Geometry,stability and aromaticity of β-diketiminate-coordinated alkaline-earth compounds

Alkaline-earth (Ae) metals have attracted a wealth of interdependent research from synthetic chemists. In Ae-catalyzed organometallic reactions, β-diketiminate is a typical ligand used to stabilize Ae catalysts by forming six-membered rings comprising Ae metals. Herein, studies focusing on the configuration of β-diketiminate-coordinated Ae compounds observed that the CC and CN bonds are homogeneous and unchanged. Furthermore, energetic studies observed that the formation of the Ae-incorporated six-membered rings results in enhanced stability of >20 kcal/mol. The nucleus-independent chemical shifts, anisotropy of the induced current density, and molecular orbital analyses demonstrated the non-aromaticity of the β-diketiminate-coordinated Ae compounds. The improved stability of these compounds can be explained by the delocalization of the π electrons derived from the β-diketiminate moiety.     

Hydroxylation of nigranoic acid to 6β-hydroxynigranoic acid by Caryospora carllicarpa YMF1.01026

Microbial transformation of nigranoic acid by Caryospora carllicarpa YMF1.01026 afforded the new derivative 6β-hydro-xynigranoic acid. Its structure was elucidated by spectroscopic methods.     

A resonance light scattering method for determination of DNA using Ru(bpy)2PIP(V)2+

A novel method for DNA detection is proposed that is based on the enhancement of resonance light scattering (RLS) of Ru(bpy)₂PIP(V)²⁺ at pH 2.7. Under optimum conditions, good linear relationships were obtained in the wide concentration range of 16–5120 ng mL⁻¹. The linear equation is I _RLS = 13.15 + 171.4 c (μg mL⁻¹), the correlation coefficient (r) is 0.9999. The detection limit of calf thymus DNA is 5.02 ng mL⁻¹. Plasmid DNA extracted from bacillus subtilis was determined by the method with satisfactory results.     

Structure determination and relative properties of novel cubic borates MM'4(BO3)3 (M = Li, M' = Sr; M = Na, M' = Sr, Ba)

A series of novel borates, MM'4(BO3)3 (M = Li, M' = Sr; M = Na, M' = Sr, Ba), have been successfully synthesized by standard solid-state reaction. The crystal structures have been determined from powder X-ray diffraction data. They crystallize in the cubic space group Iad with large lattice parameters: a = 14.95066(5) A for LiSr4(BO3)3, a = 15.14629(6) A for NaSr4(BO3)3, and a = 15.80719(8) A for NaBa4(BO3)3. The structure was built up from 64 small cubic grids, in which the M' atoms took up the corner angle and the BO3 triangles or MO6 cubic octahedra filled in the interspaces. The isolated [BO3]3- anionic groups are perpendicular to each other, distributed along three 100 directions. The anisotropic polarizations were counteracting, forming an isotropic crystal. Sr and Ba atoms were found to be completely soluble in the solid solution NaSr(4-)xBax(BO3)3 (0 < or = x < or = 4). The photoluminescence of samples doped with the ions Eu2+ and Eu3+ was studied, and effective yellow and red emission was detected, respectively. The results are consistent with the crystallographic study. The DTA and TGA curves of them show that they are chemically stable and congruent melting compounds.     

硝酸肼的量热研究

用精密自动绝热量热计测定了在220 K—370 K温度范围内硝酸肼的热容、熔化热、熔化温度和熔化熵。所得热容数据的精密度以百分偏差的均方根值表示为±0.2％。三次熔化热测定的相对偏差为±0.1％。为验证结果的可靠性, 用该装置测定了冰的熔化热和熔化温度, 其结果与文献值一致; 又用法国SETARAM公司的高温量热计测定了硝酸肼的熔化热和熔化温度, 其结果与我们用量热法测定的结果一致; 从量热结果计算出了该试样的纯度, 该结果亦与化学分析的结果一致。这些均可说明我们所测得的数据是可靠的。     

Formate--the analogue of azide: structural and magnetic properties of M(HCOO)2(4,4'-bpy).nH2O (M = Mn, Co, Ni; n = 0, 5)

