Electrochemical investigation of redox thermodynamics of immobilized myoglobin: ionic and ligation effects

In this study, we investigated redox thermodynamics of myoglobin as well as the ionic (phosphate ions) and ligation (imidazole) effects via a dynamic electrochemical approach. We employed a previously established system that features nonmediated, direct electrochemistry of myoglobin and myoglobin in an immobilized state (i.e., diffusionless electrochemistry). Thermodynamics parameters were obtained by measuring redox potential (E degrees ') of myoglobin at varied temperature (T), in the presence and in the absence of specific ions or axial ligands. As a step further, we evaluated contributions from allosteric effect and axial iron ligation by partitioning E degrees ' changes into entropic and enthalpic terms. Compensation phenomena between the entropic and enthalpic changes were observed in all these cases. On the basis of these studies, we also correlated these phenomena to possible structural variations.     

在Mo-Bi-Ce/SiO2催化剂上甲醇氧化制甲醛的Redox机理及其动力学

用外循环无梯度反应器研究了甲醇氧化制甲醛的动力学。动力学实验结果用二步骤Redox模型描述。动力学方程中的参数用线性最小二乘法估计。甲醇的反应级数m和氧的反应级数n与温度有关, m与n的和接近于1, 反应级数的变化可用Redox机理动力学解释。不同处理催化剂的XPS分析结果证实, 反应按Redox机理进行。     

Novel Pb(II), Zn(II), and Cd(II) coordination polymers constructed from ferrocenyl-substituted carboxylate and bipyridine-based ligands

Treatment of two kinds of ferrocenyl-substituted carboxylate ligands (3-ferrocenyl-2-crotonic acid, HOOC-CH=(CH(3))CFc (Fc=(eta(5)-C(5)H(5))Fe(eta(5)-C(5)H(4))) or O-ferrocecarbonyl benzoic acid, o-HOOCC(6)H(4)COFc with Pb(OAc)(2).3H(2)O, Zn(OAc)(2).2H(2)O, or Cd(OAc)(2).2H(2)O) resulted in four novel ferrocene-containing coordination polymers [[Pb(mu(2)-eta(2)-OOCCH=(CH(3))CFc)(2)].MeOH](n) (1), [[Zn(o-OOCC(6)H(4)COFc)(2)(4,4'-bipy)(H(2)O)(2)].2MeOH.2H(2)O](n) (4,4'-bipy = 4,4'-bipyridine) (2), [[Cd(o-OOCC(6)H(4)COFc)(2)(bpe)(MeOH)(2)].2H(2)O](n) (bpe = 1,2-bis(4-pyridyl)ethene) (3), and [Pb(o-OOCC(6)H(4)COFc)(eta(2)-o-OOCC(6)H(4)COFc)(bpe)](n)() (4). Their crystal structures have been characterized by single X-ray determinations. In polymer 1, Pb(II) ions are bridged by tridentate FcC(CH(3))=CHCOO(-) anions, forming an infinite chain [Pb(mu(2)-eta(2)-OOC=CH(CH(3))CFc)(2)](n). In polymers 2-4, there are three kinds of components, metal ions, o-FcCOC(6)H(4)COO(-) units, and organic bridging ligands. The bipyridine-based ligands connect metal ions leading to a one-dimensional chain with o-FcCOC(6)H(4)COO(-) units acting as monodentate or chelate ligands in the side chain. Such coordination polymers containing ferrocenyl-substituted carboxylate and bipyridine-based ligands are very rare. The solution-state differential pulse voltammetries of polymers 1-4 were determined. The results indicate that the half-wave potential of the ferrocenyl moieties is influenced by the Pb(II) ions in polymer 1 and strongly influenced by Zn(II), Cd(II), or Pb(II) ions in polymers 2-4. The thermal properties of the four polymers were also investigated.     

Cluster size effects on CO oxidation activity, adsorbate affinity, and temporal behavior of model Au(n)/TiO2 catalysts

Model catalysts were prepared by deposition of size-selected Au(n) (n = 1-7) on rutile TiO2(110), and characterized by a combination of electron spectroscopy, ion scattering, temperature-programmed desorption, and pulse-dosing mass spectrometry. CO oxidation activity was found to vary strongly with deposited cluster size, with significant activity appearing at Au3. Activity is not obviously correlated with affinity for CO, or with cluster morphology, but is strongly correlated with the clusters' ability to bind oxygen (during O2 exposure) on top of the gold. The temporal dependence of CO2 evolution in reaction of O2 pre-exposed samples with CO pulses shows an interesting cluster size dependence. For Au5 and Au6, the peak CO2 production is coincident with the peak CO flux, but for Au3, Au4, and Au7, there are significant induction periods for CO2 evolution. In addition, it is observed that some of the most active cluster sizes have the slowest CO2 evolution rates. Several mechanistic scenarios capable of accounting for the observations are laid out.     

