Siderophore mediated mineralization of struvite: A novel greener route of sustainable phosphate management.

Efficient and sustainable removal of phosphate ions from an aqueous solution is of great challenge. Herein we demonstrated a greener route for phosphate recovery through struvite formation by using bacterial siderophore. This method was efficient for removal of phosphate as low as 1.3 mM with 99% recovery efficiency. The siderophore produced by Pseudomonas taiwanensis R-12-2 act as template for the nucleation of struvite crystals and was found sustainable for recycling the phosphorous efficiently after twenty cycles. The formation of struvite crystals is driven by surrounding pH (9.0) and presence of Mg2+ and NH4+ ions along with PO43- and siderophore which was further validated by computational studies. The morphology of struvite was characterized by scanning electron microscopy, followed by elemental analysis. Furthermore, our results revealed that the siderophore plays an important role in struvite biomineralization. We have successfully demonstrated the phosphate sequestration by using industrial waste samples, as possible application for environmental sustainability and phosphate conservation. For the first time electrochemical super-capacitance performance of the struvite was studied. The specific capacitance value for the struvite was found to be 320 F g-1 at 1.87 A g-1 and retained 92 % capacitance after 250 cycles. The study revealed the potential implications of siderophore for the phosphate recycling and the new mechanism for biomineralization by sequestering into struvite.

γ-Ray-Assisted Synthesis of a Pt-Sn Bimetallic Composite Loaded on Graphene-Graphitic Carbon Nitride Hybrid: A Cocktail Electrocatalyst for the Methanol Oxidation Reaction.

The composite of Pt with transition metals is viewed as the most promising anode material for direct methanol fuel cell (DMFC) applications. Besides the decrease in the Pt loading, these multimetallic structures help in circumventing CO poisoning issues associated with a Pt catalyst. Herein, we prepared and loaded Pt-Sn bimetallic nanoparticles on an electron-rich and stable substrate consisting of graphitic nitride (GCN) and graphene oxide (GO)/reduced graphene oxide (r-GO) hybrid composites. The γ-radiolysis method was employed for coreduction of metal salts to deposit the binary composite of metal nanoparticles over the substrates. These structures were tested as the anode material for the methanol oxidation reaction (MOR). Among various possible combinations, Pt-Sn-loaded rGO-GCN (Pt-Sn/rGO-GCN) demonstrated the current density of ca. 2.4 A/mgPt. To the best of our knowledge, this value is among the highest ones, reported for similar systems in the acidic pH. Furthermore, these composites demonstrated excellent stability in the repeated cycle test. The improved performance is associated to the plenty of -OH groups provided by the Sn counterpart and a large number of adsorption sites from the electron-reached GCN counterpart.

Covalent conjugation of single-walled carbon nanotube with CYP101 mutant for direct electrocatalysis.

Covalent linkage between the single-walled carbon nanotube (SWCNT) and CYP101 through a specific site of the enzyme can provide a novel method of designing efficient enzyme electrodes using this prototype cytochrome P450 enzyme. We have chemically modified the SWCNT with linker 4-carboxy phenyl maleimide (CPMI) containing maleimide functional groups. The enzyme was covalently attached on to the SWCNT through the maleimide group of the linker (CPMI) to the thiolate group of the surface exposed Cys 58 or Cys 136 of the CYP101 forming a covalently immobilized protein on the nanotube. Thin film of the modified SWCNT-CPMI-CYP101conjugate was made on a glassy carbon (GC) electrode. Direct electrochemistry of the substrate (camphor)-bound enzyme was studied using this immobilized enzyme electrode system and the redox potential was found to be -320mV vs Ag/AgCl (3 M KCl), which agrees with the redox potential of the substrate bound enzyme reported earlier. The electrochemically driven enzymatic mono-oxygenation of camphor by this immobilized enzyme electrode system was studied by measurement of the catalytic current at different concentrations of camphor. The catalytic current was found to increase with increasing concentration of camphor in presence of oxygen. The product formed during the catalysis was identified by mass-spectrometry as hydroxy-camphor.

Experimental and Theoretical Study into Interface Structure and Band Alignment of the Cu2Zn1-x Cd x SnS4 Heterointerface for Photovoltaic Applications.

