Solar and Visible Light Driven Photocatalysis for Sacrificial Hydrogen Generation and Water Detoxification with Chemically Modified Ti02

Photocatalysis is a recognized approach where light energy is employed to excite the semiconductor material producing electron/hole pair which eventually involves in the detoxification of pollutants and/or water splitting producing hydrogen. Existing photocatalysts suffer from poor activity or no activity in visible light irradiation which restricts them from solar light utilization. This work is focused on two key applications of photocatalysis (i) sacrificial hydrogen generation, and (ii) phenol degradation in visible and/or solar light. Platinum was loaded on TiO2 photocatalyst by solar photo-deposition method. Eosin Y dye was used as a sensitizer for sensitization of platinum loaded TiO2 photocatalyst. The photocatalyst was irradiated from the top with a solar simulator. The light source was equipped with AM 1.5 G as well as a 420 nm cutoff filter to remove all the UV light. A factorial design at two levels and four factors has been carried out in order to investigate the potential for hydrogen generation using Eosin Y-sensitized TiO2/Pt catalyst under visible solar light in presence of triethanolamine as electron donor. Experimental data were analyzed using both “Pareto analysis” as well as conventional regression analysis techniques. A regression function was proposed that satisfactorily predicts hydrogen generation as a function of various operating parameters. Later, the photocatalytic behavior of the eosin Y–sensitized photocatalyst was studied in solar-UV (300-388 nm), solar-visible (420-650 nm) and full solar spectrum (300-650 nm) to explore the optimum reaction conditions such as (i) light intensity (100 mW cm-2), (ii) solution pH (7.0), (iii) platinum content (wt %) on TiO2 (0.25 %), (iv) mass of eosin Y-TiO2/ Pt (1-1.3 g L-1) , (v) concentration of trietanolamine (0.25 M), and (vi) mass ratio of eosin Y to TiO2/Pt (1:10). The reaction mechanisms were different in solar and visible lights, although in both cases formaldehyde was detected as an intermediate product. Studies in a pulsating flow reactor showed positive effects of pre-sonication, increased flow rate and bi-directional mixing mode in solar hydrogen generation. A detailed study on the photocatalytic behavior of formaldehyde for sacrificial hydrogen generation was performed for better understanding of the process. Photocatalytic hydrogen generation from formaldehyde was influenced by solution pH, platinum content (wt %) on TiO2, catalyst concentration, light intensity, and initial formaldehyde concentration. A Langmuir-type model was well fitted with the experimental data for photocatalytic hydrogen generation from both triethanolamine and formaldehyde as sacrificial agents. Apparent quantum yield (QY) was much higher for UV light driven hydrogen generation. In solar and visible light the QYs were a function of the light intensity and the wavelength range considered for the calculation. Phenol degradation with eosin Y-sensitized TiO2/Pt photocatalyst under solar-visible light was performed with triethanolamine as electron donor. About 93 % degradation of 40 ppm phenol solution was achieved within 90 minutes using Eosin Y-TiO2/Pt photocatalyst at optimum conditions (pH = 7.0, catalyst loading = 0.8 g L-1, triethnolamine concentration = 0.2 M, 0.5 % Pt loading on TiO2, visible solar light of 100 mW cm-2). Kinetic rate constant and adsorption equilibrium constant were determined and a Langmuir-Hinshelwood type equation was proposed to describe phenol degradation on TiO2 at different visible light intensities. The model equation predicts experimental results quite well

BreCAN-DB: a repository cum browser of personalized DNA breakpoint profiles of cancer genomes

BreCAN-DB (http://brecandb.igib.res.in) is a repository cum browser of whole genome somatic DNA breakpoint profiles of cancer genomes, mapped at single nucleotide resolution using deep sequencing data. These breakpoints are associated with deletions, insertions, inversions, tandem duplications, translocations and a combination of these structural genomic alterations. The current release of BreCAN-DB features breakpoint profiles from 99 cancer-normal pairs, comprising five cancer types. We identified DNA breakpoints across genomes using high-coverage next-generation sequencing data obtained from TCGA and dbGaP. Further, in these cancer genomes, we methodically identified breakpoint hotspots which were significantly enriched with somatic structural alterations. To visualize the breakpoint profiles, a next-generation genome browser was integrated with BreCAN-DB. Moreover, we also included previously reported breakpoint profiles from 138 cancer-normal pairs, spanning 10 cancer types into the browser. Additionally, BreCAN-DB allows one to identify breakpoint hotspots in user uploaded data set. We have also included a functionality to query overlap of any breakpoint profile with regions of user's interest. Users can download breakpoint profiles from the database or may submit their data to be integrated in BreCAN-DB. We believe that BreCAN-DB will be useful resource for genomics scientific community and is a step towards personalized cancer genomics

