Effect of the Seed Layer on the Growth and Charge Transfer Behavior of Zn2SnO4 Nanorods in Photoelectrochemical Water Splitting.

The growth of Zn2SnO4 nanorods on two differently prepared ZnO seed layers is demonstrated using a hydrothermal approach. The ZnO seed layers are prepared using dip-coating and electrodeposition techniques. The grown Zn2SnO4 nanorods are in the cubic phase. However, the different seed layers result in alternation in the diameter of grown Zn2SnO4 nanorods. The photocurrent of Zn2SnO4 nanorods grown on an electrodeposited ZnO seed layer is ∼4.5 times larger than that of Zn2SnO4 grown on a dip-coated ZnO seed layer. The Nyquist plots of Zn2SnO4 nanorods on the electrodeposited ZnO seed layer result in a lower charge transfer resistance (Rct = 37.7 Ω) and a lower bulk resistance (Rbulk = 64 kΩ), improving the charge transport properties. The change in diameter of Zn2SnO4 nanorods significantly alters the charge transfer behavior. The calculated charge injection efficiency did not exhibit a significant change. However, there was a 1.6-fold enhancement observed in the charge separation efficiency for Zn2SnO4 when grown on an electrodeposited seed layer.

Single Crystalline α-Fe2O3 Nanosheets with Improved PEC Performance for Water Splitting.

We report the photoelectrochemical (PEC) performance of a densely grown single crystalline hematite (α-Fe2O3) nanosheet photoanode for water splitting. Unlike expensive ITO/FTO substrates, the sheets were grown on a piece of pure Fe through controlled thermal oxidation, which is a facile low cost and one-step synthesis route. The sheets grow with a widest surface parallel to basal plane (0001). Iron oxide formed on Fe consisting of layer structure α-Fe2O3-Fe3O4-Fe is elucidated from GIXRD and correlated to spectral features observed in Raman and UV-vis spectroscopy. The top α-Fe2O3 nanosheet layer serves as a photoanode, whereas the conducting Fe3O4 layer serves to transport photogenerated electrons to the counter electrode through its back contact. Time-resolved photoluminescence (TRPL) measurements revealed significantly prolonged carrier lifetime compared to that of bulk. Compared to the thin film of α-Fe2O3 grown on the FTO substrate, ∼3 times higher photocurrent density (0.33 mA cm-2 at 1.23 VRHE) was achieved in the nanosheet sample under solar simulated AM 1.5 G illumination. The sample shows a bandgap of 2.1 eV and n-type conductivity with carrier density 9.59 × 1017 cm-3. Electrochemical impedance spectroscopy (EIS) measurements reveal enhanced charge transport properties. The results suggest that nanosheets synthesized by the simple method yield far better PEC performance than the thin film on the FTO substrate. The anodic shifts of flat band potential, delayed electron-hole recombination, and growth direction parallel to the highly conducting basal plane (0001) being some of the contributing factors to the higher photocurrent observed in the NS photoanode are discussed. Characterizations carried out before and after the PEC reaction show excellent stability of the nanosheets in an alkaline electrochemical environment.

Utilization of Time Series Tools in Life-sciences and Neuroscience.

Time series tools are part and parcel of modern day research. Their usage in the biomedical field; specifically, in neuroscience, has not been previously quantified. A quantification of trends can tell about lacunae in the current uses and point towards future uses. We evaluated the principles and applications of few classical time series tools, such as Principal Component Analysis, Neural Networks, common Auto-regression Models, Markov Models, Hidden Markov Models, Fourier Analysis, Spectral Analysis, in addition to diverse work, generically lumped under time series category. We quantified the usage from two perspectives, one, information technology professionals', other, researchers utilizing these tools for biomedical and neuroscience research. For understanding trends from the information technology perspective, we evaluated two of the largest open source question and answer databases of Stack Overflow and Cross Validated. We quantified the trends in their application in the biomedical domain, and specifically neuroscience, by searching literature and application usage on PubMed. While the use of all the time series tools continues to gain popularity in general biomedical and life science research, and also neuroscience, and so have been the total number of questions asked on Stack overflow and Cross Validated, the total views to questions on these are on a decrease in recent years, indicating well established texts, algorithms, and libraries, resulting in engineers not looking for what used to be common questions a few years back. The use of these tools in neuroscience clearly leaves room for improvement.

