The Raman spectra of serine and 3,3-dideutero-serine in aqueous solution

The Raman spectra of serine [[alpha]-amino-[beta]-hydroxypropionic acid; HOCH2CH(NH3)+COO-] and 3,3-dideutero-serine [HOCD2CH(NH3)+COO-] in aqueous solution were studied in the range 4000-300 cm-1. The data obtained for the deuterated compound are novel and provide compelling evidence that previously reported assignments for the undeuterated amino acid should be revised.http://www.sciencedirect.com/science/article/B6THW-4KNMB16-1/1/19da7b30f32b5efeacb053228a66c4a

Infrared and Raman spectroscopic characterization of the hydrogen-bonding network in l-serine crystal

The IR spectra (4000-400 cm-1) of neat and isotopically substituted (ND/OD <= 10% D and [congruent with]30% D) polycrystalline l-serine ([alpha]-amino-[beta]-hydroxypropionic acid; HO-CH2-CH(NH3)+-COO-) were recorded in the temperature range 300-10 K and assigned. The isotopic-doping/low-temperature methodology, which allows for decoupling of individual proton vibrational modes from the crystal bulk vibrations, was used for estimating the lengths and energies of the different H-bonds present in l-serine crystal. To this end, the frequency shifts observed in both the NH/OH stretching and out-of-plane bending spectral regions (relatively to reference values for these vibrations in non-hydrogen-bonded l-serine molecules) were used, together with previously developed empirical correlations between these spectral parameters and the H-bond properties. In addition, the room-temperature Raman spectrum (4000-150 cm-1) of a single crystal of neat l-serine was also recorded and interpreted. A systematic comparison was made between the spectroscopic data obtained currently for l-serine and previously for dl-serine, revealing that the vibrational spectra of the two crystals reflect well the different characteristics of their hydrogen-bond networks, and also correlate accurately with the different susceptibility of the two crystals to pressure-induced strain.http://www.sciencedirect.com/science/article/B6THW-4K4WMR3-2/1/211ac428c09ebc9eb45cf3b81d93fcb

Low-temperature infrared spectra and hydrogen bonding in polycrystalline dl-serine and deuterated derivatives

The FT-IR spectra of polycrystalline dl-serine [[alpha]-amino-[beta]-hydroxypropionic acid; HO-CH2-CH(NH3)+-COO-] and isotopically substituted [ND/ODAlcohol (90% D); CD2 (>98% D)] dl-serine were recorded in the range 4000-500 cm-1 in the temperature range 300-10 K, and fully assigned. The isotopic-doping/low-temperature methodology, which allows for decoupling of individual proton vibrational modes from the crystal bulk vibrations, was used to estimate the energies of the different H-bonds present in dl-serine crystal. To this end, the frequency shifts observed in both the NH/OH stretching and out-of-plane bending spectral regions (relatively to reference values for these vibrations in non-hydrogen-bonded dl-serine molecules) were used, together with previously developed empirical correlations. The results are compared with available structural data on this amino acid.http://www.sciencedirect.com/science/article/B6THW-4J91R39-2/1/f8f35f435466c8a5204879d330cbade

Preferred Conformers and Photochemical (λ > 200 nm) Reactivity of Serine and 3,3-Dideutero-Serine In the Neutral Form

A systematic investigation of the conformational potential energy surface of neutral serine [HOCH2CHNH2COOH] and 3,3-dideutero-serine [HOCD2CHNH2COOH] was undertaken, revealing the existence of 61 different minima. The structures and vibrational spectra of the most stable conformers, which were estimated to have relative energies within 7 kJ mol-1 and account for ca. 93% of the total conformational population at room temperature, were calculated at both the MP2 and DFT/BLYP levels of theory with the 6-311++G(d,p) basis-set and used to interpret the spectroscopic data obtained for the compounds isolated in low-temperature inert matrixes. The assignment of the main spectral infrared features observed in the range 4000−400 cm-1 to the most stable conformers of serine was undertaken. In addition, UV irradiation (λ > 200 nm) of the matrix-isolated compounds was also performed, leading to decarboxylation, which was found to be strongly dependent on the conformation assumed by the reactant molecule

Intrinsic exciton-exciton coupling in GaN-based quantum dots: Application to solid-state quantum computing

In this Rapid Communication we propose to use GaN-based quantum dots as building blocks for solid-state quantum-computing devices. The existence of a strong built-in electric field induced by the spontaneous polarization and by the piezoelectricity is exploited to generate entangled few-exciton states in coupled quantum dots without resorting to external fields. More specifically, we shall show how the built-in field induces intrinsic exciton-exciton coupling, which can be used to realize basic quantum information processing on a sub-picosecond time scale

Low temperature matrix-isolation and solid state vibrational spectra of tetrazole

