Theoretical investigation of nucleophilic substitution reaction of phenyl carbonyl isothiocyanates with pyridines in gas and polar aprotic solvent.

This study focuses on the mutual interaction of substituents in the nucleophile and substrate - cross interaction constant, ρXY, in the uncatalyzed aminolysis by substituting pyridine with phenyl carbonyl isothiocyanate. The mechanism was found to be a stepwise process with a rate-limiting breakdown of the -NCS leaving group. This stepwise reaction mechanism considers the cross-interaction constant (CIC) with rate-limiting breakdown of tetrahedral intermediate in gas and solvent phases. The corresponding Hammett coefficients are related to the substituents associated with (1) the nucleophiles (X), ρX (-1.93 to -6.54 for the gas phase and 10.5 to 18.9 in the solvent model), and with (2) the substituents associated with the phenyl ring of the substrate (Y), ρY (0.41-3.48 for the gas phase and 1.83 to -10.70 for the solvent model). It also includes the Brønsted coefficient with X, ßX (0.11-1.52 for the gas phase and -2.57 to 3.96 for the solvent model), and CIC values, ρXY (0.69 for the gas phase and 0.87 for the solvent model). In this work, the NBO analysis, reaction potential, reaction electronic flux (REF), dual descriptor, and the structure-energy relationships were considered in interpreting the mechanistic criteria.

Multifunctional Biomass-Based Ionic Liquids/CuCl-Catalyzed CO2-Promoted Hydration of Propargylic Alcohols: A Green Synthesis of α-Hydroxy Ketones.

α-Hydroxy ketones are a class of vital organic skeletons that generally exist in a variety of natural products and high-value chemicals. However, the traditional synthetic route for their production involves toxic Hg salts and corrosive H2SO4 as catalysts, resulting in harsh conditions and the undesired side reaction of Meyer-Schuster rearrangement. In this study, CO2-promoted hydration of propargylic alcohols was achieved for the synthesis of various α-hydroxy ketones. Notably, this process was catalyzed using an environmentally friendly and cost-effective biomass-based ionic liquids/CuCl system, which effectively eliminated the side reaction. The ionic liquids utilized in this system are derived from natural biomass materials, which exhibited recyclability and catalytic activity under 1 bar of CO2 pressure without volatile organic solvents or additives. Evaluation of the green metrics revealed the superiority of this CuCl/ionic liquid system in terms of environmental sustainability. Further mechanistic investigation attributed the excellent performance to the ionic liquid component, which exhibited multifunctionality in activating substrates, CO2 and the Cu component.

A physicochemical introspection of porous organic polymer photocatalysts for wastewater treatment.

Over the past decade, porous organic polymers (POPs) have emerged as powerful photocatalysts for organic transformations and wastewater decontamination. The surface properties and pore space of POPs have been tailored to find optimal physical dimensions for adsorption and catalysis, whereas playing with the donor-acceptor building units lends them unique prospects for bandgap engineering, beneficial for customized applications including the degradation of simple as well as persistent pollutants. Here in this critical perspective, we focused beyond these generic scenarios and provided a detailed physicochemical explanation for the experimental observations. Considering the invaluable role of excitons, along with mobile electrons and holes, we fundamentally justified the reactivities of POPs with regard to water treatment. Both semiconducting and molecular catalyst approaches have been considered for different types of POPs. Depending on the porosity, structural formation and defects in the POP backbone, the exciton formation, charge separation, charge diffusion, etc. are critically explained, highlighting the influence of the dielectric constant and skeletal polarizability of the material. The translation of this fundamental understanding to various reactive oxygen species generation through charge transfer (e.g., O2˙-) and exciton-exciton annihilation (e.g., 1O2) by proximity-induced FRET or Dexter pathways is discussed. The role of the hydrophilic POP skeleton in overall in-water photochemical applications is also discussed. Finally, the gaps in the current state-of-the-art are considered and the future prospects to mitigate these issues are argued.

Application of novel nanobubble-contained electrolyzed catalytic water to cleanup petroleum-hydrocarbon contaminated soils and groundwater: A pilot-scale and performance evaluation study.

