Influence of Sulfur for Oxygen Substitution in the Solvolytic Reactions of Chloroformate Esters and Related Compounds

The replacement of oxygen within a chloroformate ester (ROCOCl) by sulfur can lead to a chlorothioformate (RSCOCl), a chlorothionoformate (ROCSCl), or a chlorodithioformate (RSCSCl). Phenyl chloroformate (PhOCOCl) reacts over the full range of solvents usually included in Grunwald-Winstein equation studies of solvolysis by an addition-elimination (A-E) pathway. At the other extreme, phenyl chlorodithioformate (PhSCSCl) reacts across the range by an ionization pathway. The phenyl chlorothioformate (PhSCOCl) and phenyl chlorothionoformate (PhOCSCl) react at remarkably similar rates in a given solvent and there is a dichotomy of behavior with the A-E pathway favored in solvents such as ethanol-water and the ionization mechanism favored in aqueous solvents rich in fluoroalcohol. Alkyl esters behave similarly but with increased tendency to ionization as the alkyl group goes from 1° to 2° to 3°. N,N-Disubstituted carbamoyl halides favor the ionization pathway as do also the considerably faster reacting thiocarbamoyl chlorides. The tendency towards ionization increases as, within the three contributing structures of the resonance hybrid for the formed cation, the atoms carrying positive charge (other than the central carbon) change from oxygen to sulfur to nitrogen, consistent with the relative stabilities of species with positive charge on these atoms.     

Observations on the changes in nitrate concentrations along streams in seven upland moorland catchments in Northeast Scotland

River water has been sampled under baseflow conditions in both summer and winter at c. 250-m intervals along the length of each of seven rivers in northeast Scotland, and the nitrate contents have been determined. The resultant data have been examined in the context of the nitrogen saturation hypothesis. Capacity of the catchment soils to retain nitrate was generally minimal in winter. Although biological uptake of nitrate was evident in summer, in the upper part of each catchment substantial nitrate leaching still occurred. The phenomenon was most marked in water draining from hill peats, except where these were conspicuously waterlogged. The results are discussed in the context of possible nitrogen saturation effects on upper catchment slopes.     

伊拉克某油田注水站设计方案优化

伊拉克鲁迈拉油田CP00注水站设计规模为1 000 m3/h,注水压力为20 MPa。该注水站的设计方案及优化考虑了安全、环保、节能、节省投资等因素。重点介绍了CP00内向注水泵喂水的方案选择及设计优化,以及整体工艺流程的设计。     

The structure of latherin,a surfactant allergen protein from horse sweat and saliva

Latherin is a highly surface-active allergen protein found in the sweat and saliva of horses and other equids. Its surfactant activity is intrinsic to the protein in its native form, and is manifest without associated lipids or glycosylation. Latherin probably functions as a wetting agent in evaporative cooling in horses, but it may also assist in mastication of fibrous food as well as inhibition of microbial biofilms. It is a member of the PLUNC family of proteins abundant in the oral cavity and saliva of mammals, one of which has also been shown to be a surfactant and capable of disrupting microbial biofilms. How these proteins work as surfactants while remaining soluble and cell membrane-compatible is not known. Nor have their structures previously been reported. We have used protein nuclear magnetic resonance spectroscopy to determine the conformation and dynamics of latherin in aqueous solution. The protein is a monomer in solution with a slightly curved cylindrical structure exhibiting a ‘super-roll’ motif comprising a four-stranded anti-parallel β-sheet and two opposing α-helices which twist along the long axis of the cylinder. One end of the molecule has prominent, flexible loops that contain a number of apolar amino acid side chains. This, together with previous biophysical observations, leads us to a plausible mechanism for surfactant activity in which the molecule is first localized to the non-polar interface via these loops, and then unfolds and flattens to expose its hydrophobic interior to the air or non-polar surface. Intrinsically surface-active proteins are relatively rare in nature, and this is the first structure of such a protein from mammals to be reported. Both its conformation and proposed method of action are different from other, non-mammalian surfactant proteins investigated so far.     

Computational fluid dynamics (CFD) investigation of air flow and temperature distribution in a small scale bread-baking oven

Experimental and computational fluid dynamics (CFD) analyses of the thermal air flow distribution in a 3-zone small scale forced convection bread-baking oven are undertaken. Following industrial bread-making practise, the oven is controlled at different (constant) temperatures within each zone and a CFD model is developed and validated against experimental data collected within the oven. The CFD results demonstrate that careful selection of the flow model, together with implementation of realistic boundary conditions, give accurate temperature predictions throughout the oven. The CFD model is used to predict the flow and thermal fields within the oven and to show how key features, such as regions of recirculating flow, depend on the speeds of the impinging jets.