Development and optimization of an integrated PDMS based‐microdialysis microchip electrophoresis device with on‐chip derivatization for continuous monitoring of primary amines

An all‐PDMS on‐line microdialysis‐microchip electrophoresis with on‐chip derivatization and electrophoretic separation for near real‐time monitoring of primary amine‐containing analytes is described. Each part of the chip was optimized separately, and the effect of each of the components on temporal resolution, lag time, and separation efficiency of the device was determined. Aspartate and glutamate were employed as test analytes. Derivatization was accomplished with naphthalene‐2,3,‐dicarboxyaldehyde/cyanide (NDA/CN^?), and the separation was performed using a 15‐cm serpentine channel. The analytes were detected using LIF detection.     

Resonance Raman spectroscopic study for radial vibrational modes in ultra‐thin walled TiO2 nanotubes

The study reports the observation of radial vibrational modes in ultra‐thin walled anatase TiO₂ nanotube powders grown by rapid breakdown anodization technique using resonant Raman spectroscopic study. The as‐grown tubes in the anatase phase are around 2–5 nm in wall thickness, 15–18 nm in diameter and few microns in length. The E_{g(ν1,ν5,ν6)} phonon modes with molecular vibrations in the radial direction are predominant in the resonance Raman spectroscopy using 325 nm He–Cd excitation. Multi‐phonons including overtones and combinational modes of E_{g(ν1,ν5,ν6)} are abundantly observed. Fröhlich interaction owing to electron–phonon coupling in the resonance Raman spectroscopy of ultra‐thin wall nanotubes is responsible for the observation of radial vibrational modes. Finite size with large surface energy in these nanotubes energetically favor only one mode, B_1g(ν4) with unidirectional molecular vibrations in the parallel configuration out of the three Raman modes with molecular vibration normal to the radial modes. Enhanced specific heat with increasing temperatures in these nanotubes as compared to that reported for nanoparticles of similar diameter may possibly be related to the presence of the prominent radial mode along with other energetic phonon mode. The findings elucidate the understanding of total energy landscape for TiO₂ nanotubes. Copyright © 2015 John Wiley & Sons, Ltd.     

Invoking forbidden modes in SnO2 nanoparticles using tip enhanced Raman spectroscopy

Raman forbidden modes and surface defect‐related Raman features in SnO₂ nanostructures carry information about disorder and surface defects which strongly influence important technological applications like catalysis and sensing. Because of the weak intensities of these peaks, it is difficult to identify these features by using conventional Raman spectroscopy. Tip enhanced Raman spectroscopy (TERS) studies conducted on SnO₂ nanoparticles (NPs) of size 4 and 25 nm have offered significant insights of prevalent defects and disorders. Along with one order enhancement in symmetry allowed Raman modes, new peaks related to disorder and surface defects of SnO₂ NPs were found with significant intensity. Temperature‐dependent Raman studies were also carried out for these NPs and correlated with the TERS spectra. For quasi‐quantum dot sized 4‐nm NPs, the TERS study was found to be the best technique to probe the finite size‐related Raman forbidden modes. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of lateral substituents on the mesophases formed by some achiral banana-shaped molecules

Several compounds composed of banana-shaped molecules and exhibiting mesophases are reported. The effect of different lateral substituents on the type of mesophase formed is examined and a comparison made with unsubstituted compounds. The mesophases have been characterized using techniques such as polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction. The B₂ phase shows antiferroelectric switching behaviour.     

Coherent Stochastic Resonance in One Dimensional Diffusion with One Reflecting and One Absorbing Boundaries

It is shown that the single-step periodic signal (periodic telegraph signal) can not produce coherent stochastic resonance for diffusion on a segment with one absorbing and one reflecting end points while the multi-step periodic signal does. The general features of this process are exihibited. The resonant frequency is found to decrease and the mean first passage time at resonant frequency increases linearly, as we increase the length of the medium. The cycle variable is shown to be the proper argument to express the first passage probability at resonance. A formula for first passage probability at resonance is derived in terms of two universal functions, which clearly isolates its dependence on the length of the medium.     

Synthesis of spirocyclic thiazolidinediones using ring-closing metathesis and one-pot sequential ring-closing/cross metathesis

A novel synthetic route to spirocyclic thiazolidinediones is reported by utilizing ring-closing metathesis (RCM). A selective cross metathesis (CM) of N-allyl azaspiro derivatives with different olefins has been demonstrated to prepare substituted azaspiro-[4.4]nonenediones. The X-ray crystal structure of a spirocyclic thiazolidinedione dimer is described, which has been prepared in two steps from thiazolidinedione using a one-pot sequential ring-closing and self metathesis. Cross metathesis proceeds smoothly with both electron rich and poor olefins. The symmetrical bis-thiazolidinedione spirocyclic system can be used as CM coupling partner with olefins. One-pot sequential RCM-CM has been developed for the synthesis of substituted spirocyclic compounds. The methodology allows a quick access to thia-azaspiro-[4.4]nonene and -[4.5]decene-dione ring systems from readily available starting materials which are not otherwise accessible.     

