Recent NMR Methodological Developments for Chiral Analysis in Isotropic Solutions

Chiral auxiliaries are used for NMR spectroscopic study of enantiomers. Often the presence of impurities, severe overlap of peaks, excessive line broadening and complex multiplicity pattern restricts the chiral analysis using 1D H-1 NMR spectrum. There are few approaches to resolve the overlapped peaks. One approach is to use suitable chiral auxiliary, which induces large chemical shift difference between the discriminated peaks (Delta delta(R,S)) and minimize the overlap. Another direction of approach is to design appropriate NMR experiments to circumvent some of these problems, viz, enhancing spectral resolution, unravelling the superimposed spectra of enantiomers, and reduction of spectral complexity. Large number of NMR techniques, such as two dimensional selective F-1 decoupling, RES-TOCSY, multiple quantum detection, frequency selective homodecoupling, band selective homodecoupling, broadband homodecoupling, etc. have been reported for such a purpose. Many of these techniques have aided in chiral analysis for molecules of diverse functionality in the presence of chiral auxiliaries. The present review summarizes the recently reported NMR experimental methodologies, with a special emphasis on the work carried out in authors' laboratory.

Assessing ``inherent vulnerability'' of forests: a methodological approach and a case study from Western Ghats, India

The objective of this study is to present a methodological approach to assess the inherent vulnerability of forests and apply it to a case study. Addressing inherent vulnerability, resulting from current stresses, is a necessary step for building resilience to long-term climate change. The proposed approach includes use of analytical framework that enables selection of vulnerability criteria and indicators systematically, application of pairwise comparison method (PCM) for assigning weights, and synthesis of a composite vulnerability index. This methodological approach has been applied at local scale to Aduvalli Protected Forest in Western Ghats in South India, where a vulnerability index value of 0.248 is estimated. Results of the case study indicate that `preponderance of invasive species' and forest dependence of community are the major sources of vulnerability at present for Aduvalli Protected Forest. Adoption of this methodology can assist in development of forest management plans to enhance adaptability of Aduvalli PF to current as well as future stresses, including climate change. This methodological approach can be applied across forest-types after appropriate changes to criteria and indicators and their weights, to estimate the inherent vulnerability to enable development of adaptation strategy.

Interlaboratory comparison of magnesium isotopic compositions of 12 felsic to ultramafic igneous rock standards analyzed by MC-ICPMS

To evaluate the interlaboratory mass bias for high-precision stable Mg isotopic analysis of natural materials, a suite of silicate standards ranging in composition from felsic to ultramafic were analyzed in five laboratories by using three types of multicollector inductively coupled plasma mass spectrometer (MC-ICPMS). Magnesium isotopic compositions from all labs are in agreement for most rocks within quoted uncertainties but are significantly (up to 0.3 parts per thousand in Mg-26/Mg-24, > 4 times of uncertainties) different for some mafic samples. The interlaboratory mass bias does not correlate with matrix element/Mg ratios, and the mechanism for producing it is uncertain but very likely arises from column chemistry. Our results suggest that standards with different matrices are needed to calibrate the efficiency of column chemistry and caution should be taken when dealing with samples with complicated matrices. Well-calibrated standards with matrix elements matching samples should be used to reduce the interlaboratory mass bias.