Near infrared spectroscopy as a rapid tool to measure volatile aroma compounds in Riesling wine: Possibilities and limits

Volatile chemical compounds responsible for the aroma of wine are derived from a number of different biochemical and chemical pathways. These chemical compounds are formed during grape berry metabolism, crushing of the berries, fermentation processes (i.e. yeast and malolactic bacteria) and also from the ageing and storage of wine. Not surprisingly, there are a large number of chemical classes of compounds found in wine which are present at varying concentrations (ng L-1 to mg L-1), exhibit differing potencies, and have a broad range of volatilities and boiling points. The aim of this work was to investigate the potential use of near infrared (NIR) spectroscopy combined with chemometrics as a rapid and low-cost technique to measure volatile compounds in Riesling wines. Samples of commercial Riesling wine were analyzed using an NIR instrument and volatile compounds by gas chromatography (GC) coupled with selected ion monitoring mass spectrometry. Correlation between the NIR and GC data were developed using partial least-squares (PLS) regression with full cross validation (leave one out). Coefficients of determination in cross validation (R 2) and the standard error in cross validation (SECV) were 0.74 (SECV: 313.6 μg L−1) for esters, 0.90 (SECV: 20.9 μg L−1) for monoterpenes and 0.80 (SECV: 1658 ?g L-1) for short-chain fatty acids. This study has shown that volatile chemical compounds present in wine can be measured by NIR spectroscopy. Further development with larger data sets will be required to test the predictive ability of the NIR calibration models developed.

Quantitative assessment of total phenol contents of European oak (Quercus petraea and Quercus robur) by diffuse reflectance NIR spectroscopy on solid wood surfaces

Near infrared spectroscopy (NIRS) combined with multivariate analysis techniques was applied to assess phenol content of European oak. NIRS data were firstly collected directly from solid heartwood surfaces: in doing so, the spectra were recorded separately from the longitudinal radial and the transverse section surfaces by diffuse reflectance. The spectral data were then pretreated by several pre-processing procedures, such as multiplicative scatter correction, first derivative, second derivative and standard normal variate. The tannin contents of sawmill collected from the longitudinal radial and transverse section surfaces were determined by quantitative extraction with water/methanol (1:4, by vol). Then, total phenol contents in tannin extracts were measured by the Folin-Ciocalteu method. The NIR data were correlated against the Folin-Ciocalteu results. Calibration models built with partial least squares regression displayed strong correlation - as expressed by high determination correlation coefficient (r2) and high ratio of performance to deviation (RPD) - between measured and predicted total phenols content, and weak calibration and prediction errors (RMSEC, RMSEP). The best calibration was provided with second derivative spectra (r2 value of 0.93 for the longitudinal radial plane and of 0.91 for the transverse section plane). This study illustrates that the NIRS technique when used in conjunction with multivariate analysis could provide reliable, quick and non-destructive assessment of European oak heartwood extractives.

Electron energy loss spectroscopy (EELS) of H2O, H2S, H2Se and H2Te

Electronic excitation in H2O, H2S, H2Se and H2Te molecules has been studied by the EELS technique. Spectra of H2S and H2Se are remarkably similar with the 1b1-nd transition most intense. The intensity of the first transition 1b1-nsa1 decreases through H2O to H2Se and this transition is absent in H2Te. Transitions observed by EELS have been compared with optical absorption studies. A correlation diagram of the occupied and the excited states has been provided for these four molecules by making use of UVPES and EELS.

Correlation between NIRS generated and chemically measured feed quality data in barley (Hordeum vulgare), and potential use in QTL analysis identification

A study was performed to investigate the value of near infrared reflectance spectroscopy (NIRS) as an alternate method to analytical techniques for identifying QTL associated with feed quality traits. Milled samples from an F6-derived recombinant inbred Tallon/Scarlett population were incubated in the rumen of fistulated cattle, recovered, washed and dried to determine the in-situ dry matter digestibility (DMD). Both pre- and post-digestion samples were analysed using NIRS to quantify key quality components relating to acid detergent fibre, starch and protein. This phenotypic data was used to identify trait associated QTL and compare them to previously identified QTL. Though a number of genetic correlations were identified between the phenotypic data sets, the only correlation of most interest was between DMD and starch digested (r = -0.382). The significance of this genetic correlation was that the NIRS data set identified a putative QTL on chromosomes 7H (LOD = 3.3) associated with starch digested. A QTL for DMD occurred in the same region of chromosome 7H, with flanking markers fAG/CAT63 and bPb-0758. The significant correlation and identification of this putative QTL, highlights the potential of technologies like NIRS in QTL analysis.

