MODIFICATION OF TRANSITION METAL CATIONS TO POLYMER-STABILIZED PLATINUM COLLOIDAL CLUSTERS IN ENANTIOSELECTIVE HYDROGENATION OF METHYL PYRUVATE

Modification of transition metal cations to polymer-stabilized Pt colloidal clusters modified with cinchonidine was studied in enantioselective hydrogenation of methyl pyruvate.Compared to the enantiomeric excess(e.e.)value(71.4%) obtained without the presence of metal cations,obvious e.e.enhancement(up to 82.5%)was resulted from the addition of Zn^(2+) but with a certain decrease in activity.The reaction parameters in the presence of Zn^(2+) were also studied.It was found that the Pt colloidal catalysts in the presence of metal cations performed very differently from that in the absence of metal cations.

Alkali metal cation effects on electrocatalytic CO_(2)reduction with iron porphyrins

The electrocatalytic CO_(2)reduction reaction(CO_(2)RR)has attracted increasing attention in recentyears.Practical electrocatalysis of CO_(2)RR must be carried out in aqueous solutions containing electrolytesof alkali metal cations such as sodium and potassium.Although considerable efforts havebeen made to design efficient electrocatalysts for CO_(2)RR and to investigate the structure–activityrelationships using molecular model complexes,only a few studies have been investigated the effectof alkali metal cations on electrocatalytic CO_(2)RR.In this study,we report the effect of alkali metalcations(Na^(+)and K^(+))on electrocatalytic CO_(2)RR with Fe porphyrins.By running CO_(2)RR electrocatalysisin dimethylformamide(DMF),we found that the addition of Na^(+)or K^(+)considerably improves thecatalytic activity of Fe chloride tetrakis(3,4,5‐trimethoxyphenyl)porphyrin(FeP).Based on thisresult,we synthesized an Fe porphyrin^(N)18C6‐FeP bearing a tethered 1‐aza‐18‐crown‐6‐ether(^(N)18C6)group at the second coordination sphere of the Fe site.We showed that with the tethered^(N)18C6 to bind Na^(+)or K^(+),^(N)18C6‐FeP is more active than FeP for electrocatalytic CO_(2)RR.This workdemonstrates the positive effect of alkali metal cations to improve CO_(2)RR electrocatalysis,which isvaluable for the rational design of new efficient catalysts.

Insight into the Effect of Metal Cations in the Electrolyte on Performance for Electrocatalytic CO_(2)Reduction Reaction

This highlight indicates that the local electrostatic interactions between metal cations and key intermediates facilitate the electrocatalytic CO_(2) reduction reaction.Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)has been considered as a promising strategy to achieve a carbon-neutral cycle and produce valuable fuels and feedstocks.

Theoretical Studies on the Interaction between Metal Cations and Cytosine, Guanine

The interaction of tetra- and hexa-coordinated compounds of cytosine(C) and guanine(G) with metal cations Ca(2+), Mg(2+), Mn(2+), Ni(2+), Cu(2+), and Zn(2+) have been calculated by using the B3LYP/6-31G method at the 6-31G(d, p) basis set, while the remaining coordination bonds are saturated by water molecules ((H(2)O)(4)). All geometries were optimized without symmetry restrictions. Comparing the interaction energies we obtained the orders of selectivity of C and G for the above metal ions as follows: (a)Cu(2+)>(a)Ni(2+)>(a)Mg(2+)>(a)Mg(2+)>(b)Cu(2+)>(a)Mn(2+)>(b)Zn(2+)> Ni(2+) and (a)Cu(2+)>(a)Ni(2+> a)Zn(2+)>(a)Mg(2+)>(b)Cu(2+)>(a)Mn(2+)>(b)Zn(2+)>(b)Ni(2+) respectively ((a,b) represent tetra- and hexa-coordinated, respectively), which are in good agreement with the experimental facts. Interaction energies of complexes provide a comparatively reliable quantification of the selectivity of dimethyl phosphate anion for the studied metal ions. In addition, the influence of coordination number and coordination structure on the interaction energy and the variation of ionic energy were discussed sufficiently. After analyzing the interaction energies of two kinds of complexes, the 'mutual selectivity'as well as the nature of the interaction between metal ions and ligands was revealed.

