Search results for "Raman spectroscopy."
showing 10 items of 790 documents
Alternating, all-trans polyenynes: Model compounds for poly(diacetylene)s with defined conjugation length
1994
The syntheses of polyenynes as model compounds for poly(diacetylene)s (PDAs) are described. Variation of properties (UV–VIS, Raman, NMR and bond geometries) as a function of the chain length was investigated. After extrapolation to infinite chain length these data were compared to those for PDAs. From UV–VIS spectra a value of λ = 551 nm (2.25 eV) was calculated corresponding to the electronic transition of a single polyenyne chain. This energy is located at the low energy end of a yellow PDA solution spectrum. From Raman scattering v(CC) = 2108–2128 cm−1 and v(CC) = 1505–1532 cm−1 were calculated after extrapolation. Similarly sp-C13C NMR data yielded a shift of δ = 100 ppm. These data are…
Optical diagnostic of temperature in rocket engines by coherent Raman techniques
2004
Abstract This article reviews the study of Raman line shapes of molecular species involved in reactive media, such flames or engines, at high temperature and high pressure. This study is of interest from a fundamental as well as from a practical point of view with regards to the CARS temperature diagnostic of GH2–LOX combustion systems. We will particularly draw attention to recent investigations by means of Stimulated Raman Spectroscopy (SRS) in H2–H2O mixtures at temperature up to 1800 K. Whereas H2–X systems usually exhibit large inhomogeneous effects, due to the speed dependence of the collisional parameters, the absence of such apparent inhomogeneous signatures in the H2–H2O system all…
Understanding the Excited State Behavior of Cyclometalated Bis(tridentate)ruthenium(II) Complexes: A Combined Experimental and Theoretical Study
2015
The synthesis and characterization of the donor-acceptor substituted cyclometalated ruthenium(II) polypyridine complex isomers [Ru(dpb-NHCOMe)(tpy-COOEt)](PF6) 1(PF6) and [Ru(dpb-COOEt)(tpy-NHCOMe)](PF6) 2(PF6) (dpbH = 1,3-dipyridin-2-ylbenzene, tpy = 2,2';6,2"-terpyridine) with inverted functional group pattern are described. A combination of resonance Raman spectroscopic and computational techniques shows that all intense visible range absorption bands arise from mixed Ru → tpy/Ru → dpb metal-to-ligand charge transfer (MLCT) excitations. 2(PF6) is weakly phosphorescent at room temperature in fluid solution and strongly emissive at 77 K in solid butyronitrile matrix, which is typical for r…
Study of the benzene⋅N2 intermolecular potential-energy surface
2003
The intermolecular potential-energy surface pertaining to the interaction between benzene and N2 is investigated theoretically and experimentally. Accurate intermolecular interaction energies are evaluated for the benzene–N2 van der Waals complex using the coupled cluster singles and doubles including connected triples [CCSD(T)] method and the aug-cc-pVDZ basis set extended with a set of 3s3p2d1f1g midbond functions. After fitting the energies to an analytic function, the intermolecular Schrödinger equation is solved to yield energies, rotational constants, and Raman-scattering coefficients for the lowest intermolecular levels of several benzene–N2 isotopomers. Experimentally, intermolecula…
Aging of MCM41, MSU-H and MSU-F mesoporous systems investigated through the Raman spectroscopy
2014
Here we report an experimental investigation, based on the Raman spectroscopy, on the aging of some mesoporous silica based systems. In details, we studied the aging in air of the MCM41, the MSU-H and the MSU-F materials by acquiring the Raman spectra of as received and of mechanically pressed, at 0.2 and 0.45 GPa, powders. Our data evidenced that the starting powders of the MCM41 and of the MSU-H undergo structural modification when they are exposed to the ambient atmosphere, such modification consisting in the decrease of the D2 Raman band (originated by the three member rings). At variance the powders of the MSU-F appear to be stable. Furthermore, by pressing the starting powders to prod…