Nanoengineered Advanced Materials for Enabling Hydrogen Economy: Functionalized Graphene-Incorporated Cupric Oxide Catalyst for Efficient Solar Hydrogen Production.

Cupric oxide (CuO) is a promising candidate as a photocathode for visible-light-driven photo-electrochemical (PEC) water splitting. However, the stability of the CuO photocathode against photo-corrosion is crucial for developing CuO-based PEC cells. This study demonstrates a stable and efficient photocathode through the introduction of graphene into CuO film (CuO:G). The CuO:G composite electrodes are prepared using graphene-incorporated CuO sol-gel solution via spin-coating techniques. The graphene is modified with two different types of functional groups, such as amine (-NH2) and carboxylic acid (-COOH). The -COOH-functionalized graphene incorporation into CuO photocathode exhibits better stability and also improves the photocurrent generation compare to control CuO electrode. In addition, -COOH-functionalized graphene reduces the conversion of CuO phase into cuprous oxide (Cu2O) during photo-electrochemical reaction due to effective charge transfer and leads to a more stable photocathode. The reduction of CuO to Cu2O phase is significantly lesser in CuO:G-COOH as compared to CuO and CuO:G-NH2 photocathodes. The photocatalytic degradation of methylene blue (MB) by CuO, CuO:G-NH2 and CuO:G-COOH is also investigated. By integrating CuO:G-COOH photocathode with a sol-gel-deposited TiO2 protecting layer and Au-Pd nanostructure, stable and efficient photocathode are developed for solar hydrogen generation.

Stable and Efficient CuO Based Photocathode through Oxygen-Rich Composition and Au-Pd Nanostructure Incorporation for Solar-Hydrogen Production.

Enhancing stability against photocorrosion and improving photocurrent response are the main challenges toward the development of cupric oxide (CuO) based photocathodes for solar-driven hydrogen production. In this paper, stable and efficient CuO-photocathodes have been developed using in situ materials engineering and through gold-palladium (Au-Pd) nanoparticles deposition on the CuO surface. The CuO photocathode exhibits a photocurrent generation of ∼3 mA/cm2 at 0 V v/s RHE. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis and X-ray spectroscopy (XPS) confirm the formation of oxygen-rich (O-rich) CuO film which demonstrates a highly stable photocathode with retained photocurrent of ∼90% for 20 min. The influence of chemical composition on the photocathode performance and stability has been discussed in detail. In addition, O-rich CuO photocathodes deposited with Au-Pd nanostructures have shown enhanced photoelectrochemical performance. Linear scan voltammetry characteristic shows ∼25% enhancement in photocurrent after Au-Pd deposition and reaches ∼4 mA/cm2 at "0" V v/s RHE. Hydrogen evolution rate significantly depends on the elemental composition of CuO and metal nanostructure. The present work has demonstrated a stable photocathode with high photocurrent for visible-light-driven water splitting and hydrogen production.

Impact of molybdenum out diffusion and interface quality on the performance of sputter grown CZTS based solar cells.

