Biological applications of amide and amino acid containing synthetic macrocycles

ABSTRACT

Amino acid derived macrocycles with elaborate well-defined stereochemistry are a unique class of compounds that have been isolated from natural sources. Macrocycles like cyclosporine, octreotide, and valinomycin have been used in multiple applications, like drugs or ion sensors. Chemists have long been fascinated by the unique molecular recognition capabilities of these macrocycles and tried to design synthetic analogs with similar functions. This article is focused on reviewing current research on amide and amino acid containing macrocycles that have been developed in research laboratories for biological recognition, specifically for anion sensing, ion transport, carbohydrate sensing, and peptide sensing.     

A novel microwave assisted reverse micelle fabrication route for Th (IV)‐MOFs as highly efficient adsorbent nanostructures with controllable structural properties to CO and CH4 adsorption: Design,and a systematic study

Reducing gas contaminants by affordable and effective adsorbents is a major challenge in the 21^st century. In the present study, thorium metal organic framework (Th‐MOF) nanostructures are introduced as highly efficient adsorbents. These compounds were manufactured via a novel route resulting from the development of microwave assisted reverse micelle (MARM) and ultrasound assisted reverse micelle (UARM) methods. The products were characterized utilizing XRD, SEM, TGA/DSC, BET, and FT‐IR analyses. Based on the results, the samples synthesized by MARM had uniform size distribution, high thermal stability, and significant surface area. Calculations using DFT/B3LYP indicated that the compounds have a tendency to the polymeric form, which could theoretically confirm the formation of Th‐MOF. Results of analysis of variance (ANOVA) showed that synthesis parameters played a critical role in the manufacturing of products with distinctive properties. Response surface methodology (RSM) predicted the possibility of creating Th‐MOF adsorbents with the surface area of 2579 m²/g, which was a considerable value in comparison with the properties of other adsorbents. Adsorption studies showed that, in the optimum conditions, the Th‐MOF products had high adsorption capacity for CO and CH₄. It is believed that the synthesis protocol developed in the present study and the systematic studies conducted on the samples which lead to products with ideal adsorption properties.     

Solid-State NMR Spectroscopy: A Powerful Technique to Directly Study Small Gas Molecules Adsorbed in Metal–Organic Frameworks

Metal–organic frameworks (MOFs) have shown great potential in gas separation and storage, and the design of MOFs for these purposes is an on-going field of research. Solid-state nuclear magnetic resonance (SSNMR) spectroscopy is a valuable technique for characterizing these functional materials. It can provide a wide range of structural and motional insights that are complementary to and/or difficult to access with alternative methods. In this Concept article, the recent advances made in SSNMR investigations of small gas molecules (i.e., carbon dioxide, carbon monoxide, hydrogen gas and light hydrocarbons) adsorbed in MOFs are discussed. These studies demonstrate the breadth of information that can be obtained by SSNMR spectroscopy, such as the number and location of guest adsorption sites, host–guest binding strengths and guest mobility. The knowledge acquired from these experiments yields a powerful tool for progress in MOF development.     

Estimation of viscosities of 1-alkyl-3-methylimidazolium ionic liquids over a range of temperatures using a simple correlation

In this study, a new correlation is proposed for estimating 1-alkyl-3-methylimidazolium ionic liquid (IL) viscosities at different temperatures and atmospheric pressure. Since ILs are rather novel, many of their physical properties are still unavailable. Because of this limitation, the aim of this work was to propose a correlation with a new insight and approach, which requires a minimum number of physical properties as input parameters. In addition to minimal dependency on physical properties, further goals in the development of the model were generality, ease-of-use, simplicity and high accuracy. A total of 2073 literature viscosity datapoints at different temperatures for 38 different ILs were used and a correlation was developed which satisfied the above-mentioned goals. The IL viscosity models of Lazzús and Pulgar-Villarroel, and Gardas and Coutinho were compared to the proposed correlation. More reliable results were obtained by the proposed relation in comparison to literature models.     

Chemical Composition of Natural Hydrolates and Their Antimicrobial Activity on Arcobacter-Like Cells in Comparison with Other Microorganisms

Hydrolates obtained via the hydrodistillation and steam distillation of Lavandula angustifolia Mill., Syzygium aromaticum L., Foeniculum vulgare Mill., and Laurus nobilis L. were analyzed by gas chromatography with flame ionization detector (GC-FID) and gas chromatography coupled to mass spectrometry (GC-MS). Additionally, the hydrolates were evaluated for antimicrobial activity (disk-diffusion and microdilution method), influence on biofilm formation (Christensen method) and cytotoxicity of concentrated hydrolates against human cell lines (A549) by xCELLigence system. Using chemical analysis, 48, 9, 13 and 33 different components were detected in lavender, clove, fennel and laurel hydrolates, respectively. Lavender hydrolate contained the largest proportion of 1,8-cineol, linalool furanoxide, and linalool. The main components of laurel hydrolate were 1,8-cineol, 4-terpineol and α-terpineol. Fenchone and estragole were the most abundant in fennel hydrolate, and eugenol and eugenyl acetate in clove hydrolate. Concentrated hydrolates showed significant antimicrobial activity. Clove hydrolate was among the most antimicrobially active agents, most preferably against C. albicans, with an inhibition zone up to 23.5 mm. Moreover, concentrated hydrolates did not show any cytotoxic effect again8 st human A549 cells. In the presence of the non-concentrated hydrolates, significantly reduced biofilm formation was observed; however, with concentrated clove hydrolate, there was an increase in biofilm formation, e.g., of A. thereius, A. lanthieri, and A. butzleri. Research shows new findings about hydrolates that may be important in natural medicine or for preservation purposes.     

