离子液体电沉积CuIn_xGa_(1-x)Se_2薄膜(英文)

采用循环伏安法(CV)对离子液体Reline中三元CuCl2+InCl3+SeCl4体系和四元CuCl2+InCl3+GaCl3+SeCl4体系的电化学行为进行了研究。研究表明,In3+并入三元CIS(Cu-In-Se)薄膜体系和Ga3+并入四元CIGS(Cu-In-Ga-Se)薄膜体系均有两种途径:一是发生共沉积,二是直接还原。利用电感耦合等离子体发射光谱(ICP)和扫描电镜(SEM)对沉积电势、镀液温度和主盐浓度对CIGS薄膜组成、镀层表面形貌的影响进行了测试,结果表明通过工艺参数的选择可以控制Ga/(Ga+In)和CIGS薄膜组成并得到化学计量比为Cu1.00In0.78Ga0.27Se2.13的薄膜。     

NMR studies on interactions between diperoxovanadate and picolinamide-like ligands

To understand the effects of picolinamide-like ligands on reaction equilibrium, a series of picolinamide derivatives were synthesized and the interactions between the diperoxovanadate complex [OV(O₂)₂L]^? (L = D₂O or HOD, abbr. bpV) and picolinamide ligands in solution were explored using multinuclear (¹H, ¹³C, and ⁵¹V) magnetic resonance, COSY, and HSQC in 0.15 mol L^?1 NaCl ionic medium for mimicking physiological conditions. Formation constants among the picolinamide-like ligands are N-(1-hydroxypropan-2-yl)-picolinamide ≈N-(2-hydroxypropyl)-picolinamide>N-(3-hydroxypropyl)-picolinamide>N-propyl-picolinamide. The substituting group influences the equilibrium by electronic effects. The interactions result in a series of new seven-coordinate diperoxovanadate species [OV(O₂)₂L′]^? (L′ = picolinamide-like ligands).     

SiO2-NHC-CuI–Catalyzed N-Arylation of Imidazoles with Arylboronic Acids Under Base-Free Reaction Conditions

N-Arylation of imidazoles with arylboronic acids was efficiently carried out in the presence of a catalytic amount of SiO₂-NHC-Cu^I in methanol at room temperature under base-free reaction conditions. The reactions of a variety of arylboronic acids with imidazoles generated the corresponding products N-arylimidazoles in good to excellent yields. In addition, SiO₂-NHC-Cu^I could be recovered and recycled for six consecutive trials without significant loss of its reactivity.     

Kinetics of oxidation of benzyl alcohols with molecular oxygen catalyzed by N-hydroxyphthalimide: Role of hydroperoxyl radicals

A kinetic study of the initiated oxidation of benzyl alcohol and cumene by molecular oxygen was performed. The oxidation rate was more enhanced with N-hydroxyphthalimide (NHPI) in the case of cumene than that of benzyl alcohol. HOOH inhibits cumene oxidation and does not affect the rate of oxidation of benzyl alcohol. It was shown that termination chain reactions of phthalimid-N-oxyl radicals (PINO^•) does not occur with RОО^• and proceeds with HOO^•. A kinetic scheme of the process and an equation describing the kinetics of oxidation of benzyl alcohol in the presence of NHPI are proposed. Using the PM7 method, the thermodynamic characteristics of elementary steps of oxidation explaining the obtained results were calculated.     

离子液体电沉积CuInxGa1-xSe2薄膜

采用循环伏安法(CV)对离子液体Reline中三元CuCl₂+InCl₃+SeCl₄体系和四元CuCl₂+InCl₃+GaCl₃+SeCl₄体系的电化学行为进行了研究。研究表明,In³⁺并入三元CIS(Cu-In-Se)薄膜体系和Ga³⁺并入四元CIGS(Cu-In-Ga-Se)薄膜体系均有两种途径：一是发生共沉积,二是直接还原。利用电感耦合等离子体发射光谱(ICP)和扫描电镜(SEM)对沉积电势、镀液温度和主盐浓度对CIGS薄膜组成、镀层表面形貌的影响进行了测试,结果表明通过工艺参数的选择可以控制Ga/(Ga+In)和CIGS薄膜组成并得到化学计量比为Cu_1.00In_0.78Ga_0.27Se_2.13的薄膜。     