Infrared spectra of tetrazole (CN isolated in an argon matrix (T \10 K) and in the solid state (at room 4H2) temperature) were investigated. In the crystalline phase, tetrazole exists in its 1H-tautomeric form and new assignments of the vibrational spectra (both infrared and Raman) of this phase are presented. The infrared spectrum of the matrix-isolated monomeric form of tetrazole is now reported and assigned for the Ðrst time, showing essentially the expected signature of the 2H-tetrazole tautomer. From relative intensities of the infrared bands ascribable to the two tautomers, the amount of the 1H-tautomer in the argon matrix was estimated to be ca. 10% of the most stable tautomer. Assuming that gas-phase relative populations of the two tautomers could be efficiently trapped in the argon matrix during deposition, the energy di erence between 1H- and 2H-tetrazole (*E was then obtained. The experimental value, kJ mol~1, 1Hh2H) *E1Hh2H\6.95^1.50 now determined for the Ðrst time, compares fairly well with the theoretical predictions for the molecule in vacuum (e.g., the zero point vibrational energy corrected energy di erence obtained at the B3LYP/6È31G* level of theory is 9.96 kJ mol~1)

Low temperature matrix-isolation and solid state vibrational spectra of 5-chlorotetrazole

The vibrational spectra of 5-chlorotetrazole (CN4HCl) isolated in an argon matrix (T ¼ 8.5 K) and in the solid state (at room temperature) were studied. The infrared spectrum of monomers of 5-chlorotetrazole isolated in an argon matrix agrees well with the spectrum predicted theoretically (DFT(B3LYP)/6-31G*) for the 2Htautomer of the compound. The bands assigned to the 1H-tautomer appear in the experimental spectrum as very low intensity features. Based on the relative intensities of the bands in the spectra of the 1H- and 2Htautomers, the relative amount of the first tautomer in this matrix can be estimated as 1%. Three matrixes were deposited with different nozzle temperatures and the enthalpy difference between the tautomers DH ¼ 8.0 kJ mol 1 was estimated using the Van’t Hoff relation. The internal energy difference between the two tautomers was predicted theoretically (DFT B3LYP/6-31G*) as 12.6 kJ mol 1. This is in reasonable agreement with experimental observations. In the crystalline phase, this compound exists in its 1H-tautomeric form. Accordingly, the IR spectrum of polycrystalline 5-chlorotetrazole is well reproduced by the spectrum predicted theoretically for the 1H- tautomer

Association of increased levels of homocysteine and peripheral arterial disease in a Japanese-Brazilian population

Objectives. Our aim was to evaluate the possible association between homocysteine levels and peripheral arterial disease (PAD) in a population-based study of Japanese-Brazilians.Materials and methods. This cross-sectional study was derived from a population-based survey on the prevalence of diabetes and associated diseases conducted in Japanese-Brazilians. A total of 1330 male and female subjects aged >= 30 years were submitted to clinical examination and laboratory procedures including homocysteine measurement. the ankle-brachial index (ABI) was calculated, subjects with ABI values <0.9 were diagnosed with PAD. the evaluable population included 1008 subjects. Logistic regression was used taking PAD as the dependent variable.Results. Mean age of the population was 56.5 years and overall prevalence of PAD was 20%. A worse cardiovascular profile was found in male patients, including significantly higher homocysteine levels (11.9 +/- 1.8 vs. 9.1 +/- 1.1 mu mol/L, p < 0.001). Men with PAD had higher prevalence rates of hyperhomocysteinemia compared to women (22.7% vs 7.6%). Univariate analysis showed an odds ratio of hyperhomocysteinemia for PAD of 1.51 [1.02-2.25] in men and 1. 69 [1.06-2.68] in women. After adjustment for other cardiovascular risk factors, higher levels of homocysteine were only significantly related to PAD in men.Conclusion. in a Japanese-Brazilian population, elevated levels of homocysteine are associated with PAD in men. Prospective studies are necessary to confirm this finding.Universidade Federal de São Paulo, Dept Surg, Postgrad Course Cardiac Vasc & Thorac Surg, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Surg, Div Vasc Surg, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Pediat, São Paulo, BrazilUniv São Paulo, Sch Publ Hlth, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Surg, Postgrad Course Cardiac Vasc & Thorac Surg, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Surg, Div Vasc Surg, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Pediat, São Paulo, BrazilWeb of Scienc

Intersymbol and Intercarrier Interference in OFDM Systems: Unified Formulation and Analysis

A unified matrix formulation is presented for the analysis of intersymbol and intercarrier interference in orthogonal frequency-division multiplexing (OFDM) systems. The proposed formulation relies on six parameters and allows studying various schemes, including those with windowing in the transmitter and/or in the receiver (called windowed OFDM systems), which may add cyclic suffix and/or cyclic prefix (CP), besides the conventional CP-OFDM. The proposed framework encompasses seven different OFDM systems. It considers the overlap-and-add procedure performed in the transmitter of windowed OFDM systems, being jointly formulated with the channel convolution. The intersymbol and intercarrier interference, caused when the order of the channel impulse response is higher than the number of CP samples, is characterized. A new equivalent channel matrix that is useful for calculating both the received signal and the interference power is defined and characterized. Unlike previous works, this new channel matrix has no restrictions on the length of the channel impulse response, which means that the study is not constrained to the particular case of two or three data blocks interfering in the received signal. Theoretical expressions for the powers of three different kinds of interference are derived. These expressions allow calculating the signal-to-interference-plus-noise ratio, useful for computing the data rate of each OFDM system. The proposed formulation is applied to realistic examples, showing its effectiveness through comparisons based on numerical performance assessments of the considered OFDM systems