Time-resolved site-selection spectroscopy studies of NdAl3(BO3)4 crystals

A pulsed, tunable dye laser was used to selectively excite Nd³⁺ ions in nonequivalent crystal field sites in NdAl₃(BO₃)₄ crystals and energy transfer between ions in different types of sites was studied by monitoring the time evolution of the fluorescence spectrum. The results show that the energy transfer rate varies as t^{$\text{-1}\text{2}$} and increases with temperature. The predictions of various models of phonon-assisted energy transfer are compared to the results.     

On the Operator Semirings of a Γ-Semiring

In this paper we introduce the notion of operator semirings of a -semiring to study -semirings. It is shown that the lattices of all left (right) ideals (two-sided ideals) of a -semiring and its right (respectively left) operator semiring are isomorphic. This has many applications to characterize various -semirings.AMS Subject Classification (2000): 16Y60, 16Y99     

Zeeman effect and stark splitting of the electronic states of the rare-earth ion in the paramagnetic terbium garnets Tb<Subscript>3</Subscript>Ga<Subscript>5</Subscript>O<Subscript>12</Subscript> and Tb<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>

The Zeeman effect in the ⁷ F ₆ → ⁵ D ₄ absorption band of the Tb³⁺ ion in the paramagnetic garnets Tb₃Ga₅O₁₂ and Tb₃Al₅O₁₂ was studied. The field dependences of the Zeeman splitting of some absorption lines are found to exhibit unusual behavior: as the magnetic field increases, the band splitting decreases rather than increases. Symmetry analysis relates these lines to 4f → 4f electron transitions of the doublet-quasi-doublet or quasi-doublet-doublet type, for which the field dependences of the splitting differ radically from the well-known field dependences of the Zeeman splitting for quasi-doublet-quasi-doublet or quasi-doublet-singlet transitions in a longitudinal magnetic field.     

Effect of surface modes on the six-dimensional molecule-surface scattering dynamics of H2-Cu(100) and D2-Cu(111) systems

We include the phonon modes originating from the three layers of Cu(100)/Cu(111) surface atoms on the dynamics of molecular [H(2)(v,j)/D(2)(v,j)] degrees of freedom (DOFs) through a mean field approach, where the surface temperature is incorporated into the effective Hamiltonian (potential) either by considering Boltzmann probability (BP) or by including the Bose-Einstein probability (BEP) factor for the initial state distribution of the surface modes. The formulation of effective potential has been carried out by invoking the expression of transition probabilities for phonon modes known from the "stochastic" treatment of linearly forced harmonic oscillator (LFHO). We perform four-dimensional (4D?2D) as well as six-dimensional (6D) quantum dynamics on a parametrically time and temperature-dependent effective Hamiltonian to calculate elastic/inelastic scattering cross-section of the scattered molecule for the H(2)(v,j)-Cu(100) system, and dissociative chemisorption-physisorption for both H(2)(v,j)-Cu(100) and D(2)(v,j)-Cu(111) systems. Calculated sticking probabilities by either 4D?2D or 6D quantum dynamics on an effective potential constructed by using BP factor for the initial state distribution of the phonon modes could not show any surface temperature dependence. In the BEP case, (a) both 4D?2D and 6D quantum dynamics demonstrate that the phonon modes of the Cu(100) surface affect the state-to-state transition probabilities of the scattered H(2) molecule substantially, and (b) the sticking probabilities due to the collision of H(2) on Cu(100) and D(2) on Cu(111) surfaces show noticeable and substantial change, respectively, as function of surface temperature only when the quantum dynamics of all six molecular DOFs are treated in a fully correlated manner (6D).     

The effect of phonon modes on the H2(v, j)/D2(v, j)-Cu(1nn) scattering processes

We include the effect of the phonon modes originating from the three layers of Cu(1nn) surface atoms on the dynamics of incoming molecular [H(2)(v, j)/D(2)(v, j)] degrees of freedom (DOFs) through a mean-field approach, where the surface temperature is incorporated into the effective potential by considering Bose-Einstein probability (BEP) factor for the initial state distribution of the surface modes calculated within harmonic approximation. Such time and temperature dependent effective Hamiltonian is further subdivided assuming a weak coupling between the two sets of molecular DOFs, namely, (x, y, z, Z) and (X, Y), respectively, in particular, to reduce the computational cost and the corresponding coupled quantum dynamical equations of motion have been formulated in terms of Time Dependent Discrete Variable Representation (TDDVR) approach. We demonstrate the workability of TDDVR method to investigate the scattering of H(2)(v, j) on Cu(1nn) surface by calculating the reaction probabilities and scattering cross-sections. Calculated results show that the phonon modes affect (a) the state-to-state transition probabilities of the scattered H(2) molecule substantially but chemisorption and physisorption processes negligibly and (b) the reaction probability of the incoming D(2) molecule noticeably.     

