Chiral discrimination and the measurement of enantiomeric excess from a severely overcrowded NMR spectrum

NMR spectroscopic chiral visualization, unambiguous assignment of peaks pertaining to R and S enantiomers and the subsequent measurement of enantiomeric composition demands a highly resolved spectrum. The method fails when the spectrum is severely overcrowded or highly complex, thereby hampering the determination of enantiomeric excess. In order to circumvent such problems we propose the utility of pure shift spectrum obtained by resolving the chemical shift and coupling information in two orthogonal dimensions. The skew projected spectrum yields singlet's at the respective chemical shift positions, permitting the unravelling of the superimposed spectral transitions for each enantiomer and measurement of enantiomeric composition. (C) 2012 Elsevier B. V. All rights reserved.

Computational tools for mechanistic discrimination in the reductive and metathesis coupling reactions mediated by titanium(IV) isopropoxide

A theoretical study has been carried out at the B3LYP/LANL2DZ level to compare the reactivity of phenyl isocyanate and phenyl isothiocyanate towards titanium(IV) alkoxides. Isocyanates are shown to favour both mono insertion and double insertion reactions. Double insertion in a head-to-tail fashion is shown to be more exothermic than double insertion in a head-to-head fashion. The head-to-head double insertion leads to the metathesis product, a carbodiimide, after the extrusion of carbon dioxide. In the case of phenyl isothiocyanate, calculations favour the formation of only mono insertion products. Formation of a double insertion product is highly unfavourable. Further, these studies indicate that the reverse reaction involving the metathesis of N,N-'-diphenyl carbodiimide with carbon dioxide is likely to proceed more efficiently than the metathesis reaction with carbon disulphide. This is in excellent agreement with experimental results as metathesis with carbon disulphide fails to occur. In a second study, multilayer MM/QM calculations are carried out on intermediates generated from reduction of titanium(IV) alkoxides to investigate the effect of alkoxy bridging on the reactivity of multinuclear Ti species. Bimolecular coupling of imines initiated by Ti(III) species leads to a mixture of diastereomers and not diastereoselective coupling of the imine. However if the reaction is carried out by a trimeric biradical species, diastereoselective coupling of the imine is predicted. The presence of alkoxy bridges greatly favours the formation of the d,l (+/-) isomer, whereas the intermediate without alkoxy bridges favours the more stable meso isomer. As a bridged trimeric species, stabilized by bridging alkoxy groups, correctly explains the diastereoselective reaction, it is the most likely intermediate in the reaction.

Discrimination of alpha-Amino Acids Using Green Tea Flavonoid (-)-Epigallocatechin Gallate as a Chiral Solvating Agent

We report a special, hitherto-unexplored property of (-)-epigallocatechin gallate (EGCG) as a chiral solvating agent for enantiodiscrimination of alpha-amino acids in the polar solvent DMSO. This phenomenon has been investigated by H-1 NMR spectroscopy. The mechanism of the interaction property of EGCG with alpha-amino acids has been understood as arising out of hydrogen-bonded noncovalent interactions, where the -OH groups of two phenyl rings of EGCG play dominant roles. The conversion of the enantiomeric mixture into diastereomers yielded well-resolved peaks for D and L amino acids permitting the precise measurement of enantiomeric composition. Often one encounters complex situations when the spectra are severely overlapped or partially resolved hampering the testing of enantiopurity and the precise measurement of enantiomeric excess (ee). Though higher concentration of EGCG yielded better discrimination, the use of lower concentration being economical, we have exploited an appropriate 2D NMR experiment in overcoming such problems. Thus, in the present study we have successfully demonstrated the utility of the bioflavonoid (-)-EGCG, a natural product as a chiral solvating agent for the discrimination of large number of alpha-amino acids in a polar solvent DMSO. Another significant advantage of this new chiral sensing agent is that it is a natural product and does not require tedious multistep synthesis unlike many other chiral auxiliaries.

