[ Objective ] The paper was to solve the weakness of heavy postharvest diseases and non-endurable storage of ' Shatangju', to improve the preservation effect of ' Shatangju'. [ Method ] Fruits were dipped in diffe...[ Objective ] The paper was to solve the weakness of heavy postharvest diseases and non-endurable storage of ' Shatangju', to improve the preservation effect of ' Shatangju'. [ Method ] Fruits were dipped in different concentrations of procbloraz-manganesc chloride complex solutions. The postharvest weight loss rate, soluble solids content and decay rate of fruits were determined, and the safety of chemical agents was observed and evaluated. [ Result ] Prochloraz-manganese chloride complex had significant preservation effect on postharvest ' Shatangju' fruits, and the appropriate concentration was 0.15% -0.20% (effective content) ; the decay rates of fruits stored at room temperature for 15, 30, 45, 60 and 90 d were 0, 5%, 〈 10%, 〈 10% and 〈 30% ; there was no specific changes in smell and flavor of non-decayed fruits. [ Conclusion ] Prochloraz-manganese chloride complex solution had significant preservation effect on ' Shatangju' by inhibiting and reducing the growth and development of pathogenic bacteria, and the effect was much better under refrigeration condition.展开更多
[Objectives] This study was conducted to evaluate the toxicity risk of prochloraz-manganese chloride complex to environmental organisms. [Methods] The acute toxicity tests of prochloraz-manganese chloride complex on 8...[Objectives] This study was conducted to evaluate the toxicity risk of prochloraz-manganese chloride complex to environmental organisms. [Methods] The acute toxicity tests of prochloraz-manganese chloride complex on 8 common environmental organisms, such as Coturnix coturnix japonica, Apis mellifera L., Eisenia foetida, Bombyx mori, Trichogramma japonicum, Brachydanio rerio, Daphnia magna Straus and Scenedesmus obliquus were carried out. [Results] Prochloraz-manganese chloride complex to D. magna EC50(48 h): 1.11 mg a.i./L, with a 95% confidence limit of 1.00-1.26 mg a.i./L;B. rerio LC50(96 h): 2.84 mg a.i./L, with a 95 % Confidence limit of 2.43-3.48 mg a.i./L;S. obliquus ErC50(72 h): 1.88×10^-2 mg a.i./L, with a 95% confidence limit of 1.70×10^-2-2.16×10^-2 mg a.i./L;C. coturnix LD50(168 h): 1.01×10^3 mg a.i./kg body weight, with a 95% confidence limit of 7.87×10^2-1.27×10^3 mg a.i./kg body weight;T. japonicum LR50(24 h): 2.53×10^-3 mg a.i./cm^2, with a 95% confidence limit of 2.14×10^-3-2.99×10^-3 mg a.i./cm^2;B. mori LC50(96 h): 2.03×10^2 mg a.i./L, with a 95% confidence limit of 1.79×10^2-2.30×10^2 mg a.i./L;A. mellifera(peroral) LD50(48 h)>100 μg a.i./bee;A. mellifera(contact) LD50(48 h)>100 μg a.i./bee;E. foetida LC50(14 d)>1.00×10^2 mg a.i./kg dry soil. According to the Guidance for Evaluating and Calculating Degradation Kinetics in Environmental Media for Pesticide Registration, prochloraz-manganese chloride complex had low toxicity to A. mellifera, C. coturnix, B. mori and E. foetida, medium toxicity to D. magna and B. rerio, and high toxicity and low risk to S. obliquus and T. japonicum. [Conclusions] This study provides a data basis for the toxicity and environmental safety evaluation of the agent.展开更多
‘Gonggan’( Citrus reticulata) is a famous,high-quality and special citrus cultivar in the Xijiang River valley,Guangdong Province. However,it easily suffers from postharvest diseases,and thus is not tolerant to stor...‘Gonggan’( Citrus reticulata) is a famous,high-quality and special citrus cultivar in the Xijiang River valley,Guangdong Province. However,it easily suffers from postharvest diseases,and thus is not tolerant to storage. Based on the preliminary test results,prochloraz-manganese chloride complex was selected as the disinfectant,and prepared into different concentrations for carrying out preservation test by dipping fruits. The fruit weight loss,soluble solids content and decay rate were analyzed,and the application security and sensory evaluation for fruit freshness and flavor were observed. The results showed that dipping fruits with prochloraz-manganese chloride complex solution had significant preservation effect on‘Gonggan’fruits in postharvest storage; the suitable concentration was 2. 