Single Atom Catalysts Based on Earth-Abundant Metals for Energy-Related Applications.

Anthropogenic activities related to population growth, economic development, technological advances, and changes in lifestyle and climate patterns result in a continuous increase in energy consumption. At the same time, the rare metal elements frequently deployed as catalysts in energy related processes are not only costly in view of their low natural abundance, but their availability is often further limited due to geopolitical reasons. Thus, electrochemical energy storage and conversion with earth-abundant metals, mainly in the form of single-atom catalysts (SACs), are highly relevant and timely technologies. In this review the application of earth-abundant SACs in electrochemical energy storage and electrocatalytic conversion of chemicals to fuels or products with high energy content is discussed. The oxygen reduction reaction is also appraised, which is primarily harnessed in fuel cell technologies and metal-air batteries. The coordination, active sites, and mechanistic aspects of transition metal SACs are analyzed for two-electron and four-electron reaction pathways. Further, the electrochemical water splitting with SACs toward green hydrogen fuel is discussed in terms of not only hydrogen evolution reaction but also oxygen evolution reaction. Similarly, the production of ammonia as a clean fuel via electrocatalytic nitrogen reduction reaction is portrayed, highlighting the potential of earth-abundant single metal species.

Copper-Based Bio-MOF/GO with Lewis Basic Sites for CO2 Fixation into Cyclic Carbonates and C-C Bond-Forming Reactions.

Several measures, including crude oil recovery improvement and carbon dioxide (CO2) conversion into valuable chemicals, have been considered to decrease the greenhouse effect and ensure a sustainable low-carbon future. The Knoevenagel condensation and CO2 fixation have been introduced as two principal solutions to these challenges. In the present study for the first time, bio-metal-organic frameworks (MOF)(Cu)/graphene oxide (GO) nanocomposites have been used as catalytic agents for these two reactions. In view of the attendance of amine groups, biological MOFs with NH2 functional groups as Lewis base sites protruding on the channels' internal surface were used. The bio-MOF(Cu)/20%GO performs efficaciously in CO2 fixation, leading to more than 99.9% conversion with TON = 525 via a solvent-free reaction under a 1 bar CO2 atmosphere. It has been shown that these frameworks are highly catalytic due to the Lewis basic sites, i.e., NH2, pyrimidine, and C═O groups. Besides, the Lewis base active sites exert synergistic effects and render bio-MOF(Cu)/10%GO nanostructures as highly efficient catalysts, significantly accelerating Knoevenagel condensation reactions of aldehydes and malononitrile as substrates, thanks to the high TOF (1327 h-1) and acceptable reusability. Bio-MOFs can be stabilized in reactions using GO with oxygen-containing functional groups that contribute as efficient substitutes, leading to an expeditious reaction speed and facilitating substrate absorption.

MXenes for Bioinspired Soft Actuators: Advancements in Angle-Independent Structural Colors and Beyond.

Soft actuators have garnered substantial attention in current years in view of their potential appliances in diverse domains like robotics, biomedical devices, and biomimetic systems. These actuators mimic the natural movements of living organisms, aiming to attain  enhanced flexibility, adaptability, and versatility. On the other hand, angle-independent structural color has been achieved through innovative design strategies and engineering approaches. By carefully controlling the size, shape, and arrangement of nanostructures, researchers have been able to create materials exhibiting consistent colors regardless of the viewing angle. One promising class of materials that holds great potential for bioinspired soft actuators is MXenes in view of their exceptional mechanical, electrical, and optical properties. The integration of MXenes for bioinspired soft actuators with angle-independent structural color offers exciting possibilities. Overcoming material compatibility issues, improving color reproducibility, scalability, durability, power supply efficiency, and cost-effectiveness will play vital roles in advancing these technologies. This perspective appraises the development of bioinspired MXene-centered soft actuators with angle-independent structural color in soft robotics.

Nano/Micro-Structural Supramolecular Biopolymers: Innovative Networks with the Boundless Potential in Sustainable Agriculture.

