Volatile surfactants: Characterization and areas of application

Amphiphilic aroma molecules, representatives of fragrance molecules, are introduced as dynamic volatile surfactants. Surface tension of their aqueous solutions proves to be a sensitive and revealing quantity, used for assessment of the adsorption-evaporation behavior both under equilibrium conditions and in regimes of no instantaneous equilibrium. Such volatile amphiphiles are characterized by fast adsorption from bulk solution at an air-water interface, on a timescale of tens of microseconds, and exhibit synergetic effect in mixtures with conventional micellar-forming surfactants. Their ability to evaporate from the interface on a time scale of minutes suggests their applications as “temporal” dynamic cosurfactants in technologies involving fast formation of new surfaces. Current challenges concern evaluation of specific material parameters of volatile aroma surfactants in order to enable their selection for targeted applications.     

Beyond green with synthetic chlorophylls – Connecting structural features with spectral properties

The distinct features of chlorophylls in photosynthesis have led to the formation of numerous derivatives for applications encompassing solar energy conversion, molecular photonics, photodynamic therapy, and molecular imaging. Synthetic chlorins created de novo and bearing a geminal dimethyl group in the reduced ring have proved invaluable for fundamental studies. Four decades of research have led to accumulation of tabulated spectra for > 400 such synthetic chlorins with distinct structural frameworks (17-oxochlorins, 13¹-oxophorbines, chlorinimides) and substituents (alkyl, aryl, ethynyl, phenylethynyl, acetyl, formyl) located at specific (meso, β) positions. In this review, spectral traces (324 absorption, 247 fluorescence) are assembled along with photophysical data including the molar absorption coefficient (ε), fluorescence quantum yield (Φ_f) and singlet excited-state lifetime (τ_s). The review uses the accumulated spectral data derived from chlorins all containing a uniform molecular scaffold to (1) highlight the effects of molecular structure on spectral features, and (2) identify trends including how ε, Φ_f and τ_s vary with wavelength and other features. Use of a common geminal-dimethyl-substituted chlorin scaffold – beginning with no substituents, to one substituent at designated sites, and to 2 or more substituents – provides a systematic Aufbau approach for understanding the absorption spectra of chlorins on a path to and beyond the native chlorophylls. The review provides insights concerning the rational design of potent analogues of Nature’s preeminent red-region absorbers for potential utilization in diverse applications and is aimed at multiple audiences: those interested in spectral properties, tetrapyrrole photophysics, and the molecular design of new chromophores.     

A novel UPLC–MS/MS method for simultaneous quantification of trigonelline, 4-hydroxyisoleucine,and diosgenin from Trigonella foenum-graecum extract: Application to pharmacokinetic study in healthy and type 2 diabetic rats

Trigonelline (TR), 4-hydroxyisoleucine (4-HI), and diosgenin (DG) are the main bioactives of the purified standardized extract of the popular plant Trigonella foenum-graecum L. (TFG), and it has been proven effective for the treatment of various diseases. However, to the best of our knowledge, no study has investigated the pharmacokinetic parameters of purified standardized T. foenum-graecum extract in normal and diabetic Wistar rats. The present study has developed and validated a rapid, reliable, and sensitive simultaneous ultra-performance liquid chromatography MS method to estimate these bioactives. The chromatographic separation was achieved using methanol, acetonitrile, and 0.1% formic acid with the ideal gradient flow system on a BEH Shield RP 18 column. A positive electrospray ionization mode was selected to estimate m/z values of TR (138.14 > 94.63), 4-HI (148.19 > 74.08), and DG (415.54 > 271.33). The method was robust and reproducible over the linearity range of 60–5000, 6–5000, and 15–5000 ng/mL for TR, 4-HI, and DG, respectively. Using this novel validated method, we investigated the pharmacokinetic parameters of bioactives using Phoenix WinNonlin version 8.0 (Certera) in normal and diabetic rats. The assay was successfully applied for the estimation of pharmacokinetic parameters using noncompartmental analysis. This investigation shows that the absorption rate increased, whereas distribution and elimination processes slowed down in diabetic rats compared with normal rats.     

Graphene Nanocomposites Based Electrochemical Sensing Platform for Simultaneous Detection of Multi-drugs

Three reduced graphene oxide nanocomposites were employed to achieve the simultaneous electrochemical determination of multi-drugs including acetaminophen (ACTM), carbendazim (CB) and ciprofloxacin (CFX). All nanocomposite modified electrodes showed improved current responses for three drugs. Notably cauliflower-like platinum nanoparticles decorated reduced graphene oxide modified electrode (or Pt−RGO/GCE) exhibited the best performance in terms of electrochemical stability. Using Pt−RGO/GCE, the linear detect ranges of 30–120 μM, 25–115 μM and 10–25 μM, and detection limit values of 3.49, 2.96, and 1.53 μM were achieved for ACTM, CB and CFX respectively. The electrode was further used for the successful determination of above drugs in tap and river water using differential pulse voltammetry. From the obtained results, we believe that Pt-RGO/GCE is highly promising for the fabrication of robust electrochemical sensors for simultaneously determining ACTM, CB and CFX or similar types of drugs in the future.     

