Complexity of Gold(Ⅲ)Ion With Cefotaxime and Cefepime Drugs:Spectroscopic,Antimicrobial and Antitumor Discussions

The availability of chemical and biological data presented in this paper is the basis for understanding not only the current state of anti-cancer drugs based on gold(Ⅲ),but also the rationale for strategies for future drug design.New Au(Ⅲ)nanosized complexes of cefotaxime(ceph-3)and cefepime(ceph-4)ligands as a 3rd and 4th of cephalosporin generation drugs were synthesized.Gold(Ⅲ)complexes were discussed based on the elemental,molar conductance,thermal and magnetic moment measurements as well as spectral(FTIR,1HNMR,UV-Vis,and XRD)techniques.FT-IR spectra revealed that the ceph-3 and ceph-4 ligands reacted as a bidentate ligands through carboxylate oxygen andβ-lactam oxygen groups.The analytical analysis confirm that the molar ratio is 1∶1(Au 3+/ceph)with general formula[Au(L)(Cl)2]where L=ceph-3 or ceph-4.The structures of Au(Ⅲ)complexes were presence as a square planar geometry.X-ray diffraction patterns referred to a crystalline nature for all synthesized complexes.TEM analyses confirmed that the synthetic gold(Ⅲ)complexes have a nanosized particles.In vitro antimicrobial activities of Au(Ⅲ)complexes were evaluated towards two types of bacteria(G+&G-).The antitumor activities of gold(Ⅲ)complexes are appraised against breast(MCF-7)and colorectal adenocarcinoma(Caco-2)cell lines,which means that the two complexes may consider promising anticancer drugs.

基于金纳米粒子-纳米氧化铈-石墨烯复合物修饰电极对环境水体中As(Ⅲ)的检测

先通过滴涂法制备纳米氧化铈-石墨烯(CeO_(2)-Gr)复合物修饰玻碳电极(GCE),再在含氯金酸(HAuCl_(4))的缓冲溶液中,采用循环伏安法将Au(Ⅲ)还原到CeO_(2)-Gr表面,从而制得AuNPs/CeO_(2)/Gr/GCE。采用电化学阻抗谱法(EIS)对修饰电极进行电化学特性表征。研究了AuNPs/CeO_(2)/Gr/GCE快速、准确测定水环境中As(Ⅲ),采用差分脉冲溶出伏安法,探讨了氧化铈与石墨烯质量比、金纳米粒子沉积圈数、沉积时间和沉积电位及干扰离子等对测定结果的影响,并确定检测As(Ⅲ)的优化实验条件。在最优条件下,该电化学传感器对As(Ⅲ)具有良好的电流响应,其溶出伏安峰电流与As(Ⅲ)浓度的线性范围为13.35~387.15μmol/L,检出限为4.74μmol/L。在不同干扰离子存在的情况下,传感器对As(Ⅲ)的选择性较好。为了评估传感器的实际应用能力,以实验室自来水为样本进行As(Ⅲ)加标检测,加标回收率为90.5%~99.2%,表明该电化学传感器具有监测As(Ⅲ)的应用潜力。

Fabrication and adsorption property of novel adsorbent for potential application to wastewater with Fe(Ⅲ) ions

The spherical macroporous cellulose(SMC) was fabricated using medical absorbent cotton as raw material and nano CaCO3 as porogenic agents.And then,the phenylglycine was grafted onto the SMC to obtain the novel spherical macroporous cellulose derivative adsorbent(PSMC).FT-IR and scanning electron microscope(SEM) were employed to characterize the adsorbents and Fe3+ ions served as model solute to evaluate the adsorption property of the adsorbents.The experimental results show that the amount of porogenic agents and the value of pH have obvious influence on adsorption capacity of the adsorbents.The data of adsorption kinetic and isotherm display that the adsorbents possess excellent equilibrium adsorption capacity(348.94 mg/g) and have a bright prospect and considerable potential in the treatment of Fe3+ ions in wastewater.

