Distinct columnar and lamellar liquid crystalline phases formed by new bolaamphiphiles with linear and branched lateral hydrocarbon chains

A universal building block for the convergent synthesis of a wide variety of different T-shaped ternary amphiphiles was developed and used for the synthesis of a series of new liquid-crystalline materials composed of a rigid biphenyl core with polar glycerol groups at both ends and linear or branched alkyl chains in a lateral position. In addition, compounds with bulky achiral (2,4,6-trimethylphenoxy, adamantane-1-carboxylate, benzoate) or chiral (menthyl or cholesteryl) substituents attached to the end of the lateral alkyl chain were also investigated. In all cases the lateral chains were connected to the aromatic core by an ether linkage. The effect of the ether linking unit on mesophase stability and mesophase type is discussed with respect to conformational effects. The liquid-crystalline phases were investigated by polarizing microscopy, calorimetry, and X-ray diffraction of surface aligned samples. Upon enlarging the lateral chains a series of different polygonal cylinder phases was observed, which were replaced by lamellar phases and a non-cylinder hexagonal columnar phase by further increasing the size of these substituents. Remarkably, only pentagonal, hexagonal, and giant hexagonal cylinder phases could be observed, whereas mesophases composed of cylinders with a smaller number of sides are missing. No distinct chirality effects were observed for the menthyl- and cholesteryl-substituted compounds. However, the rodlike shape of the polycyclic cholesteryl core leads to a unique phase structure combining an organization of the alicyclic cholesteryl cores perpendicular to the layer planes and the aromatic biphenyl cores parallel to the layer planes.     

Efficient synthesis of 2-thioxo-1,3-thiazolanes from primary amines, CS2, and ethyl bromopyruvate

An efficient synthesis of 2-thioxo-1,3-thiazolanes is described via reaction of carbon disulfide, ethyl bromopyruvate, and primary amines. Correspondence: Issa Yavari, Chemistry Department, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran.     

Synthesis of S -Aryl/Alkyl Thiolcarbonates from Disulfides and Chloroformates in the Presence of the Zn/AlCl3 System

A simple, general, and high yielding method has been developed for the synthesis of S-aryl/alkyl-O-aryl/alkyl thiolcarbonates from various chloroformates and disulfides by reductive cleavage of the S–S bond with a Zn/AlCl₃ system in dry acetonitrile at 80°C.     

2‐(1H‐Benzotriazole‐1‐yl)‐1,1,3,3‐Tetramethyluronium Tetrafluoro Borate (TBTU) as an Efficient Coupling Reagent for the Esterification of Carboxylic acids with Alcohols and Phenols at Room Temperature

Esterification of carboxylic acids with alcohols and phenols by using 2‐(1H‐benzotriazole‐1‐yl)‐1,1,3,3‐tetramethyluronium tetrafluoroborate (TBTU) in the presence of triethylamine as a base proceeded smoothly under mild conditions to afford the corresponding esters in good to high yields in acetonitrile at room temperature.     

Field‐Effect Nanoparticle‐Based Glucose Sensor on a Chip: Amplification Effect of Coimmobilized Redox Species

A capacitive EIS (electrolyte‐insulator‐semiconductor) structure was modified with gold nanoparticles together with glucose oxidase and used as field‐effect‐based glucose biosensor using the constant capacitance mode. Co‐immobilization of ferrocene redox species resulted in a two‐fold increase of the biosensor sensitivity. The effect was explained by the hydrogen peroxide‐mediated oxidation of ferrocene resulting in a pool of charged species at the interface increasing the sensor response towards glucose. The studied approach was suggested as a general means to amplify signals from Si chip‐based field‐effect enzyme biosensors.     

A Robust Electrochemical Sensor Based on Butterfly-shaped Silver Nanostructure for Concurrent Quantification of Heavy Metals in Water Samples

Heavy metals in drinking water have become a severe threat to human health. Detection of heavy metals has been achieved by electrochemical sensors that are modified with complex nanocomposites; however, reproducibility of these sensors is still a big challenge when applied in commercial settings. Here, a simple, very robust, and sensitive electrochemical sensor based on a screen-printed carbon electrode modified with butterfly-shaped silver nanostructure (AgNS/SPCE) has been developed for the concurrent determination of cadmium (II), lead (II), copper (II), and mercury (II) in water samples. The electrochemical behavior of the modified electrodes was investigated using cyclic voltammetry and differential pulse anodic stripping voltammetry. The AgNS/SPCE showed distinct peak potentials and a significant increase in the peak currents for all heavy metals, attributed to the high electrical conductivity and electrocatalytic activity of the synthesized butterfly-shaped AgNS. Moreover, the excellent stability and sensitivity towards simultaneous quantification of heavy metals have been obtained with detection limits of 0.4 ppb, 2.5 ppb, 7.3 ppb, and 0.7 ppb for Cd (II), Pb (II), Cu (II), and Hg (II), respectively. Besides, the constructed sensor was successfully applied to simultaneously quantify target heavy metals in spiked water samples. Owing to excellent sensitivity, high robustness, affordability, and fast response, the presented electrochemical sensor could be incorporated into a portable and miniaturized potentiostat device, making it a promising method for on-site water analysis.     

