Deprotonation of zinc(II)-water and zinc(II)-alcohol and nucleophilicity of the resultant zinc(II) hydroxide and zinc(II) alkoxide in double-functionalized complexes: theoretical studies on models for hydrolytic zinc enzymes

The factors governing the deprotonation ability of zinc(II)-water and zinc(II)-alcohol and nucleophilicity of the resultant zinc(II) hydroxide and zinc(II) alkoxide as complex models for zinc enzymes have been investigated through Hartree-Fock and density-functional theory methods with the 6-311++G(d,p) basis set. Our calculations showed that in these double-functionalized complexes (i.e., zinc complexes having both a zinc(II)-alcohol motif and a zinc(II)-water motif) zinc(II)-alcohol is preferred in deprotonation over zinc(II)-water (i.e., zinc(II)-alcohol has a much lower pK(a) than zinc-coordinated water in the same molecule). Natural bond orbital analysis revealed that zinc(II) alkoxides are more nucleophilic than their respective counterparts zinc(II) hydroxides. The analysis of the transition state in the transformation reaction from zinc(II) hydroxide species to zinc(II) alkoxide species indicates that zinc(II) alkoxides are the preferred deprotonated species not only thermodynamically but also kinetically. Further examination of the proposed mechanisms of the zinc(II) alkoxide-promoted transesterification path and the zinc(II) hydroxide-promoted hydrolysis path revealed the structures of the intermediates and energy diagrams in the reactions. These results, entitled double-functionalized complexes, for the first time, put a firm theoretical foundation of why the zinc(II)-alcoholic OH is a better model for hydrolytic zinc enzymes (having both stronger acidity and better nucleophilicity).     

Effect of Varying Alkyl Chain Length on Thermal Decomposition Temperature of Zinc(II) Xanthates and its Impact on Curing of Epoxy Resin

Linear and branched zinc(II) xanthates with varying alkyl chain length were synthesized and characterized by ¹H NMR, ¹³C NMR, and IR spectroscopy, as well as elemental analysis. Zinc sulfide as the final decomposition product upon thermal annealing of zinc(II) xanthates was confirmed by XRD analysis. Cure time for epoxy resin composite at various temperatures was analyzed employing zinc(II) xanthates (5 % mass) as latent cure catalysts. XRD investigation of the cured epoxy resin including zinc(II) xanthates upon thermal annealing revealed the presence of ZnS in‐situ in the composite matrix, indicating the in‐situ thermal decomposition of zinc(II) xanthates as probable mechanism for curing. Thermogravimetric analysis was performed to investigate the thermal decomposition temperature trend of zinc(II) xanthates. A parallel trend was observed correlating the thermal decomposition temperature trend of zinc(II) xanthates and the order of curing catalytic efficiency utilizing zinc(II) xanthates. In the case of linear alkylzinc(II) xanthates with an increase in the alkyl chain length, both thermal decomposition temperature and the cure time were enhanced. In contrast, in case of branched alkyl chain zinc(II) xanthates with increasing alkyl chain length show decreasing thermal decomposition temperature as well as cure time.     

发芽糙米微量元素锌的生物强化

目的发芽糙米的锌生物强化培育及对人体补锌的适用性探讨。方法选取3个品种(吉梗81号、博优209号、黑糯米)的糙米为材料,用不同质量浓度锌培养液(0~250μg·m L-1)浸种24 h(28℃)并发芽36 h(30℃),在萌发过程中实行锌的生物强化,培育富锌发芽糙米。通过测定不同锌含量条件下发芽糙米的萌发参数(吸水率、发芽率),以及锌、Vc和矿物质(Fe、Mn、Mg)含量,探明培养液锌的适宜含量条件和富锌发米糙米的补锌适用性。结果对吉梗81号、博优209号、黑糯米等3个品种,富锌发芽糙米培育的锌培养液适宜质量浓度均为75~150μg·m L-1,最佳质量浓度为100μg·m L-1。3个品种发芽糙米对锌的富集能力由强到弱顺序为:吉梗81号,博优209号,黑糯米。与对照处理(CK)相比,富锌发芽糙米Vc、GABA含量较高,而矿质元素(Fe、Mn、Mg)渗漏损失略低。富锌发芽糙米每10 g(DW)的锌积累量,对吉梗81号、博优209号及黑糯米等3个品种可提供锌占中国成人RNI百分数分别是:53.8%(男性)和89.7%(女性),45.6%(男性)和76.0%(女性),以及41.1%(男性)和68.5%(女性)。结论发芽糙米可能是进行锌生物强化的优良载体,预计富锌发芽糙米适用于人体补锌。     

