Selective detection of single-enantiomer spectrum of chiral molecules aligned in the polypeptide liquid crystalline solvent: Transition selective one-dimensional H-1-H-1 COSY

One-dimensional (1D) proton NMR spectra of enantiomers are generally undecipherable in chiral orienting poly-gamma-benzyl-L-glutamate (PBLG)/CDCl3 solvent. This arises due to large number of couplings, in addition to superposition of spectra from both the enantiomers, severely hindering the H-1 detection. On the other hand in the present study the benefit is derived front the presence of several couplings among the entire network of interacting protons. Transition selective 1D H-1-H-1 correlation experiment (1D-COSY) which utilizes the Coupling assisted transfer of magnetization not only for unraveling the overlap but also for the selective detection of enantiopure spectrum is reported. The experiment is simple, easy to implement and provides accurate eanantiomeric excess in addition to the determination of the proton-proton couplings of an enantiomer within a short experimental time (few minutes). (C) 2009 Elsevier Inc. All rights reserved.

Raman spectrum of rubidium iodide

Raman spectrum of rubidium iodide has been recorded for the first time using the resonance radiation of mercury (λ 2537 ) as the exciter. The frequencies of the 24p limiting modes (p = 2, the number of non-equivalent atoms in the unit cell), postulated by Raman in 1943, which correspond to the frequencies from the critical points Γ, L and X, have been worked out using the shell model of Cochran, taking into account the nearest and the next-nearest neighbour short-range interactions and the polarization of both the ions. The observed Raman lines have been assigned to the overtones and the combinations of the phonon branches from Γ, L and X.

Raman spectrum of crystalline aminosulphonic acid

The Raman spectrum of a single crystal of sulphamic acid has been recorded withλ 2537 excitation. Thirty-eight lines have been observed, of which twenty-nine have been recorded for the first time. Seven Raman lines with shifts in the region 50–155 cm.−1 have been assigned to the lattice oscillations, two at 177 and 240 cm.−1 have been attributed to the low-frequency hydrogen bond vibrations.. The splitting of the degenerate modes and the appearance of N-H....O bonded stretching vibrations are consistent with the structural data which expect the presence of the free molecule as a Zwitter ion with only slight distortion from C3v symmetry.

Raman spectrum of crystalline cadmium acetate dihydrate

The Raman spectrum of a single crystal of cadmium acetate dihydrate has been recorded for the first time using λ 2537 excitation. Twenty-three lines have been observed out of which ten have been attributed to the internal oscillations of the acetate ion, nine to the lattice modes, two to low-frequency hydrogen bond vibrations. A line at 308 cm.−1 and the continuum 3250–3560 cm.−1 have been assigned to the Cd-O6 and internal vibrations of the water molecules.

Raman spectrum of sodium iodide

Raman spectrum of a single crystal of sodium iodide has been recorded for the first time using lambda 2537 excitation. The general features of the spectrum are discussed in the light of the existing theories on the dynamics of the alkali halides. The authors wish to thank Professor D.Y.Phadke of the Tata Institute of Fundamental Research, Bombay, for presenting the crystal of Nal used in the present investigation.

Raman spectrum of lanthanum ethyl sulphate nonahydrate

Raman spectrum of a single crystal of lanthanum ethyl sulphate has been recorded for the first time using the λ 2537 radiation Forty-one lines have been identified out of which eight belong to the lattice oscillations, seven to the internal vibrations of the water molecule and the remaining twenty-six to the internal vibrations of the ethyl sulphate group. The Raman spectrum of ethyl sulphate (liquid) has also been recorded using the λ 4358 excitation and is compared with the spectrum of lanthanum ethyl sulphate. Thirty Raman lines could be identified in the spectrum of ethyl sulphate, of which fourteen are recorded for the first time. Probable assignments of the observed frequencies are also given. The sulphate group is found to have O-SO3 structure in lanthanum ethyl sulphate, while it has a co-ordination {Mathematical expression} in ethyl sulphate.

