Spin state selective coherence transfer: a method for discrimination and complete analyses of the overlapped and unresolved 1H NMR spectra of enantiomers

In general, the proton NMR spectra of chiral molecules aligned in the chiral liquid crystalline media are broad and featureless. The analyses of such intricate NMR spectra and their routine use for spectral discrimination of R and S optical enantiomers are hindered. A method is developed in the present study which involves spin state selective two dimensional correlation of higher quantum coherence to its single quantum coherence of a chemically isolated group of coupled protons. This enables the spin state selective detection of proton single quantum transitions based on the spin states of the passive nuclei. The technique provides the relative signs and magnitudes of the couplings by overcoming the problems of enantiomer discrimination, spectral complexity and poor resolution, permitting the complete analyses of the otherwise broad and featureless spectra. A non-selective 180 degrees pulse in the middle of MQ dimension retains all the remote passive couplings. This accompanied by spin selective MQ-SQ conversion leads to spin state selective coherence transfer. The removal of field inhomogeneity contributes to dramatically enhanced resolution. The difference in the cumulative additive values of chemical shift anisotropies and the passive couplings, between the enantiomers, achieved by detecting Nth quantum coherence of N magnetically equivalent spins provides enhanced separation of enantiomer peaks. The developed methodology has been demonstrated on four different chiral molecules with varied number of interacting spins, each having a chiral centre.     

Microwave‐Assisted Synthesis and Antituberculosis Screening of Some 4‐((3‐(Trifluoromethyl)‐5,6‐dihydro‐[1,2,4]triazolo[4,3‐a]pyrazin‐7(8H)‐l)methyl)benzenamine Hybrids

In the present investigation, a series of 4‐((3‐(trifluoromethyl)‐5,6‐dihydro‐[1,2,4]triazolo[4,3‐a]pyrazin‐7(8H)‐yl)methyl)benzenamine analogs 6a–o were synthesized and characterized by IR, NMR (¹H and ¹³C), and mass spectra. All newly synthesized compounds 6a–o were prepared under conventional and microwave irradiation methods. These compounds obtained in higher yields and in shorter reaction times in the microwave irradiation method when compared with the conventional method. Synthesized compounds 6a–o were inspected for their in vitro antitubercular activity against Mycobacterium tuberculosis H₃₇Ra using an established XTT reduction menadione assay. Among the screened compounds, 6i (IC₅₀: 1.82 μg/mL), 6j (IC₅₀: 1.02 μg/mL), and 6k (IC₅₀: 1.59 μg/mL) showed excellent activity. Furthermore, compound 6i showed MIC₉₀ value of 16.02 μg/mL. In summary, the results indicate the identification of some novel, selective, and specific inhibitors against M. tuberculosis that can be explored further for the potential antitubercular drug.     

Microwave Synthesis of Fused Pyrans by Humic Acid Supported Ionic Liquid Catalyst and Their Antimicrobial,Antioxidant, Toxicity Assessment,and Molecular Docking Studies

A series of fused quinolinyl and quinolonyl pyrans were synthesized via a one‐pot reaction of quinolinyl and quinolonyl carbaldehydes, malononitrile, and a 1,3‐diketone. The reactions were catalyzed by a new humic acid supported 1‐butyl‐3‐methyl imidazolium thiocyanate ionic liquid under microwave irradiation conditions. Antimicrobial, antioxidant, and toxicity studies displayed various biological activities depending on structure of the pyrans.     

Nanohoop Rotaxanes from Active Metal Template Syntheses and Their Potential in Sensing Applications

The unique optoelectronic properties and smooth, rigid pores of macrocycles with radially oriented π systems render them fascinating candidates for the design of novel mechanically interlocked molecules with new properties. Two high‐yielding strategies are used to prepare nanohoop [2]rotaxanes, which owing to the π‐rich macrocycle are highly emissive. Then, metal coordination, an intrinsic property afforded by the resulting mechanical bond, can lead to molecular shuttling as well as modulate the observed fluorescence in both organic and aqueous conditions. Inspired by these findings, a self‐immolative [2]rotaxane was then designed that self‐destructs in the presence of an analyte, eliciting a strong fluorescent turn‐on response, serving as proof‐of‐concept for a new type of molecular sensing material. More broadly, this work highlights the conceptual advantages of combining compact π‐rich macrocyclic frameworks with mechanical bonds formed via active‐template syntheses.     