0-3. 0 g/L,and the decay rates of fruits stored at room temperature for 30,60 and 90 d were below 5%,10% and 15%,respectively. Plate inoculation test further revealed that the pathogen of‘Gonggan’was sensitive to prochloraz-manganese chloride complex,and the concentration of 1. 0 g/L was enough to produce significant antimicrobial effect. Other technical links related to postharvest preservation of‘Gonggan’with prochloraz-manganese chloride complex were discussed.展开更多
Reactions of 1,3-bis(pyridyl-4-ylthio)propan-2-one L and COCl2·6H2O under different conditions gave two new cobalt(Ⅱ)-chloride-L complexes with distinct structures. Complex [Co(L)2Cl2]·0.5CH3OH}n 1 pr...Reactions of 1,3-bis(pyridyl-4-ylthio)propan-2-one L and COCl2·6H2O under different conditions gave two new cobalt(Ⅱ)-chloride-L complexes with distinct structures. Complex [Co(L)2Cl2]·0.5CH3OH}n 1 prepared by solvothermal treatment is a 3D network, whereas complex {[Co3(L)2Cl6(DMF)4]·2CH3OH·H2O} 2 obtained in DMF-diethyl ether system is a discrete acyclic trimer. Crystal data for 1: space group lbca, a = 15.993(4), b = 18.454(5), c = 21.506(6)A, V= 6347(3) ,A^3, Z = 8, Dc = 1.462 g/cm^3,μ = 1.005 mm^-1, F(000) = 2864, C26.5H26Cl2CoN4O2.5S4, Mr = 698.58, the final R = 0.0499 and wR = 0.1024. Crystal data for 2: space group P1^-, a = 9.9177(6), b = 11.0871 (4), c = 15.5490(12) ,A, α = 83.1834(14),β = 88.910(13), γ = 71.096( 11 )°, V = 1605.8(2) A^3, Z = 1, Dc = 1.362 g/cm^3,μ= 1.194 mm^-1, F(000) = 677, C40H62Cl6Co3N8O9S4, Mr = 1316.71, the final R = 0.0666 and wR =0.1575.展开更多
The adsorption kinetics of platinum(IV) chloride complex ions on the activated carbon Norit GF40 was investigated. Experiments were carried out at different initial concentrations of Pt(IV) chloride complex ions, ...The adsorption kinetics of platinum(IV) chloride complex ions on the activated carbon Norit GF40 was investigated. Experiments were carried out at different initial concentrations of Pt(IV) chloride complex ions, temperature, rate of mixing and pH. It was found that the value of activation energy of the studied process is equal to 19.7 kJ/mol. From the ICP MS analysis it was confirmed that platinum ions (Pt(IV) and Pt(II)) are removed from the solution due to the adsorption and are further reduced to the metallic state. Such mechanism was confirmed by XPS analysis which showed that on the carbon surface three forms of platinum species, i.e. Pt(0), Pt(II) and Pt(IV), exist. The presence of platinum in the solution at different oxidation states was also confirmed spectrophotometrically by identification of their characteristic absorption bands. The metallic form of Pt present on the surface of activated carbon was observed in the form of small spherical islands with the diameter not exceeding 500 nm. Those islands consist of smaller, flake-shape particles with a thickness of about 35 nm.展开更多
Organic photoconductor, pinacyanol chloride, has been studied with infrared spectroscopy because of its thermal activation energy (Ea) and band gap (Eg = 2Ea) lying in the infrared range. Particularly, pinacyanol chlo...Organic photoconductor, pinacyanol chloride, has been studied with infrared spectroscopy because of its thermal activation energy (Ea) and band gap (Eg = 2Ea) lying in the infrared range. Particularly, pinacyanol chloride and its charge transfer (CT) complexes with chloranil, DDQ, TCNQ and TCNE as organic acceptors are studied in details. The CT complexes are having neither two absorption edges like ternary complex having one donor and two acceptors nor binary type with Lorentzian or Gaussian envelopes. The forbidden gap is direct band gap except chloranil complex due to increase in molecular distance and CT interaction. There is imperfect nesting and partial screening determining the mid-IR envelope, which is qualitatively different from the envelopes in binary systems. There is inverted parabola in some range below this envelope. It is explained how infrared absorption is related with the applications of such organic photoconductors in optoelectronic devices.展开更多
