Structure and Orientation of Tetracarboxylic Acids at Oil–Water Interfaces

Fouling caused by tetracarboxylic acids in transport and separation process chains involving petroemulsions occurs when the interfacial concentration of tetraacids becomes large enough for calcium ions in the water phase to “crosslink” the adsorbed tetraacid molecules and form a precipitate. At present, the structure and orientation of tetraacid molecules at oil–water interfaces, which influences the precipitation behavior, has not been studied in detail. In this work, molecular dynamics simulations of indigenous and synthetic tetracarboxylic acid compounds are presented to describe the structure and spatial orientation of tetraacid molecules at oil–water interfaces. Molecular distributions relative to the oil–water dividing surface along with the length and orientation angle distributions of the acidic arm groups are presented. The probability distributions determined here that describe the tetraacids at an oil–water interface can be employed to reconstruct the density of carboxylic acid groups at the oil–water interface. The interfacial carboxylic acid density can be employed to determine the fraction of adsorbed tetraacid molecules that are “crosslinked” with calcium ions based on the distances between carboxylic acid groups. The simulations presented also form a basis to calculate interfacial molecular areas and virial coefficients to employ in molecular mixed monolayer adsorption isotherms.     

Assessing protein–ligand docking for the binding of organometallic compounds to proteins

Organometallic compounds are increasingly used as molecular scaffolds in drug development projects; their structural and electronic properties offering novel opportunities in protein–ligand complementarities. Interestingly, while protein–ligand dockings have long become a spearhead in computer assisted drug design, no benchmarking nor optimization have been done for their use with organometallic compounds. Pursuing our efforts to model metal mediated recognition processes, we herein present a systematic study of the capabilities of the program GOLD to predict the interactions of protein with organometallic compounds. The study focuses on inert systems for which no alteration of the first coordination sphere of the metal occurs upon binding. Several scaffolds are used as test systems with different docking schemes and scoring functions. We conclude that ChemScore is the most robust scoring function with ASP and ChemPLP providing with good results too and GoldScore slightly underperforming. This study shows that current state‐of‐the‐art protein‐ligand docking techniques are reliable for the docking of inert organometallic compounds binding to protein. © 2013 Wiley Periodicals, Inc.     

Antioxidant Serine-(NSAID) Hybrids with Anti-Inflammatory and Hypolipidemic Potency

A series of L-serine amides of antioxidant acids, such as Trolox, (E)-3-(3,5-di-tert-butyl-4-hydroxyphenyl)acrylic acid (phenolic derivative of cinnamic acid) and 3,5-di-tert-butyl-4-hydroxybenzoic acid (structurally similar to butylated hydroxytoluene), was synthesized. The hydroxy group of serine was esterified with two classical NSAIDs, ibuprofen and ketoprofen. The Trolox derivatives with ibuprofen (7) and ketoprofen (10) were the most potent inhibitors of lipid peroxidation (IC₅₀ 3.4 μΜ and 2.8 μΜ), several times more potent than the reference Trolox (IC₅₀ 25 μΜ). Most of the compounds decreased carrageenan-induced rat paw edema (37–67% at 150 μmol/kg). They were moderate inhibitors of soybean lipoxygenase, with the exception of ibuprofen derivative 8 (IC₅₀ 13 μΜ). The most active anti-inflammatory compounds exhibited a significant decrease in lipidemic indices in the plasma of Triton-induced hyperlipidemic rats, e.g., the most active compound 9 decreased triglycerides, total cholesterol and low-density lipoprotein cholesterol by 52%, 61% and 70%, respectively, at 150 μmol/kg (i.p.), similar to that of simvastatin, a well-known hypocholesterolemic drug. Since the designed compounds seem to exhibit multiple pharmacological actions, they may be of use for the development of agents against inflammatory and degenerative conditions.     