Spectroscopic properties of the molecular ions BeX+ (X=Na,K, Rb): forming cold molecular ions from an ion–atom mixture by stimulated Raman adiabatic process

In this theoretical work, we calculate potential energy curves, spectroscopic parameters and transition dipole moments of molecular ions BeX⁺ (X=Na, K, Rb) composed of alkaline ion Be and alkali atom X with a quantum chemistry approach based on the pseudopotential model, Gaussian basis sets, effective core polarisation potentials and full configuration interaction. We study in detail collisions of the alkaline ion and alkali atom in quantum regime. Besides, we study the possibility of the formation of molecular ions from the ion–atom colliding systems by stimulated Raman adiabatic process and discuss the parameters regime under which the population transfer is feasible. Our results are important for ion–atom cold collisions and experimental realisation of cold molecular ion formation.     

In vivo encapsulation of nucleic acids using an engineered nonviral protein capsid

In Nature, protein capsids function as molecular containers for a wide variety of molecular cargoes. Such containers have great potential for applications in nanotechnology, which often require encapsulation of non-native guest molecules. Charge complementarity represents a potentially powerful strategy for engineering novel encapsulation systems. In an effort to explore the generality of this approach, we engineered a nonviral, 60-subunit capsid, lumazine synthase from Aquifex aeolicus (AaLS), to act as a container for nucleic acid. Four mutations were introduced per subunit to increase the positive charge at the inner surface of the capsid. Characterization of the mutant (AaLS-pos) revealed that the positive charges lead to the uptake of cellular RNA during production and assembly of the capsid in vivo. Surprisingly, AaLS-pos capsids were found to be enriched with RNA molecules approximately 200-350 bases in length, suggesting that this simple charge complementarity approach to RNA encapsulation leads to both high affinity and a degree of selectivity. The ability to control loading of RNA by tuning the charge at the inner surface of a protein capsid could illuminate aspects of genome recognition by viruses and pave the way for the development of improved RNA delivery systems.     

Kinetic Analysis and Optimization for the Catalytic Esterification Step of PPT Polymerization

Summary: A well‐validated kinetic scheme has been studied for PPT, poly(propylene terephthalate) polymerization process in batch and semi‐batch mode with tetrabutoxytitanium (TBOT), a proven catalyst. Optimization study and analysis for PPT are rare, as the industrial relevance of PPT just became vibrant due to the commercial availability of one of its monomers in industrial scale in the recent past. Correctness of the analysis is checked by a new approach and parameters for the model are estimated from available experimental data. Solubility of terephthalic acid (TPA) is less in reaction medium and this effect is also considered along with the reaction scheme. Several simulations have been performed to see various process dynamics and this ultimately helps in formulating optimization problems. Using recently developed and well tested real‐coded non‐dominated sorting genetic algorithm‐II, a state‐of‐the art evolutionary optimization algorithm, a couple of three objective optimization problems have been solved and corresponding Pareto sets are presented. Results show remarkably promising aspects of productivity enhancement with an improvement in product quality. Sensitivity analysis for relatively uncertain solubility parameter is also performed to estimate its effect over the proposed optimal solutions.

Multiobjective Pareto front for 3 objectives: degree of polymerization, time and (bTPA + bPG).     

Rhodium(III) complexes of 1-Alkyl-2-{(o-thioalkyl) phenylazo}imidazoles: synthesis,structure, spectral characterization,DNA binding study and DFT calculation

Transition Metal Chemistry - The Rh(III) complexes of 1-alkyl-2-{(o-thioalkyl)phenylazo}imidazole (SRaaiNR′, 1; R = R′= Me (a); R = Me, R′= Et...     

Photoinduced Dynamics and Toxicity of a Cancer Drug in Proximity of Inorganic Nanoparticles under Visible Light

Drug sensitization with various inorganic nanoparticles (NPs) has proved to be a promising and an emergent concept in the field of nanomedicine. Rose bengal (RB), a notable photosensitizer, triggers the formation of reactive oxygen species under green‐light irradiation, and consequently, it induces cytotoxicity and cell death. In the present study, the effect of photoinduced dynamics of RB upon complexation with semiconductor zinc oxide NPs is explored. To accomplish this, we successfully synthesized nanohybrids of RB with ZnO NPs with a particle size of 24 nm and optically characterized them. The uniform size and integrity of the particles were confirmed by high‐resolution transmission electron microscopy. UV/Vis absorption and steady‐state fluorescence studies reveal the formation of the nanohybrids. ultrafast picosecond‐resolved fluorescence studies of RB–ZnO nanohybrids demonstrate an efficient electron transfer from the photoexcited drug to the semiconductor NPs. Picosecond‐resolved Förster resonance energy transfer from ZnO NPs to RB unravel the proximity of the drug to the semiconductor at the molecular level. The photoinduced ROS formation was monitored using a dichlorofluorescin oxidation assay, which is a conventional oxidative stress indicator. It is observed that the ROS generation under green light illumination is greater at low concentrations of RB–ZnO nanohybrids compared with free RB. Substantial photodynamic activity of the nanohybrids in bacterial and fungal cell lines validated the in vitro toxicity results. Furthermore, the cytotoxic effect of the nanohybrids in HeLa cells, which was monitored by MTT assay, is also noteworthy.