Chemical Recycling of End-of-Life Poly(lactide) via Zinc-Catalyzed Depolymerization and Polymerization

The chemical recycling of poly(lactide) was investigated based on depolymerization and polymerization processes. Using methanol as depolymerization reagent and zinc salts as catalyst, poly(lactide) was depolymerized to methyl lactate applying microwave heating. An excellent performance was observed for zinc(II) acetate with turnover frequencies of up to 45000 h⁻¹. In a second step the monomer methyl lactate was converted to (pre)poly(lactide) in the presence of catalytic amounts of zinc salts. Here zinc(II) triflate revealed excellent performance for the polymerization process (yield: 91 %, M_n ∼8970 g/mol). Moreover, the (pre)poly(lactide) was depolymerized to lactide, the industrial relevant molecule for accessing high molecular weight poly(lactide), using zinc(II) acetate as catalyst.     

Mechanism of thermal stabilizers for poly(vinyl chloride). II. Synergistic effect of combination of metal soaps

The esterification of metal soaps, in the combination of zinc and calcium soaps, on poly(vinyl chloride) (PVC) has been carried out both in liquid and solid phase to determine why the reactivity of zinc soap decreases on addition of calcium soap, improving the long-run heat stability of PVC and causing the well-known synergism. It is suggested as the mechanism of synergism that metal soaps having low ionization-potential values, such as calcium soap, act as ester-exchangers of metal chlorides, such as zinc chloride, which is generated after the stabilization of PVC, and also decrease the reactivity of the zinc soap by forming a complex, as that of zinc soap—calcium soap. If a third material, such as organic ester silane, reacting as ester-exchanger on zinc chloride and preventing the formation of a zinc—calcium soap complex, is added to the system, these compounds have an excellent synergistic effect.     

Can Co(II) or Cd(II) substitute for Zn(II) in zinc fingers?

Zinc finger domains consist of sequences of amino acids containing cysteine and histidine residues tetrahedrally coordinated to a zinc ion. The role of zinc in a DNA binding finger was considered purely structural due to the absence of redox chemistry in zinc. However, whether other metals e.g. Co(II) or Cd(II) can substitute Zn(II) is not settled. For an answer the detailed interaction of Co(II) and Cd(II) with cysteine methylester and histidine methylester has been investigated as a model for the zinc core in zinc fingers. The study was extended to different temperatures to evaluate the thermodynamic parameters associated with these interactions. The results suggest that zinc has a unique role.     

slow release rubber formulations containing ZnSO4

Styrene butadiene (SBR) and natural rubber (NR) can be used as binding matrices to control the release of zinc (Zn) which is a micro-nutrient for plants. The leaching rate of zinc in an aqueous medium depends on the concentration of zinc sulphate loaded in the two types of rubber used, the temperature of the surrounding environment and the pH of the aqueous medium. Water uptake was increased with increasing concentration of ZnSO₄. The sustained release of zinc ions from the investigated formulations was prolonged for over five months. The mechanical properties of the vulcanizates were affected as the concentration of zinc sulphate changed.     

Photocatalytic degradation of methyl red by porous zinc hydroxide under visible light irradiation

In the present study, porous zinc hydroxide was successfully prepared via a simple sol–gel route. The synthesized porous zinc hydroxide was characterized using scanning electron microscopy (SEM), X‐ray diffraction (XRD), transmission electron microscopy (TEM), and Brunauer–Emmett–Teller (BET) techniques. In addition, the prepared porous zinc hydroxide was studied as a photocatalyst for the degradation of methyl red. The degradation behavior of porous zinc hydroxide was investigated systematically. The experimental results showed that the obtained porous zinc hydroxide displayed excellent degradation efficiency (89%) under visible light irradiation. Thus, porous zinc hydroxide can be used as an effective photocatalyst for the degradation of methyl red, which can be used for industrial wastewater treatment.     