Reaction of ferrocenoyl chloride with [Et;NH] [(μ-CO)(μ-RS) Fe;=(CO);] complexes gave bridging ferrocenoyl complexes(μ-FcCO)(μ-RS)Fe;(CO);(Fc=ferrocenyl, R=Et, i-Pr, n-Bu, t-Bu, Ph).The structures of all...Reaction of ferrocenoyl chloride with [Et;NH] [(μ-CO)(μ-RS) Fe;=(CO);] complexes gave bridging ferrocenoyl complexes(μ-FcCO)(μ-RS)Fe;(CO);(Fc=ferrocenyl, R=Et, i-Pr, n-Bu, t-Bu, Ph).The structures of all new complexes were characterised by;HNMR, IR and MS.展开更多
A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemic...A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemical calculation.The calculated results are in good agreement with that obtained in the experiments.Three Cl atoms are on the same side of Ln in LnCl_3·15-C-5 and the crown ring on the other side.forming a complex molecule with coordination number 8.LnCl_3·15-C-5 is easily hygroscopic in air because of its unsaturated coordination,which differs sharply from the stable Ln(NO_3)_3·15-C-5 com- plex of coordination number 11.The HOMO and neighboring occupied MOs are composed of Cl 3p and O2p, and the LUMO and neighboring unoccupied MOs are composed of Ln orbitals.The level structure easily pro- duces Ln3d satellite in XPS caused by L→Ln charge transfer transition.Due to the coordination,the absolute values of the charge are decreased at Ln and O atoms,but increased at Cl atoms,which is in agreement with XPS results.展开更多
Acyl chloride can efficiently be converted into anhydride under solid liquid phase transfer catalysis by using bis(triphenylphosphine)cobalt dichloride or bis(triphenylphospine)palladium dichloride as the catalyst.
Terbium can form a ternary complex having a ratio of 1:1:1 with acetylacetone and EDTA. By adding cetyl pyridinium chloride into the above system, a marked enhancement of fluorescence intensity is observed and the ter...Terbium can form a ternary complex having a ratio of 1:1:1 with acetylacetone and EDTA. By adding cetyl pyridinium chloride into the above system, a marked enhancement of fluorescence intensity is observed and the ternary complex becomes more stable than before. For analytical application, the derivative spectrofluorimetric method has high sensitivity and the effect of foreign ions is very low. The optimum conditions were obtained. The calibration graph is linear over 5~100μg/mL.展开更多
Hydrothermal reaction of 1,10-phenanthroline with CdCl2·2.5H2O in aqueous solution leads to the complex of [Cd(μ-Cl)2(phen)]n (phen = 1-10-phenanthroline). The crystal structure has been determined by X-ray anal...Hydrothermal reaction of 1,10-phenanthroline with CdCl2·2.5H2O in aqueous solution leads to the complex of [Cd(μ-Cl)2(phen)]n (phen = 1-10-phenanthroline). The crystal structure has been determined by X-ray analysis. It crystallizes in monoclinic with space group C2/c, a = 16.947(3), b = 10.529(2), c = 7.235(1) , β = 110.795(3)°, V = 1208.8(3) 3, Z = 4, Dc = 1.997 g.cm-3, μ= 2.22 mm-1, F(000) = 704, R = 0.0231, Rw = 0.0626 for 1194 reflections with I > 2σ (I). In the crystal structure, the [Cd(phen)]2+ units are bridged by chloride ions to form 1D chain. The 1D chains combine through π……π interactions of phen groups to form 2D infinite molecular zipper.展开更多
The waste water system generated in the process of production of cuprous chloride was studied.The existing forms of copper in the system and the influence of temperature and pH on the existing forms of copper ion were...The waste water system generated in the process of production of cuprous chloride was studied.The existing forms of copper in the system and the influence of temperature and pH on the existing forms of copper ion were analyzed and determined through calculating the coefficients of copper complex distribution.In the waste water system,the main forms of copper are CuSO4, Cu2 +,CuCl + ,CuCl, 2-and2- 3 CuCl.Temperature has little influence on the distribution coefficient of Cu(Ⅱ),but has significant influence on distribution