Investigation on the radiolytic stability of polybenzimidazole-based polymeric resins for the recovery of lanthanides,actinides, palladium from aqueous medium

Journal of Radioanalytical and Nuclear Chemistry - Radiolytic stability of polymeric resins is an important aspects in nuclear materials processing. The different dosage of gamma radiation was...     

Narrow band optical filter in fluorescein doped boric acid glass saturable absorber thin films

We demonstrate narrow band optical filter like frequency response with full width half maximum (FWHM) of nearly (1.75 ± 0.25) Hz in fluorescein doped boric acid glass films [10⁻⁴ M], using modulated optical phase conjugation and a nearly non-degenerate four wave mixing technique. Modulated optical phase conjugation signals are described in the limit of a weak probe and relatively strong pump beams. Both pump beams are of nearly equal intensity at a wavelength of 514.5 nm from a continuous-wave Ar⁺ laser. The probe beam frequency has been detuned with a ramp signal using a piezo electric mirror.     

Strain-induced polarization rotation in epitaxial (001) BiFeO3 thin films

Direct measurement of the remanent polarization of high quality (001)-oriented epitaxial BiFeO3 thin films shows a strong strain dependence, even larger than conventional (001)-oriented PbTiO3 films. Thermodynamic analysis reveals that a strain-induced polarization rotation mechanism is responsible for the large change in the out-of-plane polarization of (001) BiFeO3 with biaxial strain while the spontaneous polarization itself remains almost constant.     

Stability map for nanocrystalline and amorphous materials

We present a stability map which predicts the domains of shear instability due to grain rotation in nanocrystalline materials. The onset of this mode of instability is influenced by grain-size-dependent mechanisms and the length-scale of intergranular interaction. The map shows the grain size regimes that are inherently susceptible to this mode for a range of materials. In the amorphous limit, the model predicts embryonic nuclei sizes of about 10-50 nm, which agrees well with the shear band thicknesses for many metallic glasses.     

A mild and efficient synthesis of chiral tetrahydroquinolino pyranose derivatives catalyzed by lanthanum(iii) nitrate hexahydrate

A mild and highly efficient synthesis of chiral tetrahydroquinolino pyranose derivatives is described. The reaction of a chiral α,β‐unsaturated aldehyde containing a hydroxyl group with different aryl amines using lanthanum(III) nitrate hexahydrate as a catalyst afforded corresponding chiral tetrahydroquinolinated pyranosides in excellent yields. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:429–433, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20441     

Enantioselective LC–ESI–MS/MS method for quantitation of (−)-lumefantrine and (+)-lumefantrine in mice plasma and application to a pharmacokinetic study

We developed and validated a simple, sensitive, selective, and reliable LC–MS/MS–ESI method for the direct quantitation of lumefantrine (LFN) enantiomers [(−)-LFN and (+)-LFN] in mice plasma as per regulatory guideline. LFN enantiomers and carbamazepine (internal standard) were extracted from mice plasma using Strata X SPE (solid-phase extraction) cartridges. Good resolution between enantiomers was achieved on a Chiralpak IA-3 column using an isocratic mobile phase (0.1% of diethyl amine in methanol), which was delivered at a flow rate of 0.8 mL/min. Detection and quantitation were performed using multiple reaction monitoring mode following the transitions m/z 530.27 → 512.30 and 237.00 → 194.00 for LFN enantiomers and the internal standard, respectively, in the positive-ionization mode. The proposed method provided accurate and reproducible results over the linearity range of 2.39–895 ng/mL for each enantiomer. The intra- and inter-day precisions were in the range of 1.03–6.14 and 6.36–8.70 and 2.03–4.88 and 5.82–11.5 for (−)-LFN and (+)-LFN, respectively. Both (−)-LFN and (+)-LFN were found to be stable under different stability conditions. The method was successfully used to delineate stereoselective pharmacokinetics of LFN enantiomers in mice after an oral administration of rac-LFN (20 mg/kg). The pharmacokinetic results indicated that the disposition of LFN enantiomers was stereoselective in mice.