Magnetic properties of heteropolyoxometalates

The progress of the study on the magnetic properties of heteropolyoxometalates during the late decade is reviewed. Some anions of heteropolyoxometalates containing magnetic atoms, such as [M4(H2O)4(PW9O34)2]10- and[M4(H2O)4(P2W15O56)2]16-[M = Co(Ⅱ), Zn( Ⅱ ), Cu( Ⅱ ), Mn(Ⅱ ), Ni(Ⅱ)], and [GaW9O37M3(H2O)3]n-[M = Fe(Ⅲ), Cu(Ⅱ), Co(Ⅱ)] showed ferromagnetic and antiferromagnetic properties. The combination of heteropoly anions and organic π-donor of TTF+ (te-trathiofulvalene cation) results in a variety of magnetic properties. Furthermore, there is an interaction between the inorganic and organic components. The electrocrystallization technique can prepare the organic-inorganic salts of this kind, which will become the new member of molecular magnetic materials. Heteropoly blue is a kind of the mixed-valence complexes and its reduction electrons can be delocalized over anionic framework. The further study on the magnetic properties of heteropolyoxometalates will provide important information for the design of molecular materials.     

Myoglobin as Mimetic Enzyme and Its Analytical Application in Determination of H2O2

0 IntroductionSltougdiiceasl csoynstceermnsin gharveeac btieveen o txhyeg ei nm psopretcaienst ( oRbjOecSt) iinn bbiioo--medicine and analytical chemistry in recent years[1-4]. Manyi mportant life phenomena and diseases are relatedtotheinter-mediates of ROS[5-7].ROS have beeni mplicated as ani mpor-tant causative factor in cell damage,including apoptosis andnecrosis . Their proposed actions comprise lipid peroxidation,DNAdamage,the mitochondrial respiratory chain destructionand protein mo…     

Kinetic studies of the decomposition reaction of adducts of dinuclear Fe(Ⅱ)/O2

Kinetic studies of the decomposition reaction of dinuclear Fe(Ⅱ) adducts [Fe₂(N-Et-HPTB){O₂P(OPh)₂}](Cl- O₄)₂ (1) and [Fe₂(N-Et-HPTB) {O₂P(Ph)₂}] (ClO₄)₂ (2) with O₂ have been carried out at low temperature using UV-vis spectra. The decomposition reaction of Fe(Ⅱ)/O₂ adducts was first-order in the experimental conditions, and the activation parameters were obtained. ?H^¹ = 85.62 kJ·mol^-1, ?S¹ = 19.43 J·mol^-1·K^-1 for compound (1) and ?H^¹ = 97.97 kJ·mol^-1, ?S^¹ = 55.68 J·mol^-1·K^-1 for compound (2). These results are similar to those of dioxygen adducts of other metals complexes and natural enzymes such as methane mono- oxygenase (MMOH).     

Electrocatalytic oxidation of H<Subscript>2</Subscript>O<Subscript>2</Subscript> at a carbon paste electrode modified with a nickel (II)-5, 11, 17, 23-tetra-tert-butyl-25, 27-bis(Diethylcarbamoylmethoxy) calix[4] arene complex and its application

Electrochemical behavior of a carbon paste electrode (CPE) modified with nickel(II)-5, 11, 17, 23-tetra-tert-butyl-25, 27-bis(diethylcarbamoylmethoxy) calix[4]arene (Ni (II)-L) complex and its electrocatalytic activity towards the oxidation of hydrogen peroxide were investigated by cyclic voltammetric technique in a 5.0×10⁻² mol/L NaClO₄+1.0×10⁻³ mol/L NaOH solution. It was found that Ni(II)-L acts as an effective catalyst for the oxidation of hydrogen peroxide. The modified electrode exhibited a linear response over a hydrogen peroxide concentrations in the range of 2.0×10⁻⁵−1.0×10⁻⁴ mol/L with a detection limit as low as 1.0×10⁻⁶ mol/L. The relative standard deviation was 3.5% for 5 successive determinations of H₂O₂ at 1.0×10⁻⁵ mol/L. The modified electrode was used successfully in rainwater analysis. Foundation item: Supported by the Natural Science Foundation of Hubei Province (98J040). Biography: Li Chun ya(1972-), Ph. D. candidate, research direction: electroanalysis and electrosynthesis.     