Sustainable agriculture plays a crucial role in meeting the growing global demand for food while minimizing adverse environmental impacts from the overuse of synthetic pesticides and conventional fertilizers. In this context, renewable biopolymers being more sustainable offer a viable solution to improve agricultural sustainability and production. Nano/micro-structural supramolecular biopolymers are among these innovative biopolymers that are much sought after for their unique features. These biomaterials have complex hierarchical structures, great stability, adjustable mechanical strength, stimuli-responsiveness, and self-healing attributes. Functional molecules may be added to their flexible structure, for enabling novel agricultural uses. This overview scrutinizes how nano/micro-structural supramolecular biopolymers may radically alter farming practices and solve lingering problems in agricultural sector namely improve agricultural production, soil health, and resource efficiency. Controlled bioactive ingredient released from biopolymers allows the tailored administration of agrochemicals, bioactive agents, and biostimulators as they enhance nutrient absorption, moisture retention, and root growth. Nano/micro-structural supramolecular biopolymers may protect crops by appending antimicrobials and biosensing entities while their eco-friendliness supports sustainable agriculture. Despite their potential, further studies are warranted to understand and optimize their usage in agricultural domain. This effort seeks to bridge the knowledge gap by investigating their applications, challenges, and future prospects in the agricultural sector. Through experimental investigations and theoretical modeling, this overview aims to provide valuable insights into the practical implementation and optimization of supramolecular biopolymers in sustainable agriculture, ultimately contributing to the development of innovative and eco-friendly solutions to enhance agricultural productivity while minimizing environmental impact.

Toxicological Impact of Bisphenol A on Females' Reproductive System: Review Based on Experimental and Epidemiological Studies.

The study encompassing research papers documented in the last two decades pertaining to the possible influence of bisphenol A (BPA) on the fertility of females are appraised with emphasis on the influence of BPA in reproductive organs (uterus and ovaries) and pregnancy outcomes including discussion on the reproductive process (implantation, estrous cycle, hormone secretion); outcomes reveal a connection amongst BPA and female infertility. Ovary, uterus, and its shape as well as function can alter a person's ability to become pregnant by influencing the hypothalamus-pituitary axis in the ovarian model. Additionally, implantation and the estrous cycle may be affected by BPA. However, more research is warranted to comprehend the underlying action mechanisms and to promptly identify any imminent reproductive harm.

The posterity of Zebrafish in paradigm of in vivo molecular toxicological profiling.

The aggrandised advancement in utility of advanced day-to-day materials and nanomaterials has raised serious concern on their biocompatibility with human and other biotic members. In last few decades, understanding of toxicity of these materials has been given the centre stage of research using many in vitro and in vivo models. Zebrafish (Danio rerio), a freshwater fish and a member of the minnow family has garnered much attention due to its distinct features, which make it an important and frequently used animal model in various fields of embryology and toxicological studies. Given that fertilization and development of zebrafish eggs take place externally, they serve as an excellent model organism for studying early developmental stages. Moreover, zebrafish possess a comparable genetic composition to humans and share almost 70% of their genes with mammals. This particular model organism has become increasingly popular, especially for developmental research. Moreover, it serves as a link between in vitro studies and in vivo analysis in mammals. It is an appealing choice for vertebrate research, when employing high-throughput methods, due to their small size, swift development, and relatively affordable laboratory setup. This small vertebrate has enhanced comprehension of pathobiology and drug toxicity. This review emphasizes on the recent developments in toxicity screening and assays, and the new insights gained about the toxicity of drugs through these assays. Specifically, the cardio, neural, and, hepatic toxicology studies inferred by applications of nanoparticles have been highlighted.

Immunomodulatory activities and biomedical applications of melittin and its recent advances.

