Hyphenation of lipophilic ruthenium(II)-diphosphine core with 5-fluorouracil: an effective metallodrug against glioblastoma brain cancer cells.

Glioblastoma multiforme (GBM) is the most common highly aggressive malignant brain tumor, with a very limited chance for survival post-diagnosis and post-treatment. Despite significant advancement in GBM genomics implicated in molecularly targeted chemotherapies, the prognosis remains poor and requires new drug discovery approaches. We used fluoropyrimidine 5-fluorouracil (5-FU), an antimetabolite anticancer drug conjugated or 'caged' within a lipophilic Ru(II)-diphosphine (dppe) core formulated as [RuII(dppe)2(5-FU)]PF6 (Ru-DPPE-5FU), where dppe = 1,2-bis(diphenylphosphino)ethane, and evaluated its in vitro cytotoxicity in depth with aggressive GBM cells (LN229). The hydrophilic nature of 5-FU limits its passage through the blood-brain barrier (BBB), which prevents its effective accumulation and efficacy for GBM tumors. Herein, we attempted to modulate the lipophilicity of 5-FU by inserting it within a well-designed lipophilic {Ru(dppe)2}-core with anticipated higher efficiency towards GBM. The physicochemical properties of [RuII(dppe)2(5-FU)]PF6 (Ru-DPPE-5FU) were studied using various spectroscopic and analytical techniques. The molecular structure was determined using X-ray crystallography, showing a distorted {RuP4NO} octahedral geometry with bidentate (N, O) binding of 5-FU and its aromatization in the Ru(II)-bound form. The 31P-NMR spectra of Ru-DPPE-5FU showed four closely spaced distinct 31P-signals, indicating four unique chemical environments around P, and the strong coupling constants between them make it a second-order spectrum. The RuII/RuIII redox potential in Ru-DPPE-5FU shifted by ∼0.91 V towards the anodic region as compared to its precursor complex cis-[Ru(dppe)2Cl2] (Ru-DPPE-Cl). DFT-based theoretical calculations have been performed to correlate the experimental electronic absorption spectra and redox behaviours of the complexes. The electrostatic potential (ESP) plots indicate the delocalization of the charge density on the O-/F-atom from the 5-FU ligand towards Ru(II) upon its complexation. The antioxidant properties of all the compounds were quantified by a 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay. The hyphenation of the 5-fluorouracil (5-FU) ligand to the lipophilic {Ru(dppe)2}-core endowed lipophilicity to Ru-DPPE-5FU with higher in vitro cytotoxicity (IC50 = 2.37 µM) against the LN229 GBM cells as compared to the hydrophilic 5-FU, suggesting efficient cellular uptake. Further biological assays indicated that the complex is highly potent in inhibiting significant proliferation and spheroid formation and restricting the migratory potentials of the GBM cells. Increased caspase 3/7 activity and the presence of apoptotic bodies at the center of 3-D GBM spheroids as revealed by AO/EB dual staining indicated a deeper penetration of the lipophilic complex. The Ru-DPPE-5FU complex displayed lower cytotoxicity in HaCaT normal cells (IC50 = 7.27 µM) in comparison to LN229 cancer cells with a selectivity index (S.I.) of ≥3. Overall, the synergism and caging of 5-FU within the hydrophobic {Ru(dppe)2}-core improves the pharmacokinetic profile of Ru-DPPE-5FU as a potent anticancer agent for glioblastoma.

Engineered smart materials for RNA based molecular therapy to treat Glioblastoma.