Organometallic Gold(Ⅲ) Derivatives with Anionic Oxygen Ligands-mononuclear Hydroxo, Alkoxo, and Acetato Complexes: Synthesis and Spectral Study

A variety of gold（Ⅲ） adducts having a-ligated oxygen-donor ligands have been prepared from [Au（ppy）Cl2]（ppy.phenylpyridine）（1） either by partial or total replacement of the chloride ions. The new species comprise hydroxo-[Au（ppy）（OH）Cl]（2）, and [Au（ppy）（OH）2]（3）, oxo-[Au2（ppy）2（μ-O）2]（4）, acetate-[Au（ppy）（O2CMe2）] （5）, and alkoxo complexes-[Au（ppy）（OR）Cl]（6, 7） and [Au（ppy）（OR）2]（8--10）（R=Me, 6 and 8; Et, 7 and 9; Pr, 10）. The dihydroxo and the oxo complexes can be interconverted by refluxing the former in anhydrous THF and the latter in water. The hydroxides 2 and 3 and the acetato complex 5 undergo σ-ligand metathesis in ROH solution（R=Me, Et or Pr） to give the corresponding alkoxides.

膦酸功能化纤维素的制备及其对Au(Ⅲ)的吸附富集性能

为处理黄金冶炼工业产生的含金废水并实现其资源化利用,本研究通过多氨基多醚基甲叉膦酸与纤维素反应,设计合成了膦酸功能化纤维素(P-PC)吸附分离材料,利用红外光谱(FT-IR)、扫描电镜(SEM)对产物进行了表征分析。研究了P-PC对水溶液中Au(Ⅲ)的吸附富集性能。吸附实验表明,P-PC对Au(Ⅲ)的吸附行为符合伪一阶和伪二阶动力学模型及Langmuir等温吸附模型。当pH值为1.0时,P-PC对Au(Ⅲ)的吸附性能最佳。经过3次吸附与解吸循环后,P-PC对Au(Ⅲ)的吸附量仍超过0.5 mmol·g^(-1)。P-PC在吸附富集Au(Ⅲ)方面具有潜在的应用前景。

Comparative Study of Hydrogen Electrooxidation on Gold and Platinum in Solutions Containing Perchlorate Ion

The electrooxidation of hydrogen on platinum and gold electrodes is comparatively described in this paper. The reaction is faster on platinum than on the gold surface, because the reactive diffuses inside of the gold metal. This process is complicated with the lift of surface reconstruction of the (100) plane, which allows the fast penetration of the H atoms through the more open surface. The diffusion limiting current is then discontinued and the current falls. On platinum, the current fall occurs simultaneously with the metal oxide formation. It is assumed that the hydrogen helps the adsorbed OH group formation, which is the first step of metal oxidation, and it has been called “incipient hydrous oxide” (IHO). Current begins to fall slowly at the (IHO) potential. At higher potential the current falls abruptly.

Effect of Fe(Ⅲ) on the bromate reduction by humic substances in aqueous solution

Humic substances are ubiquitous redox-active organic compounds of environment. In this study, experiments were conducted to determine the reduction capacity of humic acid in the man-ix of bromate and Fe（Ⅲ） solutions and the role of Fe（Ⅲ） in this redox process. The results showed that the humic acid regenerated Fe（Ⅱ） and reduced bromate abiotically. The addition of Fe（Ⅲ） could accelerate the bromate reduction rate by forming humic acid-Fe（Ⅲ） complexes. Iron species acts as electron mediator and catalyst for the bromate reduction by humic acid, in which humic acid transfers electrons to the complexed Fe（Ⅲ） to form Fe（Ⅱ）, and the regenerated Fe（Ⅱ） donate the electrons to bromate. The kinetics study on bromate reduction further indicated that bromate reduction by humic acid-Fe（Ⅲ） complexes is pH dependent. The rate decreased by 2-fold with the increase in solution pH by one unit. The reduction capacity of Aldrich humic acid was observed to be lower than that of humic acid or natural organic matter of Suwanne River, indicating that such redox process is expected to occur in the environment.

