Recent Advances, Challenges, and Future Perspectives of ZnO Nanostructure Materials Towards Energy Applications.

In this approach, zinc oxide (ZnO) is a multipurpose substance with remarkable characteristics such as high sensitivity, a large specific area, non-toxicity, excellent compatibility, and a high isoelectric point, which make it attractive for discussion with some limitations. It is the most favorable possible option for the collection of nanostructures in terms of structure and their characteristics. The development of numerous ZnO nanostructure-based electrochemical sensors and biosensors used in health diagnosis, pharmaceutical evaluation, food hygiene, and contamination of the environment monitoring is described, as well as the production of ZnO nanostructures. Nanostructured ZnO has good chemical and temperature durability as an n-type semiconducting material, making it useful in a wide range of uses, from luminous materials to supercapacitors, batteries, solar cells, photocatalysis, biosensors, medicinal devices, and more. When compared to the bulk materials, the nanosized materials have both a higher rate of disintegration and a higher solubility. Furthermore, ZnO nanoparticles are regarded as top contenders for electrochemical sensors due to their strong electrochemical behaviors and electron transmission characteristics. The impact of many factors, including selectivity, sensitivity, detection limit, strength, and structures, arrangements, and their respective functioning processes, has been investigated. This study concentrated a substantial amount of its attention on the recent advancements that have been made in ZnO-based nanoparticles, composites, and modified materials for use in the application areas of energy storage and conversion devices as well as biological applications. Supercapacitors, Li-ion batteries, dye-sensitized solar cells, photocatalysis, biosensors, medicinal, and biological systems have been studied. ZnO-based materials are constantly analyzed for their advantages in energy and life science applications.

Progress and Perspectives on Promising Covalent-Organic Frameworks (COFs) Materials for Energy Storage Capacity.

In recent years, a new class of highly crystalline advanced permeable materials covalent-organic frameworks (COFs) have garnered a great deal of attention thanks to their remarkable properties, such as their large surface area, highly ordered pores and channels, and controllable crystalline structures. The lower physical stability and electrical conductivity, however, prevent them from being widely used in applications like photocatalytic activities and innovative energy storage and conversion devices. For this reason, many studies have focused on finding ways to improve upon these interesting materials while also minimizing their drawbacks. This review article begins with a brief introduction to the history and major milestones of COFs development before moving on to a comprehensive exploration of the various synthesis methods and recent successes and signposts of their potential applications in carbon dioxide (CO2 ) sequestration, supercapacitors (SCs), lithium-ion batteries (LIBs), and hydrogen production (H2 -energy). In conclusion, the difficulties and potential of future developing with highly efficient COFs ideas for photocatalytic as well as electrochemical energy storage applications are highlighted.

Assessment of heavy metals accumulation by vegetables irrigated with different stages of textile wastewater for evaluation of food and health risk.

Wastewater irrigation for vegetable cultivation is greatly concerned about the presence of toxic metals in irrigated soil and vegetables which causes possible threats to human health. This study aimed to ascertain the accumulation of heavy metals (HMs) in edible parts of vegetables irrigated with different stages of textile dyeing wastewater (TDW). Bio-concentration factor (BCF), Estimated daily intake (EDI), and target hazard quotient (THQ) were computed to estimate human health risks and speculate the hazard index (HI) of adults and children with the consumption of HMs contaminated vegetables at recommended doses. Five vegetables (red amaranth, Indian spinach, cauliflower, tomato, and radish) in a pot experiment were irrigated with groundwater (T1) and seven stages of TDW (T2∼T8) following a randomized complete block design (RCBD) with three replications. Among the TDW stages, T8, T7, T4, and T5 exhibited elevated BCF, EDI, THQ, and HI due to a rising trend in the accumulation of Pb, Cd, Cr, and Ni heavy metals in the edible portion of the red amaranth, followed by radish, Indian spinach, cauliflower, and tomato. The general patterns of heavy metal (HM) accumulation, regarded as vital nutrients for plants, were detected in the following sequence: Zn > Mn/Cu > Fe. Conversely, toxic metals were found to be Cd/Cr > Ni > Pb, regardless of the type of vegetables. Principal Component Analysis (PCA) identified T8, T7, and T4 of TDW as the primary contributors to the accumulation of heavy metals in the vegetables examined. Furthermore, the analysis of the heavy metals revealed that the BCF, THQ, and HI values for all studied metals were below 1, except for Pb. This suggests that the present consumption rates of different leafy and non-leafy vegetables, whether consumed individually or together, provide a low risk in terms of heavy metal exposure. Nevertheless, the consumption of T8, T7, and T4 irrigated vegetables, specifically Indian spinach alone or in combination with red amaranth and radish, by both adults and children, at the recommended rate, was found to pose potential health risks. On the other hand, T2, T3, and T6 irrigated vegetables were deemed safe for consumption. These findings indicated that the practice of irrigating the vegetables with T8, T7, and T4 stages of TDW has resulted in a significant buildup of heavy metals in the soils and edible parts of vegetables which are posing health risks to adults and children. Hence, it is imperative to discharge the T8, T7, and T4 stages of TDW after ETP to prevent the contamination of vegetables and mitigate potential health risks.