Synthesis of novel N-protected β-amino nitriles: study of their hydrolysis involving a nitrilase-catalyzed step

Several commercially available nitrilases were investigated with regard to their potential to hydrolyze N-protected β³-amino nitriles into their corresponding N-protected β³-amino acids.The biotransformations were obtained in different proportions depending on the nitrilase involved. The best hydrolysis results were achieved for the N-Cbz-β³-amino nitrile from l-alanine using the NIT-107, in a phosphate buffer at 0.05 M. However, no biotransformation into the corresponding acids was observed for the N-sulfonylamide β³-amino nitriles. Two simple and efficient procedures to prepare the β³-amino nitriles from their analogous α-amino acids are described. Thirty four new substances were synthesized and characterized over the course of this work.     

Electrochemical Study of Indium in a Water‐Stable 1‐Ethyl‐3‐Methylimidazolium Chloride/Tetrafluoroborate Room Temperature Ionic Liquid

The electrochemistry of indium species was investigated at glassy carbon, tungsten and nickel electrodes in a basic 1‐ethyl‐3‐methylimidazolium chloride/tetrafluoroborate ionic liquid. Amperometric titration experiments suggest that In(III) chloride is complexed as [InCl₅]^2? in this ionic liquid. The electrochemical reduction of [InCl₅]^2? to indium metal is preceded by overpotential driven nucleations. The effective anodic dissolution of indium to indium(III) requires, however, the presence of sufficient chloride ions at the electrode surface. The electrodeposition of indium at glassy carbon and tungsten electrodes proceeds via three‐dimensional instantaneous nucleation with diffusion‐controlled growth of the nuclei. At the nickel electrode, the deposition proceeds via three‐dimensional progressive nucleation with diffusion‐controlled growth of the nuclei. Raising the deposition temperature decreases the average radius of the individual nuclei, r. Scanning electron microscopic and x‐ray diffraction data indicated that bulk crystalline indium electrodeposits could be prepared on nickel substrates within a temperature range between 30 and 120 °C.     

Toxicity of naturally occurring Bio-fly and chitosan compounds to control the Mediterranean fruit fly Ceratitis capitata (Wiedemann)

The efficacy of five compounds of a biopolymer chitosan and Bio-fly (Beauveria bassiana fungus) as biopesticide was evaluated on Ceratitis capitata under laboratory conditions. The inhibitory effects on acetylcholinesterase (AChE) and adenosinetriphosphatase (ATPase) as biochemical indicators were also determined in vivo. The results indicated that B. bassiana based Bio-fly exhibited significant toxicity against C. capitata (LC₅₀ = 3008 and 3126 mg/L after 48 h in females and males, respectively) followed by the derivatives of chitosan, N-(4-propylbenzyl)chitosan and N-(2-nitrobenzyl)chitosan. Bio-fly displayed remarkable inhibition of AChE activity (IC₅₀ = 2220 mg/L) while N-(2-chloro,6-flourobenzyl)chitosan, N-(4-propylbenzyl)chitosan and N-(3,4-methylenedioxybenzyl) chitosan had no significant difference in inhibitory action. In adult males, N-(2-nitrobenzyl)chitosan exhibited the highest inhibitory action (IC₅₀ = 6569 mg/L). In addition, the toxic effects of the tested compounds on the activity of ATPase indicated that highly significant inhibition was found with N-(4-propylbenzyl)chitosan with an IC₅₀ of 8194 and 8035 mg/L, in females and males, respectively.     

Gallium‐Indium Ordering in the Complex [Ni2Ga3In] Network of GdNi2Ga3In

Polycrystalline samples of the isotypic quaternary compounds RENi₂Ga₃In (RE = Y, Gd – Tm) were obtained by arc‐melting of the elements. Crystals of the gadolinium compound were found by slow cooling of an arc‐melted button of the initial composition “GdNiGa₃In”. All samples were characterized by powder X‐ray diffraction. The structure of GdNi₂Ga_2.89In_1.11 was refined from single‐crystal X‐ray diffractometer data: new type, Pnma, a = 2426.38(7), b = 418.17(2), c = 927.27(3) pm, wR₂ = 0.0430, 1610 F² values and 88 variables. Two of the six crystallographically independent gallium sites show a small degree of Ga/In mixing. The nickel atoms show tricapped trigonal prismatic coordination by gadolinium, gallium, and indium. Together, the nickel, gallium, and indium atoms build up a complex three‐dimensional [Ni₂Ga₃In]^δ– network, which leaves cages for the gadolinium atoms. The indium atoms form zigzag chains with In–In distances of 337 pm. The crystal chemical similarities of the polyhedral packing in the GdNi₂Ga₃In and La₄Pd₁₀In₂₁ structures are discussed.     