SrTiO 3 -based perovskites: Preparation, characterization and photocatalytic activity in gas–solid regime under simulated solar irradiation
2015
Strontium titanate-based perovskites have been prepared in the presence of Y and Co with the aim to substitute Sr and Ti, respectively, in the ST crystalline structure. The obtained samples have been characterized by XRD, Raman spectroscopy, FE-SEM, XPS and tested as photocatalysts in two gas-solid regime reactions: (i) 2-propanol complete mineralization and (ii) propene partial oxidation, using a system simulating solar irradiation. All the tested samples resulted active as photocatalysts but with significant differences. The lattice substitution of Sr by Y displays a beneficial effect on the 2-propanol photodegradation. Conversely, the partial presence of cobalt on the ST surface, as Co-o…
Surface-Enhanced Raman Study of the Interactions between Tripodal Cationic Polyamines and Polynucleotides
2011
Raman and surface-enhanced Raman spectra of new DNA/RNA-binding compounds consisting of three imidazole (Im) and three pyridine (Py) rings connected by tripodal polyaminomethylene linkages were obtained by the near-infrared excitation at 1064 nm. Study of interactions of Im and Py polyamines with single-stranded RNA polynucleotides (poly A, poly G, poly C, poly U), double-stranded DNA polynucleotides (poly dAdT-poly dAdT, poly dGdC-poly dGdC) and calf thymus DNA (ct-DNA) by surface-enhanced Raman spectroscopy (SERS) reveals unambiguous enhancement of the Raman scattering from the small molecules as well as appearance of new bands in spectra associated mainly with nucleobases. The SERS exper…
Mollusk carbonate thermal behaviour and its implications in understanding prehistoric fire events in shell middens
2018
Abstract Archaeological shell middens are particularly important for reconstructing prehistoric human subsistence strategies. However, very little is known about shellfish processing, especially when related to the use of fire for dietary and disposal purposes. To shed light on prehistoric food processing techniques, an experimental study was undertaken on modern gastropod shells (Phorcus lineatus). The shells were exposed to high temperatures (200–700 °C) to investigate subsequent mineralogy and macro- and microstructural changes. Afterwards, the three-pronged approach was applied to archaeological shells from Haua Fteah cave, Libya (Phorcus turbinatus) and from shell midden sites in the U…
The importance of vibronic perturbations in ferrocytochrome c spectra: a reevaluation of spectral properties based on low-temperature optical absorpt…
2005
We have measured and analyzed the low-temperature (T=10 K) absorption spectrum of reduced horse heart and yeast cytochrome c. Both spectra show split and asymmetric Q(0) and Q(upsilon) bands. The spectra were first decomposed into the individual split vibronic sidebands assignable to B(1g) (nu15) and A(2g) (nu19, nu21, and nu22) Herzberg-Teller active modes due to their strong intensity in resonance Raman spectra acquired with Q(0) and Q(upsilon) excitations. The measured band splittings and asymmetries cannot be rationalized solely in terms of electronic perturbations of the heme macrocycle. On the contrary, they clearly point to the importance of considering not only electronic perturbati…
Oligophenylenevinylenes in Spatially Confined Nanochannels: Monitoring Intermolecular Interactions by UV/Vis and Raman Spectroscopy
2008
Perhydrotriphenylene-based channel-forming inclusion compounds (ICs) and thin films made of polyphenylenevinylene (PPV)-type oligomers with terminal alkoxy groups are investigated and compared in a combined experimental and theoretical approach. Interchromophore interactions and host-guest interactions are elucidated by UV/Vis and Raman spectroscopy. The impact of the local environment of the chromophore on the optical and photophysical properties is discussed in light of quantum-chemical calculations. In stark contrast to thin films where preferential side-by-side orientation leads to quenching of photoluminescence (PL) via non-emissive traps, the ICs are found to be attractive materials f…