Quantum chemical study of the geometries and stabilities of the two valence-tautomers of C2H2F+

Non-empirical SCF-MO molecular wavefunctions were computed for the two limiting structures of C₂H₂F⁺ with full geometry optimization using double-zeta quality atomic orbital basis sets. The bridged structure (fluorenium ion) was found to be an energy maximum (transition state) about 31 kcal/mole higher than the open structure (fluoro-vinyl cation). The latter, contrary to the unsubstituted vinyl cation, is slightly (4.5 °) bent away from fluorine at the electron deficient centre.     

Markov dilations and quantum detailed balance

We construct quantum stochastic processes whose multi-time correlation functions, with suitable time ordering, can be obtained from a quantum dynamical semigroup. We prove that such a process defines a stationary Markov dilation of the associated semigroup if and only if (up to technicalities) the semigroup satisfies the quantum detailed balance condition with respect to its stationary state.     

Investigating the interactions of hyaluronan derivatives with biomolecules. The use of diffusional NMR techniques

[Chemical structure: see text] The interactions between a biomaterial and biomolecules present in body fluids often determine the fate of the biomaterial. This paper presents a study on hyaluronan (HA)-containing materials (in soluble or colloidal form) that focuses on their interactions with lipids and proteins and for the first time uses PFG NMR as an analytical technique for probing these events. The interactions of HA-based polymers with phospholipids (DPPC and DPPG liposomes) are shown to depend both on charge and hydrophobicity factors. Despite the difference in behavior between albumin (substantially non-adhesive) and fibrinogen (adhesive), the interactions of the polymers with proteins do not seem to be based on hydrophobic effects but on surface polar interactions.     

Influence of the substituent on selective photocatalytic oxidation of aromatic compounds in aqueous TiO2 suspensions

Experimental results are reported showing that the photocatalytic oxidation of aromatic compounds containing an electron-donor group (EDG) gives rise mainly to ortho- and para-monohydroxy derivatives while in the presence of an electron-withdrawing group (EWG) all the monohydroxy derivatives are obtained.     

Quantum private queries

We propose a cheat sensitive quantum protocol to perform a private search on a classical database which is efficient in terms of communication complexity. It allows a user to retrieve an item from the database provider without revealing which item he or she retrieved: if the provider tries to obtain information on the query, the person querying the database can find it out. The protocol ensures also perfect data privacy of the database: the information that the user can retrieve in a single query is bounded and does not depend on the size of the database. With respect to the known (quantum and classical) strategies for private information retrieval, our protocol displays an exponential reduction in communication complexity and in running-time computational complexity.     

High-Q factor single mode circular photonic crystal nano-resonator

In this work, the analysis, fabrication and optical characterization of a two-dimensional circular photonic crystal (2D-CPC) nano-resonator based on an air/GaAs/air slab waveguide are presented. Four InAs/InGaAs quantum dots (QDs) stacked layers emitting around 1300 nm at room temperature were embedded in a GaAs waveguide layer grown on an Al_0.7Ga_0.3As layer and GaAs substrate. The patterning of the structure and the membrane release were achieved by using electron beam lithography, ICP plasma etching and selective wet etching of the AlGaAs sacrificial layer. The micro-luminescence spectrum recorded from the fabricated nano-cavity shows a narrow optical transition at the resonance wavelength of about 1282 nm with a FWHM and Q-factor of 6.2 Å and more than 2000, respectively.     

Homology computation for a class of contact structures on T^3

We consider a family of tight contact forms on the three-dimensional torus and we compute the relative Contact Homology by using the variational theory of critical points at infinity. We will also show local stability.     

Merging lithium carbenoid homologation and enzymatic reduction: A combinative approach to the HIV-protease inhibitor Nelfinavir

An effective stereocontrolled synthesis of the HIV protease inhibitor Nelfinavir is reported. Two transformations were identified crucial for achieving success: the formation of a densely functionalized α-chloroketone via the homologation of a Weinreb amide with chloromethyllithium (LiCH₂Cl), followed by its erythro selective reduction into the corresponding chiral chlorohydrin. A commercially available enzyme P2-C02 was particularly well suited for this purpose, affording the key alcohol (in an excellent 99% de), which was then smoothly converted into the active biologically active agent.     

Clifford Fields and the Relativistic Equation of the Nucleon

A relativistic equation for free fields whichtake their values in the Clifford algebra associatedwith the Minkowski metric is shown to be interpretableas the equation of the nucleon. The internal symmetry group SU(2) arises naturally from theassociative algebra structure of the representationspace. The latter structure can be used to constructcoupling terms consistent with the transformationproperties of the interacting fields; in particular, itallows the familiar couplings of the nucleon field withthe electromagnetic field and with the -mesonfield.     

Anionic N-Fries rearrangement of N-alkyl-2-iodo anilides induced by iodine-magnesium exchange: application for synthesis of strained 1,2,3-trisubstituted indoles

A superior, mild, high-yielding one-pot process for rapid access to oxo anilides has been developed that involves three cascade reactions: iodine-magnesium exchange, regiospecific ortho N-Fries rearrangement, and in situ trapping of the formed aniline anion. Coupled with McMurry cyclization, the two-step process allows ready synthesis of strained 1,2,3-trisubstituted indoles regioselectively.