Glioblastoma (GBM) is an aggressive malignancy of the central nervous system (CNS) that remains incurable despite the multitude of improvements in cancer therapeutics. The conventional chemo and radiotherapy post-surgery have only been able to improve the prognosis slightly; however, the development of resistance and/or tumor recurrence is almost inevitable. There is a pressing need for adjuvant molecular therapies that can successfully and efficiently block tumor progression. During the last few decades, non-coding RNAs (ncRNAs) have emerged as key players in regulating various hallmarks of cancer including that of GBM. The levels of many ncRNAs are dysregulated in cancer, and ectopic modulation of their levels by delivering antagonists or overexpression constructs could serve as an attractive option for cancer therapy. The therapeutic potential of several types of ncRNAs, including miRNAs, lncRNAs, and circRNAs, has been validated in both in vitro and in vivo models of GBM. However, the delivery of these RNA-based therapeutics is highly challenging, especially to the tumors of the brain as the blood-brain barrier (BBB) poses as a major obstacle, among others. Also, since RNA is extremely fragile in nature, careful considerations must be met while designing a delivery agent. In this review we have shed light on how ncRNA therapy can overcome the limitations of its predecessor conventional therapy with an emphasis on smart nanomaterials that can aide in the safe and targeted delivery of nucleic acids to treat GBM. Additionally, critical gaps that currently exist for successful transition from viral to non-viral vector delivery systems have been identified. Finally, we have provided a perspective on the future directions, potential pathways, and target areas for achieving rapid clinical translation of, RNA-based macromolecular therapy to advance the effective treatment of GBM and other related diseases.

In-Liquid Plasma-Mediated Manganese Oxide Electrocatalysts for Quasi-Industrial Water Oxidation and Selective Dehydrogenation.

The production of renewable feedstocks through the coupled oxygen evolution reaction (OER) with selective organic oxidation requires a perfect balance in the choice of a catalyst and its synthesis access, morphology, and catalytic activity. Herein we report a rapid in-liquid plasma approach to produce a hierarchical amorphous birnessite-type manganese oxide layer on 3D nickel foam. The as-prepared anode exhibits an OER activity with overpotentials of 220, 250, and 270 mV for 100, 500, and 1000 mA·cm-2, respectively, and can spontaneously be paired with chemoselective dehydrogenation of benzylamine under both ambient and industrial (6 M KOH, 65 °C) alkaline conditions. The in-depth ex-situ and in-situ characterization unequivocally demonstrate the intercalation of potassium in the birnessite-type phase with prevalent MnIII states as an active structure, which displays a trade-off between porous morphology and bulk volume catalytic activity. Further, a structure-activity relationship is realized based on the cation size and structurally similar manganese oxide polymorphs. The presented method is a substantial step forward in developing a robust MnOx catalyst for combining effective industrial OER and value-added organic oxidation.

Linker Independent Regioselective Protonation Triggered Detoxification of Sulfur Mustards with Smart Porous Organic Photopolymer.

The development of efficient metal-free photocatalysts for the generation of reactive oxygen species (ROS) for sulfur mustard (HD) decontamination can play a vital role against the stockpiling of chemical warfare agents (CWAs). Herein, one novel concept is conceived by smartly choosing a specific ionic monomer and a donor tritopic aldehyde, which can trigger linker-independent regioselective protonation/deprotonation in the polymeric backbone. In this context, the newly developed vinylene-linked ionic polymers (TPA/TPD-Ionic) are further explored for visible-light-assisted detoxification of HD simulants. Time-resolved-photoluminescence (TRPL) study reveals the protonation effect in the polymeric backbone by significantly enhancing the life span of photoexcited electrons. In terms of catalytic performance, TPA-Ionic outperformed TPD-Ionic because of its enhanced excitons formation and charge carrier abilities caused by the donor-acceptor (D-A) backbone and protonation effects. Moreover, the formation of singlet oxygen (1 O2 ) species is confirmed via in-situ Electron Spin Resonance (ESR) spectroscopy and density functional theory (DFT) analysis, which explained the crucial role of solvents in the reaction medium to regulate the (1 O2 ) formation. This study creates a new avenue for developing novel porous photocatalysts and highlights the crucial roles of sacrificial electron donors and solvents in the reaction medium to establish the structure-activity relationship.

