Cr3+ electron paramagnetic resonance study of Sn(1-x)CrxO(2) (0.00 <= x <= 0.10)

This paper reports on the liquid-helium-temperature (5 K) electron paramagnetic resonance (EPR) spectra of Cr3+ ions in the nanoparticles of SnO2 synthesized at 600 degrees C with concentrations of 0%, 0.1%, 0.5%, 1%, 1.5%, 2.0%, 2.5%, 3.0%, 5.0%, and 10%. Each spectrum may be simulated as overlap of spectra due to four magnetically inequivalent Cr3+ centers characterized by different values of the spin-Hamiltonian parameters. Three of these centers belong to Cr3+ ions in orthorhombic sites, situated near oxygen vacancies, characterized by very large zero-field splitting parameters D and E, presumably due to the presence of nanoparticles in the samples. The fourth EPR spectrum belongs to the Cr3+ ions situated at sites with tetragonal symmetry, substituting for the Sn4+ ion, characterized by a very small value of D. In addition, there appears a ferromagnetic resonance line due to oxygen defects for samples with Cr3+ concentrations of <= 2.5%. Further, in samples with Cr3+ concentrations of >2.5%, there appears an intense and wide EPR line due to the interactions among the Cr3+ ions in the clusters formed due to rather excessive doping; the intensity and width of this line increase with increasing concentration. The Cr3+ EPR spectra observed in these nanopowders very different from those in bulk SnO2 crystals.

High-resolution methyl edited GFT NMR experiments for protein resonance assignments and structure determination

Three-dimensional (3D) structure determination of proteins is benefitted by long-range distance constraints comprising the methyl groups, which constitute the hydrophobic core of proteins. However, in methyl groups (of Ala, Ile, Leu, Met, Thr and Val) there is a significant overlap of C-13 and H-1 chemical shifts. Such overlap can be resolved using the recently proposed (3,2)D HCCH-COSY, a G-matrix Fourier transform (GFT) NMR based experiment, which facilitates editing of methyl groups into distinct spectral regions by combining their C-13 chemical shifts with that of the neighboring, directly attached, C-13 nucleus. Using this principle, we present three GFT experiments: (a) (4,3)D NOESY-HCCH, (b) (4,3)D H-1-TOCSY-HCCH and (c) (4,3)D C-13-TOCSY-HCCH. These experiments provide unique 4D spectral information rapidly with high sensitivity and resolution for side-chain resonance assignments and NOE analysis of methyl groups. This is exemplified by (4,3)D NOESY-HCCH data acquired for 17.9 kDa non-deuterated cytosolic human J-protein co-chaperone, which provided crucial long-range distance constraints for its 3D structure determination.

Simultaneous acquisition of three NMR spectra in a single experiment for rapid resonance assignments in metabolomics

NMR-based approach to metabolomics typically involves the collection of two-dimensional (2D) heteronuclear correlation spectra for identification and assignment of metabolites. In case of spectral overlap, a 3D spectrum becomes necessary, which is hampered by slow data acquisition for achieving sufficient resolution. We describe here a method to simultaneously acquire three spectra (one 3D and two 2D) in a single data set, which is based on a combination of different fast data acquisition techniques such as G-matrix Fourier transform (GFT) NMR spectroscopy, parallel data acquisition and non-uniform sampling. The following spectra are acquired simultaneously: (1) C-13 multiplicity edited GFT (3,2)D HSQC-TOCSY, (2) 2D H-1- H-1] TOCSY and (3) 2D C-13- H-1] HETCOR. The spectra are obtained at high resolution and provide high-dimensional spectral information for resolving ambiguities. While the GFT spectrum has been shown previously to provide good resolution, the editing of spin systems based on their CH multiplicities further resolves the ambiguities for resonance assignments. The experiment is demonstrated on a mixture of 21 metabolites commonly observed in metabolomics. The spectra were acquired at natural abundance of C-13. This is the first application of a combination of three fast NMR methods for small molecules and opens up new avenues for high-throughput approaches for NMR-based metabolomics.

