Magnetite interaction with arsenic during sorptive removal from groundwater: a mechanistic study.

A magnetic mixed iron oxide, magnetite (Fe3O4), was synthesized in the laboratory and characterized before its use as sorbent for arsenic removal. The characterization techniques used were X-ray diffraction (XRD), specific surface area, zeta potential and particle size measurements. The sorbent was applied for arsenic removal, without any pre or post treatment, from groundwater. The efficiency of sorption can only be improved by understanding the sorbent-sorbate interaction. For onsite monitoring of the sorbent-sorbate interaction, an electrochemical investigation using cyclic voltammetry (CV) measurement was developed. The study confirmed that the sorption of As(III) on Fe3O4 is dynamic (reversible) whereas that of As(V) is static (irreversible) in nature. Detailed investigation after the sorption was carried out utilizing X-ray photoelectron spectroscopy (XPS) measurement. The complexation of As(III)-Fe3O4 and As(V)-Fe3O4 without any redox transformation was evident from the XPS data. By careful examination of the results, a mechanism of arsenic removal by Fe3O4 was proposed.

Solvated electron-induced synthesis of cyclodextrin-coated Pd nanoparticles: mechanistic, catalytic, and anticancer studies.

Herein, using in situ generated solvated electrons in the reaction media, a highly time-efficient, one-pot green approach has been employed to synthesize palladium (Pd) nanoparticles (NPs) coated with a molecular assembly of α-cyclodextrin (α-CD). The appearance of a shoulder peak at 280 nm in the UV-Vis absorption spectra indicated the formation of Pd NPs, which was further confirmed from their cubic phase XRD pattern. The nanomorphology varied considerably as a function of the dose rate, wherein sphere-shaped NPs (average size ∼ 7.6 nm) were formed in the case of high dose rate electron-beam assisted synthesis, while nanoflakes self-assembled to form nanoflower-shaped morphologies in a γ-ray mediated approach involving a low dose rate. The formation kinetics of NPs was investigated by pulse radiolysis which revealed the formation of Pd-based transients by the solvated electron-induced reaction. Importantly, no interference of α-CD was observed in the kinetics of the transient species, rather it played the role of a morphology directing agent in addition to a biocompatible stabilizing agent. The catalytic studies revealed that the morphology of the NPs has a significant effect on the reduction efficiency of 4-nitrophenol to 4-aminophenol. Another important highlight of this work is the demonstration of the morphology-dependent anticancer efficacy of Pd NPs against lung and brain cancer cells. Notably, flower-shaped Pd NPs exhibited significantly higher cancer cell killing as compared to spherical NPs, while being less toxic towards normal lung fibroblasts. Nonetheless, these findings show the promising potential of Pd NPs in anticancer treatment.

An insight into the sequestration of tetra and hexavalent actinides by tri ethoxysilyl-amino-propyl-3-oxa-glutaramic acid (SAPOGA) functionalized titania.

Silyl-amino-propyl-3-oxa-glutaramic acid (SAPOGA) functionalized titania has been synthesized for highly efficient solid phase sequestration of thorium and uranyl ions from an aqueous acidic waste stream. The XRD pattern suggested that the grafting was performed on the anatase phase, leading to a rougher surface resulting in better interaction with actinides. The successful grafting of SAPOGA bridging was confirmed using spectroscopic methods. The Langmuir isotherm and the intraparticle diffusion-based kinetics model were found to be operative with sorption capacities of 231 mg g-1 and 458 mg g-1 and rate constants of 51 mg g-1 min-1 and 48 mg g-1 min-1 for U and Th, respectively. The entropy driven sequestration process was thermodynamically favourable (ΔGU = -6.0 kJ mol-1 and ΔGTh = -9.1 kJ mol-1) and endothermic in nature. The experimentally corroborated complexation pattern was assisted by density functional theory (DFT) calculations, which gave further insight into the metal-ligand interaction.

