Theoretical study on the lithium bond interaction of furan homologues C4H4Y （Y=O,S） with LiCH3 via DFT and MP2

The optimizations geometries and interaction energy corrected by BSSE of the complexes between C4H4Y （Y=O, S） and CHiLi have been calculated at the B3LYP/6-311＋＋G^＊＊ and MP2/6-311＋＋G^＊＊ levels. Three complexes were obtained. Abnormally, the calculations showed that all the C10--Li14 bond lengths increased obviously but the blue-shift of C10-Li14 stretching frequency occurred after formed complexes. The calculated binding energy with basis set super-position error （BSSE） and zero-point vibrational energy corrections of complexes I-III is -45.757, -35.700 and -39.107 kJ·mol^-1, respectively. The analyses on the combining interaction with the atom-in-molecules theory （AIM） also showed that a relatively strong lithium bond interaction presented in furan homologues C4H4Y-LiCH3 systems. Natural bond orbital theory （NBO） analysis has been performed, and the results revealed that the complex I is formed with n-σ type lithium bond interaction between C4H40 and LiCH3, complex II is formed with TT-s type lithium bond interaction between C4H4O and LiCH3, and complex III is formed with TT-s and n-s type lithium bond interactions between C4H4S and LiCH3, respectively.     

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).     

HPLC determination of ascorbic acid using luminol-Cu (II) chemiluminescence-application to the analysis of Juice beverage

The chemiluminescence (CL) of luminol-Cu (II) was applied to HPLC determination of ascorbic acid, which was separated by a C₁₈ reverse-phase column with a mobile phase of 0.25 mol/L HAc. The eluted ascorbic acid was mixed with 0.3 mmol/L luminol and 0.05 mol/L CuSO₄. The light emission from the reaction of Cu(II) oxidized ascorbic acid and luminol was detected by a modified luminometer. The detection limit was 3.6×10⁻⁶ mol/L for ascorbic acid at aS/N ratio of 3, and the linear calibration range was 2×10⁻⁴–2×10⁻³ mol/L. The relative standard deviation for 5 replicate injections of 1×10⁻³ mol/L ascorbic acid was calculated as 4.3%. The method was successfully applied to determination of ascorbic acid in juice beverage. Foundation item: National Natural Science Foundation of China (29605001) Biography: Wu Feng-wu(1963-), male, research direction: analytical chemistry.     

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.     

Investigation of Ru （ phen ）3^2＋-Hydrazine-Ce（Ⅳ） Chemiluminescence System and Its Analytical Application

0 IntroductionThbiep ycroidmipnlee)xru ctahteinoinu mof(Ⅱ r)u t(he Rniuu(mbip,y m)3ai2n +ly) atrnids- t(r2is -,(21’ -,10-phenanthroline)ruthenium(Ⅱ) (Ru(phen)32 +) ,is a kindof sensitive analytical reagent for electrogenerated chemilumi-nescence(ECL) and chemiluminescence(CL) ,on which a par-ticular review has been presented[1]. The earliest publicationon the synthesis of Ru(bipy)32 +appeared in 1936[2], andduringthefollowing30 years ,theinvestigations relatedtothissubstance were only in…     

Lithium bond structures of HnY （n=2, 3; Y=O,S, N）…LiNH2 and the abnormal blue shift of N-Li bond

The optimized geometries of the complexes between HnY （n=2, 3; Y=O, S, N） and LiNH2 have been calculated at the B3LYP/6-311＋＋G^＊＊ and MP2/6-311＋＋G^＊＊ levels. Three stable complexes were obtained. Frequency analysis showed that the enlarged 2N-4Li presents the abnormal blue shift in three complexes. The calculated binding energy with basis set super-position error （BSSE） and zero-point vibrational energy （ZPE） corrections of complex Ⅰ-Ⅲ is -58.65, -31.66 and -69.59 kJ·mol^-1 （MP2）, respectively. Natural bond orbital theory （NBO） analysis has been performed, and the results revealed that the H2O…LiNH2 （complex I） and H3N…LiNH2 （complex Ⅲ） are formed with coexisting σ-s and n-s type lithium bond interactions, complex Ⅱ is formed with ττ-s type lithium bond interaction between HnY （n=2,3; Y=O, N） and LiNH2, and H2S…LiNH2 （complex Ⅱ） is formed with n-s type lithium bond interaction between H2S and LiNH2. Natural resonance theory （NRT） and atom in molecule （AIM） theory have also been studied to investigate the bond order and topological properties of the lithium bond structures.     

