The kinetics of the 1,3-dipolar cycloadditions (DC) of benzonitrile oxide with a series of N-substituted maleimides in micellar media have been investigated. Surfactants studied include anionic sodium dodecyl sulfate, cationic cetyltrimethylammonium bromide, and a series of nonionic alkyl poly(ethylene oxide) surfactants (CxEy). The kinetic data have been analyzed by using the pseudo-phase mode...

Coherent control of bimolecular reactions is demonstrated for 3D atom-diatom reactive scattering. In particular, a superposition of initial degenerate syjkd diatomic states is used to control reactive integral and differential cross sections in D 1 H2syjkd ! H 1 HD, where y and j are the vibrational and rotational quantum numbers of a diatom and k is the projection quantum number of the diatom ...

A simple strategy for choosing optimal bio-supramolecular mediators from the mammalian serum albumin library is proposed for bimolecular photochirogenic reactions. Thus, the enantiodifferentiating photocyclodimerization of 2-anthracencecarboxylate (AC) was optimized in chemical and optical yields, when mediated by porcine and canine serum albumins, both of which bound two AC molecules in the fi...

The potential energy surface for the Hz-I2 system was determined in analytic variational electronic structure calculations with singleand double-substitution configuration interactions for the 16 valence electrons and with effective potentials for the iodine core electrons. The favored pathway for the overall reaction H,+I,d HI + HI was found to pass through the region of the collinear configur...

The effect of three aromatic amines namely aniline (AN), dimethyl aniline (DMAN) and diethyl aniline (DEAN) on emission properties of a coumarin derivative 6-methyl-3azidoacetyl coumarin (6M3AAC) in acetonitrile was studied by means of steady state fluorescence spectroscopy. The quenching of fluorescence intensity was observed in the presence of amines. The quenching process was characterized b...

A bimolecular synthetic reaction (imine synthesis) was performed compartmentalized in micrometer-diameter emulsion droplets. The apparent equilibrium constant (Keq) and apparent forward rate constant (k1) were both inversely proportional to the droplet radius. The results are explained by a noncatalytic reaction-adsorption model in which reactants adsorb to the droplet interface with relatively...

The spontaneous oxidation of an amine group to an imine has been observed experimentally in an octa-aza macrocyclic dinucleating ligand LH(4) coordinated to Cu(II). The reaction is bimolecular and spontaneous in which amine groups of one macrocycle are oxidised and the Cu(II) centres of a second macrocyclic complex are reduced. No additional oxidating or external base agents are required. DFT c...

Conical intersections play a crucial role in the chemistry of most polyatomic molecules, ranging from the simplest bimolecular reactions to the photostability of DNA. The real-time study of the associated electronic dynamics poses a major challenge to the latest techniques of ultrafast measurement. We show that high-harmonic spectroscopy reveals oscillations in the electronic character that occ...

When oxygenic photosynthesis evolved, one of the key functions of carotenoids was to protect aerobic photosynthetic organisms against destruction by photodynamic sensitization. Aerobic photosynthesis would not exist without the coevolution of carotenoids alongside the chlorophylls. As carotenoids are abundant in nature, in many fruits and vegetables, they are able to react with excited states o...