Biospeciation of Oxidovanadium(IV) Imidazolyl-Carboxylate Complexes and Their Action on Glucose-Stimulated Insulin Secretion in Pancreatic Cells.

The reaction of the vanadyl ion (VO2+) with imidazole-4-carboxylic acid (Im4COOH), imidazole-2-carboxylic acid (Im2COOH) and methylimidazole-2-carboxylic acid (MeIm2COOH), respectively, in the presence of small bioligands (bL) [oxalate (Ox), lactate (Lact), citrate (Cit) and phosphate (Phos)] and high-molecular-weight (HMW) human serum proteins [albumin (HSA) and transferrin (hTf)] were studied in aqueous solution using potentiometric acid-base titrations. The species distribution diagrams for the high-molecular-mass (HMM) proteins with oxidovanadium(IV) under physiological pH were dominated by VO(HMM)2, VOL(HMM) for unsubstituted ligands (L- = Im4COO- and Im2COO-). However, for the N-substituted MeIm2COOH, the species distribution diagrams under physiological pH were dominated by VOL2, VO(HMM)2 and VO2L2(HMM). These species were further confirmed by LC-MS, MALDI-TOF-MS and EPR studies. The glucose-stimulated insulin secretion (GSIS) action of the complexes was investigated using INS-1E cells at a 1 µM concentration, which was established through cytotoxicity studies via the MTT assay. The neutral complexes, especially VO(MeIm2COO)2, showed promising results in the stimulation of insulin secretion than the cationic [VO(MeIm2CH2OH)2]2+ complex and the vanadium salt. Oxidovanadium(IV) complexes reduced insulin stimulation significantly under normoglycaemic levels but showed positive effects on insulin secretion under hyperglycaemic conditions (33.3 mM glucose media). The islets exposed to oxidovanadium(IV) complexes under hyperglycaemic conditions displayed a significant increase in the stimulatory index with 1.19, 1.75, 1.53, 1.85, 2.20 and 1.29 observed for the positive control (sulfonylurea:gliclazide), VOSO4, VO(Im4COO)2, VO(Im2COO)2, VO(MeIm2COO)2 and VO(MeIm2CH2OH)22+, respectively. This observation showed a potential further effect of vanadium complexes towards type 2 diabetes and has been demonstrated for the first time in this study.

The development of folate-functionalised palladium nanoparticles for folate receptor targeting in breast cancer cells.

Folate receptor-targeted therapy has excellent prospects for the treatment of breast cancer. A non-toxic concentration of folate-conjugated palladium-based nanoparticles was used to target the overexpressed folate receptor on breast cancer cells. The folate-conjugated nanoparticles were tailored to accumulate selectively in cancer cells relative to normal cells via the folate receptor. The MDA-MB-231, MDA-MB-468, MCF-7 breast cancer cell lines, and MCF-10A normal cell lines were used in the study. Qualitative and quantitative analysis of nanoparticle cellular uptake and accumulation was conducted using transmission electron microscopy and inductively coupled plasma-optical emission spectroscopy. The findings proved that folate-conjugated palladium nanoparticles successfully and preferentially accumulated in breast cancer cells. We conclude that folate-conjugated palladium nanoparticles can be potentially used to target breast cancer cells for radiopharmaceutical applications.

A New Highly Selective Colorimetric and Fluorometric Coumarin-based Chemosensor for Hg2.

A novel colorimetric and fluorometric method based on coumarin as signalling unit was developed for Hg2+ recognition and quantification. Initially, the alkyne functionality was incorporated into a coumarin system and the resulting molecule showed higher specificity and sensitivity for Hg2+ over other cations in both absorption and emission sensing assays. The Hg2+ recognition was detected as visible colour change from colourless to yellow and as fluorescence quenching. The colour change was assigned to the increased intramolecular charge transfer (ICT) in the signalling unit upon Hg2+ binding whereas a decline in the fluorescence intensity was ascribed to the heavy atom effect from Hg2+. In order to generate a material with high sensing performance level, alkyne-functionalized molecule was hosted into a polymeric material. The resulting functionalized polymer showed higher sensitivity and selectivity for Hg2+ over its corresponding coumarin molecule. The investigation of the possible binding modes for Hg2+ suggested both alkyne and triazole functionalities as potential binding sites for Hg2+. The limit of detection (LOD) and limit of quantification (LOQ) of the proposed method were evaluated and values less than a recommended maximum level of Hg2+contaminant in drinking water (2.00 µg/L) were obtained (LOD = 0.44 µg/L and LOQ = 1.33µg/L). The real-life application of the method was investigated using natural water samples containing Hg2+ levels equivalent to the maximum tolerable concentration of Hg2+ in drinking water. The outcomes suggested that the method could be used in the sensing and determination of Hg2+ level of contaminant in the environment.

