氮氧自由基研究XVII:水溶液中哌啶氮氧自由基的电化学行为和自衰变动力学研究

循环伏安法研究表明,2,2,6,6-四甲基-4-羟基哌啶-1-氧自由基和2,2,6,6-四甲基-4-氧哌啶-1-氧自由基,在水溶液中的单电子氧化电极反应的可逆性随介质酸性,扫描速度和自由基浓度增加而增加,表明电极氧化产物可进一步发生化学反应.     

Transport in amorphous solid water films: implications for self-diffusivity

Thermal desorption spectroscopy is employed to examine transport mechanisms in structured, nanoscale films consisting of labeled amorphous solid water (ASW, H(2)(18)O, H(2)(16)O) and organic spacer layers (CCl(4), CHCl(3)) prior to ASW crystallization (T approximately 150-160 K). Self-transport is studied as a function of both the ASW layer and the organic spacer layer film thickness, and the effectiveness of these spacer layers as a bulk diffusion "barrier" is also investigated. Isothermal desorption measurements of structured films are combined with gas uptake measurements (CClF(2)H) to investigate water self-transport and changes in ASW film morphology during crystallization and annealing. CCl(4) desorption is employed as a means to investigate the effects of ASW film thickness and heating schedule on vapor-phase transport. Combined, these results demonstrate that the interlayer mixing observed near T approximately 150-160 K is inconsistent with a mechanism involving diffusion through a dense phase; rather, we propose that intermixing occurs via vapor-phase transport through an interconnected network of cracks/fractures created within the ASW film during crystallization. Consequently, the self-diffusivity of ASW prior to crystallization (T approximately 150-160 K) is significantly smaller than that expected for a "fragile" liquid, indicating that water undergoes either a glass transition or a fragile-to-strong transition at a temperature above 160 K.     

基于金属卟啉的甲基磷酸二甲酯分子印迹聚合物微球的合成及性能

合成了分别以5-(4-甲基丙烯酰氧苯基)-10,15,20-三苯基锌卟啉(ZnMOTPP)和5-(4-甲基丙烯酰氧苯基)-10,15,20-三苯基钆卟啉(GdMOTPP)为功能单体, 甲基丙烯酸(MAA)为辅助功能单体的甲基磷酸二甲酯(DMMP)分子印迹聚合物微球. 扫描电子显微镜(SEM)表征结果表明, 微球平均粒径为50～100 μm, 粒度均匀. 与甲基丙烯酸作为功能单体的分子印迹聚合物微球的吸附性能和特异性进行对比发现, ZnMOTPP分子印迹微球的吸附性能优于 GdMOTPP分子印迹微球, 金属卟啉分子印迹微球的吸附性能优于仅以甲基丙烯酸作为功能单体的分子印迹微球, 并且微球对其印迹分子DMMP具有特异性吸附. Scatchard分析表明, DMMP分子印迹空穴中只存在一类结合位点, MIPMs-Zn+MAA的最大吸附量Q_max=148 μmol/g, MIPMs-Gd+MAA的Q_max=78.9 μmol/g, MIPMs-MAA的Q_max=13.57 μmol/g.     

On the free vibration response of rectangular plates,partially supported on elastic foundation

Rectangular plates on distributed elastic foundations are widely employed in footings and raft foundations of variety of structures. In particular, mounted columns and single footings may partially occupy the rectangular plate of any kind.     

The properties of the new Mn(II)–Co(II)–Mn(II)-type hetero-trinuclear oxime metal complexes with N4 and N4O2 ligands

1,3- and 1,2-calix[4]crown-7 and calix[4]crown-9 cone conformers were synthesized in acceptable yields by sequential introduction of two distal or proximal polyethylene glycolic chains with terminal hydroxyls at the lower rim, monotosylation, and intramolecular ring closure reaction. According to the two-phase extraction experiment, the title compounds showed mediocre affinity for alkali and alkaline earth metal picrates. The 1,2-calix[4]crown-9 extracted Sr²⁺ selectively among other alkaline earth metal cations.     