Novel piezoelectric thin film impact sensor: application in non-destructive material discrimination

We report on the design, development, and performance study of a packaged piezoelectric thin film impact sensor, and its potential application in non-destructive material discrimination. The impact sensing element employed was a thin circular diaphragm of flexible Phynox alloy. Piezoelectric ZnO thin film as an impact sensing layer was deposited on to the Phynox alloy diaphragm by RF reactive magnetron sputtering. Deposited ZnO thin film was characterized by X-ray diffraction (XRD), Atomic Force Microscopy (AFM), and Scanning Electron Microscopy (SEM) techniques. The d(31) piezoelectric coefficient value of ZnO thin film was 4.7 pm V-1, as measured by 4-point bending method. ZnO film deposited diaphragm based sensing element was properly packaged in a suitable housing made of High Density Polyethylene (HDPE) material. Packaged impact sensor was used in an experimental set-up, which was designed and developed in-house for non-destructive material discrimination studies. Materials of different densities (iron, glass, wood, and plastic) were used as test specimens for material discrimination studies. The analysis of output voltage waveforms obtained reveals lots of valuable information about the impacted material. Impact sensor was able to discriminate the test materials on the basis of the difference in their densities. The output response of packaged impact sensor shows high linearity and repeatability. The packaged impact sensor discussed in this paper is highly sensitive, reliable, and cost-effective.

Aluminium coated carbon nanotube film for wavelength-selective surface

We report selective optical reflectance in an aluminium (Al) coated flexible carbon nanotube (CNT) thin film over a wide range of wavelengths (500-2500 nm). Selective-wavelength surface is achieved by coating CNT surfaces with Al thin film that presented a maximum optical reflectivity of similar to 65% in the infrared region. However, CNT film alone showed a reflectance of 15-20% over a larger range of wavelengths without any structural modification, which has not been realized so far. Moreover, a tailorable reflectance in CNT is shown to be achieved by tuning various parameters, namely, the porosity of the material, angle of an incident light, and refractive index of the materials. Owing to higher infrared reflectivity and thermal diffusivity, Al coated CNT presents a potential for a high efficiency solar collector. (C) 2013 AIP Publishing LLC.

Ternary ion-pair complexation: a protocol for chiral discrimination and the assignment of absolute configuration of chiral hydroxy acids

The study demonstrates the utility of ternary ion-pair complex formed among BINOL (1,1'-Bi-2-naphthol), a carboxylic acid and an organic base, such as, dimethylpyridine (DMAP), 1,4-diazabicyclo2.2.2]octane (DABCO), as a versatile chiral solvating agent (CSA) for the enantiodiscrimination of carboxylic acids, measurement of enantiomeric excess (ee) and the assignment of absolute configuration of hydroxy acids. The proposed mechanism of ternary complex has wider application for testing the enantiopurity owing to the fact that the binary mixture using BINOL alone does not serve as a solvating agent for their discrimination. In addition, the developed protocol has an excellent utility for the assignment of the absolute configurations of hydroxy acids.

Nestmate discrimination in the social wasp Ropalidia marginata: chemical cues and chemosensory mechanism

Nestmate discrimination plays an important role in preserving the integrity of social insect colonies. It is known to occur in the primitively eusocial wasp Ropalidia marginata in which non-nestmate conspecifics are not allowed to come near a nest. However, newly eclosed females are accepted in foreign colonies, suggesting that such individuals may not express the cues that permit differentiation between nestmates and non-nestmates. As cuticular hydrocarbons (CHCs) have been implicated as chemosensory cues used in nestmate recognition in other species, we investigated, using bioassays and chemical analyses, whether CHCs can play a role in nestmate recognition in R. marginata. We found that individuals can be differentiated according to colony membership using their CHC profiles, suggesting a role of CHCs in nestmate discrimination. Non-nestmate CHCs of adult females received more aggression than nestmate CHCs, thereby showing that CHCs are used as cues for nestmate recognition. Contrarily, and as expected, CHCs of newly eclosed females were not discriminated against when presented to a foreign colony. Behavioural sequence analysis revealed the behavioural mechanism involved in sensing nestmate recognition cues. We also found that newly eclosed females had a different CHC profile from that of adult females, thereby providing an explanation for why young females are accepted in foreign colonies. (C) 2013 The Association for the Study of Animal Behaviour. Published by Elsevier Ltd. All rights reserved.