coefficient of Cu(Ⅰ).With the increase of temperature,the distribution coefficient ofCuCl, 2-increases significantly while the distribution coefficient of2- 3 CuCl decreases.The pH has nearly no influence on the distribution coefficients of various Cu(Ⅰ)-compounds,but has sizable influence on the distribution coefficients of Cu(Ⅱ)-compounds.With the increase of pH,the distribution coefficient of CuSO4(aq)increases while the distribution coefficients of Cu 2+ and CuCl + decrease.According to these results,the anion resin of 201×7 OH-and the cation resin of 732 Na were chosen to dispose the waste water solution of cuprous chloride.Finally,97.9%copper in the waste water is recovered.展开更多
The method of synthesizing ternary solid mixed ligand complexes from 1,10-phenanthroline, 2,2’-bipyridyl is reported. The series of complexes have been characterized by elemental analysis, infrared spectra, DSC-TGA a...The method of synthesizing ternary solid mixed ligand complexes from 1,10-phenanthroline, 2,2’-bipyridyl is reported. The series of complexes have been characterized by elemental analysis, infrared spectra, DSC-TGA analyses and molar conductivity. The results agree with the general formula LnL<sub>1</sub>L<sub>2</sub>Cl<sub>3</sub>·nH<sub>2</sub>O (Ln=La,Pr,Nd,Sm, Eu; Gd, Dy, Er, Tm, L<sub>1</sub>=phen, L<sub>2</sub>=bipy, n= 1,2,3).展开更多
The formation enthalpy of complex nickel(Ⅱ) histidine(His) in water was determined by means of microcalorimetry in the temperature range of 298 15-323 15 K. The standard enthalpy of the formation of Ni(His) 2...The formation enthalpy of complex nickel(Ⅱ) histidine(His) in water was determined by means of microcalorimetry in the temperature range of 298 15-323 15 K. The standard enthalpy of the formation of Ni(His) 2+ 2(aq) was calculated. On the basis of the experimental and the calculated results, three thermodynamic parameters(the activation enthalpy, the activation entropy and the activation free energy), the rate constants, three kinetic parameters(the apparent activation energy, the pre exponential constant and the reaction order) of the formation reaction of the title complex were obtained.展开更多
A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution e...A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution enthalpies of SmCl3·6H2O(s), o-HNBA(s) and phen·H2O(s) in mixed solvent (VHCl :VDMF :VDMSO=2:2:1) were determined by calorimetry at 298.15 K. The enthalpy change of the reaction was determined to be rHmΔ θ=252.49±1.60 kJ/mol. Using the relevant data in the literature and a thermochemical recycle...展开更多
The title nickel complex I and cobalt complex II were obtained separately from the direct reaction of D-(+)-leucinol with Ni(II) chloride and L-(-)-leucinol with Co(II) acetate tetra- hydrate in anhydrous met...The title nickel complex I and cobalt complex II were obtained separately from the direct reaction of D-(+)-leucinol with Ni(II) chloride and L-(-)-leucinol with Co(II) acetate tetra- hydrate in anhydrous methanol. The crystal structures of I and II were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I: [Ni(C18H45N3O3)]Cl2, orthorhombic, P212121, a = 11.2807(9), b = 14.7115(11), c = 16.3580(13) A, V = 2714.7(4) A3, Z = 4, Pcalcd = 1.177 Mg/m3, the final R = 0.0407, and 16539 reflections observed with I 〉 2σ(/); For II: [Co(C45HI08N6015)], trigonal, R3:H, a = 23.981(3), b =23.981(3), c = 10.8925(15) A, γ = 120°, V = 5425.1(14) A3, Z = 3, Pcalcd = 1.002 Mg/m3, the final R = 0.0625 for 16556 observed reflections with I 〉 2σ(I). The complexes were then used to catalyze the Henry reaction and obtained good catalytic results. The catalytic activity of the complexes was determined by IH NMR. And research is going towards the application to other organic reactions such as cyanosilylation reaction.展开更多
