Family Tree for Aqueous Organic Redox Couples for Redox Flow Battery Electrolytes: A Conceptual Review

Redox flow batteries (RFBs) are an increasingly attractive option for renewable energy storage, thus providing flexibility for the supply of electrical energy. In recent years, research in this type of battery storage has been shifted from metal-ion based electrolytes to soluble organic redox-active compounds. Aqueous-based organic electrolytes are considered as more promising electrolytes to achieve “green”, safe, and low-cost energy storage. Many organic compounds and their derivatives have recently been intensively examined for application to redox flow batteries. This work presents an up-to-date overview of the redox organic compound groups tested for application in aqueous RFB. In the initial part, the most relevant requirements for technical electrolytes are described and discussed. The importance of supporting electrolytes selection, the limits for the aqueous system, and potential synthetic strategies for redox molecules are highlighted. The different organic redox couples described in the literature are grouped in a “family tree” for organic redox couples. This article is designed to be an introduction to the field of organic redox flow batteries and aims to provide an overview of current achievements as well as helping synthetic chemists to understand the basic concepts of the technical requirements for next-generation energy storage materials.

Mass Spectrometry-Based Structural Proteomics for Metal Ion/Protein Binding Studies

Metal ions are critical for the biological and physiological functions of many proteins. Mass spectrometry (MS)-based structural proteomics is an ever-growing field that has been adopted to study protein and metal ion interactions. Native MS offers information on metal binding and its stoichiometry. Footprinting approaches coupled with MS, including hydrogen/deuterium exchange (HDX), “fast photochemical oxidation of proteins” (FPOP) and targeted amino-acid labeling, identify binding sites and regions undergoing conformational changes. MS-based titration methods, including “protein–ligand interactions by mass spectrometry, titration and HD exchange” (PLIMSTEX) and “ligand titration, fast photochemical oxidation of proteins and mass spectrometry” (LITPOMS), afford binding stoichiometry, binding affinity, and binding order. These MS-based structural proteomics approaches, their applications to answer questions regarding metal ion protein interactions, their limitations, and recent and potential improvements are discussed here. This review serves as a demonstration of the capabilities of these tools and as an introduction to wider applications to solve other questions.

Heavy Metal Pollution Reduced the Potentiality of Pen Culture in the Wetland Aquaculture in an Urban Area of Bangladesh

The Belai beel serves as an important aquatic resource for the livelihood of the local community of the Gazipur district in Bangladesh. However, water pollution in recent times, mainly from industrial wastes and sewage effluents, may disrupt its aquatic environment. Thus, the purpose of the present study was to assess the potential area of pen fish culture in the Belai beel. The study was performed in the Rajbagan (L1), Kamaria (L2) and Rewla (L3) areas of the Belai beel. Grass carp, silver carp, common carp, catla and rui of 20–30 cm in size were stocked at a rate of 15,000 fish/ha and reared for 150 days in pens installed in the L1, L2 and L3 areas, respectively. The fishes were fed with mustard oil cake and rice bran. Maximum fish production was found in Rewla (12.97 ton/ha/150 days) compared to Rajbagan (8.85 ton/ha/150 days) and Kamaria (10.67 ton/ha/150 days) due to it having comparatively good quality water. There were significant differences in metal ion concentrations (p < 0.05) among the three fish pens. In the Rajbagan area, concentrations of Cd and Cu in the water coming from the industrial effluent canal exceeded the acceptable limit. Results indicated that the Rewla area was better than Rajbagan and Kamaria due to it having relatively good quality water for pen fish culture.

Anticancer and Antibiotic Rhenium Tri- and Dicarbonyl Complexes: Current Research and Future Perspectives

Organometallic compounds are increasingly recognized as promising anticancer and antibiotic drug candidates. Among the transition metal ions investigated for these purposes, rhenium occupies a special role. Its tri- and dicarbonyl complexes, in particular, attract continuous attention due to their relative ease of preparation, stability and unique photophysical and luminescent properties that allow the combination of diagnostic and therapeutic purposes, thereby permitting, e.g., molecules to be tracked within cells. In this review, we discuss the anticancer and antibiotic properties of rhenium tri- and dicarbonyl complexes described in the last seven years, mainly in terms of their structural variations and in vitro efficacy. Given the abundant literature available, the focus is initially directed on tricarbonyl complexes of rhenium. Dicarbonyl species of the metal ion, which are slowly gaining momentum, are discussed in the second part in terms of future perspective for the possible developments in the field.