Dual Binding Site Assisted Chromogenic and Fluorogenic Recognition and Discrimination of Fluoride and Cyanide by a Peripherally Borylated Metalloporphyrin: Overcoming Anion Interference in Organoboron Based Sensors

Peripherally triarylborane decorated porphyrin (2) and its Zn(II) complex (3) have been synthesized. Compound 3 contains of two different Lewis acidic binding sites (Zn(II) and boron center). Unlike all previously known triarylborane based sensors, the optical responses of 3 toward fluoride and cyanide are distinctively different, thus enabling the discrimination of these two interfering anions. Metalloporphyrin 3 shows a multiple channel fluorogenic response toward fluoride and cyanide and also a selective visual colorimetric response toward cyanide. By comparison with model systems and from detailed photophysical studies on 2 and 3, we conclude that the preferential binding of fluoride occurs at the peripheral borane moieties resulting in the cessation of the EET (electronic energy transfer) process from borane to porphyrin core and with negligible negetive cooperative effects. On the other hand, cyanide binding occurs at the Zn(II) core leading to drastic changes in its absorption behavior which can be followed by the naked eye. Such changes are not observed when the boryl substituent is absent (e.g., Zn-TPP and TPP). Compounds 2 and 3 were also found to be capable of extracting fluoride from aqueous medium.

Broadband wavelength-selective reflectance and selective polarization by a tip-bent vertically aligned multi-walled carbon nanotube forest

The tunable optical properties of the bulk structure of carbon nanotubes (CNT) were recently revealed as a perfect black body material, optically reflective mirror and solar absorber. The present study demonstrates an enhanced optical reflectance of up to similar to 15% over a broad wavelength range in the near infrared region followed by a mechanical modification of the surface of a bulk CNT structure, which can be accounted for due to the grating-like surface abnormalities. In response to the specific arrangement of the so-formed bent tips of the CNT, a selective reflectance is achieved and results in reflecting only a dominant component of the polarized ight, which has not been realized so far. Modulation of this selective-optical reflectance can be achieved by ontrolling the degree of tip bending of the nanotubes, thus opening up avenues for the construction of novel dynamic light polarizers and absorbers.

A versatile ternary ionic complex for chiral discrimination of molecules with diverse functionalities using H-1 NMR

This study reports a simple, efficient and versatile protocol developed for NMR spectroscopic enantiodiscrimination of molecules containing diverse functional -groups, such as amino alcohols, secondary alcohols, cyanohydrins, oxazolidones, diols, thiones and epoxides, using a phosphorous based three component mixture. The simple mixing and shaking of enantiopure 1,1'-binaphthyt-2,2'-diyl hydrogenphosphate (BNPA), 4-(dimethylamino)pyridine (DMAP) and a chiral analyte in the solvent CDCl3 served as a chiral solvating agent and resulted in well dispersed peaks for each enantiomer in the H-1 NMR spectrum. Discrimination could be achieved not only for the proton at the chiral centre, but also for multiple proton sites. The devised approach also permitted the precise measurement of the enantiomeric excess (ee).

Deep searches for decametre-wavelength pulsed emission from radio-quiet gamma-ray pulsars

We report the results of extensive follow-up observations of the gamma-ray pulsar J1732-3131, which has recently been detected at decametre wavelengths, and the results of deep searches for the counterparts of nine other radio-quiet gamma-ray pulsars at 34 MHz, using the Gauribidanur radio telescope. No periodic signal from J1732-3131 could be detected above a detection threshold of 8 sigma, even with an effective integration time of more than 40 h. However, the average profile obtained by combining data from several epochs, at a dispersion measure of 15.44 pc cm(-3), is found to be consistent with that from the earlier detection of this pulsar at a confidence level of 99.2 per cent. We present this consistency between the two profiles as evidence that J1732-3131 is a faint radio pulsar with an average flux density of 200-400 mJy at 34 MHz. Despite the extremely bright sky background at such low frequencies, the detection sensitivity of our deep searches is generally comparable to that of higher frequency searches for these pulsars, when scaled using reasonable assumptions about the underlying pulsar spectrum. We provide details of our deep searches, and put stringent upper limits on the decametre-wavelength flux densities of several radio-quiet gamma-ray pulsars.

