Charge-transfer-driven enhanced room-temperature ferromagnetism in BiFeO3/Ag nanocomposite.

We report observation of more than an order of magnitude jump in saturation magnetization in BiFeO3/Ag nanocomposite at room temperature compared to what is observed in bare BiFeO3nanoparticles. Using transmission electron microscopy together with energy dispersive x-ray spectra (which maps the element concentration across the BiFeO3/Ag interface) and x-ray photoelectron spectroscopy, we show that both the observed specific self-assembly pattern of BiFeO3and Ag nanoparticles and the charge transfer between Ag and O are responsible for such an enormous rise in room-temperature magnetization. The BiFeO3/Ag nanocomposites, therefore, could prove to be extremely useful for a variety of applications including biomedical.

Wide spectral photoresponse of template assisted out of plane grown ZnO/NiO composite nanowire photodetector.

Zinc oxide (ZnO) one-dimensional nanostructures are extensively used in ultra-violet (UV) detection. To improve the optical sensing capability of ZnO, various nickel oxide (NiO) based p-n junctions have been employed. ZnO/NiO heterojunction based sensing has been limited to UV detection and not been extended to the visible region. In the present work, p-NiO/n-ZnO composite nanowire (NW) heterojunction based UV-visible photodetector is fabricated. A porous anodic aluminum oxide template based electrochemical deposition method is adopted for well separated and vertically aligned growth of composite NWs. The photoresponse is studied in an out of plane contact configuration. The fabricated photodetector shows fast response under UV-visible light with a rise and decay time of tens of ms. The wide spectral photoresponse is analyzed in terms of conduction from defect states of ZnO and interfacial defects during p-n junction formation. Light interaction with heterojunction along the length of the composite NW results in enhanced visible photoresponse of the detector and is further supported by simulation.

Role of limited hydrogen and flow interval on the growth of single crystal to continuous graphene by low-pressure chemical vapor deposition.

A method for defect-free large crystallite graphene growth remains unknown despite much research effort. In this work, we discuss the role of flow duration of H2 gas for the production of graphene as per requirement and production at a minimum flow rate considering the safety issue of hydrogen utilization. The copper substrate used for growth was treated for different time intervals (0 to 35 min) in H2 flow prior to growth. Structural and chemical changes occurring in the copper substrate surface were probed by grazing incidence x-ray diffraction and x-ray photoelectron spectroscopy. The results were correlated with the Raman spectroscopy data, which can quantify the quality of graphene. With increasing H2 flow interval, secondary nucleation sites were observed and growth favored few-layer graphene structures. The surface-adsorbed oxygen molecules and its conversion to an OH terminated surface with increasing hydrogen flow interval was found to be a key factor in enhancing nucleation density. The Stranski-Krastanov type of nucleation was observed for samples grown with different time intervals of H2 treatment, except 5 min of H2 flow prior to growth for which the Volmer-Weber type of growth favored monolayer graphene crystallite growth.

Photo-resistive properties of LaAl0.6Cr0.4O3/SrTiO3 heterostructures: a comparative study with LaAlO3/SrTiO3.

We report photoconductivity measurements on LaAl(1-x)Cr(x)O3/SrTiO3 (x=0, 0.4) heterostructures. A polar layer modification of metallic LaAlO3/SrTiO3 heterostructure with Cr in the Al sites resulted in an increased photo-response (PR) and relaxation time, in addition to a distinct shift in the spectral weight toward the red end of the spectrum. The visible light photoconductivity is explained by d-d photoconductivity of Cr3+ valence states of the x=0.4 sample. Besides the established UV sensitivity, we observe a weak peak in PR around 690 nm possibly emanating from the mid-gap states arising from oxygen vacancies.

Interaction of insulin with anionic phospholipid (DPPG) vesicles.