Determination of radioactive bulk and surface concentration by beta-detection

Electrolytes of alkaline zincate, acidified zinc sulphate, zinc-ammonia, zinc-ammonia-EDTA, zinc-EDTA/NaOH have been examined in order to verify their applicability for electrodeposition (ED) of zinc on stainless steel (SS) disc at ppm level. Operating parameters suitable for ED of zinc at 90% deposition (amount of zinc removed from plating solution) on SS disc using a total 1 ppm zinc in a 5 cm³ bath volume were determined. It helped to prepare radioactive source (⁶⁵Zn) using inactive Zn as carrier. Speciation of zinc in a Zn-oxalate-EDTA-ammonia bath has been computed.     

Determination of organo-zinc based fungicides in timber treatments employing gas chromatographic analysis with mass selective detection and/or inductively coupled plasma atomic emission spectroscopy

A method for the determination of zinc octoate (zinc 2-ethylhexanoate) and acypetacs zinc in occupational hygiene samples and wood treatments formulations is described. The zinc carboxylates are liquid-liquid partitioned between toluene and 1 M HCl, with the liberated acids being extracted into the toluene and zinc (chloride) into the acid. The carboxylic acids are then methylated using trimethylsilyldiazomethane-methanol and the resultant methyl esters are selectively and sensitively analysed by gas chromatography with mass selective detection (GC-MS). Alternatively, the zinc content of the acid extract can be analysed by inductively coupled plasma atomic emission spectroscopy (ICP-AES). GC-MS is the preferred method of analysis for zinc octoate, where a single analyte (methyl-2-ethylhexanoate) is produced for analysis. Because acypetacs zinc contains a complex mixture of carboxylates, quantitative GC-MS analysis of the methyl esters produced is impractical and ICP-AES is the preferred method for quantitation. In this case, GC-MS can be used to confirm the identity of the product used. The analysis of occupational hygiene samples (cotton pads, gloves and socks as well as Tenax tubes and GF/A filters) spiked with metal carboxylates is demonstrated. Recoveries around 70-90% and reproducibilities of 5-23% (n=6-8) were typically achieved for the determination of tin octoate (a surrogate for zinc octoate) at spiking levels ranging from 4 to 190 microg per sampling device. Recoveries around 102-106% and reproducibilities of 10-12% (n=5-6) were typically achieved for acypetacs zinc at spiking levels ranging from 100 mg per sampling device. Reaction yields for the octoate methylation reaction were in the region of 85-87%. The method was used to monitor for occupational exposure to zinc octoate and acypetacs zinc during the application of wood treatments to fences.     

MXenes在水系锌离子电池中的应用研究进展

水系锌离子电池(AZIBs)作为一种低成本、高安全的新兴且前景广阔的储能技术近年来备受关注。新型MXenes材料由于其独特的结构特征和物理化学性质,如易调节的二维结构、优异的导电性、化学组成多样和可控的表面化学特性,在AZIBs中表现出独特的应用优势。本文全面综述近年来MXenes在AZIBs中应用的研究进展,探讨MXenes应用于AZIBs正负极的结构设计及性能优化策略：在正极方面,MXenes可直接作为活性物质或活性物质前驱体、基体材料,以获得高活性、优异的循环寿命和倍率性能;在负极方面,MXenes可作为锌沉积的二维/三维载体、亲锌基体及锌金属界面保护层,以减缓电化学反应过程中锌金属的腐蚀和枝晶生长。此外,本文也对MXenes基材料在AZIBs中应用的发展方向进行展望。     

SYNTHESIS AND PHOTOCYTOTOXICITY OF SOME NEW SUBSTITUTED PHTHALOCYANINES

Some new, ring-substituted phthalocyanines have been synthesized and underwent preliminary testing for photodynamic activity using the colony forming ability of Chinese hamster cells in culture as an endpoint. Using 4-(3-N,N-diethylaminopropyl)phthalonitrile as a precursor, the previously unknown metal-free 2,9,16,23-tetra-(3-N,N-diethylaminopropyl)phthalocyanine was prepared and converted to its zinc (II) and its cationic water-soluble 2,9,16,23-tetramethylammonium zinc (II) iodide derivatives. Other new phthalocyanine derivatives tested, include a 2,9,16,23-tetra(2-hydroxymethyl-2-methylbutoxy)phthalocyaninato zinc (II) and 2,3,9,10,16,17,23,24-octahydroxyphthalocyaninato zinc (II) derivatives. Boron tribromide cleavage of the newly prepared and fully characterized 2,3,9,10,16,17,23,24-octamethoxyphthalocyanine gave the unstable metal-free octahydroxyphthalocyanine, which could only be characterized by ultraviolet-visible, NMR and IR spectroscopy.     

