The Performance Evaluation of Meso-Tetraphenyl Porphyrin and Azo Dyes as Photosensitizers in Dye-sensitized Solar Cells.

The photovoltaic properties of five different mono-azo function and meso-tetraphenyl porphyrin dyes have been investigated by computational DFT/TDDFT calculations and measurement of the J-V properties of their cells. The photovoltaic efficiency of the cells based on these dyes were determined by both experimental and theoretical methods. The efficiency-to-cost ratios of the azo-dye cells showed that they could be cheaper substitutes to porphyrin-based cells. Eriochrome blue black (EBB) and eriochrome black T (EBT) cells were shown to possess the best photovoltaic properties by the two methods employed (theory and experiment). The presence of two naphthol moieties at both ends of their -N = N- group has been adduced as possible reason for their relatively outstanding performance. The extremely low efficiency-to-cost ratio obtained for cell-POR suggests that the use of porphyrin as sensitizer may not be as economically viable as some azo dyes. MTO, EBB and EBT were found to be the most cost-effective among the investigated dyes. The porphyrin's low performance may have been amplified by the absence of an effective anchor group in its molecular structure.

Antidiabetes and antioxidant potential of Schiff bases derived from 2-naphthaldehye and substituted aromatic amines: Synthesis, crystal structure, Hirshfeld surface analysis, computational, and invitro studies.

Three Schiff bases were synthesised by the condensation reaction between 2-napthaldehyde and aromatic amines to afford (E)-N-mesityl-1-(naphthalen-2-yl)methanimine (L1), (E)-N-(2,6-dimethylphenyl)-1-(naphthalen-2-yl)methanimine (L2) and (E)-N-(2,6-diisopropylphenyl)-1-(naphthalen-2-yl)methanimine (L3). The synthesised compounds were characterised using UV-visible, NMR (13C & 1H), and Fourier transform infrared spectroscopic methods while their purity was ascertained by elemental analysis. Structural analysis revealed that the naphthalene ring is almost coplanar with the imine functional group as evident by C1-C10-C11-N1 torsion angles of 176.4(2)° and 179.4(1)° in L2 and L3, respectively. Of all the various intermolecular contacts, H⋯H interactions contributed mostly towards the Hirshfeld surfaces of both L2 (58.7 %) and L3 (69.7 %). Quantum chemical descriptors of L1 - L3 were determined using Density Functional Theory (DFT) and the results obtained showed that the energy band gap (ΔE) for L1, L2 and L3 are 3.872, 4.023 and 4.004 eV respectively. The antidiabetic potential of the three compounds were studied using α-amylase and α-glucosidase assay. Compound L1 showed very promising antidiabetic activities with IC50 values of 58.85 µg/mL and 57.60 µg/mL while the reference drug (Acarbose) had 405.84 µg/mL and 35.69 µg/mL for α-amylase and α-glucosidase respectively. In-silico studies showed that L1 docking score as well as binding energies are higher than that of acarbose, which are recognized inhibitors of α-amylase together with α-glucosidase. Further insight from the RMSF, RMSD and RoG analysis predicted that, throughout the simulation L1 showcased evident influence on the structural stability of α-amylase. The antioxidant potential of the compounds was carried out using nitric oxide (NO), ferric reducing ability power (FRAP) and 2,2-diphenyl-1-picrylhydrazyl (DPPH) assays. The compounds exhibited good to fairly antioxidant properties with L1 as well as L3 having IC50 values of 70.91 and 91.21 µg/mL respectively for NO scavenging activities assay, which comparatively outshined acarbose (reference drug) with IC50 value of 109.95 µg/mL. Pharmacology and pharmacokinetics approximations of L1 - L3 showed minimal violation of Lipinski's Ro5 and this projects them to be less toxic and orally bioavailable as potential templates for the design of therapeutics with antioxidant and antidiabetic activities.

Heptanuclear Silver Hydride Clusters as Catalytic Precursors for the Reduction of 4-Nitrophenol.

We report on the design, synthesis, and characterization of the first silver hydride clusters solely protected and stabilized by dithiophosphonate ligands and their application for the in situ generation of silver nanoparticles towards the catalytic reduction of 4-nitrophenol in an aqueous system. The synthesis of the silver monohydride cluster involves the incorporation of an interstitial hydride using sodium borohydride. Poly-nuclear magnetic resonance and mass spectrometry were used to establish the structural properties. The structural properties were then confirmed with a single-crystal X-ray diffraction analysis, which showed a distorted tetracapped tetrahedron core with one hydride ion encapsulated within the core of the silver framework. Additionally, the synthesized heptanuclear silver hydride was utilized as a precursor for the in situ generation of silver nanoparticles, which simultaneously catalyzed the reduction of 4-nitrophenol. The mechanism of the catalytic activity was investigated by first synthesizing AgNPs, which was subsequently used as a catalyst. The kinetic study showed that the pseudo-first constant obtained using the cluster (2.43 × 10-2 s-1) was higher than that obtained using the synthesized AgNPs (2.43 × 10-2 s-1). This indicated that the silver monohydride cluster was more active owing to the release of the encapsulated hydride ion and greater reaction surface prior to aggregation.

