In this review, methods to obtain the orientational order of topologically variant molecular mesogens using by one- and two-dimensional (2D) solid-state 13C nuclear magnetic resonance (NMR) spectroscopy are described. Besides 13C chemical shifts, the 13C─1H dipolar couplings measured from 2D-separated local field (SLF) technique are used for computing the order parameters of a variety of mesogens. The investigated molecules are composed of a variable number of rings in the core, that is, core ranging from simply one ring to five rings. Among the mesogens investigated, a special focus has been placed on mesogens with thiophene rings, which are gaining popularity as liquid crystalline organic semiconductors. The replacement of a phenyl ring by thiophene in the core has a dramatic influence on molecular topology, as observed from the measured order parameters. The review highlights the advantages of the 2D SLF method for understanding the local dynamics and for mapping the topology of mesogens through the measured order parameters. SLF NMR studies of as many as 24 molecular mesogens that vary in terms of the molecular structure as well as topology are covered in the review. Order parameters of the rings have been estimated from the 13C─1H dipolar couplings in the nematic, smectic A, smectic C, and tilted hexatic phases as well as in B1 and B2 mesophases of various mesogens. It is anticipated that, in the years to come, the 2D SLF method would provide advanced molecular information on structurally complex mesogens that are emerging in liquid crystal science through the incessant efforts of synthetic chemists. The mini review covers the orientational order of topologically variant molecular mesogens determined by 1D and 2D solid-state 13C NMR spectroscopy. Accordingly, rod-like, bent-core, and thiophene mesogens were subjected to 2D SLF measurements to get the order parameters from which the topology was established. The replacement of phenyl ring by thiophene and its influence on order parameters as well as on molecular topology is also discussed. 相似文献
Molecular confinement plays a significant effect on trapped gas and solvent molecules. A fundamental understanding of gas adsorption within the porous confinement provides information necessary to design a material with improved selectivity. In this regard, metal–organic framework (MOF) adsorbents are ideal candidate materials to study confinement effects for weakly interacting gas molecules, such as noble gases. Among the noble gases, xenon (Xe) has practical applications in the medical, automotive and aerospace industries. In this Communication, we report an ultra-microporous nickel-isonicotinate MOF with exceptional Xe uptake and selectivity compared to all benchmark MOF and porous organic cage materials. The selectivity arises because of the near perfect fit of the atomic Xe inside the porous confinement. Notably, at low partial pressure, the Ni–MOF interacts very strongly with Xe compared to the closely related Krypton gas (Kr) and more polarizable CO2. Further 129Xe NMR suggests a broad isotropic chemical shift due to the reduced motion as a result of confinement. 相似文献
A series of aza‐polycyles containing octahydroacridine core were prepared via an intramolecular aza‐Diels‐Alder reaction of a dimerized citral with various aromatic amines. This reaction is efficiently catalyzed by InCl3 at ambient temperature to afford the corresponding cyclized products in moderate to good yields. 相似文献
NMR spectroscopy is a powerful means of studying liquid‐crystalline systems at atomic resolutions. Of the many parameters that can provide information on the dynamics and order of the systems, 1H–13C dipolar couplings are an important means of obtaining such information. Depending on the details of the molecular structure and the magnitude of the order parameters, the dipolar couplings can vary over a wide range of values. Thus the method employed to estimate the dipolar couplings should be capable of estimating both large and small dipolar couplings at the same time. For this purpose, we consider here a two‐dimensional NMR experiment that works similar to the insensitive nuclei enhanced by polarization transfer (INEPT) experiment in solution. With the incorporation of a modification proposed earlier for experiments with low radio frequency power, the scheme is observed to enable a wide range of dipolar couplings to be estimated at the same time. We utilized this approach to obtain dipolar couplings in a liquid crystal with phenyl rings attached to either end of the molecule, and estimated its local order parameters. 相似文献
Human Mammary Tumor Virus (HMTV) or Mouse Mammary Tumor Virus holds similarity as an endogenous onco-retrovirus belongs to retroviridae family, predominantly infects the epithelial cell of human as well as mouse. With the recognition of nano-biosensor in nanotechnology, ideal interdigitated electrode (IDE) was genuinely performed for HMTV detection. Aluminium enriched IDE (AlIDE) was fabricated for high performance detection with a cost-effective photolithography technique. In this research, (3-glycidyloxypropyl) trimethoxysilane refined platform was selected to detect the conductivity with HMTV target DNA interaction on the designed AlIDE. Strong binding affinity of streptavidin-biotin with target DNA enhanced the sensitivity by empowering higher number of HMTV probe and target complementation on sensing surface. Furthermore, the target DNA was immobilized on probe modified AlIDE and a quantitative value of 100 aM attained as a lowest detection. A linear with dose-dependent duplex formation was shown with the regression coefficient value of 0.964. Negative control has shown insignificant detection at 10 pM, which justifies the higher fold discrimination with specificity. The excellence of AlIDE performance in detection of HMTV may pave the way for more verification on other diseases. 相似文献