5-Phenoxy Primaquine Analogs and the Tetraoxane Hybrid as Antimalarial Agents

The rapid emergence of drug resistance to the current antimalarial agents has led to the urgent need for the discovery of new and effective compounds. In this work, a series of 5-phenoxy primaquine analogs with 8-aminoquinoline core (7a–7h) was synthesized and investigated for their antimalarial activity against Plasmodium falciparum. Most analogs showed improved blood antimalarial activity compared to the original primaquine. To further explore a drug hybrid strategy, a conjugate compound between tetraoxane and the representative 5-phenoxy-primaquine analog 7a was synthesized. In our work, the hybrid compound 12 exhibited almost a 30-fold increase in the blood antimalarial activity (IC₅₀ = 0.38 ± 0.11 μM) compared to that of primaquine, with relatively low toxicity against mammalian cells (SI = 45.61). Furthermore, we found that these 5-phenoxy primaquine analogs and the hybrid exhibit significant heme polymerization inhibition, an activity similar to that of chloroquine, which could contribute to their improved antimalarial activity. The 5-phenoxy primaquine analogs and the tetraoxane hybrid could serve as promising candidates for the further development of antimalarial agents.     

城市轨道交通运营规模与经济发展的耦合协调性分析

城市轨道交通运营规模与经济协调发展是城市轨道交通健康发展的基础.为研究城市轨道交通运营规模与经济发展的耦合协调性,采用了物理学的耦合模型对2007-2019年城市轨道交通和经济发展数据进行了实证分析,对城市轨道交通运营规模和经济发展的综合水平、耦合度、耦合协调度进行了测算.研究表明:城市轨道交通运营规模和经济发展综合水平持续上升,城市轨道交通运营规模滞后于经济发展水平;城市轨道交通运营规模与经济发展两者具有较高的耦合度;城市轨道交通运营规模—经济发展耦合协调度是逐年提高的,2016年以后城市轨道交通运营规模和经济发展进入一个较好互动影响阶段.     

考虑多元关联关系和语义变换的直觉不确定语言多属性决策方法

针对属性值为直觉不确定语言变量的多属性决策问题,提出一种不仅可以捕获属性间的多元关联关系并且能够满足决策者不同语义转换需求的多属性决策方法。首先,考虑已有运算法则缺少封闭性和灵活性,结合语言刻度函数,提出一种新的直觉不确定语言变量运算法则和排序方法。其次,根据新的运算法则,提出可以捕获属性间多元关联关系的直觉不确定语言Hamy平均及其加权形式,并对新算子的优良性质和特例进行了探讨和分析。进而,提出一种新的多属性决策方法。最后,通过算例和对比分析验证了该方法的有效性和优越性。     

规模不经济下基于一致定价和促销努力的双渠道供应链协调策略

在制造商存在规模不经济环境下,分别针对集中决策模式和分散决策模式,建立了基于一致定价和促销努力的双渠道供应链协调策略模型,分析了规模不经济和服务负溢出效应对供应链运营决策的影响,得到了集中和分散决策下各企业最优运作策略和收益。研究指出,规模不经济的双渠道供应链在分散决策批发价契约下无法实现供应链协调;而分散决策网络渠道收益共享契约能够实现双渠道总收益等于集中决策模式下供应链收益,但无法保证各主体始终获得高于批发价合同下的收益;进一步,设计了带有固定补偿的网络渠道收益共享契约,通过对固定补偿值的有效设计,不仅可以保证双渠道总收益等于集中决策模式下供应链收益,且可以始终保证各主体收益不低于分散决策批发价契约下其所得收益,从而实现各主体利益双赢以及供应链的有效协调。     

