Spatio-temporal correlations in aqueous systems: computational studies of static and dynamic heterogeneity by 2D-IR spectroscopy

Local heterogeneity is ubiquitous in natural aqueous systems. It can be caused locally by external biomolecular subsystems like proteins, DNA, micelles and reverse micelles, nanoscopic materials etc., but can also be intrinsic to the thermodynamic nature of the aqueous solution itself (like binary mixtures or at the gas-liquid interface). The altered dynamics of water in the presence of such diverse surfaces has attracted considerable attention in recent years. As these interfaces are quite narrow, only a few molecular layers thick, they are hard to study by conventional methods. The recent development of two dimensional infra-red (2D-IR) spectroscopy allows us to estimate length and time scales of such dynamics fairly accurately. In this work, we present a series of interesting studies employing two dimensional infra-red spectroscopy (2D-IR) to investigate (i) the heterogeneous dynamics of water inside reverse micelles of varying sizes, (ii) supercritical water near the Widom line that is known to exhibit pronounced density fluctuations and also study (iii) the collective and local polarization fluctuation of water molecules in the presence of several different proteins. The spatio-temporal correlation of confined water molecules inside reverse micelles of varying sizes is well captured through the spectral diffusion of corresponding 2D-IR spectra. In the case of supercritical water also, we observe a strong signature of dynamic heterogeneity from the elongated nature of the 2D-IR spectra. In this case the relaxation is ultrafast. We find remarkable agreement between the different tools employed to study the relaxation of density heterogeneity. For aqueous protein solutions, we find that the calculated dielectric constant of the respective systems unanimously shows a noticeable increment compared to that of neat water. However, the `effective' dielectric constant for successive layers shows significant variation, with the layer adjacent to the protein having a much lower value. Relaxation is also slowest at the surface. We find that the dielectric constant achieves the bulk value at distances more than 3 nm from the surface of the protein.

Determination of band offsets at the Al:ZnO/Cu2SnS3 interface using X-ray photoelectron spectroscopy

The Al:ZnO/Cu2SnS3 semiconductor heterojunction was fabricated. The structural and optical properties of the semiconductor materials were studied. The band offset at the Al:ZnO/Cu2SnS3 heterojunction was studied using X-ray photoelectron spectroscopy technique. From the measurement of the core level energies and valence band maximum of the constituent elements, the valence band offset was calculated to be -1.1 +/- 0.24 eV and the conduction band offset was 0.9 +/- 0.34 eV. The band alignment at the heterojunction was found to be of type-I. The study of Al:ZnO/Cu2SnS3 heterojunction is useful for solar cell applications. (C) 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

Linking carbon metabolism to carotenoid production in mycobacteria using Raman spectroscopy

Bacteria can utilize multiple sources of carbon for growth, and for pathogenic bacteria like Mycobacterium tuberculosis, this ability is crucial for survival within the host. In addition, phenotypic changes are seen in mycobacteria grown under different carbon sources. In this study, we use Raman spectroscopy to analyze the biochemical components present in M. smegmatis cells when grown in three differently metabolized carbon sources. Our results show that carotenoid biosynthesis is enhanced when M. smegmatis is grown in glucose compared to glycerol and acetate. We demonstrate that this difference is most likely due to transcriptional upregulation of the carotenoid biosynthesis operon (crt) mediated by higher levels of the stress-responsive sigma factor SigF. Moreover, we find that increased SigF and carotenoid levels correlate with greater resistance of glucose-grown cells to oxidative stress. Thus, we demonstrate the use of Raman spectroscopy in unraveling unknown aspects of mycobacterial physiology and describe a novel effect of carbon source variation on mycobacteria.

RNA nucleosides as chiral sensing agents in NMR spectroscopy

The study reports chiral sensing properties of RNA nucleosides. Adenosine, guanosine, uridine and cytidine are used as chiral derivatizing agents to differentiate chiral 1 degrees-amines. A three component protocol has been adopted for complexation of nucleosides and amines. The chiral differentiating ability of nucleosides is examined for different amines based on the H-1 NMR chemical shift differences of diastereomers (Delta delta(R,S)). Enantiomeric differentiation has been observed at multiple chemically distinct proton sites. Adenosine and guanosine exhibit large chiral differentiation (Delta delta(R,S)) due to the presence of a purine ring. The diastereomeric excess (de) measured by using adenosine is in good agreement with the gravimetric values.

