Chiral trialkoxysilanols derived from terpene alcohols. Molecular structures of tris([(1S)-endo]-(-)-bornoxy)silanol and tetrakis((-)-menthoxy)silane

Terpene alcohols (−)-menthol and [(1S)-endo]-(−)-borneol react with SiCl₄ in the presence of base to give (MenO)₃SiCl (1) and (BorO)₃SiCl (2) in high yields. Hydrolysis of 1 yields (MenO)₃SiOH (4) and (MenO)₄Si (3). Hydrolysis of 2 yields only (BorO)₃SiOH (5). The crystal structures of 3 and 5 are reported.

Modeling and simulation of collisions of heavy trucks with concrete barriers

On-site collision tests of full-scale concrete barriers are an important method to understand what happens to concrete barriers when vehicles collide with them. However, such tests require both time and money, so modeling and simulation of collisions by computer have been developed as an alternative in this research. First, spring subgrade models were developed to formulate the ground boundary of concrete barriers based on previous experiments. Then, the finite element method models were developed for both heavy trucks and concrete barriers to simulate their dynamic collision performances. Comparison of the results generated from computer simulations and on-site experiments demonstrates that the developed models can be applied to simulate the collision of heavy trucks with concrete barriers, to replicate the movement of the truck at the collision, and to investigate the performance of the concrete barriers. The developed research methodology can be widely used to support the design of new concrete barriers and the safety analysis of existing ones.

Dynamic simulation of collisions of heavy high-speed trucks with concrete barriers

Real vehicle collision experiments on full-scale road safety barriers are important to determine the outcome of a vehicle versus barrier impact accident. However, such experiments require large investment of time and money. Numerical simulation has therefore been imperative as an alternative method for testing concrete barriers. In this research, spring subgrade models were first developed to simulate the ground boundary of concrete barriers. Both heavy trucks and concrete barriers were modeled using finite element methods (FEM) to simulate dynamic collision performances. Comparison of the results generated from computer simulations and on-site full-scale experiments demonstrated that the developed models could be applied to simulate the collision of heavy trucks with concrete barriers to provide the data to design new road safety barriers and analyze existing ones.

