both interfaces. However, when the ambient temperature increases to 120℃, the mobility of metal atoms/ions is enhanced, and then the grains rotate due to the anisotropic property of β-Sn.     

Characteristics of electric double layer in different aqueous electrolyte solutions for supercapacitors

Aiming to find suitable electrolytes for electric double layer capacitor (EDLC),the relationship between the formation velocity of electric double layer and the specific capacitance in different electrolyte (H 2 SO 4,KOH,KCl,NH 4 Cl,and LiOH) solutions was investigated by cyclic voltammetry and AC impedance with varying frequency and potential,which was also analyzed based on Stern model and Gouy-Chapman diffusion layer model.It shows that the capacitance is positively correlated with the formation velocity of the electric double layers,which is affected by the type of ions applied,the concentration of the electrolyte solution,and the potential and frequencies as well.The electrolyte solutions of 6 mol/L KOH and 4 mol/L H 2 SO 4 provide the largest capacitance,reaching 214 and 186 μF/cm 2,respectively.Both 6 mol/L KOH and 4 mol/L H 2 SO 4 solutions are suitable electrolytes for EDLC applications using Pt as electrodes.     

Oxygen-contact charge transfer complexes in organic bicomponent systems

The O₂-CCT absorption spectra of bicomponent systems were measured. The influences of various organic compounds as well as the component concentration on the O₂-CCT formation ability were investigated. The results show that if the difference of O₂-CCT formation ability between the two components is rather large, such as the benzene/ isopropyl ether system, only the O₂-CCT absorption of benzene appears, which arises from its higher O₂-CCT formation ability. If the difference of O₂-CCT formation ability is small, such as the isopropyl ether/ethanol system and the dioxane/isopropyl ether system, it is rather easy to form a dynamic equilibrium of two O₂-CCT between the two components, then only one absorption peak appears in the whole concentration range as a result of the repeated addition of the two kinds of O₂-CCT absorption. If the difference of O₂-CCT formation ability is in medium compared with the two cases above, such as the dioxane/ethanol system, there are two kinds of₂-CCT absorption of dioxane and ethanol in the same system in the form of an equilibrium, then two absorption peaks can be detected in the middle concentration range as a result of the repeated addition of the two kinds of₂-CCT absorption.     

Transports of K^＋, Ca^2＋ Ions in Liquid Membrane with Calixarene Derivatives as Carriers

A few derivatives of calixarenes have been synthesized and characterized by IR, ^1H NNtR, thermal and elemental analysis. The transport of potassium or calcium ion through the liquid membrane, in which the derivatives act as carriers, has been studied. The electron-effect of the substituent on the upper rim of calixarene possesses important effect on the net transport of metal ions. The p- tert-butylcalix[4]arene is the best carrier of calcium ion, compared with p-tert-calix[4]arene（n = 4, 6, 8）. The ptert-butylcalix[4]arene acid is better than p-tert-butylcalix [4]arene. The calixr43crown is the best carrier of calcium ions of all the carriers. The pH gradient between the source and receiving phase, and the concentration of K^＋ , Ca^2＋ ions in the source phase affect mainly transport. After the transport, the pH value of the source phase is found to be decreased, once the calix [n ] arene derivatives act as carrier. But it is not the case for the calix[n] crowns. It might be interpreted as the result of their different mechanisms.     

离子色谱线性梯度下分离碱金属、碱土金属和胺离子的计算机模拟

通过大量实验数据,建立了使用硫酸淋洗液时碱金属、碱土金属离子和胺离子的保留值随淋洗液浓度变化关系的数据库,并在此基础上建立了使用硫酸淋洗液时用计算机模拟离子色谱梯度淋洗分离碱金属、碱土金属离子和胺离子的新方法.研究了在线性梯度淋洗过程中不同时刻这些阳离子在色谱柱中的位置及所在位置的淋洗液浓度,得出这些阳离子在不同时间的容量因子、迁移速度,通过积分得到保留时间.模拟色谱图保留值与实验值的相对误差小于2%,模拟色谱图的色谱峰峰形与实验所得到的色谱图的色谱峰峰形非常接近.     

