Viscosity reduction of isotonic solutions of the photosensitizer TPCS2a by cyclodextrin complexation

Meso-tetraphenyl chlorin disulphonate (TPCS_2a) is a photosensitizer (PS) particularly developed and patented for use in the technology of photochemical internalization (PCI) against cancer. TPCS_2a is known to aggregate in aqueous media even at low concentrations (≥0.1?µM) and to form a high-viscosity network at clinically relevant concentrations (mM). The aim of this work was to evaluate the effect of two hydroxypropylated cyclodextrin derivatives of beta and gamma type, respectively i.e. HPβCD and HPγCD, on the aggregation and solubilization of TPCS_2a in isotonic solutions. Samples containing micromolar concentrations of TPCS_2a were studied spectrophotometrically, while samples containing a clinical relevant concentration (10?mM?=?9?mg/ml) of TPCS_2a were evaluated by dynamic viscosity measurements. HPβCD was determined to be a more suitable solubilizer of TPCS_2a than HPγCD in aqueous media both in the absence and presence of salt. The complexation stoichiometry between TPCS_2a/HPβCD at micromolar to millimolar concentrations of TPCS_2a was determined to be 1:3 and 1:2 in the absence and presence of isotonic NaCl, respectively. The network of TPCS_2a (10?mM) was broken down in the presence of 3% w/v (=?20?mM) HPβCD, i.e. a 1:2 molar ratio between TPCS_2a and the cyclodextrin. Formation of the inclusion complex resulted in low viscosity samples both in water and in the presence of isotonic NaCl or phosphate buffered saline (PBS) at 25?°C and 37?°C.     

复杂应力区段煤柱合理留设宽度仿真研究

针对南关煤矿3205运输巷道工作面掘进与支护困难、巷道变形严重且维修频繁的现状,为破解复杂应力情况下煤柱合理留设宽度这一关键性问题,借助FLAC 3D软件进行了应力场与位移场仿真分析。研究结果表明:显著的水平应力场、邻近的采动应力场与劣化的围岩稳定性三重因素的综合作用是制约3205运输巷正常掘进作业的瓶颈。在不同煤柱宽度方案比选过程中,窄煤柱在应对较强水平应力与剪切应力作用时处于劣势。煤柱宽度越大,采动应力场对煤柱及工作面的影响越小,采掘活动更为安全。经过方案比选,最终确立留设煤柱在复杂应力区段的合理宽度为30 m。     

超深层挡水放空洞复杂体型高速水流水力特性数值模拟

针对某水电站超深层挡水放空洞复杂体型,利用3D紊流数值模拟方法,采用VOF方法追踪自由水面,对泄流能力、沿程水面线、流速、压强等水力特性进行了数值模拟分析。结果表明,该放空洞结构泄流能力满足设计要求,设计体型基本合理,有压洞转弯段出现严重的偏流,需对该段体型进行优化;弧形闸室后部两侧突扩结构最小负压0.1MPa,结构易发生空化空蚀,建议减小突扩结构尺寸,延长侧墙长度,尽量减小侧墙坡度;消能工段出口底板部位最小负压为0.1MPa,建议取消挑坎末端水平段,使水流直接挑出。     

基于宽频复电阻率的含黏土沉积物中水合物饱和度计算方法

天然气水合物沉积物中的黏土成分显著影响沉积物的电学特性以及水合物饱和度的计算模型。以自主设计开发的复电阻率参数测量装置为实验平台,在20 Hz ~ 100 kHz频率范围内测试了黏土条件下含水合物海沙体系的复电阻率,分析了复电阻率的频散特性、黏土影响以及主导的电极化机制,利用泥质修正Archie公式建立了基于宽频复电阻率的水合物饱和度计算模型。研究结果表明：（1）含水合物海沙体系的复电阻率呈现出显著的频散特性,双电层极化和界面极化分别是20 Hz ~ 1 kHz和1 ~ 100 kHz频段主导的极化机制;（2）黏土颗粒表面的双电层发生形变增强了含水合物沉积物双电层极化作用,提高了复电阻率相角和虚部的绝对值;（3）在20 Hz ~ 100 kHz频率范围内泥质修正Archie公式岩性系数较为稳定,而胶结指数和饱和度指数与测试频率之间的关系在20 Hz ~ 1 kHz和1 ~ 100 kHz频段差异显著,因此应分频段建立水合物饱和度计算模型。本研究为探讨含水合物沉积物的低频电学特性和建立含黏土沉积物中水合物饱和度计算模型提供了新的途径。     

Grain boundary engineering that induces ultrahigh permittivity and decreased dielectric loss in CdCu3Ti4O12 ceramics

Dielectric materials with ultrahigh permittivity are attracting attention due to the increasing demand for these types of materials for microelectronics and energy storage applications. In this work, we successfully synthesized Zn-doped CdCu₃Ti₄O₁₂ (CdCTO) ceramics with low dielectric loss and large permittivity via an ordinary mixed-oxide technique. Remarkably, at a Zn doping level of 0.10, a CdCu_2.9Zn_0.1Ti₄O₁₂ ceramic exhibited both decreased dielectric loss tangent of ~0.058 and large dielectric permittivity > 4.0 × 10⁴, as well as a good frequency stability over a wide frequency range from 40 Hz to 10⁶ Hz. The high dielectric performance was attributed to the enhanced grain boundary resistance and internal barrier layer capacitor (IBLC) effect due to the fine and uniform grains that formed upon Zn doping. The findings reported in this work provide valuable insights into how to simultaneously realize a low dielectric loss and high permittivity in CdCTO and other related dielectric ceramics.     

