Expanding the utility of proteins as platforms for coordination chemistry

Whether for constructing advanced materials and complex biological devices or for building sophisticated coordination complexes with diverse metal-based functions, proteins are nature's favorite building blocks. Yet, our ability to control the assembly of proteins or to use them as ligand platforms for inorganic chemistry has been somewhat limited. In this review, we highlight our work from the past four years, which has aimed to exploit the utility of a protein scaffold in both regards. First, by considering proteins as “simple” ligand platforms and controlling the metal coordination chemistry on their surfaces, we show how their self-assembly can be readily dictated by metal binding. Second, we show how metal-mediated protein self-assembly leads to novel metal centers buried within protein interfaces. While on one hand our studies have pointed out the challenges of using proteins as ligands, they have also revealed how the extensive, chemically-rich protein surfaces can be exploited to form a network of covalent and non-covalent interactions around interfacial metal centers, providing a powerful handle to control their coordination chemistry.     

Synthesis,Crystal Structure and Spectrothermal Analysis of mer–Triaquanicotinamide‐orotato Cobalt(II) Trihydrate

The mixed–ligand orotato (HOr)^2? complex of cobalt(II) with nicotinamide (NA) [Co(HOr)(H₂O)₃(NA)]·3H₂O was synthesized and characterized by elemental analysis, magnetic susceptibility, conductivity, spectral methods (UV–Vis and FT–IR), simultaneous TG, DTG, DTA techniques and X–ray diffraction. The complex crystallizes in the triclinic space group P–1 with unit cell parameters a = 9.320(5), b = 9.493(5), c = 10.381(5) Å, α = 77.003(5), β = 78.852(5), γ = 80.987(5)° and Z = 2. The crystal structure has indicated that the complex has been slightly distorted octahedral geometry and is chelated by the deprotonated N(3) pyrimidine ring and by the carboxylate oxygen atom of the orotate ligand. One nicotinamide molecule is also coordinated to the metal ion by the N atom of the pyridine ring. The crystal structure consists of discrete monomeric units of the complex, which are bridged via hydrogen bonding.     

用纵横波声时比法测螺栓轴力精度研究

用纵横波测量螺栓轴力的技术已取得较大发展,本文介绍了纵横波比值法原理,通过理论推导,获得比值法计算的简易公式。建立试验平台,用现场用螺栓进行标定和测量,得出比值法在工程实践状态下的测量误差为10%以内,基本能满足工程应用的要求。此外,针对试验结果,本文还初步探讨了误差出现的原因以及提高精度的方法。本文介绍的比值法,无需精确测量标定螺栓长度和纵横波声速,现场应用更加简洁,具有较大的工程应用价值。     

一种可视化液体传感阵列农药检测新方法

以筛选出的7种染料与合成的纳米金共同构建了液体传感器阵列,每个敏感点对不同农药样品产生不同的响应光谱,通过酶标仪采集光谱数据,结合主成分分析(PCA)、分层聚类分析(HCA)、判别分析(LDA)等模式识别方法建立了一种快速检测有机磷、氨基甲酸酯、有机氯、拟除虫菊酯类农药残留的新方法。PCA结果表明,前三个主成分反映了总信息量的92.69%,且能够对5种农药进行区分;HCA结果表明,对25个样品能够正确的归类;LDA结果表明,对5种农药识别的准确率达100%。表明这种可视化的液体阵列可为农药残留检测提供一个可靠平台,在农药残留检测中具有潜在的应用价值。     

Instability of FIFO in a simple queueing system with arbitrarily low loads

We show, using a simple example, that the First-In-First-Out (FIFO) policy can be unstable in a system with arbitrarily low load. Our proof is based on the observation that the special structure of the example we use allows us to establish stability using a much simpler queueing system.     

单质碘掺杂纳米TiO2光催化剂的制备及性能

以钛酸四异丙酯和单质碘为起始原料,用改进的溶胶-凝胶法制备了掺碘的纳米TiO2的前驱体,经500 ℃煅烧得到棕黄色TiO2/I2纳米粉末.采用X射线衍射(XRD),紫外-可见(UV-Vis)漫反射光谱,透射电镜(TEM)等手段对TiO2/I2粉末进行了表征,并研究了其光催化性能.结果表明,掺杂的碘存在于TiO2内部纳米孔洞中,不会因为高温而被氧化;光催化降解甲基橙反应是一级反应;TiO2掺杂碘单质后对光响应波长拓展至可见光范围,对甲基橙的降解效率可提高15%以上.     

Exact Solutions of the Schrödinger Equation with Position-dependent Effective Mass via General Point Canonical Transformation

Exact solutions of the Schr?dinger equation are obtained for the Rosen–Morse and Scarf potentials with the position-dependent effective mass by appliying a general point canonical transformation. The general form of the point canonical transformation is introduced by using a free parameter. Two different forms of mass distributions are used. A set of the energy eigenvalues of the bound states and corresponding wave functions for target potentials are obtained as a function of the free parameter.     

Spectral and electrochemical behavior of 1-[(NO2, COOH)-substituted phenyl]-3,5-diphenylformazans

Abstract  

1-[(NO₂, COOH)-substituted phenyl]-3,5-diphenylformazans were synthesized. The compounds were characterized by infrared (IR), ultraviolet–visible (UV–vis), ¹H nuclear magnetic resonance (NMR), ¹³C NMR spectra, elemental analysis, and cyclic voltammetry. From the UV–vis spectra of substituted formazans it was seen that λ _max values were shorter than the λ _max value of unsubstituted formazan. It was observed that the shift values were dependent on the type and position of the substituents. A correlation between Hammett substituent coefficients and λ _max values was obtained. The oxidation peak potentials of substituted formazans were found more anodic than that of unsubstituted formazan. The oxidation mechanism was a single step for the NO₂-substituted formazans, and two steps for COOH-substituted formazans.     

Inside polyMOFs: layered structures in polymer-based metal–organic frameworks

In this report, we explore the internal structural features of polyMOFs consisting of equal mass ratios of metal-coordinating poly(benzenedicarboxylic acid) blocks and non-coordinating poly(ethylene glycol) (PEG) blocks. The studies reveal alternating lamellae of metal-rich, crystalline regions and metal-deficient non-crystalline polymer, which span the length of hundreds of nanometers. Polymers consisting of random PEG blocks, PEG end-blocks, or non-coordinating poly(cyclooctadiene) (COD) show similar alternation of metal-rich and metal-deficient regions, indicating a universal self-assembly mechanism. A variety of techniques were employed to interrogate the internal structure of the polyMOFs, including transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and small-angle synchrotron X-ray scattering (SAXS). Independent of the copolymer architecture or composition, the internal structure of the polyMOF crystals showed similar lamellar self-assembly at single-nanometer length scales.

In this report, we explore the internal structural features of polyMOFs consisting of equal mass ratios of metal-coordinating poly(benzenedicarboxylic acid) blocks and non-coordinating poly(ethylene glycol) (PEG) blocks.