Chiral organotin hydrides as enantioselective reducing agents

This thesis reports on the feasibility of the utilization of organotin hydrides as enaantioselective free radical reducing agents. The chiral organotin hydrides prepared contain the bulky chiral (1R,2S,5R)-menthyl substituent and in some cases also contain a stereogenic tin centre. Reaction of (1R,2S,5R)-menthylmagnesium chloride (MenMgC1) with triphenyltin chloride in THF proceeds with epimerization of the C-1 carbon of the menthyl group and results in a mixture of (1R,2S,5R)-menthyltriphenyltin and (1S,2S.5R)-menthyltriphenyltin. Addition of Lewis bases such as triphenylphosphine to the THF solution of triphenyltin chloride prior to the addition of the Grignard reagent suppresses epimerization and enables isolation of pure (1R,2S,5R)-menthyltriphenyltin. (1R,2S,5R)-Menthyltriphenyltin is the precursor for the synthesis of (1R,2S,5R)-menthyldiphenyltin hydride as well as (1R,2S,5R)-menthyl-containing organotin halide derivatives. A crystal structure of (1R,2S,5R)-menthylphenyltin dibromide and (1R,2S,5R)-menthylphenyltin dichloride confirmed the configuration of the menthyl substituent in these compounds. Reaction of MenMgC1 with diphenyltin dichloride in THF proceeds with no epimerization of the C-1 carbon of the menthyl group and bis((1R,2S,5R)-menthyl)diphenyltin is formed. A crystal structure of (1R,2S,5R)-menthyltriphenyltin confirmed the configuration of the menthyl substituent. Bis((1R,2S,5R)-menthyl)diphenyltin is used to form bis((1R,2S,5R)-menthyl)phenyltin hydride as well as other bis(1R,2S,5R)-menthyl derivatives. A series of chiral non-racemic triorganotin halides and triorganotin hydrides containing one or two (1R,2S,5R)-menthyl substituents as well as various potentially intramolecular coordination substituents were synthesized and characterized. The intramolecular substituents include the 8-(dimethylamino)naphthyl, 2-[(1S)-1-dimethylaminoethyl]phenyl, 2-(4,4-dimethyl-2-oxazoline)-5-methylphenyl and the 2-(4-(S)isopropyl-2-oxazoline)-5-methylphenyl substituents. Each compound containing a stereogenic tin centre was synthesized as diastereomeric mixtures. AM1 calculations of these compounds provide good qualitative predictability of the molecular geometries observed in the solid state as well as the diastereomeric ratios observed in solution. X-ray analysis of some of the organotin halides containing intramolecular coordination substituents revealed a tendency towards penta-coordination at the tin centre as a result of N-Sn interactions. The chiral organotin hydrides synthesized were found to be poor enantioselective free radical reducing agents. However, the addition of one molar equivalent of achiral or chiral Lewis acids to the free radical reduction reactions involving these organotin hydrides results in remarkable increases in enantioselectivity. There are numerous examples in which enantioselectivities exceed 80% and three examples of enantioselectivites which are equal and above 90% with one outstanding enantioselective outcome of ≥99%. These results appear to be the highest enantioselectivites for organotin hydride radical reductions reported to date. There is strong evidence to suggest that the chiral menthyl group of the organotin hydride directs the stereochemical outcome in the reduced product. The results also suggest that an increase in the number of menthyl substituents attached to tin or the introduction of intramolecular coordination substituents does not necessarily results in a greater increase in enantioselectivity. Preliminary studies into the synthesis of organotin hydrides containing Lewis acid functionalities are also reported. A zirconium chloride functionality was found to be incompatible with organotin hydride. However, an organotin hydride containing a trialkylboron Lewis acid functionality attached via an alkyl chain was successfully synthesized. Although this reagent was only stable in the preparative THF solution, it was still found to be effective at reducing benzaldehyde to benzyl alcohol.

An analysis of microband orientation in hot deformed aluminium alloy AA5052 using forward and reverse torsion

The effects of strain path reversal on the macroscopic orientation of microbands in AA5052 have been studied using high resolution electron backscatter diffraction. Deformation was carried using two equal steps of forward/forward or forward/reverse torsion at a temperature of 300°C and strain rate of 1s-1 to a total equivalent tensile strain of 0.5. In both cases microbands were found in the majority of grains examined with many having more than one set. The microbands appear to cluster at specific angles to the macroscopic deformation. For the forward/forward condition microbands clustered around -20° and +45° to the maximum principle stress direction and at ± 30-35° to the principal strain direction. For the forward/reverse condition significantly more spread in microband angle was observed though peaks were visible at ±35° with respect to principal stress direction and at -40° and +30° with respect to the principal strain direction of the reverse torsion. This suggests the microbands formed in the forward deformation have or are dissolving and any new microbands formed are related to the deformation conditions of the final strain path.

Formation of defects in boron nitride by low energy ion bombardment

Formation of defects in hexagonal and cubic boron nitride (h -BN and c -BN, respectively) under low-energy argon or nitrogen ion-bombardment has been studied by near-edge x-ray absorption fine structure (NEXAFS) around boron and nitrogen K -edges. Breaking of B-N bonds for both argon and nitrogen bombardment and formation of nitrogen vacancies, VN, has been identified from the B K -edge of both h -BN and c -BN, followed by the formation of molecular nitrogen, N2, at interstitial positions. The presence of N 2 produces an additional peak in photoemission spectra around N 1s core level and a sharp resonance in the low-resolution NEXAFS spectra around N K -edge, showing the characteristic vibrational fine structure in high-resolution measurements. In addition, several new peaks within the energy gap of BN, identified by NEXAFS around B and N K -edges, have been assigned to boron or nitrogen interstitials, in good agreement with theoretical predictions. Ion bombardment destroys the cubic phase of c -BN and produces a phase similar to a damaged hexagonal phase. © 2009 American Institute of Physics.