Determination of color centers in CaF2 crystals by multiple gamma-ray irradiations

Color centers of CaF2 crystals subjected to three high-dose gamma-ray irradiation treatments were studied. Three absorption bands at 349, 409 and 478 nm are ascribed to the F interstitials through the variation in difference additional absorption values. The transformation of interstitial F atoms to F ions (Fi-) is demonstrated using data with increasing radiation dose. The decrease in the 600 nm absorption band and the occurrence of the 580 nm band correspond to F2+ center conversion to F center. The complex (F~--Fi0 ) might be associated with the 962 and 1196 nm bands.     

碱土金属化合物性质实验的微型化研究

系统探讨碱土金属氢氧化物及其盐的溶解性、碱土金属元素的焰色反应、碱土金属离子的分离和鉴定等微型化实验，并将其设计成新的微型实验应用于无机化学实验教学，效果良好。     

Antibacterial and corrosive properties of copper implanted austenitic stainless steel

Copper ions were implanted into austenitic stainless steel (SS) by metal vapor vacuum arc with a energy of 100 keV and an ions dose range of (0.5-8.0)×1017 cm-2. The Cu-implanted SS was annealed in an Ar atmosphere furnace. Glancing X-ray diffraction (GXRD), transmission electron microscopy (TEM) and Auger electron spectroscopy (AES) were used to reveal the phase compositions, microstructures, and concentration profiles of copper ions in the implanted layer. The results show that the antibacterial property of Cu-implanted SS is attributed to Cu_9.9Fe_0.1, which precipitated as needles. The depth of copper in Cu-implanted SS with annealing treatment is greater than that in Cu-implanted SS without annealing treatment, which improves the antibacterial property against S. aureus. The salt wetting-drying combined cyclic test was used to evaluate the corrosion-resistance of antibacterial SS, and the results reveal that the antibacterial SS has a level of corrosion-resistance equivalent to that of un-implanted SS.     

Fragmentation mechanism of product ions from protonated proline-containing tripeptides in electrospray ionization mass spectrometry

The dissociation chemistry of primary fragment ions from the protonated proline-containing tripeptides glycylprolylglycine,prolylglycylglycine,and prolylprolylglycine was investigated by electrospray ionization multi-stage mass spectrometry.Calcula-tions showed the a 2 ions generated from b 2 ions were cyclic,which is energetically more favorable than the linear form.The prolyl residue in the structure affected the energy hypersurface of the dissociation reaction from the b 2 ion to the a 2 ion.In the fragmen-tation of a 2 ions,the iminium-imine complex corresponding to loss of CO from the a 2 ion was suggested to be an ion-neutral com-plex (INC).The a 1 ion was generated from direct separation of this INC,and the internal iminium ion,which was absent in PGG,was generated from another INC that was formed from the first INC via proton-bridged complex-mediated intramolecular proton transfer.Although these intermediates are unstable,their existence is supported by experiments and density functional theory calculations.     

Mechanisms of sodium and potassium ions transfer facilitated by dibenzo-15-crown-5 across the water /1,2-dichloroethane interface using micropipettes

The transfer of sodium and potassium ions facilitated by dibenzo-15-crown-5 (DB15C5) has been studied at the micro-water/1,2-dichloroethane (water/DCE) interface supported at the tip of a micropipette. Cyclic voltammetric measurements were performed in two limiting conditions: the bulk concentration of Na+ or K+ in the aqueous phase is much higher than that of DB15C5 in the organic phase (DB15C5 diffusion controlled process) and the reverse condition (metal ion diffusion controlled process). The mechanisms of the facilitated Na+ transfer by DB15C5 are both transfer by interfacial complexation (TIC) with 1∶1 stoichiometry under these two conditions, and the corresponding association constants were determined at log β1 = 8.97 ( 0.05 or log β1 = 8.63 ( 0.03. However, the transfers of K+ facilitated by DB15C5 show different behavior. In the former case it is a TIC process and its stoichiometry is 1∶2, whereas in the latter case two peaks during the forward scan were observed, the first of which was confirmed as the formation of K+(DB15C5)2 at the interface by a TIC mechanism, while the second one may be another TIC process with 1∶1 stoichiometry in the more positive potential. The relevant association constants calculated for the complexed ion, K+(DB15C5)2, in the organic phase in two cases, logβ2, are 13.64 ( 0.03 and 11.34 ( 0.24, respectively.     