Effect of some nitrogen-heterocyclic compounds on corrosion of tin, indium, and their alloys in HClO4

Abstract  

The effect of adenine, adenosine, and 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPTZ) on the electrochemical and corrosion behavior of tin, indium, and tin-indium alloys in 0.5 M HClO₄ solution at different temperatures was studied. The inhibition efficiency increases with an increase in the concentration of adenine and adenosine in the case of tin and indium. However, the effect of two mentioned compounds on the corrosion rate of the studied alloys gives an opposite effect. In the presence of TPTZ, the inhibition efficiency increases as the concentration of the inhibitor is increased in the case of tin. In the case of both indium and its investigated alloys, the maximum inhibition efficiency is obtained at the lowest concentration of TPTZ (10⁻⁶ M). The adsorption of the studied compounds is found to obey the Frumkin adsorption isotherm. The standard enthalpy \Updelta H_ads^° , \Updelta H_{\rm ads}^{^\circ } , entropy \Updelta S_ads^° , \Updelta S_{\rm ads}^{^\circ } , and free energy changes of adsorption \Updelta G_ads^° \Updelta G_{\rm ads}^{^\circ } are calculated and discussed.     

Synthesis,characterization, and crystal structure of Ni(II) and Cu(II) complexes with N-furoyl-N′,N′-diethylthiourea: antifungal activity

The complexes cis-bis(N-furoyl-N′,N′-diethylthioureato-k ²O,S)nickel(II) and cis-bis(N-furoyl-N′,N′-diethylthioureato-k ²O,S)copper(II) were prepared by the reaction of metal acetate with the corresponding acylthiourea derivative. The complexes were characterized by IR, ¹H-NMR, ¹³C-NMR, and single-crystal X-ray diffraction. Both complexes show two furoylthiourea ligands bonded to metal to form a four-coordinate complex with square-planar geometry. The antifungal activity of the prepared complexes was studied against the phytopathogenic fungi Botrytis cinerea and Colletotrichum gloeosporioides, responsible for important plant diseases.     

Kinetic study on the radical polymerization of 2‐methacryloyloxyethyl phosphorylcholine

Polymerization of 2‐methacryloyloxyethyl phosphorylcholine (MPC) was kinetically investigated in ethanol using dimethyl 2,2′‐azobisisobutyrate (MAIB) as initiator. The overall activation energy of the homogeneous polymerization was calculated to be 71 kJ/mol. The polymerization rate (R_p) was expressed by R_p = k[MAIB]^0.54±0.05 [MPC]^1.8±0.1. The higher dependence of R_p on the monomer concentration comes from acceleration of propagation due to monomer aggregation and also from retardation of termination due to viscosity effect of the MPC monomer. Rate constants of propagation (k_p) and termination (k_t) of MPC were estimated by means of ESR to be k_p = 180 L/mol · s and k_t = 2.8 × 10⁴ L/mol · s at 60 °C, respectively. Because of much slower termination, R_p of MPC in ethanol was found at 60 °C to be 8 times that of methyl methacrylate (MMA) in benzene, though the different solvents were used for MPC and MMA. Polymerization of MPC with MAIB in ethanol was accelerated by the presence of water and retarded by the presence of benzene or acetonitrile. Poly(MPC) showed a peculiar solubility behavior; although poly(MPC) was highly soluble in ethanol and in water, it was insoluble in aqueous ethanol of water content of 7.4–39.8 vol %. The radical copolymerization of MPC (M₁) and styrene (St) (M₂) in ethanol at 50 °C gave the following copolymerization parameters similar to those of the copolymerization of MMA and St; r₁ = 0.39, r₂ = 0.46, Q₁ = 0.76, and e₁ = +0.51. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 509–515, 2000     

Subtoichiometric determination of indium and tin by radioactivation analysis

A method of radioactivation analysis has been developed for the determination of indium and tin. It is based on substoichiometric extraction of indium diethyldithiocarbamate into carbon tetrachloride from a slightly ammoniacal solution in the presence of potassium cyanide. With this method, indium can be determined via^116m In (T=54 min) and tin via^113m In (T=104 min) which is formed by the reaction¹¹²Sn(n, ψ)¹¹³Sn. The method has been applied to the determination of indium in metallic zinc and of tin in tin-doped gallium arsenide, and 0.4 ppb of indium was analyzed in a zinc sample.     