Transglutaminase-Polyethyleneimine Nanoflowers Mediated Cellular Delivery of Anti-miR-210 for Effective Glioblastoma Therapy.

Glioblastoma (GBM) is a deadly tumor of the central nervous system (CNS) having a dismal prognosis. miRNA-based therapeutics hold immense potential for GBM therapy; however, its delivery remains a daunting challenge. MicroRNA-210 has been established as a critical oncomiR in GBM. Our group has developed novel, PEI-functionalized transglutaminase-based nanoflowers (TGNFs, ∼61 nm in diameter) for the efficient delivery of anti-miR-210 to glioblastoma cells in vitro. TGNFs show low cytotoxicity to normal human fibroblasts, do not affect the liver and kidney health of CD1 mice, and offer >95% anti-miR encapsulation efficiency, serum stability, and protection against polyanion moieties. Their synthesis is cost-effective and does not involve the application of harsh chemicals. TGNFs successfully delivered anti-miR-210 to glioblastoma cells, decreasing cellular proliferation and migration and increasing apoptosis. Overall, this research highlights the potential of TGNFs as delivery agents in miRNA inhibition therapy and encourages further preclinical studies to explore the potential of miR-210 as a therapeutic target in GBM and various other cancers where the oncogenic role of miR-210 has been well-established.

Spatio-temporal analysis identifies marine mammal stranding hotspots along the Indian coastline.

Marine mammal strandings provide vital information on species' life histories, population health and status of marine ecosystems. Opportunistic reporting of strandings also serve as a powerful low-cost tool for monitoring these elusive mammals. We collated data over ~ 270 years available through various open access databases, reports and publications. Annual strandings along the Indian coast (mean = 11.25 ± SE 9.1) increased in the last two years of the study (2015-2017, mean = 27.66 ± SE 8.5 strandings /year). We found that stranding events spike during June-September along the west coast and during December-January along the east coast. We identified several sections of the coastline, such as Mumbai (0.38 strandings/km), Kozhikode (0.28 strandings/km),  Tuticorin (0.4 strandings/km), Rameswaram (1.82 strandings/km), Chennai (0.32 strandings/km) and Bhubaneshwar (0.26 strandings/km) with a higher number of stranded animals reported. Emerging Hotspot Analysis located new and consecutive hotspots along the north-west coast, and sporadic hotspots along the south-east coast. We recommend establishing regional stranding response centres at the identified hotspots coordinated by a National Stranding Centre with adequately trained personnel and central funding support. Regular stranding response training programs for field veterinarians, and frontline personnel of State Forest Departments near stranding hotspots would provide an improved understanding of marine mammal health and threats in Indian waters. Further, the suggested National Stranding Centre needs to maintain a 'National Stranding Database' for long-term marine mammal conservation planning in India.

Synthesizing habitat connectivity analyses of a globally important human-dominated tiger-conservation landscape.

As ecological data and associated analyses become more widely available, synthesizing results for effective communication with stakeholders is essential. In the case of wildlife corridors, managers in human-dominated landscapes need to identify both the locations of corridors and multiple stakeholders for effective oversight. We synthesized 5 independent studies of tiger (Panthera tigris) connectivity in central India, a global priority landscape for tiger conservation, to quantify agreement on landscape permeability for tiger movement and potential movement pathways. We used the latter analysis to identify connectivity areas on which studies agreed and stakeholders associated with these areas to determine relevant participants in corridor management. Three or more of the 5 studies' resistance layers agreed in 63% of the study area. Areas in which all studies agree on resistance were of primarily low (66%, e.g., forest) and high (24%, e.g., urban) resistance. Agreement was lower in intermediate resistance areas (e.g., agriculture). Despite these differences, the studies largely agreed on areas with high levels of potential movement: >40% of high average (top 20%) current-flow pixels were also in the top 20% of current-flow agreement pixels (measured by low variation), indicating consensus connectivity areas (CCAs) as conservation priorities. Roughly 70% of the CCAs fell within village administrative boundaries, and 100% overlapped forest department management boundaries, suggesting that people live and use forests within these priority areas. Over 16% of total CCAs' area was within 1 km of linear infrastructure (437 road, 170 railway, 179 transmission line, and 339 canal crossings; 105 mines within 1 km of CCAs). In 2019, 78% of forest land diversions for infrastructure and mining in Madhya Pradesh (which comprises most of the study region) took place in districts with CCAs. Acute competition for land in this landscape with globally important wildlife corridors calls for an effective comanagement strategy involving local communities, forest departments, Appendix 1 and infrastructure planners. This article is protected by copyright. All rights reserved.

