A review of graphene derivative enhancers for perovskite solar cells.

Due to the finite nature, health and environmental hazards currently associated with the use of fossil energy resources, there is a global drive to hasten the development and deployment of renewable energy technologies. One such area encompasses perovskite solar cells (PSCs) that have shown photoconversion efficiencies (PCE) comparable to silicon-based photovoltaics, but their commercialisation has been set back by short-term stability and toxicity issues, among others. A tremendous potential to overcome these drawbacks is presented by the emerging applications of graphene derivative-based materials in PSCs as substitutes or components, composites with other functional materials, and enhancers of charge transport, blocking action, exciton dissociation, substrate coverage, sensitisation and stabilisation. This review aims to illustrate how these highly capable carbon-based materials can advance PSCs by critically outlining and discussing their current applications and strategically identifying prospective research avenues. The reviewed works show that graphene derivatives have great potential in boosting the performance and stability of PSCs through morphological modifications and compositional engineering. This can drive the sustainability and commercial viability aspects of PSCs.

Synthesis and characterisation of heteroatom-doped reduced graphene oxide/bismuth oxide nanocomposites and their application as photoanodes in DSSCs.

Semiconductor materials have been recently employed in photovoltaic devices, particularly dye-sensitized solar cells (DSSCs), to solve numerous global issues, especially the current energy crisis emanating from the depletion and hazardous nature of conventional energy sources, such as fossil fuels and nuclear energy. However, progress for the past years has been mainly limited by poor electron injection and charge carrier recombination experienced by DSSCs at the photoanode. Thus, novel semiconductor materials such as bismuth oxide (Bi2O3) have been investigated as an alternative photoanode material. In this study, Bi2O3 was integrated with nitrogen- or boron-doped reduced graphene oxide (N-rGO or B-rGO, respectively) via a hydrothermal approach at a temperature of 200 °C. Various instrumental techniques were used to investigate the morphology, phase structure, thermal stability, and surface area of the resulting nanocomposites. The incorporation of N-rGO or B-rGO into Bi2O3 influenced the morphology and structure of the nanocomposite, thereby affecting the conductivity and electrochemical properties of the nanocomposite. B-rGO/Bi2O3 exhibited a relatively large surface area (65.5 m2 g-1), lower charge transfer resistance (108.4 Ω), higher charge carrier mobility (0.368 cm2 V-1 s-1), and higher electrical conductivity (6.31 S cm-1) than N-rGO/Bi2O3. This led to the fabrication of B-rGO/Bi2O3 photoanode-based DSSCs with superior photovoltaic performance, as revealed by their relatively high power conversion efficiency (PCE) of 2.97%, which outperformed the devices based on N-rGO/Bi2O3, rGO/Bi2O3, and Bi2O3 photoanodes. Therefore, these results demonstrate the promising potential of heteroatom-doped rGO/Bi2O3-based nanocomposites as photoanode materials of choice for future DSSCs.

Lactate dehydrogenase and malate dehydrogenase: Potential antiparasitic targets for drug development studies.

Parasitic diseases remain a major public health concern for humans, claiming millions of lives annually. Although different treatments are required for these diseases, drug usage is limited due to the development of resistance and toxicity, which necessitate alternative therapies. It has been shown in the literature that parasitic lactate dehydrogenases (LDH) and malate dehydrogenases (MDH) have unique pharmacological selective and specificity properties compared to other isoforms, thus highlighting them as viable therapeutic targets involved in aerobic and anaerobic glycolytic pathways. LDH and MDH are important therapeutic targets for invasive parasites because they play a critical role in the progression and development of parasitic diseases. Any strategy to impede these enzymes would be fatal to the parasites, paving the way to develop and discover novel antiparasitic agents. This review aims to highlight the importance of parasitic LDH and MDH as therapeutic drug targets in selected obligate apicoplast parasites. To the best of our knowledge, this review presents the first comprehensive review of LDH and MDH as potential antiparasitic targets for drug development studies.

Design and synthesis of quinoline-pyrimidine inspired hybrids as potential plasmodial inhibitors.

