Recent advances in copper chalcogenides for CO2 electroreduction.

Transforming CO2 through electrochemical methods into useful chemicals and energy sources may contribute to solutions for global energy and ecological challenges. Copper chalcogenides exhibit unique properties that make them potential catalysts for CO2 electroreduction. In this review, we provide an overview and comment on the latest advances made in the synthesis, characterization, and performance of copper chalcogenide materials for CO2 electroreduction, focusing on the work of the last five years. Strategies to boost their performance can be classified in three groups: (1) structural and compositional tuning, (2) leveraging on heterostructures and hybrid materials, and (3) optimizing size and morphology. Despite overall progress, concerns about selectivity and stability persist and require further investigation. This review outlines future directions for developing the next-generation of copper chalcogenide materials, emphasizing on rational design and advanced characterization techniques for efficient and selective CO2 electroreduction.

Epigenetic Regulation During Hypoxia and Its Implications in Cancer.

Hypoxia is defined as a cellular stress condition caused by a decrease in oxygen below physiologically normal levels. Cells in the core of a rapidly growing solid tumor are faced with the challenge of inadequate supply of oxygen through the blood, owing to improper vasculature inside the tumor. This hypoxic microenvironment inside the tumor initiates a gene expression program that alters numerous signaling pathways, allowing the cancer cell to eventually evade adverse conditions and attain a more aggressive phenotype. A multitude of studies covering diverse aspects of gene regulation has tried to uncover the mechanisms involved in hypoxia-induced tumorigenesis. The role of epigenetics in executing widespread and dynamic changes in gene expression under hypoxia has been gaining an increasing amount of support in recent years. This chapter discusses, in detail, various epigenetic mechanisms driving the cellular response to hypoxia in cancer.

Unraveling the metabolic shift in anaerobic digestion pathways associated with the alteration of onion skin waste concentration.

Onion skin waste (OSW) is common waste in developing countries, which can cause severe environmental pollution when not properly treated. Value-added products can be chemically extracted from OSW; however, that process is not economically feasible. Alternatively, dry anaerobic digestion (DAD) of OSW is a promising approach for both energy recovery and environment protection. The main hurdles during DAD of OSW can be the hydrolysis and acidification. In batch tests, sludge digestate (SD) rich with methanogens was co-digested with different fractions of OSW for enhancing hydrolysis and raising biogas productivity. The cumulative biogas production (CBP) was 36.6 ± 0.3 mL for sole DAD of SD (100% SD) and increased up to 281.9 ± 14.1 mL for (50% SD: 50% OSW) batch. Self-delignification of OSW took place by SD addition, where the lignin removal reached 75.3 ± 10.5% for (85% SD: 15% OSW) batch. Increasing the fraction of OSW (45% SD: 55% OSW) reduced the delignification by a value of 68.8%, where initial lignin concentration was 9.48 ± 1.6% in dry weight. Lignin breaking down resulted a high fraction of phenolic compounds (345.6 ± 58.8 mg gallic acid equivalent/g dry weight) in the fermentation medium, causing CBP drop (219.0 ± 28.5 mL). The presence of elements (K, Ca, Mg, Fe, Zn, Mn, S and P) in OSW improved the enzymatic activity, facilitated phenolic compounds degradation, shifted the metabolism towards acetate fermentation pathway, and raised biogas productivity. Acidogenesis was less affected by phenolic compounds than methanogenesis, causing higher H2 contents and lower CH4 contents, at batches with high share of OSW.

Integration of aprotic CO2 reduction to oxalate at a Pb catalyst into a GDE flow cell configuration.

