Synthesis of μ2-Oxo-Bridged Iron(III) Tetraphenylporphyrin–Spacer–Nitroxide Dimers and their Structural and Dynamics Characterization by using EPR and MD Simulations

Iron(III) porphyrins have the propensity to form μ₂-oxo-dimers, the structures of which resemble two wheels on an axle. Whereas their crystal structure is known, their solution structure and internal dynamics is not. In the present work, the structure and dynamics of such dimers were studied by means of electron paramagnetic resonance (EPR) spectroscopy and quantum chemistry based molecular dynamics (MD) simulations by using the semiempirical tight-binding method (GFN-xTB). To enable EPR investigation of the dimers, a nitroxide was attached to each of the tetraphenylporphyrin cores through a linear and a bent linker. The inter-nitroxide distance distributions within the dimers were determined by continuous-wave (cw)-EPR and pulsed electron–electron double resonance (PELDOR or DEER) experiments and, with the help of MD, interpreted in terms of the rotation of the porphyrin planes with respect to each other around the Fe–O–Fe axis. It was found that such rotation is restricted to the four registers defined by the phenyl substituents. Within the registers, the rotation angle swings between 30° and 60° in the proximal and between 125° and 145° in the distal register. With EPR, all four angles were found to be equally populated, whereas the 30° and 145° angles are strongly favored to the expense of the 60° and 125° angles in the MD simulation. In either case, the internal dynamics of these dimers thus resemble the motion of a step motor.     

污泥基吸附剂对亚甲基蓝和环丙沙星的吸附性能研究

亚甲基蓝和环丙沙星是水体中2种污染物, 对生态环境有潜在危害. 本文以市政剩余活性污泥为原料, 氯化锌为活化剂热解制备污泥基吸附剂, 研究盐酸酸洗浓度、氯化锌浓度、热解温度、热解时间等对污泥基吸附剂吸附水中亚甲基蓝和环丙沙星性能的影响. 结果表明 (1)污泥基吸附剂对亚甲基蓝的吸附性能随盐酸酸洗浓度的增大而增加, 对环丙沙星的吸附性能则随盐酸酸洗浓度的增大呈先降后增趋势, 两者均在1.500mol·L-1盐酸浓度下取得最优值. (2)污泥基吸附剂对亚甲基蓝和环丙沙星的吸附性能随氯化锌浓度和热解温度的增加呈先升后降趋势, 在氯化锌浓度为4.0mol·L-1、热解温度为500℃时有最优值; 随着热解时间的延长, 污泥基吸附剂对亚甲基蓝和环丙沙星的吸附性能分别在500℃热解70min和80min时有最优值. (3)污泥基吸附剂的最佳制备条件为 氯化锌4.0mol·L-1活化2h、500℃热解70min和80min、1.500mol·L-1盐酸酸洗; 以此制得的污泥基吸附剂对亚甲基蓝和环丙沙星的去除率分别为97.7%和96.4%, 平衡吸附量分别为97.9mg·g-1和3.9mg·g-1, 且污泥基吸附剂对亚甲基蓝和环丙沙星的吸附过程均符合准二级动力学方程.     

Photoinduced dynamics of a cyanine dye: parallel pathways of non-radiative deactivation involving multiple excited-state twisted transients

Cyanine dyes are broadly used for fluorescence imaging and other photonic applications. 3,3′-Diethylthiacyanine (THIA) is a cyanine dye composed of two identical aromatic heterocyclic moieties linked with a single methine, –CH. The torsional degrees of freedom around the methine bonds provide routes for non-radiative decay, responsible for the inherently low fluorescence quantum yields. Using transient absorption spectroscopy, we determined that upon photoexcitation, the excited state relaxes along two parallel pathways producing three excited-state transients that undergo internal conversion to the ground state. The media viscosity impedes the molecular modes of ring rotation and preferentially affects one of the pathways of non-radiative decay, exerting a dominant effect on the emission properties of THIA. Concurrently, the polarity affects the energy of the transients involved in the decay pathways and further modulates the kinetics of non-radiative deactivation.     

Chemical equilibrium controlled synthesis of polyoxymethylene dimethyl ethers over sulfated titania

The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers(DMMn) were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.     