Pentaclethra macrophylla stem bark extract anchored on functionalized MWCNT-spent molecular sieve nanocomposite for the biosorption of hexavalent chromium.

NOVELTY STATEMENT: nsufficient innovative research on the sequestration of Cr(VI) from the aquatic ecosystem has made Cr(VI) a recalcitrant water contaminant that often affects water sources. In this work, a novel plant anchor-nanocomposite was fabricated from the spent molecular sieve, multi-walled carbon nanotubes, and the extract from the stem bark of Pentaclethra macrophylla. It was envisaged that due to the phytochemical constituent of the modifier, this nanocomposite could also act as potent adsorbents for the treatment of Cr(VI) polluted water. To the best of our knowledge, the application of Pentaclethra macrophylla stem bark extract as a modifier for the green fabrication of nanocomposite has not been reported. The resulting composites showed good uptake capacity for Cr(VI) as well as efficient reusability.

Drug Discovery for Mycobacterium tuberculosis Using Structure-Based Computer-Aided Drug Design Approach.

Developing new, more effective antibiotics against resistant Mycobacterium tuberculosis that inhibit its essential proteins is an appealing strategy for combating the global tuberculosis (TB) epidemic. Finding a compound that can target a particular cavity in a protein and interrupt its enzymatic activity is the crucial objective of drug design and discovery. Such a compound is then subjected to different tests, including clinical trials, to study its effectiveness against the pathogen in the host. In recent times, new techniques, which involve computational and analytical methods, enhanced the chances of drug development, as opposed to traditional drug design methods, which are laborious and time-consuming. The computational techniques in drug design have been improved with a new generation of software used to develop and optimize active compounds that can be used in future chemotherapeutic development to combat global tuberculosis resistance. This review provides an overview of the evolution of tuberculosis resistance, existing drug management, and the design of new anti-tuberculosis drugs developed based on the contributions of computational techniques. Also, we show an appraisal of available software and databases on computational drug design with an insight into the application of this software and databases in the development of anti-tubercular drugs. The review features a perspective involving machine learning, artificial intelligence, quantum computing, and CRISPR combination with available computational techniques as a prospective pathway to design new anti-tubercular drugs to combat resistant tuberculosis.

Enhanced sequestration of Cr(VI) onto plant extract anchored on carbon-coated aluminium oxide composite.

Aluminium oxide (ALU) and carbon-coated aluminium oxide modified with Kigelia africana leaf extract (KECA) were employed for the removal of toxic hexavalent chromium (Cr(VI)) from the aqueous phase. The adsorbents (ALU and KECA) were characterized by TGA, BET, FESEM, FTIR, Raman and XRD spectroscopic techniques. The potential of KECA and ALU to remove Cr(VI) from simulated wastewater was optimum at pH 2, sorbent dose of 0.025 g and a contact time of 200 min. Meanwhile, the uptake capacity of KECA and ALU was enhanced with an increase in sorbent dose, contact time and initial Cr(VI) concentration. The uptake of Cr(VI) onto the adsorbents ALU and KECA was kinetically best described by the pseudo-second-order and Elovich models, respectively. Besides, the equilibrium data acquired for ALU and KECA obeyed Freundlich and Langmuir isotherm models, respectively. ALU and KECA were observed to have optimum adsorption capacity of 56.45 mg g-1 and 258.2 mg g-1, respectively. The adsorption of Cr(VI) onto the adsorbents was thermodynamically feasible, endothermic in nature and entropy-driven. A decrease in efficiency was observed on regeneration of the absorbents, thus limiting their reusability. However, the presence of functional groups with reducing property in the extract of Kigelia africana leaves was noticed to enhance the capacity of the adsorbent to abstract Cr(VI) from the solution. Hence, this study demonstrates the potential of KECA to sequestrate Cr(VI) from an aqueous solution and provides a reference for its application to the treatment of Cr(VI)-laden industrial wastewater.

Functionalized MWCNTs-quartzite nanocomposite coated with Dacryodes edulis stem bark extract for the attenuation of hexavalent chromium.