We have investigated the impact of Cu2ZnSnS4-Molybdenum (Mo) interface quality on the performance of sputter-grown Cu2ZnSnS4 (CZTS) solar cell. Thin film CZTS was deposited by sputter deposition technique using stoichiometry quaternary CZTS target. Formation of molybdenum sulphide (MoSx) interfacial layer is observed in sputter grown CZTS films after sulphurization. Thickness of MoSx layer is found ~142 nm when CZTS layer (550 nm thick) is sulphurized at 600 °C. Thickness of MoSx layer significantly increased to ~240 nm in case of thicker CZTS layer (650 nm) under similar sulphurization condition. We also observe that high temperature (600 °C) annealing suppress the elemental impurities (Cu, Zn, Sn) at interfacial layer. The amount of out-diffused Mo significantly varies with the change in sulphurization temperature. The out-diffused Mo into CZTS layer and reconstructed interfacial layer remarkably decreases series resistance and increases shunt resistance of the solar cell. The overall efficiency of the solar cell is improved by nearly five times when 600 °C sulphurized CZTS layer is applied in place of 500 °C sulphurized layer. Molybdenum and sulphur diffusion reconstruct the interface layer during heat treatment and play the major role in charge carrier dynamics of a photovoltaic device.

Aqueous intralesional bleomycin sclerotherapy in lymphatic malformation: Our experience with children and adult.

OBJECTIVES: Lymphatic malformations (LMs) are aberrant proliferation of sequestrated lymphatic vessels during early embryogenesis and do not communicate directly with the general lymphatic system. The absence of vascular flow is the hallmark of LMs and is usually symptomless apart from painless disfiguring mass with concerns regarding cosmesis. DESIGN: Sclerotherapy has gained prominence as a preferred treatment modality for macrocystic lesions. Here, we present our experience with use of aqueous bleomycin as intralesional sclerosing agent, an economical first-line treatment for macrocystic variant of LMs in children and adults. While bleomycin microsphere in oil has been commonly used in many previous studies, we have used aqueous bleomycin solution as the sclerosing modality which is easily available and economical. MATERIALS AND METHODS: Twenty-seven patients of macrocystic LM including adults and children underwent bleomycin sclerotherapy under ultrasonography guidance. Number of sessions, dose administered, and the response to therapy along with all side effects were noted. RESULTS: Sixteen patients received 3 or less sessions while rest needed 4-6 sessions of sclerotherapy for desired response. The response was excellent in 22 patients while 5 patients showed good response. Eleven patients developed minor side effects in form of fever, local infection, intracystic bleed, and local skin discoloration. Postsclerotherapy, surgery was performed in two patients. CONCLUSION: The better response in the present study can be attributed to targeting of individual cysts in multiloculated lesion, ultrasound-guided aspiration of the cysts content before drug delivery, and postprocedure compression which increases the contact time between cyst wall and bleomycin reducing the chances of postprocedure seroma formation. Since the drug acts on the endothelial lining of the cyst, volume of the cyst is the major determinant in response. Aqueous bleomycin had comparable results with oil-based microsphere establishing it as an economical alternative treatment modality.

A Facile pH Controlled Citrate-Based Reduction Method for Gold Nanoparticle Synthesis at Room Temperature.

The synthesis of gold nanoparticles using citrate reduction process has been revisited. A simplified room temperature approach to standard Turkevich synthesis is employed to obtain fairly monodisperse gold nanoparticles. The role of initial pH alongside the concentration ratio of reactants is explored for the size control of Au nanoparticles. The particle size distribution has been investigated using UV-vis spectroscopy and transmission electron microscope (TEM). At optimal pH of 5, gold nanoparticles obtained are highly monodisperse and spherical in shape and have narrower size distribution (sharp surface plasmon at 520 nm). For other pH conditions, particles are non-uniform and polydisperse, showing a red-shift in plasmon peak due to aggregation and large particle size distribution. The room temperature approach results in highly stable "colloidal" suspension of gold nanoparticles. The stability test through absorption spectroscopy indicates no sign of aggregation for a month. The rate of reduction of auric ionic species by citrate ions is determined via UV absorbance studies. The size of nanoparticles under various conditions is thus predicted using a theoretical model that incorporates nucleation, growth, and aggregation processes. The faster rate of reduction yields better size distribution for optimized pH and reactant concentrations. The model involves solving population balance equation for continuously evolving particle size distribution by discretization techniques. The particle sizes estimated from the simulations (13 to 25 nm) are close to the experimental ones (10 to 32 nm) and corroborate the similarity of reaction processes at 300 and 373 K (classical Turkevich reaction). Thus, substitution of experimentally measured rate of disappearance of auric ionic species into theoretical model enables us to capture the unusual experimental observations.