Determination of the formation rate constant of carrier-free111In(III) with EDTA

The kinetics of reaction of indium(III)ion with EDTA (H₄ edta) has been studied in aqueous acidic solutions using carrier-free¹¹¹In and low concentrations of EDTA. The reaction takes place predominatly between indium(III) and H₃ edta. The rate constant k₃ is determined to be k₃=(1.3±0.1)·10⁵ dm³ mol^–1 s^–1 (25 °C).     

EuIrIn4 with LaCoAl4 Type Structure – Synthesis,Magnetic Properties,and 151Eu Mössbauer Spectroscopy

LaCoAl₄ type EuIrIn₄ was synthesized by induction-melting of the elements in a sealed tantalum ampoule, followed by annealing of the sample in a high-frequency or in a muffle furnace. The EuIrIn₄ structure was refined from single-crystal X-ray diffraction data: Pmma, a = 860.65(3), b = 430.33(6), c = 757.65(7) pm, wR = 0.0748, 633 F² values and 24 variables. The striking building units are iridium-centered trigonal prisms of indium atoms, distorted bcc indium cubes and a pentagonal prismatic indium coordination of the europium atoms. Within the three-dimensional [IrIn₄]^2– polyanionic network the Ir–In and In–In distances range from 260–288 pm and 306–332 pm, respectively. The divalent ground state of europium was manifested through magnetic [7.96(1) μ_B / Eu atom, T_N = 7.9(1) K] and ¹⁵¹Eu Mössbauer spectroscopic data [δ = –10.54(2) mm · s^–1; B_hf = 19.1(1) T at 6 K].     

Heterotermetallic Indium Lithium Halostannates: Low‐Temperature Single‐Source Precursors for Tin‐Rich Indium Tin Oxides and Their Application for Thin‐Film Transistors

The syntheses and structural elucidation of dimeric [Sn(OCyHex)₂] ( 1 ), its corresponding (cyclohexoxy)alkalistannates(II) [{M(OCyHex)₃Sn}₂] (M=Li ( 2 ), Na ( 3 ), K ( 4 )), and of the first heteroleptic heterotermetallic Li/In/Sn–haloalkoxide clusters [X₂In{LiSn₂(OCyHex)₆}] (X=Br ( 5 ), Cl ( 6 )) with a double seco‐norcubane core are reported. They represent suitable precursors for new amorphous indium tin oxide (ITO) materials as transparent conducting oxides with drastically reduced concentrations of expensive indium, while maintaining their high electrical performance. In fact, compounds 5 and 6 were successfully degraded under dry synthetic air at relatively low temperature, resulting in new semiconducting tin‐rich ITOs homogeneously dispersed in a tin oxide/lithium oxide matrix. The obtained particles were investigated and characterised by different analytical techniques, such as powder XRD, IR spectroscopy, SEM, TEM and energy‐dispersive X‐ray spectroscopy (EDX). The analytical data confirm that the final materials consist of tin‐containing indium oxide embedded in an amorphous tin oxide matrix. The typical broadening and shift of the observed indium oxide reflections to higher 2θ values in the powder XRD pattern clearly indicated that tin centres were successfully incorporated into the In₂O₃ lattice and partially occupied In³⁺ sites. Investigations by EDX mapping proved that Sn was homogeneously distributed in the final materials. Thin‐film field‐effect transistors (FETs) were fabricated by spin‐coating of silicon wafers with solutions of 5 in toluene and subsequent calcination under dry air (25–700 °C). The FETs prepared with precursor 5 exhibited excellent performances, as shown by a charge‐carrier mobility of 6.36×10^?1 cm² V^?1 s (calcination at 250 °C) and an on/off current ratio of 10⁶.     