To improve the constraints of kesterite Cu2ZnSnS4 (CZTS) solar cell, such as undesirable band alignment at p-n interfaces, bandgap tuning, and fast carrier recombination, cadmium (Cd) is introduced into CZTS nanocrystals forming Cu2Zn1-x Cd x SnS4 through cost-effective solution-based method without postannealing or sulfurization treatments. A synergetic experimental-theoretical approach was employed to characterize and assess the optoelectronic properties of Cu2Zn1-x Cd x SnS4 materials. Tunable direct band gap energy ranging from 1.51 to 1.03 eV with high absorption coefficient was demonstrated for the Cu2Zn1-x Cd x SnS4 nanocrystals with changing Zn/Cd ratio. Such bandgap engineering in Cu2Zn1-x Cd x SnS4 helps in effective carrier separation at interface. Ultrafast spectroscopy reveals a longer lifetime and efficient separation of photoexcited charge carriers in Cu2CdSnS4 (CCTS) nanocrystals compared to that of CZTS. We found that there exists a type-II staggered band alignment at the CZTS (CCTS)/CdS interface, from cyclic voltammetric (CV) measurements, corroborated by first-principles density functional theory (DFT) calculations, predicting smaller conduction band offset (CBO) at the CCTS/CdS interface as compared to the CZTS/CdS interface. These results point toward efficient separation of photoexcited carriers across the p-n junction in the ultrafast time scale and highlight a route to improve device performances.

High sensitive determination of dopamine through catalytic oxidation and preconcentration over gold-multiwall carbon nanotubes composite modified electrode.

Electrochemical properties of dopamine, uric acid and ascorbic acid have been investigated using gold nano particles (AuNPs) decorated functionalized multiwall carbon nanotubes (MWCNTs) nano composite modified electrode. MWCNTs were acid functionalized to introduce -COOH functionalities. The functionalized MWCNTs were used as support materials and were decorated with gold nano particles of 20 nm in size. The nano composite materials thus prepared have been named as f-MWCNTs/AuNPs composite. The composite material was characterized using FTIR, RAMAN, TEM, UV-VIS spectroscopy and atomic force microscopy measurements. Electrochemical investigations on the composite modified glassy carbon electrode for dopamine was investigated in presence of interfering agents like ascorbic acid and uric acid. The modified electrode showed sensitivity of 0.002 µAnM-1 for dopamine with the detection limit of 35 nM. Present electrode showed high selectivity for dopamine as the oxidation peak of dopamine and uric acid were very well resolved. The analytical method was found to be suitable for the simultaneous determination of dopamine and uric acid using the modified electrode. Method was applied in spiked real serum sample for the determination of dopamine.

Point contact Andreev reflection studies of a non-centro symmetric superconductor Re6Zr.

Re6Zr, a non-centrosymmetric superconductor is an interesting system as recent experimental evidence suggests that the superconducting state breaks time reversal symmetry. This implies a mixing of spin singlet-triplet states leading to a complex order parameter in this system. Here, we report point contact Andreev Reflection (PCAR) measurements on a single crystal of Re6Zr (superconducting transition temperature (Tc) = 6.78 K). We observe multiple gap features in the PCAR spectra which depends on the type of tip and contact. Spectral features appear at voltages 1.0 ± 0.1 mV, 0.75 ± 0.05 mV and 0.45 ± 0.1 mV suggesting that there are at least more than one band contributing to superconductivity. However, strong surface inter-band scattering is possibly responsible for the uncertainty in observing them together distinctly in a single contact in the PCAR measurements. Interestingly, the bulk gap (Δ = 1.95kBTc = 1.1 meV) is occasionally observed in PCAR spectra, mostly with ferromagnetic tips. The gap features associated with the other two smaller gaps disappear at the bulk Tc. In addition, no anisotropy in the upper critical field was observed. Our results suggest an unconventional superconducting order in this compound: Multiband singlet states dominated by inter-band pairing which break the time reversal symmetry or singlet mixed with triplet states.

Coupling Energy Capture and Storage - Endeavoring to make a solar battery.

