Structure modulated electronic contributions to metalloenediyne reactivity: synthesis and thermal Bergman cyclization of MLX2 compounds

The synthesis of novel metalloendiyne complexes MLRX(2) (where L = 1,4-dibenzyl/diethyl-1,4-diaza-cyclododec-8-ene-6,10-diyne, X = halogen) are reported with their X-ray crystal structures and thermal Bergman cyclization temperatures. Two distinct types of constructs are obtained; the Zn(II) compounds are tetrahedral, while the Cu(II) and the Pd(II) compounds are all distorted- or square-planar. Each possesses structurally similar enediyne conformations and critical distances (3.75-3.88 A). The tetragonal Cu(II) species all exhibit Bergman cyclization temperatures between 140 and 150 degrees C in the solid state, while the square-planar Pd(II) analogues possess similar critical distances but cyclize at significantly higher temperatures (205-220 degrees C). In contrast, the Zn(II) derivatives show a marked halogen dependence, with X = Cl having the highest Bergman cyclization temperature, which is comparable to the Pd(II) square-planar set, while the ZnLX(2) compound with X = I shows the lowest Bergman cyclization temperature (144 degrees C), similar to the Cu(II) derivatives. Moreover, for the planar constructs, the R group has little influence on the cyclization temperatures; however, for the tetrahedral ZnLX(2) compounds, the steric influence of the R group plays a more significant role in the cyclization reaction coordinate by influencing the stability of the precyclized intermediate. This complex set of results is best interpreted by a combination of steric contributions and electronic interactions between the halogen through space (in the case of Zn(II)) and through bonds (in the case of Pd(II)) and the pi orbitals of the endiyne fragment. In contrast, for Cu(II) systems, the distorted square-planar geometry permits neither direct through space nor symmetry-allowed through bond communication between the orbital partners, and thus little variation in Bergman cyclization reactivity is observed.     

Oxo- and oxoperoxo-molybdenum(VI) complexes with aryl hydroxamates: synthesis, structure, and catalytic uses in highly efficient, selective, and ecologically benign peroxidic epoxidation of olefins

A solution obtained by dissolving MoO3 in H2O2 reacts separately with secondary hydroxamic acids (viz., N-benzoyl N-phenyl hydroxamic acid (BPHAH), N-benzoyl N-ortho-, -meta-, -para-tolyl hydroxamic acids, (BOTHAH, BMTHAH, and BPTHAH, respectively), and N-cinnamoyl N-phenyl hydroxamic acid (CPHAH) affording [MoO(O2)(BPHA)2] (1), [MoO(O2)(BOTHA)2] (2), [MoO(O2)(BMTHA)2] (3), [MoO(O2)(BPTHA)2] (4), and [Mo(O)2(CPHA)2](5), respectively. The O and O2 are situated cis to each other in 2-4, but in each case, they are disordered and distributed over four sites. This disorder does not exist in the 6-coordinate cis dioxo complex 5, to which crude MoO(O2)(CPHA)2 (5') was converted during recrystallization. An aqueous molybdate solution readily reacts with all those hydroxamic acids producing [Mo(O)2(hydroxamate)2] (6). While 2, 3, and 4 possess a very distorted pentagonal bipyramidal structure, 5 has a distorted octahedral geometry. In the solid state, as well as in solution, 5 exists as two apparently enantiomerically related molecules differing in the orientation of the pendant phenyl rings. To emphasize that the formation and structural uniqueness of 5 compared to 1-4 is caused by the influence of the cinnamoyl residue, one compound of the 6 series, namely, [Mo(O)2(BPHA)2] (6A), was structurally characterized to prove directly that the special stereochemical properties of 5 rely on the special electronic structure of CPHA- ligand. Complexes 1-5, as well as 6, show high potential and selectivity as catalysts in the epoxidation of olefins at room temperature in the presence of NaHCO3 as a promoter and H2O2 as a terminal oxidant. A comparative epoxidation study has been performed to determine the relative efficiency of the catalysts. To make the epoxidation method cost effective, a study to optimize the use of H2O2 has also been performed. To obtain evidence in favor of our suggested mechanism to this homogeneous olefin --> epoxide conversion, it was necessary to synthesize a peroxo-rich compound, namely, [MoO(O2)2BMTHA]- (7), but the attempted synthesis culminated in the isolation of [MoO(O2)2(C6H5COO)]- (8), obviously, via the hydrolysis of coordinated BMTHA.     