Distribution of virulence factors and its relatedness towards the antimicrobial response of enterotoxigenic Escherichia coli strains isolated from patients in Kolkata, India.

AIM: Enterotoxigenic Escherichia coli (ETEC) is one of the most widely recognized diarrhoeal pathogens in developing countries. The advancement of ETEC vaccine development depends on the antigenic determinants of the ETEC isolates from a particular geographical region. So, the aim here was to comprehend the distribution of virulence determinants of the clinical ETEC strains of this region. Additionally, an attempt was made to find any correlation with the antimicrobial response pattern. METHODS AND RESULTS: Multiplex PCR was employed to identify virulence determinants followed by confirmatory singleplex PCR. For observation of antibiotic response, the Kirby-Bauer method was used. Out of 379 strains, 46% of strains harboured both the enterotoxins ST and LT, whereas 15% were LT only. Among the major colonization factors (CFs), CS6 (41%) was the most prevalent followed by CFA/I (35%) and CFA/III was the lowest (3%). Among the minor CFs, CS21 (25%) was most prevalent, while CS15 showed the lowest (3%) presence. Among the non-classical virulence factors, EatA (69%) was predominant. ETEC strains harbouring CS6 showed resistance towards the commonly used drug Ciprofloxacin (70%). CONCLUSION: CS6 and elt+est toxin genes co-occurred covering 51% of the isolates. CS21 was found in most strains with est genes (43%). EatA was found to occur frequently when ST was present alone or with LT. CS6-harbouring strains showed an independent correlation to antimicrobial resistance. SIGNIFICANCE AND IMPACT OF THE STUDY: This study would aid in identifying the commonly circulating ETEC isolates of Kolkata, India, and their prevalent virulence determinants. Knowledge of antibiotic resistance patterns would also help in the appropriate use of antibiotics. Furthermore, the study would aid in identifying the multivalent antigens suitable for region-specific ETEC vaccines with maximum coverage.

Iron influences the expression of colonization factor CS6 of enterotoxigenic Escherichia coli.

Enterotoxigenic Escherichia coli (ETEC) is a major pathogen of acute watery diarrhoea. The pathogenicity of ETEC is linked to adherence to the small intestine by colonization factors (CFs) and secretion of heat-labile enterotoxin (LT) and/or heat-stable enterotoxin (ST). CS6 is one of the most common CFs in our region and worldwide. Iron availability functions as an environmental cue for enteropathogenic bacteria, signalling arrival within the human host. Therefore, iron could modify the expression of CS6 in the intestine. The objective of this study was to determine the effect of iron availability on CS6 expression in ETEC. This would help in understanding the importance of iron during ETEC pathogenesis. ETEC strain harbouring CS6 was cultured under increasing concentrations of iron salt to assess the effect on CS6 RNA expression by quantitative RT-PCR, protein expression by ELISA, promoter activity by ß-galactosidase activity, and epithelial adhesion on HT-29 cells. RNA expression of CS6 was maximum in presence of 0.2 mM iron (II) salt. The expression increased by 50-fold, which also reduced under iron-chelation conditions and an increased iron concentration of 0.4 mM or more. The surface expression of CS6 also increased by 60-fold in presence of 0.2 mM iron. The upregulation of CS6 promoter activity by 25-fold under this experimental condition was in accordance with the induction of CS6 RNA and protein. This increased CS6 expression was independent of ETEC strains. Bacterial adhesion to HT-29 epithelial cells was also enhanced by five-fold in the presence of 0.2 mM iron salt. These findings suggest that CS6 expression is dependent on iron concentration. However, with further increases in iron concentration beyond 0.2 mM CS6 expression is decreased, suggesting that there might be a strong regulatory mechanism for CS6 expression under different iron concentrations.

