Annulative π-Extension by Rhodium(III)-Catalyzed Ketone-Directed C−H Activation: Rapid Access to Pyrenes and Related Polycyclic Aromatic Hydrocarbons (PAHs)

Annulative π-extension (APEX) reaction has become a powerful tool for the precise synthesis of well-defined polycyclic aromatic hydrocarbons (PAHs) such as nanographene, graphene, and other PAHs possessing unique structure. Herein, an APEX reaction has been realized at the masked bay-region for the efficient and rapid synthesis of valuable PAH, pyrene, bearing substitutions at the most challenging K-region. Rh^III-catalyzed ketone-directed C−H activation at the peri-position of a naphthyl-derived ketone, alkyne-insertion, intramolecular nucleophilic attack at the carbonyl-group, dehydration, and aromatization steps occurred in one-pot to effectuate the protocol. Employing this strategy, a two-fold APEX reaction on enantiopure BINOL-derived ketones provided access to axially-chiral bipyrene derivatives. The detailed DFT study to support proposed mechanism, and synthesis of helical PAHs like dipyrenothiophene and dipyrenofuran are other highlights of the present study.     

Insight into the Multistate Emissive N,P-doped Carbon Nano-Onions: Emerging Visible-Light Absorption for Photocatalysis

Carbon dots (CDs) have become one of the most emerging materials as an alternative solar light-induced photocatalyst in contrast to traditional metal-based systems. However, one of the major challenges is the lack of visible light absorption. Herein, we have fabricated unique N, P-co-doped CDs with a self-assembled onion-like layered structure by using a bottom-up facile synthesis technique from chitosan gel and phosphoric acid as molecular precursors. This typical layered structure of N, P-co-doped carbon nano onions (N, P-CNOs), with an average size of 25–50 nm, displays an enhanced visible light absorption. Detailed structural and elemental characterizations confirm the extensive aromatic domain with P-containing surface functionalities, while electrochemical study clarifies the lowering of band gaps as well as the creation of new electronic states in comparison to the pristine N-CDs. Furthermore, the intrinsic structural features are correlated with the underpinning photophysical processes by steady-state and time-resolved fluorescence spectroscopy. In addition, steady-state polarized emission and thermo-responsive PL properties have been carried out to unveil further the structure-property correlation of N, P-CNOs, and their comparative study with pristine N-CDs at the different excitation wavelengths. Finally, N, P-CNOs exhibit efficient visible-light-induced photocatalysis, and the detailed mechanistic study is carried out by trapping the photogenerated species in an aqueous medium. The prepared N, P-CNOs displayed an excellent visible-light photocatalytic performance over MB dye with a degradation efficiency of 75.8% within 120 min along with a degradation rate constant of ∼0.0109 min⁻¹. It is concluded that the easy to synthesize and low-cost N, P-CNOs with a unique morphology hold great potential for application in visible-light photocatalysis.     

Effect of electron correlation on positronium formation in positron-helium scattering

A three-parameter correlated wave function for the helium ground state is used to study the scattering reaction , where Ps stands for positronium atom. An exact analytical expression is constructed for the first Born scattering amplitude for Ps formation from helium. Based on this numerical results are presented for both differential and total cross-sections. It is demonstrated that the inner electronic correlation of the target atom plays a crucial role in explaining the discrepency between theory and experiment. Received: 9 April 1998 / Revised: 29 September 1998 / Accepted: 19 October 1998     

Flow and heat transfer due to impulsive motion of a cone in a viscous fluid

Numerical solution has been obtained for the development of the flow over a cone which is impulsively set into motion. Initially the flow is described by the solution of Rayleigh and then it tends to the ultimate steady state solution of Falkner-Skan equation. But due to the leading edge effect the semi-similar equation describing the transient flow changes its character after certain time and the solution depends also on the ultimate steady state solution of the Falkner-Skan equation. A second-order upwind difference scheme has been used for discretisation. The temperature distribution and heat transfer has also been obtained for constant wall temperature as well as for constant heat flux at the wall. With the increase ofm, Falkner-Skan parameter, the magnitude of skin friction and wall heat transfer increases. It has been found that form≥?0.275 flow separation does not occur.     

Combined effects of rotation and translation on a MHD flow due to compressible viscous fluid

Summary The modification of an axi-symmetric viscous flow due to a relative rotation of a disk or fluid by a translation of the boundary are studied. The fluid is taken to be compressible and electrically conducting. The equations governing the motion are solved iteratively through a central-difference scheme. The effect of an axial magnetic field and disk temperature on the flow and heat transfer are included in the present analysis. The translation of the disk or fluid generates a velocity field at each plane parallel to the disk (secondary flow). The cartesian components of the velocity due to the secondary flow are oscillatory in nature when a rigid body rotation of the free stream along with a translation of the disk is considered. The magnetic field damps out the velocity field, and reduces the thickness of the boundary layer. The cross component of wall shear due to secondary flow acts in a direction opposite to the rotation of the disk or fluid for all cases of the motion. The rise in disk temperature produces an increment in the magnitude of the wall shear associated with the secondary flow.     