Receiving sensitivity and transmitting voltage response of a fluid loaded spherical piezoelectric transducer with an elastic coating

A method is presented to determine the response of a spherical acoustic transducer that consists of a fluid-filled piezoelectric sphere with an elastic coating embedded in infinite fluid to electrical and plane-wave acoustic excitations. The exact spherically symmetric, linear, differential, governing equations are used for the interior and exterior fluids, and elastic and piezoelectric materials. Under acoustic excitation and open circuit boundary condition, the equation governing the piezoelectric sphere is homogeneous and the solution is expressed in terms of Bessel functions. Under electrical excitation, the equation governing the piezoelectric sphere is inhomogeneous and the complementary solution is expressed in terms of Bessel functions and the particular integral is expressed in terms of a power series. Numerical results are presented to illustrate the effect of dimensions of the piezoelectric sphere, fluid loading, elastic coating and internal material losses on the open-circuit receiving sensitivity and transmitting voltage response of the transducer.     

Coupling and crosstalk characteristics of hybrid silicon plasmonic waveguides

In this paper, the design and analysis of an ultracompact coupler based on a hybrid silicon plasmonic waveguide (HSPW) is proposed and its coupling and crosstalk characteristics have been theoretically investigated for the development of optical interconnects that can be realized using well-established complementary metal-oxide-semiconductor-compatible fabrication techniques. To determine the minimum horizontal separation distance and efficient coupling length for the designed coupler, the symmetric and antisymmetric supermodes are obtained and their characteristics are studied at a wavelength of 1.55 μm. Efficient light coupling is exhibited by the HSPW coupler with 75 % of power transfer between the two HSPWs with ultrashort coupling length of 2.14 μm when the separation distance is 50 nm. Further, it is shown that the crosstalk is significantly reduced with the insertion of metallic strip between the two HSPWs for realizing highly dense integrated plasmonic circuits.     

Influence of various shapes of nanoparticles on unsteady stagnation-point flow of Cu-H2O nanofluid on a flat surface in a porous medium: A stability analysis

The nanofluid and porous medium together are able to fulfill the requirement of high cooling rate in many engineering problems. So, here the impact of various shapes of nanoparticles on unsteady stagnation-point flow of Cu-H₂O nanofluid on a flat surface in a porous medium is examined. Moreover, the thermal radiation and viscous dissipation effects are considered. The problem governing partial differential equations are converted into self-similar coupled ordinary differential equations and those are numerically solved by the shooting method. The computed results can reveal many vital findings of practical importance. Firstly, dual solutions exist for decelerating unsteady flow and for accelerating unsteady and steady flows, the solution is unique. The presence of nanoparticles affects the existence of dual solution in decelerating unsteady flow only when the medium of the flow is a porous medium. But different shapes of nanoparticles are not disturbing the dual solution existence range, though it has a considerable impact on thermal conductivity of the mixture. Different shapes of nanoparticles act differently to enhance the heat transfer characteristics of the base fluid, i.e., the water here. On the other hand, the existence range of dual solutions becomes wider for a larger permeability parameter related to the porous medium. Regarding the cooling rate of the heated surface, it rises with the permeability parameter, shape factor (related to various shapes of Cu-nanoparticles), and radiation parameter. The surface drag force becomes stronger with the permeability parameter. Also, with growing values of nanoparticle volume fraction, the boundary layer thickness (BLT) increases and the thermal BLT becomes thicker with larger values of shape factor. For decelerating unsteady flow, the nanofluid velocity rises with permeability parameter in the case of upper branch solution and an opposite trend for the lower branch is witnessed. The thermal BLT is thicker with radiation parameter. Due to the existence of dual solutions, a linear stability analysis is made and it is concluded that the upper branch and unique solutions are stable solutions.     