Soil and groundwater contamination caused by petroleum hydrocarbons is a severe environmental problem. In this study, a novel electrolyzed catalytic system (ECS) was developed to produce nanobubble-contained electrolyzed catalytic (NEC) water for the remediation of petroleum-hydrocarbon-contaminated soils and groundwater. The developed ECS applied high voltage (220 V) with direct current, and titanium electrodes coated with iridium dioxide were used in the system. The developed ECS prototype contained 21 electrode pairs (with a current density of 20 mA/cm2), which were connected in series to significantly enhance the hydroxyl radical production rate. Iron-copper hybrid oxide catalysts were laid between each electrode pair to improve the radical generation efficiency. The electron paramagnetic resonance (EPR) and Rhodamine B (RhB) methods were applied for the generated radical species and concentration determination. During the operation of the ECS, high concentrations of nanobubbles (nanobubble density = 3.7 × 109 particles/mL) were produced due to the occurrence of the cavitation mechanism. Because of the negative zeta potential and nano-scale characteristics of nanobubbles (mean diameter = 28 nm), the repelling force would prevent the occurrence of bubble aggregations and extend their lifetime in NEC water. The radicals produced after the bursting of the nanobubbles would be beneficial for the increase of the radical concentration and subsequent petroleum hydrocarbon oxidation. The highly oxidized NEC water (oxidation-reduction potential = 887 mV) could be produced with a radical concentration of 9.5 × 10-9 M. In the pilot-scale study, the prototype system was applied to clean up petroleum-hydrocarbon polluted soils at a diesel-oil spill site via an on-site slurry-phase soil washing process. The total petroleum hydrocarbon (TPH)-contaminated soils were excavated and treated with the NEC water in a slurry-phase reactor. Results show that up to 74.4% of TPH (initial concentration = 2846 mg/kg) could be removed from soils after four rounds of NEC water treatment (soil and NEC water ratio for each batch = 10 kg: 40 L and reaction time = 10 min). Within the petroleum-hydrocarbon plume, one remediation well (RW) and two monitor wells (located 1 m and 3 m downgradient of the RW) were installed along the groundwater flow direction. The produced NEC water was injected into the RW and the TPH concentrations in groundwater (initial concentrations = 12.3-15.2 mg/L) were assessed in these three wells. Compared to the control well, TPH concentrations in RW and MW1 dropped to below 0.4 and 2.1 mg/L after 6 m3 of NEC water injection in RW, respectively. Results from the pilot-scale study indicate that the NEC water could effectively remediate TPH-contaminated soils and groundwater without secondary pollution production. The main treatment mechanisms included (1) in situ chemical oxidation via produced radicals, (2) desorption of petroleum hydrocarbons from soil particles due to the dispersion of nanobubbles into soil pores, and (3) enhanced TPH oxidation due to produced radicals and energy after nanobubble bursting.

Fabrication and In Vitro Biological Assay of Thermo-Mechanically Tuned Chitosan Reinforced Polyurethane Composites.

The progressive trend of utilizing bioactive materials constitutes diverse materials exhibiting biocompatibility. The innovative aspect of this research is the tuning of the thermo-mechanical behavior of polyurethane (PU) composites with improved biocompatibility for vibrant applications. Polycaprolactone (CAPA) Mn = 2000 g-mol-1 was used as a macrodiol, along with toluene diisocyanate (TDI) and hexamethylene diisocyanate (HMDI), to develop prepolymer chains, which were terminated with 1,4 butane diol (BD). The matrix was reinforced with various concentrations of chitosan (1-5 wt %). Two series of PU composites (PUT/PUH) based on aromatic and aliphatic diisocyanate were prepared by varying the hard segment (HS) ratio from 5 to 30 (wt %). The Fourier-transformed infrared (FTIR) spectroscopy showed the absence of an NCO peak at 1730 cm-1 in order to confirm polymer chain termination. Thermal gravimetric analysis (TGA) showed optimum weight loss up to 500 °C. Dynamic mechanical analysis (DMA) showed the complex modulus (E*) ≥ 200 MPa. The scanning electron microscope (SEM) proved the ordered structure and uniform distribution of chain extender in PU. The hemolytic activities were recorded up to 15.8 ± 1.5% for the PUH series. The optimum values for the inhibition of biofilm formation were recorded as 46.3 ± 1.8% against E. coli and S. aureus (%), which was supported by phase contrast microscopy.

Metal-Free Synthesis of Heteroaryl Amines or Their Hydrochlorides via an External-Base-Free and Solvent-Free C-N Coupling Protocol.

Herein, a metal-free and solvent-free protocol was developed for the C-N coupling of heteroaryl halides and amines, which afforded numerous heteroaryl amines or their hydrochlorides without any external base. Further investigations elucidated that the basicity of amines and specific interactions derived from the X-ray crystallography analysis of 3j'·HCl played pivotal roles in the reactions. Moreover, this protocol was scalable to gram scales and applicable to drug molecules, which demonstrated its practical value for further applications.