Presently, artemisinin-based combination therapy (ACT) is the first-line therapy of Plasmodium falciparum malaria. With the emergence of malaria parasites that are resistant to ACT, alternative antimalarial therapies are urgently needed. In line with this, we designed and synthesised a series of novel N-(7-chloroquinolin-4-yl)-N'-(4,6-diphenylpyrimidin-2-yl)alkanediamine hybrids (6a-7c) and evaluated their inhibitory activity against the NF54 chloroquine-susceptible strain as a promising class of antimalarial compounds. The antiplasmodial screening revealed that seven analogues showed promising to good activity with half-maximal inhibitory concentration (IC50) = 0.32 µM-4.30 µM. Compound 7a with 1,4-diamine butyl linker and 4-hydroxyl phenyl on fourth and sixth position of pyrimidine core showed the most prominent activity with an IC50 value of 0.32 ± 0.06 µM, with a favourable safety profile of 9.79 to human kidney epithelial (HEK293) cells. The remaining six analogues showed moderate activity with IC50 values ranging from 7.50 µM to 83.01 µM. We further investigated the binding affinities of the molecules to two essential cytosolic P. falciparum heat shock protein 70 homologues; PfHsp70-1 and PfHsp70-z. Compound 7a exhibited the highest binding affinity for both PfHsp70s with KD in a lower nanomolar range (4.4-11.4 nM). Furthermore, molecular docking revealed that compounds 6, 6k, 7b and 7a exhibited better fitness in PfHsp70-1 with compound 7a showing the highest and lowest binding scores of -9.8 kcal/mol. Therefore, we speculate that PfHsp70-1 is one of the targets of these inhibitors. The bioisoteric replacement of the groups at phenyl ring at the fourth and sixth position of the pyrimidine core had a constructive association with antiplasmodial activity. The promising antiplasmodial activity of the synthesised analogues illustrates how crucial molecular hybridisation is as a strategy in the development of quinoline-pyrimidine hybrids as prospective antiprotozoal agents.

Dioxin and dibenzofuran like molecular analogues from the pyrolysis of biomass materials-the emerging challenge in bio-oil production.

INTRODUCTION: The aggressive search for renewable energy resources and essential pyrosynthetic compounds has marked an exponential rise in the thermal degradation of biomass materials. Consequently, clean and sustainable transport fuels are increasingly desirable in a highly industrialized economy, for energy security and environmental protection. For this reason, biomass materials have been identified as promising alternatives to fossil fuels despite the challenges resulting from the possible formation of toxic nitrogen-based molecules during biomass degradation. In order to understand the free radical characteristic challenges facing the use of bio-oil, a brief review of the effects of free radicals in bio-oil is presented. METHODOLOGY: Pyrolysis was conducted in a tubular flow quartz reactor at a residence time of 2 s at 1 atm. pressure, for a total pyrolysis time of 5 min. The thermal degradation of biomass components was investigated over the temperature range of 200 to 700 °C typically in 50 °C increments under two reaction conditions; pyrolysis in N2 and oxidative pyrolysis in 5% O2 in N2. The pyrolysate effluent was analysed using a Gas chromatograph hyphenated to a mass selective detector (MSD). RESULTS: The yield of levoglucosan in the pyrolysis of cellulose in the entire pyrolysis temperature range was 68.2 wt % under inert conditions and 28.8 wt % under oxidative conditions. On the other hand, formaldehyde from pyrolysis of cellulose yielded 4 wt % while that from oxidative pyrolysis was 7 wt % translating to ⁓ 1.8 times higher than the yield from pyrolysis. Accordingly, we present for the first time dioxin-like and dibenzofuran-like nitrogenated analogues from an equimassic pyrolysis of cellulose and tyrosine. Levoglucosan and formaldehyde were completely inhibited during the equimassic pyrolysis of cellulose and tyrosine. CONCLUSION: Clearly, any small amounts of N-biomass components such as amino acids in cellulosic biomass materials can inhibit the formation of levoglucosan-a major constituent of bio-oil. Overall, a judicious balance between the production of bio-oil and side products resulting from amino acids present in plant matter should be taken into account to minimize economic losses and mitigate against negative public health concerns.

Recent Applications of Carbon Nanotubes in Organic Solar Cells.