Antiviral Activity of Zinc Oxide Nanoparticles and Tetrapods Against the Hepatitis E and Hepatitis C Viruses.

Hepatitis E virus (HEV) causes an acute, self-limiting hepatitis. The disease takes a severe form in pregnant women, leading to around 30% mortality. Zinc is an essential micronutrient that plays a crucial role in multiple cellular processes. Our earlier findings demonstrated the antiviral activity of zinc salts against HEV infection. Zinc oxide (ZnO) and its nanostructures have attracted marked interest due to their unique characteristics. Here we synthesized ZnO nanoparticles [ZnO(NP)] and tetrapod-shaped ZnO nanoparticles [ZnO(TP)] and evaluated their antiviral activity. Both ZnO(NP) and ZnO(TP) displayed potent antiviral activity against hepatitis E and hepatitis C viruses, with the latter being more effective. Measurement of cell viability and intracellular reactive oxygen species levels revealed that both ZnO(NP) and ZnO(TP) are noncytotoxic to the cells even at significantly higher doses, compared to a conventional zinc salt (ZnSO4). Our study paves the way for evaluation of the potential therapeutic benefit of ZnO(TP) against HEV and HCV.

3,3'-Diselenodipropionic acid (DSePA) forms 1:1 complex with Hg (II) and prevents oxidative stress in cultured cells and mice model.

Mercury is one of the most toxic heavy metal for mammals particularly in inorganic form. In present study, 3,3'-diselenodipropionic acid (DSePA), a well-known pharmacological diselenide was evaluated for its interaction with HgCl2 and ability to prevent HgCl2-induced toxicity in experimental cellular and mice models. UV-visible, stopped flow, Fourier-transform infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy studies confirmed that DSePA sequestered Hg (II) ions with stoichiometry of 1:1 and binding constant of ~104 M-1. X-ray photoelectron spectroscopy and X-ray powder diffraction analysis suggested that diselenide group of DSePA was involved in the complexation with Hg (II) ions. Further, Hg-DSePA complex degraded within 10 days to form excretable HgSe. The binding constant of DSePA and Hg (II) was comparable with that of dihydrolipoic acid, a standard disulfide compound used in heavy metal detoxification. Corroborating these observations, pre-treatment of DSePA (10 µM) significantly prevented the HgCl2 (50 µM)-induced glutathione oxidation (GSH/GSSG), decrease of thioredoxin reductase (TrxR) and glutathione peroxidase (GPx) activities and cell death in Chinese Hamster Ovary (CHO) cells. Similarly, intraperitoneal administration of DSePA at a dosage of 2 mg/kg for 5 consecutive days prior to exposure of HgCl2 (1 mg/kg) significantly suppressed oxidative stress in renal and hepatic tissues of C57BL/6 mice. In conclusion, the protective effect of DSePA against Hg induced oxidative stress is attributed to its ability to rescue the activities of GPx, TrxR and GSH by sequestering Hg (II) ions. DSePA being a relatively safer selenium-compound for in vivo administration can be explored for mercury detoxification.

Evidences on As(III) and As(V) interaction with iron(III) oxides: Hematite and goethite.

Arsenic, which is ubiquitous in nature, was found associated with iron oxides in soils and sediments. Our interest was to utilize the same mechanism for the sorptive removal of arsenic from groundwater. The iron(III) oxides: hematite, goethite, were synthesized, characterized and sorption studies of arsenic [As(III) and As(V)] were carried out in batch mode. For studying the evidence of the interaction between arsenic and iron oxide during the process of sorption, a new electrochemical method was developed. Differential pulse voltammetry (DPV) study indicated that the sorbed arsenic species is redox active on the surface of the sorbent. X-ray photoelectron spectroscopy (XPS) measurement was performed for confirmation of the changes occurring to the oxidation states of iron as well as arsenic after the sorption. XPS studies confirmed that the behavior of arsenic species on hematite/goethite was similar and occurs via a partial redox reaction. During sorption of As(III), a partial oxidation occurs resulting in As(V) species, simultaneously the Fe(III) present in the iron oxide gets reduced to Fe(II). However, during the sorption of As(V), there occurs a Fe(II) oxidation followed by As(V) reduction. Based on the results, a mechanistic scheme for sorption of arsenic on iron(III) oxides as sorbents was proposed.

