Highly Mesoporous Metal‐Organic Frameworks as Synergistic Multimodal Catalytic Platforms for Divergent Cascade Reactions

Rational engineering and assimilation of diverse chemo‐ and biocatalytic functionalities in a single nanostructure is highly desired for efficient multistep chemical reactions but has so far remained elusive. Here, we design and synthesize multimodal catalytic nanoreactors (MCNRs) based on a mesoporous metal‐organic framework (MOF). The MCNRs consist of customizable metal nanocrystals and stably anchored enzymes in the mesopores, as well as coordinatively unsaturated cationic metal MOF nodes, all within a single nanoreactor space. The highly intimate and diverse catalytic mesoporous microenvironments and facile accessibility to the active site in the MCNR enables the cooperative and synergistic participation from different chemo‐ and biocatalytic components. This was shown by one‐pot multistep cascade reactions involving a heterogeneous catalytic nitroaldol reaction followed by a [Pd/lipase]‐catalyzed chemoenzymatic dynamic kinetic resolution to yield optically pure (>99 % ee) nitroalcohol derivatives in quantitative yields.     

Phosphonate‐Modified UiO‐66 Brønsted Acid Catalyst and Its Use in Dehydra‐Decyclization of 2‐Methyltetrahydrofuran to Pentadienes

Phosphorus‐modified all‐silica zeolites exhibit activity and selectivity in certain Brønsted acid catalyzed reactions for biomass conversion. In an effort to achieve similar performance with catalysts having well‐defined sites, we report the incorporation of Brønsted acidity to metal–organic frameworks with the UiO‐66 topology, achieved by attaching phosphonic acid to the 1,4‐benzenedicarboxylate ligand and using it to form UiO‐66‐PO₃H₂ by post‐synthesis modification. Characterization reveals that UiO‐66‐PO₃H₂ retains stability similar to UiO‐66, and exhibits weak Brønsted acidity, as demonstrated by titrations, alcohol dehydration, and dehydra‐decyclization of 2‐methyltetrahydrofuran (2‐MTHF). For the later reaction, the reported catalyst exhibits site‐time yields and selectivity approaching that of phosphoric acid on all‐silica zeolites. Using solid‐state NMR and deprotonation energy calculations, the chemical environments of P and the corresponding acidities are determined.     

Nanocatalosomes as Plasmonic Bilayer Shells with Interlayer Catalytic Nanospaces for Solar‐Light‐Induced Reactions

Interest and challenges remain in designing and synthesizing catalysts with nature‐like complexity at few‐nm scale to harness unprecedented functionalities by using sustainable solar light. We introduce “nanocatalosomes”—a bio‐inspired bilayer‐vesicular design of nanoreactor with metallic bilayer shell‐in‐shell structure, having numerous controllable confined cavities within few‐nm interlayer space, customizable with different noble metals. The intershell‐confined plasmonically coupled hot‐nanospaces within the few‐nm cavities play a pivotal role in harnessing catalytic effects for various organic transformations, as demonstrated by “acceptorless dehydrogenation”, “Suzuki–Miyaura cross‐coupling” and “alkynyl annulation” affording clean conversions and turnover frequencies (TOFs) at least one order of magnitude higher than state‐of‐the‐art Au‐nanorod‐based plasmonic catalysts. This work paves the way towards next‐generation nanoreactors for chemical transformations with solar energy.     

Design and Development of Ultrafast Sinapic Acid Sensor Based on Electrochemically Nanotuned Gold Nanoparticles and Solvothermally Reduced Graphene Oxide

We report for the first time sinapic acid (SA) sensing based on nanocomposite comprising electrochemically tuned gold nanoparticles (EAuNPs) and solvothermally reduced graphene oxide (rGO). The synthesized EAuNPs, rGO, and EAuNPs‐rGO nanocomposite were characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), particle size analysis, and Raman spectroscopy. A proof‐of‐concept electrochemical sensor for SA was developed based on synthesized EAuNPs‐rGO nanocomposite, which was characterized by electrochemical techniques such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The developed sensor detected SA with a linear dynamic range (LDR) between 20 μM and 200 μM and detection limit (DL) of 33.43 (±0.21) nM (RSD<3.32 %). To show the useful purpose of the sensor probe in clinical applications, SA was detected in human urine samples, which showed the percentage recovery between 82.6 % and 92.8 %. Interferences due to various molecules such as L‐cystine, glycine, alanine, serum albumin, uric acid, citric acid, ascorbic acid, and urea were tested. Long‐term stability of the sensor probe was examined, which was found to be stable up to 6 weeks. The sensor fabricated using EAuNPs‐rGO nanocomposite has many attractive features such as; simplicity, rapidity, and label‐free detection; hence, it could be a method of choice for SA detection in various matrices.     