Xe对NO(X)微分截面和非弹性散射中的碰撞诱导旋转准直

本文对NO(X)-Xe碰撞系统在碰撞能量为519 cm^-1，测量了完全?-双峰分解的微分截面和碰撞引起的旋转准直力矩. 同时结合初始量子态选择，使用六极杆的非均质电场，借助量子态分辨的测量，利用(1+1'')共振增强的多光子电离和速度离子成像. 结果显示，微分截面以及偏振相关的微分截面均显示与从头算势能面上进行的量子力学散射计算[J. K?os etal. J. Chem. Phys. 137, 014312 (2012)]一致. 通过与准经典轨迹、硬壳势能的量子力学散射以及运动近端模型的比较，评估了势能对所测微分截面和碰撞引起的旋转准直力矩的影响.     

Influence of acid treatment on structure of clinoptilolite tuff and its adsorption of methane

This study presents the results of the methane adsorption properties of clinoptilolite tuff from Bigadic, Turkey and that of acid treated forms at 273 and 293 K up to 100 kPa using volumetric apparatus. In order to assess changes in structural and gas adsorption properties of clinoptilolite, zeolite sample was treated with acid solutions of varying concentrations (0.1, 0.5, 1.0 and 2.0 M) at 70 °C during 3 h. Structural and thermal characterization of natural and acid treated clinoptilolite samples were carried out using a combination of techniques such as X-ray diffraction, X-ray fluorescence, thermogravimetric, differential thermal analysis and nitrogen adsorption methods. At both temperatures, uptake of methane (CH₄) increased in the following order: CLN < CLN-H2 < CLN-H1 < CLN-H05 < CLN-H01. CH₄ adsorption capacities of the original and acid treated clinoptilolites were found in the range of 0.476–0.910 mmol/g and 0.398–0.691 mmol/g at 273 and 293 K, respectively.     

Paper conservation methods: a literature review

The main paper conservation methods are presented, classified in the following categories: preparation of the intervention, disinfestation and disinfection/sterilization, surface/dry cleaning, wet cleaning, chemical stabilization, paper repairs, consolidation and strengthening. Treatment documentation is also discussed. The targets, the historical aspects, the general principles, the materials and equipment, the acceptance and criticism pertaining to each method are briefly reviewed, and the most important research for their evaluation is presented. Several paper stabilization strategies, such as deacidification and iron gall ink stabilization, applicable to paper are elucidated. Specific consolidation and strengthening methods for paper, such as lamination and paper splitting are also discussed. The review mainly focuses on the established methods, but experimental, abandoned or insufficiently documented methods are also included. Shortcomings and limitations of several methods were found in the literature, concerning health issues, limited effectiveness, adverse side-effects on the treated artefacts and restricted applicability.     

Ambazone salt with p-aminobenzoic acid

In this study, we obtained a novel salt of ambazone (AMB) with p-aminobenzoic acid (PABA) that exhibits improved solubility and antibacterial activity. The salt was produced by solvent-drop grinding and characterized by powder X-ray diffraction, thermal analysis and Fourier transform infrared spectroscopy. The salt nature of the new form was confirmed by infrared spectroscopy based on the characteristic vibrational band of the protonated amino group. Based on the X-ray powder diffraction data, the compound crystallizes in the triclinic P_-1 space group with the following unit cell parameters: a = 14.294 Å, b = 9.162 Å, c = 8.777 Å, α = 95.90°, β = 100.63°, γ = 91.73°. Thermal analysis reveals the thermal events and different decomposition steps of this solid form as compared to the starting compounds. Powder dissolution measurements showed solubility improvement compared with pure ambazone of 2 and 3.3 times in water and phosphate buffer, respectively. Antibacterial tests showed higher activity of the salt to Gram-negative Escherichia coli and Salmonella bacteria as compared to AMB and PABA. The study demonstrates that the pharmaceutical salt of ambazone with p-aminobenzoic acid (AMB–PABA) can be a possible alternative to ambazone in the treatment of infections with Gram-negative bacteria.     

EPR‐Based Approach for the Localization of Paramagnetic Metal Ions in Biomolecules

Metal ions play an important role in the catalysis and folding of proteins and oligonucleotides. Their localization within the three‐dimensional fold of such biomolecules is therefore an important goal in understanding structure–function relationships. A trilateration approach for the localization of metal ions by means of long‐range distance measurements based on electron paramagnetic resonance (EPR) is introduced. The approach is tested on the Cu²⁺ center of azurin, and factors affecting the precision of the method are discussed.