Vibrational spectroscopic detection of radiation-induced structural changes in Chironomus hemoglobin.

Purpose: Chironomus hemoglobin is known to exhibit higher gamma radiation resistance compared to human hemoglobin. In the present study, we have introduced a sensitive method to analyze radiation-induced alterations in Chironomus hemoglobin using Vibrational spectroscopy and further highlighting its potential for monitoring radiotoxicity in aquatic environments. Materials and methods: Vibrational spectroscopic methods such as Raman and FT-IR spectroscopy were used to capture the distinctive chemical signature of Chironomus hemoglobin (ChHb) under both in vitro and in vivo conditions. Any radiation dose-dependent shifts could be analyzed Human hemoglobin (HuHb) as standard reference. Results: Distinctive Raman peak detected at 930 cm-1 in (ChHb) was attributed to C-N stretching in the heterocyclic ring surrounding the iron atom, preventing heme degradation even after exposure to 2400 Gy dose. In contrast, for (HuHb), the transition from deoxy-hemoglobin to met-hemoglobin at 1210 cm-1 indicated a disruption in oxygen binding after exposure to 1200 Gy dose. Furthermore, while ChHb exhibited a consistent peak at 1652 cm-1 in FT-IR analysis, HuHb on the other hand, suffered damage after gamma irradiation. Conclusion: The findings suggest that vibrational spectroscopic methods hold significant potential as a sensitive tool for detecting radiation-induced molecular alterations and damages. Chironomus hemoglobin, with its robust interaction of the pyrrole ring with Fe, serves as a reliable bioindicator molecule to detect radiation damage using vibrational spectroscopic method.

Modulation of Surface Ti-O Species in 2D-Ti3C2TX MXene for Developing a Highly Efficient Electrocatalyst for Hydrogen Evolution and Methanol Oxidation Reactions.

Developing cost-effective and earth-abundant noble-metal-free electrocatalysts is imperative for the imminent electrochemical society. Two-dimensional Ti3C2TX (MXene) exhibits tunable properties with high electrical conductivity and a large specific surface area, which improve its electrochemical performance. Herein, the low-temperature annealing method is used to enrich MXene with a maximum number of Ti-O terminals without formation of titanium dioxide (TiO2) under neutral pH conditions. MXene annealed at 200 °C is found to have a large number of Ti-O termination groups, resulting in a large electrochemically active surface area and increased active sites (-O termination groups) and hence excellent electrocatalytic performance compared to other samples as well as previous reported work. The optimized sample is found to show the lowest overpotential value of 0.07 V at 10 mA cm-2 and a Tafel slope of 0.15 V dec-1 toward the hydrogen evolution reaction (HER), whereas for the methanol oxidation reaction (MOR), the current density is 18.08 mA cm-2, and the onset potential is -0.51 V. In addition, it also shows long-term stability and durability toward HER as well as MOR.

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.

Nanostructured PdO Thin Film from Langmuir-Blodgett Precursor for Room-Temperature H2 Gas Sensing.

Nanoparticulate thin films of PdO were prepared using the Langmuir-Blodgett (LB) technique by thermal decomposition of a multilayer film of octadecylamine (ODA)-chloropalladate complex. The stable complex formation of ODA with chloropalladate ions (present in subphase) at the air-water interface was confirmed by the surface pressure-area isotherm and Brewster angle microscopy. The formation of nanocrystalline PdO thin film after thermal decomposition of as-deposited LB film was confirmed by X-ray diffraction and Raman spectroscopy. Nanocrystalline PdO thin films were further characterized by using UV-vis and X-ray photoelectron spectroscopic (XPS) measurements. The XPS study revealed the presence of prominent Pd(2+) with a small quantity (18%) of reduced PdO (Pd(0)) in nanocrystalline PdO thin film. From the absorption spectroscopic measurement, the band gap energy of PdO was estimated to be 2 eV, which was very close to that obtained from specular reflectance measurements. Surface morphology studies of these films using atomic force microscopy and field-emission scanning electron microscopy indicated formation of nanoparticles of size 20-30 nm. These PdO film when employed as a chemiresistive sensor showed H2 sensitivity in the range of 30-4000 ppm at room temperature. In addition, PdO films showed photosensitivity with increase in current upon shining of visible light.