Homogeneous photochemical water oxidation with metal salophen complexes in neutral media.

The development of water oxidation catalysts based on Earth-abundant metals that can function at neutral pH remains a basic chemical challenge. Here, we report that salophen complexes with Ni(ii), Cu(ii), and Mn(ii) can catalyse photochemical water oxidation to molecular oxygen in the presence of [Ru(bpy)3]2+ as a photosensitizer and Na2S2O8 as an oxidant in phosphate buffer of pH 7.0. Experimental results including CV, SEM, EDS, ESI-MS, and DLS measurements on the metal salophen complex-catalysed water oxidation to oxygen suggest that the catalytic activity of the catalysts is molecular in origin.

Synthesis of polydicyclopentadiene using the Cp2TiCl2/Et2AlCl catalytic system and thin-layer oxidation of the polymer in air.

The polymerization process of dicyclopentadiene using a multicomponent catalytic system based on bis(cyclopentadienyl)titanium dichloride and diethylaluminum chloride was studied. It was demonstrated that the application of an excess of the aluminum component leads to the formation of stable charged complexes of blue discoloration, which initiate cationic polymerization of dicyclopentadiene. Unstabilized thin layers of obtained polydicyclopentadiene undergo oxidation and structuring under atmospheric oxygen. Oxidation of polydicyclopentadiene films in air occurs slowly during several weeks and can be determined by the increase of carbonyl and hydroxyl adsorption bands in infrared spectra. Along with oxidation, cross-linking processes occur in polymers, which lead to a change in physical parameters of the layers, and more precisely to a decrease in the permeability of atmospheric oxygen through the layers. Consequently, this leads to the transition of the oxidation from a kinetic mode into a diffusive mode. Such structural changes do not occur in a polymer that was stabilized by adding an antioxidant.

Molecular Docking, Computational, and Antithrombotic Studies of Novel 1,3,4-Oxadiazole Derivatives.

A new series of 1,3,4-oxadiazoles derivatives was synthesized, characterized, and evaluated for their in vitro and in vivo anti-thrombotic activity. Compounds (3a⁻3i) exhibited significant clot lysis with respect to reference drug streptokinase (30,000 IU), and enhanced clotting time (CT) values (130⁻342 s) than heparin (110 s). High affinity towards 1NFY with greater docking score was observed for the compounds (3a, 3i, 3e, 3d, and 3h) than the control ligand RPR200095. In addition, impressive inhibitory potential against factor Xa (F-Xa) was observed with higher docking scores (5612⁻6270) with Atomic Contact Energy (ACE) values (-189.68 to -352.28 kcal/mol) than the control ligand RPR200095 (Docking score 5192; ACE -197.81 kcal/mol). In vitro, in vivo, and in silico results proposed that these newly synthesized compounds might be used as anticoagulant agents.

Ruthenium-Based Catalytic Systems Incorporating a Labile Cyclooctadiene Ligand with N-Heterocyclic Carbene Precursors for the Atom-Economic Alcohol Amidation Using Amines.

Transition-metal-catalyzed amide-bond formation from alcohols and amines is an atom-economic and eco-friendly route. Herein, we identified a highly active in situ N-heterocyclic carbene (NHC)/ruthenium (Ru) catalytic system for this amide synthesis. Various substrates, including sterically hindered ones, could be directly transformed into the corresponding amides with the catalyst loading as low as 0.25 mol.%. In this system, we replaced the p-cymene ligand of the Ru source with a relatively labile cyclooctadiene (cod) ligand so as to more efficiently obtain the corresponding poly-carbene Ru species. Expectedly, the weaker cod ligand could be more easily substituted with multiple mono-NHC ligands. Further high-resolution mass spectrometry (HRMS) analyses revealed that two tetra-carbene complexes were probably generated from the in situ catalytic system.

Metal organic frameworks mimicking natural enzymes: a structural and functional analogy.

In this review, we have portrayed the structure, synthesis and applications of a variety of biomimetic MOFs from an unprecedented angle. Synthetic MOF analogues of five distinct enzymes: phosphotriesterase, hydrogenase, cytochrome P450, chymotrypsin and carbonic anhydrase, have been discussed with their skeletal comparison to actual enzymatic active sites as reference, and an explanation of catalytic pathways from the mechanistic cycle of the corresponding enzymes is depicted. We demonstrated critically each of the five discrete situations by assimilating available benchmark researches in an attempt to provide a concise literature source on the ingenious design strategies and versatile biomimetic applications of this domain of materials.