Oxygen Reduction Reaction Activity of Microwave Mediated Solvothermal Synthesized CeO2/g-C3N4 Nanocomposite.

Electrocatalytic active species like transition metal oxides have been widely combined with carbon-based nanomaterials for enhanced Oxygen Reduction Reaction (ORR) studies because of the synergistic effect arising between different components. The aim of the present study is to synthesize CeO2/g-C3N4 system and compare the ORR activity with bare CeO2. Ceria (CeO2) embedded on g-C3N4 nanocomposite was synthesized by a single-step microwave-mediated solvothermal method. This cerium oxide-based nanocomposite displays enhanced ORR activity and electrochemical stability as compared to bare ceria.

Fabrication of plasmonic dye-sensitized solar cells using ion-implanted photoanodes.

Plasmonic dye-sensitized solar cells containing metal nanoparticles suffer from stability issues due to their miscibility with liquid iodine-based electrolytes. To resolve the stability issue, herein, an ion implantation technique was explored to implant metal nanoparticles inside TiO2, which protected these nanoparticles with a thin coverage of TiO2 melt and maintained the localized surface plasmon resonance oscillations of the metal nanoparticles to efficiently enhance their light absorption and make them corrosion resistant. Herein, Au nanoparticles were implanted into the TiO2 matrix up to the penetration depth of 22 nm, and their influence on the structural and optical properties of TiO2 was studied. Moreover, plasmonic dye-sensitized solar cells were fabricated using N719 dye-loaded Au-implanted TiO2 photoanodes, and their power conversion efficiency was found to be 44.7% higher than that of the unimplanted TiO2-based dye-sensitized solar cells due to the enhanced light absorption of the dye molecules in the vicinity of the localized surface plasmon resonance of Au as well as the efficient electron charge transport at the TiO2@Au@N719/electrolyte interface.

Carbon nano tubes functionalized with novel functional group- amido-amine for sorption of actinides.

The manuscript presents the results on the sorption of U(VI), Am(III) & Eu(III) from pH medium by a novel amido-amine functionalized multiwalled carbon nanotube (MWCNT). The novel functional group was introduced in the MWCNT by two step processes and characterized by various instrumental techniques like Scanning Electron Microscopy (SEM), Raman and X-ray Photoelectron Spectroscopy (XPS). The sorption process was found to be highly dependent on the pH of the solution with maximum sorption for both 233U, 241Am & 152+154Eu at pH 7.0. Kinetics of sorption was found to be fast with equilibrium reached in ∼15min and the sorption was found to be following pseudo 2nd order kinetics for the radionuclides. The sorption for both 233U and 152+154Eu followed Langmuir sorption model with maximum sorption capacity of 20.66mg/g and 16.1mg/g respectively. This has been explained by DFT calculations which shows that more negative solvation energy of U(VI) compared to Am(III) and Eu(III) and stronger U-MWCNT-AA complex is responsible for higher sorption capacity of U(VI) compared to Am(III) and Eu(III).The synthesized amido-amine functionalized MWCNT is a very promising candidate for removal of actinides and lanthanides from waste water solution with high efficiency.

Tailoring of the chlorine sensing properties of substituted metal phthalocyanines non-covalently anchored on single-walled carbon nanotubes.

