Understanding the motional dynamics of the ammonium ion in the mechanism of multiferroicity of Cr(V) peroxychromates: a 1H NMR study.

Cr(5+)-based peroxychromates, M3Cr(O2)4, with M = NH4 or a mixed NH4-alkali metal are a new class of multiferroics for potential use in molecular memory devices, with the NH4+ being a key element, but the underlying chemical mechanism is not fully understood. The NH4+ ion occupies two different sites, but their specific roles are not known. We thus performed detailed 1H NMR spin-relaxation (T1) measurements on (NH4)3Cr(O2)4 over a wide temperature range (120-300 K) to probe the displacive as well as hindered rotational dynamics of the NH4+ ions with the view of understanding their specific roles in the phase transitions. The NH4+ dynamics is seen to consist of at least three different processes with varying activation energies. The sharp jump in the T1 at around 250 K is assigned to the change in the displacive motion at one of the two sites, while a kink around 140 K is ascribed to motional slowing at the second site. Interestingly, the slowing down starts around 250 K, well above the structural phase transition at 140 K. Taken together, these results provide a clue to the role of the site and symmetry of the NH4+ ion in the mechanism of solid-solid phase transitions.

Long-term effect of seasonal and constant low temperatures on mesophilic biomass treating sewage in continuously stirred tank anaerobic granular reactor.

A Continuously Stirred Tank Anaerobic Granular Reactor seeded with mesophilic biomass was studied for 1733 days analysing the impact of seasonal (12-23 °C) and controlled (8-15 °C) low temperatures on anaerobic treatment of sewage. Aided by intermittent dosing of 0.04% (v/v) methanol, the microbiota quickly adapted to temperature fluctuations. Chemical oxygen demand (COD) removal efficiency was high but low temperatures affected methane production. Under low-temperature stress, the Methanomythylovorans and Methanosaeta-dominated methanogenic community shifted focus to cellular repair and transport, with carbon diversion towards assimilative pathways, thereby decreasing methane yields. Specific methanogenic activity at 15 °C and 30 °C increased by five and four times, respectively, from their initial values indicating microbiota retained its mesophilic properties. Despite lower methane yield, stable and high COD removals, along with low dissolved methane and volatile fatty acids indicated that low-temperature anaerobic sewage treatment using mesophilic biomass in the long run is sustainable.

Celebrating 50 years of microbial granulation technologies: From canonical wastewater management to bio-product recovery.

Microbial granulation technologies (MGT) in wastewater management are widely practised for more than fifty years. MGT can be considered a fine example of human innovativeness-driven nature wherein the manmade forces applied during operational controls in the biological process of wastewater treatment drive the microbial communities to modify their biofilms into granules. Mankind, over the past half a century, has been refining the knowledge of triggering biofilm into granules with some definite success. This review captures the journey of MGT from inception to maturation providing meaningful insights into the process development of MGT-based wastewater management. The full-scale application of MGT-based wastewater management is discussed with an understanding of functional microbial interactions within the granule. The molecular mechanism of granulation through the secretion of extracellular polymeric substances (EPS) and signal molecules is also highlighted in detail. The recent research interest in the recovery of useful bioproducts from the granular EPS is also emphasized.

The Journey from Porous Materials to Metal-organic Frameworks and their Catalytic Applications: A Review.

Metal-Organic Frameworks (MOFs), a class of inorganic-organic hybrid materials, have been at the center of material science for the past three decades. They are synthesized by metal ions and organic linker precursors and have become very potential materials for different applications ranging from sensing, separation, catalytic behaviour to biomedical applications and drug delivery, owing to their structural flexibility, porosity and functionality. They are also very promising in heterogeneous catalysis for various industrial applications. These catalysts can be easily synthesized with extremely high surface areas, tunable pore sizes, and incorporation of catalytic centers via post-synthetic modification (PSM) or exchange of their components as compared to traditional heterogeneous catalysts, which is the preliminary requirement of a better catalyst. Here, in this review, we have presented the history of MOFs, different synthesis procedures, and MOFcatalysed reactions; for instance, coupling reactions, condensation reactions, Friedel-Crafts reaction, oxidation, etc. Special attention has been given to MOFs containing different catalytic centers, including open metal sites, incorporation of catalytic centers through PSM, and bifunctional acidbase sites. The important role of catalytic centers present in MOFs and reaction mechanisms have also been outlined with examples.

