A two‐dimensional layered CdII coordination polymer with a three‐dimensional supramolecular architecture incorporating mixed multidentate N‐ and O‐donor ligands

The combination of N‐heterocyclic and multicarboxylate ligands is a good choice for the construction of metal–organic frameworks. In the title coordination polymer, poly[bis{μ₂‐1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐tetrazole‐κ²N³:N⁴}(μ₄‐butanedioato‐κ⁴O¹:O^1′:O⁴:O^4′)(μ₂‐butanedioato‐κ²O¹:O⁴)dicadmium], [Cd(C₄H₄O₄)(C₉H₈N₆)]_n, each Cd^II ion exhibits an irregular octahedral CdO₄N₂ coordination geometry and is coordinated by four O atoms from three carboxylate groups of three succinate (butanedioate) ligands and two N atoms from two 1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐tetrazole (bimt) ligands. Cd^II ions are connected by two kinds of crystallographically independent succinate ligands to generate a two‐dimensional layered structure with bimt ligands located on each side of the layer. Adjacent layers are further connected by hydrogen bonding, leading to a three‐dimensional supramolecular architecture in the solid state. Thermogravimetric analysis of the title polymer shows that it is stable up to 529 K and then loses weight from 529 to 918 K, corresponding to the decomposition of the bimt ligands and succinate groups. The polymer exhibits a strong fluorescence emission in the solid state at room temperature.     

Hydrothermal synthesis,crystal structure and photoluminescence of two homochiral zinc(II) coordination polymers

Metal–organic frameworks (MOFs) have potentially useful applications and an intriguing variety of architectures and topologies. Two homochiral coordination polymers have been synthesized by the hydrothermal method, namely poly[(μ‐N‐benzyl‐L‐phenylalaninato‐κ⁴O,O′:O,N)(μ‐formato‐κ²O:O′)zinc(II)], [Zn(C₁₆H₁₆NO₂)(HCOO)]_n, (1), and poly[(μ‐N‐benzyl‐L‐leucinato‐κ⁴O,O′:O,N)(μ‐formato‐κ²O:O′)zinc(II)], [Zn(C₁₃H₁₈NO₂)(HCOO)]_n, (2), and studied by single‐crystal X‐ray diffraction, elemental analyses, IR spectroscopy and fluorescence spectroscopy. Compounds (1) and (2) each have a two‐dimensional layer structure, with the benzyl or isobutyl groups of the ligands directed towards the interlayer interface. Photoluminescence investigations show that both (1) and (2) display a strong emission in the blue region.     

Evolution of highly symmetric curves under the shrinking curvature flow

Under the shrinking curvature flow with inner normal velocity V = k^α(α > 1), it is shown that highly symmetric, locally convex initial curves evolve into a point asymptotically like an multi‐circles. The proof relies on a crucial use of Bonnensen inequality for highly symmetric, locally convex curves. Copyright © 2016 John Wiley & Sons, Ltd.     

Nickel‐Catalyzed Barton Decarboxylation and Giese Reactions: A Practical Take on Classic Transforms

Two named reactions of fundamental importance and paramount utility in organic synthesis have been reinvestigated, the Barton decarboxylation and Giese radical conjugate addition. N ‐hydroxyphthalimide (NHPI) based redox‐active esters were found to be convenient starting materials for simple, thermal, Ni‐catalyzed radical formation and subsequent trapping with either a hydrogen atom source (PhSiH₃) or an electron‐deficient olefin. These reactions feature operational simplicity, inexpensive reagents, and enhanced scope as evidenced by examples in the realm of peptide chemistry.     

Maximum likelihood estimation for stochastic volatility in mean models with heavy‐tailed distributions

In this article, we introduce a likelihood‐based estimation method for the stochastic volatility in mean (SVM) model with scale mixtures of normal (SMN) distributions. Our estimation method is based on the fact that the powerful hidden Markov model (HMM) machinery can be applied in order to evaluate an arbitrarily accurate approximation of the likelihood of an SVM model with SMN distributions. Likelihood‐based estimation of the parameters of stochastic volatility models, in general, and SVM models with SMN distributions, in particular, is usually regarded as challenging as the likelihood is a high‐dimensional multiple integral. However, the HMM approximation, which is very easy to implement, makes numerical maximum of the likelihood feasible and leads to simple formulae for forecast distributions, for computing appropriately defined residuals, and for decoding, that is, estimating the volatility of the process. Copyright © 2017 John Wiley & Sons, Ltd.     