Chiral discrimination of secondary alcohols and carboxylic acids by NMR spectroscopy

The manuscript reports two novel ternary ion-pair complexes, which serve as chiral solvating agents, for enantiodiscrimination of secondary alcohols and carboxylic acids. The protocol for discrimination of secondary alcohols is designed by using one equivalent mixture each of enantiopure mandelic acid, 4-dimethylaminopyridine (DMAP) and a chiral alcohol. For discrimination of carboxylic acids, the ternary complex is obtained by one equivalent mixture each of enantiopure chiral alcohol, DMAP and a carboxylic acid. The designed protocols also permit accurate measurement of enantiomeric composition. Copyright (C) 2014 John Wiley & Sons, Ltd.

Associated jet and subjet rates in light-quark and gluon jet discrimination

We show that in studies of light quark- and gluon-initiated jet discrimination, it is important to include the information on softer reconstructed jets (associated jets) around a primary hard jet. This is particularly relevant while adopting a small radius parameter for reconstructing hadronic jets. The probability of having an associated jet as a function of the primary jet transverse momentum (PT) and radius, the minimum associated jet pi, and the association radius is computed up to next-to-double logarithmic accuracy (NDLA), and the predictions are compared with results from Herwig++, Pythia6 and Pythia8 Monte Carlos (MC). We demonstrate the improvement in quark-gluon discrimination on using the associated jet rate variable with the help of a multivariate analysis. The associated jet rates are found to be only mildly sensitive to the choice of parton shower and hadronization algorithms, as well as to the effects of initial state radiation and underlying event. In addition, the number of k(t) subjets of an anti-k(t) jet is found to be an observable that leads to a rather uniform prediction across different MC's, broadly being in agreement with predictions in NDLA, as compared to the often used number of charged tracks observable.

Polyfunctional Lewis Acids: Intriguing Solid-State Structure and Selective Detection and Discrimination of Nitroaromatic Explosives

Synthesis and crystal structures of three porphyrin-based polyfunctional Lewis acids 1-3 are reported. Intermolecular HgClHgCl (linear and -type) interactions in the solid state of the peripherally ArHgCl-decorated compound 3 lead to a fascinating 3D supramolecular architecture. Compound3 shows a selective fluorescence quenching response to picric acid and discriminates other nitroaromatic-based explosives. For the first time, an electron-deficient polyfunctional Lewis acid is shown to be useful for the selective detection and discrimination of nitroaromatic explosives. The Stern-Volmer quenching constant and detection limits of compound3 for picric acid are the best among the reported small-molecular receptors for nitroaromatic explosives. The electronic structure, Lewis acidity, and selective sensing characteristics of 3 are well corroborated by DFT calculations.

Study on effect of optical wavelength on photo induced strain sensitivity in carbon nanotubes using fiber Bragg grating

In this work, the role of optical wavelength on the photo induced strain in carbon nanotubes (CNT) is probed using a Fiber Bragg Grating (FBG), upon exposure to infrared (IR) (21 mu epsilon mW(-1)) and visible (9 mu epsilon mW(-1)) radiations. The strain sensitivity in CNT is monitored over a smaller range (10(-3) to 10(-9) epsilon) by exposing to a low optical power varying in the range 10(-3) to 10(-6) W. In addition, the wavelength dependent response and recovery periods of CNT under IR (tau(rise) = 150 ms, tau(fall) = 280 ms) and visible (tau(rise) = 1.07 s, tau(fall) = 1.18 s) radiations are evaluated in detail. This study can be further extended to measure the sensitivity of nano-scale photo induced strains in nano materials and opens avenues to control mechanical actuation using various optical wavelengths.