Synthesis of IONP's decorated graft copolymers and study of their magnetic force–induced wastewater treatment

Our work is focused on facile synthesis and modification of amylopectin‐grafted block copolymers by using reversible addition?fragmentation chain transfer (RAFT) polymerization technique. This technique yields polymers with controlled molecular weight and low polydispersity indexes and is feasible with a wide range of monomers. Five different grades of amylopectin‐grafted polymethacrylic acid and polyacrylamide block copolymers have been synthesized via RAFT, by varying the amount of acrylamide employing amylopectin‐based macro chain transfer agent. Graft copolymers have been upgraded as smart responsive graft copolymers, through the incorporation of iron oxide nanoparticles (IONPs) via condensation reaction. The polymeric materials have been extensively characterized by energy‐dispersive X‐ray analysis, Fourier transform infrared spectroscopy, proton magnetic resonance spectroscopy, scanning electron microscopy, ultraviolet‐visible spectroscopy, gel permeation chromatography, transmission electron microscopy, thermogravimetric analysis, and X‐ray diffraction analysis. Normal and responsive graft copolymers have been studied for removal of model contaminant (kaolin), and responsive graft copolymers have been used to remove methylene blue dye (without using any adsorbent) from water by applying external magnetic field. The upgraded block copolymers have shown best performance in wastewater treatment.     

Efficient Continuous-Flow Synthesis and Evaluation of Anticancer Activity of Novel Quinoline–Pyrazoline Derivatives

Russian Journal of Organic Chemistry - An efficient and simple continuous-flow synthetic protocol for novel quinoline-tethered pyrazoline derivatives, which involves condensation of...     

Identification and characterization of impurities in an insecticide,bifenthrin technical

The HPLC‐DAD and GC/MS methods were successfully used for the identification and characterization of the impurities in an agrochemical insecticide, bifenthrin technical. Three impurities ranging from 0.175%–0.541% were detected by the HPLC‐DAD method. The LC/MS technique with ESI or APCI source failed to detect the impurities detected by HPLC‐DAD, due to lack of ionization in ESI or APCI. The three impurities were enriched by prep‐HPLC, and then their structures were elucidated based on the GC/EIMS and CIMS data. The EI mass spectra of bifenthrin and its impurities displayed molecular ion and provided structure indicative fragment ions; the CIMS data further confirmed their molecular weight. The identity of the impurity 1 was further confirmed by the synthesis of the authentic sample followed by NMR and GC/MS data.     

Thermal conductivity of deep eutectic solvents

Journal of Thermal Analysis and Calorimetry - We have reported the thermal conductivities of three deep eutectic solvents (DESs). We have used choline chloride, N,N-diethyl ethanol ammonium...     

Comparative computational appraisal of supercritical CO2-based natural circulation loop: effect of heat-exchanger and isothermal wall

Journal of Thermal Analysis and Calorimetry - Natural circulation loop (NCL) is a geometrically simple heat transfer device in which fluid flow occurs due to density gradient of loop fluid, induced...     

Synthesis of an Alternated Heterobimetallic Supramolecular Polymer Based on Ru(II) and Fe(II)

A heterobimetallic supramolecular polymer (polyRuFe) with alternately complexed Ru(II) and Fe(II) is prepared following a stepwise synthetic route through harnessing first the strongly binding metal ion Ru(II) and then the weakly binding metal ion Fe(II). A high yield of product is achieved in each step. The heterometal ions are incorporated into the polymer chain in identical coordination environments formed by two 2,2′:6′,2″-terpyridine moieties. Characterization is accomplished by NMR spectroscopy, MALDI–TOF mass spectrometry, UV–Vis spectroscopy, and cyclic voltammetry. PolyRuFe shows a wide optical window (λ = 311–577 nm) and a broad distinct reversible redox nature of two types, originated from the coupling of the two heterometallic segments into the polymer chain. Such characteristics of polyRuFe suggest its potential for various electrochemical and electro-optical applications.