Detection of the mineral constituents in human renal calculi by vibrational spectroscopic analysis combined with allied techniques Powder XRD, TGA, SEM, IR imaging and TXRF.

Detection of the mineral constituents in a batch of 310 samples of human urinary calculi (kidney stones-235 and bladder stones-75) combined with a semi-quantitative analysis has been presented on the basis of Fourier Transform based IR and Raman spectral measurements. Some of the observed characteristic IR and Raman bands have been proposed as 'Marker Bands' for the most reliable identification of the constituents. A detailed vibrational spectral analysis combined with a DFT level calculation for the functional groups in Calcium Oxalate Monohydrate (COM), Magnesium Ammonium Phosphate Hexahydrate (MAPH), Calcium Hydrogen Phosphate Dihydrate (CHPD), Penta-Calcium Hydroxy-Triphosphate (PCHT) and Uric Acid (UA) has been proposed. It has been shown that the identified mineral constituents as major or minor components can be deduced from the application of Lambert-Beer law of radiation absorption and results are in agreement with quantitative Spectral Data base. This simple method has the potential to be integrated into the management of Urolithiasis, a process of forming renal calculi in the kidney, bladder and/or urethra. Employment of powder XRD, TGA, SEM, TXRF and IR Imaging techniques has provided additional support for the proposed foolproof identification of the mineral constituents. Among the mineral constituents, Calcium Oxalate Monohydrate, Calcium Oxalate Dihydrate or their mixture account for 85% of the total number of samples; the remaining 15% and 5% samples contain Phosphate and Uric acid stones respectively.

Role of charged impurities in thermoelectric transport in molybdenum disulfide monolayers.

A theoretical study of the electronic properties, namely, electrical conductivity (EC), electronic thermal conductivity (ETC) and thermoelectric power (TEP) in 2D MoS2 monolayers (MLs), over a wide range of temperatures (10 < T < 300 K), is presented employing Boltzmann transport formalism. Considering the electrons to be scattered by screened charged impurities and the acoustic, optical and remote phonons, the transport equation is solved using Ritz iterative method. Numerical calculations of EC, ETC and TEP presented for supported and free-standing MLs with high electron concentrations, as a function of temperature, bring out the relative importance of the various scattering mechanisms operative. The role of CIs, with regard to both concentration and separation from the substrate-ML interface, in determining the properties of supported MLs is demonstrated for the first time. Validity of Wiedemann-Franz law and Mott formula are examined for supported and free standing MLs. Calculations are in consonance with recent experimental data on mobility and TEP of exfoliated SiO2-supported MoS2 ML samples. In the case of TEP it is found that though the diffusion contribution is dominant the inclusion of the drag component, incorporating contributions from all relevant phonon scattering mechanisms, is needed to obtain good agreement with the data.

Interaction and energy transfer studies between bovine serum albumin and CdTe quantum dots conjugates: CdTe QDs as energy acceptor probes.

In this paper, a systematic investigation of the interaction of bovine serum albumin (BSA) with water-soluble CdTe quantum dots (QDs) of two different sizes capped with carboxylic thiols is presented based on steady-state and time-resolved fluorescence measurements. Efficient Förster resonance energy transfer (FRET) was observed to occur from BSA donor to CdTe acceptor as noted from reduction in the fluorescence of BSA and enhanced fluorescence from CdTe QDs. FRET parameters such as Förster distance, spectral overlap integral, FRET rate constant and efficiency were determined. The quenching of BSA fluorescence in aqueous solution observed in the presence of CdTe QDs infers that fluorescence resonance energy transfer is primarily responsible for the quenching phenomenon. Bimolecular quenching constant (kq ) determined at different temperatures and the time-resolved fluorescence data provide additional evidence for this. The binding stoichiometry and various thermodynamic parameters are evaluated by using the van 't Hoff equation. The analysis of the results suggests that the interaction between BSA and CdTe QDs is entropy driven and hydrophobic forces play a key role in the interaction. Binding of QDs significantly shortened the fluorescence lifetime of BSA which is one of the hallmarks of FRET. The effect of size of the QDs on the FRET parameters are discussed in the light of FRET parameters obtained.

Spectroscopic investigation of water-soluble alloyed QDs with bovine serum albumin.

We present here a systematic investigation on the interaction between a water-soluble alloyed semiconductor quantum dot and bovine serum albumin using various spectroscopic techniques i.e. fluorescence quenching, resonance light scattering and synchronous fluorescence spectroscopy. The analysis of fluorescence spectrum and fluorescence intensity indicates that the intrinsic fluorescence of bovine serum albumin (BSA) gets quenched by both static and dynamic quenching mechanism. The Stern-Volmer quenching constants, energy transfer efficiency parameters, binding parameters and corresponding thermodynamic parameters (ΔH0 , ΔS0 and ΔG0 ) have been evaluated by using van 't Hoff equation at different temperatures. A positive entropy change with a positive enthalpy change was observed suggesting that the binding process was an entropy-driven, endothermic process associated with the hydrophobic effect. The intermolecular distance (r) between donor (BSA) and acceptor (CdSeS/ZnS quantum dots) was estimated according to Förster's theory of non-radiative energy transfer. The synchronous fluorescence spectra revealed a blue shift in the emission maxima of tryptophan which is indicative of increasing hydrophobicity. Negative ΔG0 values implied that the binding process was spontaneous. It was found that hydrophobic forces played a role in the quenching process. Copyright © 2016 John Wiley & Sons, Ltd.