The interaction between a protein/enzyme and a lipid is critical for pharmacological activity. Here, we study the interaction between insulin and the 1,2-dipalmitoyl-sn-glycero-3-phosphoglycerol (DPPG) lipid anionic vesicle by successfully entrapping the insulin molecule into DPPG vesicles, which are biocompatible liposomes. For the insulin-DPPG complex system, steady state emission spectroscopy at room temperature (300 K) shows a new broad and structured peak between 400 nm and 500 nm along with the tyrosine fluorescence peak at 303 nm. Temperature dependent and time resolved spectroscopy reveal that the peak between 400 nm and 500 nm in the insulin-DPPG system arises due to the tyrosine phosphorescence phenomenon. This phosphorescence peak is the signature of insulin entrapment into the liposome. A molecular dynamics study of the tyrosine-DPPG system shows that the rigidity of tyrosine increases in the lipid layer. Dynamic light scattering (DLS), and zeta potential studies also establish the attachment of insulin with the anionic liposome.

Role of Surface Chemistry of Ta Metal Foil on the Growth of GaN Nanorods by Laser Molecular Beam Epitaxy and Their Field Emission Characteristics.

This study investigates the influence of surface nitridation of Ta metal foil substrates on the growth of GaN nanorods using the laser molecular beam epitaxy (LMBE) technique and the field emission characteristics of the grown GaN nanorod ensemble. Surface morphology examinations underscore the pivotal role of Ta foil nitridation in shaping the dimensions and densities of GaN nanorods. Bare Ta foil fosters the formation of high-density, vertically self-aligned GaN nanorods at a growth temperature of 700 °C. Furthermore, the density of these nanorods is directly related to the duration of Ta foil nitridation, with increased duration leading to a reduced nanorod density. X-ray Photoelectron Spectroscopy (XPS) studies reveal that the transition of the Ta foil surface from tantalum oxide to tantalum nitride during nitridation emerges as a crucial factor influencing GaN nanorod growth. Photoluminescence (PL) spectroscopy at ambient temperature reveals a strong near-band-edge (NBE) emission peak with negligible defect-related peaks, displaying the high optical quality of the GaN nanorods. The highly dense vertically aligned GaN nanorod ensemble growth without Ta prenitridation exhibits the most favorable field emission performance, featuring a turn-on field of 2.1 V/µm, a field enhancement factor of 2480, and a stable long-term operation at the emission current density of 2.26 mA/cm2. This study advances the understanding of the role of the surface chemistry of metal foil in determining GaN nanorod growth and opens up exciting possibilities for tailoring advanced optoelectronic devices for specific application requirements.

Synthesis of amphiphilic azo-anion-radical complexes of chromium(III) and the development of ultrathin redox-active surfaces by the Langmuir-Schaefer technique.

Neutral tris-chelated chromium complex [Cr(L(a))(3)] (1a), and its surfactant derivatives [Cr(L(b))(3)] (1b), [Cr(L(c))(3)] (1c), and [Cr(L(d))(3)] (1d) (where L(a)=2-(4'-methoxyphenylazo)pyridine, L(b)=2-(4'-butyloxyphenylazo)pyridine, L(c =2-(4'-octyloxyphenylazo)pyridine, and L(d)=2-(4'-dodecyloxyphenylazo)pyridine) were synthesized. The molecular structure of compound 1a, determined by X-ray diffraction, showed that the local geometry around the metal center is a distorted octahedral with meridional coordination of the ligands. The structural parameters, spectroscopic data, and density functional theory (DFT) calculations on representative complex 1a suggest that ligand L(a) is predominantly an azo-anion-radical-type, and so the complex can be represented as [Cr(III)(L(a.-))(3)]. An assessment of their physicochemical and surface properties was performed with the aim of using these triple-tailed metallosurfactants as precursors for redox-responsive films. The surface-pressure-molecular-area isotherm measurement for compound 1d shows that the complex forms a stable Langmuir film at the air/water interface. The monolayer and multilayers were successfully transferred onto the quartz substrate and the platinum working electrode at a surface pressure of 10 mN m(-1) by the Langmuir-Schaefer (LS) technique. The LS films were studied by UV/Vis spectrometry, infrared spectroscopy, field-emission scanning electron microscopy, and atomic force microscopy. A good linear relationship between the absorbance at 370 nm and the thickness of the layers against the number of deposited layers indicated the uniformity and reproducibility of this transfer process. Voltammograms for platinum-surface-bound LS film of compound 1d showed that the redox response owing to the first oxidation is stable and reproducible after many cycles (>300 cycles). Spectroscopic studies and electrochemical measurements of compound 1d on the LS films revealed that these complexes are potential candidates for molecular devices.