In recent years, carbon-based materials, particularly carbon nanotubes (CNTs), have gained intensive research attention in the fabrication of organic solar cells (OSCs) due to their outstanding physicochemical properties, low-cost, environmental friendliness and the natural abundance of carbon. In this regard, the low sheet resistance and high optical transmittance of CNTs enables their application as alternative anodes to the widely used indium tin oxide (ITO), which is toxic, expensive and scarce. Also, the synergy between the large specific surface area and high electrical conductivity of CNTs provides both large donor-acceptor interfaces and conductive interpenetrating networks for exciton dissociation and charge carrier transport. Furthermore, the facile tunability of the energy levels of CNTs provides proper energy level alignment between the active layer and electrodes for effective extraction and transportation of charge carriers. In addition, the hydrophobic nature and high thermal conductivity of CNTs enables them to form protective layers that improve the moisture and thermal stability of OSCs, thereby prolonging the devices' lifetime. Recently, the introduction of CNTs into OSCs produced a substantial increase in efficiency from ∼0.68 to above 14.00%. Thus, further optimization of the optoelectronic properties of CNTs can conceivably help OSCs to compete with silicon solar cells that have been commercialized. Therefore, this study presents the recent breakthroughs in efficiency and stability of OSCs, achieved mainly over 2018-2021 by incorporating CNTs into electrodes, active layers and charge transport layers. The challenges, advantages and recommendations for the fabrication of low-cost, highly efficient and sustainable next-generation OSCs are also discussed, to open up avenues for commercialization.

Synthesis of Carbon Nanomaterials from Biomass Utilizing Ionic Liquids for Potential Application in Solar Energy Conversion and Storage.

Considering its availability, renewable character and abundance in nature, this review assesses the opportunity of the application of biomass as a precursor for the production of carbon-based nanostructured materials (CNMs). CNMs are exceptionally shaped nanomaterials that possess distinctive properties, with far-reaching applicability in a number of areas, including the fabrication of sustainable and efficient energy harnessing, conversion and storage devices. This review describes CNM synthesis, properties and modification, focusing on reports using biomass as starting material. Since biomass comprises 60-90% cellulose, the current review takes into account the properties of cellulose. Noting that highly crystalline cellulose poses a difficulty in dissolution, ionic liquids (ILs) are proposed as the solvent system to dissolve the cellulose-containing biomass in generating precursors for the synthesis of CNMs. Preliminary results with cellulose and sugarcane bagasse indicate that ILs can not only be used to make the biomass available in a liquefied form as required for the floating catalyst CVD technique but also to control the heteroatom content and composition in situ for the heteroatom doping of the materials.

Architecture and synthesis of P,N-heterocyclic phosphine ligands.

Diverse P,N-phosphine ligands reported to date have performed exceptionally well as auxiliary ligands in organometallic catalysis. Phosphines bearing 2-pyridyl moieties prominently feature in literature as compared to phosphines with five-membered N-heterocycles. This discussion seeks to paint a broad picture and consolidate different synthetic protocols and techniques for N-heterocyclic phosphine motifs. The introduction provides an account of P,N-phosphine ligands, and their structural and coordination benefits from combining heteroatoms with different basicity in one ligand. The body discusses the synthetic protocols which focus on P-C, P-N-bond formation, substrate and nucleophile types and different N-heterocycle construction strategies. Selected references are given in relation to the applications of the ligands.

Recent advances in graphene-based materials for dye-sensitized solar cell fabrication.

In the past few years, dye-sensitized solar cells (DSSCs) have received considerable research attention, as potential alternatives to the commonly used, but expensive, silicon-based solar cells owing to the low-cost, facile fabrication procedures, less impact on the environment, capability of working even under low incoming light levels, and flexibility of DSSCs. However, the relatively low power conversion efficiencies (PCEs) and poor long-term operational stability of DSSCs still limit their large-scale and commercial applications. As a consequence, this has prompted tremendous research effort towards the realization of high performance and sustainable devices, through tailoring of the properties of the various DSSC components, via approaches such as introducing novel materials and new synthesis techniques. Among these, the application of novel materials, especially carbon-based materials, such as graphene and its derivatives, is more appealing due to their excellent optoelectronic, mechanical, thermal and chemical properties, which give them ample potential to replace or modify the traditional materials that are commonly used in the fabrication of the various DSSC components. In addition, the low-cost, abundance, non-toxicity, large specific surface area, flexibility and superior stability of graphene-based materials have enabled their recent use as photoanodes, i.e., transparent conducting electrodes, semiconducting layers and dye-sensitizers, electrolytes and counter electrodes in DSSCs. Recently, the introduction of graphene-based materials into DSSCs resulted in a pronounced increase in PCE from ∼0.13 to above 12.00%. Thus, employing the recent breakthroughs can further improve the optoelectronic properties of the various DSSC components and, hence, close the gap between DSSCs and their silicon-based counterparts that are currently exhibiting desirable PCEs of above 26%. Therefore, this review focuses on the recent applications of graphene-based materials as photoanodes, electrolytes and counter electrodes, for the possible fabrication of all-carbon-based DSSCs. The limitations, merits and future prospects of graphene-based DSSCs are discussed, so as to improve their photovoltaic performance, sustainability and cost-effectiveness.