光谱辐射照度量值复现中计算大口径固定点黑体拐点温度的新方法

我国光谱辐射照度基准量值复现的理论基础是普朗克定律,它揭示了波长、温度和光谱辐射照度之间存在着精确的定量关系。采用比较法、通过卤钨灯来进行光谱辐射照度量值的保存与传递。其中,黑体的温度测量在量值复现中是最主要的不确定来源。以往都是采用变温黑体作为量值复现的辐射源,其温度通过高温计溯源至温标固定点黑体。为满足我国对地观测、气象遥感、应对气候变化、海洋水色等领域对光谱辐射照度高精度的测量需求,中国计量科学研究院NIM建立了一套14 mm大口径钨碳-碳WC-C高温固定点黑体系统,作为基准辐射源直接复现光谱辐射照度量值,进一步缩短了量值溯源链,减少了温度测量误差。实验中高温计用来测量黑体的相对温度,采用固定点熔化温坪曲线的拐点POI值校准后得到温度绝对值。因此拐点POI的合理评估计算就十分重要。与小口径WC-C固定点黑体不同,大口径固定点的熔化温坪曲线的持续时间更长,但温度起伏也更大,因此广泛用于小口径固定点的传统拐点POI算法不再适用。提出了一种可筛选多次拟合法,用于计算大口径固定点黑体的拐点温度。采用3 mm小口径WC-C和Re-C固定点对新方法的有效性进行验证,结果表明新方法与三种传统方法的平均值的最大偏差为-0.007和-0.001 K,在500 nm引入的光谱辐射照度测量误差分别为0.002 2%和0.000 3%。进一步采用14 mm大口径WC-C大口径固定点对新方法的稳健性进行验证。分析比较了筛选条件、数据平滑处理、拟合范围对拐点POI计算结果的影响,新方法和三种传统POI计算方法的最大影响量分别为0.001和0.633 K,在500 nm引入的光谱辐射照度不确定度分别为0.000 3%和0.20%。所提出的新方法能够有效减小外界因素引入的温度误差,进一步提升光谱辐射照度量值的复现准确度,更适用于大口径高温固定点黑体拐点温度的计算。     

Superhydrophobic hierarchical surfaces fabricated by anodizing of oblique angle deposited Al-Nb alloy columnar films

A combined process of oblique angle magnetron sputtering and anodizing has been developed to tailor superhydrophobic surfaces with hierarchical morphology. Isolated submicron columns of single-phase Al-Nb alloys are deposited by magnetron sputtering at several oblique deposition angles on a scalloped substrate surface, with the gaps between columns increasing with an increase in the deposition angle from 70° to 110°. Then, the columnar films have been anodized in hot phosphate-glycerol electrolyte to form a nanoporous anodic oxide layer on each column. Such surfaces with submicron-/nano-porous structure have been coated with a fluoroalkyl phosphate layer to reduce the surface energy. The porous surface before coating is superhydrophilic with a contact angle for water is less than 10°, while after coating the contact angles are larger than 150°, being superhydrophobic. The beneficial effect of dual-scale porosity to enhance the water repellency is found from the comparison of the contact angles of the submicron columnar films with and without nanoporous oxide layers. The larger submicron gaps between columns are also preferable to increase the water repellency.     

Acetylcholinesterase Sensor Based on Polyelectrolyte Complexes with DNA Inclusion for the Determination of Reversible Inhibitors

The acetylcholinesterase (AChE) biosensor has been developed for the determination of reversible inhibitors applied in the Alzheimer's disease therapy, i. e., Huperzine A (HupA) and galantamine (Gal). For this purpose, glassy carbon electrode (GCE) was first modified with carbon black (CB) and Co phthalocyanine and then polyelectrolyte complex was self‐assembled on its surface by drop casting of reactants and washing. To extend the stability and improve biosensor performance, it was proposed for the first time to use DNA as polyanion in the complex assembly. The DNA showed higher charge density than conventional polyelectrolytes and stabilized the surface coating by adsorption of higher enzyme amount and prevention of its leaching during the biosensor operation. Complex formation and the influence of structural factors were monitored with surface plasmon resonance. Kinetic study showed mixed inhibition of the enzyme within micro‐ and nanomolar range of inhibitor concentrations. The AChE biosensor showed limit of detection of HupA equal to 0.9 and that of Gal to 70 nM. The sensitivity of drug determination was found to be close or better than that of the AChE biosensors previously reported in the literature. The biosensor was tested on the sample of artificial urine and showed 102 % recovery of the drugs determination.