A high-throughput NMR-based ee-assay using chemical shift imaging

The throughput of a previously described NMR-based -assay has been increased by a factor of at least 4 as a consequence of adapting the system to chemical shift imaging; by using a 19-capillary system the enantiomeric purity of 5600 samples can be measured per day.     

Use of an ionic liquid in a two-phase system to improve an alcohol dehydrogenase catalysed reduction

Due to favourable partition coefficients the highly enantioselective reduction of 2-octanone, catalysed by an alcohol dehydrogenase from Lactobacillus brevis, is faster in a biphasic system containing buffer and the ionic liquid [BMIM][(CF(3)SO(2))(2)N] compared to the reduction in a biphasic system containing buffer and methyl tert-butyl ether.     

Water-in-water mesophases for templating inorganics

A water-in-water mesophase that contains only hydrophilic domains is reported for the first time; the mesophase templates highly porous calcium phosphate.     

The prospects for high resolution optical brain imaging: the magnetic resonance perspective

Various analogs of NMR and MRI are now technically possible in optics; specifically, high-resolution laser-pulse shaping and complex pulse sequence generation with well-defined phase shifts has been demonstrated. Here we summarize this technology and discuss the potential for these methods to enhance optical functional imaging, competing with (and surpassing?) what is possible by functional MRI.     

Interaction-induced decoherence of atomic BLOCH oscillations

We show that the energy spectrum of the Bose-Hubbard model amended by a static field exhibits Wigner-Dyson level statistics. In itself a characteristic signature of quantum chaos, this induces the irreversible decay of Bloch oscillations of cold, interacting atoms loaded into an optical lattice, and provides a Hamiltonian model for interaction-induced decoherence.     

Pinch-off transition in Marangoni-driven thin films

We present a mathematical model and analysis for the pinch-off transition as observed in dip-coating experiments at the base of thin liquid films driven up a vertical plate by a thermally induced surface tension gradient with a counteracting gravitational force. Our results show that this transition gives rise to a complex new wave structure involving a nonclassical, reverse undercompressive shock wave.     

Photon antibunching and collective effects in the fluorescence of single bichromophoric molecules

The fluorescence of individual pairs of perylenemonoimide chromophores coupled via a short rigid linker is investigated. Photon antibunching is reported, indicating collective effects in the fluorescence, which are further substantiated by the observation of collective triplet off times and triplet lifetime shortening. The experimental findings are analyzed in terms of singlet-singlet and singlet-triplet annihilation based on F?rster type energy transfer. The results reported here demonstrate that the statistical properties of the emission light of isolated single quantum systems can serve as a hallmark of intermolecular interactions.     

End-to-end correlation for a C-12 hydrocarbon chain

The 19F nuclear spin-lattice relaxation rate constants were measured as a function of magnetic field strength for 1,12-diaminododecane labeled at one end with a nitroxide radical and at the other with a trifluoromethyl group. The magnetic relaxation dispersion profile (MRD) reports the spectral density function appropriate to the end-to-end correlation function for the doubly labeled molecule. After extrapolation to zero concentration to eliminate the intermolecular relaxation contribution to relaxation, the resulting intramolecular MRD profile was compared with several model approaches. The rotational model for the spectral density functions as included in the Solomon-Bloembergen-Morgan equations does not describe the data well. The earlier model of Freed for nuclear spin relaxation induced by a freely diffusing paramagnetic co-solute is not rigorous for this case because the paramagnet is tethered to the observed nuclear spin and only a restricted space in the immediate vicinity of the nuclear spin is accessible for pseudo-translational diffusion of one end of the molecule with respect to the other. A generalization of the Torrey model for magnetic relaxation by translational diffusion developed by Nevzorov and Freed, which includes the effect of restrictions imposed by the finite length of the chain, describes the experiment within experimental errors. A simple modification of the Hwang-Freed model that does not specifically include the dynamical effects of the finite tether also provides a good approximation to the data when the tether chain is sufficiently long.     

New pyrazolium-carboxylates as structural analogues of the pseudo-cross-conjugated betainic alkaloid nigellicine

Pyrazolium-3-carboxylates were examined as relatives of the betainic alkaloid Nigellicine and as new examples of the sparsely populated class 16 of heterocyclic pseudo-cross-conjugated mesomeric betaines (PCCMB). The title compounds were prepared in a 4-step procedure starting from beta-diketo compounds 8 which were cyclized with substituted hydrazines. The resulting isomeric pyrazole esters 9 and 10 were separated and subsequently quaternized with dimethyl sulfate in the presence of nitrobenzene to pyrazolium esters 11 and 12. Saponification was best accomplished in diluted sulfuric acid, which resulted in the formation of the pseudo-cross-conjugated mesomeric betaines 13 and 14 in one step. Protonation to the corresponding carboxylic acids required the treatment of the betaines with tetrafluoroboric acid in dichloromethane. The effect of negative solvatochromism proves the charge separation in the ground state of the molecules. X-ray crystallographic analyses, semiempirical calculations, and ESI mass spectrometric measurements were performed to gain knowledge about the phenomenon of pseudo-cross-conjugation.     

A novel preparation of nano-Cu/ZnO by photo-reduction of Cu(OCH(Me)CH2NMe2)2 on ZnO at room temperature

Room-temperature preparation of nano-Cu on ZnO by UV light induced photo-reduction of Cu(OCH(Me)CH2NMe2)2 precursor was achieved, indicating a novel method of nano-Cu/ZnO synthesis from an organometallic copper precursor in non-aqueous media without further chemical reduction.