The Raman spectrum of cyclohexanol

The Raman spectrum of cyclohexanol has been studied in detail in the liquid state at 30° C. and at about 68° C. and in the solid state at about 13° C. The O-H stretching frequency of cyclohexanol has been found to extend from 3106-3571 cm.-1 in the liquid state at 30° C. and from 3204-3652 cm.-1 at 68° C. The 38 lines recorded in the present investigation have been following frequency shifts: 342, 408, 458, 478, 555, 653, 789, 834, 843, 863, 887, 920, 966, 978, 1024, 1047, 1070, 1139, 1173, 1184, 1210, 1235, 1252, 1301, 1329, 1346, 1362, 1438, 1448, 1464, 2660, 2684, 2710, 2854, 2896, 2925, 2940, 3106 to 3511 (band). Those lines which are italicized are the additional lines observed for the first time. The Raman lines at 966 cm.-1 and 1070 cm.-1 have been assigned to C-OH stretching vibrations of the axial and equatorial isomers. The ratio of the integrated intensity of the 1070 cm.-1 line to the 966 cm.-1 gave the equilibrium constant K as 2·896 at 30° C. and as 2·66 at 68° C. Knowing K, the free energy different Δ F was calculated and it was found to be 0·64 Kcal./mole at 30° C. and 0·66 Kcal./mole at about 68° C. Reasonable assignment has been made for most of the observed Raman lines.

Raman spectrum of l-asparagine monohydrate

The Raman spectrum of l-asparagine monohydrate in the form of a single crystal has been recorded for the first time. λ 2537 excitation has been used. Fifty-three Raman frequency shifts have been recorded. They are grouped as follows: Eight Raman lines coming under the lattice spectrum, three Raman lines arising from low-frequency vibrations of the hydrogen bonds and the remaining forty-two arising from the internal oscillations of the asparagine molecule. Appropriate assignments have been given for the observed Raman lines

Visualization of enantiomers and determination of homo- and hetero-nuclear residual dipolar and scalar couplings: The natural abundant C-13 edited J/D-resolved NMR techniques

The simple two dimensional C-13-satellite J/D-resolved experiments have been proposed for the visualization of enantiomers, extraction of homo- and hetero-nuclear residual dipolar couplings and also H-1 chemical shift differences between the enantiomers in the anisotropic medium. The significant advantages of the techniques are in the determination of scalar couplings of bigger organic molecules. The scalar couplings specific to a second abundant spin such as F-19 can be selectively extracted from the severely overlapped spectrum. The methodologies are demonstrated on a chiral molecule aligned in the chiral liquid crystal medium and two different organic molecules in the isotropic solutions. (C) 2010 Elsevier B.V. All rights reserved.

Spectral Sensing of Adaptive Frequency Hopping Signal for Cognitive Radio

The issue of dynamic spectrum scene analysis in any cognitive radio network becomes extremely complex when low probability of intercept, spread spectrum systems are present in environment. The detection and estimation become more complex if frequency hopping spread spectrum is adaptive in nature. In this paper, we propose two phase approach for detection and estimation of frequency hoping signals. Polyphase filter bank has been proposed as the architecture of choice for detection phase to efficiently detect the presence of frequency hopping signal. Based on the modeling of frequency hopping signal it can be shown that parametric methods of line spectral analysis are well suited for estimation of frequency hopping signals if the issues of order estimation and time localization are resolved. An algorithm using line spectra parameter estimation and wavelet based transient detection has been proposed which resolves above issues in computationally efficient manner suitable for implementation in cognitive radio. The simulations show promising results proving that adaptive frequency hopping signals can be detected and demodulated in a non cooperative context, even at a very low signal to noise ratio in real time.

Fatigue crack growth under an eqivalent falstaff spectrum

Optical fractography was used to estimate growth of small cracks at notches under programmed FALSTAFF loading in an Al-Cu alloy. Crack sizes as low as 25 microns and growth rates over two orders of magnitude could be resolved using this technique. Randomized MiniFALSTAFF load sequence was modified into a programmed load equivalent with major loads either preceding or following marker loads. Crack growth rate under programmed FALSTAFF spectrum as estimated by optical fractography conformed to compliance based estimates on a SE(T) specimen. Long crack growth rates under programmed and randomized MiniFALSTAFF spectrum were essentially similar. Spectrum load fatigue crack growth was studied in central hole coupons under notch inelastic conditions. Scatter in growth rates for small notch cracks was found to be of the same magnitude as that of long cracks. Multiple fatigue cracks are observed at the notch root, and they appear to influence each other.

