Regioselective N‐Alkylation of Ethyl 4‐Benzyloxy‐1,2,3‐triazolecarboxylate: A Useful Tool for the Synthesis of Carboxylic Acid Bioisosteres

Acidic 4‐hydroxy‐1,2,3‐triazole is a proven bioisostere of acidic functions that has recently been used to replace the acidic moieties of biologically active leads. Straightforward chemical strategies for the synthesis of the three possible N‐alkylated 4‐hydroxy‐1,2,3‐triazole regioisomers have been designed and reported herein, by identifying the optimal conditions under which the alkylation of ethyl 4‐benzyloxy‐1,2,3‐triazolecarboxylate (compound 19 ) can be regiodirected to the triazole N(b) position and thus produce the only isomer that cannot be obtained via the cycloaddition reaction. Furthermore, an innovative platform for parallel synthesis, called Arachno and which has been patented by the authors' group, has been used to speed up the process, and an NMR study has been carried out to better understand the reactivity of compound 19 towards the N(b) position. A library of benzyloxy protected 4‐hydroxy‐1,2,3‐triazoles has been prepared using the two strategies: regiodirection for the N(b) and N(c) isomers and cycloaddition for the N(a) isomers; the processes are described herein. The three N‐alkylated regioisomer series have been characterized spectroscopically (NMR and MS). The subsequent catalytic hydrogenation of the 4‐benzyloxy protective group on the N‐alkylated‐4‐benzyloxy‐5‐ethoxycarbonyl‐1,2,3‐triazoles provided the corresponding substituted 4‐hydroxy‐1,2,3‐triazoles.     

Fluorometric Recognition of Nucleotides within a Water‐Soluble Tetrahedral Capsule

The design of aqueous probes and binders for complex, biologically relevant anions presents a key challenge in supramolecular chemistry. Herein, a tetrahedral assembly with cationic faces and corners is reported that is capable of discriminating between anionic and neutral guests in water. Electrostatic repulsion between subcomponents can be overcome by the addition of an anionic template, or generating a robust covalent framework by incorporating tris(2‐aminoethyl)amine (TREN). The resultant TREN‐capped, water‐soluble, fluorescent cage binds mono‐ and poly‐phosphoric esters, including nucleotides. Its covalent skeleton renders it stable at micromolar concentrations in water, enabling the fluorometric detection of biologically relevant guests in an aqueous environment. Selective supramolecular encapsulants, such as 1 , could enable new sensing applications, such as recognition of toxins and drugs, under biological conditions.     

Linear‐Dendritic Alternating Copolymers

Herein, the design, synthesis, and characterization of an unprecedented copolymer consisting of alternating linear and dendritic segments is described. First, a 4th‐generation Hawker‐type dendron with two azide groups was synthesized, followed by a step‐growth azide‐alkyne “click” reaction between the 4th‐generation diazido dendron and poly(ethylene glycol) diacetylene to create the target polymers. Unequal reactivity of the functional groups was observed in the step‐growth polymerization. The resulting copolymers, with alternating hydrophilic linear and hydrophobic dendritic segments, can spontaneously associate into a unique type of microphase‐segregated nanorods in water.     

A Conditional Curie–Weiss Model for Stylized Multi-group Binary Choice with Social Interaction

This paper proposes a conditional Curie–Weiss model as a model for decision making in a stylized society made up of binary decision makers that face a particular dichotomous choice between two options. Following Brock and Durlauf (Discrete choice with social interaction I: theory, 1955), we set-up both socio-economic and statistical mechanical models for the choice problem. We point out when both the socio-economic and statistical mechanical models give rise to the same self-consistent equilibrium mean choice level(s). Phase diagram of the associated statistical mechanical model and its socio-economic implications are discussed.     