Degradation of Phenolic Compounds Through UV and Visible- Light-Driven Photocatalysis: Technical and Economic Aspects

Phenolic compounds are found in surface and groundwater as well as wastewater from several industries. It is necessary to eliminate phenols and phenolic compounds from contaminated water before releasing into water bodies due to their toxicity to human beings. Photocatalytic degradation seems to be a promising technology for the degradation of several phenolic compounds. Complete mineralization of phenol and phenolic compound has been achieved with TiO2-based photocatalysts under both UV and visible-light irradiation. This chapter will evaluate the conventional processes and advanced oxidation processes for the degradation of phenol and phenolic compounds. The process economics and efficiencies of different advanced oxidation processes will also be discussed. The main focus of the chapter is photocatalytic degradation processes under UV and visible light along with a detailed review of several factors affecting degradation of phenol and phenolic compounds. Photocatalytic degradation process is governed by reactions with hydroxyl radical or superoxide ion. The extent of degradation depends on light sources (UV, visible, and solar), the type of photocatalyst, and experimental conditions (pH, photocatalyst dosage, initial concentration of phenolic compounds, light intensity, electron donor concentration, etc.).Visible-light-active photocatalysts are applied by several researchers to exploit sunlight and to make the photocatalysis process sustainable. In the future, using sunlight in place of UV could make photocatalysis economically more efficient

Dynamic instability of microtubules: effect of catastrophe-suppressing drugs

Microtubules are stiff filamentary proteins that constitute an important component of the cytoskeleton of cells. These are known to exhibit a dynamic instability. A steadily growing microtubule can suddenly start depolymerizing very rapidly; this phenomenon is known as ``catastrophe''. However, often a shrinking microtubule is ``rescued'' and starts polymerizing again. Here we develope a model for the polymerization-depolymerization dynamics of microtubules in the presence of {\it catastrophe-suppressing drugs}. Solving the dynamical equations in the steady-state, we derive exact analytical expressions for the length distributions of the microtubules tipped with drug-bound tubulin subunits as well as those of the microtubules, in the growing and shrinking phases, tipped with drug-free pure tubulin subunits. We also examine the stability of the steady-state solutions.Comment: Minor corrections; final published versio

Circular geodesics and accretion disks in Janis-Newman-Winicour and Gamma metric

We study here circular timelike geodesics in the Janis-Newman-Winicour and Gamma metric spacetimes which contain a strong curvature naked singularity and reduce to the Schwarzschild metric for a specific value of one of the parameters. We show that for both the metrics the range of allowed parameters can be divided into three regimes where structure of the circular geodesics is qualitatively different. It follows that the properties of the accretion disks around such naked singularities can be significantly different from those of disks around black holes. This adds to previous studies showing that if naked singularities exist in nature, their observational signature would be significantly different from that of the black hole

Van Wyk-Grumbach syndrome: a rare presentation of a common endocrine disorder

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Circular geodesics and accretion disks in Janis-Newman-Winicour and Gamma metric

We study here circular timelike geodesics in the Janis-Newman-Winicour and Gamma metric spacetimes which contain a strong curvature naked singularity and reduce to the Schwarzschild metric for a specific value of one of the parameters. We show that for both the metrics the range of allowed parameters can be divided into three regimes where structure of the circular geodesics is qualitatively different. It follows that the properties of the accretion disks around such naked singularities can be significantly different from those of disks around black holes. This adds to previous studies showing that if naked singularities exist in nature, their observational signature would be significantly different from that of the black hole.Comment: 13 pages, 16 figures, version accepted for publication by PR

Genome-wide distribution of histone H4 Lysine 16 acetylation sites and their relationship to gene expression