Thermal radiation effect on a mixed convection flow and heat transfer of the Williamson fluid past an exponentially shrinking permeable sheet with a convective boundary condition

The thermal radiation effect on a steady mixed convective flow with heat transfer of a nonlinear (non-Newtonian) Williamson fluid past an exponentially shrinking porous sheet with a convective boundary condition is investigated numerically. In this study, both an assisting flow and an opposing flow are considered. The governing equations are converted into nonlinear ordinary differential equations by using a suitable transformation. A numerical solution of the problem is obtained by using the Matlab software package for different values of the governing parameters. The results show that dual nonsimilar solutions exist for the opposing flow, whereas the solution for the assisting flow is unique. It is also observed that the dual nonsimilar solutions exist only if a certain amount of mass suction is applied through the porous sheet, which depends on the Williamson parameter, convective parameter, and radiation parameter.     

Tunnelling Dynamics of Kicked Systems: A Route to Tunnelling Control

The effects of discontinuously time-varying perturbations on the dynamics of a particle moving in harmonic, symmetric double well and symmetric triple well potentials, are investigated both classically and quantum mechanically. The quantum dynamics is followed using the time-dependent Fourier grid Hamiltonian (TDFGH) method while the classical dynamics is analyzed within the framework of classical Hamiltonian mechanics. Depending on the spatial symmetry of the perturbation and the characteristic features of the reversal time , different types of ‘phase space’ structures are observed in each of the potentials. For symmetric double and triple well potentials, quantum dynamics reveals that complete destruction of tunnelling (CDT) can be achieved in the presence of a time-dependent spatially asymmetric perturbing field that is continuous in time. Any discontinuity in time-variation of the perturbation may induce over the barrier transition. The relevance of these results in the context of (i) tunnelling control and (ii) quantum computing with 3-state or 2-state quantum registers is briefly discussed.     

Unveiling the Noncovalent Interaction of Thiazol-2-ylidene and Its Derivatives as N-heterocyclic Carbene with Different Proton Donor Molecules

The importance of noncovalent interaction has gained attention in various domains covering drug and novel catalyst design. The present study mainly characterizes the role of hydrogen bond (H-bond) and other intermolecular interactions in different (1 : 1) complex analogues formed between the N-aryl-thiazol-2-ylidene (YR) and five proton donor (HX) molecules. The analysis of the singlet-triplet energy gap ( ) confirmed the stability of the singlet state for this class of N-aryl-thiazol-2-ylidenes than the triplet state. The interaction energy values of the YR-HX complexes follow the order: YR-NH₃<YR-HCN<YR-H₂O<YR-MeOH<YR-HF. In addition, substituting the H-atom of the N−H bond with bulky groups (−R) leads to an increase in the interaction energy of the YR-HX complexes. Hence, it was found that the replacement of N-atom in N-heterocyclic carbene (NHC) by S-atom forming N-aryl-thiazol-2-ylidene results in comparable intermolecular interactions with proton donor molecules similar to imidazole-2-ylidene (NHC). The current study enlightened the role of noncovalent interactions in carbene complexes with proton donor molecules. We hope that our work on carbene chemistry will pave the way for its application in the designing and synthesis of efficient catalysts.     

Numerical study supplemented with simplified model on electrophoresis of a hydrophobic colloid incorporating finite ion size effects and ion-solvent interactions

We consider a modified electrokinetic model to study the electrophoresis of a hydrophobic particle by considering the finite sized ions. The mathematical model adopted in this study incorporates the ion steric repulsion, ion-solvent interactions as well as Maxwell stress on the electrolyte. The dielectric permittivity and viscosity of the electrolyte is considered to vary with the local ionic volume fraction. Based on this modified model for the electrokinetics we have analyzed the electrophoresis in a single as well as mixture of electrolytes of monovalent and non-$z:z$ electrolytes. The dependence of viscosity on local ionic volume fraction modifies the hydrodynamic drag as well as diffusivity of ions, which are ignored in existing studies on electrophoresis. A simplified model for electrophoresis of a hydrophobic particle incorporating the ion steric repulsion and ion-solvent interactions is developed based on the first-order perturbation on applied electric field. This simplified model is established to be efficient for a Debye layer thinner than the particle size and a smaller range of slip length. This model can be implemented for any number of ionic species as well as non-$z:z$ electrolytes. It is established that the ion steric interactions and dielectric decrement creates a counterion saturation in the Debye layer leading to an enhanced mobility compared to the standard model. However, experimental data for non-dilute cases often under predicts the theoretically determined mobility. The present modified model fills this lacuna and demonstrate that the consideration of finite ion size modifies the medium viscosity and hence, ionic mobility, which in combination lowers the mobility value.