Preservation Effect of Prochloraz-manganese Chloride Complex on Postharvest ‘Shatangju'( Citrus reticulata)Fruits

[ 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.

Evaluation of the Acute Toxicity of Prochloraz-manganese Chloride Complex to Environmental Species

[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.

Preservation Effect of Prochloraz-manganese Chloride Complex on ‘Gonggan’ (Citrus reticulata) Fruits

‘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.

Syntheses and Crystal Structures of Cobalt(II) Chloride Complexes of 1,3-Bis(pyridyl-4-ylthio)propan-2-one

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.

Spectroscopic Analysis and Study of Charge Transport Properties for Pinacyanol Chloride-Organic Acceptor Complex as Potential Optoelectronics Material

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.

ELECTRONIC STRUCTURE AND BOND CHARACTER OF COMPLEXES OF RARE EARTH CHLORIDES WITH CROWN ETHERS

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.

SOLID-LIQUID PHASE TRANSFER AND COBALT OR PALLADIUM COMPLEX CATALYZED SYNTHESIS OF ANHYDRIDES FROM ACYL CHLORIDES

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.

Synthesis and Crystal Structure of 1D Chloride Bridged Cadmium(Ⅱ) Chain

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.

Disposal of cuprous chloride waste water

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.

SYNTHESIS AND CHARACTERIZATION OF THE MIXED LIGAND COORDINATION COMPOUND FROM RARE EARTH CHLORIDE AND THE NEUTRAL LIGANDS CONTAINING NITROGEN

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 LnL1L2Cl3·nH2O （Ln=La,Pr,Nd,Sm, Eu; Gd, Dy, Er, Tm, L1=phen, L2=bipy, n= 1,2,3）.

氯化镁-氯化铝-EMImBF_(4)/有机醚可充镁电池电解液

可充镁电池(RMBs)是下一代最具潜力的储能体系之一,电解液对RMBs的性能具有重要影响.本文通过将1-乙基-3-甲基咪唑鎓四氟硼酸盐(EMImBF_(4))添加到MgCl_(2)+AlCl_(3)电解液(MACC)中,构建了一种MACC-EMImBF_(4)/有机醚(MACCE)可充镁电池电解液体系;采用循环伏安(CV)、线性扫描伏安(LSV)、电化学交流阻抗谱(EIS)和恒流充放电曲线(GCD)等方法测试了MACCE电解液的电化学性能及全电池性能;并通过场发射扫描电子显微镜(FESEM)、X射线衍射仪(XRD)和X射线光电子能谱仪(XPS)对循环后的电极表面进行了分析.结果表明,EMImBF_(4)的添加有效改善了电解液的性能,MgCl_(2)-AlCl_(3)与EMImBF_(4)的最佳摩尔比为5∶1.MACCE电解液的离子电导率为3.94 mS/cm,Mg^(2+)沉积-溶出过电位为59 mV,库仑效率达97.5%以上,氧化稳定电位可达2.8 V(vs.Mg/Mg^(2+))且循环时间超过500 h.MACCE电解液在循环过程中可在Mg负极表面形成一层纳米颗粒层,有助于改善循环稳定性.MACCE电解液与正极材料Mo6S8的兼容性好,Mo6S8|MACCE|Mg全电池的放电平均比容量可达64.4mA∙h/g(12.88mA/g,0.1C),100次循环后比容量保持率可达73.2%.

H_(2)SO_(4)/ZnCl_(2)复合活化微波法制备污泥活性炭研究

以城市剩余污泥为原料,H_(2)SO_(4)和ZnCl_(2)为复合活化剂,采用微波法制备污泥活性炭,研究微波活化温度、功率、辐照时间及固液比对污泥活性炭碘吸附值影响,并利用TG、BET、FTIR、SEM等对产物进行表征。结果表明:当固液比1∶1.5、微波功率2000 W、活化温度600℃和辐照时间20 min时,污泥活性炭碘吸附值最高约为1360 mg·g^(-1)。与干污泥相比,加活化剂干污泥的热解仍为3个阶段,但半焦生成焦炭阶段的失重有较大提高,污泥活性炭的比表面积约为331 m^(2)·g^(-1),表面可见大小不一且未被堵塞的孔洞,平均孔径约为13 nm,有相对较多的含氧官能团。

