A Raman study of CdSe and ZnSe nanostructures

Raman studies have been carried out on CdSe nanotubes and ZnSe nanorods produced by surfactant-assisted synthesis. The Raman spectrum of CdSe nanotubes shows modes at 207.5 and 198 cm(-1); the former arises from the longitudinal optic phonon mode red-shifted with respect to the bulk mode because of phonon confinement, and the latter is the I = 1 surface phonon. Analysis based on the phonon confinement model demonstrates that the size of the nanoparticle responsible for the red-shift is about 4 nm, close to the estimate from the blue-shift of the photoluminescence. The Raman spectrum of ZnSe,nanorods shows modes at 257 and 213 cm(-1), assigned to longitudinal and transverse optic phonons, blue-shifted with respect to the bulk ZnSe modes because of compressive strain. The mode at 237 cm(-1) is the surface phonon.

Excited state structure and dynamics of p-benzoquinone and bromanil from time-resolved resonance Raman spectra and simulation

p-Benzoquinone and its halogen substituted derivatives are known to have differing reactivities in the triplet excited state. While bromanil catalyzes the reduction of octaethylporphyrin most efficiently among the halogenated p-benzoquinones, the reaction does not take place in presence of the unsubstituted p-benzoquinone (T. Nakano and Y. Mori, Bull. Chem. Soc. Jpn., 67, 2627 (1994)). Understanding of such differences requires a detailed knowledge of the triplet state structures, normal mode compositions and excited state dynamics. In this paper, we apply a recently presented scheme (M. Puranik, S. Umapathy, J. G. Snijders, and J. Chandrasekhar, J. Chem, Phys., 115, 6106 (2001)) that combines parameters from experiment and computation in a wave packet dynamics simulation to the triplet states of p-benzoquinone and bromanil. The absorption and resonance Raman spectra of both the molecules have been simulated. The normal mode compositions and mode specific excited state displacements have been presented and compared. Time-dependent evolution of the absorption and Raman overlaps for all the observed modes has been discussed in detail. In p-benzoquinone, the initial dynamics is along the C=C stretching and C-H bending modes whereas in bromanil nearly equal displacements are observed along all the stretching coordinates.

Investigation of short-time isomerization dynamics in p-nitroazobenzene from resonance Raman intensity analysis

Resonance Raman (RR) spectra are presented for p-nitroazobenzene dissolved in chloroform using 18 excitation Wavelengths, covering the region of (1)(n --> pi*) electronic transition. Raman intensities are observed for various totally symmetric fundamentals, namely, C-C, C-N, N=N, and N-O stretching vibrations, indicating that upon photoexcitation the excited-state evolution occurs along all of these vibrational coordinates. For a few fundamentals, interestingly, in p-nitroazobenzene, it is observed that the RR intensities decrease near the maxima of the resonant electronic (1)(n --> pi*) transition. This is attributed to the interference from preresonant scattering due to the strongly allowed (1)(pi --> pi*) electronic transition. The electronic absorption spectrum and the absolute Raman cross section for the nine Franck-Condon active fundamentals of p-nitroazobenzene have been successfully modeled using Heller's time-dependent formalism for Raman scattering. This employs harmonic description of the lowest energy (1)(n --> pi*) potential energy surface. The short-time isomerization dynamics is then examined from a priori knowledge of the ground-state normal mode descriptions of p-nitroazobenzene to convert the wave packet motion in dimensionless normal coordinates to internal coordinates. It is observed that within 20 fs after photoexcitation in p-nitroazobenzene, the N=N and C-N stretching vibrations undergo significant changes and the unsubstituted phenyl ring and the nitro stretching vibrations are also distorted considerably.

Mapping of B-cell epitopes of hemagglutinin protein of rinderpest virus

Monoclonal antibodies (mAbs) against secreted hemagglutinin (H) protein of rinderpest virus (RPV) expressed by a recombinant baculovirus were generated to characterize the antigenic sites on H protein and regions of functional significance. Three of the mAbs displayed hemagglutination inhibition activity and these mAbs were unable to neutralize virus infectivity. Western immunoblot analysis of overlapping deletion mutants indicated that three mAbs recognize antigenic regions at the extreme carboxy terminus (between amino acids 569 and 609) and the fourth mAb between amino acids 512 and 568. Using synthetic peptides, aa 569-577 and 575-583 were identified as the epitopes for E2G4 and D2F4, respectively. The epitopic domains of A12A9 and E2B6 mAbs were mapped to regions encompassing aa 527-554 and 588-609. Two epitopes spanning the extreme carboxy terminal region of aa 573 to 587 and 588 to 609 were shown to be immunodominant employing a competitive ELISA with polyclonal sera form vaccinated cattle. The D2F4 mAb which recognizes a unique epitope on RPV-H is not present on the closely related peste des petits ruminant virus FIN protein and this mAb could serve as a tool in the seromonitoring program after rinderpest vaccination. (C) 2002 Elsevier Science (USA).