Mining wastewater treatment technologies and resource recovery techniques: A review.

Mining wastewater can have adverse effects on the ecosystem; thus, treatment before discharging into the environment is of utmost importance. This manuscript reports on the effect of mining wastewater on the environment. Moreover, the currently used, effective and commercialised mine wastewater treatment technologies such as SAVMIN®, SPARRO®, Biogenic sulphide, and DESALX® are reported in this study. These technologies integrate two or more separation processes, which have been proven to be effective for the high recovery of salts and water for reuse. Some of the technologies reported can significantly recover salts and >95% of water. Modern pilot-stage and laboratory-scale treatment systems used for the recovery and removal of metals are also reported herein. Since some treatment technologies can generate highly toxic sludge and other waste products, the management of the generated waste was also considered. Some studies have focused on the treatment of wastewater at the laboratory level using the adsorption process. Most adsorbents exhibit promising results; however, there is insufficient research on reusability, toxic sludge management, and the economic analysis of the systems. Moreover, the implementation of adsorption systems in wastewater is necessary. Furthermore, the integration of treatment systems to recover precious metals at low concentrations is desirable in addition to water reclamation to achieve circular mine water.

Aqueous phase adsorption of phenothiazine derivative onto zinc oxide doped activated carbon.

Plant-mediated synthesis of nanoparticles is a sustainable approach that has gained widespread scientific acceptance due to its numerous benefits and applications. In this study, a zinc oxide-doped activated carbon (ZAC) derived from palm kernel shells (PKS) was synthesized via a bioreduction route using a water-based extract of Nymphaea lotus leaves as a reducing agent. The synthesized ZAC nanocomposites were characterized using microscopic (TEM, SEM) and spectroscopic (FTIR, EDS, XRD, and UV-Vis) analyses. The adsorptive properties of ZAC and efficiency in scavenging a phenothiazine derivative (methylene blue) from an aqueous solution were investigated. Results reveal that nano-scale ZAC particles were crystalline, exhibited irregular shapes, with an average size of 45 nm, and were highly dispersed. The optimum quantity adsorbed was 248 mg/g at a methylene blue concentration of 140 mg/L for 60 min using 0.02 g/100 mL of ZAC. Adsorption and kinetics data closely aligned with the Freundlich isotherm and the pseudo-second-order model, respectively indicating heterogeneous surface adsorption and chemisorption as the dominant mechanisms. The regeneration study of ZAC shows that over five cycles, thermal regeneration maintained high adsorption capacity with minimal decline and chemical regeneration significantly led to reduction in the adsorption capacity but solvent washing offered a balance between efficacy and structural preservation.

Azo-hydrazone tautomerism in a simple coumarin azo dye and its contribution to the naked-eye detection of Cu2+ and other potential applications.

A new tailor-made azo dye of coumarin connected to phenolic derivative is presented herein. Azo-hydrazone tautomerism in aqueous solution of the dye was observed and studied using spectroscopic assays such as 1H NMR, absorption and emission assays, and theoretical studies. Tautomerism was attributed to the presence of a labile phenolic hydrogen in the ortho position to the azo functionality and the hydrazone was found to be the more dominant tautomer. Influence of metal ions on the azo-hydrazone chemical equilibrium and how the accompanying colour and spectroscopic changes can be exploited for various functions, especially the detection and quantification of Cu2+ in aqueous environments was explored. The presence of Cu2+ affects the azo-hydrazone equilibrium resulting in visual appearance and spectroscopic changes and the likely binding sites for Cu2+ were evaluated. Cu2+ pushes the azo-hydrazone equilibrium towards the more conjugated form and the presence of other metal ions does not have any perceivable impact on this mechanism. The dye showed potential applications as a sensor in colorimetric and spectroscopic detection and quantification of Cu2+ in domestic and environmental water samples, photo-imprinting and as a logic gate. The limits of detection (LOD) and quantification (LOQ) for Cu2+ were found to be 0.0779 mg/L and 0.236 mg/L, respectively, much lower than the World Health Organization (WHO) guideline limit for Cu2+ levels in drinking water.