Potential of microRNA based diagnostics and therapeutics in glioma: a patent review.

INTRODUCTION: Glioma is a group of tumors that are usually derived from the glial cells of the central nervous system and glioblastoma is the deadliest among them. It has a dismal prognosis and no potential cure at this point. Thus, there is an utmost need for novel, more effective therapeutics, and early and accurate diagnostics for improved survival of glioma patients. MicroRNAs, having altered expression in glioma and being excellent regulators of gene expression with multi-pathway targeting abilities, offer to be a suitable candidate. AREAS COVERED: This review summarizes microRNA-based patents that have been granted in the fields of diagnostics and therapeutics of glioma until May 2020. A comprehensive discussion has been attempted, delving into the claims and basis of each patent. EXPERT OPINION: MicroRNA-based anti-cancer research has been extensively carried out throughout the last decade and the results look promising. These molecules can be efficient biomarkers of glioma and used as therapeutic targets/agents. But, just like any other evolving medical technology, it also faces challenges for moving from the bench to the bedside. However, if correctly addressed, these problems can be overcome, and microRNA-based technologies can advance to be efficient tools for the treatment of glioma.

Development of novel ruthenium(II)-arene complexes displaying potent anticancer effects in glioblastoma cells.

Glioblastomas (GBs) are highly aggressive and malignant brain tumors, which are highly resistant to conventional multimodal treatments, leading to their abysmal prognosis. Herein, we designed two organometallic half-sandwich Ru(ii)-η6-p-cymene complexes containing Schiff bases derived from 3-aminoquinoline and 2-hydroxy-benzaldehyde (L1) and 2-hydroxy-naphthaldehyde (L2), namely [Ru(η6-p-cymene)(L1)Cl] (1) and [Ru(η6-p-cymene)(L2)Cl] (2), respectively, and studied their activity on GB cells. Both complexes were structurally characterized using single-crystal X-ray diffraction, which exhibited their half-sandwich three-legged piano-stool geometry. Furthermore, we studied their physicochemical behavior, solution speciation, aquation kinetics, and photo-substitution reactions using various spectroscopic methods. The complexes exhibited a moderate binding affinity with calf-thymus (CT)-DNA (Kb ∼ 105 M-1). The complexes effectively interacted with human serum albumin (HSA) (K ∼ 105 M-1) with preferential tryptophan binding, as determined via synchronous fluorescence studies. The in vitro studies showed their significant antiproliferative activity against an aggressive human GB cell line, LN-229 (IC50 = 22.8 µM), with moderate selectivity relative to normal mouse fibroblast L929 cells. Notably, [Ru(η6-p-cymene)(L1)Cl] (1) exhibited a higher selectivity index (S.I.) than [Ru(η6-p-cymene)(L2)Cl] (2) and cisplatin. We evaluated the clonogenic potential of the GB cells using a colony formation assay in the presence of complex 1. Excitingly, it showed ∼75% inhibition of the clonogenic potential of GB cells at the IC50 concentration. Complex 1 also effectively lowered the migratory potential of the GB cells, as assessed by the wound healing assay. The studied compound led to the apoptosis of GB cells, as evidenced by nuclear condensation, blebbing, and enhanced caspase 3/7 activity, and thus has anticipated utility in the treatment of GBs using photochemotherapy.