Dopant-Free Pyrene-Based Hole Transporting Material Enables Efficient and Stable Perovskite Solar Cells.

Dopant-free hole transporting materials (HTMs) is significant to the stability of perovskite solar cells (PSCs). Here, we developed a novel star-shape arylamine HTM, termed Py-DB, with a pyrene core and carbon-carbon double bonds as the bridge units. Compared to the reference HTM (termed Py-C), the extension of the planar conjugation backbone endows Py-DB with typical intermolecular π-π stacking interactions and excellent solubility, resulting in improved hole mobility and film morphology. In addition, the lower HOMO energy level of the Py-DB HTM provides efficient hole extraction with reduced energy loss at the perovskite/HTM interface. Consequently, an impressive power conversion efficiency (PCE) of 24.33 % was achieved for dopant-free Py-DB-based PSCs, which is the highest PCE for dopant-free small molecular HTMs in n-i-p configured PSCs. The dopant-free Py-DB-based device also exhibits improved long-term stability, retaining over 90 % of its initial efficiency after 1000 h exposure to 25 % humidity at 60 °C. These findings provide valuable insights and approaches for the further development of dopant-free HTMs for efficient and reliable PSCs.

New Opportunities in Metal-Organic Framework Catalysis: From Bifunctional to Frustrated Lewis Pairs Catalysis.

This article highlights novel prospects for metal-organic frameworks (MOFs) in heterogeneous catalysis as having frustrated Lewis acid-base pairs (FLPs) or as bifunctional acid-base solid catalysts able to activate molecular hydrogen. Starting from the extensive application MOFs as Lewis acid and Lewis base catalysts, this article uses catalytic hydrogenation to briefly summarize the efforts made to heterogenize boron and amine in MOFs to mimic molecular FLP systems. The core of this concept is based on recent findings which demonstrate the ability of two commonly used MOFs, namely UiO-66 and MIL-101, to catalyze the selective hydrogenation of polar double X=Y bonds at moderate H2 pressures below 10 bar. The influence of electron-donating, the withdrawal of substituents on the linker, and the aniline poisoning effect highlight the significance of Lewis acid sites, while density-functional theory calculations indicate the heterolytic H-H bond cleavage at the MOF metal oxo clusters. It is expected that this new perspective on MOFs as solid FLP systems will spur further research to explore and define the potential of dual sites in the catalytic activation of small molecules.

Improved Alkaline Seawater Splitting of NiS Nanosheets by Iron Doping.

Seawater electrolysis driven by renewable electricity is deemed a promising and sustainable strategy for green hydrogen production, but it is still formidably challenging. Here, we report an iron-doped NiS nanosheet array on Ni foam (Fe-NiS/NF) as a high-performance and stable seawater splitting electrocatalyst. Such Fe-NiS/NF catalyst needs overpotentials of only 420 and 270 mV at 1000 mA cm-2 for the oxygen evolution reaction and hydrogen evolution reaction in alkaline seawater, respectively. Furthermore, its two-electrode electrolyzer needs a cell voltage of 1.88 V for 1000 mA cm-2 with 50 h of long-term electrochemical durability in alkaline seawater. Additionally, in situ electrochemical Raman and infrared spectroscopy were employed to detect the reconstitution process of NiOOH and the generation of oxygen intermediates under reaction conditions.

