Carbon-13 NMR spectroscopy of some pentacyclic triterpenoids

Carbon-13 NMR signal assignment of a number of polyoxygenated triterpenes of the olean-12-ene and urs-12-ene series, carried out by considering the changes in chemical shift produced by the change of oxygenation pattern(s), and using methyl oleanolate as a model, are reported.     

Nonequilibrium quantum criticality in open electronic systems

A theory is presented of quantum criticality in open (coupled to reservoirs) itinerant-electron magnets, with nonequilibrium drive provided by current flow across the system. Both departures from equilibrium at conventional (equilibrium) quantum critical points and the physics of phase transitions induced by the nonequilibrium drive are treated. Nonequilibrium-induced phase transitions are found to have the same leading critical behavior as conventional thermal phase transitions.     

Identifiability issues in dynamic stress–strength modeling

In many real-life scenarios, system reliability depends on dynamic stress–strength interference, where strength degrades and stress accumulates concurrently over time. In some other cases, shocks appear at random time points, causing damage which is only effective at the instant of shock arrival. In this paper, we consider the identifiability problem of a system under deterministic strength degradation and stochastic damage due to shocks arriving according to a homogeneous Poisson process. We provide conditions under which the models are identifiable with respect to lifetime data only. We also consider current status data and suggest to collect additional information and discuss the issues of model identifiability under different data configurations.     

In-situ and ex-situ study of crystallization behaviour of magnetron sputtered Ni63Zr37 amorphous thin film

ABSTRACT

The stages of crystallization of magnetron sputter-deposited Ni₆₃Zr₃₇ film with mostly amorphous structure have been investigated by differential scanning calorimetry (DSC) and in-situ annealing at 300°C by use of heating stage on a high-resolution transmission electron microscope (HRTEM). These results have been further confirmed by grazing incidence X-ray diffraction analyses of thin film specimens annealed ex-situ at 300°C for various durations. The temperature for crystallization found by DSC has been found to increase from 371°C to 434°C with an increase in heating rate from 3°C/min to 10°C/min, and the apparent activation energy for amorphous to crystalline transformation has been found as ～260.2?kJ/mol from the Kissinger plot. Studies on HRTEM using in-situ heating stage have shown the crystallization to occur on annealing at 300°C for ～10?min. Crystallization at a temperature lower than that found by DSC is attributed to structural relaxation with reduction of free volume due to thermal activation. It has been observed that Ni₃Zr forms first due to its large negative enthalpy of formation, and is followed by the formation of Ni-rich solid solution (Ni_ss) grains. HRTEM studies have shown grain rotation with the formation of partial dislocations at Ni₃Zr-Ni_ss interfaces as well as twinning followed by detwinning with dislocation formation in the Ni_ss matrix possibly to reduce the interfacial energy.     

Interactions of Nile Blue with Micelles, Reverse Micelles and a Genomic DNA

In this contribution we report studies on the nature of binding of a small ligand/drug Nile blue (NB) with sodium dodecyl sulfate (SDS) micelles, bis-(2-ethylehexyl) sulfosuccinate (AOT)/isooctane reverse micelles (RM) and a genomic DNA extracted from Salmon sperm. With detailed steady state and picosecond resolved optical spectroscopic techniques, we examined the fluorescence quenching of the ligand upon complexation with the SDS monomers and DNA. Polarization analyzed picosecond-resolved fluorescence measurements reveal geometrical restriction on the probe in SDS micelles, AOT-RM and DNA. Steady state and time resolved studies on the probe in nanocages of AOT RM with various degrees of hydration (w₀) reveal the existence of NB as two distinct species namely, neutral and cationic. This study confirms that the emission of NB in aqueous micelles and DNA solution is due to the cationic form of the drug. Our experiments clearly identified non-specific electrostatic and intercalative modes of interaction of the probe with the DNA at lower and higher DNA concentrations respectively. The nature of binding of NB in presence of the DNA and SDS micelles reveals that the binding affinity of the probe is higher with the micelles than with the DNA. The complex rigidity of NB with DNA and its fluorescence quenching with DNA elucidate a strong recognition mechanism between NB and DNA.     

Two photon exchange contributions to elastic $\vec{e}+p\rightarrow e+\vec{p}$ process in the non-local field formalism

We compute the two photon exchange contributions to elastic scattering of polarized electrons from target protons. We use a non-local field theory formalism for this calculation. The formalism maintains gauge invariance and provides a systematic procedure for making this calculation. The results depend on one unknown parameter, . We compute the two photon exchange correction to the ratio of electric to magnetic form factors extracted using polarization transfer experiments. The correction is found to be small if . However, for larger values of , the correction can be quite significant. The correction to the polarization transfer results goes in the right direction to explain their difference with the ratio measured by the Rosenbluth separation method. We find that the difference between the two experimental results can be explained for a wide range of values of the parameter . We also find that the corrections due to two photon exchange depend on the photon longitudinal polarization ε. Hence, we predict an ε dependence of the form factor ratio extracted using the polarization transfer technique. Finally, we obtain a limit on by requiring that the non-linearity in ε dependence of the unpolarized reduced cross section is within experimental errors.     

Edge Capping of 2D‐MXene Sheets with Polyanionic Salts To Mitigate Oxidation in Aqueous Colloidal Suspensions

MXenes have shown promise in myriad applications, such as energy storage, catalysis, EMI shielding, among many others. However, MXene oxidation in aqueous colloidal suspensions when stored in water at ambient conditions remains a challenge. It is now shown that by simply capping the edges of individual MXene flakes, Ti₃C₂T_z and V₂CT_z, by polyanions such as polyphosphates, polysilicates or polyborates, it is possible to quite significantly reduce their propensity for oxidation even when held in aerated water for weeks. This breakthrough resulted from the realization that the edges of MXene sheets are positively charged. It is thus an example of selectively functionalizing the edges differently from the MXene sheet surfaces.