Electrochemical CO2 reduction to oxalic acid in aprotic solvents could be a potential pathway to produce carbon-neutral oxalic acid. One of the challenges in aprotic CO2 reduction are the limited achievable current densities under standard conditions, despite the increased CO2 solubility compared to aqueous applications. The application of aprotic solvents can reduce CO2 rather selectively to oxalate, and faradaic efficiencies (FEs) of up to 80% were achieved in this study with a Pb catalyst in acetonitrile, the FE being mainly dictated by the local CO2 concentration at the electrode. This process was integrated into a flow cell employing a two-layered carbon-free lead (Pb) gas diffusion electrode (GDE) and a sacrificial zinc (Zn) anode. With the application of this GDE the applicable current densities could be improved up to a current density of j = 80 mA cm-2 at a FE(oxalate) = 53%, which is within the range of the highest j reported in the literature. In addition, we provide an explanation for the deactivation mechanism of metal catalysts observed in the aprotic CO2 reduction literature. The deactivation is not related to a mass transport limitation but to cathodic corrosion observed at highly negative potential when employing quaternary ammonium supporting electrolyte cations, promoting catalyst leaching.

Environmental biomonitoring by snails.

Background: Bio-indicator systems are vital in terms of monitoring of pollutants around the world. The impact of environmental change can be monitored by employing the responsive behaviour of snails. Heavy metal and organic pollutants affects snail reproduction, mortality, and normal metabolic activities. Various changes like a discontinuity in food intake, growth rate, twitching, and quenching of tentacles, are the biomarkers of the snails for biomonitoring. Different snails can bio-monitor eco-toxicological urban pollution, oil pollutant, terrestrial pollution, pesticide pollutants, mercury contamination, ammonia, chlorinated paraffin in soil, ethanol in water, ocean acidification pollutions. These animals can also make bio-sense about diverse environment spheres, which include the biosphere, lithosphere, anthroposphere, cryosphere, and hydrosphere.Methods: We examined the scientific literature and related articles listed in Pub-med, Google Scholar reporting on biomonitoring potential and biomarkers expression of various snail species and consequently explore the value of snails in the respective field by discussing various outcomes of a number of studies on the pollution biomonitoring and biosensing capabilities.Results: Several terrestrial, freshwater and sea snail species are characterized by the high sense of biomonitoring and biosensing potential. Various biomarkers such as expression of heat shock proteins and metallothioneins in the body are found to be the essential in-vivo biomarkers for pollution biomonitoring.Conclusion: It is observed that snails offer an environment friendly approach for the environmental bio monitoring by expressing their numerous physiological, biochemical, genetical and histological biomarkers in their body. Thus, it proved to be a critical bio monitoring tool and early warning indicators.

Human health and snails.

Snails can provide a considerable variety of bioactive compounds for cosmetic and pharmaceutical industries, useful for the development of new formulations with less toxicity and post effects compared to regular compounds used for the purpose. Compounds from crude extract, mucus, slime consist of glycans, polypeptides, proteins, etc., and can be used for curing diseases like viral lesions, warts, and different dermal problems. Some particular uses of snails involve treating post-traumatic stress. Micro RNA of Lymnaea stagnalis, was known to be responsible for the development of long-term memory and treatment of Alzheimer's and Dementia like diseases. This review explores the application of various bioactive compounds from snails with its potential as new translational medicinal and cosmetic applications. Snail bioactive compounds like ω-MVIIA, µ-SIIIA, µO-MrVIB, Xen2174, δ-EVIA, α-Vc1.1, σ-GVIIA, Conantokin-G, and Contulakin-G, conopeptides can be used for the development of anti-cancer drugs. These compounds target the innate immunity and improve the defense system of humans and provide protection against these life-threatening health concerns.AbbreviationsFDA: Food and Drug Administration; UTI: urinal tract infection; nAChRs: nicotinic acetylcholine receptors; NMDA: N-methyl-D-aspartate; CNS: central nervous system; CAR T: chimeric antigen receptors therapy; Micro RNA: micro ribonucleic acid.

Phytochemical Investigations and In Vitro Bioactivity Screening on Melia azedarach L. Leaves Extract from Nepal.

