Electrothermal volatilization of aluminum as 1-phenyl-3-methyl-4-benzoylpyrazolone[5] chelate for gaseous sample introduction in ICP-AES

Based on gaseous compound introduction as 1-phenyl-3-methyl-4-benzoylpyrazolone[5](PMBP) chelate of aluminum by electrothermal vaporization in ICP-AES, a method for determination of trace aluminum was developed. Trace aluminum was vaporized at temperature of 1000 degrees C, and the vaporization behavior of aluminum chelate was detailedly investigated. Under the optimum conditions, the detection limit of aluminum was 0.6 ng ml(-1), and the relative standard deviation for 0.1 mug ml(-1) aluminum was 4.7% (n=8). The proposed method was applied to the determination of trace aluminum in rice flour reference materials, and the results well agreed with the reference values.     

Synthesis, crystal structure and magnetic properties of a novel complex [Cu(NIT2Py)(PDA)(H2O)]·(CH3OH)(H2O)

A novel complex [Cu(NIT2Py)(PDA)(H₂O)]·(CH₃OH)(H₂O) has been synthesized and structurally characterized by X-ray diffraction methods. It crystallizes in the monoclinic space group P2(1)/c. The structure consists of [Cu(NIT2Py)(PDA)(H₂O)] moiety, one solvent methanol molecule and one water molecule. The copper(II) ion is in a distorted octahedral environment: one nitrogen atom and one oxygen atom from the NIT2Py, one nitrogen atom from the PDA (2,6-pyridine dicarboxylic acid) and one oxygen atom from the aqueous in the basal plane; two oxygen atoms from the PDA in the axial position. The units of [Cu(NIT2Py)(PDA)(H₂O)] were connected as one dimension chain by the intermolecular hydrogen bonds. The complex exhibits intramolecular antiferromagnetic interactions between the Cu(II) ion and the NIT2Py.     

A Mets motif peptide found in copper transport proteins selectively binds Cu(I) with methionine-only coordination

Mets motifs, which refer to methionine-rich sequences found in the high-affinity copper transporter Ctr1, also appear in other proteins involved in copper trafficking and homeostasis, including other Ctrs as well as Pco and Cop proteins isolated from copper-resistant bacteria. To understand the coordination chemistry utilized by these proteins, we studied the copper binding properties of a peptide labeled Mets7-PcoC with the sequence Met-Thr-Gly-Met-Lys-Gly-Met-Ser. By comparing this sequence to a series of mutants containing noncoordinating norleucine in place of methionine, we confirm that all three methionine residues are involved in a thioether-only binding site that is selective for Cu(I). Two independent methods, one based on mass spectrometry and one based on rate differences for the copper-catalyzed oxidation of ascorbic acid, provide an effective K(D) of approximately 2.5 microM at pH 4.5 for the 1:1 complex of Mets7-PcoC with Cu(I). These results establish that a relatively simple peptide containing an MX(2)MX(2)M motif is sufficient to bind Cu(I) with an affinity that corresponds well with its proposed biological function of extracellular copper acquisition.     

Speciation of dissolved iron(II) and iron(III) in environmental water samples by gallic acid-modified nanometer-sized alumina micro-column separation and ICP-MS determination

A method has been developed for the speciation of trace dissolved Fe(II) and Fe(III) in water by coupling gallic acid (GA) modified nanometer-sized alumina micro-column separation with inductively coupled plasma mass spectrometry (ICP-MS). The separation of Fe(II) and Fe(III) was achieved based on the obvious difference in reaction kinetics between Fe(II) and Fe(III) with GA. Fe(III) was selectively retained on the micro-column at pH 5.5-6.5, while Fe(II) could not be retained by the micro-column at the whole tested pH range of 1.0-6.5, and passed through the micro-column. The Fe(II) can be determined by ICP-MS directly without preconcentration/separation procedure, while Fe(III) retained on the micro-column was then eluted with 1.0 mL of 1 mol L(-1) HCl and determined by ICP-MS. The parameters affecting the separation of Fe(II) and Fe(III) were investigated systematically and the optimum separation conditions were established. Under the optimized conditions, the detection limits of 0.48 microg L(-1) and 0.24 microg L(-1) with relative standard deviation of 5.6% and 4.3%(C= 5 microg L(-1), n= 7) for Fe(II) and Fe(III) were found, respectively. No obvious effect on the speciation of Fe(II) and Fe(III) was found with the change of the ratio of Fe(II) and Fe(III) from 0 ratio 10 to 10 ratio 0. The proposed method was applied for the determination of trace Fe(II) and Fe(III) in environmental water and the recoveries for spiked samples were found to be in the range of 97-105%.     

