2-Halo-diketopiperazines as chiral glycine cation equivalents

A range of (2S,5S)-5-isopropyl-2-halo-N,N′-bis-(p-methoxybenzyl)-piperazine-3,6-diones 8 (Cl), 11, 12 (F) and 13 (Br) have been prepared, either via electrophilic halogenation of the corresponding lithiated diketopiperazine, or via transhalogenation from fluoro-11 and 12. The product distribution and stereoselectivity of additions of allyltrimethylsilane, sodium thiophenolate and a range of organomagnesium reagents to chloro 8 are reported. In the reactions with Grignard reagents the observed stereo- and regioselectivities are dependent on the reagent employed, with C-3 carbonyl addition products predominating upon addition of allyl or methylmagnesium chloride and stereodivergent formal C-2 addition predominating with benzyl or isopropylmagnesium chloride. A model to account for the different reactivity and stereoselectivity in these reactions is proposed.     

Transition metal nitrosyl compounds,Part XXV1 Studies of some nitrosyl complexes of molybdenum and tungsten

Summary On u.v. irradiation, the dinitrosyldithiocarbamato M(NO)₂ (S2 CNR2 )2 (M = Mo or W) complexes are converted quantitatively into the mononitrosyl M(NO)(S₂CNR₂)₃ complexes. The tungsten complex exhibits nonrigid behaviour at high temperatures; the activation energy for this process has been determined and compared to that of the molybdenum analogue. The M(NO)₂ (MeCOCHCOMe)₂ and M(NO)₂ [(O)SCNR₂]₂ compounds have been prepared; these undergo conversion into uncharacterized nitrosyl derivatives upon irradiation. Cationic complexes of the type [M(NO)₂ (MeCN)₄]2+, [M(NO)₂ (MeCN)₃ X]+ and [M(NO)₂ (MeCN)₂ (MeCOCHCOMe)]+ have been prepared and their exchange with CD₃CN studied. Exchange occursvia a dissociative process and is stereospecific for [M(NO)₂ (MeCN)₄ ]2+ (M = Mo or W) and [M(NO)₂ (MeCN)₃ X]+ (M = MO, X = Cl; M = W, X = Br).     

Advances in clinical chemistry over the past 25 years

A survey is presented of developments over the past 25 years of several important areas of clinical chemistry. These areas are instrumentation, reagents, electrochemical sensors, computing, statistics, quality control, enzymology, drug monitoring, trace elements and nucleic acid probes.     

SINGLET OXYGEN INDUCES FRANK STRAND BREAKS AS WELL AS ALKALI- AND PIPERIDINE-LABILE SITES IN SUPERCOILED PLASMID DNA

A covalently closed, circular, supercoiled plasmid was exposed to singlet oxygen by a separated-surface sensitizer. For each exposure, the quantity of single oxygen entering the DNA target solution was estimated by its oxidation of histidine. After singlet oxygen exposure, some DNA samples were treated to disclose occult lesions. Agarose gel electrophoresis was then used to resolve the unrelaxed supercoils from the relaxed circular and linear species, and all bands were quantitated fluorometrically. Exposure of supercoiled plasmid DNA to singlet oxygen induced frank DNA strand breaks, alkali-labile sites (pH 12.5, 90 degrees C, 30 min), and piperidine-labile sites (0.4 M, 60 degrees C, 30 min), all in a dose-dependent manner. Yields of alkali-labile and piperidine-labile sites ranged from one to four times the frank strand break yield. Replacement of buffered H2O by buffered D2O as the DNA solvent for singlet oxygen exposures increased DNA lesion yields by a factor of 2.6 (averaged over lesion classes). Our data for the detection of frank strand breaks is at variance with published results from studies in which singlet oxygen was derived from a thermolabile endoperoxide dissolved in the DNA solution.     