Melittin (MLT), a peptide containing 26 amino acids, is a key constituent of bee venom. It comprises ∼40%-60% of the venom's dry weight and is the main pricing index for bee venom, being the causative factor of pain. The unique properties of MLT extracted from bee venom have made it a very valuable active ingredient in the pharmaceutical industry as this cationic and amphipathic peptide has propitious effects on human health in diverse biological processes. It has the ability to strongly impact the membranes of cells and display hemolytic activity with anticancer characteristics. However, the clinical application of MLT has been limited by its severe hemolytic activity, which poses a challenge for therapeutic use. By employing more efficient mechanisms, such as modifying the MLT sequence, genetic engineering, and nano-delivery systems, it is anticipated that the limitations posed by MLT can be overcome, thereby enabling its wider application in therapeutic contexts. This review has outlined recent advancements in MLT's nano-delivery systems and genetically engineered cells expressing MLT and provided an overview of where the MLTMLT's platforms are and where they will go in the future with the challenges ahead. The focus is on exploring how these approaches can overcome the limitations associated with MLT's hemolytic activity and improve its selectivity and efficacy in targeting cancer cells. These advancements hold promise for the creation of innovative and enhanced therapeutic approaches based on MLT for the treatment of cancer.

Integration of MXene and Microfluidics: A Perspective.

The fusion of MXene-based materials with microfluidics not only presents a dynamic and promising avenue for innovation but also opens up new possibilities across various scientific and technological domains. This Perspective delves into the intricate synergy between MXenes and microfluidics, underscoring their collective potential in material science, sensing, energy storage, and biomedical research. This intersection of disciplines anticipates future advancements in MXene synthesis and functionalization as well as progress in advanced sensing technologies, energy storage solutions, environmental applications, and biomedical breakthroughs. Crucially, the manufacturing and commercialization of MXene-based microfluidic devices, coupled with interdisciplinary collaborations, stand as pivotal considerations. Envisioning a future where MXenes and microfluidics collaboratively shape our technological landscape, addressing intricate challenges and propelling innovation forward necessitates a thoughtful approach. This viewpoint provides a comprehensive assessment of the current state of the field while outlining future prospects for the integration of MXene-based entities and microfluidics.

Highly selective and sensitive recognition of multi-ions in aqueous solution based on polymer-grafted nanoparticle as visual colorimetric sensor.

A novel, selective and sensitive colorimetric sensor for naked-eye detection and adsorption of multi-ions in aqueous solution was synthesized using hybridization of organic-inorganic phase. The polymer-grafted nanoparticles (PGNPs) was synthesized via atom transfer radical polymerization (ATRP) of monomers on modified TiO2 NPs and applied under optimized conditions for naked-eye detection: sensor mass: 15 mg; response time: 30 s with limits of detection (LODs) as small as 10, 1, 0.5, and 1 ppb Hg (II), Cd (II), Cu (II), and UO2 (II) at pH = 8, 9, 6, and 7, respectively. The efficient selectivity of the naked eye sensor to multi-ions in the presence of various ions was affirmed wherein the color of the chemosensor in the presence of Hg (II), Cd (II), Cu (II), and UO2 (II) shifted from gray to violet, orange, green and yellow, respectively. The salient advantages of this method comprise expeditious, selectable, high reproducibility, with reasonable adsorption capacity (133 mg g-1) and inexpensive nature for rapid detection of heavy metal ions contamination in aqueous solution in an inexpensive manner. The adsorption mechanism was studied via adsorption kinetics and adsorption isotherm models and the accuracy of the chemosensor has been confirmed and supported by XRD, FT-IR, TGA, 1H-NMR, SEM, TEM, EDX mapping, DLS, BET, and EDS analysis.

A review of chitosan nanoparticles: Nature's gift for transforming agriculture through smart and effective delivery mechanisms.

Chitosan nanoparticles (CNPs) have emerged as a promising tool in agricultural advancements due to their unique properties including, biocompatability, biodegradability, non-toxicity and remarkable versatility. These inherent properties along with their antimicrobial, antioxidant and eliciting activities enable CNPs to play an important role in increasing agricultural productivity, enhancing nutrient absorption and improving pest management strategies. Furthermore, the nano-formulation of chitosan have the ability to encapsulate various agricultural amendments, enabling the controlled release of pesticides, fertilizers, plant growth promoters and biocontrol agents, thus offering precise and targeted delivery mechanisms for enhanced efficiency. This review provides a comprehensive analysis of the latest research and developments in the use of CNPs for enhancing agricultural practices through smart and effective delivery mechanisms. It discusses the synthesis methods, physicochemical properties, and their role in enhancing seed germination and plant growth, crop protection against biotic and abiotic stresses, improving soil quality and reducing the environmental pollution and delivery of agricultural amendments. Furthermore, the potential environmental benefits and future directions for integrating CNPs into sustainable agricultural systems are explored. This review aims to shed light on the transformative potential of chitosan nanoparticles as nature's gift for revolutionizing agriculture and fostering eco-friendly farming practices.