A determination of the structure of the intramolecular charge transfer state of 4-dimethylaminobenzonitrile (DMABN) by time-resolved resonance Raman spectroscopy

Picosecond time-resolved resonance Raman spectra of the A (intramolecular charge transfer, ICT) state of DMABN, DMABN-d(6) and DMABN-N-15 have been obtained. The isotopic shifts identify the nu (s)(ph-N) mode as a band at 1281 cm(-1). The similar to 96 cm(-1) downshift of this mode from its ground state frequency rules out the electronic coupling PICT model and unequivocally supports the electronic decoupling TICT model. However, our results suggest some pyramidal character of the A state amino conformation.

Temperature dependence of infrared and Raman modes in polymeric RbC60

Temperature dependence of the intra-molecular vibrational modes Of C-60 in the quasi-1D polymeric RbC60, across the low temperature transition at similar to50 K, has been probed through infrared (IR) and Raman spectroscopies. With the lowering of temperature, the split IR modes of RbC60 are seen to harden but below 50 K a small but definitive signature of an anomalous softening is observed. In addition, the background IR transmission shows an increase below 50 K with the opening of a well defined gap in the electronic spectrum. The implications of these results, along with those of Raman measurements, are discussed in terms of the interaction of intra-molecular phonons with electrons and spin excitations in the system. (C) 2002 Published by Elsevier Science Ltd.

The restriction mapping problem revisited

In computational molecular biology, the aim of restriction mapping is to locate the restriction sites of a given enzyme on a DNA molecule. Double digest and partial digest are two well-studied techniques for restriction mapping. While double digest is NP-complete, there is no known polynomial-time algorithm for partial digest. Another disadvantage of the above techniques is that there can be multiple solutions for reconstruction. In this paper, we study a simple technique called labeled partial digest for restriction mapping. We give a fast polynomial time (O(n(2) log n) worst-case) algorithm for finding all the n sites of a DNA molecule using this technique. An important advantage of the algorithm is the unique reconstruction of the DNA molecule from the digest. The technique is also robust in handling errors in fragment lengths which arises in the laboratory. We give a robust O(n(4)) worst-case algorithm that can provably tolerate an absolute error of O(Delta/n) (where Delta is the minimum inter-site distance), while giving a unique reconstruction. We test our theoretical results by simulating the performance of the algorithm on a real DNA molecule. Motivated by the similarity to the labeled partial digest problem, we address a related problem of interest-the de novo peptide sequencing problem (ACM-SIAM Symposium on Discrete Algorithms (SODA), 2000, pp. 389-398), which arises in the reconstruction of the peptide sequence of a protein molecule. We give a simple and efficient algorithm for the problem without using dynamic programming. The algorithm runs in time O(k log k), where k is the number of ions and is an improvement over the algorithm in Chen et al. (C) 2002 Elsevier Science (USA). All rights reserved.

Time-Resolved Resonance Raman Spectroscopic Studies on the Triplet Excited State of Thioxanthone

Thioxanthone has been investigated extensively owing to its unique photochemical and photophysical applications and its solvatochromic behavior. Here, we report the time-resolved resonance Raman studies on the structure of the lowest triplet excited state of thioxanthone in carbon tetrachloride. In addition, FT-IR and FT-Raman techniques have been used to study the vibrational structure in the ground state. To corroborate the experimental findings, density functional theory calculations have been carried out. Isotopic calculations and normal coordinate analysis have been used to help in assigning the observed bands to Raman vibrational modes. Structural information derived from this study is expected to help in better understanding the triplet state photochemistry of thioxanthone.

Self-assembled microtubes and rhodamine 6G functionalized Raman-active gold microrods from 1-hydroxybenzotriazole

1-Hydroxybenzotriazole spontaneously self-assembles to form hollow, linear microtubes initiated by controlled evaporation from water. The tube cavities act as thermo-labile micromoulds for the synthesis of linear gold microrods. Rhodamine 6G-labelled gold microrods, exhibiting surface enhanced resonance Raman activity, have been synthesized using the HOBT microtubes.