Nucleation on a sphere: the roles of curvature,confinement and ensemble

ABSTRACT

By combining Monte Carlo simulations and analytical models, we demonstrate and explain how the gas-to-liquid phase transition of colloidal systems confined to a spherical surface depends on the curvature and size of the surface, and on the choice of thermodynamic ensemble. We find that the geometry of the surface affects the shape of the free energy profile and the size of the critical nucleus by altering the perimeter–area ratio of isotropic clusters. Confinement to a smaller spherical surface results in both a lower nucleation barrier and a smaller critical nucleus size. Furthermore, the liquid domain does not grow indefinitely on a sphere. Saturation of the liquid density in the grand canonical ensemble and the depletion of the gas phase in the canonical ensemble lead to a minimum in the free energy profile, with a sharp increase in free energy for additional growth beyond this minimum.     

Robust general N user authentication scheme in a centralized quantum communication network via generalized GHZ states

Quantum communication provides an enormous advantage over its classical counterpart: security of communications based on the very principles of quantum mechanics. Researchers have proposed several approaches for user identity authentication via entanglement. Unfortunately, these protocols fail because an attacker can capture some of the particles in a transmitted sequence and send what is left to the receiver through a quantum channel. Subsequently, the attacker can restore some of the confidential messages, giving rise to the possibility of information leakage. Here we present a new robust General Nuser authentication protocol based on N-particle Greenberger–Horne–Zeilinger (GHZ) states, which makes eavesdropping detection more effective and secure, as compared to some current authentication protocols. The security analysis of our protocol for various kinds of attacks verifies that it is unconditionally secure, and that an attacker will not obtain any information about the transmitted key. Moreover, as the number of transferred key bits N becomes larger, while the number of users for transmitting the information is increased, the probability of effectively obtaining the transmitted authentication keys is reduced to zero.     

Low-field NMR measurement procedure when SQUID detection is used

In reported low-field nuclear magnetic resonance (NMR) measurements using Superconducting Quantum Interference Device (SQUID) detection, the pre-polarizing magnetic field has been usually oriented orthogonal to the measuring field, B_p  B_m. Melton et al. systematically analyzed the consequences of B_p decay in time after turnoff and showed that this decay should be nonadiabatic. We evaluated our measuring procedure in the light of that analysis, and found good quantitative agreement. It was showed that, when the decay time constant is comparable to the precession period of the magnetization of the sample, M, the optimum procedure is to orient B_p parallel to B_m and to apply a π/2 pulse to flip M, similar as in the case of conventional NMR.     

Synthesis of diverse N-acyl-pyrazoles via cyclocondensation of hydrazides with α-oxeketene dithioacetal

Molecular Diversity - An elegant, efficient, and highly regioselective approach for the synthesis of novel methyl 5-amino-3-(methylthio)-1-differently substituted-1H-pyrazole-4-carboxylates is...     

TiO2-based Photocatalysis: Toward Visible Light-Responsive Photocatalysts Through Doping and Fabrication of Carbon-Based Nanocomposites

Elimination of toxic organic compounds from wastewater and provision of safe, clean, and cheap water to communities is currently one of the most important global topics in water-pollution control. TiO₂ has emerged as one of the most fascinating material in the modern era due to its potential catalytic properties. In spite of extensive efforts to apply TiO₂ for environmental remediation, photocatalytic activity in the visible region has remained quite low hence the need to fabricate highly photoactive catalysts through modification of TiO₂ and to apply them for water remediation using the abundantly available solar radiation.

Carbon materials are promising candidates for application as functional materials due to their superior physico-chemical properties. This has prompted investigations into their possible application in environmental clean-up. Nanocomposite assemblies composed of different types and proportions of carbon based materials (i.e., carbon nanotubes, graphene, fullerenes, activated carbon, carbon nanofibers) and TiO₂ have also found widespread applicability in water decontamination studies using UV or visible light. This article surveys the literature and highlights recent progress in the development of TiO₂ and nanocarbon/TiO₂ photocatalysts for water decontamination. The nitty-gritties, on-going challenges, areas of controversy, “hotspots” and possible new directions are outlined in this article.