A combined experimental and theoretical approach revealing a direct mechanism for bifunctional water splitting on doped copper phosphide.

A cost-effective electrocatalyst should have a high dispersion of active atoms and a controllable surface structure to optimize activity. Additionally, bifunctional characteristics give an added benefit for the overall water splitting. Herein, we report the synthesis and fabrication of Fe-doped Cu/Cu3P supported on a flexible carbon cloth (CC) with a hydrophilic surface for efficient bifunctional water electrolysis under alkaline conditions. Surface doping of Fe in the hexagonal Cu3P does not alter the lattice parameters, but it promotes the surface metallicity by stimulating Cuδ+ and Cu0 sites in Cu3P, resulting in an augmented electroactive surface area. Cu2.75Fe0.25P composition exhibits unprecedented OER activity with a low overpotential of 470 mV at 100 mA cm-2. Under a two electrode electrolyzer system the oxygen and hydrogen gas was evolved with an unprecedented rate at their respective electrode made of same catalyst. Density functional theory further elucidates the role of the Fe center toward electronic state modulation, which eventually alters the entire adsorption behavior of the reaction intermediates and reduces the overpotential on Fe-doped system over pristine Cu3P.

The Design of a New Cobalt Sulfide Nanoparticle Implanted Porous Organic Polymer Nanohybrid as a Smart and Durable Water-Splitting Photoelectrocatalyst.

Development of an inexpensive, efficient and robust nanohybrid catalyst as a substitute for platinum in photoelectrocatalytic hydrogen production has been considered intriguing and challenging. In this study, the design and sequential synthesis of a novel cobalt sulfide nanoparticle grafted Porous Organic Polymer nanohybrid (CoSx @POP) is reported and used as an active and durable water-splitting photoelectrocatalyst in the hydrogen evolution reaction (HER). The specific textural and relevant chemical properties of as-synthesised nanohybrid materials (Co3 O4 @POP &CoSx @POP) were investigated by means of XRD, XPS, FTIR, 13 C CP MAS NMR, spectroscopy, HR-TEM, HAADF-STEM with the corresponding elemental mapping, FE-SEM and nitrogen physisorption studies. CoSx @POP has been evaluated as a superior photoelectrocatalyst in HER, achieving a current density of 6.43 mA cm-2 at 0 V versus the reversible hydrogen electrode (RHE) in a 0.5 m Na2 SO4 electrolyte which outperforms its Co3 O4 @POP analogue. It was found that the nanohybrid CoSx @POP catalyst exhibited a substantially enhanced catalytic performance of 1.07 µmol min-1 cm-2 , which is considered to be ca. 10 and 1.94 times higher than that of pristine POP and CoSx , respectively. Remarkable photoelectrocatalytic activity of CoSx @POP compared to Co3 O4 @POP toward H2 evolution could be attributed to intrinsic synergistic effect of CoSx and POP, leading to the formation of a unique CoSx @POP nanoarchitecture with high porosity, which permits easy diffusion of electrolyte and efficient electron transfer from POP to CoSx during hydrogen generation with a tunable bandgap, that straddles between the reduction and oxidation potential of water.

Fabrication of mixed phase TiO2 heterojunction nanorods and their enhanced photoactivities.