离子色谱法测定蓝藻培养液中有机酸和无机阴离子

建立了一种利用阴离子交换色谱柱分离,电导检测器同时测定17种有机酸和7种阴离子的方法。采用Ionpac AS11-HC阴离子交换柱,KOH溶液作为淋洗液,梯度洗脱,流量为1.0mL/min,柱温为30℃,进样体积为25μL。24种分析物测定结果的相对标准偏差在0.31%~2.67%之间,线性相关系数均大于0.996,平均加标回收率在80.3%~108.5%之间。该方法可用于微生物培养液中有机酸和阴离子的同时测定。     

Performance studies of energy consumption for single and multiple nozzle systems under impinging air jets

Impinging air jets of various shapes, sizes and configurations are commonly used in heating, cooling and drying industrial processes. An analytical study has been carried out to optimise the thermal performance of single and multiple nozzle systems using impinging air jets. The optimisation of the nozzle array was given for practical purposes. The results show that within practical limits, a narrower nozzle size results in a greater heat and mass transfer coefficient. An economical analysis of the drying processes is also given for slot nozzles.     

CO2 Injection into Saline Carbonate Aquifer Formations II: Comparison of Numerical Simulations to Experiments

Sequestration of carbon dioxide in geological formations is an alternative way of managing extra carbon. Although there are a number of mathematical modeling studies related to this subject, experimental studies are limited and most studies focus on injection into sandstone reservoirs as opposed to carbonate ones. This study describes a fully coupled geochemical compositional equation-of-state compositional simulator (STARS) for the simulation of CO₂ storage in saline aquifers. STARS models physical phenomena including (1) thermodynamics of sub- and supercritical CO₂, and PVT properties of mixtures of CO₂ with other fluids, including (saline) water; (2) fluid mechanics of single and multiphase flow when CO₂ is injected into aquifers; (3) coupled hydrochemical effects due to interactions between CO₂, reservoir fluids, and primary mineral assemblages; and (4) coupled hydromechanical effects, such as porosity and permeability change due to the aforementioned blocking of pores by carbonate particles and increased fluid pressures from CO₂ injection. Matching computerized tomography monitored laboratory experiments showed the uses of the simulation model. In the simulations dissolution and deposition of calcite as well as adsorption of CO₂ that showed the migration of CO₂ and the dissociation of CO₂ into HCO₃ and its subsequent conversion into carbonate minerals were considered. It was observed that solubility and hydrodynamic storage of CO₂ is larger compared to mineral trapping.     

Time-Dependent Shape Factors for Uniform and Non-Uniform Pressure Boundary Conditions

Matrix–fracture transfer functions are the backbone of any dual-porosity or dual-permeability formulation. The chief feature within them is the accurate definition of shape factors. To date, there is no completely accepted formulation of a matrix–fracture transfer function. Many formulations of shape factors for instantly-filled fractures with uniform pressure distribution have been presented and used; however, they differ by up to five times in magnitude. Based on a recently presented transfer function, time-dependent shape factors for water imbibing from fracture to matrix under pressure driven flow are proposed. Also new matrix–fracture transfer pressure-based shape factors for instantly-filled fractures with non-uniform pressure distribution are presented in this article. These are the boundary conditions for a case for porous media with clusters of parallel and disconnected fractures, for instance. These new pressure-based shape factors were obtained by solving the pressure diffusivity equation for a single phase using non-uniform boundary conditions. This leads to time-dependent shape factors because of the transient part of the solution for pressure. However, approximating the solution with an exponential function, one obtains constant shape factors that can be easily implemented in current dual-porosity reservoir simulators. The approximate shape factors provide good results for systems where the transient behavior of pressure is short (a case commonly encountered in fractured reservoirs).