A new Pd-PEPPSI complex(2) with the bromo groups on the para-positions of N-aryl moieties of NHC has been synthesized and characterized by NMR and X-ray single-crystal diffraction. Complex 2 crystallizes in monoclinic...A new Pd-PEPPSI complex(2) with the bromo groups on the para-positions of N-aryl moieties of NHC has been synthesized and characterized by NMR and X-ray single-crystal diffraction. Complex 2 crystallizes in monoclinic, space group P2_1/c with a = 11.8790(8), b = 14.3038(10), c = 15.9905(11) ?, β = 101.291(2)°, V = 2664.4(3) ?3, Z = 4, D_c = 1.722 Mg/m^3, μ = 3.913 mm^(-1), F(000) = 1352, the final R = 0.0682 and wR = 0.1914 for 15113 observed reflections(I > 2σ(I)), R(all data) = 0.0970, w R(all data) = 0.2115, completeness to theta of 25.00 is 100.0% and GOOF = 1.035. Influenced by the electron-withdrawing bromo groups, the Pd-PEPPSI complex(2) showed high catalytic activity for the Suzuki-Miyaura cross-coupling reactions of aryl chlorides and arylboronic acids with a low catalyst loading(0.05 mol%) at room temperature in air.展开更多
基金Supported by Science and Technology Project of Guangdong Province(2014A020208143)Natural Science Foundation of Guangdong Province(S2013010015195)+1 种基金Science and Technology Innovation Project of Guangdong Department of Education(2013KJCX0192)Special Fund for Introduced Talents in Colleges and Universities in Guangdong Province(2010)
文摘[ Objective ] The paper was to solve the weakness of heavy postharvest diseases and non-endurable storage of ' Shatangju', to improve the preservation effect of ' Shatangju'. [ Method ] Fruits were dipped in different concentrations of procbloraz-manganesc chloride complex solutions. The postharvest weight loss rate, soluble solids content and decay rate of fruits were determined, and the safety of chemical agents was observed and evaluated. [ Result ] Prochloraz-manganese chloride complex had significant preservation effect on postharvest ' Shatangju' fruits, and the appropriate concentration was 0.15% -0.20% (effective content) ; the decay rates of fruits stored at room temperature for 15, 30, 45, 60 and 90 d were 0, 5%, 〈 10%, 〈 10% and 〈 30% ; there was no specific changes in smell and flavor of non-decayed fruits. [ Conclusion ] Prochloraz-manganese chloride complex solution had significant preservation effect on ' Shatangju' by inhibiting and reducing the growth and development of pathogenic bacteria, and the effect was much better under refrigeration condition.
基金Supported by Hunan Scientific and Technological Innovation Planning Project(2019NK4170)Fund for Hunan Province Double First-Class Applied Discipline Plant Protection。
文摘[Objectives] This study was conducted to evaluate the toxicity risk of prochloraz-manganese chloride complex to environmental organisms. [Methods] The acute toxicity tests of prochloraz-manganese chloride complex on 8 common environmental organisms, such as Coturnix coturnix japonica, Apis mellifera L., Eisenia foetida, Bombyx mori, Trichogramma japonicum, Brachydanio rerio, Daphnia magna Straus and Scenedesmus obliquus were carried out. [Results] Prochloraz-manganese chloride complex to D. magna EC50(48 h): 1.11 mg a.i./L, with a 95% confidence limit of 1.00-1.26 mg a.i./L;B. rerio LC50(96 h): 2.84 mg a.i./L, with a 95 % Confidence limit of 2.43-3.48 mg a.i./L;S. obliquus ErC50(72 h): 1.88×10^-2 mg a.i./L, with a 95% confidence limit of 1.70×10^-2-2.16×10^-2 mg a.i./L;C. coturnix LD50(168 h): 1.01×10^3 mg a.i./kg body weight, with a 95% confidence limit of 7.87×10^2-1.27×10^3 mg a.i./kg body weight;T. japonicum LR50(24 h): 2.53×10^-3 mg a.i./cm^2, with a 95% confidence limit of 2.14×10^-3-2.99×10^-3 mg a.i./cm^2;B. mori LC50(96 h): 2.03×10^2 mg a.i./L, with a 95% confidence limit of 1.79×10^2-2.30×10^2 mg a.i./L;A. mellifera(peroral) LD50(48 h)>100 μg a.i./bee;A. mellifera(contact) LD50(48 h)>100 μg a.i./bee;E. foetida LC50(14 d)>1.00×10^2 mg a.i./kg dry soil. According to the Guidance for Evaluating and Calculating Degradation Kinetics in Environmental Media for Pesticide Registration, prochloraz-manganese chloride complex had low toxicity to A. mellifera, C. coturnix, B. mori and E. foetida, medium toxicity to D. magna and B. rerio, and high toxicity and low risk to S. obliquus and T. japonicum. [Conclusions] This study provides a data basis for the toxicity and environmental safety evaluation of the agent.