Diffusiophoresis in suspensions of highly charged soft particles

Diffusiophoresis phenomenon of aoft particles suspended in binary electrolyte solutions is explored theoretically in this study based on the spherical cell model, focusing on the chemiphoresis component in absence of diffusion potential. Both the electrostatic and hydrodynamic aspects of the boundary confinement, or steric effect, due to the presence of neighboring particles are examined extensively under various electrokinetic conditions. Significant local extrema are found in mobility profiles expressed as functions of the Debye length in general, synchronized with the strength of the motion-inducing double layer polarization. Moreover, a seemingly peculiar phenomenon is observed that the soft particles may move faster in more concentrated suspensions. The competition between the simultaneous enhancement of the motion-inducing electric driving force and the motion-retarding hydrodynamic drag force from the boundary confinement effect of the neighboring particles is found to be responsible for it. The above findings are also demonstrated experimentally in a very recent study on the diffusiophoretic motion of soft particles through porous collagen hydrogels. The results presented here are useful in various practical applications of soft particles like drug delivery.     

An efficient strategy based on two-stage chromatography and in vitro evaluation for rapid screening and isolation of acetylcholinesterase inhibitors from Scutellaria baicalensis Georgi

The extraction of Scutellaria baicalensis Georgi was investigated using the response surface methodology-genetic algorithm mathematical regression model, and the extraction variables were optimized to maximize the flavonoid yield. Furthermore, a simple and efficient ultrafiltration–liquid chromatography–mass spectrometry and molecular docking methods were developed for the rapid screening and identification of acetylcholinesterase inhibitors present in Scutellaria baicalensis Georgi. Subsequently, four major chemical constituents, namely baicalein, norwogonin, wogonin, and oroxylin A, were identified as potent acetylcholinesterase inhibitors. This novel approach, involving the use of ultrafiltration–liquid chromatography–mass spectrometry and molecular docking methods combined with stepwise flow rate counter-current chromatography and semi-preparative high-performance liquid chromatography, could potentially provide a powerful tool for the screening and extraction of acetylcholinesterase inhibitors from complex matrices and be a useful platform for the production of bioactive and nutraceutical ingredients.     

Rational Tuning of the Reactivity of Three-Membered Heterocycle Ring Openings via SN2 Reactions

The development of small-molecule covalent inhibitors and probes continuously pushes the rapidly evolving field of chemical biology forward. A key element in these molecular tool compounds is the “electrophilic trap” that allows a covalent linkage with the target enzyme. The reactivity of this entity needs to be well balanced to effectively trap the desired enzyme, while not being attacked by off-target nucleophiles. Here we investigate the intrinsic reactivity of substrates containing a class of widely used electrophilic traps, the three-membered heterocycles with a nitrogen (aziridine), phosphorus (phosphirane), oxygen (epoxide) or sulfur atom (thiirane) as heteroatom. Using quantum chemical approaches, we studied the conformational flexibility and nucleophilic ring opening of a series of model substrates, in which these electrophilic traps are mounted on a cyclohexene scaffold (C₆H₁₀Y with Y=NH, PH, O, S). It was revealed that the activation energy of the ring opening does not necessarily follow the trend that is expected from C−Y leaving-group bond strength, but steeply decreases from Y=NH, to PH, to O, to S. We illustrate that the HOMO_Nu–LUMO_Substrate interaction is an all-important factor for the observed reactivity. In addition, we show that the activation energy of aziridines and phosphiranes can be tuned far below that of the corresponding epoxides and thiiranes by the addition of proper electron-withdrawing ring substituents. Our results provide mechanistic insights to rationally tune the reactivity of this class of popular electrophilic traps and can guide the experimental design of covalent inhibitors and probes for enzymatic activity.     

多重短程有序准化学模型:有序原子对的对立与统一

在准化学模型框架下, 假设有序原子对同时具有可区分与不可区分的双重属性, 首先构造了双重短程有序准化学模型, 然后讨论了该模型所能满足的各类理论极限. 经总结提炼, 提出了有序原子对的对立统一理论. 基于该理论, 进一步将双重短程有序准化学模型做了一般化推广, 开发了多重短程有序准化学模型. 该模型能够有效描述二元熔体中存在多重短程有序构型时的热力学行为. 选取了至少存在两重短程有序构型的Bi-K熔体来检验模型的合理性和可靠性. 结果表明, 除配位数外, 只需4个模型参数就能合理再现该二元熔体所有的热化学数据.     

Modified Burgers-Reimschuessel model for moisture-sensitive polymers

Viscoelastic properties of moisture-sensitive polymers can be significantly affected by moisture in the ambient environment, resulting in drastic changes in the properties as the absorbed moisture content increases. In this article, a simple yet important modification to the Reimschuessel model is introduced by considering both plasticization and anti-plasticization induced by water molecules. The proposed model is validated against the results of four different polymers obtained by Onogi et al., which demonstrates its capability of describing the available data. This model can be used to estimate the performance and service life of products produced using moisture-sensitive polymers. It also reveals that small amounts of diffused moisture might have a stiffening effect on the mechanical properties of hydrophilic polymers.