To investigate how central metal tunes the synergetic interactions between substituted metallo-phthalocyanine and single-walled carbon nanotubes in enhancing the gas sensing properties, a comparative study has been performed by varying the central metal ion in fluorinated metal phthalocyanines and single-walled carbon nanotube hybrid. Hybrids of metal(ii)-1,2,3,4,8,9,10,11,15,16,17,18-24,25-hexa-decafluoro-29H,31H-phthalocyanine/single-walled carbon nanotube (F16MPc/SWCNTs-COOH, where M = Co, Zn) have been synthesized through π-π stacking interactions using the solution route. Spectroscopic (FT-IR, UV-vis, XPS and Raman), electron microscopic (TEM and FE-SEM) and TGA investigations have confirmed the successful functionalization and interaction of SWCNTs-COOH with F16MPc. Parts per billion (ppb) level Cl2-selective chemiresistive gas sensors have been fabricated on glass substrates with precoated gold electrodes by using these hybrids. The responses of various F16MPc/SWCNTs-COOH sensors have demonstrated the central metal ion-dependence in the sensitivity of Cl2.

Mixed-matrix membranes with enhanced antifouling activity: probing the surface-tailoring potential of Tiron and chromotropic acid for nano-TiO2.

Mixed-matrix membranes (MMMs) were developed by impregnating organofunctionalized nanoadditives within fouling-susceptible polysulfone matrix following the non-solvent induced phase separation (NIPS) method. The facile functionalization of nanoparticles of anatase TiO2 (nano-TiO2) by using two different organoligands, viz. Tiron and chromotropic acid, was carried out to obtain organofunctionalized nanoadditives, FT-nano-TiO2 and FC-nano-TiO2, respectively. The structural features of nanoadditives were evaluated by X-ray diffraction, X-ray photoelectron spectroscopy, Raman and Fourier transform infrared spectroscopy, which established that Tiron leads to the blending of chelating and bridging bidentate geometries for FT-nano-TiO2, whereas chromotropic acid produces bridging bidentate as well as monodentate geometries for FC-nano-TiO2. The surface chemistry of the studied membranes, polysulfone (Psf): FT-nano-TiO2 UF and Psf: FC-nano-TiO2 UF, was profoundly influenced by the benign distributions of the nanoadditives enriched with distinctly charged sites ([Formula: see text]), as evidenced by superior morphology, improved topography, enhanced surface hydrophilicity and altered electrokinetic features. The membranes exhibited enhanced solvent throughputs, viz. 3500-4000 and 3400-4300 LMD at 1 bar of transmembrane pressure, without significant compromise in their rejection attributes. The flux recovery ratios and fouling resistive behaviours of MMMs towards bovine serum albumin indicated that the nanoadditives could impart stable and appreciable antifouling activity, potentially aiding in a sustainable ultrafiltration performance.

Change in the Affinity of Ethylene Glycol Methacrylate Phosphate Monomer and Its Polymer Anchored on a Graphene Oxide Platform toward Uranium(VI) and Plutonium(IV) Ions.

The complexation behavior of the carbonyl and phosphoryl ligating groups bearing ethylene glycol methacrylate phosphate (EGMP) monomer and its polymer fixed on a graphene oxide (GO) platform was studied to understand the coordination ability of segregated EGMP units and polymer chains toward UO2(2+) and Pu(4+) ions. The cross-linked poly(EGMP) gel and EGMP dissolved in solution have a similar affinity toward these ions. UV-initiator induced polymerization was used to graft poly(EGMP) on the GO platform utilizing a double bond of EGMP covalently fixed on it. X-ray photoelectron spectroscopy (XPS) of the GO and GO-EGMP was done to confirm covalent attachment of the EGMP via a -C-O-P- link between GO and EGMP. The extent of poly(EGMP) grafting on GO by thermal analyses was found to be 5.88 wt %. The EGMP units fixed on the graphene oxide platform exhibited a remarkable selectivity toward Pu(4+) ions at high HNO3 conc. where coordination is a dominant mode involved in the sorption of ions. The ratio of distribution coefficients of Pu(IV) to U(VI) (DPu(IV)/DU(VI)) followed a trend as cross-linked poly(EGMP) (0.95) < EGMP in solvent methyl isobutyl ketone (1.3) < GO-poly(EGMP) (25) < GO-EGMP (181); the DPu(IV)/DU(VI) values are given in parentheses. The density functional theory computations have been performed for the complexation of UO2(2+) and Pu(4+) ions with the EGMP molecule anchored on GO in the presence of nitrate ions. This computational modeling suggested that Pu(4+) ion formed a strong coordination complex with phosphoryl and carbonyl ligating groups of the GO-EGMP as compared to UO2(2+) ions. Thus, the nonselective EGMP becomes highly selective to Pu(IV) ions when it interacts as a single unit fixed on a GO platform.