Melia azedarach is a common tree used in the traditional medicine of Nepal. In this work, leaves were considered as source of bioactive constituents and composition of methanol extract was evaluated and compared with starting plant material. Flavonoid glycosides and limonoids were identified and quantified by HPLC-DAD-MSn approaches in dried leaves and methanolic extract, while HPLC-APCI-MSn and GC/MS analysis were used to study phytosterol and lipid compositions. ß-Sitosterol and rutin were the most abundant constituents. HPLC-APCI-MSn and HPLC-DAD-MSn analysis revealed high levels of phytosterols and flavonoids in methanolic extract accounting 9.6 and 7.5 % on the dried weight, respectively. On the other hand, HPLC/MSn data revealed that limonoid constituents were in minor amount in the extract <0.1 %, compared with leaves (0.7 %) indicating that degradation occurred during extraction or concentration procedures. The methanol extract was subjected to different bioassays, and antioxidant activity was evaluated. Limited inhibitory activity on acetyl and butyryl cholinesterase, as well as on amylase were detected. Moreover, tyrosinase inhibition was significant resulting in 131.57±0.51 mg kojic acid equivalents/g of dried methanol extract, suggesting possible use of this M. azedarach extract in skin hyperpigmentation conditions. Moderate cytotoxic activity, with IC50 of 26.4 µg/mL was observed against human ovarian cancer cell lines (2008 cells). Our findings indicate that the Nepalese M. azedarach leaves can be considered as valuable starting material for the extraction of phenolics and phytosterols, yielding extracts with possible cosmetic and pharmaceutical applications.

The role of biofilm in the development and dissemination of ubiquitous pathogens in drinking water distribution systems: an overview of surveillance, outbreaks, and prevention.

A variety of pathogenic microorganisms can survive in the drinking water distribution systems (DWDS) by forming stable biofilms and, thus, continually disseminating their population through the system's dynamic water bodies. The ingestion of the pathogen-contaminated water could trigger a broad spectrum of illnesses and well-being-related obstacles. These waterborne diseases are a significant concern for babies, pregnant women, and significantly low-immune individuals. This review highlights the recent advances in understanding the microbiological aspects of drinking water quality, biofilm formation and its dynamics, health issues caused by the emerging microbes in biofilm, and approaches for biofilm investigation its prevention and suppression in DWDS.

Electrosynthesis of Biobased Chemicals Using Carbohydrates as a Feedstock.

The current climate awareness coupled with increased focus on renewable energy and biobased chemicals have led to an increased demand for such biomass derived products. Electrosynthesis is a relatively new approach that allows a shift from conventional fossil-based chemistry towards a new model of a real sustainable chemistry that allows to use the excess renewable electricity to convert biobased feedstock into base and commodity chemicals. The electrosynthesis approach is expected to increase the production efficiency and minimize negative health for the workers and environmental impact all along the value chain. In this review, we discuss the various electrosynthesis approaches that have been applied on carbohydrate biomass specifically to produce valuable chemicals. The studies on the electro-oxidation of saccharides have mostly targeted the oxidation of the primary alcohol groups to form the corresponding uronic acids, with Au or TEMPO as the active electrocatalysts. The investigations on electroreduction of saccharides focused on the reduction of the aldehyde groups to the corresponding alcohols, using a variety of metal electrodes. Both oxidation and reduction pathways are elaborated here with most recent examples. Further recommendations have been made about the research needs, choice of electrocatalyst and electrolyte as well as upscaling the technology.

An Integrated LC-ESI-MSn and High Resolution LC-ESI-QTOF Approach for the Identification of Phloroglucinols from Nepalese Hypericum japonicum.

Phloroglucinols are characteristic constituents of Hypericumjaponicum that are claimed to exert several bioactivities, such as anti-inflammatory, anti-depressant and anti-viral ones. Phloroglucinols are unstable compounds and their synthesis is challenging; thus, isolation from natural sources is still one of the main strategies for obtaining these constituents in purified form. Assessing the presence of phloroglucinols in plant materials can be of interest for compound isolation, and LC-MS approaches afford sensitivity and specificity in this regard. In this work, we combined data from quadrupole-time of flight (QTOF) and ion trap (IT) mass spectrometers in order to assess the presence of the phloroglucinols characteristic of H. japonicum and to elucidate their MS fragmentation pathways. The identified compounds present similar structures bearing the 1,3,5-trihydroxybenzene core with different substitutions, which, in constituents at higher MW, is linked to 3',3'-dimethyl-6'-oxo-phlorisobutyrophenone by a methylene bridge. Differences in MS2 spectra of the considered phloroglucinols are useful for compound identification and differentiation, and to perform dereplication studies. Overall, the proposed approach could be useful for the analysis of phloroglucinols in H. japonicum and other plant species.

