Enantiomeric excess measurements in weakly oriented chiral liquid crystal solvents through 2D H selective refocusing experiments

In this article, a simple and robust method is proposed for simplifying the analysis of proton spectra of molecules dissolved in weakly oriented chiral media. The NMR approach investigated is based on the use of proton selective refocusing 2D experiments (SERF) to measure proton–proton dipolar couplings from unresolved lines. This technique is applied to the case of enantiomers dissolved in chiral polypeptide liquid crystals. It is shown that an accurate determination of enantiomeric excess is possible within a short experimental time.     

Homo- and heteronuclear 2D NMR approaches to analyse a mixture of deuterated unlike/like stereoisomers using weakly ordering chiral liquid crystals

We describe several homo- and heteronuclear 2D NMR strategies dedicated to the analysis of anisotropic (2)H spectra of a mixture of dideuterated unlike/like stereoisomers with two remote stereogenic centers, using weakly orienting chiral liquid crystals. To this end, we propose various 2D correlation experiments, denoted "D(H)(n)D" or "D(H)(n)C" (with n=1, 2), that involve two heteronuclear polarization transfers of INEPT-type with one or two proton relays. The analytical expressions of correlation signals for four pulse sequences reported here were calculated using the product-operators formalism for spin I=1 and S=1/2. The features and advantages of each scheme are presented and discussed. The efficiency of these 2D sequences is illustrated using various deuterated model molecules, dissolved in organic solutions of polypeptides made of poly-gamma-benzyl-L-glutamate (PBLG) or poly-epsilon-carbobenzyloxy-L-lysine (PCBLL) and NMR numerical simulations.     

Theoretical and experimental investigation of (13)C relayed (2)H-(2)H-COSY 2D experiments: application to the analysis of weakly aligned solutes

We describe new NMR 2D experiments denoted DECADENCY for DEuterium CArbon DEuterium Nuclear Correlation spectroscopY dedicated to the analysis of anisotropic deuterium spectra. They belong to the class of X-relayed Y,Y-COSY 2D experiments that was initially explored in the case of a (1)H-X-(1)H fragment (I(X)=1/2) in isotropic medium. DECADENCY 2D experiments permit to correlate the quadrupolar doublets associated with two inequivalent deuterium nuclei in an oriented CD(2) fragment through heteronuclear polarization transfers. Two kinds of pulse sequences are described here using either a double INEPT-type or DEPT-type process. DECADENCY 2D experiments provide an interesting alternative to (2)H-(2)H COSY experiments when the geminal (2)H-(2)H total coupling (scalar and dipolar) is null or too small to provide visible cross-correlation peaks. Such a situation is typically observed for geminal deuteriums in prochiral or chiral molecules dissolved in chiral liquid crystals. The efficiency of these techniques is illustrated using dideuterated prochiral molecules, the phenyl[(2)H(2)]methanol and the 1-chloro[1-(2)H(2)]nonane, both dissolved in organic solutions of poly-gamma-benzyl-l-glutamate. The advantages of each sequence are presented and discussed. It is shown that the relative sign of the quadrupolar doublets can be determined.     

光纤-手征光纤耦合光波导偏振响应特性的实验研究

在 D形微孔光纤中注入手征液体 ,制作出了光纤 -手征光纤耦合光波导。对其输出端的偏振响应特性进行测试发现 ,与未注入手征液体的 D形微孔光纤相比 ,传播的光矢量方向发生了旋转。这种效应是由光纤与手征光纤相互耦合而引起的 ,将有可能应用到许多新器件的制作中     

SERF-filtered experiments: new enantio-selective tools for deciphering complex spectra of racemic mixtures dissolved in chiral oriented media

The use of chiral liquid crystals as NMR solvent is a powerful tool to visualize and quantify enantiomers. This technique is much more robust than traditional liquid state techniques. Recent developments have been performed to simplify proton spectra obtained in these solvents which are usually complex to analyze. In the different published sequences the enantiomeric differentiation can be visualized but none of them rely the different (1)H-(1)H couplings to have a coherent set for each enantiomer especially in cases of racemic mixtures. In this work to overcome such limitations, we present a new NMR pulse sequence using semi-selective pulses to assign for each enantiomer the different (1)H-(1)H couplings. The aim is to obtain the signal of only one enantiomer, through a first Selective ReFocussing (SERF) filtering block implemented for the enantio-selection followed by a second SERF block for measuring a chosen coupling. The whole sequence is called (1)H SERF-filtered-SERF. These techniques permit for the first time to assign all dipolar couplings to each enantiomer of racemic mixtures dissolved in chiral oriented media. We demonstrate that using this experiment it is possible to visualize enantio-differentiation even in the case where the multiplets are not resolved in the SERF experiments, pushing back the limits of the enantiomeric visualization.     