Preparation, crystallization, and wetting of ZnO-Al2O3-B2O3-SiO2 glass-ceramics for sealing to Kovar

A novel type of ZnO-Al₂O₃-B₂O₃-SiO₂ glass-ceramics sealing to Kovar in electronic packaging was developed, whose thermal expansion coefficient and electrical resistance are 5.2×10-6/℃ and over 1×1013 Ω·cm, respectively. The major crystalline phases in the glass-ceramic seals were ZnAl₂O₄, ZnB₂O₄, and NaSiAl₂O₄. The dielectric resistance of the glass-ceramic could be remarkably enhanced through the control of alkali metal ions into crystal lattices. It was found that crystallization happened first on the surface of the sample, leaving the amorphous phase in the inner, which made the glass suitable for sealing. The glass-ceramic showed better wetting on the Kovar surface, and sealing atmosphere and temperature had great effect on the wetting angle. Strong interracial bonding was obtained, which was mainly attributed to the interracial reaction between SiO₂ and FeO or Fe₃O₄.     

金属离子对鲍鱼碱性磷酸酶活力的影响

碱性磷酸酶(ALP,EC3.1.3.1)是一种金属酶,其结构的维持和酶活性的表现均需金属离子.本文研究了几种金属离子分别对鲍鱼ALP活力的影响.结果表明,Li ,Na 和K 等正一价碱金属离子对酶活力没有任何效应;碱土金属离子Mg2 ,Ca2 和Ba2 对酶有激活作用,其激活程度依次为:Mg2 >Ca2 >Ba2 ,而且Mg2 在5.0mmol/L时可以使酶活力提高267%;在过渡金属离子中,Zn2 ,Mn2 ,Co2 和Cu2 对酶的效应不同,Zn2 、Cu2 为抑制作用,而Co2 、Mn2 表现为激活作用;重金属离子Hg2 、Pb2 、Ag 和Cd2 对酶有抑制作用,其中Hg2 的抑制效应最强,1.0mmol/LHg2 可使酶活力抑制94%.研究Mn2 和Cu2 的抑制类型表明,Mn2 为混合型激活作用,而Cu2 对酶的抑制类型为非竞争性抑制作用,其抑制常数(KI)为0.316mmol/L.     

配位络合催化热钾碱吸收CO_2动力学研究

在常压和接近工业生产温度、浓度条件下，测定了若干过渡金属离子与多元胺配位络合催化的吸收速率和解吸速率。进而用最佳配位络合剂研究了影响吸收速率的因素、金属离子和配位活化剂的活性顺序以及最佳工艺特性；并分析了配位络合活化反应的机理，提出机理模型。由实验数据进行多元回归得到的数学模型中的各个参数，可望为改进目前的ＤＥＴＡ脱碳工艺提供有益的依据，     

Low concentrations of NaHSO3 enhance NAD(P)H dehydrogenase-dependent cyclic photophosphorylation and alleviate the oxidative damage to improve photosynthesis in tobacco

Bisulfite at low concentrations(L-NaHSO3) increases cyclic electron transport around photosystem I(PSI) and photosynthesis.However,little is known regarding the detailed contribution of cyclic electron transport to the promoted photosynthesis by L-NaHSO3.In the present work,we used tobacco mutant defective in ndhC-ndhK-ndhJ(ndhCKJ) to investigate the role of NAD(P)H dehydrogenase(NDH)-dependent cyclic electron transport around PSI in an increase in photosynthesis by L-NaHSO3.After the treatment of tobacco leaves with L-NaHSO3(10 μmol L-1),the NDH-dependent cyclic electron transport,monitored by a transient post-illumination increase in Chl fluorescence and the amount of NDH,was notably up-regulated in wild type(WT).The NDH-dependent cyclic electron transport was severely impaired in ndhCKJ and was not significantly affected by treatment with L-NaHSO3.Accordingly,the NDH-dependent transthylakoid membrane proton gradient(pH),as reflected by the slow phase of millisecond-delayed light emission(ms-DLE),was increased by L-NaHSO3 in WT,but not in ndhCKJ;the enhancement of cyclic photophosphorylation(PSP) activity by L-NaHSO3 was more obvious in WT than ndhCKJ.The accumulation of both superoxide and hydrogen peroxide was reduced in WT when subjected to L-NaHSO3 treatment,but not in ndhCKJ.Furthermore,the increase of photosynthetic O 2 evolution rate by L-NaHSO3 was more significant in WT than in ndhCKJ.We therefore conclude that L-NaHSO3 alleviates the photo-oxidative damage by the enhancement of NDH-dependent cyclic PSP,thereby improving photosynthesis.     

