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Biomedical subjects

H M Davies

Publications and source records attributed to H M Davies.

At least 19 recordsLinked to original sources
PubMed2005

Direct observation of the alpha-epsilon transition in shock-compressed iron via nanosecond x-ray diffraction.

In situ x-ray diffraction studies of iron under shock conditions confirm unambiguously a phase change from the bcc (alpha) to hcp (epsilon) structure. Previous identification of this transition in shock-loaded iron has been inferred from the correlation between shock-wave-profile analyses and static high-pressure x-ray measurements. This correlation is intrinsically limited because dynamic loading can markedly affect the structural modifications of solids. The in situ measurements are consistent with a uniaxial collapse along the [001] direction and shuffling of alternate (110) planes of atoms, and are in good agreement with large-scale nonequilibrium molecular dynamics simulations.

Journal Article↗
PubMed2001

Catalytic asymmetric allylic C-H activation as a surrogate of the asymmetric Claisen rearrangement.

[reaction: see text]. Tetrakis[N-[4-dodecylphenyl)sulfonyl]-(S)-prolinato]-dirhodium [Rh2(S-DOSP)4] catalyzed decomposition of methyl aryldiazoacetates in the presence of alkenes results in allylic C-H activation by means of a rhodium-carbene induced C-H insertion. The resulting gamma,delta-unsaturated esters are equivalent to products that would be traditionally obtained from an asymmetric Claisen rearrangement. Highly regio- and enantioselective C-H insertions can be achieved, and in certain cases, good diastereocontrol is also possible.

Journal Article↗
PubMed2001

Catalytic asymmetric cyclopropanation of heteroaryldiazoacetates.

Rh(2)(S-DOSP)(4)-catalyzed decomposition of heteroaryldiazoacetates in the presence of styrene results in highly diastereoselective and enantioselective cyclopropanations. Heteroaryldiazoacetates containing both electron-rich and electron-deficient heterocycles, such as thiophene, furan, pyridine, indole, oxazole, isoxazole, and benzoxazole, are effective in this chemistry. These studies broaden the range of diazo compounds containing both electron-withdrawing and electron-donating groups, which undergo highly diastereoselective cyclopropanations.

Catalysis↗
PubMed2001

Measurement of instability growth in a magnetized Z pinch in the finite-Larmor-radius regime.

The development of the m = 0 instability in a Z pinch was followed and the measured growth rates compared with 2D MHD simulations. Where MHD is valid, the measured growth rates agree well with simulation. Where the ions are magnetized, i.e., where the ion-cyclotron frequency is smaller than the ion-collision frequency and the ratio of the ion Larmor radius to pinch radius is of the order of 0.1, the growth rate was smaller than expected by a factor of 2.5. This is as predicted by finite-Larmor-radius theory. The product of the wave number and the pinch radius was ka approximately 2pi and was the same for all conditions. Perturbations as large as 30% of the pinch radius were observed; no nonlinear saturation was evident.

Journal Article↗
PubMed2001

Kinetic resolution and double stereodifferentiation in catalytic asymmetric C-H activation of 2-substituted pyrrolidines.

Dirhodium tetrakis(S-(N-dodecylbenzenesulfonyl)prolinate) (Rh(2)(S-DOSP)(4)) catalyzed decomposition of methyl aryldiazoacetates in the presence of 2-substituted pyrrolidines results in highly diastereoselective and enantioselective C-H insertions. These reactions can proceed with impressive levels of double stereodifferentiation and kinetic resolution, which allows for three stereocenters to be controlled during the C-H insertion step.

Catalysis↗
PubMed2001

Asymmetric intramolecular C_H insertions of aryldiazoacetates.

[reaction: see text] The enantioselectivity of Rh(2)(S-DOSP)(4) catalyzed C-H insertion of aryldiazoacetates is very dependent on the site of the C-H insertion. The highest enantioselectivity is obtained for insertion into methine C-H bonds.

Journal Article↗
PubMed2001

Synthesis of 2beta-acyl-3beta-(substituted naphthyl)-8-azabicyclo[3.2.1]octanes and their binding affinities at dopamine and serotonin transport sites.

A series of 3beta-naphthyltropane derivatives were synthesized and found to show high affinity at both the dopamine and serotonin transporter sites, leading to some of the most potent inhibitors known based on the tropane structure. Comparative molecular field analysis (CoMFA) models were developed for both dopamine and serotonin transporter binding data. These models provide insights into those factors that influence binding at the two transporters.

Animals↗
PubMed2001

Relationships between third metacarpal bone parameters and surface strains.

The relationships were explored between measurements of bone quality, size (quantity) and shape, and strain data collected during treadmill exercise at 4 and 12 m/s from the third metacarpal bones of 6 yearling and 6 mature Thoroughbred racehorses. Peak strains in yearling and mature Thoroughbred horses during exercise were related to the size and shape of the third metacarpal bone. The peak strains were significantly lower in horses with a greater cross-sectional area of bone and with a greater proportion of the bone in the dorsal cortex. There was no consistent relationship between peak strains and bone quality assessed by ultrasound speed, single photon absorptiometry and direct measurement of porosity and specific gravity. It was concluded that measurement of the dorsal cortical proportions of the third metacarpal bone may provide a way of estimating the level of strains caused by fast exercise in this part of the bone, and hence the modelling response to be expected.

Animals↗
PubMed2001

Analysis of a radiographic technique for measurement of equine metacarpal bone shape.