冰晶石-氧化铝熔体结构的计算机模拟研究

用Monte Carlo法对冰晶石-氧化铝系熔体结构作了计算机模拟研究。结果表明: 熔体中既有含“氧桥”和“氟桥”的“多核”离子集团, 如F3Al-O-AlF_3、F_3Al-AlF_3、F_3Al—F—AlF_3—F等; 也有“单核”离子集团如AlF_5~(2-)、AlOF_3~(2-)等。熔体中还存在较松散的xNa~+·yF~-离子集团。熔体中不存在AlO_2~-或AlO_3~(3-)集团。     

An integrated console for capsule-based,automated organic synthesis

The current laboratory practices of organic synthesis are labor intensive, impose safety and environmental hazards, and hamper the implementation of artificial intelligence guided drug discovery. Using a combination of reagent design, hardware engineering, and a simple operating system we provide an instrument capable of executing complex organic reactions with prepacked capsules. The machine conducts coupling reactions and delivers the purified products with minimal user involvement. Two desirable reaction classes – the synthesis of saturated N-heterocycles and reductive amination – were implemented, along with multi-step sequences that provide drug-like organic molecules in a fully automated manner. We envision that this system will serve as a console for developers to provide synthetic methods as integrated, user-friendly packages for conducting organic synthesis in a safe and convenient fashion.

Using a combination of reagent design, hardware engineering, and a simple operating system we provide an instrument capable of executing complex organic reactions using prepacked capsules with minimal user involvement.     

Triangular halogen trimers. A DFT study of the structure, cooperativity, and vibrational properties

Triangular halogen trimers (RX)3, where X = Br, I and R represents H, H3C, H2FC, HF2C, F3C, CH2=CH, CH[triple bond]C, and Ph, have been investigated using the density functional theory in the Perdew, Burke, and Ernzerhof method. We report herein the optimized geometries of the stable structures, their vibrational frequencies, and binding energies with the two- and three-body terms. All trimer structures possess a cyclic array of halogen atoms in the type II approach by virtue of the nonspherical atomic charge distribution around the halogens. The Br...Br interactions in trimers are very weak, whereas the I...I interactions in trimers are relatively stronger. While all bromine trimers and most of iodine trimers are predicted to be noncooperative, three of iodine trimers show weak cooperativity. The analysis of vibration modes reveals that all halogen trimers exhibit no especially remarkable frequency shifts. It is also shown that the electrostatic contribution plays a major role in the halogen...halogen interactions in halogen trimers. In contrast to bromine trimers, the relative contribution of charge-transfer component to the halogen...halogen interactions becomes more important for iodine trimers.     

Pt／钇稳定氧化锆固体电解质在高温下的电化学性质

用交流阻抗技术研究了二电极、三电极Ｐｔ／钇稳定氧化锆（简称ＹＳＺ）高温固体电化学体系．开路电位下，Ｐｔ／ＹＳＺ体系只有一个阻抗半圆，对应于电极体系的电化学活化控制过程，极化电阻随温度变化的表观活化能为１７１．５ｋＪ／ｍｏｌ．Ｐｔ／ＹＳＺ界面的双电层电容约为３００μＦ／ｃｍ２．阳极极化下，交流阻抗极化电阻显著减小；阴极极化下，极化电阻反而增大，并出现浓差控制现象．     

Palladium‐Catalyzed Three‐Component Coupling Reaction of Allyl Carboxylates,Norbornenes and Diboronates Involving Sequential Olefins Insertion and Borylation Reaction

An efficient Pd‐catalyzed three‐component coupling reaction of allyl carboxylates, norbornenes and diboronates is described, which allows efficient assembly of C(sp³)—C(sp³) and C(sp³)—B bonds in a single process. Moreover, this approach shows advantages of good chemo‐ and regioselectivity, as well as good substrates suitability.     

聚硅氧烷涂敷的反相高效液相色谱固定相

用甲基乙烯基聚硅氧烷涂敷于硅烷化的微粒硅胶上，制备出一种新型的涂敷型反相高效液相色谱固定相。该固定相对极性、非极性和碱性化合物均有良好的分离能力，峰对称性好。对其恶性循环 了考察，连续使用三个月后，固定相的碳量和色谱性能仍保持不变。