芳基三氮烯4-位取代基对抗癌活性影响的构象分析

传统的药物设计和新药开发主要是依靠随机筛选,这种方法误差大,且需要费大量时间和经费,其结果也经常不能达到预期的设想。即使是一个国际性的大制药集团,每年平均要合成上万个化合物才能从中筛选出一个可以成为商品的新药。这种状况迫使我们去寻找一条新的打破常规的途径研究新药。近年来,随着计算机图形系统的广泛应用,对药物构效关系的研究得到了卓有成效的发展,取得了一些成功的例子。如抗菌抗癌琥珀酰-L脯氨酸就是计算化学与分子图形技术相结合的成果,目前已投放市场。     

Reverse depletion effects and the determination of ligand density on some spherical bioparticles

In cell environments crowded with macromolecules, the depletion effects act and assist in the assembly of a wide range of cellular structures, from the cytoskeleton to the chromatin loop, which are well accepted. But a recent quantum dot experiment indicated that the dimensions of the receptor–ligand complex have strong effects on the size-dependent exclusion of proteins in cell environments. In this article, a continuum elastic model is constructed to resolve the competition between the dimension of the receptor–ligand complex and depletion effects in the endocytosis of a spherical virus-like bioparticle. Our results show that the depletion effects do not always assist endocytosis of a spherical virus-like bioparticle; while the dimension of the ligand–receptor complex is larger than the size of a small bioparticle in cell environments, the depletion effects do not work and reverse effects appear. The ligand density covered on the virus can be identified quantitatively.     

The application of scanning electrochemical microscopy to the discovery of Pd–W electrocatalysts for the oxygen reduction reaction that demonstrate high activity, stability, and methanol tolerance

An array of Pd–W alloys was fabricated, and the electrocatalytic activity of the alloys for the oxygen reduction reaction (ORR) in acidic media was screened by scanning electrochemical microscopy. The Pd_0.7W_0.3 showed the highest activity for the ORR, close to that for Pd_0.8Co_0.2 and Pt. A Pd–W electrocatalyst loaded on carbon black was formed by the NaBH₄-reduction method, exhibiting high activity and stability, suggesting that it is a good candidate for the proton exchange membrane fuel cell cathode.     

Periodic solutions for second order singular damped differential equations

We study the existence of positive periodic solutions for second order singular damped differential equations by combining the analysis of the sign of Green?s functions for the linear damped equation, together with a nonlinear alternative principle of Leray–Schauder. Recent results in the literature are generalized and significantly improved.     

Determination of hydroxysafflor yellow A in biological fluids of patients with traumatic brain injury by UPLC‐ESI‐MS/MS after injection of Xuebijing

A simple, novel, specific, rapid and reproducible ultra‐performance liquid chromatography electrospray ionization tandem mass spectrometry method has been developed and validated for the determination of hydroxysafflor yellow A (HSYA) in biological fluids (plasma, urine and cerebrospinal fluid) of patients with traumatic brain injury after intravenous injection of Xuebijing (XBJ). Liquid–liquid extraction was performed, and separation was carried out on an Acquity UPLC? BEH C₁₈ column, with gradient elution using a mobile phase composed of methanol and 0.1% formic acid at a flow rate of 0.3 mL/min. A triple quadrupole tandem mass spectrometer with electrospray ionization was used for the detection of HSYA. The mass transition followed was m/z 611.0 → 491. The retention time was less than 3.0 min. The calibration curve was linear in the concentration range from 2 to 6125 ng/mL for cerebrospinal fluid, plasma and urine. The intra‐ and inter‐day precisions were <10%, and the relative standard deviation of recovery was <15% for HSYA in biological matrices. The method was successfully applied for the first time to quantify HSYA in the biological fluids (especially in cerebrospinal fluid) of patients with traumatic brain injury following intravenous administration of XBJ. Copyright © 2014 John Wiley & Sons, Ltd.