Metal-organic molecular cages: applications of biochemical implications.

New well-designed materials are highly demanded with the prospect of versatile properties, offering successful applications as alternates to conventional materials. Major new insights into metal-organic self-assembled structures assisting biochemical purposes have recently emerged. Metal-organic polyhedral cages are highlighted as new research materials to be used for therapeutic, sensing and imaging, purposes etc. This tutorial review covers achievements in the biochemical applications of these multinuclear complexes. Examples of their ability to aid the ionic transport, biomolecular sensing, imaging, and drug delivery are presented.

Metal-organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations.

Novel catalytic materials are highly demanded to perform a variety of catalytic organic reactions. MOFs combine the benefits of heterogeneous catalysis like easy post reaction separation, catalyst reusability, high stability and homogeneous catalysis such as high efficiency, selectivity, controllability and mild reaction conditions. The possible organization of active centers like metallic nodes, organic linkers, and their chemical synthetic functionalization on the nanoscale shows potential to build up MOFs particularly modified for catalytic challenges. In this review, we have summarized the recent research progress in heterogeneous catalysis by MOFs and their catalytic behavior in various organic reactions, highlighting the key features of MOFs as catalysts based on the active sites in the framework. Examples of their post functionalization, inclusion of active guest species and metal nanoparticles have been discussed. Finally, the use of MOFs as catalysts for asymmetric heterogeneous catalysis and stability of MOFs has been presented as separate sections.

Catalytic asymmetric synthesis of enantioenriched heterocycles bearing a C-CF3 stereogenic center.

Given the important agricultural and medicinal application of optically pure heterocycles bearing a trifluoromethyl group at the stereogenic carbon center in the heterocyclic framework, the exploration of efficient and practical synthetic strategies to such types of molecules remains highly desirable. Catalytic enantioselective synthesis has one clear advantage that it is more cost-effective than other synthetic methods, but remains limited by challenges in achieving excellent yield and stereoselectivities with a low catalyst loading. Thus far, numerous models of organo- and organometal-catalyzed asymmetric reactions have been exploited to achieve this elusive goal over the past decade. This review article describes recent progress on this research topic, and focuses on an understanding of the catalytic asymmetric protocols exemplified in the catalytic enantioselective synthesis of a wide range of complex enantioenriched trifluoromethylated heterocycles.

Polymer-based stimuli-responsive recyclable catalytic systems for organic synthesis.

The introduction of stimuli-responsive polymers into the study of organic catalysis leads to the generation of a new kind of polymer-based stimuli-responsive recyclable catalytic system. Owing to their reversible switching properties in response to external stimuli, these systems are capable of improving the mass transports of reactants/products in aqueous solution, modulating the chemical reaction rates, and switching the catalytic process on and off. Furthermore, their stimuli-responsive properties facilitate the separation and recovery of the active catalysts from the reaction mixtures. As a fascinating approach of the controllable catalysis, these stimuli-responsive catalytic systems including thermoresponsive, pH-responsive, chemo-mechano-chemical, ionic strength-responsive, and dual-responsive, are reviewed in terms of their nanoreactors and mechanisms.

Water-soluble NHC-Cu catalysts: applications in click chemistry, bioconjugation and mechanistic analysis.

Copper(I)-catalyzed 1,3-dipolar cycloaddition of azides and terminal alkynes (CuAAC), better known as "click" reaction, has triggered the use of 1,2,3-triazoles in bioconjugation, drug discovery, materials science and combinatorial chemistry. Here we report a new series of water-soluble catalysts based on N-heterocyclic carbene (NHC)-Cu complexes which are additionally functionalized with a sulfonate group. The complexes show superior activity towards CuAAC reactions and display a high versatility, enabling the production of triazoles with different substitution patterns. Additionally, successful application of these complexes in bioconjugation using unprotected peptides acting as DNA binding domains was achieved for the first time. Mechanistic insight into the reaction mechanism is obtained by means of state-of-the-art first principles calculations.

Metal-organic frameworks for upgrading biogas via CO2 adsorption to biogas green energy.

In the midst of the global climate change phenomenon, mainly caused by fossil fuel burning to provide energy for our daily life and discharge of CO2 into the atmosphere, biogas is one of the important renewable energy sources that can be upgraded and applied as a fuel source for energy in daily life. The advantages of the production of hybrid materials, metal-organic framework (MOF) adsorbents, expected for the biogas upgrading, rely on the bulk separation of CO2 under near-ambient conditions. This review highlights the challenges for MOF adsorbents, which have the greatest upgrading abilities for biogas via selective passage of methane. The key factors improving the ideal MOF materials for these high CO2 capture and selectivity uses for biogas upgrading to produce bio-methane and reduce fossil-fuel CO2 emission will be discussed.