Green synthesis of sustainable magnetic nanoparticles Fe3O4 and Fe3O4-chitosan derived from Prosopis farcta biomass extract and their performance in the sorption of lead(II).

The sustainable processes are now in tremendous demand for nanomaterial synthesis as a result of their unique properties and characteristics. The magnetic nanoparticles comprised of Fe3O4 and its conjugate with abundant and renewable biopolymer, chitosan, were synthesized using Prosopis farcta biomass extract, and the resulting materials were used to adsorb Pb (II) from aqueous solution. Thermodynamic parameters revealed that the sorption of lead (II) on Fe3O4 as well as Fe3O4-Chitosan (Fe3O4-CS) has been an endothermic and self-regulating procedure wherein the sorption kinetics was defined by a pseudo-second-order pattern and the sorption isotherms corresponded to the Freundlich pattern. A multivariable quadratic technique for adsorption process optimization was implemented to optimize the lead (II) adsorption on Fe3O4 and Fe3O4-chitosan nanoparticles, the optimal conditions being pH 7.9, contact time of 31.2 min, initial lead concentration of 39.2 mg/L, adsorbent amount of 444.3 mg, at a 49.7 °C temperature. The maximum adsorption efficiencies under optimal conditions were found to be 69.02 and 89.54 % for Fe3O4 and Fe3O4-CS adsorbents, respectively. Notably, Fe3O4 and Fe3O4-CS can be easily recovered using an external magnet, indicating that they are a viable and cost-effective lead removal option.

Immunomodulatory effects of copper nanoparticles against mitogen-stimulated rat splenic and thymic lymphocytes.

In the present study, we have evaluated the effects of copper (Cu) nanoparticles (NPs) on the primary B-and T-lymphocytes proliferation, cytokine levels, and bio-distribution through in vitro, in vivo and ex-vivo studies to allow the possible exploitations of CuNPs in biomedical applications. CuNPs were characterized by UV-Visible spectroscopy, transmission electron microscopy (TEM), and nanoparticle tracking analysis (NTA). The proliferative response of lymphocytes was studied by 3H-thymidine incorporation assay and lymphocyte viability through trypan blue assay. The bio-distribution of CuNPs into lymphoid organs was examined by using ex-vivo imaging system. Cytokine levels in plasma of control and CuNPs treated animal groups were determined by enzyme-linked immunosorbent assay (ELISA) method along with other biochemical analysis. CuNPs significantly suppressed the proliferation of primary splenic and thymic lymphocytes in a dose dependent manner. Ex-vivo imaging exhibited the distribution of CuNPs in spleen and thymus. Oral administration of CuNPs (2 mg and 10 mg/kg body weight) significantly inhibited the proliferation of splenic and thymic lymphocytes along with lowered cytokines levels (TNF-alpha and IL-2) on comparison with controls. The results indicated the significant inhibition of lymphocytes proliferative response and secretion of cytokines, thus unveiling the immunomodulatory effects of CuNPs.

Linear-Structure Single-Atom Gold(I) Catalyst for Dehydrogenative Coupling of Organosilanes with Alcohols.