Emergence of CuInS2 derived photocatalyst for environmental remediation and energy conversion.

Hydrogen production, catalytic organic synthesis, carbon dioxide reduction, environmental purification, and other major fields have all adopted photocatalytic technologies due to their eco-friendliness, ease of use, and reliance on sunlight as the driving force. Photocatalyst is the key component of photocatalytic technology. Thus, it is of utmost importance to produce highly efficient, stable, visible-light-responsive photocatalysts. CIS stands out among other visible-light-response photocatalysts for its advantageous combination of easy synthesis, non-toxicity, high stability, and suitable band structure. In this study, we took a brief glance at the synthesis techniques for CIS after providing a quick introduction to the fundamental semiconductor features, including the crystal and band structures of CIS. Then, we discussed the ways doping, heterojunction creation, p-n heterojunction, type-II heterojunction, and Z-scheme may be used to modify CIS's performance. Subsequently, the applications of CIS towards pollutant degradation, CO2 reduction, water splitting, and other toxic pollutants remediation are reviewed in detail. Finally, several remaining problems with CIS-based photocatalysts are highlighted, along with future potential for constructing more superior photocatalysts.

Investigation of the impacts of simple electrolytes and hydrotrope on the interaction of ceftriaxone sodium with cetylpyridinium chloride at numerous study temperatures.

Herein, interactions between cetylpyridinium chloride (CPC) and ceftriaxone sodium (CTS) were investigated applying conductivity technique. Impacts of the nature of additives (e.g. electrolytes or hydrotrope (HDT)), change of temperatures (from 298.15 to 323.15 K), and concentration variation of CTS/additives were assessed on the micellization of CPC + CTS mixture. The conductometric analysis of critical micelle concentration (CMC) with respect to the concentration reveals that the CMC values were increased with the increase in CTS concentration. In terms of using different mediums, CMC did not differ much with the increase in electrolyte salt (NaCl, Na2SO4) concentration, but increased significantly with the rise of HDT (NaBenz) amount. In the presence of electrolyte, CMC showed a gentle increment with temperature, while the HDT showed the opposite trend. Obtained result was further correlated with conventional thermodynamic relationship, where standard Gibb's free energy change (ΔGmo), change of enthalpy (ΔHmo), and change of entropy (ΔSmo) were utilized to investigate. The ΔGmo values were negative for all the mixed systems studied indicating that the micellization process was spontaneous. Finally, the stability of micellization was studied by estimating the intrinsic enthalpy gain (ΔHmo,∗) and compensation temperature (Tc). Here, CPC + CTS mixed system showed more stability in Na2SO4 medium than the NaCl, while in NaBenz exhibited the lowest stability.

DNA binding and cleavage, BRCA1 gene interaction, antiglycation and anticancer studies of transition metal complexes of sulfonamides.

A series of 4-((4-methylphenylsulfonamido)methyl)cyclohexanecarboxylic acid (NaMSCCA) transition metal complexes [Cu(II), Zn(II), Ni(II), Mn(II), and Co(II)] have been synthesized by precipitation method. The characterization was done by physical techniques, FT-IR spectroscopy, mass spectrometry, and NMR spectroscopy. The molecular structures of nickel (II) AZ-3 and cobalt (II) AZ-5 complexes were determined by the X-ray diffraction technique and found to crystallize in the triclinic space group P-1. The coordination geometry around the central nickel (AZ-3) and cobalt (AZ-5) atoms was square planar bipyramidal. Molecular docking was performed with duplex DNA of sequence d(CGCGAATTCGCG)2 DNA to determine the probable binding mode of compounds. Then these synthesized compounds were used to perform DNA cleavage activity through the agarose gel electrophoresis method. Among the compounds, compounds AZ-1 and AZ-2 exhibited good nuclease activity. The DNA sequence of breast-cancer suppressor gene 1 (BRCA1) was amplified through PCR and interaction studies of compounds AZ-1 and AZ-2 were performed through gel electrophoresis and fluorescence emission spectroscopy. The expression analysis of the BRCA1 gene was also performed to quantify the expression relative fold change (2^-(∆∆CT)) after treatment with compounds. All synthesized compounds were evaluated for their antioxidant and antiglycation activities and AZ-2 exhibited excellent results. The molecular docking study of these compounds was performed against the protein structure of advanced glycation end products to support the experimental results. Anticancer activity of compounds was performed through MTT assay. Copper and zinc complexes depicted the highest anticancer activity against human breast adenocarcinoma (MCF7) and human corneal epithelial cell (HCEC) cell lines.