Multiwalled carbon nanotubes/quartzite nanocomposite modified with the extract of Dacryodes edulis leaves was synthesized and designated as Q, which was applied for the removal of Cr(VI) from water. The adsorbents (PQ and Q) were characterized using the SEM, EDX, FTIR, TGA, XRD, and BET analyses. The XRD revealed the crystalline composition of the nanocomposite while the TGA indicated the incorporated extract as the primary component that degraded with an increase in temperature. The implication of the modifier was noticed to enhance the adsorption capacity of Q for Cr(VI) by the introduction of chemical functional groups. Optimum Cr(VI) removal was noticed at a pH of 2.0, adsorbent dose (50 mg), initial concentration (100 mg dm-3), and contact time (180 min). The kinetic adsorption data for both adsorbents was noticed to fit well to the pseudo-second-order model. The adsorption equilibrium data were best described by the Langmuir model. The uptake of Cr(VI) onto PQ and Q was feasible, endothermic (ΔH: PQ = 1.194 kJ mol-1 and Q = 34.64 kJ mol-1) and entropy-driven (ΔS : PQ = 64.89 J K-1 mol-1 and q = 189.7 J K-1 mol-1). Hence, the nanocomposite demonstrated potential for robust capacity to trap Cr(VI) from aqueous solution.

Thermodynamics, kinetics and isothermal studies of chromium (VI) biosorption onto Detarium senegalense stem bark extract coated shale and the regeneration potentials.

A low-cost adsorbent (Detarium senegalense stem bark extract coated shale (DSMS)) comprising pristine shale (PSH) coated with D. senegalense stem bark extract was prepared and utilized for the adsorption of Cr(VI). The DSMS and PSH were characterized by the SEM, XRD, FTIR, EDX, TGA, and BET. The batch adsorption experiment results showed that DSMS exhibited an excellent ability to adsorb chromium with a maximum removal occurring at pH 2, dosage of 0.05 g and 180 min contact time. The adsorption process was best described by the pseudo-second-order for DSMS and Elovich model for PSH which depicts chemisorption as the major mechanism responsible for the uptake of Cr(VI) onto the adsorbents. Langmuir model provided the best fit to the isotherm analysis on both materials. The maximum adsorption capacity of DSMS and PSH were 64.98 mg g-1 and 29.97 mg g-1 respectively. The thermodynamics revealed that the adsorption of Cr(VI) was feasible, endothermic and entropy driven. Furthermore, after five cycles of reuse, both DSMS and PSH demonstrated effective regeneration and reusability for Cr(VI) uptake. The structural properties, reusability, and high adsorption capabilities of DSMS indicate that they could be used as low-cost adsorbents in large-scale Cr(VI) wastewater treatment. Novelty statement Plant extracts are packed with a variety of polyphenolic compounds, such as aldehydes, alcohols, carboxylics, ethers, ketones, and phenols which contains several functionalities useful in the adsorption of toxic metals. Despite this, research on the use of plant extracts in the modification of adsorbent materials for enhanced adsorption is rare. This study reports for the first time the use of Detarium senegalense stem bark extract coated shale adsorbent for the efficient uptake of Cr(VI) ion.

Crystal, spectroscopic and quantum mechanics studies of Schiff bases derived from 4-nitrocinnamaldehyde.

Two Schiff bases, (E)-1-(4-methoxyphenyl)-N-((E)-3-(4-nitrophenyl)allylidene)methanamine (compound 1) and (E)-N-((E)-3-(4-nitrophenyl)allylidene)-2-phenylethanamine (compound 2) have been synthesized and characterized using spectroscopic methods; time of flight MS, 1H and 13C NMR, FT-IR, UV-VIS, photoluminescence and crystallographic methods. The structural and electronic properties of compounds 1 and 2 in the ground state were also examined using the DFT/B3LYP functional and 6-31 + G(d,p) basis set, while the electronic transitions for excited state calculations were carried out using the TD-DFT/6-31 + G(d,p) method. The Schiff base compounds, 1 and 2 crystallized in a monoclinic crystal system and the P21/c space group. The emission spectra of the compounds are attributed to conjugated π-bond interaction while the influence of the intra-ligand charge transfer resulted in a broad shoulder for 1 and a double emission peak for 2. The calculated transitions at 450 and 369 nm for 1 and 2 respectively are in reasonable agreement with the experimental results. The higher values of dipole moment, linear polarizability and first hyperpolarizability of 1, suggest a better optical property and better candidate for the development of nonlinear optical (NLO) materials.

Nanocrystalline cellulose isolated from discarded cigarette filters.

We report the isolation of nanocrystalline cellulose (NCC) produced from discarded cigarette filters (DCF). The DCF were processed into cellulose via ethanolic extraction, hypochlorite bleaching, alkaline deacetylation, and then converted into NCC by sulfuric acid hydrolysis. The morphological structures of the isolated NCC established with TEM showed that the nanocrystals were needle-like with a mean length of 143nm. FEGSEM showed the morphological transition of the micro-sized DCF to self-assembled NCC while EDX revealed the presence of Ti (as TiO2) in DCF, which was retained in the NCC. A NCC sample was freeze-dried and showed a specific surface area of 7.78m2/g. The crystallinity of the NCC film and freeze-dried samples were 96.77% and 94.47%, respectively. Crystallite sizes of the freeze-dried (8.4nm) and film (7.6nm) samples correlated with the mean width (8.3nm) of the NCC observed under TEM.