Metal-insulator transition of naxwo3 studied by angle-resolved photoemission spectroscopy

The electronic structure of sodium tungsten bronzes NaxWO3 is investigated by high-resolution angle-resolved photoemission spectroscopy (ARPES). The ARPES spectra measured in both insulating and metallic phases of NaxWO3 reveals the origin of metal-insulator transition (MIT) in sodium tungsten bronze system. It is found that in insulating NaxWO3 the states near the Fermi level (E-F) are localized due to the strong disorder caused by the random distribution of Na+ ions in WO3 lattice. Due to the presence of disorder and long-range Coulomb interaction of conduction electrons, a soft Coulomb gap arises, where the density of states vanishes exactly at E-F. In the metallic regime the states near E-F are populated and the Fermi level shifts upward rigidly with increasing electron doping (x). Volume of electron-like Fermi surface (FS) at the Gamma(X) point of the Brillouin zone gradually increases with increasing Na concentration due to W 5d t(2g) band filling. A rigid shift of the Fermi energy is found to give a qualitatively good description of the Fermi surface evolution. As we move from bulk-sensitive to more surface sensitive photon energy, we found the emergence of Fermi surfaces at X(M) and M(R) point similar to the one at the Gamma(X) point in the metallic regime, suggesting that the reconstruction of surface was due to rotation/deformation of WO6 octahedra.

The effects of manganese content and mould size on abrasion and slurry erosion behaviour of chromium-manganese iron systems investigated by positron lifetime spectroscopy

Abrasion and slurry erosion behaviour of chromium-manganese iron samples with chromium (Cr) in the range similar to 16-19% and manganese (Mn) at 5 and 10% levels have been characterized for hardness followed by microstructural examination using optical and scanning electron microscopy. Positron lifetime studies have been conducted to understand the defects/microporosity influence on the microstructure. The samples were heat treated and characterized to understand the structural transformations in the matrix. The data reveals that hardness decreased with increase in Mn content from 5 to 10% in the first instance and then increase in the section size in the other case, irrespective of the sample conditions. The abrasion and slurry erosion losses show increase with increase in the section size as well as with increase in Mn content. The positron results show that as hardness increases from as-cast to heat treated sample, the positron trapping rate and hence defect concentration showed opposite trend as expected. So a good correlation between defects concentration and the hardness has been observed. These findings also corroborate well with the microstructural features obtained from optical and scanning electron microscopy. (C) 2009 Elsevier B. V. All rights reserved.

Correlation of Oxygen Storage Capacity and Structural Distortion in Transition-Metal-, Noble-Metal-, and Rare-Earth-Ion-Substituted CeO2 from First Principles Calculation

Oxygen storage/release (OSC) capacity is an important feature common to all three-way catalysts to combat harmful exhaust emissions. To understand the mechanism of improved OSC for doped CeO2, we undertook the structural investigation by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H-2-TPR (temperature-programmed hydrogen reduction) and density functional theoretical (DFT) calculations of transition-metal-, noble-metal-, and rare-earth (RE)-ion-substituted ceria. In this report, we present the relationship between the OSC and structural changes induced by the dopant ion in CeO2. Transition metal and noble metal ion substitution in ceria greatly enhances the reducibility of Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu, Pd, Pt, Ru), whereas rare-earth-ion-substituted Ce(1-x)A(x)O(2-delta) (A = La, Y) have very little effect in improving the OSC. Our simulated optimized structure shows deviation in cation oxygen bond length from ideal bond length of 2.34 angstrom (for CeO2). For example, our theoretical calculation for Ce28Mn4O62 structure shows that Mn-O bonds are in 4 + 2 coordination with average bond lengths of 2.0 and 3.06 angstrom respectively. Although the four short Mn-O bond lengths spans the bond distance region of Mn2O3, the other two Mn-O bonds are moved to longer distances. The dopant transition and noble metal ions also affects Ce coordination shell and results in the formation of longer Ce-O bonds as well. Thus longer cation oxygen bonds for both dopant and host ions results in enhanced synergistic reduction of the solid solution. With Pd ion substitution in Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu) further enhancement in OSC is observed in H-2-TPR. This effect is reflected in our model calculations by the presence of still longer bonds compared to the model without Pd ion doping. The synergistic effect is therefore due to enhanced reducibility of both dopant and host ion induced due to structural distortion of fluorite lattice in presence of dopant ion. For RE ions (RE = Y, La), our calculations show very little deviation of bonds lengths from ideal fluorite structure. The absence of longer Y-O/La-O and Ce-O bonds make the structure much less susceptible to reduction.

