Quantum wavepacket ab initio molecular dynamics: generalizations using an extended Lagrangian treatment of diabatic states coupled through multireference electronic structure

We present a generalization to our previously developed quantum wavepacket ab initio molecular dynamics (QWAIMD) method by using multiple diabatic electronic reduced single particle density matrices, propagated within an extended Lagrangian paradigm. The Slater determinantal wavefunctions associated with the density matrices utilized may be orthogonal or nonorthogonal with respect to each other. This generalization directly results from an analysis of the variance in electronic structure with quantum nuclear degrees of freedom. The diabatic electronic states are treated here as classical parametric variables and propagated simultaneously along with the quantum wavepacket and classical nuclei. Each electronic density matrix is constrained to be N-representable. Consequently two sets of new methods are derived: extended Lagrangian-QWAIMD (xLag-QWAIMD) and diabatic extended Lagrangian-QWAIMD (DxLag-QWAIMD). In both cases, the instantaneous potential energy surface for the quantum nuclear degrees of freedom is constructed from the diabatic states using an on-the-fly nonorthogonal multireference formalism. By introducing generalized grid-based electronic basis functions, we eliminate the basis set dependence on the quantum nucleus. Subsequent reuse of the two-electron integrals during the on-the-fly potential energy surface computation stage yields a substantial reduction in computational costs. Specifically, both xLag-QWAIMD and DxLag-QWAIMD turn out to be about two orders of magnitude faster than our previously developed time-dependent deterministic sampling implementation of QWAIMD. Energy conservation properties, accuracy of the associated potential surfaces, and vibrational properties are analyzed for a family of hydrogen bonded systems.     

Sulfonated polyaniline network grafted multi-wall carbon nanotubes for enzyme immobilization, direct electrochemistry and biosensing of glucose

A new nanomaterial was prepared by grafting a layer of sulfonated polyaniline network (SPAN-NW) on to the surface of multi-walled carbon nanotube (MWNT) and effectively utilized for immobilization of an enzyme and for the fabrication of a biosensor. SPAN-NW was formed on the surface of MWNT by polymerizing a mixture of diphenyl amine 4-sulfonic acid (DPASA), 4-vinyl aniline (VA) and 2-acrylamido-2-methyl-1-propane sulfonic acid (APASA) in the presence of amine functionalized MWNT (MWNT-NH₂). The MWNT-g-SPAN-NW was immobilized with glucose oxidase (GOx) to fabricate the SPAN-NW/GOx biosensor. MWNT-g-SPAN-NW/GOx electrode showed direct electron transfer (DET) for GOx with a fast heterogeneous electron transfer rate constant (k_s) of 4.11 s^− 1. The amperometric current response of MWNT-g-SPAN-NW/GOx biosensor shows linearity up to 9 mM of glucose, with a correlation coefficient of 0.99 and a detection limit of 0.11 μM (S/N = 3). At a low applied potential of − 0.1 V, MWNT-g-SPAN-NW/GOx electrode possesses high sensitivity (4.34 μA mM^− 1) and reproducibility towards glucose.     

A novel chromone-substituted trimeric dihydroflavonol from <Emphasis Type="Italic">Anogeissus pendula</Emphasis>

A new chromone-substituted dihydrotriflavonol, (2S,3S)[6-{(3S) 3″,5″-dihydroxy-6″-methoxydihydrochromone}5,3′,4′,5′-tetrahydroxy-7-methoxy-3-O-8-dihydroflavone]₂ 3-O-8[6-{(3S) 3″,5″-dihydroxy-6″methoxydihydrochromone}3,5,3′,4′,5′-pentahydroxy-7-methoxydihydroflavonol] was isolated from the leaves of Anogeissus pendula. The structure was determined by UV, ¹H NMR, ¹³C NMR, HMBC, and CD data.     

Partial eigenvalue assignment for structural damage mitigation

In partial eigenvalue assignment, not all eigenvalues of the open loop system matrix are modified through a multiple input state or output feedback controller. This freedom available to assign selected eigenvalues of the closed loop system matrix has been widely used in design contexts such as to eliminate spillover effects in structural control problems. Similar approach is also required to modify damping and/or stiffness characteristics in selected eigenmodes of a damaged structure. When an external force acts on the damaged structure, partial eigenvalue assignment in this fashion will attempt to use minimal control effort and keep the structure active with safe operation. In this paper, a new approach to partial eigenvalue assignment and its application to structural damage mitigation are presented. A three mass spring-damper model with damage in one of the springs is illustrated with damping modifications at specific eigenmodes. The procedure is repeated for a second example, which is a cantilever beam modeled using two inputs and 10 state variables.     

Scaffold-directed and traceless synthesis of tricyclic quinoxalinone imidazoles under microwave irradiation

Traceless synthesis of 2-aminoimidazoquinoxalinones has been performed on soluble polymer support under open-vessel microwave dielectric heating. The reaction progression is monitored directly by the conventional proton NMR which indicated no release of the substrate from the support. Fmoc-deprotected amino acid polymer conjugates react with 1,5-difluoro-2,4-dinitro benzene to yield polymer bound dinitro fluoro amines, which are further substituted by various primary amines to yield PEG-immobilized dinitrodiamines. Simultaneous reduction of aromatic meta-dinitro group leads to the traceless release of 2-quinoxalinones, followed by N-hetero cyclization with various isothiocyanates in the presence of mercury(II)chloride to furnish 2-aminoimidazoquinolinone rings with three points of diversity at rapid pace.