Alkylation and aldol reactions of acyl derivatives of N-1-(1′-naphthyl)ethyl-O-tert-butylhydroxylamine: asymmetric synthesis of α-alkoxy-, α-substituted-β-alkoxy- and α,β-dialkoxyaldehydes

Treatment of a range of O-protected glycolate derivatives of the chiral auxiliary N-1-(1′-naphthyl)ethyl-O-tert-butylhydroxylamine with KHMDS in the presence of 18-crown-6 followed by addition of an alkyl halide generates α-substituted derivatives with very high levels of diastereoselectivity. Alternatively, reaction of the potassium enolate of a propanoate or O-protected glycolate derivative of N-1-(1′-naphthyl)ethyl-O-tert-butylhydroxylamine with a range of aldehydes gives syn-aldol products with high levels of diastereoselectivity. These adducts may be reductively cleaved with LiAlH₄ to give enantiopure α-alkoxy-, α-substituted-β-alkoxy- and α,β-dialkoxyaldehydes in good yield.     

The drag of three-dimensional rectangular cavities

Cavities and other surface cut-outs are present on aircraft in numerous forms, from cargo bays and landing gear housing to rivet depressions and panel handles. Although these surface imperfections make a significant contribution to the overall drag on an aircraft, relatively little is known about the flow mechanisms associated with cavities, particularly those which have a strongly three-dimensional geometry. The present work is a wind tunnel investigation of the drag forces and flow regimes associated with cavities having a 2:1 rectangular planform geometry. The effects of both the cavity depth and the flow incidence angle have been examined in terms of the overall cavity drag increment and the mean surface pressure distributions. The drag forces have been determined from both integrated pressures and direct force balance measurements. For the model normal to the flow direction the flow within the cavity was remarkably symmetrical in all the configurations examined. In most cases the cavity flow is dominated by a single large eddy. However, for cavities yawed to other incidence angles there is considerable flow asymmetry, with strong vorticity shedding and high drag in some cases, notably with depth/narrowest width ratio of 0.4–0.5 at 45–60° incidence. The present data correspond well with established results and extend the scope of information available for design purposes and for the development of numerical models.Nomenclature A _p planform area of model - C _D pressure drag coefficient (F _D /(A _p · q)) - C _D drag coefficient increase due to cavity (C _D – c_f) - c _f local skin friction coefficient - C _L pressure lift coefficient (F _L /(A _p · q)) - C _p mean surface pressure coefficient (P – P _s )/q) - F _D drag force - F _L lift force - h depth - L longest planform dimension of model - P surface pressure on model - P _s freestream static pressure - P _t freestream total pressure - q freestream dynamic pressure (P _t – P_s) - Re Reynolds number (U _R · W/v) - U _R freestream velocity - W narrowest planform dimension of model - Z vertical cartesian coordinate - incidence angle - kinematic viscosity     

The flow regime in the turbulent near wake of a hemisphere

The work presented is a wind tunnel study of the near wake region behind a hemisphere immersed in three different turbulent boundary layers. In particular, the effect of different boundary layer profiles on the generation and distribution of near wake vorticity and on the mean recirculation region is examined. Visualization of the flow around a hemisphere has been undertaken, using models in a water channel, in order to obtain qualitative information concerning the wake structure.List of symbols C _p pressure coefficient, - D diameter of hemisphere - n vortex shedding frequency - p pressure on model surface - p ₀ static pressure - Re Reynolds number, - St Strouhal number, - U, V, W local mean velocity components - mean freestream velocity inX direction - U ^* shear velocity, - u, v, w velocity fluctuations inX, Y andZ directions - X Cartesian coordinate in longitudinal direction - Y Cartesian coordinate in lateral direction - Z Cartesian coordinate in direction perpendicular to the wall - it* boundary layer displacement thickness, - diameter of model surface roughness - elevation angleI - O boundary layer momentum thickness, - _w wall shearing stress - dynamic viscosity of fluid - density of fluid - streamfunction - _x longitudinal component of vorticity, - _y lateral component of vorticity, - _z vertical component of vorticity, This paper was presented at the Ninth symposium on turbulence, University of Missouri-Rolla, October 1–3, 1984     

Solvent extraction of selenium, chromium, iron and zinc from ashed serum samples.

The extraction by APDC in MIBK of Se, Cr, Fe and Zn from serum ashed in a low-temperature dry asher is described. Extraction temperatures of 25, 40, 55, and 70°C were studied; 40°C provided the best overall extraction efficiencies. However, in no case could quantitative extractions be obtained. Losses of metals during the processing steps were shown to be insignificant.