Imaging Flow Cytometry With Femtosecond Laser-Micromachined Glass Microfluidic Channels

Microfluidic/optofluidic microscopy is a versatile modality for imaging and analyzing properties of cells/particles while they are in flow. In this paper, we demonstrate the integration of fused silica microfluidics fabricated using femtosecond laser machining into optofluidic imaging systems. By using glass for the sample stage of our microscope, we have exploited its superior optical quality for imaging and bio-compatibility. By integrating these glass microfluidic devices into a custom-built bright field microscope, we have been able to image red blood cells in flow with high-throughputs and good fidelity. In addition, we also demonstrate imaging as well as detection of fluorescent beads with these microfluidic devices.

Screening and assignment of phenylboronic acid and its anhydride formation by NMR spectroscopy

The study discusses an approach that allows simultaneous determination of boronic acid and its anhydride without the need for tedious physical separation of the mixture. The assignment of the proton spectra of monomer, dimer and trimer was achieved by combining utility of 1D and 2D experimental techniques including 2D DOSY. The differential intensities of NMR peaks and supplementary resonances were detected in low polar solvents, such as, chloroform, toluene and in a non-polar solvent benzene. A fascinating phenomenon is observed at lower temperature where there is a formation of aryl boronic acid with the disappearance of boraxine formation. (C) 2015 Elsevier B.V. All rights reserved.

Photosensitivity study of GeS2 chalcogenide glass under femtosecond laser pulses irradiation

The present study discusses the photosensitivity of GeS2 chalcogenide glass in response to irradiation with femtosecond pulses at 1047 nm. Bulk GeS2 glasses are prepared by conventional melt quenching technique and the amorphous nature of the glass is confirmed using X-ray diffraction. Ultrafast laser inscription technique is used to fabricate the straight channel waveguides in the glass. Single scan and multi scan waveguides are inscribed in GeS2 glasses of length 0.65 cm using a master oscillator power amplifier Yb doped fiber laser (IMRA mu jewel D400) with different pulse energy and translation speed. Diameters of the inscribed waveguides are measured and its dependence on the inscription parameters such as translation speed and pulse energy is studied. Butt coupling method is used to characterize the loss measurement of the inscribed optical waveguides. The mode field image of the waveguides is captured using CCD camera and compared with the mode field image of a standard SMF-28 fibers.

A simple and rapid approach for testing enantiopurity of hydroxy acids and their derivatives using H-1 NMR spectroscopy

A rapid and the simple chiral derivatizing protocol involving the coupling of 2-formylphenylboronic acid and an optically pure 1,1-binaphthalene]-2,2-diamine is introduced for the accurate determination of the enantiopurity of hydroxy acids and their derivatives, possessing one or two optically active centers, using H-1 NMR spectroscopy.

New symmetrical dinucleating ligand based assembly of bridged dicopper(II) and dizinc(II) centers: Synthesis, structure, spectroscopy, magnetic properties and glycoside hydrolysis