Determination of zinc(II) in biological samples by anodic stripping voltammetry

The use ofN-benzyltrimethylammonium methoxide as a digesting solvent, for the determination of zinc(II) in biological samples using anodic-stripping voltammetry is reported. It was found possible to determine zinc directly in biological samples containing such metals as copper(II), lead(II), iron(III), arsenic(III) and selenium(IV). The results for zinc in bovine liver and oyster tissue are reported.     

Metal dicarboxylates as thermal stabilizers for PVC

Different metal dicarboxylates such as calcium glutarate, zinc glutarate, calcium sebacate and zinc sebacate were investigated in this paper as thermal stabilizers (without and with calcium stearate and pentaerythritol as costabilizers) of poly(vinyl chloride) (PVC). The thermal stability of the PVC films was determined by two different methods which are visual color comparison and measurement of HCl release from heated pellets. Both zinc dicarboxylates and calcium dicarboxylates exhibited good thermal stability. With respect to stabilizing performance, zinc glutarate (ZnGa) was more effective than zinc sebacate (ZnSe), particularly in the presence of a large amount of pentaerythritol. Similarly, calcium glutarate (CaGa) was more effective than calcium sebacate (CaSe). And the relative order of stabilizing effectiveness of metal dicarboxylates was as follows: CaGa > CaSe > ZnGa > ZnSe. Moreover, the Ca-Zn complex thermal stabilizer and the Pe-Zn complex thermal stabilizer were also studied. It was found that no more than 20% of the zinc compound exhibited better stabilizing performance.     

Parameters affecting carbofuran photocatalytic degradation in water using ZnO nanoparticles

Carbofuran photodegradation in water using zinc oxide nanoparticles as a catalyst was examined as well as some parameters influencing its percentage degradation rate such as zinc oxide load, initial concentration of carbofuran, the temperature of the reaction, the initial pH of the solution, and doping of zinc oxide nanoparticles with 5% (w:w) silver. Zinc oxide and Ag-doped zinc oxide nanoparticles were produced using solvothermal and photoreduction methods, respectively, and silver doping effects on the structural, optical, and photocatalytic properties of zinc oxide nanoparticles were investigated using XRD, UV-VIS spectrophotometer, TEM, SEM, SEM/EDX, and FTIR. The average diameter of the synthesized samples was 26.6, 30.55 nm for undoped zinc oxide and Ag-doped zinc oxide, respectively. Zinc oxide doping with silver did not change the shape of the zinc oxide crystal, but decreased the reflection in the visible region, as well as the energy of the bandgap, and increased the zinc oxide photocatalytic activity.     

镉基体中微量锌的富集与分离研究

提出了一种用于富集分离镉基体中的微量锌的分离体系,研究了从镉基体中富集分离微量锌的可行性——采用二安替比林甲烷(DAM)作为络合剂,与硫氰酸铵、锌在盐酸介质中形成三元离子缔合物,用三氯甲烷作为萃取剂,最后用氨水作为反萃剂将有机相中的锌洗脱出来与镉分离。试验发现,当15%的硫氰酸铵用量为1.5mL,DAM的用量为1.5mL,加入20mL4mol/L的盐酸时,用20mL的三氯甲烷萃取两次,10mL1:3的氨水反萃两次,锌的回收率达到95%以上,相对误差小于0.5%。     

Quantitative separation of zinc traces from cadmium matrices by solid-phase extraction with polyurethane foam