Ultrasensitive Boron-Nitrogen-Codoped CVD Graphene-Derived NO2 Gas Sensor.

Recent trends in 2D materials like graphene are focused on heteroatom doping in a hexagonal honeycomb lattice to tailor the desired properties for various lightweight atomic thin-layer derived portable devices, particularly in the field of gas sensors. To design such gas sensors, it is important to either discover new materials with enhanced properties or tailor the properties of existing materials via doping. Herein, we exploit the concept of codoping of heteroatoms in graphene for more improvements in gas sensing properties and demonstrate a boron- and nitrogen-codoped bilayer graphene-derived gas sensor for enhanced nitrogen dioxide (NO2) gas sensing applications, which may possibly be another alternative for an efficient sensing device. A well-known method of low-pressure chemical vapor deposition (LPCVD) is employed for synthesizing the boron- and nitrogen-codoped bilayer graphene (BNGr). To validate the successful synthesis of BNGr, the Raman, XPS, and FESEM characterization techniques were performed. The Raman spectroscopy results validate the synthesis of graphene nanosheets, and moreover, the FESEM and XPS characterization confirms the codoping of nitrogen and boron in the graphene matrix. The gas sensing device was fabricated on a Si/SiO2 substrate with prepatterned gold electrodes. The proposed BNGr sensor unveils an ultrasensitive nature for NO2 at room temperature. A plausible NO2 gas sensing mechanism is explored via a comparative study of the experimental results through the density functional theory (DFT) calculations of the adsorbed gas molecules on doped heteroatom sites. Henceforth, the obtained results of NO2 sensing with the BNGr gas sensor offer new prospects for designing next-generation lightweight and ultrasensitive gas sensing devices.

Interaction of glucose with hemoglobin: a study in aqueous solution and at the air-water interface using the Langmuir-Blodgett technique.

Here, we report the glycosylation of human adult hemoglobin (Hb) studied in aqueous solution and at the air-water interface by the Langmuir-Blodgett (LB) technique. Pressure-area (π-A) and pressure-time (π-t) measurements show that the concentration of glucose (GLC) and interaction time have an effect on Hb molecular area as well as on surface activity. Solution studies by UV-vis absorption and emission spectroscopy show that the GLC can alter the local conformation of Hb to some extent at the tryptophan and heme residues. CD spectroscopic studies in solution indicate that the α-helix content increases in the presence of GLC at the secondary structure level, which may be the cause of an increased adsorption rate of Hb. Also, secondary structure calculation using FTIR technique in the LB film follows the decrease in α-helix and increase in ß-sheet structure as well as the formation of intermolecular aggregates. AFM images of Hb in the LB film indicate the transition from globular to an ellipsoid-like structure of Hb in the presence of GLC. FTIR studies of the LB film support the AFM imaging and the analysis of π-t kinetics. The molecular docking study revealed that Val 1 and Lys 132 are the most favorable docked sites along with some other sites such as Hem 147, Trp 37, Asp 94, Tyr 145, Leu 91, His 143, Glu 43 etc. The overall study may predict the processes of interactions with the increased concentration of GLC on Hb as well as on other long lived proteins.

Influence of KCl on the interfacial activity and conformation of hemoglobin studied by Langmuir-Blodgett technique.

We report here the influence of KCl on the interfacial surface activity and conformation of human adult hemoglobin (Hb) using Langmuir and Langmuir-Blodgett (LB) techniques. The studies were done in absence and in presence of KCl salt in the subphase. We have studied the surface pressure-area (π-A) isotherm and surface pressure-time (π-t) kinetics of Hb with the variation of KCl concentrations (C(KCl)). The π-t study shows that the surface activity as well as the magnitude of diffusion and rearrangement of Hb at air/water interface is a function of C(KCl). Conformational study was done by CD spectroscopy and by the FTIR technique. Both the studies show an increasing trend of the α-helix form of Hb in the presence of KCl which may be responsible for the increased surface activity of Hb. The free energy calculations show that the compression of the Hb monolayer is involved in the small free energy change (∼5-25 kcal mol(-1)) of Hb. The changes in area per molecule and free energy, as well as other results, indicate that the influence of KCl on the Hb monolayer is in line with modified DLVO theory of ion-protein interaction. FE-SEM study shows that the LB films in absence of KCl comprise higher aggregates, whereas in the presence of KCl (0.5 M) it comprises lower aggregates, indicating the structural change of Hb. KCl salt here enhances the α-helix from of Hb, promoting the folded conformation by perturbing the water structure. The overall results show that the intermolecular forces and the surface activity as well as the population of the α-helix of Hb can be tuned by KCl salt.

