Progress toward chemical accuracy in the computer simulation of condensed phase reactions.

We describe a procedure for the generation of chemically accurate computer-simulation models to study chemical reactions in the condensed phase. The process involves (i) the use of a coupled semiempirical quantum and classical molecular mechanics method to represent solutes and solvent, respectively; (ii) the optimization of semiempirical quantum mechanics (QM) parameters to produce a computationally efficient and chemically accurate QM model; (iii) the calibration of a quantum/classical microsolvation model using ab initio quantum theory; and (iv) the use of statistical mechanical principles and methods to simulate, on massively parallel computers, the thermodynamic properties of chemical reactions in aqueous solution. The utility of this process is demonstrated by the calculation of the enthalpy of reaction in vacuum and free energy change in aqueous solution for a proton transfer involving methanol, methoxide, imidazole, and imidazolium, which are functional groups involved with proton transfers in many biochemical systems. An optimized semiempirical QM model is produced, which results in the calculation of heats of formation of the above chemical species to within 1.0 kcal/mol (1 kcal = 4.18 kJ) of experimental values. The use of the calibrated QM and microsolvation QM/MM (molecular mechanics) models for the simulation of a proton transfer in aqueous solution gives a calculated free energy that is within 1.0 kcal/mol (12.2 calculated vs. 12.8 experimental) of a value estimated from experimental pKa values of the reacting species.

Phase separation in aqueous solutions of lens gamma-crystallins: special role of gamma s.

We have studied liquid-liquid phase separation in aqueous ternary solutions of calf lens gamma-crystallin proteins. Specifically, we have examined two ternary systems containing gamma s--namely, gamma IVa with gamma s in water and gamma II with gamma s in water. For each system, the phase-separation temperatures (Tph (phi)) alpha as a function of the overall protein volume fraction phi at various fixed compositions alpha (the "cloud-point curves") were measured. For the gamma IVa, gamma s, and water ternary solution, a binodal curve composed of pairs of coexisting points, (phi I, alpha 1) and (phi II, alpha II), at a fixed temperature (20 degrees C) was also determined. We observe that on the cloud-point curve the critical point is at a higher volume fraction than the maximum phase-separation temperature point. We also find that typically the difference in composition between the coexisting phases is at least as significant as the difference in volume fraction. We show that the asymmetric shape of the cloud-point curve is a consequence of this significant composition difference. Our observation that the phase-separation temperature of the mixtures in the high volume fraction region is strongly suppressed suggests that gamma s-crystallin may play an important role in maintaining the transparency of the lens.

Solubility, Density, Refractive Index, and Viscosity for the Polyhydric Alcohol + CsBr + H2O Ternary Systems at Different Temperatures

The solubility, density, refractive index, and viscosity data for the ethylene glycol + CsBr + H2O, 1,2-propanediol + CsBr + H2O, and glycerin + CsBr + H2O ternary systems have been determined at (288.15, 298.15, and 308.15) K. In all cases, the solubility of CsBr in aqueous solutions was decreased significantly due to the presence of polyhydric alcohol. The liquid–solid equilibrium experimental data were correlated using the NRTL (nonrandom two-liquid) activity coefficient model, considering nondissociation of the dissolved salt in the liquid phase, and new interaction parameters were estimated. The mean deviations between calculated and experimental compositions were low, showing the good descriptive quality and applicability of the NRTL model. The refractive indices, densities, and viscosities for the unsaturated solutions of the three ternary systems have also been measured at three temperatures. Values for all of the properties were correlated with the salt concentrations and proportions of polyhydric alcohol in the solutions.

Degradation of [14C]GlcDGD in the marine sediment by monitoring radioactivity in the aqueous and gas phase using liquid scintillation counting (LSC) techniques