Microstructure-property relationship of the high strength low alloy steels during tensile testing at high strain rates

Positive The influence of strain-rate on the room temperature mechanical properties of the Dual-Phase and Transformation Induced Plasticity (TRIP) steels was investigated.The results showed that both the plastic strain, and strength properties increased with increasing strain rates at high strain rates.At strain rates lower than approximateil 1s ~ (-1) the properties no longer have an advantageous proportionality to strain rate and remain strain rate neutral.Possible explanations are offered for trends exhibited, in terms of thermal and athermal considerations, in relation to the respective microstructures of the two steels

Risk of falls and motor vehicle collisions in glaucoma

PURPOSE. To investigate the risk of falls and motor vehicle collisions (MVCs) in patients with glaucoma.

METHODS. The sample comprised 48 patients with glaucoma (mean visual field mean deviation [MD] in the better eye = −3.9 dB; 5.1 dB SD) and 47 age-matched normal control subjects, who were recruited from a university-based hospital eye care clinic and are enrolled in an ongoing prospective study of risk factors for falls, risk factors for MVCs, and on-road driving performance in glaucoma. Main outcome measures at baseline were previous self-reported falls and MVCs, and police-reported MVCs. Demographic and medical data were obtained. In addition, functional independence in daily living, physical activity level and balance were assessed. Clinical vision measures included visual acuity, contrast sensitivity, standard automated perimetry, useful field of view (UFOV), and stereopsis. Analyses of falls and MVCs were adjusted to account for the possible confounding effects of demographic characteristics, medications, and visual field impairment. MVC analyses were also adjusted for kilometers driven per week.

RESULTS. There were no significant differences between patients with glaucoma and control subjects with respect to number of systemic medical conditions, body mass index, functional independence, and physical activity level (P > 0.10). At baseline, 40 (83%) patients with glaucoma and 44 (94%) control subjects were driving. Compared with control subjects, patients with glaucoma were over three times more likely to have fallen in the previous year (odds ratio [OR]adjusted = 3.71; 95% CI, 1.14–12.05), over six times more likely to have been involved in one or more MVCs in the previous 5 years (ORadjusted = 6.62; 95% CI, 1.40–31.23), and more likely to have been at fault (ORadjusted = 12.44; 95% CI, 1.08–143.99). The strongest risk factor for MVCs in patients with glaucoma was impaired UFOV selective attention (ORadjusted = 10.29; 95% CI, 1.10–96.62; for selective attention >350 ms compared with ≤350 ms).

CONCLUSIONS. There is an increased risk of falls and MVCs in patients with glaucoma.

The raft-promoting property of virion-associated cholesterol, but not the presence of virion-associated brij 98 rafts, is a determinant of human immunodeficiency virus type 1 infectivity

Lipid rafts are enriched in cholesterol and sphingomyelin and are isolated on the basis of insolubility in detergents, such as Brij 98 and Triton X-100. Recent work by Holm et al. has shown that rafts insoluble in Brig 98 can be found in human immunodeficiency virus type 1 (HIV-1) virus-like particles, although it is not known whether raft-like structures are present in authentic HIV-1 and it is unclear whether a virion-associated raft-like structure is required for HIV replication. Independently, it was previously reported that virion-associated cholesterol is critical for HIV-1 infectivity, although the specific requirement of virion cholesterol in HIV-1 was not examined. In the present study, we have demonstrated that infectious wild-type HIV-1 contains Brij 98 rafts but only minimal amounts of Triton X-100 rafts. To directly assess the functional requirement of virion-associated rafts and various features of cholesterol on HIV-1 replication, we replaced virion cholesterol with exogenous cholesterol analogues that have demonstrated either raft-promoting or -inhibiting capacity in model membranes. We observed that variable concentrations of exogenous analogues are required to replace a defined amount of virion-associated cholesterol, showing that structurally diverse cholesterol analogues have various affinities toward HIV-1. We found that replacement of 50% of virion cholesterol with these exogenous cholesterol analogues did not eliminate the presence of Brij 98 rafts in HIV-1. However, the infectivity levels of the lipid-modified HIV-1s directly correlate with the raft-promoting capacities of these cholesterol analogues. Our data provide the first direct assessment of virion-associated Brij 98 rafts in retroviral replication and illustrate the importance of the raft-promoting property of virion-associated cholesterol in HIV-1 replication.