Generalization of the Kelvin equation for arbitrarily curved surfaces

Capillary condensation, which takes place in confined geometries, is the first-order vapor-to-liquid phase transition and is explained by the Kelvin equation, but the equation's applicability for arbitrarily curved surface has been long debated and is severe problem. Recently, we have proposed generic dynamic equations for moving surfaces. Application of the equations to the vapor/fluid interfaces in chemical equilibrium conditions nearly trivially solves the generalization problem for the Kelvin equation. The equations are universally true for any surfaces: atomic, molecular, micro or macro scale, real or virtual, Riemannian or pseudo-Riemannian, active or passive.     

FLTD三电极场畸变气体开关寿命特性

针对设计的一种场畸变气体开关,研究中间电极材料分别为不锈钢和黄铜条件下的烧蚀特性,结合开关寿命期间静态与触发特性的变化规律,获得决定开关寿命的关键因素,为三电极场畸变气体开关的性能优化提供理论支撑。研究结果表明,采用不锈钢和黄铜作为中间电极的烧蚀区域以及表面粗糙度均随着放电次数增加而增大,黄铜电极烧蚀较为严重且表面有明显的烧蚀圆斑,不锈钢电极则具有更高的表面粗糙度,阴阳极表面烧蚀存在明显差异,随着放电次数的增加,击穿点向电极边缘区域集中,影响开关的沿面绝缘特性,是导致开关寿命终结的主要原因。     

Solutions with concentration for conservation laws with discontinuous flux and its applications to numerical schemes for hyperbolic systems

Measure-valued weak solutions for conservation laws with discontinuous flux are proposed and explicit formulae have been derived. We propose convergent discontinuous flux-based numerical schemes for the class of hyperbolic systems that admit nonclassical -shocks, by extending the theory of discontinuous flux for nonlinear conservation laws to scalar transport equation with a discontinuous coefficient. The article also discusses the concentration phenomenon of solutions along the line of discontinuity, for scalar transport equations with a discontinuous coefficient. The existence of the solutions for transport equation is shown using the vanishing viscosity approach and the asymptotic behavior of the solutions is also established. The performance of the numerical schemes for both scalar conservation laws and systems to capture the -shocks effectively is displayed through various numerical experiments.     

气相色谱–质谱法快速分析化妆品中3种香精香料

建立气相色谱-质谱法快速测定化妆品中甲基柏木酮、甲基柏木醚、壬酸3种香精香料的方法。样品用甲醇超声提取,经高速冷冻离心,上清液干燥脱水后经0.45 μm滤膜过滤,直接注入气相色谱-质谱仪进行测定,用选择离子和保留时间定性,外标法定量。甲基柏木酮、甲基柏木醚、壬酸在各自的质量浓度范围内与色谱峰面积成良好的线性关系,相关系数分别为0.9992,0.9991,0.9994,检出限分别为0.05,0.1,0.1 mg/kg。测定结果的相对标准偏差为2.1%~6.6%(n=5),样品加标回收率为91.5%~97.7%。该方法准确度和灵敏度高,样品用量少,前处理简单,可同时测定化妆品中3种香精香料。     

Correlating conductivity and Seebeck coefficient to doping within crystalline and amorphous domains in poly(3-(methoxyethoxyethoxy)thiophene)

Molecular doping of conjugated polymers (CPs) plays a vital role in optimizing organic electronic and energy applications. For the case of organic thermoelectrics, it is commonly believed that doping CPs with a strong dopant could result in higher conductivity (σ) and thus better power factor (PF). Herein, by investigating thermoelectric performance of a polar side-chain bearing CP, poly(3-(methoxyethoxyethoxy)thiophene) (P3MEET), vapor doped with fluorinated-derivative of tetracyanoquinodimethane FnTCNQ (n = 1, 2, 4), we show that using strong dopants can in fact have detrimental effects on the thermoelectric performance of CPs. Despite possessing higher electron affinity, doping P3MEET with F4TCNQ only results in a σ (27.0 S/cm) comparable to samples doped with other two weaker dopants F2TCNQ and F1TCNQ (26.4 and 20.1 S/cm). Interestingly, F4TCNQ-doped samples display a marked reduction in the Seebeck coefficient (α) compared to F1TCNQ- and F2TCNQ-doped samples from 42 to 13 μV/K, leading to an undesirable suppression of the PF. Structural characterizations coupled with Kang-Snyder modeling of the α–σ relation show that the reduction of α in F4TCNQ-doped P3MEET samples originates from the generation of low mobility carrier within P3MEET's amorphous domain. Our results demonstrate that factors such as dopant distribution and doping efficiency within the crystalline and amorphous domains of CPs should play a crucial role in advancing rational design for organic thermoelectrics.