Storage of solar radiation is currently accomplished by coupling two separate devices, one that captures and converts the energy into an electrical impulse (a photovoltaic cell) and another that stores this electrical output (a battery or a supercapacitor electrochemical cell). This configuration however has several challenges that stem from a complex coupled-device architecture and multiple interfaces through which charge transfer has to occur. As such presented here is a scheme whereby solar energy capture and storage have been coupled using a single bi-functional material. Two electroactive semiconductors BiVO4 (n-type) and Co3O4 (p-type) have been separately evaluated for their energy storage capability in the presence and absence of visible radiation. Each of these have the capability to function as a light harvester and also they have faradaic capability. An unprecedented aspect has been observed in that upon photo-illumination of either of these semiconductors, in situ charge carriers being generated play a pivotal role in perturbing the electroactivity of the redox species such that the majority charge carriers, viz. electrons in BiVO4 and holes in Co3O4, influence the redox response in a disproportionate manner. More importantly, there is an enhancement of ca. 30% in the discharge capacity of BiVO4 in the presence of light and this directly provides a unique route to augment charge storage during illumination.

Boosting the Efficiency of Quantum Dot-Sensitized Solar Cells through Formation of the Cation-Exchanged Hole Transporting Layer.

In search of a viable way to enhance the power conversion efficiency (PCE) of quantum dot-sensitized solar cells, we have designed a method by introducing a hole transporting layer (HTL) of p-type CuS through partial cation exchange process in a postsynthetic ligand-assisted assembly of nanocrystals (NCs). High-quality CdSe and CdSSe gradient alloy NCs were synthesized through colloidal method, and the charge carrier dynamics was monitored through ultrafast transient absorption measurements. A notable increase in the short-circuit current concomitant with the increase in open-circuit voltage and the fill factor led to 45% increment in PCE for CdSe-based solar cells upon formation of the CuS HTL. Electrochemical impedance spectroscopy further revealed that the CuS layer formation increases recombination resistance at the TiO2/NC/electrolyte interface, implying that interfacial recombination gets drastically reduced because of smooth hole transfer to the redox electrolyte. Utilizing the same approach for CdSSe alloy NCs, the highest PCE (4.03%) was obtained upon CuS layer formation compared to 3.26% PCE for the untreated one and 3.61% PCE with the conventional ZnS coating. Therefore, such strategies will help to overcome the kinetic barriers of hole transfer to electrolytes, which is one of the major obstacles of high-performance devices.

A novel inhibition based biosensor using urease nanoconjugate entrapped biocomposite membrane for potentiometric glyphosate detection.

A potentiometric biosensor based on agarose-guar gum (A-G) entrapped bio-nanoconjugate of urease with gold nanoparticles (AUNps), has been reported for the first time for glyphosate detection. The biosensor is based on inhibition of urease activity by glyphosate, which was measured by direct potentiometry using ammonium ion selective electrode covered with A-G-urease nanoconjugate membrane. TEM and FTIR analysis revealed nanoconjugate formation and its immobilization in A-G matrix respectively. The composite biopolymer employed for immobilization yields thin, transparent, flexible membrane having superior mechanical strength and stability. It retains the maximum activity (92%) of urease with negligible leaching. The conjugation of urease with AUNps allows improvement in response characteristics for potentiometric measurement. The biosensor shows a linear response in the glyphosate concentration range from 0.5ppm-50ppm, with limit of detection at 0.5ppm, which covers maximum residual limit set by WHO for drinking water. The inhibition of catalytic activity of urease nanoconjugate by gyphosate was confirmed by FTIR analysis. The response of fabricated biosensor is selective towards glyphosate as against various other pesticides. The biosensor exhibits good performance in terms of reproducibility and prolonged storage stability of 180days. Thus, the present biosensor provides an alternative method for simple, selective and cost effective detection of glyphosate based on urease inhibition.

Nanostructured MoS2/BiVO4 Composites for Energy Storage Applications.

We report the optimized synthesis and electrochemical characterization of a composite of few-layered nanostructured MoS2 along with an electroactive metal oxide BiVO4. In comparison to pristine BiVO4, and a composite of graphene/BiVO4, the MoS2/BiVO4 nanocomposite provides impressive values of charge storage with longer discharge times and improved cycling stability. Specific capacitance values of 610 Fg-1 (170 mAhg-1) at 1 Ag-1 and 166 Fg-1 (46 mAhg-1) at 10 Ag-1 were obtained for just 2.5 wt% MoS2 loaded BiVO4. The results suggest that the explicitly synthesized small lateral-dimensioned MoS2 particles provide a notable capacitive component that helps augment the specific capacitance. We discuss the optimized synthesis of monoclinic BiVO4, and few-layered nanostructured MoS2. We report the discharge capacities and cycling performance of the MoS2/BiVO4 nanocomposite using an aqueous electrolyte. The data obtained shows the MoS2/BiVO4 nanocomposite to be a promising candidate for supercapacitor energy storage applications.