ADSORPTION MECHANISM OF SOME BIVALENT HEAVY METAL CATIONS IN SOLUTIONS USING MONTMORILLONITE

The frontier orbital energies of montmorillonite molecule and[Me(H_(2)O)_(6)]^(2+)(Me=Cu^(2+),Zn^(2+),Co^(2+)and Ni^(2+))were calculated by INDO method.Results showed that the chemical interaction between montmorillonite molecule and[Cu(H_(2)O)_(6)]^(2+)or[Zn(H_(2)O)_(6)]^(2+)was possible.The experimental results of powder X-ray diffraction and isothermal adsorption supported the above-mentioned calculation results.

Third-Order Nonlinear Optical Responses of Bis(15-crown-5)-stilbenes Binding to One-or Two-Alkali Metal Cation(Li^(+),Na^(+)and K^(+))

Bis(15-crown-5)-stilbenes containing crown ether parts have been widely used in a variety of chemical applications,such as cation detectors,because of their ability to selectively bind to alkali metal cations,Bis(15-crown-5)-stilbenes and its derivatives with complexation of one-or two-alkali metal cation(Li^(+),Na^(+)and K^(+))have been theoretically investigat-ed by quantum chemistry methods.The coordination of alkali cations results in partial shrinkage of crown ethers,which directly affected natural distribution analysis charges and molecular orbital energy levels.The number of alkali metal ions has significant effects on absorption spectra and mean second hyperpolarizability.When one alkali metal ion was added to the anticonformer of bis(15-crown-5)-stilbene,the absorption spectra were obvious-ly redshifted and the mean second hyperpolarizability values were slightly increased;while two alkali metal ions were added to bis(15-crown-5)-stilbene,the absorption spectra were ob-viously blue shifted and the mean second hyperpolarizability values decreased.On the other hand,as the radius of the alkali ions increased,the mean second hyperpolarizability values of the compounds increased gradually.It is indicated that the mean second hyperpolarizability value is sensitive to the number and radius of the alkali metal cations,thus the third order nonlinear optical response can be used as a signal to detect the number and type of alkali met-al ions.

Metal cation exchanged silica gel for identification of cationic and nonionic surfactants with preliminary separation by thin layer chromatography

Silica gel impregnated with 1% aqueous solutions of different metal cations （Li^＋, Mg^2＋, Zn^2＋, Cu^2＋, Co^2＋, Ni^2＋, Ba^2＋and Th^4＋） has been used for the analysis of nonionic and cationic surfaetants using simple aqueous acetone as mobile phase system. Co^2＋ was found the most suitable impregnant for the mutual separation of nonionic surfactants （Brij-35 and Brij-57） and cationic from nonionic surfactants （tetmdecyltrimethylammonium bromide and Cween-20）. Zinc sulphate impregnation （Zn^2＋-silica gel） shows identical chromatographic behavior and these layers are useful to separate nonionic surfactant （Brij-35） from cationic surfaetant （cetylpyridinium chloride）. The mutual separation of B J-35 and B J-57 is not influenced by the presence of optical brightener in the sample.

Alkali metal cation doping of metal-organic framework for enhancing carbon dioxide adsorption capacity

Metal-organic frameworks （MOFs） have attracted much attention as adsorbents for the separation of CO2 from flue gas or natural gas. Here, a typical metal-organic framework HKUST-I（also named Cu-BTC or MOF-199） was chemically reduced by doping it with alkali metals （Li, Na and K） and they were further used to investigate their CO2 adsorption capacities. The structural information, surface chemistry and thermal behavior of the prepared adsorbent samples were characterized by X-ray powder diffraction （XRD）, thermo-gravimetric analysis （TGA） and nitrogen adsorption-desorption isotherm analysis. The results showed that the CO2 storage capacity of HKUST-1 doped with moderate quantities of Li＋, Na＋ and K＋, individually, was greater than that of unmodified HKUST-1. The highest CO2 adsorption uptake of 8.64 mmol/g was obtained with 1K-HKUST-1, and it was ca. 11% increase in adsorption capacity at 298 K and 18 bar as compared with HKUST- 1. Moreover, adsorption tests showed that HKUST-1 and 1K-HKUST-1 displayed much higher adsorption capacities of CO2 than those of N2. Finally, the adsorption/desorption cycle experiment revealed that the adsorption performance of 1K-HKUST-1 was fairly stable, without obvious deterioration in the adsorption capacity of CO2 after 10 cycles.

