Absorption Experiments (absorption + experiment)

Distribution by Scientific Domains

Selected Abstracts

Thermally oxidized palm olein exposure increases triglyceride polymer levels in rat small intestine

Raul Olivero David
Abstract The origin and presence of triglyceride polymers in small intestine have been poorly studied. The present study combined a short in vivo absorption experiment and high-performance size-exclusion chromatography determination. Groups of six male Wistar rats were administered by esophageal probe 1,g/100,g body weight unused palm olein and palm oleins used in 40 and 90 potato frying operations. Small intestines were dissected, cleaned of luminal fat, and analyzed for the presence of triglyceride polymers (oligomers and/or dimers) after 4,h oil administration. The intestinal fat content did not change but the polymers content was positively and significantly correlated (r,=,0.5983; p<0.01) with the amount of polymers present in the oil tested. The small intestine contained 5.05,mg [median and percentile 25 (1.57,mg),percentile 75 (10.40,mg)] of polymers after 4-h exposure to palm olein used for frying 90 times. The results suggested that 2.7,4.9% of the triglyceride polymers administered were present in the small intestine 4,h after ingestion. TBARS levels (p<0.05) and the redox index (oxidized glutathione/total glutathione) (p<0.01) in the small intestine increased significantly after exposure to the palm olein used in 90 frying operations. In conclusion, administration of altered oil increased the presence of resynthesized polymers in the small intestine, thus contributing to small intestine oxidative stress. [source]

Oligonucleotide Duplexes with Tethered Photoreactive Ruthenium(II) Complexes: Influence of the Ligands and Their Linker on the Photoinduced Electron Transfer and Crosslinking Processes of the Two Strands

Stéphanie Deroo
Abstract The photoreactivity of new RuII -oligonucleotide conjugates is investigated in the presence of their complementary strands. The goal is to determine the origins of different effects of parameters that control the photocrosslinking process of the two strands. Therefore, two RuII compounds, either [Ru(tap)3]2+or [Ru(tap)2phen]2+ (tap = 1,4,5,8-tetraazaphenanthrene, phen = 1,10-phenanthroline) with different oxidation powers, were tethered with different linkers to either the 5,- or 3,-phosphate end of the probe strand before hybridization with the complementary strand. These systems were studied by time-resolved emission spectroscopy, UV/Vis absorption experiments, PAGE and MS (ESI) analyses. The best yields of photocrosslinking (45,%) obtained with [Ru(tap)3]2+ tethered to the 3,-position are due to (i) a higher oxidation power of the complex and (ii) its attachment at the 3,-position. Indeed, this tethering favours the interaction of the Ru compound with the duplex and, therefore, inhibits its photodechelation. This work allows better design of sequence-specific DNA photodamaging agents prior to biological applications.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

Photo-initiated energy transfer in nanostructured complexes observed by near-field optical microscopy

G. A. Wurtz
Summary We report an apertureless near-field optical study on nanostructured objects formed by J-aggregates adsorbed on silver (Ag) nanoparticles. Near-field images reveal that the enhanced near-field from the dressed particle's (DP) resonantly excited plasmon oscillation is efficiently absorbed by the J-aggregates. The sensitivity of the near-field images recorded at the harmonics of the probe vibration frequency suggests that the DP is releasing part of the absorbed energy radiatively upon interaction with the probe. The role of the probe in providing this new radiative relaxation channel is further confirmed as fluorescence from the J-aggregates on the particle is detected on the particle location only. We based the interpretation of our results on the near-field optical response from a bare Ag particle excited at the plasmon resonance as well as on far-field emission and transient absorption experiments. [source]

X-ray birefringence and dichroism obtained from magnetic materials

S. W. Lovesey
In the past decade, synchrotron radiation has triggered a surge in studies of the polarization dependence of X-ray beams passing through non-isotropic materials. A vast range of experimental results concerning polarization-dependent absorption (dichroism) and dispersion (birefringence, for example) are available from materials which are either magnetic or exhibit preferred directions due to the local atomic environment. This article aims to bring together the diversity of modern experiments in this field with established methods of optical calculus, in a way that highlights the simplicity of the underlying physics. A useful framework is formed when observable quantities, in the X-ray case, are related to atomic variables of the sample material. Atomic descriptions of absorption spectra with various levels of complexity are considered, and some well documented sum-rules are encountered. The framework is the most general allowed within the electric dipole approximation. By way of illustration, dichroic X-ray absorption by two materials with highly anisotropic properties and magnetic ions with different valence shells are considered; namely, a 3d -transition ion in ferrous niobate, and a lanthanide ion in dysprosium borocarbide. Both materials display interesting magnetic properties that are challenging to interpret at an atomic level of detail, and it is shown how absorption experiments can contribute to resolving some issues. [source]