Excitation and correlation of N-14 overtone transitions and measurement of heteronuclear dipolar coupling using DAPT

For studying systems containing nitrogen, limited use of N-14 NMR spectroscopy has been made because of the large quadrupolar interaction experienced by the N-14 nucleus and the absence of a central transition. To overcome the above problem, use of overtone spectroscopy has been suggested. Though this approach has limited applicability for powder samples due to second order quadrupole broadening, it is useful for studying oriented samples and single crystals. Here, we demonstrate the use of the recently proposed dipolar assisted polarization transfer (DAPT) pulse scheme for exciting the overtone transitions. The pulse sequence may also be utilized as a two-dimensional experiment to obtain H-1-N-14 dipolar couplings and H-1 chemical shifts. (C) 2010 Elsevier B.V. All rights reserved.

Diffusing wave spectroscopy of dense colloids: Liquid, crystal and glassy states

Using intensity autocorrelation of multiply scattered light, we show that the increase in interparticle interaction in dense, binary colloidal fluid mixtures of particle diameters 0.115µm and 0.089µm results in freezing into a crystalline phase at volume fraction? of 0.1 and into a glassy state at?=0.2. The functional form of the field autocorrelation functiong (1)(t) for the binary fluid phase is fitted to exp[??(6k 0 2 D eff t)1/2] wherek 0 is the magnitude of the incident light wavevector and? is a parameter inversely proportional to the photon transport mean free pathl*. TheD eff is thel* weighted average of the individual diffusion coefficients of the pure species. Thel* used in calculatingD eff was computed using the Mie theory. In the solid (crystal or glass) phase, theg (1)(t) is fitted (only with a moderate success) to exp[??(6k 0 2 W(t))1/2] where the mean-squared displacementW(t) is evaluated for a harmonically bound overdamped Brownian oscillator. It is found that the fitted parameter? for both the binary and monodisperse suspensions decreases significantly with the increase of interparticle interactions. This has been justified by showing that the calculated values ofl* in a monodisperse suspension using Mie theory increase very significantly with the interactions incorporated inl* via the static structure factor.

Biaxial strain induced electrical inhomogenities and phase separation in the ferromagnetic metallic phase in thin films of La0.7Ca0.3MnO3: A scanning tunneling potentiometry/spectroscopy study

We have investigated the effect of biaxial strain on local electrical/electronic properties in thin films of La0.7Ca0.3MnO3 with varying degrees of biaxial strain in them. The local electrical properties were investigated as a function of temperature by scanning tunneling spectroscopy (STS) and scanning tunneling potentiometry (STP), along with the bulk probe like conductance fluctuations.The results indicate a positive correlation between the lattice mismatch biaxial strain and the local electrical/electronic inhomogenities observed in the strained sample. This is plausible since the crystal structure of the manganites interfere rather strongly with the magnetic/electronic degrees of freedom. Thus even a small imbalance (biaxial strain) can induce significant changes in the electrical properties of the system.

Spin State Selective Excitation of Single Quantum Transitions Using Multiple Quantum Spectroscopy- an Aid to Analyse Complex Proton NMR spectra of Oriented Molecules

NMR spectra of molecules oriented in liquid-crystalline matrix provide information on the structure and orientation of the molecules. Thermotropic liquid crystals used as an orienting media result in the spectra of spins that are generally strongly coupled. The number of allowed transitions increases rapidly with the increase in the number of interacting spins. Furthermore, the number of single quantum transitions required for analysis is highly redundant. In the present study, we have demonstrated that it is possible to separate the subspectra of a homonuclear dipolar coupled spin system on the basis of the spin states of the coupled heteronuclei by multiple quantum (MQ)−single quantum (SQ) correlation experiments. This significantly reduces the number of redundant transitions, thereby simplifying the analysis of the complex spectrum. The methodology has been demonstrated on the doubly 13C labeled acetonitrile aligned in the liquid-crystal matrix and has been applied to analyze the complex spectrum of an oriented six spin system.