Accuracy and limitations of a radiographic technique were established for measurement of metacarpal bone shape in horses. A radiographic index (RI) has been used to measure changes in third metacarpal (Mc3) bone shape in response to training in young racehorses. The aim of these experiments was to determine the effects of positioning of the radiographic equipment on RI measurements from lateromedial radiographs of a left ex vivo metacarpus. Repeatability of the RI measurement in left lateromedial and right mediolateral view Mc3s were evaluated. The width of the dorsal cortex (DC), palmar cortex (PC) and medulla (M) were measured at a position 25 mm distal to the nutrient foramen and the RI calculated where RI = [(DC + PC)/M] x [DC/PC]. The reference RI values were obtained from 12 standard lateromedial radiographs. Factors analysed included the optimum focus-object distance, the angle at which the x-ray machine was positioned, the distance of the cassette from the limb, and the horizontal angle and vertical tilt of the cassette. The RI values included within the confidence interval (mean +/- 1.96 x s.d.) were considered sufficiently accurate. The optimum focus-object distance was 1 m. Accurate measurements were obtained when the cassette was held as close to the limb as possible with the horizontal angle not exceeding 5 degrees. The x-ray machine needed to be orientated within 6 degrees of the lateromedial plane. These findings suggest that the radiographic index can be used to measure Mc3 bone shape, providing there is accurate alignment of the x-ray machine, cassette, and limb, with respect to one another.

Animals↗
PubMed2000

A cocaine analog, 2beta-propanoyl-3beta-(4-tolyl)-tropane (PTT), reduces tyrosine hydroxylase in the mesolimbic dopamine pathway.

Tyrosine hydroxylase (TH) is the rate-limiting enzyme in catecholamine biosynthesis. Previously published results have established that chronic cocaine administration (30-45 mg/kg per day, 10-14 days) resulted in an upregulation of TH gene expression in dopaminergic pathways of rats. The present studies tested the effects of a tropane analog, PTT (2beta-propanoyl-3beta-(4-tolyl)-tropane), on TH expression. This drug has similar actions to cocaine, but possesses markedly different pharmacokinetics (20 times more potent at binding the dopamine transporter, markedly increased metabolic stability, and 10-20 times more potent in behavioral measures). Moreover, PTT demonstrates an increased selectivity for the dopamine (DA) and norepinephrine (NE) transporters compared with cocaine. In direct contrast to the previously reported effects of cocaine, 10 days of PTT administration (3.0 mg/kg per day, i.p.) produced a uniform downregulation of TH protein and activity gene expression. TH activity and immunoreactive protein where decreased by 54 and 69%, respectively in the nucleus accumbens. Within the ventral tegmental area, TH activity and protein were decreased by 33 and 19%, respectively. The underlying mechanisms for these fundamental differences are unclear, but likely reflect varying and selective affinities and lengths of occupancy at biogenic amine transporters.

Animals↗
PubMed2000

An exploratory study of type II [3 + 4] cycloadditions between vinylcarbenoids and dienes.

The intramolecular type II [3 + 4] cycloaddition between vinylcarbenoids and furans is a practical method for the construction of 5-oxo-10-oxatricyclo[6.2.1.0(4,9)]undeca-3, 8(11)-dienes, containing two anti-Bredt double bonds. These tricyclic systems are well functionalized for eventual elaboration to the natural product CP-263,114. The rhodium-stabilized vinylcarbenoids are generated by dirhodium tetracarboxylate catalyzed decomposition of vinyldiazoacetates. The [3 + 4] cycloaddition is generally considered to occur by a tandem cyclopropanation/Cope rearrangement, although evidence is presented that with these substrates the [3 + 4] cycloaddition may occur in a concerted manner.

Alkenes↗
PubMed2000

A comparison of the behavioral effects of the repeated administration of PTT, 2beta-propanoyl-3beta-(4-tolyl)tropane and cocaine.

In the present study the effects of the repeated administration of the novel tropane analog PTT (2beta-propanoyl-3beta(4-tolyl)tropane) on spontaneous locomotor activity were compared to those of cocaine. Previous reports describing the in vivo effects of PTT have focused solely on its acute effects following a single administration. In Experiment 1, PTT (1.0, 3.0 mg/kg), cocaine (30 mg/kg), or vehicle were administered intraperitoneally to male Sprague-Dawley rats daily for 10 consecutive days and locomotor activity was assessed. In Experiment 2, the locomotor effects of PTT (1.0 mg/kg) and cocaine (15 mg/kg) were assessed following 5 days of drug exposure to either PTT (1.0, 3.0 mg/kg) or cocaine (30 mg/kg) and 18 days of withdrawal. In both paradigms, PTT (1.0, 3.0 mg/kg) and cocaine (30 mg/kg) produced marked increases in locomotor activity acutely and an augmented response to drug challenge following repeated exposure, indicative of behavioral sensitization. These data indicate that, despite differences in the pharmacological profiles of PTT and cocaine, both drugs produce behavioral sensitization. These data are consistent with previous reports in the literature describing the effects of the repeated administration of other dopamine reuptake inhibitors and suggest that the development of behavioral sensitization is a uniform characteristic of this class of drugs.

Animals↗
PubMed2000

Stereoselectivity of methyl aryldiazoacetate cyclopropanations of 1,1-diarylethylene. Asymmetric synthesis of a cyclopropyl analogue of tamoxifen.

[formula: see text] Dirhodium tetrakis(S-(N-dodecylbenzenesulfonyl)prolinate) (Rh2(S-DOSP)4)-catalyzed decomposition of methyl phenyldiazoacetate in the presence of 1,1-diarylethylenes results in intermolecular cyclopropanation with high enantioselectivity (up to 99% ee) and moderate diastereoselectivity (up to 80% de). The reaction was applied to the asymmetric synthesis of a cyclopropyl analogue of tamoxifen.

Benzene Derivatives↗