Modified z-gradient filtering as a mean to obtain phased deuterium autocorrelation 2D NMR spectra in oriented solvents

We describe a modified z-gradient filter scheme specifically designed to obtain pure absorption mode deuterium 2D NMR spectra recorded in oriented solvents. The proposed technique is investigated by analysing the evolution of the density operator for a spin I=1. The method is applied to the recently designed Q-COSY and Q-resolved 2D experiments to simplify the analysis of chiral molecules dissolved in weakly orienting chiral liquid crystals. The efficiency of this z-gradient filtering technique is illustrated using the perdeuterated 1-butanol, a prochiral molecule of average Cs symmetry, dissolved in an organic solution of poly-gamma-benzyl-L-glutamate (PBLG). The experimental results as well as the advantages of the new experiments compared with the previous ones are described and discussed.     

Localization of matters on the bent brane in bulk

We investigate the possibility of localizing various matter fields on a bent AdS₄ (dS₄) thick brane in AdS₅. For spin 0 scalar field, we find a massless zero mode and an excited state which can be localized on the bent brane. For spin 1 vector field, there is only a massless zero mode on the bent brane. For spin 1/2 fermion field, it is shown that, in the case of no Yukawa coupling of scalar-fermion, there is no existence of localized massless zero mode for both left and right chiral fermions. In order to localize massless fermions, some kind of Yukawa coupling must be included. We study two types of Yukawa couplings as examples. Localization property of chiral fermions is related to the parameters of the brane model, the Yukawa coupling constant and the cosmological constant of the 4-dimensional space–time.     

1H and 13C NMR studies of glycine in anisotropic media: double-quantum transitions and the effects of chiral interactions

The (1)H NMR spectrum of glycine in stretched gelatin gel and in cromolyn liquid crystal displays a well-resolved doublet due to (1)H-(1)H dipolar interaction. Multiple spectra were obtained within a wide range of offset frequencies of partially saturating radio-frequency (RF) radiation to generate steady-state irradiation envelopes or z-spectra of glycine. Maximal suppression of the doublet occurred when the irradiation was applied exactly at the centre frequency, between the two glycine peaks. This phenomenon is due to double-quantum transitions and is similar to our previous work on quadrupolar nuclei (2)H (HDO) and (23)Na(+). When the (13)C isotopomer glycine-2-(13)C was used, the same effect was found in twice, split by (1)J(CH)+2D(CH). Additional signals in (1)H and (13)C NMR due to prochiral-chiral interactions were found when glycine-2-(13)C was dissolved in chiral anisotropic gelatin and κ-carrageenan gels. The NMR spectra were successfully simulated assuming a (2)J(HH) coupling constant of -16.5Hz and two distinct dipolar coupling constants for the -(13)CH(2)- group (D(C,HA), and D(C,HB)).     

Measurement of small spin-spin splittings in the presence of chemical exchange: case of deuteriated water

A new implementation of a described data processing for measuring small scalar coupling constant J is proposed. It is applied particularly to situations where the coupling constant is around the linewidth at half-height, and in the presence of chemical exchange. This modified data processing uses only a simple "one-pulse" experiment instead of a series of spin echoes experiments required by the previous processing. The FID recorded in the one pulse experiment is used by a reconstitution program to generate a set of signals, which are analyzed in the time domain to obtain a spectrum where the scalar coupling constant is apparently multiplied by n+1, where n is positive. The new processing is tested with simulated spectra. The coupling constant between proton and deuterium is measured in the proton spectrum of a solution of 80% of D(2)O and 20% of H(2)O. It was found to be J=1.54+/-0.01 Hz.     