Tuning Coordination in ZIF-67 Through the Solid-State Thermal Synthesis for Balancing Structural Stability and Catalytic Reactivity.

Tailor-made unsaturated coordination of metal ions or organic linkers in zeolitic imidazole frameworks (ZIFs) has great potential in tuning the ZIFs' properties and reactivity for their applications. Taking advantage of the solid-state thermal (SST) method as a facile and eco-friendly synthesis method, the rational coordination of metal ions with imidazole ligands in ZIF-67 through the SST method is investigated. The rational precursor ratio (metal-to-ligand source) under the solvent-free SST method emerges as a perfect strategy to tune the coordinately unsaturated sites within the ZIF-67 frameworks. Different analysis techniques, computational methods (DFT), and catalytic model reactions examine unsaturated coordination in ZIF-67 materials (defect structures). The unsaturated coordination provides unique characteristic properties on materials with excellent catalytic performance. However, the higher reactive properties are negotiated with weaker structural stability on materials. In addition, the post-SST approach is applied to enable rational coordination and modify the pristine ZIF-67 materials. The post-SST method rearranges and modifies coordination in the framework of materials. These findings are crucial to understanding the role of the uncoordinated degree to balance with structural stability based on ZIF-67, which is critical for effective heterogeneous catalysts.

Highly efficient aramid fiber supported polypropylene membranes modified with reduced graphene oxide based metallic nanocomposites: antimicrobial and antiviral capabilities.

Polypropylene hybrid polymeric membranes with aramid support have been fabricated using Thermally Induced Phase Separation (TIPS). Different modifying materials, such as metallic nanoparticles and reduced graphene oxide (rGO), improve the properties of these membranes. The nanomaterials and the fabricated membranes have been characterized with FTIR spectrometer, SEM and UV-Vis Spectrophotometer. Following that, the disinfection capabilities of the fabricated hybrid membranes were investigated. The antibacterial capability of the membranes is established through the testing of the membranes against bacterial strains S. aureus and E. coli, whereas the antiviral evaluation of the membranes was made against H9N2 and IBV strains. This research aims to develop advanced hybrid membranes that effectively disinfect water by incorporating novel nanomaterials and optimizing fabrication techniques.

Development of innovative and green adsorbents for in situ cleanup of fluoride-polluted groundwater: Mechanisms and field-scale studies.

In this study, the magnesium oxide (MgO)-based adsorbents [granulated MgO aggregates (GA-MgO) and surface-modified MgO powder (SM-MgO)] were developed to remediate a fluoride-contaminated groundwater site. Both GA-MgO and SM-MgO had porous, spherical, and crystalline structures. Diameters for GA-MgO and SM-MgO were 1-1.7 mm and 1-10 µm, respectively. The pseudo second-order dynamic adsorption and the Freundlich isotherm could be applied to express the chemical adsorption phenomena. The monolayer adsorption was the dominant mechanism at the initial adsorption period. During the latter part of fluoride adsorption, the multilayer adsorption became the dominant mechanism for fluoride removal from the water phase, which also resulted in the increased adsorption capacity. Higher hydroxide, phosphate, and carbonate concentrations caused a decreased fluoride removal efficiency due to the competition of sorption sites between fluoride and other anions with similar electronic properties. Fluoride removal mechanism using GA-MgO and SM-MgO as the adsorbents was mainly carried out by the chemical adsorption. Reaction paths contained two main processes: (1) formation of magnesium hydroxide after the reaction of MgO with water, and (2) the hydroxyl group of the magnesium hydroxide was replaced by fluoride ions to form magnesium fluoride precipitation. Results from column tests show that up to 61 and 73% of fluoride removal (initial fluoride concentration = 9.3 mg/L) could be obtained after 50 pore volumes of groundwater pumping with GA-MgO and SM-MgO injection, respectively. The GA-MgO system could be applied to contain and remediate fluoride-contaminated groundwater, and SM-MgO could be applied as an immediate fluoride removal alternative to achieve a rapid pollutant removal for emergency responses. Up to 71% of fluoride removal (fluoride concentration = 10.8 mg/L) could be obtained with GA-MgO injection after 30 days of operation. The developed GA-MgO system is a potential and green remediation alternative to contain the fluoride plume significantly.