Golgi Metal Ion Homeostasis in Human Health and Diseases

The Golgi apparatus is a membrane organelle located in the center of the protein processing and trafficking pathway. It consists of sub-compartments with distinct biochemical compositions and functions. Main functions of the Golgi, including membrane trafficking, protein glycosylation, and sorting, require a well-maintained stable microenvironment in the sub-compartments of the Golgi, along with metal ion homeostasis. Metal ions, such as Ca2+, Mn2+, Zn2+, and Cu2+, are important cofactors of many Golgi resident glycosylation enzymes. The homeostasis of metal ions in the secretory pathway, which is required for proper function and stress response of the Golgi, is tightly regulated and maintained by transporters. Mutations in the transporters cause human diseases. Here we provide a review specifically focusing on the transporters that maintain Golgi metal ion homeostasis under physiological conditions and their alterations in diseases.

Orthogonal Activation of Metabotropic Glutamate Receptor Using Coordination Chemogenetics

Cell-surface receptors play a pivotal role as transducers of extracellular input. Although different cell types express the same receptor, the physiological roles of the receptor are highly dependent on cell type. To understand each role, tactics for cell-specific activation of the target receptor are in high demand. Herein, we developed an orthogonal activation method targeting metabotropic glutamate receptor 1 (mGlu1), a G-protein coupled receptor. In this method, direct activation via coordination-based chemogenetics (dA-CBC) was adopted, where activation of mGlu1 was artificially induced by a protein conformational change in response to the coordination of a metal ion or metal-ion complex. Our structure-based protein design and screening approach identified mGlu1 mutants that were directly activated by the coordination of Cu2+ or Zn2+, in addition to our previous Pd-complex-sensitive mGlu1 mutant. Notably, the activation of the mutants was mutually orthogonal, resulting in cell-type selective activation in a model system using HEK293 cells.

Zinc- and Copper-Loaded Nanosponges from Cellulose Nanofibers Hydrogels: New Heterogeneous Catalysts for the Synthesis of Aromatic Acetals

Herein we report the synthesis of cellulose-based metal-loaded nano-sponges and their application as heterogeneous catalysts in organic synthesis. First, the combination in water solution of TEMPO-oxidized cellulose nanofibers (TOCNF) with branched polyethyleneimine (bPEI) and citric acid (CA), and the thermal treatment of the resulting hydrogel, leads to the synthesis of an eco-safe micro- and nano-porous cellulose nano-sponge (CNS). Subsequently, by exploiting the metal chelation characteristics of CNS, already extensively investigated in the field of environmental decontamination, this material is successfully loaded with Cu (II) or Zn (II) metal ions. Efficiency and homogeneity of metal-loading is confirmed by scanning electron microscopy (SEM) analysis with an energy dispersive X-ray spectroscopy (EDS) detector and by inductively coupled plasma-optical emission spectrometry (ICP-OES) analysis. The resulting materials perform superbly as heterogeneous catalysts for promoting the reaction between aromatic aldehydes and alcohols in the synthesis of aromatic acetals, which play a fundamental role as intermediates in organic synthesis. Optimized conditions allow one to obtain conversions higher than 90% and almost complete selectivity toward acetal products, minimizing, and in some cases eliminating, the formation of carboxylic acid by-products. ICP-OES analysis of the reaction medium allows one to exclude any possible metal-ion release, confirming that catalysis undergoes under heterogeneous conditions. The new metal-loaded CNS can be re-used and recycled five times without losing their catalytic activity.

MntP and YiiP Contribute to Manganese Efflux in Salmonella enterica Serovar Typhimurium under Conditions of Manganese Overload and Nitrosative Stress

Transition metal cations are required for the function of many proteins but can mediate toxicity when present in excess. Identifying transporters that facilitate metal ion export, the conditions under which they are expressed, and the role they play in bacterial physiology is an evolving area of interest for environmental and pathogenic organisms.