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.     

Site selectivity in the reactions of the hexanuclear platinum cluster [Pt6(mu-PtBu2)4(CO)6][CF3SO3]2

The previously reported hexanuclear cluster [Pt(6)(mu-PtBu(2))(4)(CO)(6)](2+)[Y](2) (1-Y(2): Y=CF(3)SO(3) (-)) contains a central Pt(4) tetrahedron bridged at each of the opposite edges by another platinum atom; in turn, four phosphido ligands bridge the four Pt-Pt bonds not involved in the tetrahedron, and, finally, one carbonyl ligand is terminally bonded to each metal centre. Interestingly, the two outer carbonyls are more easily substituted or attacked by nucleophiles than the inner four, which are bonded to the tetrahedron vertices. In fact, the reaction of 1-Y(2) with 1 equiv of [nBu(4)N]Cl or with an excess of halide salts gives the monochloride [Pt(6)(mu-PtBu(2))(4)(CO)(5)Cl](+)[Y], 2-Y, or the neutral dihalide derivatives [Pt(6)(mu-PtBu(2))(4)(CO)(4)X(2)] (3: X=Cl; 4: X=Br; 5: X=I). Moreover, the useful unsymmetrically substituted [Pt(6)(mu-PtBu(2))(4)(CO)(4)ICl] (6) was obtained by reacting equimolar amounts of 2 and [nBu(4)N]I, and the dicationic derivatives [Pt(6)(mu-PtBu(2))(4)(CO)(4)L(2)](2+)[Y](2) (7-Y(2): L=(13)CO; 8-Y(2): L=CNtBu; 9-Y(2): L=PMe(3)) were obtained by reaction of an excess of the ligand L with 1-Y(2). Weaker nitrogen ligands were introduced by dissolving the dichloride 3 in acetonitrile or pyridyne in the presence of TlPF(6) to afford [Pt(6)(mu-PtBu(2))(4) (CO)(4)L(2)](2+)[Z](2) (Z=PF(6) (-), 10-Z(2): L=MeCN; 11-Z(2): L=Py). The "apical" carbonyls in 1-Y(2) are also prone to nucleophilic addition (Nu(-): H(-), MeO(-)) affording the acyl derivatives [Pt(6)(mu-PtBu(2))(4)(CO)(4)(CONu)(2)] (12: Nu=H; 13: Nu=OMe). Complex 12 is slowly converted into the dihydride [Pt(6)(mu-PtBu(2))(4)(CO)(4)H(2)] (14), which was more cleanly prepared by reacting 3 with NaBH(4). In a unique case we observed a reaction involving also the inner carbonyls of complex 1, that is, in the reaction with a large excess of the isocyanides R-NC, which form the corresponding persubstituted derivatives [Pt(6)(mu-tPBu(2))(4)(CN-R)(6)](2+)[Y](2), (15-Y(2): R=tBu; 16-Y(2) (2-): R=-C(6)H(4)-4-C triple bond CH). All complexes were characterized by microanalysis, IR and multinuclear NMR spectroscopy. The crystal and molecular structures of complexes 3, 5, 6 and 9-Y(2) are also reported. From the redox viewpoint, all complexes display two reversible one-electron reduction steps, the location of which depends both upon the electronic effects of the substituents, and the overall charge of the original complex.     

Fatty acid composition and volatile compounds of caviar from farmed white sturgeon (Acipenser transmontanus)

The present study was conducted to characterize caviar obtained from farmed white sturgeons (Acipenser transmontanus) subjected to different dietary treatments. Twenty caviar samples from fish fed two experimental diets containing different dietary lipid sources have been analysed for chemical composition, fatty acids and flavour volatile compounds. Fatty acid make up of caviar was only minimally influenced by dietary fatty acid composition. Irrespective of dietary treatments, palmitic acid (16:0) and oleic acid (OA, 18:1 n-9) were the most abundant fatty acid followed by docosahexaenoic acid (DHA, 22:6 n-3) and eicopentaenoic (EPA, 20:5 n-3). Thirty-three volatile compounds were isolated using simultaneous distillation-extraction (SDE) and identified by GC-MS. The largest group of volatiles were represented by aldehydes with 20 compounds, representing the 60% of the total volatiles. n-Alkanals, 2-alkenals and 2,4-alkadienals are largely the main responsible for a wide range of flavours in caviar from farmed white surgeon.