Two dinuclear copper(II) complexes Li(H2O)(3)(CH3OH)](4)Cu2Br4]Cu-2(cpdp)(mu-O2CCH3)](4)(OH)(2) (1), Cu (H2O)(4)]Cu-2(cpdp)(mu-O2CC6H5)](2)Cl-2 center dot 5H(2)O (2), and a dinuclear zinc(II) complex Zn-2(cpdp)(mu-O2CCH3)] (3) have been synthesized using pyridine and benzoate functionality based new symmetrical dinucleating ligand, N, N'-Bis2-carboxybenzomethyl]-N, N'-Bis2-pyridylmethyl]-1,3-diaminopropan-2-ol (H(3)cpdp). Complexes 1, 2 and 3 have been synthesized by carrying out reaction of the ligand H3cpdp with stoichiometric amounts of Cu-2(O2CCH3)(4)(H2O)(2)], CuCl2 center dot 2H(2)O/C6H5COONa, and Zn(CH3COO)(2)center dot 2H(2)O, respectively, in methanol in the presence of NaOH at ambient temperature. Characterizations of the complexes have been done using various analytical techniques including single crystal X-ray structure determination. The X-ray crystal structure analyses reveal that the copper(II) ions in complexes 1 and 2 are in a distorted square pyramidal geometry with Cu-Cu separation of 3.455(8) angstrom and 3.492(1)angstrom, respectively. The DFT optimized structure of complex 3 indicates that two zinc(II) ions are in a distorted square pyramidal geometry with Zn-Zn separation of 3.492(8)angstrom. UV-Vis and mass spectrometric analyses of the complexes confirm their dimeric nature in solution. Furthermore, H-1 and C-13 NMR spectroscopic investigations authenticate the integrity of complex 3 in solution. Variable-temperature (2-300 K) magnetic susceptibility measurements show the presence of antiferromagnetic interactions between the copper centers, with J = -26.0 cm(-1) and -23.9 cm(-1) ((H) over cap = -2JS(1)S(2)) in complexes 1 and 2, respectively. In addition, glycosidase-like activity of the complexes has been investigated in aqueous solution at pH similar to 10.5 by UV-Vis spectrophotometric technique using p-nitrophenyl-alpha-D-glucopyranoside (4) and p-nitrophenyl-beta-D-glucopyranoside (5) as model substrates. (C) 2015 Elsevier B.V. All rights reserved.

The X-ray photoelectron spectroscopy and high-temperature structural studies of Zn1-xNixO/NiO two-phase composites

Detailed investigation of the chemical states and local atomic environment of Ni and Zn in the two-phase composites of Zn1-xNixO/NiO was reported. The X-ray photoelectron spectra of both Ni-2p and Zn-2p revealed the existence of a doublet with spin-orbit splitting approximate to 17.9 and 23.2eV, respectively confirming the divalent oxidation state of both Ni and Zn. However, the samples fabricated under oxygen-rich conditions exhibit significant difference in the binding energy approximate to 18.75eV between the 2p3/2 and 2p1/2 states of Ni. The shift in the satellite peaks of Ni-2p with increasing the Ni composition x within the Zn1-xNixO/NiO matrix signifies the attenuation of nonlocal screening because of reduced site occupancy of two adjacent Zn ions. The temperature dependence of X-ray diffraction analysis reveals a large distortion in the axial-rhombohedral angle for oxygen-rich NiO. Conversely, no significant distortion was noticed in the NiO system present as a secondary phase within Zn1-xNixO. Nevertheless, the unit-cell volume of both wurtzite h.c.p. Zn1-xNixO and f.c.c. NiO exhibits an anomalous behavior between 150 and 300 degrees C. The origin of such unusual change in the unit-cell volume was discussed in terms of oxygen stoichiometry.

Probing complex heterostructures using hard X-ray photoelectron spectroscopy (HAXPES)

X-ray Photoelectron Spectroscopy (XPS) plays a central role in the investigation of electronic properties as well as compositional analysis of almost every conceivable material. However, a very short inelastic mean free path (IMFP) and the limited photon flux in standard laboratory conditions render this technique very much surface sensitive. Thus, the electronic structure buried below several layers of a heterogeneous sample is not accessible with usual photoemission techniques. An obvious way to overcome this limitation is to use a considerably higher energy photon source, as this increases the IMFP of the photo-ejected electron, thereby making the technique more depth and bulk sensitive. Due to this obvious advantage, Hard X-ray Photo Electron Spectroscopy (HAXPES) is rapidly becoming an extremely powerful tool for chemical, elemental, compositional and electronic characterization of bulk systems, more so with reference to systems characterized by the presence of buried interfaces and other types of chemical heterogeneity. The relevance of such an investigative tool becomes evident when we specifically note the ever-increasing importance of heterostructures and interfaces in the context of a wide range of device applications, spanning electronic, magnetic, optical and energy applications. The interest in this nondestructive, element specific HAXPES technique has grown rapidly in the past few years; we discuss critically its extensive use in the study of depth resolved electronic properties of nanocrystals, multilayer superlattices and buried interfaces, revealing their internal structures. We specifically present a comparative discussion, with examples, on two most commonly used methods to determine internal structures of heterostructured systems using XPS. (C) 2015 Elsevier B.V. All rights reserved.