Disordered self assembled monolayer dielectric induced hysteresis in organic field effect transistors.

A memory device using an organic field effect transistor (OFET) with copper phthalocyanine (CuPc) as active material was fabricated and studied. For this purpose, SiO2 dielectric surface was modified with a disordered self assembled monolayer (SAM) of octadecyltrichlorosilane (OTS) molecule which was found to induce large disorder in CuPc film thereby generating more traps for charge carriers. Drain current-drain voltage characteristics at zero gate voltage exhibited large hysteresis which was not observed in OFET devices with ordered OTS monolayer modified and unmodified SiO2 dielectrics. The extent of hysteresis and drain current on/off ratio, reading voltage etc. were found to be dependent on the sweep rate/step voltage employed during scanning. Highest hysteresis with on/off ratio of about 240 was obtained for an optimum step voltage of 2 V while it decreased with further reduction in the same. This was attributed to the longer scanning time leading to release of trapped carriers during forward scan itself. The OFET device was found to exhibit excellent memory retention capability where OFF and ON current measured for about 2 hours after stressing the device at write and erase voltages showed good retention of on/off ratio.

A new route for the fabrication of an ultrathin film of a PdO-TiO2 composite photocatalyst.

Ultrathin PdO-TiO(2) composite films have been prepared for the first time by thermal decomposition of the multilayer Langmuir-Blodgett (LB) films of octadecyl amine-metal (Ti and/or Pd) ion complexes. The composite oxide film has been characterized by various spectroscopic techniques and compared with the pure ultrathin TiO(2) film. The results of X-ray diffraction (XRD) and Raman spectroscopy reveal the formation of a mostly crystalline anatase phase in the pure TiO(2) thin film whereas separate phases of PdO and TiO(2) in the composite thin film. Crystallite sizes of 4-7 nm have been estimated from the XRD line broadening. Atomic force microscopy images also reveal oriented aggregates of nanocrystallites in the ultrathin films. The results of absorption spectroscopy have shown allowed direct transitions in both films. Pure TiO(2) and the composite films have been compared for their ability to act as photocatalysts in hydrogen generation from a methanol-water mixture. It is found that the composite film has a uniform hydrogen generation rate for a long period of time and shows drastic enhancement in hydrogen production as compared to pure TiO(2) film. This is because Pd in the composite film acts as an electron trapping centre and thereby decreases the recombination process in the oxide catalyst. The present study demonstrates the potential of the LB technique to fabricate high quality composite metal oxide films useful for photocatalytic hydrogen generation.

Growth, characterization and gas sensing properties of nanotetrapod ZnO.

ZnO nanotetrapods have been obtained in large quantities by carbothermal reduction of ZnO powder. These were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, UV-visible spectroscopy and photoluminescence. Electron microscopy revealed that the overall size of the tetrapods is 1.5-2 microm and legs are 30-50 nm in diameter. The size of tetrapods as well as diameter of the legs was found to increase with deposition temperature. Photoluminescence spectra revealed that green emission originating from oxygen vacancies overwhelmed that of the near-band-edge ultraviolet peak. A band gap of 3.27 eV was calculated from optical absorption spectra which agreed well with that estimated from PL spectra. Gas sensing properties of tetrapods were investigated and these were found to be 5 times more sensitive to H2S gas at room temperature in comparison to ZnO bulk polycrystalline material.

Improved performance of polyaniline-uricase biosensor.

Uricase has been covalently immobilized using glutaraldehyde as cross-linker onto electrochemically synthesized polyaniline (PANI) films. These PANI-uricase electrodes have been characterized using spectroscopic, cyclic voltammetry and impedance measurements. The morphology and covalent linkage of uricase lead to high enzyme loading and better shelf life. The value of the Michaelis-Menton constant obtained as 5.1x10(-3) mM L(-1) for the immobilized uricase compared to 3.4x10(-1) mM L(-1) for the free uricase enzyme, suggests enhancement in affinity and/or activity of uricase attached to PANI. The influence of pH, temperature and concentration on electrode activity were studied. The enzyme electrodes were found to retain 95% of activity after 17-18 weeks when stored at 4 degrees C. These electrodes have a response time of about 60 s and have been used to measure uric acid concentration in serum. These PANI-uricase electrodes can be used for about 30 times for electrochemical measurements while retaining about 90% of its activity indicating improved performance.