Hydrazine (N2H4) adsorption on Ni(1 0 0) – Density functional theory investigation

A theoretical study on the structure and adsorption mechanism of hydrazine (N₂H₄) on Ni(1 0 0) are presented. The hydrazine molecule was found to adsorb on the surface through one of its nitrogen atom in its anti-conformation. The charge transfer from hydrazine lone pair orbitals played a key role in the formation of the bonding. The mechanism involved in the bonding was found to reduce the necessity of hyper-conjugation interaction, that reduces the gauche effect found in hydrazine at the gas-phase. Upon adsorption to the surface, the reduced interaction resulted in the promotion of a more favored conformation through its anti-conformation.     

Economy of effort in different speaking conditions. I. A preliminary study of intersubject differences and modeling issues

This study explores the hypothesis that clear speech is produced with greater "articulatory effort" than normal speech. Kinematic and acoustic data were gathered from seven subjects as they pronounced multiple repetitions of utterances in different speaking conditions, including normal, fast, clear, and slow. Data were analyzed within a framework based on a dynamical model of single-axis frictionless movements, in which peak movement speed is used as a relative measure of articulatory effort (Nelson, 1983). There were differences in peak movement speed, distance and duration among the conditions and among the speakers. Three speakers produced the "clear" condition utterances with movements that had larger distances and durations than those for "normal" utterances. Analyses of the data within a peak speed, distance, duration "performance space" indicated increased effort (reflected in greater peak speed) in the clear condition for the three speakers, in support of the hypothesis. The remaining four speakers used other combinations of parameters to produce the clear condition. The validity of the simple dynamical model for analyzing these complex movements was considered by examining several additional parameters. Some movement characteristics differed from those required for the model-based analysis, presumably because the articulators are complicated structurally and interact with one another mechanically. More refined tests of control strategies for different speaking styles will depend on future analyses of more complicated movements with more realistic models.     

Photochemistry of thiophene‐S‐oxide derivatives

Photolysis of substituted thiophene‐S‐oxides in solution results in the formation of either the corresponding thiophene or furan, in addition to uncharacterized materials. No good rationalization is available for the choice of which pathway may predominate, but it is demonstrated that the photolysis of 2,5‐bistrimethylsilylthiopene‐ S‐oxide produces O(³P) in the same manner as the well‐established photolysis of dibenzothiophene‐S‐oxide. Copyright © 2008 John Wiley & Sons, Ltd.     

Observing photochemical transients by ultrafast x-ray absorption spectroscopy

Accurate determination of the transient electronic structures, which drive photochemical reactions, is crucial in chemistry and biology. We report the detection of transient chemical changes on the picosecond time scale by x-ray-absorption near-edge structure of photoexcited aqueous [Ru(bpy)(3)](2+). Upon ultrashort laser pulse excitation a charge transfer excited state having a 300 ns lifetime is formed. We detect the change of oxidation state of the central Ru atom at its L3 and L2 edges, at a temporal resolution of 100 ps with the zero of time unambiguously determined.     

Thiophene isosteres of 9,10-dithioanthraquinone

[reaction: see text] The preparation of 1,3,5,7-tetramethyl-4,8-dihydrobenzo[1,2-c:4,5-c']dithiophene-4,8-dione and its conversion to the corresponding mono- and dithione are described.     

Magnetic response of microbially synthesized transition metal- and lanthanide-substituted nano-sized magnetites

The magnetic susceptibility (κ_RT) and saturation magnetization (M_S) of microbially synthesized magnetites were systematically examined. Transition metal (Cr, Mn, Co, Ni and Zn)- and lanthanide (Nd, Gd, Tb, Ho and Er)-substituted magnetites were microbially synthesized by the incubation of transition metal (TM)- and lanthanide (L)-mixed magnetite precursors with either thermophilic (TOR-39) or psychrotolerant (PV-4) metal-reducing bacteria (MRB). Zinc incorporated congruently into both the precursor and substituted magnetite, while Ni and Er predominantly did not. Microbially synthesized Mn- and Zn-substituted magnetites had higher κ_RT than pure biomagnetite depending on bacterial species and they exhibited a maximum κ_RT at 0.2 cationic mole fraction (CMF). Other TMs’ substitution linearly decreased the κ_RT with increasing substitution amount. Based on the M_S values of TM- and L-substituted magnetite at 0.1 and 0.02 CMF, respectively, Zn (90.7 emu/g for TOR-39 and 93.2 emu/g for PV-4)- and Mn (88.3 emu/g by PV-4)-substituted magnetite exhibited higher M_S than standard chemical magnetite (84.7 emu/g) or pure biomagnetite without metal substitution (76.6 emu/g for TOR-39 and 80.3 emu/g for PV-4). Lanthanides tended to decrease M_S, with Gd- and Ho-substituted magnetites having the highest magnetization. The higher magnetization of microbially synthesized TM-substituted magnetites by the psychrotroph, PV-4 may be explained by the magnetite formation taking place at low temperatures slowing mechanics, which may alter the magnetic properties compared to the thermophile, through suppression of the random distribution of substituted cations.     

A nanoscale understanding of the adhesion of polybutylene terephthalate on aluminum

The adhesion strength of polybutylene terephthalate (PBT) on aluminum was investigated using density functional theory-based total energy calculations. Aluminum atom was connected to a PBT monomer at different orientations and total energies were calculated in order to determine the most stable orientation. The energy differences showed that the Al oriented at 180° with the ester group of the monomer bonded strongly. Using this orientation, the PBT monomer-adhesion on aluminum surface and the aluminum atom adhesion on PBT bulk were also investigated.     

Organocatalytic depolymerization of poly(ethylene terephthalate)

We describe the organocatalytic depolymerization of poly(ethylene terephthalate) (PET), using a commercially available guanidine catalyst, 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD). Postconsumer PET beverage bottles were used and processed with 1.0 mol % (0.7 wt %) of TBD and excess amount of ethylene glycol (EG) at 190 °C for 3.5 hours under atmospheric pressure to give bis(2‐hydroxyethyl) terephthalate (BHET) in 78% isolated yield. The catalyst efficiency was comparable to other metal acetate/alkoxide catalysts that are commonly used for depolymerization of PET. The BHET content in the glycolysis product was subject to the reagent loading. This catalyst influenced the rate of the depolymerization as well as the effective process temperature. We also demonstrated the recycling of the catalyst and the excess EG for more than 5 cycles. Computational and experimental studies showed that both TBD and EG activate PET through hydrogen bond formation/activation to facilitate this reaction. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Cold Molecules: Preparation,Applications, and Challenges

Research with cold molecules has developed rapidly in recent years. There is now a variety of established methods for cooling molecules into the millikelvin range. Nevertheless, a focal point of current research is directed toward finding new ways to bring the temperature of molecules even closer to absolute zero. Samples of cold molecules offer not only important applications for high‐resolution spectroscopy, which benefit from the increased interaction time of slow molecules with electromagnetic radiation; they also promise access to an exotic regime of chemical reactivity, in which phenomena such as quantum tunneling and quantum resonances predominate. This review begins with an introduction to the methods by which cold molecules can be prepared, with special emphasis on Stark deceleration and traps. In addition to applications of cold molecules that have already been partially achieved, an important focus of the review concentrates on possible future applications, and both aspects are illustrated with selected examples.