An experiment was conceived in which we monitored degradation of GlcDGD. Independent of the fate of the [14C]glucosyl headgroup after hydrolysis from the glycerol backbone, the 14C enters the aqueous or gas phase whereas the intact lipid is insoluble and remains in the sediment phase. Total degradation of GlcDGD then is obtained by combining the increase of radioactivity in the aqueous and gaseous phases. We chose two different sediment to perform this experiment. One is from microbially actie surface sediment sampled in February 2010 from the upper tidal flat of the German Wadden Sea near Wremen (53° 38' 0N, 8° 29' 30E). The other one is deep subsurface sediments recovered from northern Cascadia Margin during Integrated Ocean Drilling Program Expedition 311 [site U1326, 138.2 meters below seafloor (mbsf), in situ temperature 20 °C, water depth 1,828 m. We performed both alive and killed control experiments for comparison. Surface and subsurface sediment slurry were incubated in the dark at in situ temperature, 4 °C and 20 °C for 300 d, respectively. The sterilized slurry was stored at 20 °C. All incubations were carried out under N2 headspace to ensure anaerobic conditions. The sampling frequency was high during the first half-month, i.e., after 1, 2, 7, and 14 d; thereafter, the sediment slurry was sampled every 2 months. At each time point, samples were taken in triplicate for radioactivity measurements. After 300 d of incubation, no significant changes of radioactivity in the aqueous phase were detected. This may be the result of either the rapid turnover of released [14C] glucose or the relatively high limit of detection caused by the slight solubility (equivalent to 2% of initial radioactivity) of GlcDGD in water. Therefore, total degradation of GlcDGD in the dataset was calculated by combining radioactivity of DIC, CH4, and CO2, leading to a minimum estimate.

Integrated motorist information system (IMIS) feasibility and design study. Phase I: feasibility study. Volume 2 - appendices. Final report.

Federal Highway Administration, Office of Research and Development, Washington, D.C.

Integrated motorist information (IMIS) feasibility and design study. Phase II: generalized methodology for IMIS feasibility studies. Volume 2--validation and application of feasibility study handbook. Final report.

Federal Highway Administration, Office of Research and Development, Washington, D.C.

Vehicle integration and evaluation of advanced restraint systems. Phase B - test report: Torino-to-Volvo tests.

National Highway Traffic Safety Administration, Washington, D.C.

Rear lighting system changeover study. Phase I: a final report. Volume II - systems study.

National Highway Safety Bureau, Washington, D.C.

Vehicle integration and evaluation of advanced restraint systems. Phase A - test report: Volvo-to-Volvo [and] Volvo-to-barrier test.

National Highway Traffic Safety Administration, Washington, D.C.

Bajo de la Alumbrera copper-gold deposit: Stable isotope evidence for a porphyry-related hydrothermal system dominated by magmatic aqueous fluids

Alteration zones at the gold-rich Bajo de la Alumbrera porphyry copper deposit in northwestern Argentina are centered on several porphyritic intrusions. They are zoned from a central copper-iron sulfide and gold-mineralized potassic (biotite-K-feldspar +/- quartz) core outward to propylitic (chlorite-illite-epidote-calcite) assemblages. A mineralized intermediate argillic alteration assemblage (chlorite-illite +/- pyrite) has overprinted the potassic alteration zone across the top and sides of the deposit and is itself zoned outward into phyllic (quartzinuscovite-illite +/- pyrite) alteration. This study contributes new data to previously reported delta(18)O and delta D compositions of fluids responsible for the alteration at Bajo de la Alumbrera, and the data are used to infer likely ore-forming processes. Measured and calculated delta(18)O and delta D values of fluids (+8.3 to +10.2 and -33 to -81 parts per thousand, respectively) confirm a primary magmatic origin for the earliest potassic alteration phase. Lower temperature potassic alteration formed from magmatic fluids with lower delta D values (down to -123 parts per thousand). These depleted compositions are distinct from meteoric water and consistent with degassing and volatile exsolution of magmatic fluids derived from an underlying magma. Variability in the calculated composition of fluid associated with potassic alteration is explained in terms of phase separation (or boiling). if copper-iron sulfide deposition occurred during cooling (as proposed elsewhere), this cooling was largely a result of phase separation. Magmatic water was directly involved in the formation of overprinting intermediate argillic alteration assemblages at Bajo de la Alumbrera. Calculated delta(18)O and delta D values of fluids associated with this alteration range from +4.8 to +8.1 and -31 to -71 per mil, respectively Compositions determined for fluids associated with phyllic alteration (-0.8 to +10.2 and -31 to -119 parts per thousand) overlap with the values determined for the intermediate argillic alteration. We infer that phyllic alteration assemblages developed during two stages; the first was a high-temperature (400 degrees-300 degrees C) stage with D-depleted water (delta D = -66 to -119 parts per thousand). This compositional range may have resulted from magma degassing and/or the injection of new magmatic water into a compositionally evolved hydrothermal system. The isotopic variations also can be explained by increased fluid-rock interaction. The second stage of phyllic alteration occurred at a lower temperature (similar to 200 degrees C), and variations in the modeled isotopic compositions imply mixing of magmatic and meteoric waters. Ore deposition that occurred late in the evolution of the hydrothermal system was probably associated with further cooling of the magmatic fluid, in part caused by fluid-rock interaction and phase separation. Changing pH and/or oxygen fuoracity may have caused additional ore deposition. The ingress of meteoric water appears to postdate the bulk of mineralization and occurred as the system at Bajo de la Alumbrera waned.