Amperometric detection of gold by differential pulse voltammetry using a DNA biosensor

A DNA biosensor with [Ru（DA-bpy）3]Cl2（DA-bpy：4,4＇-diamino-2,2＇-bipyridine） （RuL） as the electrochemical probe was prepared on pyrolytic graphite electrode （PGE） through the supramolecular interaction between RuL complex and DNA template. Cyclic voltammetry of RuL-DNA film showed a pair of stable and reversible peaks corresponding to the Ru（Ⅲ）/Ru（Ⅲ） redox potential of-0.165 V versus AglAgCl in pa 7.4 0.1 mol·L^-1Tris-HCl. The electron transfer was expected across the double-strand DNA by an ＂electron tunneling＂ mechanism. When the DNA biosensor was immerged in gold （Ⅲ） buffer solution, the current peak signal （I） of the RuL-DNA supramolecular depressed and △I was linear in the concentration range of Au ion from 1×10^-7 to 2×10^-5 mol·L^-1 with a regression coefficient of 0.9879. The detection limit was 5×10^-8 mol·L^-1. The developed procedures were applied to the analysis of synthetic samples of real materials with good sensitivity and selectivity.

Solid-phase extraction of trace Au(Ⅲ) with SDG and determination by the catalytic spectrophotometric method

The new catalytic kinetic spectrophotometric method for Au（III） determination was developed and validated. It was based on the catalytic effect of gold on the oxidation of sudan red III by ammonium peroxodisulfate （（NH4）2S2O8） with nitrilo triacetic acid as an activator in microemulsion and H2SO4 medium. Under optimum conditions, there was the linearity of the calibration curve in the concentration range from 0 to 20 μg/L Au（Ⅲ） at 520 nm. The relative standard deviation was 3.0% with a correlation coefficient of 0.9986. The detection limit achieved was 9.75 × 10^-5 μg/mL. A new method using a column packed with sulfhydryl dextrose gel （SDG） as a solid-phase extractant has been developed for the preconcentration and separation of Au（Ⅲ） ions. The method has been applied to the determination of trace gold with satisfactory results.

Kinetics and Mechanism of Iridium(Ⅲ)-Catalyzed Oxidation of Ethanol Amine by Cerium(Ⅳ) in Sulfuric Acid Media

In this study, the kinetics and mechanism of the iridium（ Ⅲ ） -catalyzed oxidation of ethanol amine（EAN） by cerium（Ⅳ） in a sulfuric acid medium was investigated using titrimetric technique of redox in a temperature range of 298--313 K. It was found that the reaction is of first order with respect to Ce（ Ⅳ ） and It（ Ⅲ ）, and a positive fractional order with respect to EAN. It was also found that the pseudo-first-order （ [EAN ] 〉〉 [ Ce （ Ⅳ） ] ） rate constant koba decreases with the increase of [ H^＋ ] and [ HSO^-4 ]. Under the protection of nitrogen gas, the reaction system can initiate the polymerization of acrylonitrile, indicating the generation of free radicals. On the basis of the experimental results, a suitable mechanism was proposed. From the dependence of koba on the concentration of hydrogen sulfate, Ce（SO4）2 was found to be the kinetically active species. The rate constants of the rote-determining step together with the activation parameters were evaluated.

Cr(Ⅲ)离子印迹聚合物的制备及性能研究

以Cr(Ⅲ)为模板离子,采用表面印迹法,将氨基化多壁碳纳米管改性为乙烯化多壁碳纳米管作为固体基质,通过印迹体系的优化,制备了一系列Cr(Ⅲ)离子印迹聚合物[Cr(Ⅲ)-IIPs]及相应的非印迹聚合物[Cr(Ⅲ)-NIPs].在较优实验条件下制备的Cr(Ⅲ)-IIP1,吸附量为3.82 mmol·g^(−1),印迹因子为1.65.通过扫描电子显微镜(SEM)、氮气吸附/脱附(BET)、红外光谱(FIR)、热重分析(TG)等对Cr(Ⅲ)-IIP1及相应的Cr(Ⅲ)-NIP1,进行结构表征和性能评价.研究结果表明,Cr(Ⅲ)-IIP1属于热稳定性良好的吸附材料,吸附行为符合准二级动力学模型和Freundlich等温吸附模型,以化学吸附和多分子层吸附为主;在“竞争离子”Co(Ⅱ)、Ni(Ⅱ)和Pb(Ⅱ)共存条件下,对Cr(Ⅲ)离子具有较强的吸附能力和良好的选择性.说明在较优实验条件下制备的Cr(Ⅲ)-IIP1,有望作为一种新型的Cr(Ⅲ)离子吸附材料,去除和回收废水中的Cr(Ⅲ)离子.