CZTS x Se1-x nanocrystals: Composition dependent method of preparation, morphological characterization and cyclic voltammetry data analysis.

In this article, synthesis procedures of preparation of copper zinc tin sulpho-selenide (CZTS x Se1-x ) alloy nanocrystals and the data acquired for the material characterization are presented. This data article is related to the research article doi: http://dx.doi.org/10.1016/j.solmat.2016.06.030 (Jadhav et al., 2016) [1]. FTIR data have been presented which helped in confirmation of adsorption of oleylamine on CZTS x Se1-x . Transmission electron microscopy (TEM), Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) data have been presented which have been used to reveal the morphological details of the nanocrystals. The Energy dispersive X-ray analysis (EDAX) based elemental mapping data has been presented to confirm the elemental composition of nanocrystals. Procedure for the preparation of CZTS x Se1-x based working electrode for the CV measurements have been given. The summary table for the optical, electrochemical band gaps, valance and conduction band edges as a function of composition are listed for the ready reference.

Electrocatalyst on insulating support?: Hollow silica spheres loaded with Pt nanoparticles for methanol oxidation.

Electrocatalytic oxidation of methanol on silica hollow spheres, loaded with platinum nanoparticles (Pt-SiO2-HS), is reported. The functionalized hollow silica spheres were prepared by the surfactant (lauryl ester of tyrosine) template-assisted synthesis. These spheres were loaded with platinum nanoparticles by γ-radiolysis. Energy-dispersive X-ray analysis (EDAX) and X-ray photoelectron spectroscopy (XPS) analyses confirmed presence of Si and Pt in the composite. High-resolution transmission electron microscopy showed the formation of uniformly deposited Pt nanoparticles over the hollow spheres with a predominant Pt(111) lattice plane on the surface. In spite of the poor conducting nature of the silica support, the oxidation potential and current density per unit mass for methanol oxidation were noted to be ca. 0.72 V vs NHE and 270 mA mg(-1), respectively, which are among the best values reported in its class. The composite did not show any sign of a degradation even after repeated use. In fact, the anodic current was found to increase under constant polarization, which is attributed to a facile reaction between adsorbed CO with a surface hydroxyl group present on the silica support. These results are in favor of Pt-SiO2-HS as a promising electrocatalyst material in the direct methanol fuel cell (DMFC) applications.

A facile methodology for the design of functionalized hollow silica spheres.

A new amino acid derived amphiphile, lauryl ester of tyrosine (LET) is shown to provide a facile methodology for the preparation of hollow silica spheres. In a previous study on the interface adsorption, it was shown that phenolic OH group in LET plays a key role in the formation and stabilization of close packed structures, typically at the oil/water interface. Drawing an analogy between the air/water and the oil/water interface, we detail here a procedure where air droplets are capped with LET aggregated structures, and in turn they are utilized as viable templates in the production of hollow silica spheres. We demonstrate that hollow silica spheres are formed at pH 4.0 specifically under conditions of vortexing within a short period of time (ca. 15 min). The dimensions of the structures are 0.43±0.15 µm in diameter and they have then subsequently been used as templates for directing the synthesis of silica-silver and silica-polyanthranilic composite hollow spheres.

Outer sphere electroreduction of CCl4 in 1-butyl-3-methylimmidazolium tetrafluoroborate: an example of solvent specific effect of ionic liquid.

Electrodics of CCl4 reduction in 1-butyl-3-methylimmidazolium tetrafluoroborate [BMIM][BF4] room temperature ionic liquid (RTIL) is reported. A convolutive analysis of the cyclic voltammograms suggests that CCl4 electroreduction follows stepwise (outer sphere) dissociative electron transfer pathway, rather than the sticky dissociative (inner sphere) electron transfer, as in the case of conventional organic solvents. This difference in the mechanism of electron transfer initiated bond cleavage is attributed to the solvent specific effects, namely, stabilization of CCl4*- intermediate radical anion in RTIL, which in turn decreases the electron transfer rate and thus the carbon-halogen bond cleavage rates. Electroreduction of CCl4 in RTIL through outer sphere electron transfer would be a promising pathway for its direct conversion to methane.

Determination of band structure parameters and the quasi-particle gap of CdSe quantum dots by cyclic voltammetry.