The utility of phase alternated pulses for the measurement of dipolar couplings in 2D-SLF experiments

The measurement of hetero-nuclear dipolar coupling using two-dimensional separated local field (SLF-2D) NMR experiments is a powerful technique for the determination of the structure and dynamics of molecules in the solid state and in liquid crystals. However, the experiment is sensitive to a number of factors such as the Hartmann–Hahn match condition, proton frequency off-set and rf heating. It is shown here that by the use of phase alternated pulses during spin-exchange the effect of rf mismatch on the dipolar coupling measurement can be compensated over a wide range of off-sets. Phase alternation together with time and amplitude modulation has also been considered and incorporated into a pulse scheme that combines spin exchange with homonuclear spin decoupling based on magic sandwich sequence and named as SAMPI4. Such time and amplitude averaged nutation experiments use relatively low rf power and generate less sample heating. One of these schemes has been applied on liquid crystal samples and is observed to perform well and yield spectra with high resolution.     

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

One-dimensional (1D) proton NMR spectra of enantiomers are generally undecipherable in chiral orienting poly-γ-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 ¹H detection. On the other hand in the present study the benefit is derived from the presence of several couplings among the entire network of interacting protons. Transition selective 1D ¹H–¹H 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).     

Tailoring enhanced chiroptical effect with Fabry–Perot cavity-coupled sandwich chiral metamaterials

Cavity-coupled plasmonic structure is demonstrated to be a simple and effective tool to manipulatelight,enhance the biosensing figure of merit, and control the polarization state. In this Letter, we demonstrate the tunability of the chiroptical effect of cavity-coupled chiral structure, i.e., sandwich chiral metamaterials(SCMs), in whichradiation coupling dominates the interaction between particles. Two types of SCMs whose building blocks are 3D chiral and 2D chiral, respectively, are numerically studied. Distinct responses are observed in these two materials. The chiroptical effect can be effectively manipulated and enhanced in the 2D case, while the SCMs consisting of 3D chiral layers keep the chiroptical effecta constant. A theoretical analysis based on matrix optics is developed to explain the corresponding phenomena, which gives a reasonable agreement with numerical simulations.     

Muon capture on the proton and deuteron

By measuring the lifetime of the negative muon in pure protium (¹H), the MuCap experiment determines the rate of muon capture on the proton, from which the proton’s pseudoscalar coupling g _p may be inferred. A precision of 15% for g _p has been published; this is a step along the way to a goal of 7%. This coupling can be calculated precisely from heavy baryon chiral perturbation theory and therefore permits a test of QCD’s chiral symmetry. Meanwhile, the MuSun experiment is in its final design stage; it will measure the rate of muon capture on the deuteron using a similar technique. This process can be related through pionless effective field theory and chiral perturbation theory to other two-nucleon reactions of astrophysical interest, including proton-proton fusion and deuteron breakup. for the MuCap [1] and MuSun [2] Collaborations     

In Vivo3D LocalizedC Spectroscopy Using Modified INEPT and DEPT

The 3D localized¹³C spectroscopy methods LINEPT and LODEPT, which are modifications of INEPT and DEPT, are proposed. As long as a¹³C inversion pulse (180-degree pulse) is applied at 1/(4J) before the proton echo time in LINEPT and a¹³C excitation pulse (90-degree pulse) is applied at 1/(2J) before the proton echo time in LODEPT, the proton echo time can be set to any value longer than 1/(2J) in LINEPT and longer than 1/Jin LODEPT. As a result, the proton and the¹³C pulses can be applied separately and these proton pulses can be made slice-selective pulses. These localization features of LINEPT and LODEPT were evaluated using a phantom consisting of a cylinder filled with ethanol placed inside another cylinder filled with oil, and localized ethanol spectra could be obtained.In vivo3D localized¹³C spectra from the brain of a monkey could be obtained using decoupled LINEPT, and glutamate C-4 appeared directly after the administration of glucose C-1, followed by the appearance of glutamate C-2, C-3 and glutamine C-2, C-3, C-4.     

η − η′ photoproduction and the axial isoscalar neutral current coupling

We show that coherentη andη′ photoproduction by means of the Primakoff Effect on the proton depends on the strange component of the neutral axial current coupling. We construct polarization asymmetries that are sensitive to this coupling through theγ?Z interference. Theη′ is not a Goldstone boson of a spontaneously broken chiral symmetry, but a phenomenological analysis of theη andη′ production through chiral perturbation theory allows to calculate the observables of interest. The polarized proton or polarized photon asymmetries are predicted to be close to 10^?4 for ?q ²～0.1?0.5 GeV².     