Effects of metal cations on sorption-desorption of p-nitrophenol onto wheat ash

The mutual effects of metal cations （Cu2＋, Pb2＋, Zn2＋, and Cd2＋） and p-nitrophenol （NP） on their adsorption desorption behavior onto wheat ash were studied. Results suggested that Cu2＋, Pb2＋, and Zn2＋ diminished the adsorption and increased the desorption of NP remarkably, while Cd2＋ had no such effect. In contrast, NP diminished the adsorption of Cu2＋, Pb2＋, and Zn2＋ onto ash, however, this suppression effect depended on the initial concentrations of metal cations. NP had no effect on Cd〉 adsorption on ash. Fourier transform infrared （FT-IR） and X-ray absorption spectroscopic （XAS） studies suggested the following mechanisms responsible for the metal suppression effect on NP adsorption： （1） large hydrated Cu2＋, Pb2＋, and Zn〉 shells occupied the surface of ash and prevent nonspecific adsorption of NP onto ash surface; （2） Cu2＋, Pb2＋, and Zn2＋ may block the micropores of ash, resulting in decreased adsorption of NP; （3） cornplexation of Cu2＋, Pb2＋, and Zn2＋ was likely via carboxyl, hydroxylic and phenolic groups of wheat ash and these same groups may also react with NP during adsorption. As a ＂soft acid＂, Cd2＋ is less efficient in the complexation of oxygencontaining acid groups than Cu2＋, Pb2＋, and Zn2＋. Thus, Cd2＋ had no effect on the adsorption of NP on wheat ash.

Effect of Metal Cations on Corrosion Behavior and Surface Structure of Carbon Steel in Chloride Ion Atmosphere

In order to better understand why the corrosion behavior of carbon steel exposed in Nansha atmospheric environment is very serious, the effect of sodium, potassium and magnesium chlorides deposited on carbon steel surface has been studied under atmosphere conditions by wet/dry accelerated test. The difference of corrosion behavior and surface structure in Na+, K+, and Mg2+ containing atmosphere has been investigated by thickness loss, scanning electron microscope, X-ray diffraction and electrochemical techniques. The results indicate that the thickness loss of carbon steel exposed in different metal cations containing atmospheric environment increases in the order of Na+, K+, Mg2+. The hard metal cation can promote the dissolution of the steel to a certain extent. In Mg2+ containing atmosphere, the relative content of β-FeOOH is rather higher and the protective ability index α */γ * decreases in the order of Na+, K+, Mg2+. The corrosion current density of both bare carbon steel and the rusted carbon steel increases in the order of Na+, K+, Mg2+. The polarization resistance and the charge transfer resistance decreases in the order of Na+, K+, Mg2+.

Influence of Metal Cations and Cholesterol on Lipid-amphotericin Membrane

Amphotericin B（AmB） has been widely used in antifungal therapy. AraB molecules combine with cholesterol to form pores that can be toxic to human cells, thus greatly limiting its clinical application. The interaction between Arab and the cell membrane may be influenced by potassimn, sodium and calcium ions. Lq this study, the bilayer in large unilamellar lipid-drug liposomes with or without cholesterol was employed as a model membrane. N-（7-Nitrobenz-2-oxa-1,3-diazol-4-yl）-1,2-dipalmitoyl-sn-glycero-3-phosphoetheanolamine（N-BD-PE） and 1-palmi-toyl-2-[6（7-nitrobenz-2-oxa-1,3-diazol-4-yl）aminodoclecanoyl]-sn-glysero-3-phosphocholine（6-NBD-PC） are two kinds of fluorescent lipid probes, and the NBD group is attached to the polar lipid headgroup in the former, but to the sn-2 fatty acyl chain in the latter. The effect of these metal cations on the lipid-drug membrane was monitored by red edge excitation shift（REES）, fluorescence polarization, and the fluorescence lifetime of lipid probes in hydrophilic and hydrophobic areas of the membrane. These ions have different effects on the lipid-AraB membrane. Cholesterol can strengthen the packing ability of the membrane, which is influenced differently by potassium, sodium and calcium ions. Moreover, the influence of these ions on the membrane may be relative to the method of ion transportation through the membrane. This study is significant to understand the reduction of AraB＇s cellular toxicity.

Study of the Complexation Behavior of Calixarene with Transition Metal Cations by UV-vis and Fluorescent Spectra

A new fluorescent compound based on calixarene skeleton was synthesized. Its complexation ability with transition metal ions, such as Fe 3+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ and Ag +, was investigated by UV vis and fluorescent spectra.

