Polarity inversion of donor-acceptor cyclopropanes: disubstituted δ-lactones via enantioselective iridium catalysis

The coupling of carbonyl electrophiles at the donor position of donor-acceptor cyclopropanes is described, representing an inversion of polarity with respect to conventional reactivity modes displayed by these reagents. Specifically, upon exposure of donor-acceptor cyclopropanes to alcohols in the presence of a cyclometalated iridium catalyst modified by (S)-BINAP, catalytic C-C coupling occurs, providing enantiomerically enriched products of carbonyl allylation. Identical products are obtained upon isopropanol-mediated transfer hydrogenation of donor-acceptor cyclopropanes in the presence of aldehydes. The reaction products are directly transformed to cis-4,5-disubstituted δ-lactones.     

Communication: uncovering molecule-TiO2 interactions with nonlinear spectroscopy

Femtosecond transient grating experiments are used to investigate electronic structures and transport mechanisms in dye-sensitized nanocrystalline TiO(2) films. This study examines two molecular sensitizers spanning the weak (a phosphonated Ruthenium complex) and strong (catechol) molecule-TiO(2) coupling regimes. It is shown that strong molecule-TiO(2) interactions give rise to photoinduced vibrational coherences at the interface between species. We suggest that the amplitudes of these coherences reflect the molecule-TiO(2) coupling strength and signify the delocalization of excited state wavefunctions.     

Exciton delocalization and energy transport mechanisms in R-phycoerythrin

Energy transport mechanisms in R-Phycoerythrin (RPE), a light harvesting protein located at the top of the phycobilisome antenna in red algae, are investigated using nonlinear optical spectroscopies and theoretical models. The RPE hexamer possesses a total of 30 bilin pigments, which can be subdivided into three classes based on their molecular structures and electronic resonance frequencies. Of particular interest to this study is the influence of exciton delocalization on the real-space paths traversed by photoexcitations as they concentrate on the lowest energy pigment sites. Transient grating measurements show that significant nuclear relaxation occurs at delay times less than 100 fs, whereas energy transport spans a wide range of time scales depending on the proximity of the initial and final states involved in the process. The fastest energy transport dynamics within the RPE complex are close to 1 ps; however, evidence for sub-100 fs exciton self-trapping is also obtained. In addition, photon echo experiments reveal vibronic interactions with overdamped and underdamped nuclear modes. To establish signatures of exciton delocalization, energy transport is simulated using both modified Redfield and Fo?rster theories, which respectively employ delocalized and localized basis states. We conclude that exciton delocalization occurs between six pairs of phycoerythrobilin pigments (i.e., dimers) within the protein hexamer. It is interesting that these dimers are bound in locations analogous to the well-studied phycocyanobilin dimers of cyanobacterial allophycocyanin and c-phycocyanin in which wave function delocalization is also known to take hold. Strong conclusions regarding the electronic structures of the remaining pigments cannot be drawn based on the present experiments and simulations due to overlapping resonances and broad spectroscopic line widths, which prevent the resolution of dynamics at particular pigment sites.     

Electrokinetic Mechanisms and Synergistic Effect on Ion-Tuned Wettability in Oil-Brine-Rock Systems

Transport in Porous Media - Wettability alteration has been recognized as the dominant mechanism of ion-tuned waterflooding, where the ionic composition of injecting brine is modified to improve...     

Free surface Nvier-Stokes flows with simultaneous heat transfer and solidification/melting

A mathematical model to analyse some key aspects of the metal cast process is described involving the filling of the mould by liquid metal and simultaneously, undergoing both cooling and solidification (re-melting) phase change. A computational solution procedure based upon a finite volume discretisation approach, on both structured and unstructured meshes, is described. The overall flow solution procedure is based on the pressure correction algorithm SIMPLE suitably adapted to: (a) solve for the free surface with minimal smearing by the SEA algorithm, and (b) solve for the solidification/melting phase change using an enthalpy conservation algorithm developed by Voller, but with its root in the work of Crank many years ago.Dedicated to Professor J. Crank on the occasion of his 80th birthday     

Crystallographic report: Bis(triphenylphosphoranylidene)ammonium phenyltetrachlorotellurate

Unlike most previously described organotetrachlorotellurate complexes, neither secondary Te·Cl interactions nor significant cation–anion interaction are observed in the molecular structure of [Ph₃PNPPh₃][PhTeCl₄]. Copyright © 2005 John Wiley & Sons, Ltd.     

Bi-stranded, multisite replication of a base pair between difluorotoluene and adenine: confirmation by ‘inverse’ sequencing

Background: The nonpolar nucleoside of difluorotoluene (F) was previously found to behave similarly to thymidine in single-site deoxynucleoside triphosphate (dNTP) insertion experiments with the Klenow fragment (KF) of DNA polymerase I. Further study was needed, first to see whether F-A base pairs could be replicated in more than one sequence context; second to investigate whether specific base pair replication occurs in the presence of four dNTPs; and third to confirm the presence of F in a replicated DNA strand.Results: A primer bound to a template strand containing eight F residues was extended by KF using the four natural dNTPs at 20 μM. Similarly, the complement (containing eight adenines) was extended using dATP, dGTP, dCTP and dFTP. Comparison of the new strands to authentic strands using standard and ‘inverse’ chemical sequencing showed identical composition within ± 5%.Conclusions: The results confirm that F in a template strand encodes the insertion of dATP and that adenine in a template encodes the insertion of dFTP with good specificity in at least six different nearest neighbor contexts. The results confirm that analog F behaves similarly to thymidine despite its poor hydrogen-bonding ability.     

Nitrogen determination in plant samples by fast neutron activation analysis

For the non-destructive deermination of the nitrogen content in plant samples 14-MeV neutron activation analysis was applied. Using powder samples of 0.7 g, irradiation time of 1 h and measuring time of 10 min, the accuracy of the determination is about +15%. The potassium content of the plant samples was determined by X-ray fluorescence analysis and correction was made for their contribution to the nitrogen activities.This work was supported in part by the Hungarian Academy of Sciences.     

De haas-van alphen effect in stage 2 graphite-AsF5

We have observed dHvA frequencies in several samples of stage 2 graphite-AsF₅ intercalation compound. A consistent interpretation is given in terms of two nested hole surfaces located at each of the 6 corners of the 2D graphite zone. A fractional ionization f = 0.42 is obtained, consistent with spin susceptibility, with the Blinowski-Rigaux analysis of reflectivity, and with recent chemical results.