Measurement of Interproton, Nuclear Spin Dipolar Couplings in Liquid Crystalline Samples by Combining Variable Angle Sample Spinning, Isotope Dilution, and Deuterium Decoupling

The proton NMR spectra of liquid crystalline samples can be simplified by selective, partial deuteration followed by deuterium decoupling. This leaves strong peaks from the protons at the undeuterated sites, but also weak resonances from the coupling of these protons to those at low abundance (2% in the present case) at the deuterated sites. The weak resonances can be separated from the strong by recording spectra while spinning the sample at a series of angles to the magnetic field.     

Resolution enhancement in spectra of natural products dissolved in weakly orienting media with the help of 1H homonuclear dipolar decoupling during acquisition: application to 1H-13C dipolar couplings measurements

In weakly orienting media such as poly-gamma-benzyl-L-glutamate (PBLG) a polymer that forms a chiral liquid crystal in organic solvents, the spectral resolution for embedded molecules is usually poor because of numerous (1)H, (1)H dipolar couplings that generally broaden proton spectra. Therefore (1)H, (13)C dipolar couplings are difficult or impossible to measure. Here, we incorporate Flip-Flop decoupling during detection into an HSQC experiment. Flip-Flop removes the (1)H, (1)H dipolar couplings and scales the chemical shifts of the protons as well as the (1)H, (13)C dipolar couplings during detection. A resolution gain by a factor 1.5-4.2 and improved signal intensity by an average factor of 1.6-1.7 have been obtained. This technique is demonstrated on (+)-menthol dissolved in a PBLG/CDCl(3) phase.     

Quantitative experimental determination of the Landau-potential of chiral enantiomer doped ferroelectric liquid crystals

The full Landau potential was determined for a ferroelectric liquid crystal doped with varying concentrations of the chiral dopant R1011 and its enantiomer S1011. A multi-curve fitting procedure using temperature and electric field dependent tilt angle and polarization data was employed to the generalized Landau model of ferroelectric liquid crystals. From this analysis the three Landau coefficients as well as the polarization-tilt coupling parameters were obtained as a function of dopant concentration and configuration. It is shown that the two most varied parameters are those of the first Landau coefficient α and the (chiral) linear polarization-tilt coupling constant C. The effect on the first Landau term is equivalent for the two dopants of opposite handedness indicating its achiral nature, while the effect on the (chiral) bilinear coupling term differs for the R1011 and S1011 dopant, increasing and decreasing the coupling between tilt and polarization respectively. This difference in the bilinear coupling term quantifiably evidences that the R1011 dopant increases and S1011 dopant reduces the inherent chirality in this system.     

Proton and deuteron magnetic resonance of methanes,silanes and GeH3D dissolved in nematic liquid crystals

The proton and deuteron magnetic resonance spectra of CH₄, CH₃D, CH₂D₂, CHD₃, CD₄, SiH₄, SiH₃D, SiH₂D₂, SiH₃D, SiD₄, GeH₃D, dissolved in nematic liquid crystals, are reported. It was found that these molecules, which are essentially tetrahedral, exhibit anisotropic interactions and are partially oriented in the nematic phase. This effect is presumably due to slight deformations induced by the anisotropic medium. Some of the aspects related to the interpretation of the results are discussed.     

The new HMQC-based technique for the quantitative determination of heteronuclear coupling constants. Application for the measurement of 3J(H'(i),P(i+1)) in DNA oligomers

A new general J-HMQC-based technique is presented, which allows an accurate determination of heteronuclear coupling constants. The most important feature of this new approach includes acquisition of the two data sets with and without the additional pi(S)-pulse at the end of coupling evolution period. This enables preservation and separation of the two orthogonal terms of coupling evolution, which are manifested by in- and antiphase cross-peaks, respectively. The coupling magnitudes are evaluated by the nonlinear least-squares fitting of the ratios of integrated signal volumes for both kinds of signals. The effectiveness of the new sequence is demonstrated by determination of the 3J(H3'(i),P(i+1)) couplings in DNA octamer duplex d(GCGTACGC)(2) sample. Additionally, the ability of the new method for the measurement at the natural abundance level of 13C nuclei is presented for the beta-cyclodextrin.