A system for separation of zinc traces from large amounts of cadmium is proposed in this paper. It is based on the solid-phase extraction of the zinc in the form of thiocyanate complexes by the polyurethane foam. The following parameters were studied: effect of pH and of the thiocyanate concentration on the zinc extraction, shaking time required for quantitative extraction, amount of PU foam necessary for complete extraction, conditions for the separation of zinc from cadmium, influence of other cations and anions on the zinc sorption by PU foam, and required conditions for back extraction of zinc from the PU foam. The results show that zinc traces can be separated from large amounts of cadmium at pH 3.0±0.50, with the range of thiocyanate concentration from 0.15 to 0.20 mol l⁻¹, and the shaking time of 5 min. The back extraction of zinc can be done by shaking it with water for 10 min. Calcium, barium, strontium, magnesium, aluminum, nickel and iron(II) are efficiently separated. Iron(III), copper(II) and cobalt(II) are extracted simultaneously with zinc, but the iron reduction with ascorbic acid and the use of citrate to mask copper(II) and cobalt(II) increase the selectivity of the zinc extraction. The anions nitrate, chloride, sulfate, acetate, thiosulphate, tartarate, oxalate, fluoride, citrate, and carbonate do not affect the zinc extraction. Phosphate and EDTA must be absent. The method proposed was applied to determine zinc in cadmium salts using 4-(2-pyridylazo)-resorcinol (PAR) as a spectrophotometric reagent. The result achieved did not show significant difference in the accuracy and precision (95% confidence level) with those obtained by ICP–AES analysis.     

寡聚酸合锌(Ⅱ)的合成及对烟草病毒病的防治

在水-乙醇介质中,用寡聚酸钾与硫酸锌反应合成的寡聚酸合锌(Ⅱ)配合物,采用正交实验考察了V水∶V乙醇,反应温度,反应时间对螯合反应的影响,最优反应条件为:V水∶乙醇=1∶1;温度60℃;时间5h.通过红外光谱、紫外光谱和差热-热重分析测试手段对配合物进行了表征.红外光谱和紫外光谱均显示,Zn2+与寡聚酸配位.寡聚酸合锌(Ⅱ)配合物中金属配位方式为单齿和双齿配位.热分析表明,配合物稳定性较强.应用寡聚酸合锌(Ⅱ)防治烟草病毒病,试验结果表明寡聚酸合锌(Ⅱ)具有较强的防治烟草病毒病的作用.寡聚酸合锌(Ⅱ)作为新型的抗病毒制剂具有广阔的开发前景.     

Synthesis, Reactivity, and Spectroscopic Properties of meso-Triaryl-5-oxaporphyrins

[meso-Triaryl-21,23-didehydro-23H-5-oxaporphyrinato](trifluoroacetato)zinc(II) was prepared by the reaction of meso-triarylbilindione with acetic anhydride and zinc acetate, and it was isolated as a trifluoroacetate salt. The X-ray crystallographic study demonstrated that the trifluoroacetate anion was coordinated to the zinc ion. [21,23-Didehydro-10,15,20-tris(4-methoxycarbonylphenyl)-23H-5-oxaporphyrinato](trifluoroacetato)zinc(II) 3a was dissolved in various organic solvents such as toluene, chloroform, diethyl ether, ethyl acetate, acetone, acetonitrile, methanol, DMSO, and DMF, although it readily reacted with alcohols and DMF to yield linear tetrapyrroles. The solubility of 3a in toluene was 4.2 ± 0.1 g dm(-3) at room temperature. 3a showed characteristic UV-vis absorption at 649 nm and fluorescence emission at 657 nm in chloroform. The fluorescence quantum yields of 3a, [21,23-didehydro-10,15,20-triphenyl-23H-5-oxaporphyrinato](trifluoroacetato)zinc(II) (3c), and [21,23-didehydro-10,15,20-tris(4-methoxyphenyl)-23H-5-oxaporphyrinato](trifluoroacetato)zinc(II) (3b) were 0.071, 0.071, and 0.050, respectively. Reaction of 3a with EtOH afforded the zinc complex of 19-ethoxybilinone, and it proceeded 2 orders of magnitude faster than that of [β-octaalkyl-21,23-didehydro-23H-5-oxaporphyrinato]zinc(II). The reaction with alcohols was sensitive to steric bulk of the alcohols; the rate of reaction with i-PrOH was 2700 times faster than that of t-BuOH at 303 K. The reaction of [meso-triaryl-21,23-didehydro-23H-5-oxaporphyrinato]zinc(II) with water proceeded 3 orders of magnitude slower than that with EtOH.