SnO2 quantum dots decorated on RGO: a superior sensitive, selective and reproducible performance for a H2 and LPG sensor.

We report the H2 and LPG gas sensing behavior of RGO/SnO2 QDs synthesized by a surfactant assisted hydrothermal method. The RGO/SnO2 QD based sensor shows a high response of ∼89.3% to H2 and ∼92.4% to LPG for 500 ppm test gas concentration at operating temperatures of 200 °C and 250 °C, respectively. Further, the RGO/SnO2 QD based sensor shows good selectivity for H2 and LPG in the presence of other interfering gases such as ammonia, chloroform, toluene, benzene, acetone, n-butylacetate, acetic acid and formic acid. We observed that the gas response to H2 is 29.8 times higher than that to acetic acid whereas the gas response to LPG is 17.8 times higher than that to formic acid. Long-term analyses have also been performed to demonstrate the reproducible nature of the RGO/SnO2 QD based sensor over passing time which shows excellent reproducibility.

Tuning the observability of surface plasmon in silica-gold raspberry shaped nanoparticles using cuprous oxide shell.

A raspberry shaped silica-gold nanoparticle system has been coated with a cuprous oxide shell using a simple wet chemical approach. The optical properties of such particles depend on thin dielectric shell material, and we calculate far-field scattering and extinction of cuprous oxide coated silica-gold composite. In accordance with our theoretical findings, for ultrasmall gold nanoparticles (AuNPs < 5 nm) attached over silica, the localized surface plasmon resonance (LSPR) peak is completely suppressed after Cu2O coating. The cloaking (nonobservability) of the LSPR peak in extinction spectra has been explained via calculation of contribution from absorbance (<10%) and scattering (>90%) in the composite nanostructure. For larger particles (>5 nm), the traditional red-shift of the plasmon peak (from 532 to 588 nm) is still significant due to the large dielectric constant (approx. 8.0 @ 600 nm) of cuprous oxide (Cu2O) coating. A complete and controlled suppression of LSPR in small sized gold nanoparticles due to high dielectric refractory oxide shell could play a significant role in plasmon derived applications.

A novel catalyst-free synthesis of vertically aligned silicon nanowire-carbon nanotube heterojunction arrays for high performance electron field emitters.

A novel, catalyst-free strategy for the direct synthesis of vertically aligned silicon nanowire-carbon nanotube (SiNW-CNT) heterojunction arrays is presented. Such a heterojunction with the junction area in the nanoscale displays enhanced field emission characteristics at low turn-on field, with a nearly three times increase in the field enhancement factor.

Electrochemical unzipping of multi-walled carbon nanotubes for facile synthesis of high-quality graphene nanoribbons.

Here we report a remarkable transformation of carbon nanotubes (CNTs) to nanoribbons composed of a few layers of graphene by a two-step electrochemical approach. This consists of the oxidation of CNTs at controlled potential, followed by reduction to form graphene nanoribbons (GNRs) having smooth edges and fewer defects, as evidenced by multiple characterization techniques, including Raman spectroscopy, atomic force microscopy, and transmission electron microscopy. This type of "unzipping" of CNTs (single-walled, multi-walled) in the presence of an interfacial electric field provides unique advantages with respect to the orientation of CNTs, which might make possible the production of GNRs with controlled widths and fewer defects.

Synthesis of Rh-carbon nanotube based heterostructures and their enhanced field emission characteristics.

Selective decoration of Rh nanospheres on acid functionalized carbon nanotubes has been demonstrated using Al as a sacrificial substrate. Remarkable field emission has been observed for this heterostructure as a high current density of 170 microA cm(-2) is generated at an ultra-low threshold of 300 V microm(-1), compared to much smaller values for Rh nanospheres and carbon nanotubes separately.