Reaction of transition metal formate M(HCOO)(2).2H2O (M = Mn, Co, Ni) with 4,4'-bpy (4,4-bipyridine) has led to four new compounds with the formula M(HCOO)2(4,4'-bpy).nH2O (M = Mn, Co (1.Mn, 2.Co), n = 0; M = Co, Ni (3.Co, 4.Ni), n = 5). Compounds 1.Mn and 2.Co are isomorphous and crystallized in the tetragonal crystal system with the chiral space group P4(1)2(1)2. They are of three-dimensional diamondoid structure connected by anti-anti formate with 4,4'-bpy in the cavities of the framework reinforcing the intermetallic connections; the diamond-like net was observed also in their azide analogue (Mn(N3)2(4,4'-bpy)). Compounds 3.Co and 4.Ni are isomorphous also but crystallized in the monoclinic crystal system with the space group Cc. Both structures are uninterpenetrated 3D "CdSO4" type with big channels, constructed by anti-anti formate and 4,4'-bpy. This type of net was not observed in their azide analogue. Residing in the channels, water molecules form a new type of 1D tape constructed by vertex-sharing cyclic pentamers. Magnetic measurements were performed on all of these four compounds. 1.Mn and 2.Co are weak ferromagnets with the critical temperature Tc = 5.3 and 7.4 K, respectively. 3.Co is an antiferromagnet with Neel temperature TN = 3.0 K, and 4.Ni is a weak ferromagnet below 20 K. Hysteresis loop can be observed for 2.Co and 4.Ni at 1.8 K. As an analogue of azide, formate can be used to construct molecular architectures, which structurally and magnetically have great similarities to and also differences from those of azide. This offers a promising method for the design of new molecular architectures with formate.     

Scalable synthesis of multi-shelled hollow N-doped carbon nanosheet arrays with confined Co/CoP heterostructures from MOFs for pH-universal hydrogen evolution reaction

Developing low-cost but efficient hydrogen evolution reaction(HER)electrocatalysts over whole pH values is a significant but daunting task for the large-scale application of electrochemical hydrogen production.Herein,we develop,for the first time,a scalable MOF-assisted strategy for the fabrication and microstructural optimization of multi-shelled hollow N-doped carbon nanosheet arrays with confined Co/CoP heterostructures on carbon cloth(Co/CoP@NC/CC)for boosting HER performances.The key to this strategy is the step-by-step epitaxial growth of unprecedented multilayer ZIF-L arrays on carbon cloth,which are subsequently pyrolyzed and controllably phosphorized to achieve the precise control over the shell number and nanoarchitectures of the Co/CoP@NC/CC.Impressively,the HER performances can be significantly enhanced by increasing hollow shell number,and the optimal triple-shelled hollow Co/CoP@NC/CC exhibits low overpotentials of 86,78 and 145 mV in acidic,alkaline and neutral media to deliver a current density of 10 mA cm^-2,respectively,ranking as one of the best Co-based HER electrocatalysts over whole pH values.Further DFT calculations suggest that the Co/CoP heterostructures can effectively boost the cleavage of H–OH to generate protons and optimize the adsorption energy of hydrogen(ΔG_H*),which,together with the large electrode/electrolyte interface and accelerated charge/mass transfer of multi-shelled hollow array structure as well as the good conductivity and dispersity,are responsible for the remarkably improved HER performances.This study not only provides a new toolbox for enriching the family of multi-shelled nanoarchitecture materials,but also points out a general and effective route to develop highly efficient self-supported electrode materials for energy-related applications and beyond.     

Palladacyclic complexes bearing CNN-type ligands as catalysts in the Heck reaction

Preparations of novel unsymmetrical, tridentate nitrogen ligand precursors, PhN=C(CMe2)(NPh)C=N(CH2)2NMe2(1) and PhN=C(CMe2)(NPh)C=N(CH2)Py (2), are described. Treatment of 1 with 1 molar equiv. (COD)PdCl2 in the presence of NEt3 or with 1 molar equiv. Pd(OAc)2 affords orthometallated palladium(II) complexes, [PhN=C(CMe2)(N-eta1-Ph)C=N(CH2)2NMe2]PdX (X=Cl (3); X=OAc (4)), respectively. Compound can be yielded via the reaction of with an excess of LiCl in methanol. Treatment of with 1 molar equiv. of (COD)PdCl2, Pd(OAc)2 or Pd(TFA)2 affords orthometallated palladium(II) complexes, [PhN=C(CMe2)(N-eta1-Ph)C=NCH2Py]PdX (X=Cl (5); X=OAc (6); X=TFA (7)), respectively. The crystal and molecular structures are reported for compounds 2, 3, 5 and 6. The application of these novel palladacyclic complexes to the Heck reaction with aryl halide substrates was examined.     

Molecular dynamics studies on octadecylammonium chloride at the air/liquid interface

Molecular dynamics simulations on surfactant octadecylammonium chloride at the air/liquid interface were performed. It was found that the alkyl chains of octadecylammonium would change to order with increasing the concentration of octadecylammonium at the air/liquid interface. Some functions, such as the concentration distributions, the radial distribution function and the mean squared displacement (MSD) were evaluated to investigate the structural properties of interface. We found that the salts can affect octadecylammonium aggregate at the interface: (1) univalent ions, such as chloride and sodium ions, affect slightly the structure of monolayer and (2) bivalent ions, such as sulfate or calcium ions, affect greatly, especially for the bivalent negative ions.     

四价锗与3, 4－二羟墓苯甲醛配合物的极谱研究

本文采用极谱法研究了Ge(Ⅳ)-3,4-二羟基苯甲醛(DHB)配合物的组成,条件稳定常数.并对该配合物的极谱波性质进行了研究.