A Convenient One-Step Synthesis of 1,1,4,4-Tetrachloro-1,3-butadiene

During the course of our studies on selective chlorination by copper (II) chlorida¹ we considared it of intarest to tast the stability of the solvent commonly amployed by us – sulfolane– ⁺⁾ towards this haloganating agent.     

Identification of putative proteins involved in granule biogenesis of tick salivary glands.

Ticks secrete bioactive components during feeding that assist them in gaining a blood meal. Compounds secreted are stored in granules until a stimulus induces secretion during feeding. Biogenesis of tick secretory granules has not been investigated before. An adequate understanding of granule biogenesis could advance our understanding of tick salivary gland biology and could aid in the rational design of tick control methods. Putative tick salivary gland proteins 1-4 (TSGP1-4) involved in granule biogenesis were identified in this study based on their abundance in salivary gland extracts and granule preparations and their ability to aggregate under conditions of slight acidity and high calcium concentration. TSGP2 and TSGP3 have been identified as previously described toxic and nontoxic homologues, respectively, while toxicity was also associated with TSGP4.     

Charge transfer between isomer domains on n(+)-doped Si(111)-2?×?1: energetic stabilization

Domains of different surface reconstruction-negatively or positively buckled isomers-have been previously observed on highly n-doped Si(111)-2?×?1 surfaces by angle-resolved ultraviolet photoemission spectroscopy and scanning tunneling microscopy/spectroscopy. At low temperature, separate domains of the two isomer types are apparent in the data. It was argued in the previous work that the negative isomers have a lower energy of their empty surface states than the positive isomers, providing a driving force for the formation of the negative isomers. In this work we show that the relative abundance of these two isomers shows considerable variation from sample to sample, and it is argued that the size of the isomer domains is likely to be related to this variation. A model is introduced in which the electrostatic effect of charge transfer between the domains is computed, yielding total energy differences between the two types of isomer. It is found that the transfer of electrons from domains of positive isomers to negative ones leads to an energetic stabilization of the negative isomers. The model predicts a dependence of the isomer populations on doping that is in agreement with most experimental results. Furthermore, it accounts, at least qualitatively, for the marked lineshape variation from sample to sample observed in photoemission spectra.     

Electronic states and Fermi surface properties of α-phase PdHx

Calculations based on a muffin tin model for the electronic structure of the random interstitial alloy PdH_x are presented together with the first high resolution de Haas-van Alphen data for this system in the α-phase. In the dilute limit good agreement is obtained for the concentration dependence of the areas of several extremal orbits. The behavior of the PdH_x Fermi surface is unique in that the Γ-centered electron orbits are found to grow at approximately the rate predicted by the rigid band model while the X-centered hole pockets shrink at only half the rigid band rate.     

Average multipolarity of continuum transitions in nuclei at high angular momentum

The multipolarity of continuum transitions deexciting high-spin states has been deduced from measured conversion coefficients. The investigated ¹⁴⁶Nd(²⁰Ne, 4n or 5n) ^162,161Yb reactions were selected by gating on discrete lines. The average multipolarity gradually changes from E2 at 0.5 MeV to E1 above 1.5 MeV.     

Kinetic H/D isotope effects for gas phase hydroxylation of benzene and chlorobenzene between 520–1080 K. Hydroxyl radical versus O(3P) atom attack

Gas phase slow combustion of (chloro)benzene in O₂/N₂ mixtures, and induced by addends such as tert butylhydroperoxide, cyclohexane, or methanol, leads to (chloro)-phenol as the only important aromatic product. Using C₆H₆/C₆D₆ mixtures, formation of phenol/perdeuterophenol was studied between 520–1080 K. The temperature dependence of this product ratio was found to obey the Arrhenius expression for the intermolecular isotope effect log k_H/k_D = ?0.14 ± 0.03 + (1240 ± 80)/2.303RT (R in cal/mol K). Essentially the same result was obtained for the intramolecular isotope effect, measuring the change in isomer distribution for the chlorophenols formed from p-deuterio-chlorobenzene versus those for chlorobenzene. These results are in accordance with H(D)-abstraction by ·OH, via a linear transition state, as the first and (relative) rate determining step. Whereas above 1000 K, at reduced pressure, the intramolecular isotope effect continues to prevail, C₆H₆/C₆D₆ do not show differences in rate of formation of C₆H₅OH/C₆D₅OH. Under these conditions, the only effective reaction of arene to phenol appears to be set in by addition of O(³P).     

Atom lithography with two-dimensional optical masks

With a two-dimensional (2D) optical mask at =1083 nm, nanoscale patterns are created for the first time in an atom lithography process using metastable helium atoms. The internal energy of the atoms is used to locally damage a hydrophobic resist layer, which is removed in a wet etching process. Experiments have been performed with several polarizations for the optical mask, resulting in different intensity patterns, and corresponding nanoscale structures. The results for a linear polarized light field show an array of holes with a diameter of 260 nm, in agreement with a computed pattern. With a circularly polarized light field a line pattern is observed with a spacing of /2^0.5=766 nm. Simulations taking into account many possible experimental imperfections can not explain this pattern. PACS 32.80.Lg; 39.25.+k; 81.16.Nd     

Improving efficiency of large time-scale molecular dynamics simulations of hydrogen-rich systems

A systematic analysis is performed on the effectiveness of removing degrees of freedom from hydrogen atoms and/or increasing hydrogen masses to increase the efficiency of molecular dynamics simulations of hydrogen-rich systems such as proteins in water. In proteins, high-frequency bond-angle vibrations involving hydrogen atoms limit the time step to 3 fs, which is already a factor of 1.5 beyond the commonly used time step of 2 fs. Removing these degrees of freedom from the system by constructing hydrogen atoms as dummy atoms, allows the time step to be increased to 7 fs, a factor of 3.5 compared with 2 fs. Additionally, a gain in simulation stability can be achieved by increasing the masses of hydrogen atoms with remaining degrees of freedom from 1 to 4 u. Increasing hydrogen mass without removing the high-frequency degrees of freedom allows the time step to be increased only to 4 fs, a factor of two, compared with 2 fs. The net gain in efficiency of sampling configurational space may be up to 15% lower than expected from the increase in time step due to the increase in viscosity and decrease in diffusion constant. In principle, introducing dummy atoms and increasing hydrogen mass do not influence thermodynamical properties of the system and dynamical properties are shown to be influenced only to a moderate degree. Comparing the maximum time step attainable with these methods (7 fs) to the time step of 2 fs that is routinely used in simulation, and taking into account the increase in viscosity and decrease in diffusion constant, we can say that a net gain in simulation efficiency of a factor of 3 to 3.5 can be achieved. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 786–798, 1999