Synthesis, crystal structures and electrochemical properties of ferrocenyl imidazole derivatives.

Six ferrocenyl imidazole derivatives substituted with -Cl, -NO2 and -CH3 on the 2-position of the 1H-imidazole ring have been synthesized. Of the six compounds, the di-substituted ferrocenes, i.e. compounds 4 (1,1'-ferrocenylmethyl(2-chloroimidazole)), 5 (1,1'-ferrocenyl(2-nitroimidazole)), and 6 (1,1'-ferrocenylmethyl(2-methylimidazole)) are reported for the first time. The structure-property relationships of compounds 4, 5 and 6 were investigated by means of UV-visible, FTIR, 1H-NMR, 13C-NMR spectroscopy and electrochemical studies. UV-visible analysis in acetonitrile showed that the π -π* band of compounds 2 (1-ferrocenylmethyl(2-nitroimidazole)) and 5 appeared at longer wavelength compared to 1 (1-ferrocenylmethyl(2-chloroimidazole)), 3 (1-ferrocenylmethyl(2-methylimidazole)), 4 and 6. This phenomenon is due to the different electronics around the imidazole moieties. In cyclic voltammetry analysis, all compounds exhibited a quasi-reversible redox wave for the ferrocenyl and imidazole moieties. Density functional theoretical (DFT) calculations with the B3LYP/6-311+G(d) basis set were performed on compounds 1-6, and the calculated HUMO-LUMO band gap energies correlated with those obtained from electrochemical and spectroscopic data. The X-ray crystallographic analysis highlighted the effect of electron-withdrawing and electron-donating substituents on the conformation of the cyclopentadienyl rings attached to the ferrocenyl moiety.

Mechanistic formation of hazardous molecular heterocyclic amines from high temperature pyrolysis of model biomass materials: cellulose and tyrosine.

BACKGROUND: Research inventories on the co-pyrolysis of major biomass components such as cellulose with amino acid materials is scarce in literature despite the fact that such studies are critical in understanding toxic product relations from high temperature cooking, combustion of bio-fuels, cigarette smoking and forest fires. This paper explores, quantitatively, the yields of heterocyclic nitrogenated molecular reaction products of grave mutagenetic concern from the co-pyrolysis of model biomass materials; tyrosine and cellulose. Research has established that heterocyclic amines such as isocyanates are mutagens as well precursors for asthma, and other respiratory disorders. METHODS: An equimassic mixture of tyrosine and cellulose (50 ± 2 mg) by weight were pyrolyzed in a tubular quartz reactor in flowing nitrogen at 1 atm. Besides, varying combinations of tyrosine and cellulose in the ratios 3:1 and 1:3 were also explored for comparison. The reaction time was set at 2 s so as to simulate combustions events in nature. The pyrolysate was collected over 5 mL dichloromethane and characterized using a gas chromatograph coupled to a mass spectrometer detector. RESULTS: Evidently, it was noted that 1-methylindazole was released in high yields at 300 °C, constituting ~ 300 µg in the entire pyrolysis temperature range (200-700 °C). Nonetheless, isoindazole gave the highest yield ~ 730 µg while 1-naphthyl isocyanate gave a total yield of ~ 336 µg in the same temperature range. Remarkably, the change in char yield between 300 and 450 °C for the pyrolysis of 25% tyrosine in 75% cellulose was found to be ~ 48% whereas the change in char yield for the pyrolysis of 75% tyrosine in 25% cellulose was 49%. CONCLUSION: The char and tar yields considered important residues of biomass burning have been reported in this study and found to be consistent with other research output in literature. The striking similarities of % yield of char across all temperatures for various combinations was the most significant observation in this investigation-char yield was independent of the mixing ratio during pyrolysis. From a mechanistic standpoint, it was noted that tyrosine inhibited cellulose based nitrogenated products. Thus N-products dominated the O-products.