Influence of chemical aging on physico-chemical properties of mineral dust particles: A case study of 2016 dust storms over Delhi.

The physico-chemical properties of dust particles collected During Dust Storm (DDS) and After Dust Storm (ADS) events were studied using Scanning Electron Microscope coupled with Energy Dispersive X-ray Spectroscopy (SEM-EDS), X-ray Fluorescence Spectroscopy (XRF) and X-ray Photoelectron Spectroscopy (XPS). Morphological and compositional change in dust particles were observed as they react with the anthropogenic pollutants present in the urban environment. The calcite rich particles were observed to transform into calcium chloride, calcium nitrate, and calcium sulfate on reacting with the chlorides, nitrates, and sulfates present in the urban atmosphere. The frequency distributions of Aspect Ratio (AR) for the DDS and ADS particles were observed to be bimodal (mode peaks at 1.2 and 1.5) and monomodal (mode peak at 1.1), respectively. The highly irregular shaped solid dust particles were observed to transform into nearly spherical semisolid particles in the urban environment. XPS analysis confirms the high concentration of oxides, nitrates, and chlorides at the surface of ADS samples which show the signatures of mineral dust particles aging. Species with a high value of imaginary part of refractive index (like Cr metal, Fe metal, Cr2O3, FeO, Fe2O3) were observed at the surface of dust particles. At 550 nm wavelength, the light-absorbing potential of the observed species along with black carbon (BC) was found to vary in the order; Cr metal > Fe metal > Cr2O3> FeO > BC > Fe2O3> FeOOH. The presence of the aforementioned species on the surface of ADS particles will tremendously affect the particle optical and radiative properties compared to that of DDS particles. The present work could reduce the uncertainty in the radiation budget estimations of mineral dust and assessment of their climatic impacts over Delhi.

Effect of salt on the formation of alcohol-dehydrogenease monolayer: a study by the Langmuir-Blodgett technique.

We report here the effect of salt (KCl) on the interfacial surface activity of yeast alcohol dehydogenease (ADH) at air/water interface using the Langmuir-Blodgett technique. Effect of salt content in the water subphase on ADH structure has been studied. The change of area/molecule, compressibility, rigidity, and unfolding of ADH are insignificant up to 10 mM KCl concentration. The significant changes are observed above 0.1 M KCl concentrations. Observations are explained in the context of DLVO theory. FTIR study of amide band together with AFM imaging of ADH monolayer indicate that KCl perturbs the ADH monolayer by the increment of beta-structure resulting into larger unfolding and intermolecular aggregates at high salt concentration.

Fabrication of ovalbumin-phospolipid thin film with minimal protein aggregation by different self-assembly methods.

This paper describes a new approach for the preparation of Ovalbumin (OVA)-phospholipids (DPPC) thin film, where we minimize the aggregation among protein molecules. A comparative study on the films fabricated by self-assembly (SA) of protein-lipid mixed vesicle on hydrophilic glass substrate and SA of protein alone on prefabricated Langmuir-Blodgett (LB) film of DPPC is being carried out. Far UV circular dichroism spectroscopy, FTIR analysis of amide bands and surface morphology study by FE-SEM imaging is being used to examine the extent of conformational change as well as aggregation of protein. Protein-lipid thin film prepared by the former method provides the secondary structure of individual OVA molecules with increment of alpha-helical segments. In this process, OVA molecules do not show larger aggregation among themselves. However, in the second method, we find unfolded larger aggregated structure of OVA with increment of beta-structure of OVA.

Interaction of ovalbumin with phospholipids Langmuir-Blodgett film.