Solvent promoted tautomerism in thione-containing tetraazatricyclics: evidence from 1H NMR spectroscopy and transition state studies.

Tautomerism in the nitro substituted thione-containing traazatricyclics has been investigated. Evidence from 1H NMR indicating the existence of the tautomers has been augmented with computational studies providing evidence of the stability or otherwise of these tautomers. The role of water and DMSO in the formation of the tautomers has been explained. The role of the nitro group in assisting in the formation of the tautomers has been discussed.

Perspectives on strategies for improving ultra-deep desulfurization of liquid fuels through hydrotreatment: Catalyst improvement and feedstock pre-treatment.

Reliance on crude oil remains high while the transition to green and renewable sources of fuel is still slow. Developing and strengthening strategies for reducing sulfur emissions from crude oil is therefore imperative and makes it possible to sustainably meet stringent regulatory sulfur level legislations in end-user liquid fuels (mostly less than 10 ppm). The burden of achieving these ultra-low sulfur levels has been passed to fuel refiners who are battling to achieve ultra-deep desulfurization through conventional hydroprocessing technologies. Removal of refractory sulfur-containing compounds has been cited as the main challenge due to several limitations with the current hydroprocessing catalysts. The inhibitory effects of nitrogen-containing compounds (especially the basic ones) is one of the major concerns. Several advances have been made to develop better strategies for achieving ultra-deep desulfurization and these include: improving hydroprocessing infrastructure, improving hydroprocessing catalysts, having additional steps for removing refractory sulfur-containing compounds and improving the quality of feedstocks. Herein, we provide perspectives that emphasize the importance of further developing hydroprocessing catalysts and pre-treating feedstocks to remove nitrogen-containing compounds prior to hydroprocessing as promising strategies for sustainably achieving ultra-deep hydroprocessing.

Reaction of Perrhenate with Phthalocyanine Derivatives in the Presence of Reducing Agents and Rhenium Oxide Nanoparticles in Biomedical Applications.

A novel alternative route to access rhenium(V)-phthalocyanine complexes through direct metalation of metal-free phthalocyanines (H2 Pcs) with a rhenium(VII) salt in the presence of various two-electron reducing agents is presented. Direct ion metalation of tetraamino- or tetranitrophthalocyanine with perrhenate (ReO4- ) in the presence of triphenylphosphine led to oxidative decomposition of the H2 Pcs, giving their respective phthalonitriles. Conversely, treatment of H2 Pcs with ReO4- employing sodium metabisulfite yielded the desired ReV O-Pc complex. Finally, reaction of H2 Pcs with ReO4- and NaBH4 as reducing agent led to the formation of rhenium oxide (Rex Oy ) nanoparticles (NPs). The NP synthesis was optimised, and the Rex Oy NPs were capped with folic acid (FA) conjugated with tetraaminophthalocyanine (TAPc) to enhance their cancer cell targeting ability. The cytotoxicity profile of the resultant Rex Oy -TAPc-FA NPs was assessed and found to be greater than 80 % viability in four cell lines, namely, MDA-MB-231, HCC7, HCC1806 and HEK293T. Non-cytotoxic concentrations were determined and employed in cancer cell localization studies. The particle size effect on localization of NPs was also investigated using confocal fluorescence and transmission electron microscopy. The smaller NPs (≈10 nm) were found to exhibit stronger fluorescence properties than the ≈50 nm NPs and exhibited better cell localization ability than the ≈50 nm NPs.

A novel multidentate pyridyl ligand: A turn-on fluorescent chemosensor for Hg2+ and its potential application in real sample analysis.