Enhanced thermoelectric properties of selenium-deficient layered TiSe(2-x): a charge-density-wave material.

In the present work, we report on the investigation of low-temperature (300-5 K) thermoelectric properties of hot-pressed TiSe2, a charge-density-wave (CDW) material. We demonstrate that, with increasing hot-pressing temperature, the density of TiSe2 increases and becomes nonstoichiometric owing to the loss of selenium. X-ray diffraction, scanning electron microscopy, and transimission electron microscopy results show that the material consists of a layered microstructure with several defects. Increasing the hot-press temperature in nonstoichiometric TiSe2 leads to a reduction of the resistivity and enhancement of the Seebeck coefficient in concomitent with suppression of CDW. Samples hot-pressed at 850 °C exhibited a minimum thermal conductivity (κ) of 1.5 W/m·K at 300 K that, in turn, resulted in a figure-of-merit (ZT) value of 0.14. This value is higher by 6 orders of magnitude compared to 1.49 × 10(-7) obtained for cold-pressed samples annealed at 850 °C. The enhancement of ZT in hot-pressed samples is attributed to (i) a reduced thermal conductivity owing to enhanced phonon scattering and (ii) improved power factor (α(2)σ).

Charge transport in ultrathin iron-phthalocyanine thin films under high electric fields.

The temperature dependent current-voltage (J-V) characteristics of 20 nm thick iron-phthalocyanine films are investigated in the temperature range of 300-30 K, and in the bias range of ±200 V. In the temperature range of 300-100 K, the charge transport is governed by bulk-limited processes with a bias dependent crossover from Ohmic (J∼V) to exponentially distributed shallow trap mediated space-charge-limited conduction (J∼V(α), α ≥ 2) to space-charge-limited conduction with field enhanced mobility (lnµâˆ¼E(1/2)). However, at temperatures less than 100 K, the charge transport is electrode-limited, and undergoes a bias dependent transition from Schottky (lnJ∼V(1/2)) to multistep tunneling. From shallow trap mediated space-charge-limited conduction data the estimated room temperature mobility was found to be ∼1.9 cm(2) V (-1) s(-1). The high mobility of films is attributed to better structural organization due to the face-on stacking of molecules, which is supported by x-ray diffraction and UV-visible spectroscopy data.

Room temperature ppb level Cl2 sensing using sulphonated copper phthalocyanine films.

We present room temperature chemiresistive gas sensing characteristics of drop casted sulphonated copper phthalocyanine (CuTsPc) films. It has been demonstrated that these films are highly selective to Cl(2) and the sensitivity in the 5-2000 ppb range varies linearly between 65 and 625%. However, for concentrations >or=2000 ppb, the response becomes irreversible, which is found to be due to the chemical bond formation between Cl(2) and SO(3)Na group of CuTsPc films. The X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) data confirms the oxidation of SO(3)Na group by Cl(2) gas.

Temperature dependent current-voltage characteristics of iron-phthalocyanine thin films.