Himalayan Nettle Girardinia diversifolia as a Candidate Ingredient for Pharmaceutical and Nutraceutical Applications-Phytochemical Analysis and In Vitro Bioassays.

Girardinia diversifolia, also known as Himalayan nettle, is a perennial herb used in Nepal to make fiber as well as in traditional medicine for the treatment of several diseases. To date, phytochemical studies and biological assays on this plant are scarce. Thus, in the present work, the G. diversifolia extracts have been evaluated for their potential pharmaceutical, cosmetic and nutraceutical uses. For this purpose, detailed phytochemical analyses were performed, evidencing the presence of phytosterols, fatty acids, carotenoids, polyphenols and saponins. The most abundant secondary metabolites were ß- and γ-sitosterol (11 and 9% dw, respectively), and trans syringin (0.5 mg/g) was the most abundant phenolic. Fatty acids with an abundant portion of unsaturated derivatives (linoleic and linolenic acid at 22.0 and 9.7 mg/g respectively), vitamin C (2.9 mg/g) and vitamin B2 (0.12 mg/g) were also present. The antioxidant activity was moderate while a significant ability to inhibit acetylcholinesterase (AChE), butyrilcholinesterase (BuChE), tyrosinase, α-amylase and α-glucosidase was observed. A cytotoxic effect was observed on human ovarian, pancreatic and hepatic cancer cell lines. The effect in hepatocarcinoma cells was associated to a downregulation of the low-density lipoprotein receptor (LDLR), a pivotal regulator of cellular cholesterol homeostasis. These data show the potential usefulness of this species for possible applications in pharmaceuticals, nutraceuticals and cosmetics.

Microbe-mediated sustainable bio-recovery of gold from low-grade precious solid waste: A microbiological overview.

In an era of electronics, recovering the precious metal such as gold from ever increasing piles of electronic-wastes and metal-ion infested soil has become one of the prime concerns for researchers worldwide. Biological mining is an attractive, economical and non-hazardous to recover gold from the low-grade auriferous ore containing waste or soil. This review represents the recent major biological gold retrieval methods used to bio-mine gold. The biomining methods discussed in this review include, bioleaching, bio-oxidation, bio-precipitation, bio-flotation, bio-flocculation, bio-sorption, bio-reduction, bio-electrometallurgical technologies and bioaccumulation. The mechanism of gold biorecovery by microbes is explained in detail to explore its intracellular mechanistic, which help it withstand high concentrations of gold without causing any fatal consequences. Major challenges and future opportunities associated with each method and how they will dictate the fate of gold bio-metallurgy from metal wastes or metal infested soil bioremediation in the coming future are also discussed. With the help of concurrent advancements in high-throughput technologies, the gold bio-exploratory methods will speed up our ways to ensure maximum gold retrieval out of such low-grade ores containing sources, while keeping the gold mining clean and more sustainable.

Towards the development of a biobased economy in Europe and India.

India has emerged as a key player with a high potential to develop a biomass and biobased economy due to its large geographic size and the massive amounts of agricultural and non agricultural biomass produced. India has joined hands with Europe to synchronize its efforts to create and facilitate the development of a biobased economy in this country. This paper aims to examine common research and development actions between the European Union (EU) and India to facilitate the development of these biobased economies. As a base, a thorough study has been performed considering the biomass potential and current status of the bioeconomy in both the EU and India based on the distillation of a series of 80 potential recommendations. The recommendations were grouped into four major categories: (1) biomass production, (2) by-products/waste, (3) biorefineries and (4) policy, market, and value-added products. A questionnaire was designed and distributed to key stakeholders belonging to: academia, industry, and policymakers in both India and the EU. A total of 231 responses were received and analyzed, based on the key recommendations made for the essential research and development topics that are of prime importance to develop biobased economies in both the EU and India. The findings of this study suggest recognizing the value-added contributions made by biobased products such as: food, feed, valuable materials and chemicals in both regions. It is important to reduce the overall process costs and minimize the environmental impacts of such a biobased economy.