Time-Resolved Resonance Raman Spectroscopy: Exploring Reactive Intermediates

The study of reaction mechanisms involves systematic investigations of the correlation between structure, reactivity, and time. The challenge is to be able to observe the chemical changes undergone by reactants as they change into products via one or several intermediates such as electronic excited states (singlet and triplet), radicals, radical ions, carbocations, carbanions, carbenes, nitrenes, nitrinium ions, etc. The vast array of intermediates and timescales means there is no single ``do-it-all'' technique. The simultaneous advances in contemporary time-resolved Raman spectroscopic techniques and computational methods have done much towards visualizing molecular fingerprint snapshots of the reactive intermediates in the microsecond to femtosecond time domain. Raman spectroscopy and its sensitive counterpart resonance Raman spectroscopy have been well proven as means for determining molecular structure, chemical bonding, reactivity, and dynamics of short-lived intermediates in solution phase and are advantageous in comparison to commonly used time-resolved absorption and emission spectroscopy. Today time-resolved Raman spectroscopy is a mature technique; its development owes much to the advent of pulsed tunable lasers, highly efficient spectrometers, and high speed, highly sensitive multichannel detectors able to collect a complete spectrum. This review article will provide a brief chronological development of the experimental setup and demonstrate how experimentalists have conquered numerous challenges to obtain background-free (removing fluorescence), intense, and highly spectrally resolved Raman spectra in the nanosecond to microsecond (ns-mu s) and picosecond (ps) time domains and, perhaps surprisingly, laid the foundations for new techniques such as spatially offset Raman spectroscopy.

Strong electron correlation of Re 5d electrons in Ca2FeReO6

We have investigated the electronic structure of a double perovskite Ca2FeReO6 using photoemission spectroscopy and LDA+U bandstructure calculations. Small spectral weight at the Fermi level observed above the metal–insulator transition temperature, gradually disappears with decreasing T, forming a small (≤50 meV) energy gap. To reproduce this small energy gap, we require a very large effective U (Ueff) for Re (4 eV) in addition to Ueff of 4 eV for Fe. From simple calculations in terms of the ionic radii, we demonstrate that the Fe–Re bandwidth is smaller than that of Fe–Mo in Ca2FeMoO6, which should yield a strong electron correlation in the Re 5d bands.

Theoretical description of coherent doublon creation via lattice modulation spectroscopy

Using a recently developed strong-coupling method, we present a comprehensive theory for doublon production processes in modulation spectroscopy of a three-dimensional system of ultracold fermionic atoms in an optical lattice with a trap. The theoretical predictions compare well to the experimental time traces of doublon production. For experimentally feasible conditions, we provide a quantitative prediction for the presence of a nonlinear ``two-photon'' excitation at strong modulation amplitudes.

Correlation between local structural dynamics of proteins inferred from NMR ensembles and evolutionary dynamics of homologues of known structure

Conformational changes in proteins are extremely important for their biochemical functions. Correlation between inherent conformational variations in a protein and conformational differences in its homologues of known structure is still unclear. In this study, we have used a structural alphabet called Protein Blocks (PBs). PBs are used to perform abstraction of protein 3-D structures into a 1-D strings of 16 alphabets (a-p) based on dihedral angles of overlapping pentapeptides. We have analyzed the variations in local conformations in terms of PBs represented in the ensembles of 801 protein structures determined using NMR spectroscopy. In the analysis of concatenated data over all the residues in all the NMR ensembles, we observe that the overall nature of inherent local structural variations in NMR ensembles is similar to the nature of local structural differences in homologous proteins with a high correlation coefficient of .94. High correlation at the alignment positions corresponding to helical and beta-sheet regions is only expected. However, the correlation coefficient by considering only the loop regions is also quite high (.91). Surprisingly, segregated position-wise analysis shows that this high correlation does not hold true to loop regions at the structurally equivalent positions in NMR ensembles and their homologues of known structure. This suggests that the general nature of local structural changes is unique; however most of the local structural variations in loop regions of NMR ensembles do not correlate to their local structural differences at structurally equivalent positions in homologues.