响应曲面法优化氯化物体系三价铬电沉积工艺

[目的]三价铬电沉积过程中伴随的剧烈析氢反应导致局部pH升高,是镀速急剧下降、镀层难以增厚及镀层性能恶化的主要原因。[方法]采用甲酸钠、草酸钠和尿素为氯化物体系三价铬电镀的配位剂,以在150 mA/cm^(2)电流密度下电沉积10 min的沉积速率为响应因子,采用响应曲面法优化了镀液配方,建立了氯化物体系三价铬电沉积速率的多项式模型方程。通过单因素实验研究了添加剂、pH、温度、电流密度和沉积时间对沉积速率、镀液深镀能力和镀层耐蚀性的影响。[结果]三价铬电沉积的最佳配方和工艺条件为:三氯化铬0.6 mol/L,甲酸钠0.8 mol/L,草酸钠0.2 mol/L,尿素0.3 mol/L,pH 1.8,温度30℃,电流密度150 mA/cm^(2),时间30 min。在该条件下所得Cr镀层为非晶态结构,厚度在12μm以上,耐蚀性良好。[结论]选用合适的配位剂抑制电沉积过程中铬的羟桥化反应,是维持较高镀速和改善镀层性能的有效手段。

A Thermochemical Study on Complex Nickel(Ⅱ) L-α-Histidine

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.

Thermochemical studies on complex of [Sm(o-NBA)_3phen]_2

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...

Synthesis and Catalytic Activity of Nickel(Ⅱ)and Cobalt(Ⅱ) Complexes Involving Chiral Leucinol

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.

Synthesis, Crystal Structure and Catalytic Activity of a Pd-PEPPSI Complex Bearing Bromine Group

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.

Determination of Boron Trifluoride in Boron Trifluoride Complex by Fluoride Ion Selective Electrode

A method was proposed to determine boron trifluoride in boron trifluoride complex using fluoride ion selective electrode(ISE). Hydroxide was chosen to mask aluminum for the determination of 0.01—0.1 mol/L of fluoride. The simulation indicated that the permissible aluminum masked at a certain p H value was limited and hardly related to F-concentration and boric acid. It is better to control p H value below 11.5 and the aluminum concentration within 0.025 mol/L to minimize the interference of hydroxide to the fluoride ISE. The decomposition conditions of boron trifluoride by aluminum chloride were investigated. It is found that the F-detection ratio will approach 1.0 if the Al/F molar ratio is 0.3—0.7 and aluminum concentration is no more than 0.02 mol/L when heated at 80 ℃ for 10 min. In one word, hydroxide is quite fit to mask aluminum for samples which contain high content of fluoride and aluminum and the BF3 content can be successfully determined by this method.

Thermochemical Study on Coordination Complex of Neodymium Trichloroacetic Acid with 8-Hydroxyquinoline

Two coordinate reactions, NdCl 3·6H 2O(s) +3CCl 3COOH(s)( or TCA) =Nd(TCA) 3·3H 2O(s) +3HCl(g) +3H 2O(l) and Nd(TCA) 3·3H 2O(s) +2C 9H 7NO(s)= Nd(TCA)(C 9H 6NO) 2 (s) +2CCl 3COOH(s) +3H 2O(l), were studied by the classical solution calorimetry at 298.15K. The molar dissolution enthalpies of the reactants and the products in certain solvent (the first reaction in 1 mol·L -1 HCl, the second in a mixed solution consisting of absolute ethyl alcohol, dimethyl sulfoxide and 4 mol·L -1 HCl ) were measured by using an isoperibol calorimeter at 298.15K . From the results and other auxiliary quantities, the standard molar formation enthalpies of [Nd(TCA) 3·3H 2O,s,298.15K] and [Nd(TCA) (C 9H 6NO) 2 ,s, 298.15K] are determined as Δ fH m °[Nd(TCA) 3·3H 2O,s,298.15K]= -3053.3 kJ·mol -1 and Δ fH m° [Nd(TCA) (C 9H 6NO) 2 ,s, 298.15K] = -1355.6 kJ·mol -1 .

Synthesis and Crystal Structure of Cobalt(Ⅱ) and Copper(Ⅱ) Complexes Involving L-Aamino Alcohols

Two novel L-amino alcohol coordination cobalt and copper complexes I and Ⅱ were obtained separately from the direct reaction of L-plenylglycinol with Co（Ⅱ） acetate tetrahydrate in anhydrous ethanol and L-leucinol with Cu（Ⅱ） chloride dihydrate in anhydrous methanol. The structures of I and Ⅱ were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I： [Co3（C51H66N3O16）]2（OAc）, monoclinic, space group P21, a = 15.022（3）, b = 14.242（3）, c = 28.922（6） A, β = 98.944（4）°, V = 6112（2） A3, Z = 4, Dc = 1.339 g/cm^3, the final R = 0.0860 for 21906 observed reflections with I 〉 2（I）. For Ⅱ： Cu2[C24H58N4O7Cl]Cl, orthorhombic, space group P212121, a = 6.1861（13）, b = 20.838（4）, c = 28.274（6） , V = 3644.6（13） 3, Z = 4, Dc = 1.310 g/cm^3, the final R = 0.0642 for 11106 observed reflections with I 〉 2（I）. The complexes were then used to catalyze the Henry reaction and catalytic activity determined by 1H NMR.