Green-Chemistry-Inspired Synthesis of Cyclobutane-Based Hole-Selective Materials for Highly Efficient Perovskite Solar Cells and Modules.

Hybrid lead halide perovskite solar cells (PSCs) have emerged as potential competitors to silicon-based solar cells with an unprecedented increase in power conversion efficiency (PCE), nearing the breakthrough point toward commercialization. However, for hole-transporting materials, it is generally acknowledged that complex structures often create issues such as increased costs and hazardous substances in the synthetic schemes, when translated from the laboratory to manufacture on a large scale. Here, we present cyclobutane-based hole-selective materials synthesized using simple and green-chemistry inspired protocols in order to reduce costs and adverse environmental impact. A series of novel semiconductors with molecularly engineered side arms were successfully applied in perovskite solar cells. V1366-based PSCs feature impressive efficiency of 21 %, along with long-term operational stability under atmospheric environment. Most importantly, we also fabricated perovskite solar modules exhibiting a record efficiency over 19 % with an active area of 30.24 cm2 .

Asymmetrically Substituted 10H,10'H-9,9'-Spirobi[acridine] Derivatives as Hole-Transporting Materials for Perovskite Solar Cells.

Hole-transporting materials (HTMs) based on the 10H, 10'H-9,9'-spirobi [acridine] core (BSA50 and BSA51) were synthesized, and their electronic properties were explored. Experimental and theoretical studies show that the presence of rigid 3,6-dimethoxy-9H-carbazole moieties in BSA 50 brings about improved hole mobility and higher work function compared to bis(4-methoxyphenyl)amine units in BSA51, which increase interfacial hole transportation from perovskite to HTM. As a result, perovskite solar cells (PSCs) based on BSA50 boost power conversion efficiency (PCE) to 22.65 %, and a PSC module using BSA50 HTM exhibits a PCE of 21.35 % (6.5×7 cm) with a Voc of 8.761 V and FF of 79.1 %. The unencapsulated PSCs exhibit superior stability to devices employing spiro-OMeTAD, retaining nearly 90 % of their initial efficiency after 1000 h operation output. This work demonstrates the high potential of molecularly engineered spirobi[acridine] derivatives as HTMs as replacements for spiro-OMeTAD.

NiFe Layered-Double-Hydroxide Nanosheet Arrays on Graphite Felt: A 3D Electrocatalyst for Highly Efficient Water Oxidation in Alkaline Media.

It is of great importance to rationally design and develop earth-abundant nanocatalysts for high-efficiency water electrolysis. Herein, NiFe layered double hydroxide was in situ grown hydrothermally on a 3D graphite felt (NiFe LDH/GF) as a high-efficiency catalyst in facilitating the oxygen evolution reaction (OER). In 1.0 M KOH, NiFe LDH/GF requires a low overpotential of 214 mV to deliver a geometric current density of 50 mA cm-2 (η50 mA cm-2 = 214 mV), surpassing that NiFe LDH supported on a 2D graphite paper (NiFe LDH/GP; η50 mA cm-2 = 301 mV). More importantly, NiFe LDH/GF shows good durability at 50 mA cm-2 within 50 h of OER catalysis testing and delivers a faradaic efficiency of nearly 100% in the electrocatalysis of OER.