Molecular dynamics simulation perception study of the binding affinity performance for main protease of SARS-CoV-2.

Like common cold and flu, SARC-CoV-2 virus spreads by droplets of sneezes or coughs which virus affects people of various age groups. Today, this virus is almost distributed all over the world. Since binding process plays a crucial role between host and receptor, therefore, we studied the molecules intended toward inhibition process through molecular docking and molecular dynamics simulation process. From the molecular docking study, it is noteworthy that remdesivir shows better binding affinity toward the main protease of SARS-CoV2 compared to other studied drugs. Within studied phytochemicals, carnosic acid shows better binding poses toward main protease of SARS-CoV2 among studied phytochemicals. The amino acid residues GLN110 and PHE294 were almost found in all the studied interactions of drugs and phytochemicals with main protease of SARS-CoV-2. Furthermore, the results show a larger contribution of the Van der Waals energies as compared to others like electrostatic energies suggesting that ligands at the binding pocket are predominantly stabilized by hydrophobic interactions. The conformational change during ligand binding was predicted from Gibbs free energy landscape analysis through molecular dynamics simulation. We observed that, there were two main free energy basins for both docked carnosic acid complex and for docked remdesivir complex, only one main free energy basin was found in the global free energy minimum region.Communicated by Ramaswamy H. Sarma.

Green Solvent: Green Shadow on Chemical Synthesis.

The natural beauty and purity of our planet has been contaminated deeply due to human selfish activities such as pollution, improper waste management, and various industrial and commercial discharges of untreated toxic by-products into the lap of nature. The collective impact of these hazardous suspensions into the natural habitat is very deadly. Challenges due to human activity on the environment have become ubiquitous. The chemical industry has a major role in human evolution and, predictably, opened gates of increased risk of pollution if the production is not done sustainably. In these circumstances, the notion of Green Chemistry has been identified as the efficient medium of synthesis of chemicals and procedures to eradicate the toxic production of harmful substances. Principles of Green Chemistry guide the scientist in their hunt towards chemical synthesis which requires the use of solvents. These solvents contaminate our air, water, land and surrounding due to its toxic properties. Even though sufficient precautions are taken for proper disposal of these solvents but it is difficult to be recycled. In order to preserve our future and coming generation from the adverse impacts associated with solvents it is very important to find alternative of this which will be easy to use, reusable and also eco-friendly. Solvents are used daily in various industrial processes as reaction medium, as diluters, and in separation procedures. As reaction medium, the role of solvent is to bring catalysts and reactants together and to release heat thus affecting activity and selectivity. The proper selection of the solvent considering its biological, physical and chemical properties is very necessary for product separation, environmental, safety handling and economic factors. Green solvents are the boon in this context. They are not only environmentally benign but also cost effective. The biggest challenge faced by the chemists is adaptation of methods and selection of solvents during chemical synthesis which will give negligible waste product and will remain human and nature friendly. During designing compounds for a particular reaction it is difficult to give assurance regarding the toxicity and biodegradability of the method. Chemists are still far away from predicting the various chemical and biological effects of the compounds on the back of the envelope. To achieve that point is formidable task but it will definitely act as inspiration for the coming generation of chemists. The green solvents are undoubtedly a far better approach to eliminate the negative impacts and aftermath of any chemical synthesis on the environment. Our study in this review covers an overview of green solvents, their role in safer chemical synthesis with reference to some of the important green solvents and their detail summarization.

A thiazolo[5,4-d]thiazole-bridged porphyrin organic framework as a promising nonlinear optical material.