聚合物改性膨润土对钢渣渗滤液及其Cr(Ⅲ)离子的阻隔与吸附特性研究

【目的】针对传统膨润土防渗衬垫在侵蚀性环境中防渗性能会大幅劣化的难题,自主研发了一种聚合物改性膨润土。【方法】通过渗透实验研究了聚合物改性膨润土对高盐溶液、强碱溶液和实际钢渣渗滤液的渗透系数,并采用Batch吸附实验探究了吸附时间、溶液pH值和溶液浓度对聚合物改性膨润土吸附钢渣渗滤液中Cr(Ⅲ)离子的影响。【结果】实验结果表明:未改性的钠化钙基膨润土对侵蚀性溶液的刚性壁渗透系数高达1×10^(-8)m/s,而聚合物改性膨润土对高盐、强碱和钢渣渗滤液的柔性壁渗透系数均小于1×10^(-11)m/s,且刚性壁渗透系数约为3×10^(-11)m/s,在高盐、强碱等侵蚀性环境中表现出更优越的防渗性能。【结论】聚合物改性膨润土对Cr(Ⅲ)的吸附量随着吸附时间、溶液pH值和溶液浓度的增加而增加。钠化钙基膨润土和聚合物改性膨润土对Cr(Ⅲ)吸附符合准二阶吸附动力学模型;Langmuir等温吸附模型更好地描述了钠化钙基膨润土和聚合物改性膨润土对Cr(Ⅲ)的吸附特性。

Effect of chloride ion on bacterial pre-oxidation of arsenic-containing gold concentrate

The bacterial pre-oxidation process of arsenic-containing gold concentrates and the bacterial activity under different chloride ion concentrations were studied by using a mixture of thermophilic strains TCJ domesticated in production.The experimental result shows that with different samples and leaching systems,the adaptability and Cl- tolerance of bacteria are different,and that appropriate chloride ion concentration is conductive to bacterial oxidation,while higher chloride ion concentration will inhibit the bacterial activity and affect the pre-oxidation performance.Under the present production conditions,TCJ can adapt to the changes of water quality in the source of water and its critical chloride ion tolerance value is 2.7 g/L.

Separation of indium(Ⅲ), gallium(Ⅲ), and zinc(Ⅱ) with Levextrel resin containing di(2-ethylhexyl) phosphoric acid (CL-P204): Part Ⅱ. Mechanism and kinetics of adsorbing indium(Ⅲ)

The mechanism of adsorbing indium(Ⅲ) from sulfate solutions with CL-P204Levextrel resin containing di(-2-ethylhexyl) phosphoric acid was examined by batch operation andinfrared spectra. The results showed that the P204 adsorbed on the resin behaved in the similar wayto solvent extraction except that it was as a monomer in resin adsorbing but in dimeric form insolvent extraction. Three factors including temperature, indium(Ⅲ) concentration of solution, andthe size of resin particles which influence the In^(3+)/H^+ exchange on CL-P204 Levextrel resin wereinvestigated by the modified limited batch technique in order to determine the kinetics ofIn^(3+)/H^+ exchange. It was found that the rate of ion exchange increased with the temperature andthe concentration of solution increasing and with the size of the resin particles decreasing.According to the expression developed by Boyd et al., the controlling factor of In^(3+)/H^+ exchangeon CL-P204 Levextrel resin was the diffusion through the resin particles. The effective diffusioncoefficient, activation energy, and entropy of activation in the particle-diffusion were determinedas 1.57 x 10^(-10) m^2/s, 11.9 kJ/mol, -84.1 J/(mol·K), respectively.

Electroreduction of Co(Ⅱ) and La(Ⅲ)in UreaMelt

Electroreduction of Co(Ⅱ)to metallic cohalt in urea melt is irrevsible in one step.The transfer coeffi-cient of electrode reaction of Co(Ⅱ)+2e=Co(O)and the diffusion coefficient of Co(Ⅱ)were determined.The lanthanum can be inductively codeposited with cobalt. The contents of lanthanum in cobalt-lanthanum de-posts increase with the shift of electrode potential to the negative direction and the raise of La(Ⅲ)/Co(Ⅱ)mo-lar ratio in the melt. The cyclic voltammetry,open circuit potential-time curve after potentiostatic electrolysisand electron probe analyas were used.