Toward efficient functionalization of polystyrene backbone through ketene chemistry: Synthesis,characterization, and DFT study

In this study, polystyrene was functionalized with Meldrum's acid toward the introduction of the ketenes (CCO) system to its backbone for producing a dramatically reactive intermediate. Meldrum's acid, as a ketene source, was reacted by poly(styrene-co-p-chloromethyl styrene) through a simple nucleophilic reaction to synthesize poly(styrene-co-styryl Meldrum's acid). Then, the pendant Meldrum's acid under thermal treatment converted to ketene intermediate resulting in highly reactive polystyrenes derivatives, which rapidly reacted by nucleophilic reagents to afford ultimate organic building blocks. The polystyrene derivatives were characterized using elemental analysis, FT-IR, high-resolution solid-state NMR, thermogravimetric analysis (TGA), and differential thermogravimetric analysis (DTG). To clarify the evolutionary mechanisms of polystyrene products, density functional theory (DFT) method B3LYP with the 6–311++G(2d,p) basis set was used. We studied the preparation of polystyrene model compounds through Meldrum's acid thermolysis and nucleophilic substitution. The kinetic and thermodynamic parameters in all reactions and the structural and electronic properties of all molecules were calculated. These data exhibited that based on Gibbs Free energy values, the structure of syndiotactic polystyrene is more stable than that of isotactic polystyrene. Furthermore, it was found that the presence of an electron donor or acceptor substituent on the polystyrene structure affects the electronic bandgap.     

Connectivity of Pore Space as a Control on Two-Phase Flow Properties of Tight-Gas Sandstones

We predict capillary-pressure (drainage) curves in tight-gas sandstones which have little matrix or microporosity using a quantitative grain-scale model. The model accounts for the geometric results of some depositional and diagenetic processes important for porosity and permeability reduction in tight-gas sandstones, such as deformation of ductile grains during burial and quartz cementation. The model represents the original sediment as a dense, disordered packing of spheres. We simulated the evolution of this model sediment into a low-porosity sandstone by applying different amounts of ductile grains and quartz precipitation. A substantial fraction of original pore throats in the sediment is closed by the simulated diagenetic alteration. Because the percolation threshold corresponds to closure of half of the pore throats, the pore space in this type of tight-gas sandstone is poorly connected and is often close to being completely disconnected. The drainage curve for different model rocks was computed using invasion percolation in a network taken directly from the grain-scale geometry and topology of the model. Some general trends follow classical expectations and were confirmed by experimental measurements: increasing the amount of cement shifts the drainage curve to larger pressures. This is related to reduction of the connectivity of pore space resulting from closure of throats. Existence of ductile grains in the ductile grain model also reduces the connectivity of pore space but it treats the throats distribution differently causing the drainage curves to be shifted to larger irreducible water saturation when cement is added to the model. The range of porosities in which these connectivity effects are important corresponds to the range of porosities common for tight gas sandstones. Consequently these rocks can exhibit small effective permeability to gas even at large gas saturations. This problem occurs at larger porosities in rocks with significant content of ductile grains because ductile deformation blocks a significant fraction of pore throats even before cementation begins. Predicted drainage curves agree with measurements on two samples with little microporosity, one dominated by rigid grains, the other containing a significant fraction of ductile grains. We conclude that connectivity of the matrix pore space is an important factor for an understanding of flow properties of tight-gas sandstones.     

Nonadiabatic coupling and diabatic electronic population dynamics on 11A2 and 11B1 states of ozone molecule

In this work, we examine nonadiabatic population dynamics for 1¹B₁ and 1¹A₂ states of ozone molecule (O₃). In O₃, two lowest singlet excited states, ¹A₂ and ¹B₁, can be coupled. Thus, population transfer between them occurs through the seam involving these two states. At any point of the seam (conical intersection), the Born-Oppenheimer approximation breaks down, and it is necessary to investigate nonadiabatic dynamics. We consider a linear vibronic coupling Hamiltonian model and evaluate vibronic coupling constant, diabatic frequencies for three modes of O₃, bilinear and quadratic coupling constants for diabatic potentials, displacements, and Huang-Rhys coupling constants using ab initio calculations. The electronic structure calculations have been performed at the multireference configuration interaction and complete active space with second-order perturbation theory with a full-valence complete active space self-consistent field methods and augmented Dunning's standard correlation-consistent-polarized quadruple zeta basis set to determine ab initio potential energy surfaces for the ground state and first two excited states of O₃, respectively. We have chosen active space comprising 18 electrons distributed over 12 active orbitals. Our calculations predict the linear vibronic coupling constant 0.123 eV. We have obtained the population on the 1¹B₁ and 1¹A₂ excited electronic states for the first 500 fs after photoexcitation.     

Probing Gallate-Mediated Selectivity and High-Affinity Binding of Epigallocatechin Gallate: a Way-Forward in the Design of Selective Inhibitors for Anti-apoptotic Bcl-2 Proteins

Selective inhibition is a key focus in the design of chemotherapeutic compounds that can abrogate the oncogenic activities of anti-apoptotic Bcl-2 proteins. Although recent efforts have led to the development of highly selective BH3 mimetics, setbacks such as toxicities have limited their use in cancer therapy. Epigallocatechingallate (EGCG) has been widely reported to selectively inhibit Bcl-2 and Bcl-xL compared to other green tea phenols due to its gallate group. Herein, we investigate the interaction dynamics of EGCG at the hydrophobic grooves of Bcl-2 and Bcl-xL and the consequential effects on their BH4 domains. Arg143 and Asp108 (Bcl-2), and Glu96 and Tyr195 (Bcl-xL) formed high-affinity hydrogen interactions with the gallate group while non-gallate groups of EGCG formed weak interactions. EGCG-bound proteins showed systemic perturbations of BH4 domains coupled with the burial of crucial surface-exposed residues such as Lys17 (Bcl-2) and Asp11 (Bcl-xL); hence, a distortion of non-canonical domain interactions. Interactions of gallate group of EGCG with key hydrophobic groove residues underlie EGCG selectivity while concurrent BH4 domain perturbations potentiate EGCG inhibitory activities. Findings will aid the optimization and design of selective inhibitors that could suppress anti-apoptotic activities of Bcl2-family proteins with minimal toxicities.