A novel pyridyl-based ligand with multiple binding sites was developed as potential turn on fluorescent probe for mercuric ion. In comparison with other transition metal ions, the ligand displayed a significant optical selectivity and sensitivity for Hg2+ in aqueous solution with a remarkable fluorescence enhancement. The obtained spectroscopic response was related to the inhibition of the photo-chemical mechanism known as photo-induced electron transfer (PET) in the ligand and CN isomerization by Hg2+ binding. A good linearity between fluorescence responses and Hg2+ concentration was obtained in the range 3.3 × 10-9 M-1.6 × 10-8 M and a nanomolar level limit of detection (LOD) (1.4 × 10-9 M ~ 0.28 ppb) and limit of quantification (LOQ) (4.8 × 10-9 M ~ 0.93 ppb) were obtained. Both LOD and LOQ values are very low compared to the reported permissible Hg2+ level in drinking water (2 ppb) by US Environmental Protection Agency (EPA). The possible binding mode between ligand and Hg2+ were determined using Job's plot analysis and density functional theory (DFT) calculations and a complex with 1:1 stoichiometric ratio was suggested. The response of the pyridyl ligand upon Hg2+ addition was noted to be fast without any time delay and reversible. The performance of the ligand at nanomolar level of Hg2+ and real sample application of the proposed method was investigated and satisfactory results were obtained.

New VIVO-complexes for oxidative desulfurization of refractory sulfur compounds in fuel: synthesis, structure, reactivity trend and mechanistic studies.

A series of 5-coordinate oxidovanadium(iv) complexes based on 2-(2'-hydroxyphenyl)imidazole (HPIMH), with substituent groups of different electronegativities on the phenolic para position (HPIMX; X = -H, -Br, -OMe and -NO2), were synthesized and characterized. Three of these complexes were characterized by single crystal X-ray diffraction, [VIVO(PIMH)2], [VIVO(PIMBr)2] and [VIVO(PIMNO2)2], as well as a dioxidovanadium(v) compound ([VVO2(PIMH)(PIMH2)]). The complexes were tested for their catalytic activities in the oxidation of dibenzothiophene (DBT), the major refractory organosulfur compound found in fuel. The nitro substituted compound [VIVO(PIMNO2)2] had the highest catalytic oxidation activity followed by: [VIVO(PIMH)2] > [VIVO(PIMBr)2] > [VIVO(PIMMeO)2]. The decrease in activity is attributed to the different electronegativities of the substituent groups, which influence the electron density on the metal center, the V[double bond, length as m-dash]O bond distances and infrared stretching bands. Geometry index (τ) values calculated from single crystal X-ray diffraction (SC-XRD) data and DFT studies provided further insights on the trend in activity observed. SC-XRD, EPR, 51V NMR and UV-Vis spectroscopies, and DFT studies were instrumental in studying the mechanism of the catalyzed reaction and proposal of intermediate species. Both radical and non-radical pathways are plausible for the catalytic oxidation and participation of reactive oxygen species in both pathways is also postulated.

Benzimidazole or Diamide From a Reaction of Diamines and Carboxylic Acids or Acid Chlorides: Crystal Structures and Theoretical Studies.

A reaction of an acid chloride with a diamine yielded a diamide. m-Toluic acid was chlorinated to m-toluoyl chloride and subsequently reacted with 4-methyl-o-phenylenediamine in pyridine to obtain 3-methyl-N-[2-(3-methylbenzamido)phenylbenzamide (I). 2-(3-Methylphenyl)-1H-benzimidazole (II) has been obtained upon reacting o-phenylenediamine with m-toluic acid in polyphosphoric acid and toluene. The compounds have been characterized by IR, NMR, microanalyses and GC-MS. The crystal structures of the compounds have been discussed. DFT calculations of the frontier orbitals of the precursor compounds have been carried out to ascertain the groups that contribute to the HOMO and LUMO, and to study their contribution to the reactivity in the formation of the diamides and benzimidazoles. The synthesis of the amide from a diamine was seen to be favoured in the presence of a good leaving group attached to the carbonyl as in the case of acid chloride. However, the synthesis of benzimidazoles was found to be favoured in the presence of an excess of a protonating agent and high temperature.

pH-metric chemical speciation modeling and studies of in vitro antidiabetic effects of bis[(imidazolyl)carboxylato]oxidovanadium(IV) complexes.