Preparation and kinetics of the thermal decomposition of nanosized CuC2O4−ZnC2O4·2H2O

The physical mixture of nanosized CuC₂O₄−ZnC₂O₄·2H₂O, as precursors of CuO−ZnO, have been prepared by the one-step solid state reaction method at room temperature. The thermal decomposition processes taking place in the solid state oxalate mixture of nanometer CuC₂O₄−ZnC₂O₄·2H₂O have been studied in static air using TG, DSC, XRD and TEM techniques. TEM showed that the grain size of the decomposition product is 5–15 nm. The values of the activation energyE _α were determined using the isoconversional procedure of KAS method and the Ozawa method. The most possible mechanism functionf(α) of the thermal decompositions of nanosized CuC₂O₄−ZnC₂O₄·2H₂O are defined using the comparative method, function models of the decomposition of CuC₂O₄ and ZnC₂O₄ follow the same mechanism function “Avrami-Erofeev equation”. The pre-exponential factorA is obtained on the basis ofE _α andf(α), thus the thermal analysis kinetic triplet of the decompositions of nanosized CuC₂O₄−ZnC₂O₄·2H₂O are determined. Foundation item: Supported by the key Natural Science Fund of Deparartment of Science and Technology of Hubei Province (2001ABA099). Biography: CHEN Donghua(1946-), male, Professor, research direction: material synthesize and thermal, analysis kinetics.     

Standard molar enthalpy of formation of morin studied by rotating-bomb combustion calorimetry

Flavonols are plant pigments that are ubiquitous in nature. Morin and other related plant flavonols have come into recent prominence because of their usefulness as anticancer, anti-tumor, anti-AIDS, and other important therapeutic activities of significant potency and low systemic toxicity. The heat of combustion of morin (molecular formula, C₁₅H₁₀O₇·H₂O) in oxygen was measured by a rotating-bomb type combustion calorimeter, the standard molar enthalpy of combustion of morin at T = 298.15 K was determined to be Δ_c H _m^⦵ (C₁₅H₁₀O₇·H₂O, s) = −(5 937.99 ± 2.99) kJ · mol⁻¹. The derived standard molar enthalpy of the formation of morin in solid powder state at T = 298.15 K, Δ_f H _m^⦵ (C₁₅H₁₀O₇·H₂O, s), was −(1 682.12 ± 3.58) kJ · mol⁻¹, which provide an accurate data of the stability of morin to the pharmacy and pharmacology. Biography: HOU Hanna(1956–), female, Visiting researcher, Associate professor of Hubei University of Education, research direction: thermochemistry.     

Degradation of 2, 4-D acid using Mn2+ as catalyst under UV irradiation

In this paper, the oxidative degradation of 2, 4-dichlorophenoxyacetic acid (2, 4-D) using Mn²⁺/H₂O₂ reagent under UV irradiation was studied. The results show that 2, 4-D was degraded more completely in Mn²⁺/H₂O₂ solution than traditional Fenton solutions. The effects of the concentration of Mn²⁺, H₂O₂ and pH were also investigated. And under the optimal condition of 1.48×10⁻⁴ mol/L, 8.99×10⁻⁵ mol/L and pH 3.38, the formation of ·OH was the most, both the decomposition rate of H₂O₂ and the degradation rate of 2, 4-D were the fastest. In addition, the photoreaction process was monitored using spin-trapping electron paramagnetic resonance (EPR), and the results indicated that the oxidative process was predominated mainly by the hydroxyl radical (·OH) gennerated in the system. Biography: HUANG Yingping (1964–), Professor, Ph. D., research direction: pollution ecology and water pollution control.     

Inorganic-organic hybrids constructed of bis（undecatungstogerma- nate）lanthanates polyoxoanions and oxalate-bridged dinuclear copper complexes and their magnetic properties

A series of inorganic-organic hybrids K₂Na _m H_9−m [{Ln(GeW₁₁O₃₉)₂}{Cu₂(bpy)₂(μ-ox)}]·nH₂O (bpy = 2,2-bipyridine and ox = oxalate; Ln = La, Nd, Sm, Eu, Gd; n = 19, 17, 22, 20, 19; m = 4, 4, 4, 9, 2) were isolated after reacting in a potassium acetate buffer. X-ray structural analyses show that compounds 1–5 are isomorphic and consist of [Ln(GeW₁₁O₃₉)₂]¹³⁻ polyoxoanion building blocks and oxalate-bridged dinuclear copper metalorganic complex with a 1D chain structure. The 1D chain further connects into the 3D framework by π-π interactions with neighboring bpy groups. The magnetic susceptibility data indicate that antiferromagnetic coupling between the neighboring Cu²⁺ ions in the structure and the rare earth ions affects magnetic property of the structure.     