Effect of Doping Temperatures and Nitrogen Precursors on the Physicochemical, Optical, and Electrical Conductivity Properties of Nitrogen-Doped Reduced Graphene Oxide.

The greatest challenge in graphene-based material synthesis is achieving large surface area of high conductivity. Thus, tuning physico-electrochemical properties of these materials is of paramount importance. An even greater problem is to obtain a desired dopant configuration which allows control over device sensitivity and enhanced reproducibility. In this work, substitutional doping of graphene oxide (GO) with nitrogen atoms to induce lattice-structural modification of GO resulted in nitrogen-doped reduced graphene oxide (N-rGO). The effect of doping temperatures and various nitrogen precursors on the physicochemical, optical, and conductivity properties of N-rGO is hereby reported. This was achieved by thermal treating GO with different nitrogen precursors at various doping temperatures. The lowest doping temperature (600 °C) resulted in less thermally stable N-rGO, yet with higher porosity, while the highest doping temperature (800 °C) produced the opposite results. The choice of nitrogen precursors had a significant impact on the atomic percentage of nitrogen in N-rGO. Nitrogen-rich precursor, 4-nitro-ο-phenylenediamine, provided N-rGO with favorable physicochemical properties (larger surface area of 154.02 m2 g-1) with an enhanced electrical conductivity (0.133 S cm-1) property, making it more useful in energy storage devices. Thus, by adjusting the doping temperatures and nitrogen precursors, one can tailor various properties of N-rGO.

Free radicals and ultrafine particulate emissions from the co-pyrolysis of Croton megalocarpus biodiesel and fossil diesel.

BACKGROUND: The atmosphere has become a major transport corridor for free radicals and particulate matter from combustion events. The motivation behind this study was to determine the nature of particulate emissions and surface bound radicals formed during the thermal degradation of diesel blends in order to assess the health and environmental hazards of binary transport fuels. METHODOLOGY: Accordingly, this contribution explored the interactions that occur when Croton megalocarpus biodiesel and fossil diesel in the ratio of 1:1 by weight were co-pyrolyzed in a quartz reactor at a residence time of 0.5 s under an inert flow of nitrogen at 600 °C. The surface morphology of the thermal char formed were imaged using a Feld emission gun scanning electron microscope (FEG SEM) while Electron paramagnetic resonance spectrometer (EPR) was used to explore the presence of free radicals on the surface of thermal char. Molecular functional groups adsorbed on the surface of thermal char were explored using Fourier transform infrared spectroscopy (FTIR). RESULTS: FTIR spectrum showed that the major functional groups on the surface of the char were basically aromatic and some methylene groups. The particulate emissions detected in this work were ultrafine (~ 32 nm). The particulates are consistent with the SEM images observed in this study. Electron paramagnetic resonance results gave a g-value of 2.0027 characteristic of carbon-based radicals of aromatic nature. Spectral peak-to-peak width (∆Hp-p) obtained was narrow (4.42 G). CONCLUSIONS: The free radicals identified as carbon-based are medically notorious and may be transported by various sizes of particulate matter on to the surface of the human lung which may trigger cancer and pulmonary diseases. The nanoparticulates determined in this work can precipitate severe biological health problems among humans and other natural ecosystems.

Environmentally persistent free radicals and particulate emissions from the thermal degradation of Croton megalocarpus biodiesel.

Pyrolysis of biodiesel at high temperatures may result in the formation of transient and stable free radicals immobilized on particulate emissions. Consequently, free radicals adsorbed on particulates are believed to be precursors for health-related illnesses such as cancer, cardiac arrest, and oxidative stress. This study explores the nature of free radicals and particulate emissions generated when Croton megalocarpus biodiesel is pyrolyzed at 600 °C in an inert environment of flowing nitrogen at a residence time of 0.5 s at 1 atm. The surface morphology of thermal emissions were imaged using a field emission gun scanning electron microscope (FEG SEM) while the radical characteristics were investigated using an electron paramagnetic resonance spectrometer (EPR). A g-value of 2.0024 associated with a narrow ∆Hp-p of 3.65 G was determined. The decay rate constant for the radicals was low (1.86 × 10-8 s-1) while the half-life was long ≈ 431 days. The observed EPR characterization of Croton megalocarpus thermal particulates revealed the existence of free radicals typical of those found in coal. The low g-value and low decay rate constant suggests that the free radicals in particulates are possibly carbon-centered. The mechanistic channel for the formation of croton char from model biodiesel component (9-dodecenoic acid, methyl ester) has been proposed in this study.