Chemical-biological hybrid systems for the metal recovery from waste lithium ion battery.

The metals in the waste lithium-ion battery (LIB) are in complex form with coating materials. It consists of copper and aluminium as coiling metals for anode and cathode covered by black powder containing lithium and cobalt. Chemical-biological hybrid systems are found to be useful for the process of metal extraction from LIB waste compared with the individual technique. Lysinibacillus - citric acid hybrid combination provides a noble pathway for the recovery of lithium and cobalt in one pot process. Citric acid (CA) treatment is used to separates copper and aluminum foil from black powder. It leaves lithium and cobalt in the resultant extractant and by the proposed hybrid combination lithium is further separate through leaching and cobalt through biosorbtion. The hrbrid treatment increases lithium leaching by 25% and cobalt biosorption by 98%.

Enteric bacteria from the earthworm (Metaphire posthuma) promote plant growth and remediate toxic trace elements.

This work aimed at elucidating the role of bacteria present in the gut of the earthworm Metaphire posthuma in plant growth promotion and toxic trace elements (TTEs) bioremediation. We isolated and identified three bacterial strains Bacillus safensis (MF 589718), Bacillus flexus (MF 589717) and Staphylococcus haemolyticus (MF 589719) among which the Bacillus strains appeared to be significantly more potent than the Staphylococcus strain (P < 0.05) in promoting plant growth and removing TTE (Cr(VI), Cu(II) and Zn(II)) from aqueous media. These strains exhibited several plant growth promoting traits (e.g., indole acetic acid (IAA), gibberellic acid (GA) and ammonium ion production, 1-aminocyclopropane- 1-carboxylic acid (ACC) deaminase activity, and phosphate solubilizing potential). In a pot trial, the gut isolates improved Vigna radiata seed germination, and enhanced the leaf area (30-79%), total chlorophyll content (26-67%) and overall root-shoot biomass (32-83%) as compared to the control. Bacillus safensis and Bacillus flexus were equipotent in removing Cr(VI) (40.5 and 40.3%) from aqueous media; the former triumphed for Zn(II) removal (52.8%), while the latter performed better for Cu(II) removal (43.5%). The gut isolates successfully solubilized phosphate even in TTE-contaminated conditions. The results demonstrate that the earthworm's enteric bacteria possess inherent plant growth promoting, TTE resistance and phosphate solubilization (even under TTE stress) properties which can be further explored for their application in sustainable crop production and environmental management.

Phytochemical Fingerprinting and In Vitro Bioassays of the Ethnomedicinal Fern Tectaria coadunata (J. Smith) C. Christensen from Central Nepal.

Tectaria coadunata, an ethnomedicinal fern used in Nepal to treat a large number of diseases, has been poorly studied with regard to its phytochemical composition and possible bioactivity. This study was performed with the aim of supporting traditional medicine as a new source of bioactive constituents. Phytochemical compositions of methanol extracts were determined by nuclear magnetic resonance (NMR), liquid chromatography-diode array detector-mass spectrophotometry (LC-DAD-MS), and liquid chromatography-fluorescence-mass spectrometry. Quali-quantitative data revealed large amount of procyanidins, mainly of the A-type, as well as eriodictyol-7-O-glucuronide and luteolin-7-O-glucoronide as main constituents. The antioxidant, cytotoxic, and inhibitory activity of five enzymes that are implicated in human diseases was evaluated for the extract and fractions. High free-radical scavenging activity in 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) assays and inhibitory activities against cholinesterases and tyrosinase were observed. Furthermore, a moderate cytotoxic effect was observed on the 2008 and BxPC3 cell lines. Overall results showed potential usefulness of this fern as a source of phytochemicals for pharmaceutical uses.