基金Supported by Science and Technology Project of Guangdong Province(2014A020208143)Natural Science Foundation of Guangdong Province(S2013010015195)+1 种基金Science and Technology Innovation Project of Guangdong Department of Education(2013KJCX0192)Special Fund for the Introduction of Talents in Colleges and Universities of Guangdong Province(2010)
文摘‘Gonggan’( Citrus reticulata) is a famous,high-quality and special citrus cultivar in the Xijiang River valley,Guangdong Province. However,it easily suffers from postharvest diseases,and thus is not tolerant to storage. Based on the preliminary test results,prochloraz-manganese chloride complex was selected as the disinfectant,and prepared into different concentrations for carrying out preservation test by dipping fruits. The fruit weight loss,soluble solids content and decay rate were analyzed,and the application security and sensory evaluation for fruit freshness and flavor were observed. The results showed that dipping fruits with prochloraz-manganese chloride complex solution had significant preservation effect on‘Gonggan’fruits in postharvest storage; the suitable concentration was 2. 0-3. 0 g/L,and the decay rates of fruits stored at room temperature for 30,60 and 90 d were below 5%,10% and 15%,respectively. Plate inoculation test further revealed that the pathogen of‘Gonggan’was sensitive to prochloraz-manganese chloride complex,and the concentration of 1. 0 g/L was enough to produce significant antimicrobial effect. Other technical links related to postharvest preservation of‘Gonggan’with prochloraz-manganese chloride complex were discussed.
基金This work was financially support by NNSFC (No. 20231020), NSF of Fujian Province and the Key Project from CAS
文摘Reactions of 1,3-bis(pyridyl-4-ylthio)propan-2-one L and COCl2·6H2O under different conditions gave two new cobalt(Ⅱ)-chloride-L complexes with distinct structures. Complex [Co(L)2Cl2]·0.5CH3OH}n 1 prepared by solvothermal treatment is a 3D network, whereas complex {[Co3(L)2Cl6(DMF)4]·2CH3OH·H2O} 2 obtained in DMF-diethyl ether system is a discrete acyclic trimer. Crystal data for 1: space group lbca, a = 15.993(4), b = 18.454(5), c = 21.506(6)A, V= 6347(3) ,A^3, Z = 8, Dc = 1.462 g/cm^3,μ = 1.005 mm^-1, F(000) = 2864, C26.5H26Cl2CoN4O2.5S4, Mr = 698.58, the final R = 0.0499 and wR = 0.1024. Crystal data for 2: space group P1^-, a = 9.9177(6), b = 11.0871 (4), c = 15.5490(12) ,A, α = 83.1834(14),β = 88.910(13), γ = 71.096( 11 )°, V = 1605.8(2) A^3, Z = 1, Dc = 1.362 g/cm^3,μ= 1.194 mm^-1, F(000) = 677, C40H62Cl6Co3N8O9S4, Mr = 1316.71, the final R = 0.0666 and wR =0.1575.
基金supported by the European Grant No. POIG.01.01.02.-00-015/09-00
文摘The adsorption kinetics of platinum(IV) chloride complex ions on the activated carbon Norit GF40 was investigated. Experiments were carried out at different initial concentrations of Pt(IV) chloride complex ions, temperature, rate of mixing and pH. It was found that the value of activation energy of the studied process is equal to 19.7 kJ/mol. From the ICP MS analysis it was confirmed that platinum ions (Pt(IV) and Pt(II)) are removed from the solution due to the adsorption and are further reduced to the metallic state. Such mechanism was confirmed by XPS analysis which showed that on the carbon surface three forms of platinum species, i.e. Pt(0), Pt(II) and Pt(IV), exist. The presence of platinum in the solution at different oxidation states was also confirmed spectrophotometrically by identification of their characteristic absorption bands. The metallic form of Pt present on the surface of activated carbon was observed in the form of small spherical islands with the diameter not exceeding 500 nm. Those islands consist of smaller, flake-shape particles with a thickness of about 35 nm.