Germanium quantum dot/nitrogen-doped graphene nanocomposite for high-performance bulk heterojunction solar cells.

This study presents the successful synthesis of a novel nanocomposite, namely a germanium quantum dot/nitrogen-doped graphene nanocomposite (GeQD/NGr), and its use in the modification of the photoactive medium of bulk heterojunction solar cells (BHJ-SCs). The nanocomposite was prepared in two sequential steps. Firstly, a reduced graphene oxide-germanium oxide nanocomposite (rGO-GeO2) was synthesized by microwave-assisted solvothermal reaction. The second step involved simultaneous N-doping of graphene and reduction of GeO2 to obtain the GeQD/NGr nanocomposite by thermal treatment. The nanocomposite consists of highly crystalline, spherical shaped GeQDs with a mean diameter of 4.4 nm affixed on the basal planes of NGr sheets. Poly-3-hexylthiophene (P3HT), (6-6)phenyl-C60-butyric acid methyl ester (PCBM) and GeQD/NGr were used as the photoactive layer blend in the fabrication of BHJ-SCs. Enhanced short-circuit current density (J sc) and fill factor (FF) is derived from the incorporation of the GeQD/NGr nanocomposite in the active layer. The nanocomposite in the active layer blend serves to ensure effective charge separation and transportation to the respective electrodes. Consequently, an improvement of up to 183% in the power conversion efficiency is achieved in the BHJ-SCs by the GeQD/NGr modification.

Reduced graphene oxide-germanium quantum dot nanocomposite: electronic, optical and magnetic properties.

Graphene provides numerous possibilities for structural modification and functionalization of its carbon backbone. Localized magnetic moments can, as well, be induced in graphene by the formation of structural defects which include vacancies, edges, and adatoms. In this work, graphene was functionalized using germanium atoms, we report the effect of the Ge ad atoms on the structural, electrical, optical and magnetic properties of graphene. Reduced graphene oxide (rGO)-germanium quantum dot nanocomposites of high crystalline quality were synthesized by the microwave-assisted solvothermal reaction. Highly crystalline spherical shaped germanium quantum dots, of diameter ranging between 1.6-9.0 nm, are anchored on the basal planes of rGO. The nanocomposites exhibit high electrical conductivity with a sheet resistance of up to 16 Ω sq-1. The electrical conductivity is observed to increase with the increase in Ge content in the nanocomposites. High defect-induced magnetization is attained in the composites via germanium adatoms. The evolution of the magnetic moments in the nanocomposites and the coercivity showed marked dependence on the Ge quantum dots size and concentration. Quantum confinement effects is evidenced in the UV-vis absorbance spectra and photoluminescence emission spectra of the nanocomposites which show marked size-dependence. The composites manifest strong absorption in the UV region, strong luminescence in the near UV region, and a moderate luminescence in the visible region.

Facile Synthesis of Three-Dimensional Mg-Al Layered Double Hydroxide/Partially Reduced Graphene Oxide Nanocomposites for the Effective Removal of Pb2+ from Aqueous Solution.

A series of three-dimensional (3D) porous nanocomposites, comprised of partially reduced graphene oxide (pRGO) and CO32- containing Mg-Al layered double hydroxide, were synthesized in two steps. In the first step, graphene oxide (GO) was fabricated by a modified Hummers' method, and, subsequently, in the second step layered double hydroxide (LDH) nanosheets were homogeneously grown on the surface of the GO sheets by an in situ crystallization approach, involving a facile coprecipitation technique. The alkaline medium used for the in situ growth of LDH on the GO surface resulted in the partial reduction of GO to pRGO, which was confirmed by XRD. XRD also revealed the successful formation of crystalline LDH nanosheets on the surface of pRGO, whereas FTIR spectroscopy confirmed the presence of different functional groups in the nanocomposites. Nitrogen adsorption-desorption studies of the prepared nanocomposites revealed them as high surface area porous materials. Electron microscopic techniques, like TEM and SEM, confirmed that the architectures of the prepared nanocomposites displayed an interconnected 3D network, where a number of LDH nanosheets were interwoven on the surface of pRGO. The elemental mapping and EDX analysis qualitatively confirmed the presence of all of the expected elements in the fabricated nanocomposites. Because of the unique 3D porous network and the presence of a large number of oxygen-containing functional groups, the prepared nanocomposites proved suitable for the adsorption of Pb2+ ions from aqueous solution with a maximum adsorption capacity of 116.2 mg g-1. Equilibrium was achieved after 180 min on conducting the adsorption experiments at pH 4.5. Desorption experiments established the possibility of recovering the metal ions as well as the regeneration of adsorbents for repeated use.