A chromium complex under water oxidation: A conversion mechanism and a comprehensive hypothesis

Water splitting toward hydrogen production is a promising method to store energy, but water oxidation is a bottleneck for water splitting. First-row transition metal complexes have been extensively used for water-oxidation reaction. However, only one chromium complex has been applied for water-oxidation reaction until now. Thus, the reinvestigation of water-oxidation reaction by this chromium complex in detail is interesting. Herein, water-oxidation reaction by the chromium complex with diphenoxy N,N′-ethylenebis(salicylimine) (SALEN) ligand is reinvestigated using scanning electron microscopy, energy dispersive spectrometry, X-ray diffraction studies, X-ray photoelectron spectroscopy, thermal gravimetric analysis, elemental analysis, Fourier-transform infrared spectroscopy, and electrochemical methods. All the experiments showed that the chromium complex is neither a catalyst nor a precatalyst for water-oxidation reaction. During OER, a relationship between first-row transition metal complexes and the related metal oxides has been proposed.     

A dinuclear iron complex as a precatalyst for water oxidation under alkaline conditions

Water oxidation is a key reaction for water splitting. The decomposition of Fe-based-molecular structures toward Fe-based oxides is a promising method for oxygen-evolution reaction (OER) through water oxidation. The decomposition of Fe-based-molecular structures method results in a slow decomposition of precatalysts and forms Fe oxide-based catalysts. In this study, the Fe species formed through the decomposition of a dinuclear Fe(III) complex under OER is investigated by X-ray photoelectron spectroscopy, scanning electron microscopy, energy dispersive spectrometry, X-ray diffraction, and the electrochemical method. In addition, using Ni(OH)₂, a new approach is reported for detecting trace Fe species on the electrode surface. The resulting Fe oxide-based catalyst shows a catalytic current with an onset of 621 mV overpotential and the Tafel slope of 113.7 mV/decade at pH 11 in a buffer phosphate.     

复杂系统的设计认知和创新

目的研究复杂系统设计过程中设计师的设计认知和设计创新行为。方法通过国内外相关文献的研究和分析,总结归纳复杂系统设计问题界定和解决方案构思的认知过程、复杂系统创新设计构思的生成机制、复杂系统的创新设计策略,分析复杂系统设计认知和创新研究领域将发生的变革和未来发展的趋势。结论系统探讨了复杂系统设计认知与创新过程中的设计问题界定和解决方案构思的联合演化机制、给定和自发性解决方案示例,给设计师带来的认知固化和类比推理创新启发作用、结构化和机会主义的创新设计策略,发现当下的复杂系统创新设计理论和实践研究,还需要进一步开展跨学科知识融合激励的复杂系统创新设计研究,与此同时,加强关于设计师主观认知不确定性的定量建模研究,从而更好、更有针对性地探究复杂系统创新设计中认知过程的自然本质。     

Encapsulation of Synthesized Plant Growth Regulator Based on Copper(II) Complex in Chitosan/Alginate Microcapsules

A new copper complex, trans-diaqua-trans-bis [1-hydroxy-1,2-di (methoxycarbonyl) ethenato] copper (abbreviation Cu(II) complex), was synthesized and its plant growth regulation properties were investigated. The results show a sharp dependence of growth regulation activity of the Cu(II) complex on the type of culture and its concentration. New plant growth regulator accelerated the development of the corn root system (the increase in both length and weight) but showed a smaller effect on the development of the wheat and barley root systems. Stimulation of corn growth decreased with increasing Cu(II) complex concentration from 0.0001% to 0.01% (inhibition at high concentrations—0.01%). The development of corn stems was also accelerated but to a lesser extent. Chitosan-coated calcium alginate microcapsules suitable for delivery of Cu(II) complex to plants were prepared and characterized. Analysis of the FTIR spectrum showed that complex molecular interactions between functional groups of microcapsule constituents include mainly electrostatic interactions and hydrogen bonds. Microcapsules surface exhibits a soft granular surface structure with substructures consisting of abundant smaller particles with reduced surface roughness. Release profile analysis showed Fickian diffusion is the rate-controlling mechanism of Cu(II) complex releasing. The obtained results give new insights into the complexity of the interaction between the Cu(II) complex and microcapsule formulation constituents, which can be of great help in accelerating product development for the application in agriculture     

Synthesis of Janus polyaniline–polyelectrolyte complex membrane via in situ confined polymerization

Polyelectrolyte complex (PEC) membranes prepared from poly(styrene sulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC) were modified by crossflow polymerization of aniline (ANI). The PEC membranes were used as separators in a two-compartment setup where ANI monomer and ammonium persulfate (APS) oxidant diffused through the membranes to form polyaniline (PANI). APS and ANI having different distributions throughout the membranes, the reaction led to the asymmetric polymerization of PANI on one face of each PEC membrane thus producing Janus membranes. Due to the excess PANI content, the membrane displayed distinct asymmetric electrical conductivities on each face. Interestingly, very different ANI polymerizations were obtained when nonstoichiometric PEC membranes having different molar ratio of cationic and anionic polyelectrolytes (P⁺:P^? represents PDADMAC:PSS) were used and transport of APS was fastest through the 2:1 PEC when compared to the 1:2 PEC. In all experiments, the polymerization was most intense on the ANI side of the membranes. Also, the influence of NaCl both during PEC fabrication and during polymerization was studied and found to have some effect on the solute permeability. Results showed that a higher content of PANI was formed on PEC membranes having excess P⁺ and with no NaCl added during PEC fabrication. Although X-ray diffraction confirmed the presence of PANI on both sides of each membrane, scanning electron microscopy images demonstrated that both sides of each membrane had different PANI content deposited. Electrical conductivity measurements using a four-point probe setup also showed that the PEC–PANI exhibits asymmetric electrical property on different sides. © 2021 Society of Industrial Chemistry.