THE STIMULATORY EFFECT OF HEAVY METAL CATIONS ON PROLIFERATION OF AORTIC SMOOTH MUSCLE CELLS

Heavy metal cations Cd^(2+), Pb^(2+), and Hg^(2+)were added to substitute for Ca^(2+)in culture media to study their effect on the relationship between CaM and the proliferation of cultured rabbit aortic smooth muscle cells (ASMC). It was found that all the heavy metal cations studied stimulated the proliferation of ASMC in varying degrees, increased the CaM content in cells at late G_1 stage and decreased the activity of cAMP PDE. These results suggest that the adverse effect of heavy metals may be related to the pathogenesis of atherosclerosis and hypertensive disease.

Monitoring the binding of metal cations and histones to DNA in real time using fluorescence assays

The binding of cations (Na +,K +,Mg 2+,Ca 2+,Mn 2+) and histones to DNA can be studied using fluorescence assays.Here,we measured the fluorescence intensity and fluorescence anisotropy of DNA and DNA-histone complexes in the presence of cations.We demonstrate that when different cations are added into a DNA solution,the fluorescence intensities of the stained DNA are reduced by different amounts.Compared with divalent cations,monovalent cations had a weaker effect on fluorescence intensity and fluorescence anisotropy.Divalent (Mn 2+,Mg 2+,Ca 2+) cations markedly enhanced the fluorescence anisotropy of DNA.The binding modes of monovalent and divalent cations to DNA may be different.Divalent cations can change the structure of DNA molecules,or promote the assembly of DNA strands.The addition of histones causes DNA condensation,which mostly occurs during the first few seconds.Cation binding to DNA is abrupt,and is much faster than that of histones.

Infrared Spectroscopy of CO2 Transformation by Group Ⅲ Metal Monoxide Cations

Infrared photodissociation spectroscopy of mass-selected[MO(CO2)n]^+(M=Sc,Y,La)complexes indicates that the conversion from the solvated structure into carbonate one can be achieved by the ScO^+ cation at n=5 and by the YO^+ cation at n=4,while only the solvated structures are observed for the LaO^+ cation.These findings suggest that both the ScO^+ and YO^+cations are able to fix CO2 into carbonate.Quantum chemical calculations are performed on[MO(CO2)n]^+ to identify the structures of the low-lying isomers and to assign the observed spectral features.Theoretical analyses show that the[YO(CO2)n]^+ complex has the smallest barrier for the conversion from the solvated structure into carbonate one,while[LaO(CO2)n]^+ exhibits the largest conversion barrier among the three metal oxide cations.The present system affords a model in clarifying the effect of different metals in catalytic CO2 transformation at the molecular level.

EFEECT OF METALLIC CATIONS ON Si-O BONDS IN SILICATES

The effect of metallic cations on the Si-O(br) bond and the Si-O(ter) bond was studied with CNDO/2 MO calculations. The characteristics of them were discussed, which were found to vary with the bonding and coordi nation situation of oxygen as well as the effect of metallic cations on oxygen. The conclusions obtained may be well used in the fields of mineralogy, geochemistry, silicate materials, pyrometallurgy and so on.

Metal cation sensing material based on the assembly of meso-terakis(4-N,N,N-trimethylamiophenyl) porphyrin and mesoporous molecular sieve MCM-41

The metal cation sensing material was prepared by entrapment of a water-soluble porphyrin compound, meso- terakis(4-N,N,N-trimethylamiophenyl) porphyrin (TTMAPP), in mesoporous molecular sieve MCM-41. The powder X-ray diffraction (XRD) spectra results demonstrated that after the introduction of TTMAPP, the ordered channel arrangement of MCM-41 remained. The assembly material, TTMAPP/ MCM-41, exhibited a typical absorption feature of porphyrin compound. Emission spectrum study revealed that the in-troduction of zinc (II) cation resulted in the formation of a new emission peak at 600 nm for TTMAPP/MCM-41, while the presence of copper (II) cation at low concentration led to that the luminescent intensity of TTMAPP/MCM-41 was obviously reduced by 68.42%. The experiment results dem-onstrated that TTMAPP/MCM-41 is a cation sensing mate-rials with good performance.

Novel Properties of Supramolecular Complexes Formed by Pairing Cationic Porphyrin and Anionic Metal-Oxo Cluster

MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the relatively stable aggregates contain equal numbers of MTBPyP4(+) and SiW12O404-.