Substantial efforts have been made in recent times in solving the major limiting factors affecting the efficiency of a photocatalyst. The fabrication of efficient junction architectures is one of the viable approaches to resolve this setback. We have developed a facile and systematic approach for the synthesis of anatase TiO2 () nanoparticles and 1-D anatase and rutile TiO2 () heterojunction nanorods to enhance the interfacial contact area by adjusting the titanium(iv) butoxide (TBOT) to titanium chloride (TiCl4) volume ratio. Their narrower band gap, increasing surface area and anatase phase composition engineered by adjusting the relative concentrations of titanium butoxide (TBOT) and titanium chloride (TiCl4) (TBOT/TiCl4, 1 : 0, 1 : 0.25, 1 : 1 and 1 : 4 v/v for , , and respectively) are also addressed. The materials showed impressive photocatalytic activity for H2 evolution from water/methanol and the photodegradation of organic pollutants like rhodamine B (RhB) and methylene blue (MB) dyes. showed superior activity (16.4 mmol g(-1) h(-1)) with an apparent quantum efficiency (AQE) of 7.7% together with its long-term stability. This is attributed to the synergistic effect observed in the mixed phase nanorod heterojunction photocatalyst. Methyl viologen (MV(2+)) has been used as a probe to elucidate the photocatalytic activities and highlight the heterojunction driven separation of photo-excited charge carriers for enhanced hydrogen production.

Synthesis of MOF templated Cu/CuO@TiO2 nanocomposites for synergistic hydrogen production.

A copper metal-organic framework (Cu-MOF) provides access to Cu/CuO@TiO2 hybrid nanocomposites with highly dispersive copper species adsorbed on a TiO2 semiconducting system. This novel nanostructure exhibits efficient hydrogen evolution performance under solar illumination of intensity ∼1 Sun. The rate of H2 production was systematically optimized under different operational parameters. Experimental observation reveals that mesoporous Cu/CuO@TiO2 nanocomposite with 0.5 wt% Cu loading showed the highest rate of H2 production (286 mmol g(-1) h(-1)), which is considerably higher than that of CuO loaded TiO2 prepared using a conventional impregnation method. This high photocatalytic H2 production activity is attributed predominantly to the presence of surface deposited Cu(0) species and the small size of the heterojunction (1-2 nm) between CuO and TiO2, which facilitate interfacial charge carrier transfer from the TiO2 nanoparticles. The catalyst showed good recyclability under prolonged exposure (30 h) to solar irradiation. Unlike many Pt decorated TiO2 photocatalysts, this hybrid photocatalyst provides an inexpensive means of harnessing solar energy.

Modulated Binary-Ternary Dual Semiconductor Heterostructures.

A generic modular synthetic strategy for the fabrication of a series of binary-ternary group II-VI and group I-III-VI coupled semiconductor nano-heterostructures is reported. Using Ag2 Se nanocrystals first as a catalyst and then as sacrificial seeds, four dual semiconductor heterostructures were designed with similar shapes: CdSe-AgInSe2 , CdSe-AgGaSe2 , ZnSe-AgInSe2 , and ZnSe-AgGaSe2 . Among these, dispersive type-II heterostructures are further explored for photocatalytic hydrogen evolution from water and these are observed to be superior catalysts than the binary or ternary semi-conductors. Details of the chemistry of this modular synthesis have been studied and the photophysical processes involved in catalysis are investigated.

First Study on Phosphonite-Coordinated Ruthenium Sensitizers for Efficient Photocatalytic Hydrogen Evolution.

For the first time we report the design and syntheses of phosphonite coordinated ruthenium(II) sensitizers bearing CN̂N ligand and/or terpyridine derivatives carboxylate anchor (GS11, GS12. and GS13) and its application for hydrogen production over Pt-TiO2 system. These heteroleptic complexes exhibit broad metal-to-ligand charge transfer transition band over the whole visible regime extending up to 900 nm. DFT calculations of these complexes show that the HOMO is distributed over the Ru and Cl atom whereas; LUMO is localized on the polypyridile ligand, which are anchored on TiO2 surface. Among the sensitizers tested for photocatalytic hydrogen evolution, GS12 exhibited a maximum turnover number (TON) 8605 (for 8 h), which is very high compared to the reference sensitizer (N719) with TON 163 under similar evaluation condition. The dependence of the hydrogen evolution rate at different pH using GS11, GS12, GS13, and DX-1-sensitized Pt-TiO2 has been studied and the maximum H2 production yield was obtained at pH 7 for all sensitizers.