Identification of mineral compositions in some renal calculi by FT Raman and IR spectral analysis.

We present in this paper accurate and reliable Raman and IR spectral identification of mineral constituents in nine samples of renal calculi (kidney stones) removed from patients suffering from nephrolithiasis. The identified mineral components include Calcium Oxalate Monohydrate (COM, whewellite), Calcium Oxalate Dihydrate (COD, weddellite), Magnesium Ammonium Phosphate Hexahydrate (MAPH, struvite), Calcium Hydrogen Phosphate Dihydrate (CHPD, brushite), Pentacalcium Hydroxy Triphosphate (PCHT, hydroxyapatite) and Uric Acid (UA). The identification is based on a satisfactory assignment of all the observed IR and Raman bands (3500-400c m(-1)) to chemical functional groups of mineral components in the samples, aided by spectral analysis of pure materials of COM, MAPH, CHPD and UA. It is found that the eight samples are composed of COM as the common component, the other mineral species as common components are: MAPH in five samples, PCHT in three samples, COD in three samples, UA in three samples and CHPD in two samples. One sample is wholly composed of UA as a single component; this inference is supported by the good agreement between ab initio density functional theoretical spectra and experimental spectral measurements of both sample and pure material. A combined application of Raman and IR techniques has shown that, where the IR is ambiguous, the Raman analysis can differentiate COD from COM and PCHT from MAPH.

Spectroscopic investigation of alloyed quantum dot-based FRET to cresyl violet dye.

Quantum dots (QDs), bright luminescent semiconductor nanoparticles, have found numerous applications ranging from optoelectronics to bioimaging. Here, we present a systematic investigation of fluorescence resonance energy transfer (FRET) from hydrophilic ternary alloyed quantum dots (CdSeS/ZnS) to cresyl violet dye with a view to explore the effect of composition of QD donors on FRET efficiency. Fluorescence emission of QD is controlled by varying the composition of QD without altering the particle size. The results show that quantum yield of the QDs increases with increase in the emission wavelength. The FRET parameters such as spectral overlap J(λ), Förster distance R0, intermolecular distance (r), rate of energy transfer k(T)(r), and transfer efficiency (E) are determined by employing both steady-state and time-resolved fluorescence spectroscopy. Additionally, dynamic quenching is noticed to occur in the present FRET system. Stern-Volmer (K(D)) and bimolecular quenching constants (k(q)) are determined from the Stern-Volmer plot. It is observed that the transfer efficiency follows a linear dependence on the spectral overlap and the quantum yield of the donor as predicted by the Förster theory upon changing the composition of the QD.

UV laser radiation alters the embryonic protein profile of adrenal-kidney-gonadal complex and gonadal differentiation in the lizard, Calotes Versicolor.

PURPOSE: To examine the impact of ultraviolet (UV) laser radiation on the embryos of Calotes versicolor in terms of its effects on the protein profile of the adrenal-kidney-gonadal complex (AKG), sex determination and differentiation, embryonic development and hatching synchrony. MATERIALS AND METHODS: The eggs of C. versicolor, during thermo-sensitive period (TSP), were exposed to third harmonic laser pulses at 355 nm from a Q-switched Nd:YAG laser for 180 sec. Subsequent to the exposure they were incubated at the male-producing temperature (MPT) of 25.5 ± 0.5°C. The AKG of hatchlings was subjected to protein analysis by sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE) and to histology. RESULTS: The UV laser radiation altered the expression of the protein banding pattern in the AKG complex of hatchlings and it also affected the gonadal sex differentiation. SDS-PAGE of AKG of one-day-old hatchlings revealed a total of nine protein bands in the control group whereas UV laser irradiated hatchlings expressed a total of seven protein bands only one of which had the same Rf as a control band. The UV laser treated hatchlings have an ovotestes kind of gonad exhibiting a tendency towards femaleness instead of the typical testes. CONCLUSIONS: It is inferred that 355 nm UV laser radiation during TSP induces changes in the expression of proteins as well as their secretions. UV laser radiation had an impact on the gonadal differentiation pathway but no morphological anomalies were noticed.

Rotational diffusion of coumarins: a dielectric friction study.

The rotational diffusion of three probes: coumarin 522B (C522B), coumarin 307 (C307) and coumarin 138 (C138) with nearly identical size was studied at room temperature employing steady-state and time-resolved fluorescence anisotropy techniques in series of alcohols and alkanes. Experimental observations indicate faster rotation of C138 compared to the other two dyes in alcohols and a faster rotation of C522B than C307 in alkanes. The dielectric friction theories of Nee-Zwanzig (NZ) and van der Zwan-Hynes (ZH) were employed to estimate the friction experienced by the probes in alcohols, in addition to the mechanical friction calculated using Stokes-Einstein-Debye (SED) hydrodynamic with slip boundary condition and Dote-Kivelson-Schwartz (DKS) quasihydrodynamic theories. The observed reorientation times for the three probes do not follow the trend predicted by dielectric friction theories of NZ and ZH. The dipole moments determined from solvatochromic techniques were found to be different for the three probes.