Bypass of aflatoxin B1 adducts by the Sulfolobus solfataricus DNA polymerase IV

Aflatoxin B(1) (AFB(1)) is oxidized to an epoxide in vivo, which forms an N7-dG DNA adduct (AFB(1)-N7-dG). The AFB(1)-N7-dG can rearrange to a formamidopyrimidine (AFB(1)-FAPY) derivative. Both AFB(1)-N7-dG and the β-anomer of the AFB(1)-FAPY adduct yield G→T transversions in Escherichia coli, but the latter is more mutagenic. We show that the Sulfolobus solfataricus P2 DNA polymerase IV (Dpo4) bypasses AFB(1)-N7-dG in an error-free manner but conducts error-prone replication past the AFB(1)-FAPY adduct, including misinsertion of dATP, consistent with the G→T mutations observed in E. coli. Three ternary (Dpo4-DNA-dNTP) structures with AFB(1)-N7-dG adducted template:primers have been solved. These demonstrate insertion of dCTP opposite the AFB(1)-N7-dG adduct, and correct vs incorrect insertion of dATP vs dTTP opposite the 5'-template neighbor dT from a primed AFB(1)-N7-dG:dC pair. The insertion of dTTP reveals hydrogen bonding between the template N3 imino proton and the O(2) oxygen of dTTP, and between the template T O(4) oxygen and the N3 imino proton of dTTP, perhaps explaining why this polymerase does not efficiently catalyze phosphodiester bond formation from this mispair. The AFB(1)-N7-dG maintains the 5'-intercalation of the AFB(1) moiety observed in DNA. The bond between N7-dG and C8 of the AFB(1) moiety remains in plane with the alkylated guanine, creating a 16° inclination of the AFB(1) moiety with respect to the guanine. A binary (Dpo4-DNA) structure with an AFB(1)-FAPY adducted template:primer also maintains 5'-intercalation of the AFB(1) moiety. The β-deoxyribose anomer is observed. Rotation about the FAPY C5-N(5) bond orients the bond between N(5) and C8 of the AFB(1) moiety out of plane in the 5'-direction, with respect to the FAPY base. The formamide group extends in the 3'-direction. This improves stacking of the AFB(1) moiety above the 5'-face of the FAPY base, as compared to the AFB(1)-N7-dG adduct. Ternary structures with AFB(1)-β-FAPY adducted template:primers show correct vs incorrect insertion of dATP vs dTTP opposite the 5'-template neighbor dT from a primed AFB(1)-β-FAPY:dC pair. For dATP, the oxygen atom of the FAPY formamide group participates in a water-mediated hydrogen bond with Arg332. The insertion of dTTP yields a structure similar to that observed for the AFB(1)-N7-dG adduct. The differential accommodation of these AFB(1) adducts within the active site may, in part, modulate lesion bypass.     

Slow dynamics in a liquid crystal: 1H and 19F NMR relaxometry

Spin-lattice relaxation rates (R(1H) and R(1F)) of two nuclear species ((1)H and (19)F) are measured at different temperatures in the isotropic phase of a liquid crystal (4(')-butoxy-3(')-fluoro-4-isothiocyanatotolane-4OFTOL), over a wide range of Larmor frequency (10 kHz-50 MHz). Their dispersion profiles are found to be qualitatively very different, and the R(1F) in particular shows significant dispersion (varying over two orders of magnitude) in the entire isotropic range, unlike R(1H). The proton spin-lattice relaxation, as has been established, is mediated by time modulation of magnetic dipolar interactions with other protons (case of like spins), and the discernable dispersion in the mid-frequency range, observed as the isotropic to nematic transition is approached on cooling, is indicative of the critical slowing of the time fluctuations of the nematic order. Significant dispersion seen in the R(1F) extending to very low frequencies suggests a distinctly different relaxation path which is exclusively sensitive to the ultra slow modes apparently present in the system. We find that under the conditions of our experiment at low Zeeman fields, spin-rotation coupling of the fluorine with the molecular angular momentum is the dominant mechanism, and the observed dispersion is thus attributed to the presence of slow torques experienced by the molecules, arising clearly from collective modes. Following the arguments advanced to explain similar slow processes inferred from earlier detailed ESR measurements in liquid crystals, we propose that slowly relaxing local structures representing such dynamic processes could be the likely underlying mechanism providing the necessary slow molecular angular momentum correlations to manifest as the observed low frequency dispersion. We also find that the effects of the onset of cross-relaxation between the two nuclear species when their resonance lines start overlapping at very low Larmor frequencies (below ~400 kHz), provide an additional relaxation contribution.     

Generalized Second Law of Thermodynamics in Emergent Universe

In this letter, we have considered the FRW model of the emergent universe, which was presented in our previous work (Debnath, in Class. Quantum Gravity 25:205019, 2008). We have chosen one of the form of scale factor in such a way that the emergent scenario is possible in the universe. We have also considered the universe as a thermodynamical system with the horizon surface as a boundary of the system. The entropy and the radius of the event horizon have been calculated in the emergent scenario. When the emergent scenario occurs, we have shown that the generalized second law of thermodynamics is always satisfied for open, flat and closed models of the universe.