Wavepacket dynamical studies on trans-azobenzene: absorption spectrum and resonance Raman excitation profiles of the n??* transition

Time-dependent wavepacket propagation techniques have been used to calculate the absorption spectrum and the resonance Raman excitation profiles of the n-pi* transition in azobenzene. A comparison of both the calculated absorption spectrum and excitation profiles with experiment has been made. From an analysis of the data, it is concluded that the Raman intensities are mainly due to resonance from the n-pi* transition and not from the pre-resonance of the pi-pi* transition, as reported earlier. We find that the isomerization pathway is through the inversion mechanism rather than by rotation. This is the first direct spectroscopic evidence for the isomerization pathway in trans-azobenzene.

Investigation of short-time isomerization dynamics in p-nitroazobenzene from resonance Raman intensity analysis

Resonance Raman (RR) spectra are presented for p-nitroazobenzene dissolved in chloroform using 18 excitation Wavelengths, covering the region of (1)(n --> pi*) electronic transition. Raman intensities are observed for various totally symmetric fundamentals, namely, C-C, C-N, N=N, and N-O stretching vibrations, indicating that upon photoexcitation the excited-state evolution occurs along all of these vibrational coordinates. For a few fundamentals, interestingly, in p-nitroazobenzene, it is observed that the RR intensities decrease near the maxima of the resonant electronic (1)(n --> pi*) transition. This is attributed to the interference from preresonant scattering due to the strongly allowed (1)(pi --> pi*) electronic transition. The electronic absorption spectrum and the absolute Raman cross section for the nine Franck-Condon active fundamentals of p-nitroazobenzene have been successfully modeled using Heller's time-dependent formalism for Raman scattering. This employs harmonic description of the lowest energy (1)(n --> pi*) potential energy surface. The short-time isomerization dynamics is then examined from a priori knowledge of the ground-state normal mode descriptions of p-nitroazobenzene to convert the wave packet motion in dimensionless normal coordinates to internal coordinates. It is observed that within 20 fs after photoexcitation in p-nitroazobenzene, the N=N and C-N stretching vibrations undergo significant changes and the unsubstituted phenyl ring and the nitro stretching vibrations are also distorted considerably.

A Coalitional Game Framework for Cooperative Secondary Spectrum Access

We consider a framework in which several service providers offer downlink wireless data access service in a certain area. Each provider serves its end-users through opportunistic secondary spectrum access of licensed spectrum, and needs to pay primary license holders of the spectrum usage based and membership based charges for such secondary spectrum access. In these circumstances, if providers pool their resources and allow end-users to be served by any of the cooperating providers, the total user satisfaction as well as the aggregate revenue earned by providers may increase. We use coalitional game theory to investigate such cooperation among providers, and show that the optimal cooperation schemes can be obtained as solutions of convex optimizations. We next show that under usage based charging scheme, if all providers cooperate, there always exists an operating point that maximizes the aggregate revenue of providers, while presenting each provider a share of the revenue such that no subset of providers has an incentive to leave the coalition. Furthermore, such an operating point can be computed in polynomial time. Finally, we show that when the charging scheme involves membership based charges, the above result holds in important special cases.

A hybrid pre-whitening technique for detection of additive spread spectrum watermarks in audio signals

Pre-whitening techniques are employed in blind correlation detection of additive spread spectrum watermarks in audio signals to reduce the host signal interference. A direct deterministic whitening (DDW) scheme is derived in this paper from the frequency domain analysis of the time domain correlation process. Our experimental studies reveal that, the Savitzky-Golay Whitening (SGW), which is otherwise inferior to DDW technique, performs better when the audio signal is predominantly lowpass. The novelty of this paper lies in exploiting the complementary nature to the two whitening techniques to obtain a hybrid whitening (HbW) scheme. In the hybrid scheme the DDW and SGW techniques are selectively applied, based on short time spectral characteristics of the audio signal. The hybrid scheme extends the reliability of watermark detection to a wider range of audio signals.