Feshbach modulation spectroscopy of the Fermi-Hubbard model

In the vicinity of a Feshbach resonance, a system of ultracold atoms in an optical lattice undergoes rich physical transformations which involve molecule formation and hopping of molecules on the lattice and thus goes beyond a single-band Hubbard model description. We explore theoretically the response of this system to a harmonic modulation of the magnetic field, and thus of the scattering length, across the Feshbach resonance. In the regime in which the single-band Hubbard model is still valid, we provide results for the doublon production as a function of the various parameters, such as frequency, amplitude, etc., that characterize the field modulation, as well as the lattice depth. The method may uncover a route towards the efficient creation of ultracold molecules and also provide an alternative to conventional lattice-depth-modulation spectroscopy.

Light Induced Metastable State of Silver Nitroprusside Probed by Raman Spectroscopy

Low temperature Raman spectroscopic measurements on silver nitroprusside (AgNP), Ag-2Fe(CN)(5)NO] powders display reversible features of a partially converted metastable state. The results are compared with similarly observed metastable state in case of sodium nitroprusside (NaNP) and the differences have been discussed in terms of possible resistance to metastable state formation offered by silver atoms on the basis of hard soft acid base (HSAB) theory.

Detection and estimation of liquid flow through a pipe in a tissue-like object with ultrasound-assisted diffuse correlation spectroscopy

Using coherent light interrogating a turbid object perturbed by a focused ultrasound (US) beam, we demonstrate localized measurement of dynamics in the focal region, termed the region-of-interest (ROI), from the decay of the modulation in intensity autocorrelation of light. When the ROI contains a pipe flow, the decay is shown to be sensitive to the average flow velocity from which the mean-squared displacement (MSD) of the scattering centers in the flow can be estimated. While the MSD estimated is seen to be an order of magnitude higher than that obtainable through the usual diffusing wave spectroscopy (DWS) without the US, it is seen to be more accurate as verified by the volume flow estimated from it. It is further observed that, whereas the MSD from the localized measurement grows with time as tau(alpha) with alpha approximate to 1.65, without using the US, a is seen to be much less. Moreover, with the local measurement, this super-diffusive nature of the pipe flow is seen to persist longer, i.e., over a wider range of initial tau, than with the unassisted DWS. The reason for the super-diffusivity of flow, i.e., alpha < 2, in the ROI is the presence of a fluctuating (thermodynamically nonequilibrium) component in the dynamics induced by the US forcing. Beyond this initial range, both methods measure MSDs that rise linearly with time, indicating that ballistic and near-ballistic photons hardly capture anything beyond the background Brownian motion. (C) 2015 Optical Society of America

Probing Photoexcited Carriers in a Few-Layer MoS2 Laminate by Time-Resolved Optical Pump-Terahertz Probe Spectroscopy

We report the dynamics of photoinduced carriers in a free-standing MoS2 laminate consisting of a few layers (1-6 layers) using time-resolved optical pump-terahertz probe spectroscopy. Upon photoexcitation with the 800 nm pump pulse, the terahertz conductivity increases due to absorption by the photoinduced charge carriers. The relaxation of the non-equilibrium carriers shows fast as well as slow decay channels, analyzed using a rate equation model incorporating defect-assisted Auger scattering of photoexcited electrons, holes, and excitons. The fast relaxation time occurs due to the capture of electrons and holes by defects via Auger processes, resulting in nonradiative recombination. The slower relaxation arises since the excitons are bound to the defects, preventing the defect-assisted Auger recombination of the electrons and the holes. Our results provide a comprehensive understanding of the non-equilibrium carrier kinetics in a system of unscreened Coulomb interactions, where defect-assisted Auger processes dominate and should be applicable to other 2D systems.