Adsorption of Rare Earth Ion La(Ⅲ) on Yunnan Bowl Tea Surface from Aqueous Solution

The adsorption characteristics of rare earth ion La(Ⅲ) on Yunnan bowl tea surface from aqueous solution and effects of various surfactants on the adsorption were studied. It was found that Yunnan bowl tea can adsorb strongly La(Ⅲ) and pH may affect drastically the adsorption amount of La(Ⅲ). The adsorption law of La(Ⅲ) on Yunnan bowl tea surface follows the Langmuir equation. The maximum adsorption amount of La(Ⅲ) can reach 15 mg·g (-1). A comprehensive adsorption model is suggested according to the experimental results.

Rapid Synthesis of Size-controlled Gold Nanoparticles by Complex Intramolecular Photoreduction

A rapid synthesis of size-controlled gold nanoparticles was proposed.The method is based on the sensitive intramolecular photoreduction reaction of Fe（Ⅲ）-EDTA complex in chloroacetic acid-sodium acetate buffer solution,where Fe（Ⅱ）-EDTA complex generated by photo-promotion acts as a reductant of AuCl-4 ions.Gold nanoparticles formed were stabilized by EDTA ligand or other protective agents added.As a result,well-dispersed gold nanoparticles with an average diameter range of 6.7 to 50.9 nm were obtained.According to the characterizations by the UV spectrum and TEM,the intramolecular charge transfer of the excited states of complex Fe（Ⅲ）-EDTA and the mechanism of forming gold nanoparticles were discussed in detail.

PREPARATION AND CHARACTERIZATION OF NOVEL CHITOSAN DERIVATIVES:ADSORPTION EQUILIBRIUM OF IRON(Ⅲ) ION

The adsorption of Fe(Ⅲ)ions from aqueous solution by chitosan alpha-ketoglutaric acid(KCTS)and hydroxamated chitosan alpha-ketoglutaric acid(HKCTS)was studied in a batch adsorption system.Experiments were carried out as function of pH,temperature,agitation rate and concentration of Fe(Ⅲ)ions.The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and isotherm constants were determined.The Langmuir model agrees very well with experimental data.The pseudo-first-order a...

Fe(Ⅲ)表面印迹硅胶聚合物的制备及其吸附性能研究

选用硅胶为基质材料、乙烯基膦酸为功能单体、Fe^(3+)为模板离子、乙二醇双甲基丙烯酸酯为交联剂,通过表面印迹技术制备了一种新型膦酸功能化的Fe(Ⅲ)印迹硅胶聚合物。对印迹吸附材料的吸附条件、吸附选择性和重复利用率进行了研究。通过FT-IR、SEM、EDX、TG和N_(2)吸附/脱附分析对印迹材料进行了表征,分析了印迹吸附剂对Fe^(3+)的吸附机理。结果表明:印迹吸附剂在8 min可达吸附平衡,最大吸附量达16.12 mg/g,吸附行为符合准二级动力学方程和Langmuir吸附等温式,印迹吸附剂展现出较高的选择性识别能力,与Cr^(3+)、Mn^(2+)和Zn^(2+)相比,对Fe^(3+)的选择性系数k分别为8.9、10.75和12.37。经过6次吸附-解吸试验,印迹材料吸附Fe^(3+)的能力仅下降了5.9%,证明其具有很好的可重复使用性能。

Switching Optimally Balanced Fe-N Interaction Enables Extremely Stable Energy Storage

The interaction between electrode materials and charge carriers is one of the central issues dominating underlying energy storage mechanisms.To address the notoriously significant volume changes accompanying intercalation or formation of alloy/compounds,we aim to introduce and utilize a weak,reversible Fe-N interaction during the(de)intercalation of ammonium ions(NH_(4)^(+))within iron(Ⅲ)hexacyanoferrate(FeHCF),inspired by manipulating the electrostatic adsorption between N and Fe in the early stages of ammonia synthesis(Bosch-Harber Process,Chemical Engineering)and steel nitriding processes(Metal Industry).Such strategy of switching well-balanced Fe-N interaction is confirmed in between the nitrogen of ammonium ions and highspin Fe in FeHCF,as observed by using X-ray absorption spectroscopy.The resulting material provided an extremely stable energy storage(58 mAh g^(-1) after 10000 cycles at current density of 1 A g^(-1))as well as high-rate performance(23.6 mAh g^(-1) at current density of 10 A g^(-1)).