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…     

Electrochemical behavior of novel bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins

Bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins, M (Por)-(H₂NR)₂ and M(Por)(HNR′₂)₂, [M=Ru and Os; Por=meso-tetrakis (p-tolyl) porphyrinato (TTP), meso-tetrakis (4-chlorophenyl) porphyrinato (4-Cl-TPP), meso-tetrakis (3, 5-dichlorophenyl) porphyrinato (3, 5-Cl-TPP) and meso—tetraphenyl porphyrinato(TPP); R=methyl, ethyl, iso-propyl and t-butyl; R′=methyl and ethyl] were synthesized by us. The electrochemical behavior of these complexes in 1, 2-dichloroethane with TBABF₄ as supporting electrolyte, has been studied by cyclic voltammetry and controlled potential electrolysis. Bis (aliphatic amine) ruthenium (II) porphyrins under go reversible one-electron oxidation and one-electron reduction processes in 1,2-dichloroethane solution. The osmium (II) analogues is shown two oxidation couples III and V, an additional small wave IV. The redox potentials of these complexes are markedly dependent on the nature of the substituent bound to the phenyl group of the porphyrin ring. It is obvious that redox potentials increases the electron-withdrawing power of the substituents increases. The couple I was found at −0.34, −0.23 and −0.15 V vs Cp₂ Fe^+/0 (Cp₂Fe=ferrocene) for Ru(TPP)(H₂NBu-t)₂, Ru(4-Cl-TPP) (H₂NBu-t)₂ and Ru(3,5-Cl-TPP)(H₂NBu-t)₂ respectively. Supported by the foundation of the Chinese Education Commission Li Zaoying: born in 1949, Associate Professor     

Electrochemical behavior of novel bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins

Bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins, M (Por)-(H₂NR)₂ and M(Por)(HNR′₂)₂, [M=Ru and Os; Por=meso-tetrakis (p-tolyl) porphyrinato (TTP), meso-tetrakis (4-chlorophenyl) porphyrinato (4-Cl-TPP), meso-tetrakis (3, 5-dichlorophenyl) porphyrinato (3, 5-Cl-TPP) and meso—tetraphenyl porphyrinato(TPP); R=methyl, ethyl, iso-propyl and t-butyl; R′=methyl and ethyl] were synthesized by us. The electrochemical behavior of these complexes in 1, 2-dichloroethane with TBABF₄ as supporting electrolyte, has been studied by cyclic voltammetry and controlled potential electrolysis. Bis (aliphatic amine) ruthenium (II) porphyrins under go reversible one-electron oxidation and one-electron reduction processes in 1,2-dichloroethane solution. The osmium (II) analogues is shown two oxidation couples III and V, an additional small wave IV. The redox potentials of these complexes are markedly dependent on the nature of the substituent bound to the phenyl group of the porphyrin ring. It is obvious that redox potentials increases the electron-withdrawing power of the substituents increases. The couple I was found at −0.34, −0.23 and −0.15 V vs Cp₂ Fe^+/0 (Cp₂Fe=ferrocene) for Ru(TPP)(H₂NBu-t)₂, Ru(4-Cl-TPP) (H₂NBu-t)₂ and Ru(3,5-Cl-TPP)(H₂NBu-t)₂ respectively. Supported by the foundation of the Chinese Education Commission Li Zaoying: born in 1949, Associate Professor     

Laser cooling using anti-stokes fluorescence in Yb3+-doped fluorozirconate glasses

The fluorozirconate glasses ZBLANP (ZrF₄−BaF₂−LaF₃−NaF−PbF₂) doped with different Yb³⁺ concentration were prepared. The Raman spectra and absorption spectra are measured to substantiate the existence of phonon-assisted emission. After analyzing the normalized absorption spectra of samples with different Yb³⁺-doped concentration, we calculated the maximum cooling effect in the 3 wt% Yb³⁺-doped sample pumped at 1 012.5 nm. The corresponding cooling capability is about −4.09 °C/W and the cooling efficiency reaches 1.76%. Foundation item: Supported by the Key Science Foundation of Wuhan (9601P0223) Biography: Xu Tian-ming (1978-), female, Master candidate, research direction: information optics and nonlinear optics.     