A dual-purpose silver nanoparticles biosynthesized using aqueous leaf extract of Detarium microcarpum: An under-utilized species.

The need for green synthesis of emerging industrial materials has led to the biosynthesis of nanoparticles from plants to circumvent the adverse by-products of chemical synthesis. In this study, the leaf extract of Detarium mirocarpum Guill & Perr, a small tree belonging to the family Fabaceae (Legume), was used to synthesize silver nanoparticles (DAgNPs). DAgNPs were characterized using spectroscopic techniques (Ultraviolet-Visible spectroscopy and Fourier Transform Infrared spectroscopy) which showed hydroxyl and carbonyl functional groups to be responsible for their synthesis. DAgNPs were observed to be crystalline and spherical. The average size, determined by transmission electron microscopy (TEM) was 17.05nm. The antioxidant activity of DAgNPs ranked from moderate to good. The ability of DAgNPs to sense Hg(2+) and Fe(3+) ions in aqueous medium was also investigated. The quenching of the SPR peak at 430nm was used to monitor the toxic and heavy metal ions with linear ranges of 20-70µgmL(-1) and 10-40µgmL(-1) for Hg(2+) and Fe(3+), respectively. The limit of detection (LOD) and limit of quantification (LOQ) obtained for Hg(2+) was 2.05µgmL(-1) and 6.21µgmL(-1), respectively and for Fe(3+) was 5.01µgmL(-1) and 15.21µgmL(-1), respectively. The intra- and inter-day assessments of accuracy and repeatability gave relative errors less than 1% in all instances. DAgNPs can therefore provide a convenient method of sensing the toxic metals easily.

Kinetics and mechanistic investigation into the possible activation of imidazolium trans-[tetrachloridodimethylsulfoxideimidazoleruthenate(III)], NAMI-A, by 2-mercaptoethane sulfonate.

Imidazolium trans-[tetrachloridodimethylsulfoxideimidazoleruthenate(III)], NAMI-A, is a promising antimetastatic prodrug with high specificity for metastatic cancer cells. Limited activity of NAMI-A against primary tumor suggests that its use in combination with other anticancer drug(s) might present a more desirable therapeutic outcome. The mechanism of activation and action of this prodrug is still largely unknown. The biological targets, as well, have not yet been delineated. The kinetics and mechanism of interaction of NAMI-A with 2-mercaptoethane sulfonate, MESNA, a chemoprotectant, have been studied spectrophotometrically under pseudo-first order conditions of excess MESNA. The reaction is characterized by initial reduction of NAMI-A and formation of dimeric MESNA as evidenced by electospray ionization mass spectrometry. A first order dependence on both NAMI-A and MESNA was obtained and a bimolecular rate constant of 0.71 ± 0.06 M(-1) s(-1) was deduced. Activation parameters determined (ΔS(≠) = -178.12 ± 0.28 J K(-1) mol(-1), ΔH(≠) = 20.64 ± 0.082 kJ mol(-1) and ΔG(≠) = 75.89 ± 1.76 kJ mol(-1) at 37 ± 0.1 °C and pH 7.4) are indicative of formation of an associative intermediate prior to product formation and subsequent hydrolysis of the reduced complex. Our results suggest that MESNA might be able to activate the prodrug while still protecting against toxicity when given in a regimen involving NAMI-A and chemotherapy drug(s) that induce bladder and kidney toxicities.

1-(Ferrocen-1-ylmeth-yl)-3-methyl-imidazol-3-ium hexa-fluorido-phosphate.

The crystal structure of the title compound, [Fe(C(5)H(5))(C(10)H(12)N(2))]PF(6), consists of a ferrocene-1-methyl-(3-methyl-imidazolium) cation and a hexa-fluorido-phosphate anion. The ferrocenyl rings are skewed by 6.7 (4)° from the ideal eclipsed conformation. The inter-planar angle between the plane of the substituted cyclo-penta-dienyl ring and that of the imidazole ring is 89.9 (4)°. The crystal packing is stabilized by C-H⋯F hydrogen bonds.