Measurements of photon interference X-ray absorption fine structure (,XAFS)

Larc Tröger
Experimental data are presented which demonstrate the existence of a fine structure in extended X-ray absorption spectra due to interference effects in the initial photon state (,XAFS). Interference occurs between the incident electromagnetic wave and its coherently scattered waves from neighboring atoms. Using fine platinum and tungsten powders as well as polycrystalline platinum foil, ,XAFS was measured in high-precision absorption experiments at beamline X1 at HASYLAB/DESY over a wide energy range. ,XAFS is observed below and above absorption-edge positions in both transmission and total-electron-yield detection. Based on experimental data it is shown that ,XAFS is sensitive to geometric atomic structure. Fourier-transformed ,XAFS data carry information, comparable with that of EXAFS, about the short-range-order structure of the sample. Sharp structures occur in ,XAFS when a Bragg backscattering condition of the incident X-rays is fulfilled. They allow precise measurement of long-range-order structural information. Measured data are compared with simulations based on ,XAFS theory. Although ,XAFS structures are similarly observed in two detection techniques, the importance of scattering off the sample for the measurements needs to be investigated further. Disentangling ,XAFS, multielectron photoexcitations and atomic XAFS in high-precision measurements close to absorption edges poses a challenge for future studies. [source]

A Photodissociation Reaction: Experimental and Computational Study of 2-Hydroxy-2,2-dimethylacetophenone,

X. Allonas
ABSTRACT The photophysical parameters controlling the cleavage process of 2-hydroxy-2,2-dimethylacetophenone (HDMA) were investigated in detail. Time-resolved picosecond absorption experiments show that the formation of the triplet state occurs within 20 ps after excitation and decays within hundreds of picoseconds depending on the solvent polarity. Molecular modeling reveals that three stable conformations exist in the ground state, the most stable one exhibiting an intramolecular hydrogen bond that modifies the electronic properties of the molecule. This explains quite well the steady-state absorption properties. The conformation of the most stable triplet state is twisted by 180° with respect to the ground state. Computation of the potential energy surface along the molecular coordinate for the dissociation reaction evidences an electronic state crossing yielding a final ,,* state, in perfect agreement with the state correlation diagram. Optimization of the transition state allows the calculation of the activation energy and the use of the transition-state theory leads to an estimate of 100 ps for the cleavage process in the gas phase. Single-point energy calculations using a solvent model predict an increase of the dissociation rate constant with the increase of the solvent polarity, in good agreement with the value deduced from kinetic measurements. [source]

Environmental Effects on the Photochemistry of A2-E, a Component of Human Retinal Lipofuscin,

Laura Ragauskaite
ABSTRACT Several retinal dystrophies are associated with the accumulation of lipofuscin, a pigment mixture, in the retinal pigment epithelium (RPE). One of the major fluorophores of this mixture has been identified as the bis-retinoid pyridinium compound, A2-E. Because this compound absorbs incident radiation that is transmitted by the anterior segment of the human eye, photophysical and photochemical studies were performed to determine if A2-E could photosensitize potentially damaging reactions. Steady-state fluorescence measurements indicate that the fluorescence emission maximum and quantum yield are very sensitive to the chemical environment and a correlation between these two parameters and the solvent dielectric constant is observed. Time-resolved absorption experiments of A2-E in pure organic solvents showed no formation of transient species on the timescale of our experiments. However, when these measurements were repeated for A2-E in Triton X-100 micelles, a short-lived (,, 14 ,s), weak absorption was observed. This species is quenched by oxygen (k= 2 × 109M,1 s,1) and by the addition of the antioxidants, cysteine and N,N,N,,N, -tetramethylphenylenediamine. Quenching of this species by 2,3,5-trimethylhydroquinone results in the formation of the 2,3,5-trimethylsemiquinone free radical and an increase in yield of the A2-E,derived species. Sensitization of the A2-E triplet excited state indicates that the species observed in micelles upon direct excitation is not consistent with the triplet excited state. Based on these data we tentatively assign this absorption to a free radical. In the RPE these initial processes can ultimately lead to damage to the tissue through the formation of peroxides and other oxidized species. [source]

