Synthesis of Glycoluril using Urea Phosphate

Russian Journal of Organic Chemistry - Glycolurils are building blocks for the synthesis of cucurbiturils that are important host materials for several applications. Glycolurils are prepared...     

Gelation Kinetics-Structure Analysis of pH-triggered Low Molecular Weight Hydrogelators

Properties such as shear modulus, gelation time, structure of supramolecular hydrogels are strongly dependent on self-assembly, gelation triggering mechanism and processes used to form the gel. In our work we extend reported rheology analysis methodologies to pH-triggered supramolecular gels to understand structural insight using a model system based on N−N’ Dibenzoyl-L-Cystine pH-triggered hydrogelator and Glucono-δ-Lactone as the trigger. We observed that Avrami growth model when applied to time-sweep rheological data of gels formed at lower trigger concentrations provide estimates of fractal dimension which agree well compared with visualization of the microstructure as seen via Confocal Laser Scanning Microscopy, for a range of gelator concentrations.     

18‐Crown‐6 Catalyzed Microwave‐mediated Synthesis of Symmetric Bis‐Heterocyclic Compounds under Solvent‐free Condition

An efficient, solvent‐free and 18‐crown‐6 catalyzed method for the synthesis of N‐alkyl‐4‐(4‐(5‐(2‐(alkyl‐amino)thiazol‐4‐yl)pyridin‐3‐yl)phenyl)thiazol‐2‐amine, N‐alkyl‐4‐(5‐(2‐alkyamino)thiazol‐4‐yl)pyridine‐3‐yl)thiazol‐2‐amine, and 4,4′‐bis‐{2‐[amino]‐4‐thiazolyl}biphenyl bis‐heterocyclic derivatives via microwave accelerated cyclization is presented.     

Two‐Dimensional Covalent Organic Frameworks for Carbon Dioxide Capture through Channel‐Wall Functionalization

Ordered open channels found in two‐dimensional covalent organic frameworks (2D COFs) could enable them to adsorb carbon dioxide. However, the frameworks’ dense layer architecture results in low porosity that has thus far restricted their potential for carbon dioxide adsorption. Here we report a strategy for converting a conventional 2D COF into an outstanding platform for carbon dioxide capture through channel‐wall functionalization. The dense layer structure enables the dense integration of functional groups on the channel walls, creating a new version of COFs with high capacity, reusability, selectivity, and separation productivity for flue gas. These results suggest that channel‐wall functional engineering could be a facile and powerful strategy to develop 2D COFs for high‐performance gas storage and separation.     

Pyrene-Hydrazone-π···Hole Coupled Turn-on Fluorescent and Naked- Eye Colorimetric Sensor for Cyanide: Role of Homogeneous π-Hole Dispersion in Anion Selectivity

A pyrene based probe associated with π···hole – hydrazone as one of the recognizing elements is synthesized and its turn in to a selective colorimetric and turn-on fluorescent sensor, (L³) for cyanide anion. This chemo sensor show high selectivity towards cyanide anion through photo electron transfer (PET) mechanism. The binding strength and sensitivity of the chemo sensor L³ towards cyanide are found to be 2.0 X 10⁴, and 4.44 x 10^-4 respectively. We have compared this high selectivity of the receptor towards cyanide, with our previously reported receptors L¹ and L². The detailed UV-Vis, Emission, ¹H-NMR, IR spectroscopic and Molecular Electrostatic Potential (MEP) studies reveals that the homogeneous π···hole dispersion in the aromatic ring governing the selectivity of the receptor towards cyanide anion. Such a positive π···hole homogeneous dispersion is missing in the case of sensor L², instead we have polarized π···hole dispersion towards 2^nd and 4^th position of di-nitrophenyl chromophoric unit in L².

Graphical Abstract

     

Rational Design of Microporous MOFs with Anionic Boron Cluster Functionality and Cooperative Dihydrogen Binding Sites for Highly Selective Capture of Acetylene

Separation of acetylene (C₂H₂) from carbon dioxide (CO₂) or ethylene (C₂H₄) is important in industry but limited by the low capacity and selectivity owing to their similar molecular sizes and physical properties. Herein, we report two novel dodecaborate‐hybrid metal–organic frameworks, MB₁₂H₁₂(dpb)₂ (termed as BSF‐3 and BSF‐3‐Co for M=Cu and Co), for highly selective capture of C₂H₂. The high C₂H₂ capacity and remarkable C₂H₂/CO₂ selectivity resulted from the unique anionic boron cluster functionality as well as the suitable pore size with cooperative proton‐hydride dihydrogen bonding sites (B?H^δ????H^δ+?C≡C?H^δ+???H^δ??B). This new type of C₂H₂‐specific functional sites represents a fresh paradigm distinct from those in previous leading materials based on open metal sites, strong electrostatics, or hydrogen bonding.     

Hydrophilic interaction LC–MS/MS method to avoid endogenous interference in the analysis of 4-hydroxy isoleucine from dietary supplementation of fenugreek

4-Hydroxy isoleucine is one of the potent hypoglycemic active constituents of fenugreek seeds. A method capable of reducing biological interferences is required for bioavailability studies. An isocratic separation of 4-hydroxy isoleucine from endogenous interferences was achieved in ZIC-cHILIC column using 0.1% formic acid in water and acetonitrile (20:80, % v/v) pumped at 0.5 ml/min. Quantification was performed in multiple reaction monitoring mode using the transitions of m/z 148.1→102.1 and m/z 276.1→142.2 for 4-hydroxy isoleucine and homatropine (as internal standard), respectively. After full method validation, 4-hydroxy isoleucine levels in human plasma and commercial fenugreek formulations were determined. This method showed good linearity in the range of 50–2000 ng/mL. Intra- and interday accuracies were in the range of 90.64–109.0% and precision was <4.82% CV. The mean (SD) plasma concentration of 4-hydroxy isoleucine in healthy individuals at 2 h after oral administration of fenugreek tablet was found to be 1590 (260) ng/mL. Half of marketed formulations were found to contain <0.05% of 4-hydroxy isoleucine content. We developed a rapid hydrophilic interaction liquid chromatography–tandem mass spectrometry method for analysis of 4-hydroxy isoleucine in human plasma. This method can be applied directly to conduct the clinical pharmacokinetics studies of 4-hydroxy isoleucine in human population.