A dendrimer facilitates resonance energy transfer between hydrophobic aromatic guest molecules in water

A water soluble third generation poly(alkyl aryl ether) dendrimer was examined for its ability to solubilize hydrophobic polyaromatic molecules in water and facilitate non-radiative resonance energy transfer between them. One to two orders of magnitude higher aqueous solubilities of pyrene (PY), perylene (PE), acridine yellow (AY) and acridine orange (AO) were observed in presence of a defined concentration of the dendrimer. A reduction in the quantum yield of the donor PY* emission and a partial decrease in lifetime of the donor excited state revealed the occurrence of energy transfer from dendrimer solubilized excited PY to ground state PE molecules, both present within a dendrimer. The energy transfer efficiency was estimated to be similar to 61%. A cascade resonance energy transfer in a three component system, PY*-to-PE-to-AY and PY*-to-PE-to-AO, was demonstrated through incorporation of AY or AO in the two component PY-PE system. In the three-component system, excitation of PY resulted in emission from AY or AO via a cascade energy transfer process. Careful choice of dye molecules with good spectral overlap and the employment of dendrimer as the medium enabled us to expand absorption-emission wavelengths, from similar to 330 nm to similar to 600 nm in aqueous solution. (C) 2015 Elsevier B.V. All rights reserved.

Electron spin resonance absorption in organic metal polyaniline and its blend with PMMA

The electron spin resonance absorption in the synthetic metal polyaniline (PANI) doped with PTSA and its blend with poly(methylmethacrylate) (PMMA) is investigated in the temperature range between 4.2 and 300 K. The observed line shape follows Dyson's theory for a thick metallic plate with slowly diffusing magnetic dipoles. At low temperatures the line shape become symmetric and Lorentzian when the sample dimensions are small in comparison with the skin depth. The temperature dependence of electron spin relaxation time is discussed. (C) 1999 Elsevier Science Ltd. All rights reserved.

Time-Resolved Resonance Raman Spectroscopic Studies on the Radical Anions of Menaquinone and Naphthoquinone

Quinones and their radical ion intermediates have been much studied by vibrational spectroscopy to understand their structure-function relationships in various biological processes. In this paper, we present a comprehensive analysis of vibrational spectra in the structure-sensitive region of both the naphthoquinone (NQ) and 2-methyl-1,4-naphthoquinone (MQ, menaquinone) radical anions using time-resolved resonance Raman and ab initio studies. Specific vibrational mode assignments have been made to all the vibrational frequencies recorded in the experiment. It is observed that the carbonyl and C-C stretching frequencies show considerable coupling in NQ and MQ radical anions. Further, the asymmetric substitution present in MQ with respect to NQ shows important signatures in the radical anion spectrum. It is concluded that assignments of vibrational frequencies of asymmetrically substituted quinones must take into consideration the influence of asymmetry on structure and reactivity.

Helium Gas Purity Monitor based on Low Frequency Acoustic Resonance

Monitoring gas purity is an important aspect of gas recovery stations where air is usually one of the major impurities. Purity monitors of Katherometric type ate commercially available for this purpose. Alternatively, we discuss here a helium gas purity monitor based on acoustic resonance of a cavity at audio frequencies. It measures the purity by monitoring the resonant frequency of a cylindrical cavity filled with the gas under test and excited by conventional telephone transducers fixed at the ends. The use of the latter simplifies the design considerably. The paper discusses the details of the resonant cavity and the electronic circuit along with temperature compensation. The unit has been calibrated with helium gas of known purities. The unit has a response time of the order of 10 minutes and measures the gas purity to an accuracy of 0.02%. The unit has been installed in our helium recovery system and is found to perform satisfactorily.

Intermittent Dynamics, Stochastic Resonance and Dynamical Heterogeneity in Supercooled Liquid Water

Here we find through computer simulations and theoretical analysis that the low temperature thermodynamic anomalies of liquid water arises from the intermittent fluctuation between its high density and low density forms, consisting largely of 5-coordinated and 4-coordinated water molecules, respectively. The fluctuations exhibit strong dynamic heterogeneity (defined by the four point time correlation function), accompanied by a divergence like growth of the dynamic correlation length, of the type encountered in fragile supercooled liquids. The intermittency has been explained by invoking a two state model often employed to understand stochastic resonance, with the relevant periodic perturbation provided here by the fluctuation of the total volume of the system.