Characterization of Fe 3d states in CuFeS2 by resonant X-ray emission spectroscopy

Katsuaki Sato
Abstract Resonant X-ray emission spectroscopy (RXES) experiments were carried out in a single crystal of chalcopyrite CuFeS2, an antiferromagnetic semiconductor with a golden lustre, to unravel the overlapping d,d and charge-transfer transitions extending well above the absorption edge, which cannot be observed by conventional optical absorption experiments. The observed RXES spectra have been analyzed by means of cluster-model calculation with configuration interaction, which leads to the conclusion that CuFeS2 is a Haldane,Anderson insulator with a negative value of charge transfer energy, , = ,3 eV. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]

Application of wavelength-resolved optically-detected XAS methods to phase-segregated silicates

N. R. J. Poolton
Abstract Wavelength-resolved optically-detected X-ray absorption experiments are described that monitor the emission from naturally occurring phase-exsolved aluminosilicate feldspars, when exciting across the Ca and K L2,3 core levels. The results from a selection of example cases are presented that demonstrate the power of the technique in examining the structural and optical properties of phase segregated materials that could not easily be achievable by other methods. The results highlight that in these materials, extrinsic point defects such as Mn2+ and Fe3+ can also become preferentially associated with particular exsolved phases. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]

Modified suspension-PVC particles as absorbents of ortho -dichlorobenzene from water

M. Shach-Caplan
Abstract Modified porous PVC particles are studied as absorbents of o-dichlorobenzene (DCB), from water. The modified particles were produced by an in-situ stabilizer-free polymerization/crosslinking of a monomer/crosslinker/peroxide solution absorbed within commercial porous suspension-type PVC particles. The modifying monomers used include styrene with divinyl benzene (DVB) as a crosslinking comonomer, methyl methacrylate (MMA), butyl acrylate (BA), or ethylhexyl acrylate (EHA) with ethylene glycol dimethacrylate (EGDMA) as a crosslinking comonomer. The effect of the nature of the monomers, morphology, porosity, surface area and composition of the modified PVC particles on DCB absorption was studied. Batch experiments (absorption rate and isotherms) were used to screen the PVC absorbents on the basis of absorption rate and absorption capacity. Continuous absorption column experiments were conducted to study the parameters characterizing the absorption process. Both the unmodified and modified PVC particles absorb DCB from water. The PBA and PEHA-modified PVC particles approach equilibrium capacity faster and have greater absorption capacity than neat PVC, PS-modified PVC and PMMA-modified PVC particles. The absorption characteristics are influenced by the modifying polymer's Tg. The rubbery nature of PBA and PEHA yields better absorption in spite of the significantly lower surface area and porosity obtained in the modified PVC particles. Thus, indicating that fast adsorption followed by bulk absorption of DCB is taking place. A clear influence of the crosslinking effect was not established. The continuous absorption experiments were found more efficient than the batch absorption experiments. Copyright © 2003 John Wiley & Sons, Ltd. [source]

Photochemical Z,E Isomerization of a Hemithioindigo/Hemistilbene ,-Amino Acid

CHEMPHYSCHEM, Issue 11 2007
Thorben Cordes
Abstract The molecule HTI, which combines hemithioindigo and hemistilbene molecular parts, allows reversible switching between two isomeric states. Photochromic behaviour of the HTI molecule is observed by irradiation with UV/Vis light. The photochemical reaction, a Z/E isomerization around the central double bond connecting the two molecular parts, is investigated by transient absorption and emission spectroscopy. For a special HTI molecule, namely, an ,-amino acid, the Z,E isomerization process occurs on a timescale of 30 ps. In the course of the reaction fast processes on the 1,10 ps timescale are observed which point to motions of the molecule on the potential-energy surface of the excited state. The combination of transient absorption experiments in the visible spectral range with time-resolved fluorescence and infrared measurements reveal a photochemical pathway with three intermediate states. Together with a theoretical modelling procedure the experiments point to a sequential reaction scheme and give indications of the nature of the involved intermediates. [source]