Porphyrin-based porous organic frameworks are an important group of materials gaining interest due to their structural diversity and distinct opto-electronic properties. However, these materials are seldom explored for nonlinear optical (NLO) applications. In this work, we investigate a thiazolo[5,4-d]thiazole-bridged porous, porphyrin framework (Por-TzTz-POF) with promising NLO properties. The planar TzTz moiety coupled with integrated porphyrin units enables efficient π-conjugation and charge distribution in the Por-TzTz-POF resulting in a high nonlinear absorption coefficient (ß = 1100 cm GW-1) with figure of merit (FoM) σ1/σ0 = 5571, in contrast to analogous molecules and material counterparts e.g. metal-organic frameworks (MOFs; ß = ∼0.3-0.5 cm GW-1), molecular porphyrins (ß = ∼100-400 cm GW-1), graphene (ß = 900 cm GW-1), and covalent organic frameworks (Por-COF-HH; ß = 1040 cm GW-1 and FoM = 3534).

Encapsulation of zinc-rifampicin complex into transferrin-conjugated silver quantum-dots improves its antimycobacterial activity and stability and facilitates drug delivery into macrophages.

In order to improve the chemotherapy of tuberculosis, there is an urgent need to enhance the efficacy of existing agents and also to develop more efficient drug delivery systems. Here, we synthesized a novel anti-TB drug complex consisting of zinc and rifampicin (Zn-RIF), and encapsulated it into transferrin-conjugated silver quantum-dots (Zn-RIF-Tf-QD) to improve delivery in macrophages. Successful synthesis of Zn-RIF and Zn-RIF-Tf-QD was confirmed by UV/Vis-spectroscopy, TEM, FTIR, photoluminescence, XRD, XPS, and NMR. The sizes of silver QDs and transferrin-conjugated QDs were found to be in the range of 5-20 nm. Activity assays showed that Zn-RIF-Tf-QD exhibited 10-fold higher antibacterial activity against Mycobacterium smegmatis and Mycobacterium bovis-BCG as compared to Zn-RIF, RIF and Zn. Immunofluorescence studies showed that Zn-RIF-Tf-QD-conjugates were actively endocytosed by macrophages and dendritic cells, but not by lung epithelial cells. Treatment with Zn-RIF-Tf-QD efficiently killed mycobacteria residing inside macrophages without exhibiting cytotoxicity and genotoxicity. Moreover, the conjugates remained stable for upto 48 h, were taken up into the late endosomal compartment of macrophages, and released the drug in a sustainable manner. Our data demonstrate that Zn-RIF-Tf-QDs have a great potential as anti-TB drugs. In addition, transferrin-conjugated QDs may constitute an effective drug delivery system for tuberculosis therapy.

Zinc-Oxide Nanoparticles Exhibit Genotoxic, Clastogenic, Cytotoxic and Actin Depolymerization Effects by Inducing Oxidative Stress Responses in Macrophages and Adult Mice.

Zinc oxide nanoparticles (ZnO-NPs) have wide biological applications, which have raised serious concerns about their impact on the health and environment. Although, various studies have shown ZnO-NP toxicity on different cells underin vitroconditions, sufficient information is lacking regarding toxicity and underlying mechanisms underin vivoconditions. In this work, we investigated genotoxic, clastogenic, and cytotoxic effects of ZnO-NPs on macrophages and in adult mice. ZnO-NP-treated mice showed signs of toxicity such as loss in body weight, passive behavior and reduced survival. Further mechanistic studies revealed that administration of higher dose caused severe DNA damage in peripheral blood and bone marrow cells as evident by the formation of COMET tail, micronuclei, chromosomal fragmentation, and phosphorylation of H2A histone family member X. Moreover, ZnO-NPs inhibited DNA repair mechanism by downregulating the expression offen-1andpolBproteins. Histopathological examinations showed severe inflammation and damage to liver, lungs, and kidneys. Cell viability and wound healing assays revealed that ZnO-NPs killed macrophages in a dose-dependent manner, caused severe wounds and inhibited cellular migration by irreversible actin depolymerization and degradation. Reduction in the viability of macrophages was due to the arrest of the cell cycle at the G0/G1 phase, inhibition of superoxide dismutase and catalase and eventually reactive oxygen species. Furthermore, treatment with an antioxidant drug N-acetyl cysteine significantly reduced the ZnO-NP induced genotoxicity bothin vitroandin vivo Altogether, this study gives detailed pathological insights of ZnO-NP that impair cellular functions, thus will enable to arbitrate their biological applications.