Convergence Theory for Preconditioned Eigenvalue Solvers in a Nutshell

Preconditioned iterative methods for numerical solution of large matrix eigenvalue problems are increasingly gaining importance in various application areas, ranging from material sciences to data mining. Some of them, e.g., those using multilevel preconditioning for elliptic differential operators or graph Laplacian eigenvalue problems, exhibit almost optimal complexity in practice; i.e., their computational costs to calculate a fixed number of eigenvalues and eigenvectors grow linearly with the matrix problem size. Theoretical justification of their optimality requires convergence rate bounds that do not deteriorate with the increase of the problem size. Such bounds were pioneered by E. D’yakonov over three decades ago, but to date only a handful have been derived, mostly for symmetric eigenvalue problems. Just a few of known bounds are sharp. One of them is proved in doi: 10.1016/S0024-3795(01)00461-X for the simplest preconditioned eigensolver with a fixed step size. The original proof has been greatly simplified and shortened in doi: 10.1137/080727567 by using a gradient flow integration approach. In the present work, we give an even more succinct proof, using novel ideas based on Karush–Kuhn–Tucker theory and nonlinear programming.     

Determination of macrolides in livestock excreta by syringe purification coupled with liquid chromatography tandem mass spectrometryEI北大核心CSCD

A method of syringe-dispersive solid-phase extraction combined with ultrahigh performance liquid chromatography with tandem mass spectrometry for the simultanous determination of 10 macrolides in manurebased fertilizers was developed. After extraction with methanol and acetonitrile,the extracts were purified by insyringe dispersion solid-phase extraction in syringes pre-filled with 60 mg PSA and 30 mg C18. The resulted extracts were further separated by a BEH C18 column,detected by multiple reaction monitoring in electrospray positive ion mode,and quantified by matrix-matched external standard method. The results showed that the recoveries of the target compounds ranged from 70% to 110% at three spiked levels（10,30,and 50 μµg/kg）with the relative standard deviations ranged from 1.4% to 12%. The limits of detection and quantification were 0.57 1.75 and 2.77-5.40 μµg/kg,respectively. This method was suitable for the simultaneous determination of residual macrolides in organic fertilizers. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

三核过渡金属配合物在催化反应中的研究进展

多核过渡金属配合物作为一类广泛应用的均相催化剂,其设计灵感往往来自天然酶的多金属活性位点所发挥的重要作用.目前,三核金属配合物作为活化小分子的多金属催化剂受到了广泛的关注.为深入理解三核过渡金属配合物在催化反应中作用特点,对近年报道的代表性三核过渡金属配合物按金属中心进行分类,并对配体环境形成特点及催化应用进行综述.从金属中心出发,讨论了三核过渡金属配合物的几何结构和电子特征;从配体环境出发,总结了关联三个独立的金属位点的配位环境特征;在催化应用方面,重点综述了三核过渡金属配合物在涉及特定化学键活化反应的催化作用机制,最后对三核过渡金属配合物的催化应用前景进行展望.     

Molecular Nickel Thiolate Complexes for Electrochemical Reduction of CO2 to C1–3 Hydrocarbons

We report the unprecedented electrocatalytic activity of a series of molecular nickel thiolate complexes ( 1 – 5 ) in reducing CO₂ to C_1–3 hydrocarbons on carbon paper in pH-neutral aqueous solutions. Ni(mpo)₂ ( 3 , mpo=2-mercaptopyridyl-N-oxide), Ni(pyS)₃⁻ ( 4 , pyS=2-mercaptopyridine), and Ni(mp)₂⁻ ( 5 , mp=2-mercaptophenolate) were found to generate C₃ products from CO₂ for the first time in molecular complex. Compound 5 exhibits Faradaic efficiencies (FEs) of 10.6 %, 7.2 %, 8.2 % for C₁, C₂, C₃ hydrocarbons respectively at −1.0 V versus the reversible hydrogen electrode. Addition of CO to the system significantly promotes the FE_C1–C3 to 41.1 %, suggesting that a key Ni−CO intermediate is associated with catalysis. A variety of spectroscopies have been performed to show that the structures of nickel complexes remain intact during CO₂ reduction.     

Rich-defect carbon nanotubes for highly sensitive detection of Dopamine

Dopamine (DA) plays an essential role in the central nervous, renal, hormonal and cardiovascular systems. Various modified carbon nanotubes (CNT)-based dopamine sensors have been reported, but inexpensive, highly sensitive plain CNT-based ones are seldom studied. In this work, a facile and inexpensive CNT-based DA sensor is made by rich-defect multi-walled carbon nanotubes (RD-CNT) via an ultrasound method. The defect and elemental states of the RD-CNT are systematically studied by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM), Raman spectroscopy, X-ray powder diffraction (XRD) and X-ray-photoelectron spectroscopy (XPS). Results show that massive holes and cracks exist in RD-CNT. The level of defects increases from the additional exposed edges. The electrochemical characterizations indicate that the electrochemical sensor has the highest sensitivity of 438.4 μA/(μM ⋅ cm²) among all carbon materials-based DA sensors while well meeting the clinically required detection range and selectivity. The DA sensor was further used to detect live healthy human serum and live PC12 cells with satisfactory results, thus holding great promise for an inexpensive but sensitive DA sensor in practical applications of clinical diagnosis and biological research.