Fabrication of hierarchical ZnO/CdS heterostructured nanocomposites for enhanced hydrogen evolution from solar water splitting.

ZnO/CdS heterostructured nanocomposites were fabricated with enhanced light harvesting capability and photostability using sequential sonochemical and hydrothermal methods from ZnO rods and particles. Interestingly, in the composite made up of CdS sensitized ZnO rods, both ZnO and CdS exist in the hexagonal wurtzite form with different morphologies. On the other hand, in the composite made up of CdS sensitized ZnO particles, ZnO exists in the hexagonal wurtzite form, whereas CdS in the cubic form but with a similar morphology. The synthesized photocatalysts under simulated solar irradiation exhibited hydrogen evolution rates of 870 and 1007 µmol h(-1) g(-1) for the ZnO rod/CdS and ZnO nanoparticle/CdS composites, respectively, compared to the native ZnO (40 µmol h(-1) g(-1) for rods and 154 µmol h(-1) g(-1) for particles) and CdS (208 µmol h(-1) g(-1)) structures. The apparent quantum yield of CdS was only 1.2%, whereas the composites exhibited much higher quantum yields of 4.9% and 5.7%. Our results confirmed that the morphology of the host matrix ZnO played a crucial role in forming ZnO/CdS heterostructures with improved interface for the direct Z-scheme mechanism with enhanced hydrogen evolution efficiency.

Dithiafulvalene functionalized diketopyrrolopyrrole based sensitizers for efficient hydrogen production.

We have designed and synthesized two new diketopyrrolopyrrole (DPP) based organic sensitizers (DPPCA and DPPCN) with the dithiafulvalene (DTF) unit as donor and cyanoacrylic acid/malononitrile as acceptor moieties. These dyes showed excellent efficiency of photocatalytic hydrogen production over a Pt-TiO2 composite via solar-induced water splitting. The sensitizers showed broad absorptions over the wide visible regime (500-800 nm). In DPPCN, the malononitrile moiety led to strong intra-molecular charge transfer, as evidenced by red shifted (∼24 nm) absorption maxima with highly enhanced molar absorptivity (108 190 M(-1) cm(-1)). The electrochemical characterization of as-prepared sensitizers confirmed the feasible electron injection from the dye to the TiO2 conduction band (CB) which has been further validated by theoretical studies. In this study, the rate of the photocatalytic activity was found to be dependent on the acceptor part of the dye molecule as DPPCN sensitized Pt-TiO2 (DNPT) exhibited remarkable (1208 µmol) hydrogen evolution yield in comparison to DPPCA sensitized Pt-TiO2 (DAPT) (840 µmol). The rigid DPP core made the sensitizers significantly photo-stable as affirmed by their high hydrogen production efficiency over 80 h of prolonged irradiation. As predicted from density functional theory (DFT) calculations, ground state geometry of the dyes was almost planar, facilitating continuous conjugation throughout the molecule. Time-dependent DFT (TD-DFT) calculations were also carried out to make clear the understanding of charge transfer transition of the dye molecules.

Synthesis, crystal structure and optical properties of a naphthylbisimide-Ni complex: a framework on TiO2 for visible light H2 production.

A novel ligand N,N'-di-(3-(pyridin-2-yl)-1H-pyrazole-5-carbohydrazide) naphthalene 1,4,5,8-tetracarboxylic acid bisimide (PPNB) and its nickel (ii) complex (Ni-PPNB) were synthesized and systematically characterized. Both the molecules show higher sensitization activity on the TiO2 semiconducting system. These composites have interesting photophysical properties as they enable photocatalytic hydrogen production from water with a sacrificial electron donor (SED) using visible light, while neither component alone is able to do so. The photocatalysts have shown long term stability and a maximum turnover number (TON) of 7866 based on Ni-PPNB was obtained after 6 h of irradiation at a catalyst concentration of 2.5 × 10(-5) mol g(-1).