Synthesis, Characterization and Calorimetry of Ni（C4H8N2O3）2Cl2

A coordination complex was synthesized from NiCl2 and dipeptide glycylglycine（GG）. It was characterized by element analysis, NMR and TG methods, and then was determined to be Ni（C4HsN2O3）2Cl2. Using an isoperibolic reaction calorimeter, the standard molar enthalpy of formation of Ni（GG）2Cl2（solid） has been determined to be -（1 674.66±2.02） kJ · mol^-1 at 298.15 K.     

Synthesis and X-ray crystal structure of a new manganese 18-metallacrown-6

0　IntroductionThemetalionsinmetallamacrocylesformedbysupramolecularself assemblycantaketrigonal,square planar,andtetrahe dralconfiguration[1 ,2 ] .Metallacrownisaspecialclassofmetalla macrocyle,theyareanalogoustocrownethersinbothstructureandfunctionexceptthatthemetalionsarenowtakingthepositionsofcoordinationatomsincrownether[3,4] .Themetallacrownswithdifferentnumberof [M—N—O]repeatunithavedifferentcavitysizes,suchas 9 MC 3[5 7] ,12 MC 4 [4,8 1 4 ] and 15 MC 5 [1 5] .Thereportedazameta…     

Mechanism of oxidative damage to DNA by Fe-loaded MCM-41 irradiated with visible light

The mechanism of oxidative damage to deoxyribonucleic acid (DNA) by iron-containing mesoporous molecular sieves (MCM-41) irradiated with visible light was elucidated. Fe-loaded MCM-41 (Fe/MCM-41) was used as a photocatalyst and the damage to calf thymus DNA caused by hydrogen peroxide (H2O2) was studied. The damage and extent of oxidation of DNA were measured by high-performance liquid chromatography (HPLC) and intermediate products were detected by HPLC/electrospray ionization tandem mass spectrometry. Electron spin resonance was used to detect changes in reactive oxygen species and peroxidase catalytic spectrophotometry was used to determine the concentration of H2O2. The results indicated that Fe/MCM-41 efficiently activated H2O2 in solution at pH 4.0-8.0 under irradiation with visible light. The photocatalytic system degraded DNA most effectively at pH 5.0-6.0 but also operated at pH 8.0. At pH 4.2, the degree of DNA damage reached 25.65% after 5 h and the kinetic constant was 5.89×10 2 min 1. Damage to DNA was predominantly caused by hydroxyl radicals generated in the system. The mechanism of DNA damage is of potential concern to human health because it can occur in neutral solutions irradiated by visible light.     

Direct electrochemistry and electrocatalysis of horseradish peroxidase in MnO2 nanosheet film

A novel material MnO2 nanosheet has been used as the support matrix for the immobilization of horseradish peroxidase （HRP）. HRP entrapped in MnO2 nanosheet film exhibits facile direct electron transfer with the electron transfer rate constant of 6.86 s^-1. The HRP/MnO2 nanosheet film gives a reversible redox couple with the apparent formal peak potential （E^0＇） of -0.315 V （vs. Ag/AgCl） in pH 6.5 phosphate buffer solution （PBS）. The formal potential E^0＇ of HRP shifts linearly with pH with a slope of -53.75 mV.pH^-1, denoting that an electron transfer accompanies single-proton transportation. The immobilized HRP shows an electrocatslytic activity to the reduction of H2O2. The response time of the biosensor for H2O2 is less than 3 s, and the detection limit is 0.21 μmol · L^-1 based on signal/noise = 3.     

Synthesis and crystal structure of new supramolecular adducts of [PtCl6]2− with cucurbit [7] uril: [(H3O)2 (PtCl6)]3 (C42H42N28O14)2·H2O

A novel supramolecular adduct [(H₃O)₂ (PtCl₆)]₃ (C₄₂H₄₂N₂₈O₁₄)₂·H₂O (1) was synthesized by mixing [PtCl₆]²⁻ and cucurbit [7] uril in solution of hydrochloric acid. The crystal structure was determined by single crystal X-ray diffraction analysis. The crystal belongs to orthorhombic system and space group F dd2 with cell dimensions:a=4. 705 33 (5) nm,b=7. 153 80 (6) nm,c=1. 894 61 (2) nm,Z=16,V=63, 7744 (11) nm³,D _c =1.534 g/cm³, μ=3. 007 mm⁻¹,F(000)=29 120,R ₁=0.070 7,wR ₂=0. 169 2. In crystal, the cucurb [7] uril molecules from two zig-zag chains. Foundation item: Supported by the National Natural Science Foundation of China (20172040) Biography: Yan kun (1977-), female, Master, research direction: macrocyclic chemistry.     