Band structure parameters such as the conduction band edge, the valence band edge and the quasi-particle gap of diffusing CdSe quantum dots (Q-dots) of various sizes were determined using cyclic voltammetry. These parameters are strongly dependent on the size of the Q-dots. The results obtained from voltammetric measurements are compared to spectroscopic and theoretical data. The fit obtained to the reported calculations based on the semi-empirical pseudopotential method (SEPM)-especially in the strong size-confinement region, is the best reported so far, according to our knowledge. For the smallest CdSe Q-dots, the difference between the quasi-particle gap and the optical band gap gives the electron-hole Coulombic interaction energy (J(e1,h1)). Interband states seen in the photoluminescence spectra were verified with cyclic voltammetry measurements.

Electrochemical biosensor for catechol using agarose-guar gum entrapped tyrosinase.

An electrochemical biosensor using tyrosinase was constructed for the determination of catechol. The enzyme was extracted from a plant source Amorphophallus companulatus and entrapped in agarose-guar gum composite biopolymer matrix. Catechol was determined by direct reduction of biocatalytically liberated quinone species at -0.1 V versus Ag/AgCl (3M KCl). The response was found to be linear and concentration dependent in the range of 6 x 10(-5) to 8 x 10(-4)M with a lower detection limit of 6 microM. It has reusability up to 20 cycles and a shelf life of more than 2 months when stored at 4 degrees C.

Synthesis and characterization of uncapped gamma-Fe2O3 nanoparticles prepared by flame pyrolysis of ferrocene in ethanol.

Nanoparticles of iron(III) oxide were synthesized by spontaneous combustion of ferrocene in ethanol solution using a simple spirit lamp. X-ray powder diffraction and electron diffraction analysis of the powder suggested the formation of gamma-Fe2O3 (Maghemite phase) having lattice constant 8.3539 +/- 0.0209 A. Transmission Electron Micrograph suggested the formation of spherical particles with an average diameter of 24.7 +/- 1.6 nm. A sextet with an isomeric shift of 0.328 mm s(-1) seen in the Mossbauer spectrum recorded at room temperature, further supports the formation of gamma-Fe2O3. The particles were dispersed freely in the polar solvents like ethanol, dimethyl sulfoxide, and water. Infra Red spectrum gave bands at 400, 432, 565, and 638 cm(-1), which confirms the presence of gamma-Fe2O3 phase.

Synthesis and characterization of stable organosols of silver nanoparticles by electrochemical dissolution of silver in DMSO.

Stable organosols of silver nanoparticles (AgNPs) without any capping agents have been synthesized by an electrochemical dissolution of a sacrificing silver electrode in dimethyl sulfoxide (DMSO). The peak at 425 +/- 5 nm observed in the UV-vis spectra was attributed to the surface plasmon resonance for silver. The formation of nanoparticles of silver was confirmed by X-ray diffraction analysis (XRD). In TEM, three ranges of particle size were observed, namely, 3.75 +/- 0.8, 6.25 +/- 0.5, and 9.25 +/- 0.3 nm. The correlation among these sizes was explained by a new model based on a droplet coalition. Based on that, sizes correlation fits very well in the empirical formula 5d(1)(3)n' + (3 - n')d(2)(3) = d(3)(3) where d(1), d(2), and d(3) are three sizes of particles and n' is an integer having values 0, 1, 2, 3, .... The sols prepared in DMSO were stable against flocculation for months. An unusual solution stability without any capping agents was attributed to the formation of Ag(I)DMSO complex on particle surface, which was confirmed by FTIR, fluorescence spectroscopy, and thermal analysis.

Development of electrochemical biosensor based on tyrosinase immobilized in composite biopolymeric film.

An electrochemical enzyme electrode for dopa and dopamine was developed via an easy and effective immobilization method. The enzyme tyrosinase was extracted from a plant source Amorphophallus companulatus and immobilized in a novel composite of two biopolymers: agarose and guar gum. This composite matrix-containing enzyme forms a self-adhering layer on the active surface of glassy carbon electrode, making it a selective and sensitive phenol sensor. Dopa and dopamine were determined by the direct reduction of biocatalytically liberated quinone species at -0.18V versus Ag/AgCl (3M KCl). The analytical characteristics of this sensor, including linear range, lower detection limit, pH, and storage stability, are described. It has reusability up to 15 cycles and a shelf life of more than 2 months.