Mapping of local electronic properties in nanostructured CMR thin films by Scanning Tunneling Microscopy (STM) and Local Conductance Map (LCMAP)

We have investigated the local electronic properties and the spatially resolved magnetoresistance of a nanostructured film of a colossal magnetoresistive (CMR) material by local conductance mapping (LCMAP) using a variable temperature Scanning Tunneling Microscope (STM) operating in a magnetic field. The nanostructured thin films (thickness ≈500nm) of the CMR material La0.67Sr0.33MnO3 (LSMO) on quartz substrates were prepared using chemical solution deposition (CSD) process. The CSD grown films were imaged by both STM and atomic force microscopy (AFM). Due to the presence of a large number of grain boundaries (GB's), these films show low field magnetoresistance (LFMR) which increases at lower temperatures. The measurement of spatially resolved electronic properties reveal the extent of variation of the density of states (DOS) at and close to the Fermi level (EF) across the grain boundaries and its role in the electrical resistance of the GB. Measurement of the local conductance maps (LCMAP) as a function of magnetic field as well as temperature reveals that the LFMR occurs at the GB. While it was known that LFMR in CMR films originates from the GB, this is the first investigation that maps the local electronic properties at a GB in a magnetic field and traces the origin of LFMR at the GB.

Mapping of large scale 158 mu m [CII] line emission: Orion A

We present the first results of an observational programme undertaken to map the fine structure line emission of singly ionized carbon ([ CII] 157 : 7409 mum) over extended regions using a Fabry Perot spectrometer newly installed at the focal plane of a 100 cm balloon- borne far- infrared telescope. This new combination of instruments has a velocity resolution of similar to 200 km s(-1) and an angular resolution of 1.'5. During the first flight, an area of 30' x 15' in Orion A was mapped. These observations extend over a larger area than previous observations, the map is fully sampled and the spectral scanning method used enables reliable estimation of the continuum emission at frequencies adjacent to the [ CII] line. The total [ CII] line luminosity, calculated by considering up to 20% of the maximum line intensity is 0.04% of the luminosity of the far- infrared continuum. We have compared the [ CII] intensity distribution with the velocity- integrated intensity distributions of (CO)-C-13(1- 0), CI(1- 0) and CO( 3- 2) from the literature. Comparison of the [ CII], [ CI] and the radio continuum intensity distributions indicates that the largescale [ CII] emission originates mainly from the neutral gas, except at the position of M 43, where no [ CI] emission corresponding to the [ CII] emission is seen. Substantial part of the [ CII] emission from here originates from the ionized gas. The observed line intensities and ratios have been analyzed using the PDR models by Kaufman et al. ( 1999) to derive the incident UV flux and volume density at a few selected positions. The models reproduce the observations reasonably well at most positions excepting the [ CII] peak ( which coincides with the position of theta(1) Ori C). Possible reason for the failure could be the simplifying assumption of a homogeneous plane parallel slab in place of a more complicated geometry.

Structural changes in single-walled carbon nanotubes under non-hydrostatic pressures: x-ray and Raman studies

Using in situ x-ray diffraction and Raman scattering techniques, we have investigated the behaviour of single-walled carbon nanotubes bundles under non-hydrostatic pressures. It is seen that the diffraction line corresponding to the two-dimensional triangular lattice in the bundles is not reversible for pressures beyond 5 GPa, in sharp contrast to earlier results under hydrostatic pressure conditions. Most interestingly, radial breathing and tangential Raman modes of the pressure-cycled samples from 21 and 30 GPa match very well with those of the starting sample. Raman and x-ray results put together clearly suggest that the ordering of tubes in the bundles is only marginally regained with a very short coherence length on decompression.

Structural characterization of DC magnetron-sputtered TiO2 thin films using XRD and Raman scattering studies

Titanium dioxide films have been deposited using DC magnetron sputtering technique onto well-cleaned p-silicon substrates at an oxygen partial pressure of 7 x 10(-5) mbar and at a sputtering pressure (Ar + O-2) Of I X 10(-3) mbar. The deposited films were calcinated at 673 and 773 K. The composition of the films as analyzed using Auger electron spectroscopy reveals the stoichiometry with an 0 and Ti ratio 2.08. The influence of post-deposition annealing at 673 and 773 K on the structural properties of the titanium dioxide thin films have been studied using XRD and Raman scattering. The structure of the films deposited at the ambient was found to be amorphous and the films annealed at temperature 673 K and above were crystalline with anatase structure. The lattice constants, grain size, microstrain and the dislocation density of the film are calculated and correlated with annealing temperature. The Raman scattering study was performed on the as-deposited and annealed samples and the existence of Raman active modes A(1g), B-1g and E-g corresponding to the Raman shifts are studied and reported. The improvement of crystallinity of the TiO2 films was also studied using Raman scattering studies. (C) 2003 Elsevier Ltd. All rights reserved.