Chitosan is a natural based polymer obtained by alkaline deacetylation of chitin, exhibiting excellent properties such as non‐toxicity, biocompatibility and biodegradability. N‐Methylenephenyl phosphonic chitosan (NMPPC) is synthesized from chitosan by reacting with phenyl phosphonic acid using formaldehyde. The NMPPC was characterized by FTIR, 31P‐NMR, X‐ray diffraction, scanning electron microscopy, thermogravimeteric analysis and solubility studies. A significant decrease of molecular weight was observed in the NMPPC. The TGA studies suggested that NMPPC has less thermal stability than chitosan. The X‐ray diffraction analysis showed that NMPPC was amorphous in nature. The solubility property of the polymer was improved after the incorporation of a phenyl phosphonic group. 相似文献
Gel combustion method was used to prepare nano-alumina from aluminum nitrate and stoichiometric amount of glycine as fuel. The TG–DTA pattern of the as-prepared powder (combustion product) exhibited exotherms with peaks around 500 and 900 °C accompanied with loss of weight of 25 and 5 % attributed to burning away of carbon left behind and decomposition of residual reaction intermediates left behind, respectively. Even though mass stability is attained above 900 °C, the DTA exhibited an exotherm around 1,150 °C attributed to transformation of gamma to alpha form of alumina. The XRD studies revealed that the powder heated to 900 °C was chemically pure nano-crystalline alumina while that heated above 1,150 °C was crystalline alpha form. As nano-crystalline powders are sinter-active, the nano-crystalline alumina formed by calcination at 900 °C was used to form the coating. A morphological feature of the agglomerates of nano-alumina powders were evaluated using SEM. The powder was de-agglomerated by wet grinding method. The dispersion conditions to form slurry using 900 °C calcined powder for slurry-based coating was optimized using zeta-potential studies, and it was found to exhibit a maximum value of ?45 mV at a pH of 9. After 8 h of grinding, the median agglomerate size reduced to 2 μm. Rheological studies exhibited desired pseudoplastic behavior in the range of 10–20 vol.% of solid while the slurry with 15 vol.% only form crack free, dense, and adherent coating after heat treatment at 1,150 °C. The morphology of the coating was found to be uniform and dense. 相似文献
One-pot synthesis of 3-aryl-4(3H)-quinazolinones has been realized through a cascade annulation. Reaction of aryldiazonium salt with a nitrile provides in situ generation of a reactive nitrilium ion, which is attacked by the amino group of 2-aminobenzoate followed by cyclization to deliver the desired product. This strategy offers a convenient and easy access to a wide range of functionalized quinazolinone. 相似文献
Polymer electrolytes comprising polyvinyl pyrrolidone (PVP) as host polymer and Mg(ClO4)2 as dopant salt have been prepared by solution casting technique using double-distilled water as solvent. The changes in the structural properties on the incorporation of dopant were investigated by XRD and FTIR analysis. The ionic conductivity and dielectric behavior were explored using AC impedance spectroscopy. The ionic conductivity increases with increasing dopant concentration. The conductivity enhancement with the increasing salt concentration is correlated with the increase in amorphous nature of the electrolytes. The frequency dependence of electrical conductivity obeys the universal Jonscher power law. The electrical modulus representation shows a loss feature in the imaginary component. The distribution of relaxation times was indicated by a deformed arc form of the Argand plot. The relative dielectric constant (εr) decreases with increase in frequency in the low frequency region whereas a frequency-independent behavior is observed in the high frequency region. The total ionic transference number studies have confirmed that the mobile charge carriers are ions. Results obtained by cyclic voltammetry on SS/60 mol% PVP/40 mol% Mg(ClO4)2 SPE/SS symmetrical cell show evidence for reversibility.
The effect of electric field assisted annealing on the microstructure, composition and ionic conductivity properties in CeO2/YSZ oxide heterostructures have been investigated using molecular dynamics simulations. Amorphization–recrystallization steps were performed with and without external electric field of strength 10?MV/cm along three different orientations: in-plane (YZ), normal (X) and 45° resultant (XY) with respect to the oxide heterointerfaces. The microstructural and compositional differences at the interfaces and in the interior of the oxide heterolayers were evaluated and were found to show a clear correlation with the orientations of the applied field. In particular, the XY configuration displayed a compressive lattice strain of ~9% along with a reduced oxygen vacancy concentration when compared to the others. Ionic density profiles suggest pronounced segregation (~60% higher compared to the average value in the interior) of yttrium ions closer to the YSZ/CeO2 interface for the XY configuration. Other configurations exhibit minimal to no such variations. These microstructural differences are found to affect the number of mobile charge carriers and the activation barriers associated with ionic migration through the oxide lattice and consequently, influence the ionic conductivity. 相似文献