Ambient synthesis and characterization of high-quality CdSe quantum dots by an aqueous route.

Herein, we report the ambient synthesis of CdSe nanoparticles of widely tunable particle size by a solution route. The proposed protocol uses hydrazine hydrate to form an air-stable complex of selenium. These nanoparticles are characterized by X-ray diffraction, FTIR, optical absorption, photoluminescence, and transmission electron microcopy measurements. By varying the molarities of Cd(2+) and Se(2-) ions in solution with 3-mercaptopropionic acid as the capping ligand, the method permits us to synthesize nanoparticles of size ranging from 1.58 to 3.42 nm (estimated from optical absorption edge measurements) by controlling the annealing time of the starting colloid at 100 degrees C. The extracted quantum dots are of high quality (40% photoluminescence quantum yield) and exhibit colors ranging from deep blue to red. The resulting colloids are very stable, and no precipitate is observed over a period of 6 months. Thus, the method is simple and easily scalable to synthesize fluorescent CdSe nanoparticles.

Formation of electronic junctions on molecularly modified surfaces by lift-and-float electrical contacts.

Here, we report a simple method of forming electrical contacts on soft surfaces of organic monolayers and organically capped nanoparticles. It is based on the lift of predefined contacts of silver paste on a water surface and their pickup and float on a soft surface by capillary force. Three different surfaces of silicon--hydrogen terminated, covalently bonded organic molecules, and a thin film of organically capped CdSe nanoparticles--were used to constitute electronic junctions by lift and float of individual contacts. Charge transport measurements clearly demonstrate that these junctions are free from shorting and wrinkling of the top contact and damage of molecular films. Hence, the method is simple, effective, nondestructive, and economical to form electronic junctions on molecular surfaces.

Molecularly controlled metal-semiconductor junctions on silicon surface: a dipole effect.

Silicon surface was chemically modified by covalent attachment of homologous organic molecules having different dipole moments. Surface photovoltage measurements clearly confirm that organic molecules have a profound effect on surface band bending of semiconductor. Metal-molecules--silicon junctions were constituted for molecules belonging to ethynylbenzene series using soft mercury contact. These junctions show a systematic change in the electrical charge transport with dipole moment of molecules. Parameters such as ideality factor, barrier height, and density of interface states of various junctions are estimated to understand the role of organic molecules. These studies offer the prospect to develop molecular electronics, which may find potential applications in solar cells and chemical and biological sensors.

Solvent effect on absorption and fluorescence spectra of coumarin laser dyes: evaluation of ground and excited state dipole moments.

The effect of solvents on absorption and fluorescence spectra and dipole moments of coumarin 307 (C307) and coumarin 522B (C522B) have been studied extensively in various solvents, viz., general solvents, alcohols and binary mixtures (acetonitrile-benzene) at 298K. The bathchromic shift observed in absorption and fluorescence spectra of C307 and C522B with increasing solvent polarity indicates that transition involved are pi-->pi*. Solvatochromic correlations were used to obtain the ground and excited state dipole moments. The excited state dipole moments are observed to be greater than their ground state counterparts in all the solvents studied. Further, the experimentally obtained Deltamu were compared with those using normalized polarity terms E(T)(N) from Reichardt equation.

Rotational diffusion and solvatochromic correlation of coumarin 6 laser dye.

Rotational diffusion of coumarin 6 (C6) laser dye has been examined in n-decane and methanol as a function of temperature. The rotational reorientation of this probe has been measured in these solvents. It is observed that the decrease in viscosity of the solution is responsible for the decrease in the rotational relaxation time of the probe molecule. The molecule C6 has long reorientation times in n-decane solvent as compared to methanol over all temperatures. It is found that the coumarin 6 rotates slower in n-decane than in methanol especially at higher values of viscosity over temperature. Two methods are chosen to determine the ground state and excited state dipole moments. The change in dipole moments is estimated from Bakhshiev-Chamma-Viallet equations and, the ground and excited state dipole moments from Kawski et al. equations, by using the variations of the Stokes shifts with the dielectric constant and refractive index of the solvent. Our results are quite reliable which are solvatochromic correlation obtained using solvent polarity functions. The reported results show that excited state dipole moment is greater than ground state dipole moment, which indicates that the excited state is more polar than the ground state.

Solvent effects on the absorption and fluorescence spectra of coumarins 6 and 7 molecules: determination of ground and excited state dipole moment.

Absorption and fluorescence emission spectra of coumarins 6 and 7 were recorded in solvents with different solvent parameters, viz., dielectric constant epsilon and refractive index n. The fluorescence lifetime of these dyes were measured in butanol at higher values of viscosity over temperature. Experimental ground and excited state dipole moments are determined by means of solvatochromic shift method and also the excited state dipole moments are determined in combination with ground state dipole moments. It was determined that dipole moments of the excited state were higher than those of the ground state in both the molecules.