Mass transfer characteristics of two-aqueous-phase liquid-liquid mixtures

Mass transfer rates were studied using the falling drop method. Cibacron Blue 3 GA dye was the transferring solute from the salt phase to the PEG phase. Measurements were undertaken for several concentrations of the dye and the phase-forming solutes and with a range of different drop sizes, e.g. 2.8, 3.0 and 3.7 mm. The dye was observed to be present in the salt phase as finely dispersed solids but a model confirmed that the mass transfer process could still be described by an equation based upon the Whitman two-film model. The overall mass transfer coefficient increased with increasing concentration of the dye. The apparent mass transfer coefficient ranged from 1 x 10-5 to 2 x 10 -4 m/s. Further experiments suggested that mass transfer was enhanced at high concentration by several mechanisms. The dye was found to change the equilibrium composition of the two phases, leading to transfer of salt between the drop and continuous phases. It also lowered the interfacial tension (i.e. from 1.43 x 10-4 N/m for 0.01% w/w dye concentration to 1.07 x 10-4 N/m for 0.2% w/w dye concentration) between the two phases, which could have caused interfacial instabilities (Marangoni effects). The largest drops were deformable, which resulted in a significant increase in the mass transfer rate. Drop size distribution and Sauter mean drop diameter were studied on-line in a 1 litre agitated vessel using a laser diffraction technique. The effects of phase concentration, dispersed phase hold-up and impeller speed were investigated for the salt-PEG system. An increase in agitation speed in the range 300 rpm to 1000 rpm caused a decrease in mean drop diameter, e.g. from 50 m to 15 m. A characteristic bimodal drop size distribution was established within a very short time. An increase in agitation rate caused a shift of the larger drop size peak to a smaller size.

All-optical phase and amplitude regenerator for next-generation telecommunications systems

Fibre-optic communications systems have traditionally carried data using binary (on-off) encoding of the light amplitude. However, next-generation systems will use both the amplitude and phase of the optical carrier to achieve higher spectral efficiencies and thus higher overall data capacities(1,2). Although this approach requires highly complex transmitters and receivers, the increased capacity and many further practical benefits that accrue from a full knowledge of the amplitude and phase of the optical field(3) more than outweigh this additional hardware complexity and can greatly simplify optical network design. However, use of the complex optical field gives rise to a new dominant limitation to system performance-nonlinear phase noise(4,5). Developing a device to remove this noise is therefore of great technical importance. Here, we report the development of the first practical ('black-box') all-optical regenerator capable of removing both phase and amplitude noise from binary phase-encoded optical communications signals.

Quasi-pilot aided phase noise estimation for coherent optical OFDM systems

In this letter, a novel phase noise estimation scheme has been proposed for coherent optical orthogonal frequency division multiplexing systems, the quasi-pilot-aided method. In this method, the phases of transmitted pilot subcarriers are deliberately correlated to the phases of data subcarriers. Accounting for this correlation in the receiver allows the required number of pilots needed for a sufficient estimation and compensation of phase noise to be reduced by a factor of 2 in comparison with the traditional pilot-aided phase noise estimation method. We carried out numerical simulation of a 40 Gb/s single polarization transmission system, and the outcome of the investigation indicates that by applying quasi-pilot-aided phase estimation, only four pilot subcarriers are needed for effective phase noise compensation. © 2014 IEEE.

Interleavers and BCH codes for coherent DQPSK systems with laser phase noise

The relatively high phase noise of coherent optical systems poses unique challenges for forward error correction (FEC). In this letter, we propose a novel semianalytical method for selecting combinations of interleaver lengths and binary Bose-Chaudhuri-Hocquenghem (BCH) codes that meet a target post-FEC bit error rate (BER). Our method requires only short pre-FEC simulations, based on which we design interleavers and codes analytically. It is applicable to pre-FEC BER ∼10-3, and any post-FEC BER. In addition, we show that there is a tradeoff between code overhead and interleaver delay. Finally, for a target of 10-5, numerical simulations show that interleaver-code combinations selected using our method have post-FEC BER around 2× target. The target BER is achieved with 0.1 dB extra signal-to-noise ratio.