Protein electrochemistry using graphene-based nano-assembly: an ultrasensitive electrochemical detection of protein molecules via nanoparticle-electrode collisions

We describe a new electrochemical detection approach towards single protein molecules (microperoxidase-11, MP-11), which are attached to the surface of graphene nanosheets. The non-covalently functionalized graphene nanosheets exhibit enhanced electroactive surface area, where amplified redox current is produced when graphene nanosheets collide with the electrode.

The hot working flow stress and microstructure in magnesium AZ31

The evolution of flow stress and microstructure for wrought magnesium alloy AZ31 was characterised using torsion and compression testing. Temperatures ranging between 300°C and 450°C and strain rates between 0.001s^-1 and 1s^-1, were employed. Constitutive equations were developed for the flow stress at a strain of 1.0 for torsion, and 0.6 for compression. The flow stress was found to be strongly dependent on deformation mode at low strains. This can be explained in terms of the influence of the deformation accommodating processes of prismatic slip and dynamic recrystallisation (DRX). At higher strains, when the change in flow stress with strain is lower, the flow stress was relatively insensitive to deformation mode. Optical microscopy carried out on torsion samples quenched after twisting to strains between 0.2 and 2 revealed dynamically recrystallised (DRX) grains situated on pre-existing grain boundaries. The average grain size was reduced from 22.5μm down to 7.3 μm after a strain of 2, with the initial grain size being halved after a strain of 0.5.

Validity of a trunk-mounted accelerometer to measure physical collisions in contact sports

CONTEXT: Accelerometer peak impact accelerations are being used to measure player physical demands in contact sports. However, their accuracy to do so has not been ascertained. PURPOSE: To compare peak-impact-acceleration data from an accelerometer contained in a wearable tracking device with a 3-dimensional motion-analysis (MA) system during tackling and bumping. METHODS: Twenty-five semielite rugby athletes wore a tracking device containing a 100-Hz triaxial accelerometer (MinimaxX S4, Catapult Innovations, Australia). A single retroreflective marker was attached to the device, with its position recorded by a 12-camera MA system during 3 physical-collision tasks (tackle bag, bump pad, and tackle drill; N = 625). The accuracy, effect size, agreement, precision, and relative errors for each comparison were obtained as measures of accelerometer validity. RESULTS: Physical-collision peak impact accelerations recorded by the accelerometer overestimated (mean bias 0.60 g) those recorded by the MA system (P < .01). Filtering the raw data at a 20-Hz cutoff improved the accelerometer's relationship with MA data (mean bias 0.01 g; P > .05). When considering the data in 9 magnitude bands, the strongest relationship with the MA system was found in the 3.0-g or less band, and the precision of the accelerometer tended to reduce as the magnitude of impact acceleration increased. Of the 3 movements performed, the tackle-bag task displayed the greatest validity with MA. CONCLUSIONS: The findings indicate that the MinimaxX S4 accelerometer can accurately measure physical-collision peak impact accelerations when data are filtered at a 20-Hz cutoff frequency. As a result, accelerometers may be useful to measure physical collisions in contact sports.