Enzymatic Electrosynthesis of Formic Acid through Carbon Dioxide Reduction in a Bioelectrochemical System: Effect of Immobilization and Carbonic Anhydrase Addition.

The enzymatic electrosynthesis of formic acid from the reduction of carbon dioxide (CO2 ) by using formate dehydrogenase (FDH) as a catalyst at the cathode in both its free and immobilized forms was studied in detail in a bioelectrochemical system (BES). The essential role of solubilizing CO2 for its conversion was also studied by adding carbonic anhydrase (CA) to the FDH enzyme in both its free and immobilized forms. FDH alone in the free form showed large variation in the reduction current [(-6.2±3.9) A m-2 ], whereas the immobilized form showed less variation [(-3.8±0.5) A m-2 ] due to increased enzyme stability. The addition of CA with FDH increased the consumption of the current in both forms due to the fact that it allowed rapid dissolution of CO2 , which made it available for the catalytic reaction with FDH. Remarkably, stable consumption of the current was observed throughout the operation if both CA and FDH were immobilized onto the electrode [(-3.9±0.2) A m-2 ]. Product formation by the immobilized enzyme was also continued for three repetitive cycles, which revealed the longevity of the enzyme after immobilization. The recyclability of NADH (NAD=nicotinamide adenine dinucleotide) was also clearly evidenced on the derivative voltammetric signature. Extension of this study for continuous and long-term operation may reveal more possibilities for the rapid capture and conversion of CO2 .

Bioelectrochemical conversion of CO2 to chemicals: CO2 as a next generation feedstock for electricity-driven bioproduction in batch and continuous modes.

The recent concept of microbial electrosynthesis (MES) has evolved as an electricity-driven production technology for chemicals from low-value carbon dioxide (CO2) using micro-organisms as biocatalysts. MES from CO2 comprises bioelectrochemical reduction of CO2 to multi-carbon organic compounds using the reducing equivalents produced at the electrically-polarized cathode. The use of CO2 as a feedstock for chemicals is gaining much attention, since CO2 is abundantly available and its use is independent of the food supply chain. MES based on CO2 reduction produces acetate as a primary product. In order to elucidate the performance of the bioelectrochemical CO2 reduction process using different operation modes (batch vs. continuous), an investigation was carried out using a MES system with a flow-through biocathode supplied with 20 : 80 (v/v) or 80 : 20 (v/v) CO2 : N2 gas. The highest acetate production rate of 149 mg L-1 d-1 was observed with a 3.1 V applied cell-voltage under batch mode. While running in continuous mode, high acetate production was achieved with a maximum rate of 100 mg L-1 d-1. In the continuous mode, the acetate production was not sustained over long-term operation, likely due to insufficient microbial biocatalyst retention within the biocathode compartment (i.e. suspended micro-organisms were washed out of the system). Restarting batch mode operations resulted in a renewed production of acetate. This showed an apparent domination of suspended biocatalysts over the attached (biofilm forming) biocatalysts. Long term CO2 reduction at the biocathode resulted in the accumulation of acetate, and more reduced compounds like ethanol and butyrate were also formed. Improvements in the production rate and different biomass retention strategies (e.g. selecting for biofilm forming micro-organisms) should be investigated to enable continuous biochemical production from CO2 using MES. Certainly, other process optimizations will be required to establish MES as an innovative sustainable technology for manufacturing biochemicals from CO2 as a next generation feedstock.

Sulfide as an alternative electron donor to glucose for power generation in mediator-less microbial fuel cell.

The objective of this study was to investigate the power generation in a dual-chamber microbial fuel cell (MFC). As one of the effective parameters, glucose concentration was studied in the range of 100-1000 mg/L. At the optimum concentration of 500 mg/L of glucose, maximum power generation was 186 mW/m2. As an alternative, sulfide was used as an electron donor and maximum power output was 401 mW/m2 at the concentration of 100 mg/L; which was more than twice of power produced using glucose. Moreover, sulfide removal efficiencies of 70%, 66%, 60%, and 64% were obtained when initial sulfide concentrations of 10, 20, 80, and 100 mg/L were used, respectively.