Manganese(III) acetate-mediated synthesis of N-substituted fulleropyrrolines via the reaction of [60]fullerene with α-monosubstituted acetaldehydes and primary amines.

The simple one-step reaction of [60]fullerene with α-monosubstituted acetaldehydes and primary amines in the presence of Mn(OAc)3·2H2O under air conditions afforded a series of novel N-substituted fulleropyrrolines with trisubstituted CC bonds in moderate to good yields. The addition of Mn(OAc)3·2H2O played a crucial role in the successful synthesis of N-aryl fulleropyrrolines with trisubstituted CC bonds, which would be extremely difficult to prepare by known methods as a result of the decreased nucleophilicity of arylamines due to the p-π conjugation effect. Intriguingly, arylamines displayed abnormally higher reactivity as compared with non-arylamines in the current reaction system by the observation of obviously decreased equivalent of Mn(OAc)3·2H2O, higher product yields, and lower reaction temperature probably due to the radical reaction mechanism initiated by Mn(OAc)3·2H2O. On the basis of experimental observations, a plausible formation pathway for N-substituted fulleropyrrolines with trisubstituted CC bonds was proposed to elucidate the above-mentioned reaction process.

Nanomaterials-Based Sensors for Respiratory Viral Detection: A Review.

Contagious diseases are the principal cause of mortality, particularly respiratory viruses, a real menace for public health and economic development worldwide. Therefore, timely diagnosis and treatments are the only life-saving strategy to overcome any epidemic and particularly the ongoing prevailing pandemic COVID-19 caused by SARS-CoV-2. A rapid identification, point of care, portable, highly sensitive, stable, and inexpensive device is needed which is exceptionally satisfied by sensor technology. Consequently, the researchers have directed their attention to employing sensors targeting multiple analyses of pathogenic detections across the world. Nanostructured materials (nanoparticles, nanowires, nanobundles, etc.), owing to their unique characteristics such as large surface-to-volume ratio and nanoscale interactions, are widely employed to fabricate facile sensors to meet all the immediate emerging challenges and threats. This review is anticipated to foster researchers in developing advanced nanomaterials-based sensors for the increasing number of COVID-19 cases across the globe. The mechanism of respiratory viral detection by nanomaterials-based sensors has been reported. Moreover, the advantages, disadvantages, and their comparison with conventional sensors are summarized. Furthermore, we have highlighted the challenges and future potential of these sensors for achieving efficient and rapid detection.

Mechanochemical Gold(III)-Carbon Bond Formation.

Starting from a [(MeO C^N^C)AuCl] complex as precursor, a direct substitution by C,H-activation from sp-, sp2 - or sp3 -C,H-bonds under basic conditions in a planetary ball mill was achieved. Because of the extraordinary photophysical properties of the target compounds, this protocol provides an easy access to a highly valued complex class. In contrast to existing protocols, no pre-functionalization of the starting materials is necessary and the use of expensive transition metal catalysts can be avoided, which makes this application appealing also for industrial purposes. In addition the methodology was not restricted to pincer complexes, which was demonstrated by the substitution of chelate type [(tpy)AuCl2 ] complexes.

Honeycomb Carbon Nanofibers: A Superhydrophilic O2 -Entrapping Electrocatalyst Enables Ultrahigh Mass Activity for the Two-Electron Oxygen Reduction Reaction.

Electrocatalytic two-electron oxygen reduction has emerged as a promising alternative to the energy- and waste-intensive anthraquinone process for distributed H2 O2 production. This process, however, suffers from strong competition from the four-electron pathway leading to low H2 O2 selectivity. Herein, we report using a superhydrophilic O2 -entrapping electrocatalyst to enable superb two-electron oxygen reduction electrocatalysis. The honeycomb carbon nanofibers (HCNFs) are robust and capable of achieving a high H2 O2 selectivity of 97.3 %, much higher than that of its solid carbon nanofiber counterpart. Impressively, this catalyst achieves an ultrahigh mass activity of up to 220 A g-1 , surpassing all other catalysts for two-electron oxygen reduction reaction. The superhydrophilic porous carbon skeleton with rich oxygenated functional groups facilitates efficient electron transfer and better wetting of the catalyst by the electrolyte, and the interconnected cavities allow for more effective entrapping of the gas bubbles. The catalytic mechanism is further revealed by in situ Raman analysis and density functional theory calculations.