Theoretical study of N(C)―H…H―B multi-dihydrogen bonds

The optimized geometries, frequencies and interaction energy corrected with basis set superposition error (BSSE) of the multi-dihydrogen bond complexes C₄H₄NH…BH₄^–. and CH≡CH…BH₄^–. have been calculated at both the B3LYP/6-311++G** and the MP2/6-311++G** levels. The calculations were per-formed to study the nature of the N―H…H3―B and C―H…H2―B red shift multi dihydrogen bond in complex C4H4NH…BH^–₄ and CH≡CH…BH4–. The BSSE-corrected multi-dihydrogen bond interaction en-ergy of complex I (C₄H₄NH…BH₄^–.) and complexⅡ(CH≡CH…BH₄^–.) is -76.62 and -33.79 kJ/mol (MP2/6- 311++G**), respectively. From the natural bond orbital（NBO）analysis, we detailedly discussed the orbital interactions, electron density transfers, rehybridizations and the essential of the correlative bond length changes in the two complexes. In addition, solvent effect on the geometric structures, vibration frequencies and interaction energy of the monomer and complexes was studied in detail. It is relevant to the relatively dielectric constants (ε).     

Electronic properties and stabilities of methoxy-substituted Lindqvist polyoxometalates [Nb<Subscript>2</Subscript>W<Subscript>4</Subscript>O<Subscript>19</Subscript>CH<Subscript>3</Subscript>]<Superscript>3−</Superscript> by DFT

The electronic properties and stabilities of five [Nb₂W₄O₁₈OCH₃]³⁻ isomers have been investigated using a density functional theory method. The results show that the isomer with the methoxy group occupying a bridging position between two tungsten atoms (two tungsten atoms in the plane that contains two niobium atoms) in the [Nb₂W₄O₁₈OCH₃]3⁻ framework is the most stable isomer in acetonitrile. The stability of the one-electron-reduced isomers changes little. The most stable one-electron-reduced isomer has the methoxy group occupying a bridging position between niobium atoms in the [Nb₂W₄O₁₈OCH₃]⁴⁻ framework. The M-Ob (M = Nb, W; b denotes bridging) bond lengths in anions in which the metal atoms are connected by a methoxy group are longer than those in [Nb₂W₄O₁₉]⁴⁻. The highest occupied molecular orbitals (HOMO) in [Nb₂W₄O₁₉]⁴⁻ mainly delocalize over the bridging oxygen atoms of two niobium atoms and two tungsten atoms located in the equatorial plane, and the bridging oxygen atoms on the axial surface. The lowest unoccupied molecular orbitals (LUMO) of [Nb₂W₄O₁₉]⁴⁻ are mainly concentrated on the tungsten atoms and antibonding oxygen atoms. Methoxy substitution modifies the electronic properties of the [Nb₂W₄O₁₈OCH₃]³⁻ isomers. The HOMOs in the five isomers formally delocalize over the bridging oxygen atoms, which are distant from the surface containing the methoxy group and four metal atoms. The LUMOs delocalize over the d-shells of the four metal atoms that are close to the methoxy group, and the p-orbitals of oxygen. One-electron reduction occurred at the tungsten atoms, not the niobium atoms.     

Quantum chemical studies on tuning the second-order nonlinear optical molecular switching of triarylborane derivatives

In this work, density functional theory (DFT) combined with the finite field (FF) method has been adopted to analyze the second-order nonlinear optical (NLO) properties of the triarylborane (TAB) derivatives obtained by introducing different inductive electron groups into the phenylene ring of the TAB (RTAB, where R=2-C6H5-C2B10H10(1),R=F(2), R=Me(3),R=NO2(4),R=NH2(5)). The static first hyperpolarizabilities (βtot) of the RTAB molecules can be switched by binding one F- to the boron center (RTAB′) or one-electron reduction (RTAB"). The DFT-FF calculations show that the βtot values of 2′, 3′ and 5′ decrease while those of 1′ and 4′ increase compared with the values of their neutral molecules, which was attributed to the fact that the charge transfers of 2, 3 and 5 become smaller and those of 1 and 4 become larger by binding one F- ion to the boron center, according to time-domain DFT (TD-DFT) analysis. However, the incorporation of one electron enhances the second-order NLO properties of the RTAB molecules remarkably, especially for system 1. It is notable that the βtot value of reduced form 1″ is 508.69×10-30 esu, i.e. about 578 times larger than that of system 1. Frontier molecular orbital (FMO) and natural bond orbital (NBO) analyses suggest that the reversal of the charge distribution between the neutral molecules and their reduced forms leads to low HOMO-LUMO energy gaps (E0) and thus large βtot values for the reduced forms.     