Interaction of native ovalbumin (OVA) with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) Langmuir-Blodgett monolayer has been studied at the air-water interface. A compressibility study shows the positive association with DPPC. Adsorption kinetics shows that the protein adsorption is a one-step process and the amount of protein adsorbed depends on the concentration of protein at the water subphase. Incorporation of protein into the DPPC layer is surface-pressure dependent. The compressibility study indicates that the DPPC-OVA interaction is hydrophobic in nature and structural reorganization is eminent to adjust the hydrophobic mismatch between DPPC acyl chains and OVA hydrophobic moieties. At higher pressure, OVA tends to squeeze out from the DPPC monolayer. A nanometer scale FE-SEM image confirms this observation. Globular aggregates of protein of dimension 60-80 nm were observed in DPPC-OVA supported film. Steady-state fluorescence spectroscopy suggests that the tryptophan residues of OVA are main emitting species. The blue shift of tryptophan fluorescence in supported film may be due to the tryptophan molecule of protein exposed to the hydrophobic air phase.

Interaction and incorporation of ovalbumin with stearic acid monolayer: Langmuir-Blodgett film formation and deposition.

In this communication, the surface activity of the ovalbumin (OVA) at the air/water interface was studied to establish the nature of the interaction with the stearic acid (SA) monolayer, based on Langmuir-Blodgett (LB) technique. The interaction was monitored by studying the time (t) variation of surface pressure (pi) at constant area (A). The growth of pi with time indicates a positive association between the SA and the OVA molecules. The surface compressibility analysis has been performed to specify the phase transition of OVA-SA mixed monolayer. Incorporation/association of OVA within the SA monolayer led to noteworthy changes in surface compressibility and was surface pressure as well as protein concentration dependent. Both the hydrophobic and the Vander wall type interactions are found to be responsible for the association. The quenching of tyrosine band in tryptophan excitation spectrum is observed in steady-state fluorescence spectroscopy. This suggests that the tyrosine is the probable binding site with SA. Due to incorporation of SA, the energy transfer from tyrosine to tryptophan is hindered. At higher pressure, OVA tend to squeeze out from the SA monolayer. The high-resolution field emission scanning electron microscope (FE-SEM) image confirms this observation. Aggregated protein structure observed at high pressure indicates unfolding of protein.

Incorporation of ovalbumin within cationic octadecylamine monolayer and a comparative study with zwitterionic DPPC and anionic stearic acid monolayer.

In this communication we demonstrated the incorporation of water-soluble surface-active protein OVA within an insoluble cationic ODA monolayer and compared with zwitterionic (DPPC) and anionic (SA) monolayer. The incorporation of OVA is found to be more in ODA as compared to that of DPPC and SA. The kinetics of protein adsorption in lipid monolayer gives the idea that unfolding of OVA is less in case of DPPC than SA and ODA. The pi-A isotherm and compressibility study gives the information about the different states of the protein-lipid mixed monolayer. At higher pressure, OVA tend to squeeze out from the lipids monolayer. High-resolution field emission scanning electron microscope (FE-SEM) images confirm this observation. The surface morphology of DPPC-OVA LB film is far better than ODA-OVA and SA-OVA LB film. OVA forms large irregular aggregates on SA and ODA monolayer. Fluorescence study reveals that protein structure is perturbed more in SA and ODA system compared to that of DPPC. The overall results indicate that DPPC monolayer is better to get protein lipid mixed film than SA and ODA monolayer.

Novel optically active lead-free relaxor ferroelectric (Ba0.6Bi0.2Li0.2)TiO3.

We discovered a near-room-temperature lead-free relaxor-ferroelectric (Ba0.6Bi0.2Li0.2)TiO3 (BBLT) having A-site compositionally disordered ABO3 perovskite structure. Microstructure-property relations revealed that the chemical inhomogeneities and development of local polar nano-regions (PNRs) are responsible for dielectric dispersion as a function of probe frequencies and temperatures. Rietveld analysis indicates mixed crystal structure with 80% tetragonal structure (space group P4mm) and 20% orthorhombic structure (space group Amm2), which is confirmed by the high resolution transmission electron diffraction (HRTEM). Dielectric constant and tangent loss dispersion with and without illumination of light obey nonlinear Vogel-Fulcher (VF) relations. The material shows slim polarization-hysteresis (P-E) loops and excellent displacement coefficients (d 33 ~ 233 pm V(-1)) near room temperature, which gradually diminish near the maximum dielectric dispersion temperature (T m ). The underlying physics for light-sensitive dielectric dispersion was probed by x-ray photon spectroscopy (XPS), which strongly suggests that mixed valence of bismuth ions, especially Bi(5+) ions, comprise most of the optically active centers. Ultraviolet photoemission measurements showed most of the Ti ions are in 4 + states and sit at the centers of the TiO6 octahedra; along with asymmetric hybridization between O 2p and Bi 6s orbitals, this appears to be the main driving force for net polarization. This BBLT material may open a new path for environmental friendly lead-free relaxor-ferroelectric research.