Biomimetic Assembly of a Polydopamine Layer on Graphene as an Electron Gate for Fluorescent MicroRNA Detection in Living Cells.

A novel strategy was developed for microRNA detection based on the fluorescence quenching of polydopamine (PDA)-coated reduced graphene oxide (RGO) nanosheets (RGO@PDA). Compared with graphene oxide (GO), the reduction of GO and modification of the surface of RGO by PDA not only improve the stability, dispersity, biocompatibility, and cellular uptake without degeneration of the unique electronic properties of graphene, but also add an electron gate for harvesting electrons, as well as enabling efficient and forward electron transfer to avoid unwanted electron transfer and realize highly sensitive miRNA detection; thus a lower detection limit can be achieved in this sensing system. Remarkably, nanoprobes consisting of RGO@PDA and fluorescein-labeled single-stranded DNA can naturally enter cancer cells without the aid of transfection agents, as well as resisting enzymatic lysis and showing almost no effect on the cell viability. More importantly, intense and time-dependent fluorescence responses were observed from the important tumor marker microRNA-21 (miR-21) in living cells; thus suggesting that the proposed sensing platform shows great promise for applications in disease diagnosis and fundamental research into biochemistry.

Facile access to amino-substituted cyclopentafullerenes: novel reaction of [60]fullerene with ß-substituted propionaldehydes and secondary amines in the absence/presence of magnesium perchlorate.

A series of scarce amino-substituted cyclopentafullerenes instead of the expected N-alkyl-2,5-disubstituted fulleropyrrolidines were synthesized in moderate to excellent yields via the simple one-step reaction of [60]fullerene with cheap and easily available ß-substituted propionaldehydes and secondary amines in the absence/presence of magnesium perchlorate. The in situ generation of allylic amines from ß-substituted propionaldehydes and secondary amines played a crucial role in the successful preparation of amino-substituted cyclopentafullerenes without additional carbons. With the addition of magnesium perchlorate, secondary amines containing ethyl group(s) could produce novel amino-substituted cyclopentafullerenes with two additional carbons. All the obtained cyclopentafullerenes displayed high stereoselectivity with cis isomers as the exclusive or major products. Plausible reaction mechanisms are proposed to elucidate the above-mentioned reaction process.

Stereoselective synthesis of amino-substituted cyclopentafullerenes promoted by magnesium perchlorate/ferric perchlorate.

A facile one-step reaction of [60]fullerene with cinnamaldehydes and amines promoted by magnesium perchlorate/ferric perchlorate under air conditions afforded a series of rare amino-substituted cyclopentafullerenes in moderate to good yields. Stereoselectivity was readily achieved. Secondary amines exclusively produced N,N-disubstituted cyclopentafullerenes as cis isomers, while arylamines gave N-monosubstituted cyclopentafullerenes with a preference of cis isomers as major products. N-Monosubstituted cyclopentafullerenes could be further converted into other scarce cyclopentafullerenes in the presence of acid chloride or paraformaldehyde. A possible reaction pathway was proposed to elucidate the formation of amino-substituted cyclopentafullerenes.

Synthesis of Nitrogen Containing Chalcone: A Highly Sensitive and Selective Fluorescent Chemosensor for the Fe3+ Metal Ion in Aqueous Media.

Title compound (PTPO) was synthesized by the reaction of 2-acetyl pyridine with 3,4,5-trimethoxy benzaldehyde. The structure of the compound has been confirmed by spectroscopic techniques. Interaction of chalcone with different metal cations was analyzed based on the fluorescence behavior. Results show that chalcone act as on-off switching fluorescent chemosensor for selective and sensitive detection iron metal ion. Mechanism of quenching and complexation were resolute by Benesi-Hildebrand, Stern-Volmer plot and Job-plot.