A strategy for the synthesis of a gold-based single-atom catalyst (SAC) via a one-step room temperature reduction of Au(III) salt and stabilization of Au(I) ions on nitrile-functionalized graphene (cyanographene; G-CN) is described. The graphene-supported G(CN)-Au catalyst exhibits a unique linear structure of the Au(I) active sites promoting a multistep mode of action in dehydrogenative coupling of organosilanes with alcohols under mild reaction conditions as proven by advanced XPS, XAFS, XANES, and EPR techniques along with DFT calculations. The linear structure being perfectly accessible toward the reactant molecules and the cyanographene-induced charge transfer resulting in the exclusive Au(I) valence state contribute to the superior efficiency of the emerging two-dimensional SAC. The developed G(CN)-Au SAC, despite its low metal loading (ca. 0.6 wt %), appear to be the most efficient catalyst for Si-H bond activation with a turnover frequency of up to 139,494 h-1 and high selectivities, significantly overcoming all reported homogeneous gold catalysts. Moreover, it can be easily prepared in a multigram batch scale, is recyclable, and works well toward more than 40 organosilanes. This work opens the door for applications of SACs with a linear structure of the active site for advanced catalytic applications.

Visible light mediated synthesis of 1,3-diarylated imidazo[1,5-a]pyridines via oxidative amination of C-H catalyzed by graphitic carbon nitride.

Graphitic carbon nitride (g-C3N4) as a novel heterogeneous catalyst is employed for the visible light-mediated synthesis of the imidazo[1,5-a]pyridines via the oxidative amination of C-H bond at room temperature without the need for any additional solvent. Extensive characterization of the catalyst was performed using techniques such as FT-IR, PXRD, TGA, SEM and EDX analysis. The optimized conditions enabled the successful and expeditious conversion of a wide range of substrates to imidazo[1,5-a]pyridines in good yields; a notable advantage of this catalyst being recyclability, as it can be reused for up to five cycles without significant loss of activity. This feature makes it suitable for gram-scale synthesis of imidazo[1,5-a]pyridines. Additionally, this approach offers several benefits from a green chemistry perspective as affirmed by its favorable green chemistry metrics (GCM), including low process mass intensity (PMI), low E-factor, high atom economy (AE), and good reaction mass efficiency (RME) relative to existing protocols. In addition, chemical yield (CY), mass intensity (MI), mass productivity (MP) and optimum efficiency were also calculated. This environmentally friendly method offers multiple advantages and represents a significant advancement in the synthesis of imidazo[1,5-a]pyridines.

Smart stimuli-responsive polysaccharide nanohydrogels for drug delivery: a review.

Polysaccharides have found extensive utilization as biomaterials in drug delivery systems owing to their remarkable biocompatibility, simple functionalization, and inherent biological properties. Within the array of polysaccharide-based biomaterials, there is a growing fascination for self-assembled polysaccharide nanogels (NG) due to their ease of preparation and enhanced appeal across diverse biomedical appliances. Nanogel (or nanohydrogel), networks of nanoscale dimensions, are created by physically or chemically linking polymers together and have garnered immense interest as potential carriers for delivering drugs due to their favorable attributes. These include biocompatibility, high stability, the ability to adjust particle size, the capacity to load drugs, and their inherent potential to modify their surface to actively target specific cells or tissues via the attachment of ligands that can recognize corresponding receptors. Nanogels can be engineered to respond to specific stimuli, such as pH, temperature, light, or redox conditions, allowing controlled release of the encapsulated drugs. This intelligent targeting capability helps prevent drug accumulation in unintended tissues and reduces the potential side effects. Herein, an overview of nanogels is offered, comprising their methods of preparation and the design of stimulus-responsive nanogels that enable controlled release of drugs in response to specific stimuli.

Facile synthesis of carbon quantum dot/silver nanocomposite and its antimicrobial, catalytic and sensing applications.

Environmentally benign synthesis of nanocomposite, a pivotal facet of nanotechnology, and gaining prominence due to the increasing demand for facile, sustainable, and safe synthesis methods. The present research reports an facile/cost-effective method for the preparation of carbon dots (CDs) and carbon dot silver nanocomposites ( CD@AgNCs) via a hydrothermal treatment of peanut shells. The well-dispersed and spherical CDs with an average diameter of 5-6 nm were obtained and further employed for the preparation of CD@AgNCs. The formation of CD@AgNCs. was confirmed by optical and microscopic studies and ared shift in the λmax from 277 nm (CDs) to 450 nm (CD@AgNCs) with a size range of 30-40 nm was observed. The synthesized CD@AgNCs exhibit excellent catalytic potency for the reduction of 4-nitrophenol to 4-aminophenol, and also displaying a unique interaction and sensing ability towards heavy metal ions (Hg2+), causing a pronounced change in color from reddish-brown to transparent with limit of detection (LOD) of 23.47 ppm. Also, the prepared composite exhibit efficient antimicrobial potential against gram-negative (Escherichia coli) bacteria. Consequently, this study delves into a unified effective remediation platform with the integration of catalysis, sensing, and antimicrobial potentials.