Influence of 2'-deoxy sugar moiety on excited-state protonation equilibrium of adenine and adenosine with acridine inside SDS micelles: a time-resolved study with quantum chemical calculations

The protonation dynamics of the DNA base adenine (Ade) and its nucleoside 2'-deoxyadenosine (d-Ade) are investigated by monitoring the deprotonation kinetics of an N-heterocyclic DNA intercalator, acridine (Acr), in the confined environment of sodium dodecyl sulfate (SDS) micelles. Protonation of acridine (AcrH(+)) occurs at the hydrophilic interface and this species remains in dynamic equilibrium with its deprotonated counterpart (Acr) inside the hydrophobic core of SDS micelles. Quenching of the fluorescence of AcrH(+)* at 478 nm is observed after addition of Ade and d-Ade with Stern-Volmer constant (K(SV)) 298 and 75 M(-1), respectively, with a concomitant increment in Acr* at 425 nm. Time-resolved fluorescence studies reveal quenching in the lifetime of AcrH(+)*. The relative amplitude of AcrH(+)* decreases from 0.97 to 0.51 and 0.97 to 0.89 with equimolar addition of Ade and d-Ade, respectively. These observations are explained by excited-state proton transfer (ESPT) from AcrH(+)* to the bases. The reduced K(SV) value and negligible change in the relative amplitudes of AcrH(+)* with d-Ade infer that ESPT is hindered substantially by the presence of a 2'-deoxy sugar unit. Transient time-resolved absorption spectra of Acr reflect that Ade reduces the absorbance of (3)AcrH(+)*; however, d-Ade keeps it unaltered for more than a time delay of 2 μs. The optimized geometries calculated by quantum chemical methods reflect deprotonation of AcrH(+)* with protonation at the N1 position of Ade, while it remains protonated with d-Ade. The hindered ESPT between AcrH(+)* and d-Ade singles out the significance of the 2'-deoxy sugar moiety in controlling the deprotonation kinetics.     

One-pot thioetherification of aryl halides with thiourea and benzyl bromide in water catalyzed by Cu-grafted furfural imine-functionalized mesoporous SBA-15

Surface functionalization of SBA-15 followed by its reaction with Cu(OAc)(2) has been carried out to develop a new Cu-grafted functionalized mesoporous material, which catalyzes one-pot three component coupling of different aryl halides with thiourea and benzyl bromide in aqueous medium to produce aryl thioethers in very good yields (80-88%).     

Unraveling siRNA unzipping kinetics with graphene

Using all atom molecular dynamics simulations, we report spontaneous unzipping and strong binding of small interfering RNA (siRNA) on graphene. Our dispersion corrected density functional theory based calculations suggest that nucleosides of RNA have stronger attractive interactions with graphene as compared to DNA residues. These stronger interactions force the double stranded siRNA to spontaneously unzip and bind to the graphene surface. Unzipping always nucleates at one end of the siRNA and propagates to the other end after few base-pairs get unzipped. While both the ends get unzipped, the middle part remains in double stranded form because of torsional constraint. Unzipping probability distributions fitted to single exponential function give unzipping time (τ) of the order of few nanoseconds which decrease exponentially with temperature. From the temperature variation of unzipping time we estimate the energy barrier to unzipping.     

Exploring sequential quantum adiabatic switching across supersymmetric partners for finding the eigenstates of a system

We demonstrate that one can exhaustively determine the n‐bound eigenstates of a Hamiltonian H by constructing a sequence of supersymmetric (SUSY) partner Hamiltonians and invoking a time‐dependent quantum adiabatic switching algorithm for passage from the ground state of one to the other. The ground states of the initial pair H⁽⁰⁾ and H⁽¹⁾ are constructed by solving the Riccati equation for the superpotential ?⁽⁰⁾ for H⁽⁰⁾ and adiabatically switching from the ground state Ψ of H⁽⁰⁾ to the ground state Ψ of H⁽¹⁾. The charge operator Q is then used to recover the first excited state Ψ of H⁽⁰⁾. The procedure is repeated for the ground states of SUSY pairs H^{(n + 1)} and H^{(n + 2)}, and appropriate charge operators lead to the excited states Ψ of H⁽⁰⁾ with , thereby exhausting the full eigenspectrum of H⁽⁰⁾. The workability of the proposed method is shown with several well‐known examples. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011