Concentration-dependent surface-enhanced resonance Raman scattering of a porphyrin derivative adsorbed on colloidal silver particles.

Surface-enhanced Raman spectra (SERS) of 5,10,15,20-tetrakis(1-decylpyridium-4-yl)-21H,23H-porphintetrabromide or Por 10 (H(2)Tdpyp) adsorbed on silver hydrosols are compared with the FTIR and resonance Raman spectrum (RRS) in the bulk and in solution. Comparative analysis of the RR and the FTIR spectra indicate that the molecule, in its free state, has D(2h) symmetry rather than C(2v). The SERS spectra, obtained on adsorption of this molecule on borohydride-reduced silver sol, indicate the formation of silver porphyrin. With the change in the adsorbate concentration, the SERS shows that the molecule changes its orientation on the colloidal silver surface. The appearance of longer wavelength band in the electronic absorption spectra of the sol has been attributed to the coagulation of colloidal silver particles in the sol. The long wavelength band is found to be red-shifted with the decrease in adsorbate concentration. The excitation profile study indicates that the resonance of the Raman excitation radiation with the original sol band is more important than that with the new aggregation band for the SERS activity. This indicates a large contribution of electromagnetic effect to surface enhancement.

Quantum-mechanical DFT calculation supported Raman spectroscopic study of some amino acids in bovine insulin.

In this article Quantum mechanical (QM) calculations by Density Functional Theory (DFT) have been performed of all amino acids present in bovine insulin. Simulated Raman spectra of those amino acids are compared with their experimental spectra and the major bands are assigned. The results are in good agreement with experiment. We have also verified the DFT results with Quantum mechanical molecular mechanics (QM/MM) results for some amino acids. QM/MM results are very similar with the DFT results. Although the theoretical calculation of individual amino acids are feasible, but the calculated Raman spectrum of whole protein molecule is difficult or even quite impossible task, since it relies on lengthy and costly quantum-chemical computation. However, we have tried to simulate the Raman spectrum of whole protein by adding the proportionate contribution of the Raman spectra of each amino acid present in this protein. In DFT calculations, only the contributions of disulphide bonds between cysteines are included but the contribution of the peptide and hydrogen bonds have not been considered. We have recorded the Raman spectra of bovine insulin using micro-Raman set up. The experimental spectrum is found to be very similar with the resultant simulated Raman spectrum with some exceptions.

Hemangioendothelioma of soft tissue: Cytological dilemma in two cases at unusual sites.

Hemangioendothelioma is a rare vascular tumor of intermediate malignancy. Cytologically, it can simulate a non-vascular malignant tumor. We report two cases of this tumor, which were misdiagnosed at cytology. In the first case, a 27-year-old man presented with an anterior abdominal wall tumor. Fine needle aspiration cytology (FNAC) of the tumor showed polygonal cells with vacuolated cytoplasm in clusters having moderate nuclear atypia in a background of necrosis. A diagnosis of metastatic carcinoma was made. The histological examination showed features of epithelioid hemangioendothelioma. In the second case, a 13-year-old female child presented with unilateral enlargement of the right tonsil. At ultrasound-guided FNAC, a diagnosis of, 'small round cell tumor, could be consistent with alveolar rhabdomyosarcoma,' was made. The histological examination showed features of papillary intralymphatic angioendothelioma (Dabska's tumor). We conclude that epithelioid hemangioendothelioma should be considered in the differential diagnosis of metastatic carcinoma and small round cell tumor even at unusual sites.