Black Phosphorus-based Photocatalysts: Synthesis, Properties, and Applications.

Photocatalysis is considered as an eco-friendly and sustainable strategy, since it uses abundant light for the advancement of the reaction, which is freely accessible and is devoid of environmental pollution. During the last decades, (nano)photocatalysts have gained broad industrial applications in terms of purification and detoxification of water as well as production of green fuels and hydrogen gas due to their special attributes. The degradation or remediation of toxic and hazardous compounds from the environment or changing them into non-toxic entities is a significant endeavor and necessary for the safety of humans, animals, and the environment. Black phosphorus (BP), a two-dimensional single-element material, has a marvelous structure, tunable bandgap, changeable morphology from bulk to nanosheet/quantum dot, and unique physicochemical properties, which makes it attractive material for photocatalytic applications, especially for sustainable development purposes. Since it can serve as a photocatalyst with or without coupling with other semiconductors, various aspects for multidimensional exploitation of BP are deliberated including their preparation via solvothermal, ball milling, calcination, and sonication methods to obtain BP from red phosphorus. The techniques for improving the photocatalytic and stability of BP-based composites are discussed along with their multifaceted applications for environmental remediation, pollution degradation, water splitting, N2 fixation, CO2 reduction, bacterial disinfection, H2 generation, and photodynamic therapy. Herein, most recent advancements pertaining to the photocatalytic applications of BP-based photocatalyst are cogitated, with a focus on their synthesis and properties as well as crucial challenges and future perspectives.

Nano/micro-cellulose-based materials as remarkable sorbents for the remediation of agricultural resources from chemical pollutants.

Overusing pesticides, fertilizers, and synthetic dyes has significantly increased their presence in various parts of the environment. The transportation of these pollutants into agricultural soil and water through rivers, soils, and groundwater has seriously threatened human and ecosystem health. Applying techniques and materials to clean up agricultural sources from pesticides, heavy metals (HMs), and synthetic dyes (SDs) is one of the major challenges in this century. The sorption technique offers a viable solution to remediate these chemical pollutants (CHPs). Cellulose-based materials have become popular in nano and micro scales because they are widely available, safe to use, biodegradable, and have a significant ability to absorb substances. Nanoscale cellulose-based materials exhibit greater capacity in absorbing pollutants compared to their microscale counterparts because they possess a larger surface area. Many available hydroxyl groups (-OH) and chemical and physical modifications enable the incorporation of CHPs on to cellulose-based materials. Following this potential, this review aims to comprehensively summarize recent advancements in the field of nano- and micro-cellulose-based materials as effective adsorbents for CHPs, given the abundance of cellulosic waste materials from agricultural residues. The recent developments pertaining to the enhancement of the sorption capacity of cellulose-based materials against pesticides, HMs, and SDs, are deliberated.

Metal-organic frameworks (MOFs) as effectual diagnostic and therapeutic tools for cancer.

Metal-organic frameworks (MOFs) are a class of multifunctional organometallic compounds that include metal ions combined with assorted organic linkers. Recently, these compounds have received widespread attention in medicine, due to their exceptional qualities, including a wide surface area, high porosity, outstanding biocompatibility, non-toxicity, etc. Such characteristic qualities make MOFs superb candidates for biosensing, molecular imaging, drug delivery, and enhanced cancer therapies. This review illustrates the key attributes of MOFs and their importance in cancer research. The structural and synthetic aspects of MOFs are briefly discussed with primary emphasis on diagnostic and therapeutic features, as well as their performance and significance in modern therapeutic methods and synergistic theranostic strategies including biocompatibility. This review offers cumulative scrutiny of the widespread appeal of MOFs in modern-day oncological research, which may stimulate further explorations.