文摘Organic photoconductor, pinacyanol chloride, has been studied with infrared spectroscopy because of its thermal activation energy (Ea) and band gap (Eg = 2Ea) lying in the infrared range. Particularly, pinacyanol chloride and its charge transfer (CT) complexes with chloranil, DDQ, TCNQ and TCNE as organic acceptors are studied in details. The CT complexes are having neither two absorption edges like ternary complex having one donor and two acceptors nor binary type with Lorentzian or Gaussian envelopes. The forbidden gap is direct band gap except chloranil complex due to increase in molecular distance and CT interaction. There is imperfect nesting and partial screening determining the mid-IR envelope, which is qualitatively different from the envelopes in binary systems. There is inverted parabola in some range below this envelope. It is explained how infrared absorption is related with the applications of such organic photoconductors in optoelectronic devices.
基金The project was supported by Youth Science Foundation of Shandong University
文摘Reaction of ferrocenoyl chloride with [Et;NH] [(μ-CO)(μ-RS) Fe;=(CO);] complexes gave bridging ferrocenoyl complexes(μ-FcCO)(μ-RS)Fe;(CO);(Fc=ferrocenyl, R=Et, i-Pr, n-Bu, t-Bu, Ph).The structures of all new complexes were characterised by;HNMR, IR and MS.
文摘A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemical calculation.The calculated results are in good agreement with that obtained in the experiments.Three Cl atoms are on the same side of Ln in LnCl_3·15-C-5 and the crown ring on the other side.forming a complex molecule with coordination number 8.LnCl_3·15-C-5 is easily hygroscopic in air because of its unsaturated coordination,which differs sharply from the stable Ln(NO_3)_3·15-C-5 com- plex of coordination number 11.The HOMO and neighboring occupied MOs are composed of Cl 3p and O2p, and the LUMO and neighboring unoccupied MOs are composed of Ln orbitals.The level structure easily pro- duces Ln3d satellite in XPS caused by L→Ln charge transfer transition.Due to the coordination,the absolute values of the charge are decreased at Ln and O atoms,but increased at Cl atoms,which is in agreement with XPS results.
文摘Acyl chloride can efficiently be converted into anhydride under solid liquid phase transfer catalysis by using bis(triphenylphosphine)cobalt dichloride or bis(triphenylphospine)palladium dichloride as the catalyst.
基金Project supported by the National Natural Science Foundation of China
文摘Terbium can form a ternary complex having a ratio of 1:1:1 with acetylacetone and EDTA. By adding cetyl pyridinium chloride into the above system, a marked enhancement of fluorescence intensity is observed and the ternary complex becomes more stable than before. For analytical application, the derivative spectrofluorimetric method has high sensitivity and the effect of foreign ions is very low. The optimum conditions were obtained. The calibration graph is linear over 5~100μg/mL.
文摘Hydrothermal reaction of 1,10-phenanthroline with CdCl2·2.5H2O in aqueous solution leads to the complex of [Cd(μ-Cl)2(phen)]n (phen = 1-10-phenanthroline). The crystal structure has been determined by X-ray analysis. It crystallizes in monoclinic with space group C2/c, a = 16.947(3), b = 10.529(2), c = 7.235(1) , β = 110.795(3)°, V = 1208.8(3) 3, Z = 4, Dc = 1.997 g.cm-3, μ= 2.22 mm-1, F(000) = 704, R = 0.0231, Rw = 0.0626 for 1194 reflections with I > 2σ (I). In the crystal structure, the [Cd(phen)]2+ units are bridged by chloride ions to form 1D chain. The 1D chains combine through π……π interactions of phen groups to form 2D infinite molecular zipper.
基金Projects(5087408750978212)supported by the National Natural Science Foundation of China+1 种基金Project(2006E106)supported by Natural Science Foundation of Shaanxi Province,ChinaProject(07JK302)supported by Special Natural Science Foundation of Shaanxi Province Education Office,China
文摘The waste water system generated in the process of production of cuprous chloride was studied.The existing forms of copper in the system and the influence of temperature and pH on the existing forms of copper ion were analyzed and determined through calculating the coefficients of copper complex distribution.In the waste water system,the main forms of copper are CuSO4, Cu2 +,CuCl + ,CuCl, 2-and2- 3 CuCl.Temperature has little influence on the distribution coefficient of Cu(Ⅱ),but has significant influence on distribution coefficient of Cu(Ⅰ).With the increase of temperature,the distribution coefficient ofCuCl, 2-increases significantly while the distribution coefficient of2- 3 CuCl decreases.The pH has nearly no influence on the distribution coefficients of various Cu(Ⅰ)-compounds,but has sizable influence on the distribution coefficients of Cu(Ⅱ)-compounds.With the increase of pH,the distribution coefficient of CuSO4(aq)increases while the distribution coefficients of Cu 2+ and CuCl + decrease.According to these results,the anion resin of 201×7 OH-and the cation resin of 732 Na were chosen to dispose the waste water solution of cuprous chloride.Finally,97.9%copper in the waste water is recovered.