Corrosion resistance properties and preparation of α-C3N4 thin films

Well adhered C₃N₄ films were prepared by Plasma Enhanced Chemical Vapor Deposition (PECVD) on industrial pure iron substrates using ternary Si−N−C films as buffer layer. XRD measurement showed that the C₃N₄ films belong to the α-C₃N₄ phase. Electrochemical experiments showed that the corrosive resistance of the pure iron raised by two orders of magnitude after being covered with the α-C₃N₄ coating. Foundation item: Supported by the National Natural Science Foundation of China(19875037) Biography: ZHANG Wei(1975-), male, Graduate student. Research direction: thin film.     

Studies on the interaction of DNA and Ru (1,10-phenanthroline)2− (dipyrido[3,2−a:2′,3′−c]phenazine)2+

The interaction of Ru(phen)₂(dppz)²⁺(phen=1,10-phenanthroline,dppz=dipyrido[3,2−1:2′,3′−c]phenazine) and the calfthymus DNA were studied with fluorescence and ultraviolet visible absorption spectroscopy. The ultraviolet visible absorption spectrum of Ru(phen)₂(dppz)²⁺ calfthymus DNA, and their interaction demonstrated that Ru(phen)₂(dppz)²⁺ intercalated into the double helix of DNA via the ligand dppz. Fe(CN)₆ ⁴⁻ and NaCl can not quench the fluorescence of Ru(phen)₂(dppz)²⁺-DNA, which was in agreement with the intercalation mode. Foundation item: Supported by National Natural Science Foundation of China Biography: LING Lian-sheng (1972-), male, PhD, candidate.     

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).     

Application of an Optical Biosensor to Study the Interaction between Porphyrins and Wheat Germ Agglutinin

0Introduction Porphyrinderivativeshavebeenusedasphotosensitizersinphotodynamictherapy(PDT),anewapproachdevel opedforthetreatmentofcancer[1].Cationwater solublepor phyrinsareofconsiderableinterestowingtotheirpossiblebio medicalapplications[2].Inwhich,theinhibiteffectonthe growthmetabolismofE.coliandcancercellHL60ofmeso tetra(4N ethylacetatepyridyl)porphyrin(H2NEAE pp)and itsZn(Ⅱ)complexform(ZnNEAE pp)havebeenrecentlyin vestigated[3,4].Toenhancetumor locationandanticancerac tivitiesofdr…     

Chemiluminescence determination of tetracycline and oxytetracycline in pharmaceutical preparations using Ru (bipy)3 2+-cerium (IV) system

A new chemiluminescence (CL) method for the determination of tetracycline and oxytetracycline is developed, based on the CL reaction of tetracycline and oxytetracycline with Ru (bipy)₃ ²⁺ and Ce (IV). In sulfuric acid medium, the CL emission is generated upon continuous oxidtion of Ru(bipy)₃ ²⁺ by cerium (IV). The emission intensity is greatly enhanced when tetracycline and oxytetracycline are introduced into the reaction system after acid degradation. Under the optimum conditions, the calibration curves are linear over the range of 8.0×10⁻⁸∼4.0×10⁻⁶ mol/L for tetracycline and of 2.0×10⁻⁷∼4.0×10⁻⁵ mol/L for oxytetracycline, with the detection limits are 4.2×10⁻⁸ mol/L for tetracycline and 1.5×10⁻⁷ mol/L for oxytetracycline, respectively. The proposed method was used for the determination of tetracycline and oxytetracycline in pharmaceutical formulations with good results. Foundation item: Supported by the National Natural Science Foundation of China and the Natural Science Foundation of Hubei Province. Biography: HAH He-you (1962), male, Associate profeddor, Ph.D graduate candidate. Present address, Department of Chemistry, Huainan Teacher's College, Huainan.     