BACKGROUND: Histone post-translational modifications are critical determinants of chromatin structure and function, impacting multiple biological processes including DNA transcription, replication, and repair. The post-translational acetylation of histone H4 at lysine 16 (H4K16ac) was initially identified in association with dosage compensation of the Drosophila male X chromosome. However, in mammalian cells, H4K16ac is not associated with dosage compensation and the genomic distribution of H4K16ac is not precisely known. Therefore, we have mapped the genome-wide H4K16ac distribution in human cells. RESULTS: We performed H4K16ac chromatin immunoprecipitation from human embryonic kidney 293 (HEK293) cells followed by hybridization to whole-genome tiling arrays and identified 25,893 DNA regions (false discovery rate <0.005) with average length of 692 nucleotides. Interestingly, although a majority of H4K16ac sites localized within genes, only a relatively small fraction (~10%) was found near promoters, in contrast to the distribution of the acetyltransferase, MOF, responsible for acetylation at K16 of H4. Using differential gene expression profiling data, 73 genes (> ±1.5-fold) were identified as potential H4K16ac-regulated genes. Seventeen transcription factor-binding sites were significantly associated with H4K16ac occupancy (p < 0.0005). In addition, a consensus 12-nucleotide guanine-rich sequence motif was identified in more than 55% of the H4K16ac peaks. CONCLUSIONS: The results suggest that H4K16 acetylation has a limited effect on transcription regulation in HEK293 cells, whereas H4K16ac has been demonstrated to have critical roles in regulating transcription in mouse embryonic stem cells. Thus, H4K16ac-dependent transcription regulation is likely a cell type specific process

Nature-inspired Enzyme engineering and sustainable catalysis: biochemical clues from the world of plants and extremophiles

The use of enzymes to accelerate chemical reactions for the synthesis of industrially important products is rapidly gaining popularity. Biocatalysis is an environment-friendly approach as it not only uses non-toxic, biodegradable, and renewable raw materials but also helps to reduce waste generation. In this context, enzymes from organisms living in extreme conditions (extremozymes) have been studied extensively and used in industries (food and pharmaceutical), agriculture, and molecular biology, as they are adapted to catalyze reactions withstanding harsh environmental conditions. Enzyme engineering plays a key role in integrating the structure-function insights from reference enzymes and their utilization for developing improvised catalysts. It helps to transform the enzymes to enhance their activity, stability, substrates-specificity, and substrate-versatility by suitably modifying enzyme structure, thereby creating new variants of the enzyme with improved physical and chemical properties. Here, we have illustrated the relatively less-tapped potentials of plant enzymes in general and their sub-class of extremozymes for industrial applications. Plants are exposed to a wide range of abiotic and biotic stresses due to their sessile nature, for which they have developed various mechanisms, including the production of stress-response enzymes. While extremozymes from microorganisms have been extensively studied, there are clear indications that plants and algae also produce extremophilic enzymes as their survival strategy, which may find industrial applications. Typical plant enzymes, such as ascorbate peroxidase, papain, carbonic anhydrase, glycoside hydrolases and others have been examined in this review with respect to their stress-tolerant features and further improvement via enzyme engineering. Some rare instances of plant-derived enzymes that point to greater exploration for industrial use have also been presented here. The overall implication is to utilize biochemical clues from the plant-based enzymes for robust, efficient, and substrate/reaction conditions-versatile scaffolds or reference leads for enzyme engineering

Loss-of-function analysis suggests that omi/htra2 is not an essential component of the pink1/parkin pathway in vivo

Recently, a mutation in the mitochondrial protease Omi/HtrA2, G399S, was found in sporadic Parkinson's disease (PD) patients, leading to the designation of Omi/HtrA2 as PD locus 13 (PARK13). G399S reportedly results in reduced Omi protease activity. In vitro studies have suggested that Omi/HtrA2 acts downstream of PINK1, mutations in which mediate recessive forms of PD. We, as well as other, have previously shown that the Drosophila homologs of the familial PD genes, PINK1 (PARK6) and PARKIN (PARK2), function in a common genetic pathway to regulate mitochondrial integrity and dynamics. Whether Omi/HtrA2 regulates mitochondrial integrity and whether it acts downstream of PINK1 in vivo remain to be explored. Here, we show that Omi/HtrA2 null mutants in Drosophila, in contrast to pink1 or parkin null mutants, do not show mitochondrial morphological defects. Extensive genetic interaction studies do not provide support for models in which Omi/HtrA2 functions in the same genetic pathway as pink1, or carries out partially redundant functions with pink1, at least with respect to regulation of mitochondrial integrity and dynamics. Furthermore, Omi/HtrA2 G399S retains significant, if not full, function of Omi/HtrA2, compared with expression of protease-compromised versions of the protein. In light of recent findings showing that G399S can be found at comparable frequencies in PD patients and healthy controls, we do not favor a hypothesis in which Omi/HtrA2 plays an essential role in PD pathogenesis, at least with respect to regulation of mitochondrial integrity in the pink1/parkin pathway