文摘The method of synthesizing ternary solid mixed ligand complexes from 1,10-phenanthroline, 2,2’-bipyridyl is reported. The series of complexes have been characterized by elemental analysis, infrared spectra, DSC-TGA analyses and molar conductivity. The results agree with the general formula LnL<sub>1</sub>L<sub>2</sub>Cl<sub>3</sub>·nH<sub>2</sub>O (Ln=La,Pr,Nd,Sm, Eu; Gd, Dy, Er, Tm, L<sub>1</sub>=phen, L<sub>2</sub>=bipy, n= 1,2,3).
基金Supported by the National Natural Science Foundation of China(No.2 0 170 36 )
文摘The formation enthalpy of complex nickel(Ⅱ) histidine(His) in water was determined by means of microcalorimetry in the temperature range of 298 15-323 15 K. The standard enthalpy of the formation of Ni(His) 2+ 2(aq) was calculated. On the basis of the experimental and the calculated results, three thermodynamic parameters(the activation enthalpy, the activation entropy and the activation free energy), the rate constants, three kinetic parameters(the apparent activation energy, the pre exponential constant and the reaction order) of the formation reaction of the title complex were obtained.
基金supported by the National Natural Sciences Foundation of China (20773034)the Natural Science Foundation of Hebei Province (B2007000237)
文摘A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution enthalpies of SmCl3·6H2O(s), o-HNBA(s) and phen·H2O(s) in mixed solvent (VHCl :VDMF :VDMSO=2:2:1) were determined by calorimetry at 298.15 K. The enthalpy change of the reaction was determined to be rHmΔ θ=252.49±1.60 kJ/mol. Using the relevant data in the literature and a thermochemical recycle...
文摘The title nickel complex I and cobalt complex II were obtained separately from the direct reaction of D-(+)-leucinol with Ni(II) chloride and L-(-)-leucinol with Co(II) acetate tetra- hydrate in anhydrous methanol. The crystal structures of I and II were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I: [Ni(C18H45N3O3)]Cl2, orthorhombic, P212121, a = 11.2807(9), b = 14.7115(11), c = 16.3580(13) A, V = 2714.7(4) A3, Z = 4, Pcalcd = 1.177 Mg/m3, the final R = 0.0407, and 16539 reflections observed with I 〉 2σ(/); For II: [Co(C45HI08N6015)], trigonal, R3:H, a = 23.981(3), b =23.981(3), c = 10.8925(15) A, γ = 120°, V = 5425.1(14) A3, Z = 3, Pcalcd = 1.002 Mg/m3, the final R = 0.0625 for 16556 observed reflections with I 〉 2σ(I). The complexes were then used to catalyze the Henry reaction and obtained good catalytic results. The catalytic activity of the complexes was determined by IH NMR. And research is going towards the application to other organic reactions such as cyanosilylation reaction.
基金Supported by the Natural Science Foundation of Tianjin(No.16JCYBJC19700)the National Natural Science Foundation of China(No.21771138)the Foundation of Development Program of Future Expert in Tianjin Normal University(No.WLQR201704)
文摘A new Pd-PEPPSI complex(2) with the bromo groups on the para-positions of N-aryl moieties of NHC has been synthesized and characterized by NMR and X-ray single-crystal diffraction. Complex 2 crystallizes in monoclinic, space group P2_1/c with a = 11.8790(8), b = 14.3038(10), c = 15.9905(11) ?, β = 101.291(2)°, V = 2664.4(3) ?3, Z = 4, D_c = 1.722 Mg/m^3, μ = 3.913 mm^(-1), F(000) = 1352, the final R = 0.0682 and wR = 0.1914 for 15113 observed reflections(I > 2σ(I)), R(all data) = 0.0970, w R(all data) = 0.2115, completeness to theta of 25.00 is 100.0% and GOOF = 1.035. Influenced by the electron-withdrawing bromo groups, the Pd-PEPPSI complex(2) showed high catalytic activity for the Suzuki-Miyaura cross-coupling reactions of aryl chlorides and arylboronic acids with a low catalyst loading(0.05 mol%) at room temperature in air.