异丙醇-硫酸铵-PAN双水相萃取光度法测定镍(Ⅱ)

研究了异丙醇水溶液与(NH4)2SO4的双水相体系下,螯合剂PAN(1-(2-吡啶偶氮)-2-萘酚)与Ni 2+以及吐温80形成的缔合物在两相间的分配行为.结果表明,该缔合物的最大吸收波长为562nm,与PAN和异丙醇水溶液的混合液相比,最大吸收发生了97nm红移.应用该缔合物体系分离测定镍时,其线性范围为0.10~0.60mg/L,线性相关系数为0.999 2,表观摩尔吸光系数为1.7×105 L·mol-1·cm-1.利用该方法萃取测定Ni(Ⅱ)时,干扰离子铅(Ⅱ)、锌(Ⅱ)、铝(Ⅲ)、锰(Ⅱ)、钼(Ⅶ)、Fe(Ⅲ)、铬(Ⅶ)不被萃取,实现Ni(Ⅱ)与上述干扰离子的分离.     

镍渣表面理化特性及对Pb2+、Cu2+的吸附研究

利用多种表征手段对镍渣的组成和表面特性进行分析,证实了镍渣具备吸附废水中重金属的能力。本实验所采用的水淬二次镍渣中含有含量较高的SiO₂、Al₂O₃、CaO、MgO等活性成分,且具备由不同聚合度的Si-O四面体、Al-O四面体或Al-O八面体组成的岛状、链状或网状骨架结构,能够通过离子交换和专性吸附去除溶液中的重金属离子。此外,镍渣粉体表面的碱中心可以为金属阳离子提供有效的吸附位点,且表面在pH=4~12的范围内均带负电,这些都有利于金属阳离子的吸附。镍渣粉体对模拟废液中的Pb²⁺、Cu²⁺吸附实验结果显示,其对废液中的Pb²⁺、Cu²⁺均表现出较好的吸附效果,且对Pb²⁺表现出更好的选择性吸附效果。     

Synthesis and properties of crown ether benzotellurazole heterocyclic styryl cyanines and merocyanines

Two Crown ether benzotellurastyryl cyanines and three crown ether benzotelluramerocyanines are synthesized via the key intermediate-3-methyl-5,6(15-crown-5)-2 (β-acetanilide) vinyl benzotellurazolium iodide. The reactive conditions are discussed. The influence of alkali (-earth) metal ions on the visible absorption spectra of these two types of crown ether cyanines are also studied. Supported by the National Natural Science Foundation of China Ke Weijun: born in 1971, Ph.D.     

相变吸收剂捕集二氧化碳的研究进展

人类工业活动排放的大量CO_2气体是导致全球变暖的主要因素,CO_2捕集、封存与利用(CCUS)是实现碳减排和应对全球变暖最有效的技术方向。常用的CO_2捕集技术中,采用有机胺类化学吸收剂的水溶液捕集CO_2面临的主要技术难题是再生能耗高,如何降低能耗将直接关系到CCUS技术的未来走向。相变吸收剂在吸收CO_2时具有优异的吸收特性,而且可分离为液-液或液-固两相,其中一相富集CO_2,在降低能耗方面呈现出较大优势。通过对传统有机胺水溶液脱除CO_2工艺的能耗结构进行分析,综述了CO_2相变吸收体系在碳捕集方面的研究现状,并对相变吸收剂的研究动向和技术发展前景进行了展望:探索相变吸收剂的相变机理,解决其组成和工艺稳定性问题;开展微胶囊、极性摆动等新型吸收剂和耐热酶、固体酸等催化再生技术方面的研究。