The current-voltage (I-V) characteristics of the crystalline alpha-phase iron phthalocyanine (FePc) thin films grown by molecular beam epitaxy have been investigated by using a planar geometry in which the metal electrodes are separated by 15 microm. By carrying out the room temperature I-V measurements on vacuum annealed (200 degrees C for 30 min under 10(-6) torr) FePc thin films under vacuum and after exposing them to the air, we demonstrate that the hysteresis in FePc films is intimately related to the filling and de-filling of surface traps created by chemisorbed oxygen. The presence of chemisorbed oxygen has been confirmed by the X-ray photoelectron spectroscopy. Room temperature I-V characteristics of air exposed films showed ohmic conduction in the lower voltage range and space-charge-limited-conductivity (SCLC) in the relatively high voltage. Temperature dependent measurements show that the hysteresis disappears at 250 K and the surface traps are distributed in energy about 0.22 eV deep.

Cellulose acetate phthalate, a common pharmaceutical excipient, inactivates HIV-1 and blocks the coreceptor binding site on the virus envelope glycoprotein gp120.

BACKGROUND: Cellulose acetate phthalate (CAP), a pharmaceutical excipient used for enteric film coating of capsules and tablets, was shown to inhibit infection by the human immunodeficiency virus type 1 (HIV-1) and several herpesviruses. CAP formulations inactivated HIV-1, herpesvirus types 1 (HSV-1) and 2 (HSV-2) and the major nonviral sexually transmitted disease (STD) pathogens and were effective in animal models for vaginal infection by HSV-2 and simian immunodeficiency virus. METHODS: Enzyme-linked immunoassays and flow cytometry were used to demonstrate CAP binding to HIV-1 and to define the binding site on the virus envelope. RESULTS: 1) CAP binds to HIV-1 virus particles and to the envelope glycoprotein gp120; 2) this leads to blockade of the gp120 V3 loop and other gp120 sites resulting in diminished reactivity with HIV-1 coreceptors CXCR4 and CCR5; 3) CAP binding to HIV-1 virions impairs their infectivity; 4) these findings apply to both HIV-1 IIIB, an X4 virus, and HIV-1 BaL, an R5 virus. CONCLUSIONS: These results provide support for consideration of CAP as a topical microbicide of choice for prevention of STDs, including HIV-1 infection.

Quantitative structure-activity relationship (QSAR) paradigm--Hansch era to new millennium.

The analysis of structure-activity relationships started probably more than hundred years ago but the concept of quantitatively correlating physicochemical properties of molecules with their biological activities, termed as quantitative structure-activity relationship (QSAR), was initiated by Corwin Hansch and his groups in early 1960. Many new methods have emerged since then. The concept evolved from 2D QSAR to 3D QSAR and lately another dimension (4D QSAR) has been added. This evolution is briefly reviewed here.

A salt bridge between an N-terminal coiled coil of gp41 and an antiviral agent targeted to the gp41 core is important for anti-HIV-1 activity.

HIV-1 envelope glycoprotein transmembrane subunit gp41 play a critical role in the fusion of viral and target cell membranes. The gp41 C-terminal heptad repeat region interacts with the N-terminal coiled-coil region to form a six-stranded core structure. Peptides derived from gp41 C-terminal heptad repeat region (C-peptides) are potent HIV-1 entry inhibitors by binding to gp41 N-terminal coiled-coil region. Most recently, we have identified two small organic compounds that inhibit HIV-1-mediated membrane fusion by blocking the formation of gp41 core. These two active compounds contain both hydrophobic and acidic groups while the inactive compounds only have hydrophobic groups. Analysis by computer modeling indicate that the acidic groups in the active compounds can form salt bridge with Lys 574 in the N-terminal coiled-coil region of gp41. Asp 632 in a C-peptide can also form a salt bridge with Lys 574. Replacement of Asp 632 with positively charged residues or hydrophobic residues resulted in significant decrease of HIV-1 inhibitory activity. These results suggest that a salt bridge between an N-terminal coiled coil of the gp41 and an antiviral agent targeted to the gp41 core is important for anti-HIV-1 activity.