Long range resonance energy transfer from a dye molecule to graphene has (distance)-4 dependence

In our previous report on resonance energy transfer from a dye molecule to graphene [J. Chem. Phys.129, 054703 (2008)], we had derived an expression for the rate of energy transfer from a dye to graphene. An integral in the expression for the rate was evaluated approximately. We found a Yuwaka-type dependence of the rate on the distance. We now present an exact evaluation of the integral involved, leading to very interesting results. For short distances (z < 20 A), the present rate and the previous rate are in good agreement. For larger distances, the rate is found to have a z(-4) dependence on the distance, exactly. Thus we predict that for the case of pyrene on graphene, it is possible to observe fluorescence quenching up to a distance of 300 A. This is in sharp contrast to the traditional fluorescence resonance energy transfer where the quenching is observable only up to 100 A.

Magnetization, magnetotransport and electron magnetic resonance studies of nanoparticles and nanowires of Pr0.5Sr0.5MnO3

In this paper, we present the preparation and characterization of nanoparticles and nanowires of Pr0.5Sr0.5MnO3 (PSMO). The main results of this investigation are as follows: (a) a comparison with the properties of the bulk material shows that the ferromagnetic (FM) transition at 270 K remains unaffected but the anti-ferromagnetic (AFM) transition at TN = 150 K disappears in the nanoparticles, (b) the size induced ground state magnetic phase (below 150 K) is predominantly FM, coexisting with a residual AFM phase, and (c) the temperature dependence of magnetic anisotropy shows complex behaviour, being higher in the nanoparticles at high temperatures and lower at moderately lower temperatures in comparison with the bulk. The results obtained from the extensive magnetization, magnetotransport and electron magnetic resonance studies made on various samples are presented and discussed in detail.

Resonance raman intensity analysis of polyatomic molecules

A time-dependent quantum mechanical (TDQM) method of wavepacket propagation in computing resonance Raman intensities for polyatomic systems, has been developed and demonstrated by applying it tocis-stilbene andtrans-azobenzene. In the case of the former, Raman excitation profiles (REPs) for the various vibrational modes have also been computed. It is observed that the calculated absorption spectrum and the REPs compare very well with the experimental results. A comparison of these results with those of the often semiclassical approach reveals that the TDQM method can be used to study polyatomic systems with as much ease as the semiclassical wavepacket method.

Effect of curve crossing on absorption and resonance Raman spectra: analytical treatment for delta-function coupling in parabolic potentials

We propose an exactly solvable model for the two-state curve-crossing problem. Our model assumes the coupling to be a delta function. It is used to calculate the effect of curve crossing on the electronic absorption spectrum and the resonance Raman excitation profile.

Zeeman effect of chlorine nuclear quadrupole resonance and hydrogen bonding in 2,6-, 2,5- and 3,5-dichlorophenols

The Zeeman effect of chlorine nuclear quadrupole resonance in polycrystalline samples of 2,6-, 2,5 and 3,5-dichlorophenol has been investigated at room temperature in order to study the effect of hydrogen bonding on the electric field gradient asymmetry parameter n. While the two n.q.r. lines in 3,5-dichlorophenol gave an asymmetry parameter of 10%, those in 2,6- and 2,5-dichlorophenol gave different values of n for the two chlorines. The chlorine atom which is ortho to the OH group and involved in hydrogen bonding (i.e., corresponding to the low frequency line) gave an asymmetry parameter of 0.21 in 2,6-dichlorophenol and 0.17 in 2,5-dichlorophenol while the other chlorine (i.e., corresponding to the high frequency line) gave a lower value of 0.12 in 2,6-dichlorophenol and 0.11 in 2,5-dichlorophenol. These values of n are discussed in terms of hydrogen bonding and bond parameters.

A 1h And 13c Magnetic Resonance And Infrared Spectroscopic Study Of Coordinated 2-Aminocyclopentene-1-Dithiocarboxylic Acid And Its S-Methyl Ester

The ligating properties of 2-aminocyclopentene-1-dithiocarboxylic acid and its S-methyl esters were investigated. Complexes with Zn(II), Cd(II) and Hg(II) halides were synthesized and characterized by infrared and proton and carbon-13 NMR studies. The results are concordant with a bidentate coordination of the -CS2 group to the metal ions