A range of bidentate N,O-donor ligands of the imidazolyl-carboxylate moiety, which partially mimic naturally occurring bioligands, were prepared and reacted with the oxidovanadium(IV) ion to form the corresponding bis-coordinated oxidovanadium(IV) complexes. The aqueous pH-metric chemical speciation was investigated using glass electrode potentiometry, which allowed for the determination of protonation and stability constants of the ligands and complexes, respectively. The species distribution diagrams generated from this information gave evidence that the bis[(imidazolyl)carboxylato]oxovanadium(IV) complexes possess a broad pH-metric stability. The complexes improved glucose uptake in cell cultures using 3T3-L1 adipocytes, C2C12 muscle cells and Chang liver cells. The PTP inhibition studies indicated that the mechanism underlying insulin-stimulated glucose uptake was possibly via the protein tyrosine phosphorylation through the inhibition of the protein tyrosine phosphatase 1B (PTP 1B). The vanadium compounds also demonstrated the inhibition of D-dimer formation, suggesting that these compounds could potentially relieve a hypercoagulative state in diabetic patients.

Design, fabrication and evaluation of intelligent sulfone-selective polybenzimidazole nanofibers.

Molecularly imprinted polybenzimidazole nanofibers fabricated for the adsorption of oxidized organosulfur compounds are presented. The imprinted polymers exhibited better selectivity for their target model sulfone-containing compounds with adsorption capacities of 28.5±0.4mg g(-1), 29.8±2.2mg g(-1) and 20.1±1.4mg g(-1) observed for benzothiophene sulfone (BTO2), dibenzothiophene sulfone (DBTO2) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO2) respectively. Molecular modeling based upon the density functional theory (DFT) indicated that hydrogen bond interactions may take place between sulfone oxygen groups with NH groups of the PBI. Further DFT also confirmed the feasibility of π-π interactions between the benzimidazole rings and the aromatic sulfone compounds. The adsorption mode followed the Freundlich (multi-layered) adsorption isotherm which indicated possible sulfone-sulfone interactions. A home-made pressurized hot water extraction (PHWE) system was employed for the extraction/desorption of sulfone compounds within imprinted nanofibers at 1mL min(-1), 150°C and 30 bar. PHWE used a green solvent (water) and achieved better extraction yields compared to the Soxhlet extraction process. The application of molecularly imprinted polybenzimidazole (PBI) nanofibers displayed excellent sulfur removal, with sulfur in fuel after adsorption falling below the determined limit of detection (LOD), which is 2.4mg L(-1)S, and with a sulfur adsorption capacity of 5.3±0.4mg g(-1) observed for application in the fuel matrix.

Oxovanadium(IV)-catalysed oxidation of dibenzothiophene and 4,6-dimethyldibenzothiophene.

The reaction between [V(IV)OSO(4)] and the tetradentate N(2)O(2)-donor Schiff base ligand, N,N-bis(o-hydroxybenzaldehyde)phenylenediamine (sal-HBPD), obtained by the condensation of salicylaldehyde and o-phenylenediamine in a molar ratio of 2 : 1 respectively, resulted in the formation of [V(IV)O(sal-HBPD)]. The molecular structure of [V(IV)O(sal-HBPD)] was determined by single crystal X-ray diffraction, and confirmed the distorted square pyramidal geometry of the complex with the N(2)O(2) binding mode of the tetradentate ligand. The formation of the polymer-supported p[V(IV)O(sal-AHBPD)] proceeded via the nitrosation of sal-HBPD, followed by the reduction with hydrogen to form an amine group that was then linked to Merrifield beads followed by the reaction with [V(IV)OSO(4)]. XPS and EPR were used to confirm the presence of oxovanadium(IV) within the beads. The BET surface area and porosity of the heterogeneous catalyst p[V(IV)O(sal-AHBPD)] were found to be 6.9 m(2) g(-1) and 180.8 Å respectively. Microanalysis, TG, UV-Vis and FT-IR were used for further characterization of both [V(IV)O(sal-HBPD)] and p[V(IV)O(sal-AHBPD)]. Oxidation of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was investigated using [V(IV)O(sal-HBPD)] and p[V(IV)O(sal-AHBPD)] as catalysts. Progress for oxidation of these model compounds was monitored with a gas chromatograph fitted with a flame ionization detector. The oxidation products were characterized using gas chromatography-mass spectrometry, microanalysis and NMR. Dibenzothiophene sulfone (DBTO(2)) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO(2)) were found to be the main products of oxidation. Oxovanadium(IV) Schiff base microspherical beads, p[V(IV)O(sal-AHBPD)], were able to catalyse the oxidation of sulfur in dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) to a tune of 88.0% and 71.8% respectively after 3 h at 40 °C. These oxidation results show promise for potential application of this catalyst in the oxidative desulfurization of crude oils.