Effects of anions on the biosorption of microelement cations by macroalga <Emphasis Type="Italic">Enteromorpha prolifera</Emphasis> in single- and multi-metal systems

The results of research on the effects of anions on the biosorption of microelement cations by the edible marine macroalga Enteromorpha prolifera in singleand multi-metal systems are discussed in this paper. It was shown that the maximum biosorption capacity (qmax) in a single-metal system of Co(II) ions decreased in the following sequence: Cl- (46.0 mg g-1) > SO42- (42.8 mg g-1) > NO3- (41.9 mg g-1). In multi-metal systems, in which the ratios of Cl-, NO3-, and SO42- were 0:0:4, 1:1:2, 3:0:1, and 4:0:0, there were clear differences among the biosorption capacities. In all the examined systems (other than the 0:0:4 system), inhibition of the binding of microelement cations by the macroalga was observed. In all the systems, the highest value of qmax was obtained for Cu(II) cations; the value ranged from 31.9 mg g-1 in 0:0:4 (SO42- only) to 18.2 mg g-1 in 4:0:0 (Cl-only).     

Fluorescence Determination of Artemisinin Using Hemoglobin as Catalyst and Pyronine B as Substrate

0 IntroductionMaalnadria siusb atr ompajicosr .he aAltrthe pmrisoibnlienmi (n qtihneghtraoopsiucs,QHS,Fig.1) is a sesquiterpene endoperoxide isola-ted fromArtemisia annuaL., an ancient Chineseherbal medicine usedfor treatment of fever and ma-laria.Studies of the structure and activity relation-ship have shownthat endoperoxide groupis essentialfor anti malarial activity of QHS and absence of thismoiety lead to completely loss in activity of thedrug. Many techniques have been developed to de…     

Syntheses and lyotropic liquid crystal properties of a series of sandwich-type tungstoarsenates heteropoly compounds with As/W ratio of 4/30

A series of sandwich-type tungstoarsenates heteropoly compounds with As/W ratio of 4/30, Na16[As4W30M4(H2O)2O112]·XH2O (M = Zn,Cu,Co,Ni,Mn and Cd), have been synthesized for the first time and structurally characterized by elemental analysis, IR and 183W NMR spectra. The crystal structure of Na16[As4W30Cu4(H2O)2O112]·63H2O was determined to be a triclinic system, of P1 symmetry, a = 1.2721(3) nm, b = 2.451 6(5) nm, c = 2.6450(5) nm, α= 89.90(3)°,β= 77.32(3)°, γ= 89.96(3)°, 2=2. Using tetrahepty lammonium bromide as a phase transfer reagent, [As4W30Cu4(H2O)2O112]16- was transferred from aqueous solution to organic phase (benzene), and the heteropolyanion lost the coordination water molecules to form the coordination-unsaturated ion. After lactic acid was added to the benzene solution, the coordination-saturation was recovered. By esterification reaction between lactic acid and cholesterin, the latter was attached to the heteropolyanion indirectly. Therefore, a new type of lyotropic liquid crystal was obtained, which was characterized by a polarimicroscope, DSC and variable temperature wide-angle X-ray diffraction.     

Preparation,crystal structure and quantum chemical investigation of [Li(NTO) (H2O)]

[Li(NTO)(H₂O)₂] was prepared by mixing the aqueous solution of 3-nitro-1,2,4-triazol-5-one (NTO) and lithium hydroxide. The crystal structure of [Li(NTO)(H₂O)₂] was determined by single crystal diffraction analysis. The crystal is monoclinic, space group P2₁/n with crystal parameters of a = 0.742 0(2) nm, b = 0.344 9(1) nm,c = 2.490 6(3) nm, β= 94.89(1)°, Z = 4,D _c , = 1.799 g cm⁻³,V = 0.635 nm³, μ = 1.591 cm⁻¹, F(000) = 392. The finalR is 0.051. The MNDO MO calculation shows that the coordinate bonds of title compound possess certain extent of covalent character. O₂ atom of NTO anion is bonded to Li atom; the nitro group will be lost first when NTO is decomposed.