Method for trace determination of N-nitrosamines impurities in metronidazole benzoate using high-performance liquid chromatography coupled with atmospheric-pressure chemical ionization tandem mass spectrometry

Genotoxic impurity control has been a great concern in the pharmaceutical industry since the recall of the large round of sartans worldwide in 2018. In these sartans, N-nitrosamines were the main contaminants in active pharmaceutical ingredients and formulations. Numerous analytical methods have been developed to detect N-nitrosamines in food, drugs, and environmental samples. In this study, a sensitive method is developed for the trace determination of N-nitrosamine impurities in metronidazole benzoate pharmaceuticals using high-performance liquid chromatography/atmospheric-pressure chemical ionization tandem mass spectrometry in the multiple reaction monitoring mode. The method was validated regarding system suitability, selectivity, linearity, accuracy, precision, sensitivity, solution stability, and robustness. The method showed good linearity with R² ≥ 0.999 and F_Mandel < F_tab(95%) ranging from 0.33 to 8.00 ng/ml. The low limits of detection of N-nitrosamines were in the range of 0.22–0.80 ng/ml (0.0014–0.0050 ppm). The low limits of quantification were in the range of 0.33–1.20 ng/ml (0.0021–0.0075 ppm), which were lower than the acceptable limits in metronidazole benzoate pharmaceuticals and indicated the high sensitivity of the method. The recoveries of N-nitrosamines ranged from 84% to 97%. Thus, this method exhibits good selectivity, sensitivity, and accuracy. Moreover, it is a simple, convenient, and scientific strategy for detecting N-nitrosamine impurities in pharmaceuticals to support the development of the pharmaceutical industry.     

Radiochemical proton activation analysis for the determination of cadmium and lead in sediment reference materials

Proton activation analysis was used for the determination of cadmium and lead in three sediment reference materials. The method is based on the^111,112Cd(p, xn)¹¹¹ In and the^206,207,208Pb(p, xn)²⁰⁶Bi reactions.¹¹¹In and²⁰⁶Bi were chemically separated by anion exchange. The results obtained were taken into account for the certification of the materials and are in the excellent agreement with the certified values.     

D-谷氨酰胺的制备

报道了以化学合成和生物转化的方法制备光学纯D-谷氨酰胺. 首先在中试规模上用化学方法合成DL-谷氨酰胺. 即以廉价的DL-谷氨酸为原料, 采用邻苯二甲酰基作为保护基保护L-谷氨酸的α-氨基, 醋酐回流15 min, 使其分子内脱水生成N-邻苯二甲酰-DL-谷氨酸酐, 在常温、常压条件下, 分别与2 mol/L氨水反应生成中间产物N-邻苯二甲酰-DL-谷氨酰胺, 中间产物在室温条件下与0.5 mol/L水合肼反应48 h脱除保护基, 以57%总收率得到DL-谷氨酰胺. 在37 ℃, pH 4.8的条件下, 利用大肠杆菌(E. coli. AS 1.505)脱羧酶将底物浓度30 g/L的DL-谷氨酰胺中L型对映体在8 h内完全转化为4-氨基丁酰胺, 分离得到D-谷氨酰胺.     

Determination of cadmium in oyster tissue using isotope dilution inductively coupled plasma mass spectrometry: comparison of results obtained in the standard and He/H2 cell modes

An inductively coupled plasma quadrupole mass spectrometer equipped with an octopole collision/reaction cell was used for the determination of cadmium in oyster tissue samples using isotope dilution inductively coupled plasma mass spectrometry. The oyster samples in question were found to contain Mo and Zr. In our feasibility study on a Cd standard solution (10 μg L⁻¹) containing a matrix of Mo (1000 μg L⁻¹) or Zr (250 μg L⁻¹), the potentially interfering species (MoO⁺ or ZrO⁺) present at the analytical mass of cadmium concerned (m/z 111, 112 or 114) was reduced effectively through the use of a mixture of He and H₂ as cell gases. The accuracy of the method was validated by the analysis of a matrix-matched certified reference material (CRM) of NIST SRM 1566b. The CRM was analyzed under the standard and He/H₂ cell modes. Two isotopic pairs of ¹¹⁴Cd/¹¹¹Cd and ¹¹²Cd/¹¹¹Cd were selected for quantification purposes. The recoveries of cadmium obtained in the two cell modes were compared with each other. The validated method was applied successfully to the APMP.QM-P5 pilot study for international comparability purposes.