Synthesis of Novel Covalent-linked Linear Porphyrin-Thiophene Copolymers

0　IntroductionTheconstructionofmacro molecularsystemcontainingmul tipleredoxcentersorphotosensitizersisanimportantsub jectinthedesignofmolecularelectronicdevices[1 ,2 ] .Forsuchobjectives,systematizationofdonor (redoxcenter) acceptortriadmoleculesintolargemolecularsystemsisoneofthemostfeasibleapproaches,becausetheexquisiteincorporationofthephotosensi tizersandsuitableelectrondonorsand /oracceptorsintoapoly mericchainisusefulforvariousmolecularsystembasedonphoto inducedelectrontransfer[3 ,4] …     

Electrochemical determination of trace amounts of lead (II) and cadmium (II) at a calix[6]arene modified carbon paste electrode

An electrochemical method for the simultaneous determination of lead(II) and Cadmium(II) with a calix[6]arene modified carbon paste electrode (CPE) has been developed. Pb²⁺ and Cd²⁺ were accumulated at the surface of the modified electrode via formation of chemical complexes with calix[6]arene, and reduced at 1.40 V. During the following anodic potential sweep, reduced lead and cadmium were oxidized, and two well-defined striping peaks appeared at about −0.60 V and −0.84 V. Compared with a bare carbon paste electrode, the calix[6]arene modified CPE greatly improves the sensitivity of determining lead and cadmium. The stripping peak currents change linearly with the concentration of Pb²⁺ 3.0×10⁻⁸–8.0×10⁻⁶ mol·L⁻¹ and with that of Cd²⁺ 6.0×10⁻⁸–1.0×10⁻⁵ mol ·L⁻¹. The detection limits of Pb²⁺ and Cd²⁺ are found to be 8.0×10⁻⁹ mol·L⁻¹ and 2.0×10⁻⁸ mol·L⁻¹, respectively. The modified carbon paste electrode was applied to determine trace levels of lead and cadmium in water samples. Comparing with that of atomic absorption spectrometry, the results suggests that the calix[6]arene modified CPE has great potential for the practical sample analysis. Foundation item: Supported by the National Natural Science Foundation of China (60171023) Biography: JI Xiao-bo (1980-), male, Master, research direction: electroanalytical chemistry.     

Enolate chelating N-heterocyclic carbene complexes of Fe(II): Synthesis, structure and their catalytic activity for ring-opening polymerization of ε-caprolactone

The reaction of anhydrous FeBr2 with two equivalents of anionic N-heterocyclic carbene (NaL1 and NaL2), which are generated in situ by the reaction of the corresponding salt [4-R-C6H4COCH2{CH- (NCHCHNiPr)}Br] (R = OCH3, H2L1Br, 1; R = F, H2L2Br, 2) with two equivalents of NaN(SiMe3)2, affords bis-ligand Fe(II) complexes of L12Fe (3) and L22Fe (4) in high yield, respectively. Attempt to synthesize mono-ligand Fe(II) bromide by the 1:1 molar ratio of NaL to FeBr2 is unsuccessful, and the same com- plexes of 3 and 4 were obtained. Both 3 and 4 have been depicted by elemental analysis and X-ray structure determination. Preliminary studies show that both 3 and 4 can be used as single-component catalyst for the ring-opening polymerization of ε-caprolactone, and the catalytic activity of 3 is higher than that of 4.     

Sanitary Sewage Treatment with Jet Inner-loop Bioreactor

0　IntroductionThejetloopreactorhasthecharacteristicsofbothjetandloopflow .Ononehand ,theairsuckedinisdispersedintosmallgasbubblesbecauseoftheshearingforcecausedbythehighvelocityjet,producinganincreasedinterfacialcontactbe tweengasandliquid ,thusthemasstransferefficiencyisin creased .Ontheotherhand ,aregularloopflowisformedbecauseofmutualimpetusofbothjetandair lift,thusdramaticallyim provestheperformancesofmixture ,diffusion ,masstransferandheattransferofthematerial.Withoutmechanicdriving ,the…     

Coordination behavior between zinc salts and L-α-methionine

The solubility properties of ZnCl\-2/ZnAc\-2/ZnSO\-4_Met_H\-2O systems at 25℃ in the whole cocentration range have been investigated by phase equilibrium method. The results indicate that ZnAc\-2 and ZnSO\-4 systems are both simple systems, which do not exist any compound; there are 2 complexes formed in ZnCl\-2 system: Zn(Met)Cl\-2 and Zn(Met)\-2Cl\-2·2H\-2O. Under the direction of phase equilibrium result, 2 solid complexes have been prepared in water and characterized by chemical analysis, IR, X_ray diffraction. Their combustion energies have also been determined by means of a RBC_type_1 rotating_bomb calorimeter, and their standard enthalpies of formation, Δ f, coor(s)H O-, have been calculated which are (-828.32±3.00) kJ·mol -1 and (-1 117.08±6.15) kJ·mol -1, respectively.