Rapid determination of actinides in asphalt samples

A new rapid method for the determination of actinides in asphalt samples has been developed that can be used in emergency response situations or for routine analysis. If a radiological dispersive device, improvised nuclear device or a nuclear accident such as the accident at the Fukushima Nuclear Power Plant in March, 2011 occurs, there will be an urgent need for rapid analyses of many different environmental matrices, including asphalt materials, to support dose mitigation and environmental clean-up. The new method for the determination of actinides in asphalt utilizes a rapid furnace step to destroy bitumen and organics present in the asphalt and sodium hydroxide fusion to digest the remaining sample. Sample preconcentration steps are used to collect the actinides and a new stacked TRU Resin + DGA Resin column method is employed to separate the actinide isotopes in the asphalt samples. The TRU Resin plus DGA Resin separation approach, which allows sequential separation of plutonium, uranium, americium and curium isotopes in asphalt samples, can be applied to soil samples as well.     

Synthesis of 4-benzyl-3-phenylbutenolide natural products

The first total synthesis of eutypoid A and a new synthesis of racemic microperfuranone and gymnoascolide A have been achieved. The key steps in our synthetic strategy involve a Suzuki coupling reaction to install the C3 aryl ring and a Mannich-type reaction for the construction of the 4-benzylbutenolide core.     

Modulation of Prins Cyclization by Vibrational Strong Coupling

Light‐molecule strong coupling has emerged within the last decade as a new method to control chemical reactions. A few years ago it was discovered that chemical reactivity could be altered by vibrational strong coupling (VSC). Only a limited number of reactions have been investigated under VSC to date, including solvolysis and deprotection reactions. Here the effect of VSC on a series of aldehydes and ketones undergoing Prins cyclization, an important synthetic step in pharmaceutical chemistry, is investigated. A decrease of the second‐order rate constant with VSC of the reactant carbonyl stretching groups is observed. We also observe an increased activation energy due to VSC, but proportional changes in activation enthalpy and entropy, suggesting no substantive change in reaction pathway. The addition of common cycloaddition reactions to the stable of VSC‐modified chemical reactions is another step towards establishing VSC as a genuine tool for synthetic chemistry.     

Discrepancies in NMRON Knight Shifts of impurity nuclei in ferromagnets

Precision NMRON field shift studies have been carried out up to 8T on a⁵⁴MnNi single crystal along a hard [100] direction and on a¹²⁵SbFe single crystal along a hard [110] direction. For both systems, high field (B _app>-1T) and low field (0.3T<B _app<0.8T) data sets are obtained. The analysis reveals a significant discrepancy between the apparent Knight Shift dependent on whether the low field or high field data set is utilised. For both systems, consideration of the high field data sets yield a zero Knight Shift K(⁵⁴MnNi)=+0.0(0.2)% and K(¹²⁵SbFe)=+0.2(1.4)%, whereas the low field data sets yield K(⁵⁴MnNi)=+7.5(3.9)% and K(¹²⁵SbFe)=−5.4(3.3)% respectively. The field range dependence of K suggests that only Knight shifts measured in large fields (>-1T) are meaningful for establishing systematics. This casts some doubt on the greater bulk of the literature’s NMRON Knight shift studies, where predominantly low fields have been used to determine K.     

Transient NMRON of brute force oriented110mAgAg

A novel technique involving electrodeposition has been used to prepare an elemental silver specimen wherein radioactive^110mAg probe nuclei are confined to a surface layer of approximately 0.1 μm depth. This specimen was then brute force oriented in a field of 8T and the continuous wave (CW) nuclear magnetic resonance on oriented nuclei (NMRON) spectrum showed an integrated destruction of some 58%. Moreover the transient NMRON techniques of single and modulated adiabatic passage were successfully applied, resulting in a determination of the electric quadrupole interaction strength at the^110mAg site in polycrystalline silver of P/h=+0.74(5)kHz with a FWHM of ΔP/h=0.75(8)kHz. The resulting mode electric field gradient is V_zz=+1.87(23)×10¹⁸Vm⁻¹. Analysis of the single passage data provides an estimate for the nuclear spin lattice relaxation constant in silver at 8T of C_k=1.6(3)s.K.     

A mathematical model of aging-related and cortisol induced hippocampal dysfunction

Background  

The hippocampus is essential for declarative memory synthesis and is a core pathological substrate for Alzheimer's disease (AD), the most common aging-related dementing disease. Acute increases in plasma cortisol are associated with transient hippocampal inhibition and retrograde amnesia, while chronic cortisol elevation is associated with hippocampal atrophy. Thus, cortisol levels could be monitored and managed in older people, to decrease their risk of AD type hippocampal dysfunction. We generated an in silicomodel of the chronic effects of elevated plasma cortisol on hippocampal activity and atrophy, using the systems biology mark-up language (SBML). We further challenged the model with biologically based interventions to ascertain if cortisol associated hippocampal dysfunction could be abrogated.     

Continuous-wave magnetic resonance imaging of short T(2) materials

There is growing interest in the use of magnetic resonance imaging (MRI) to examine solid materials where the restricted motion of the probed spins leads to broad lines and short T(2) values, rendering many interesting systems invisible to conventional 2DFT pulsed imaging methods. In EPR T(2) seldom exceeds 0.1 mus and continuous-wave methods are adopted for spectroscopy and imaging. In this paper we demonstrate the use of continuous-wave MRI to obtain 2-dimensional images of short T(2) samples. The prototype system can image samples up to 50 mm in diameter by 60 mm long and has been used to image polymers and water penetration in porous media. Typical acquisition times range between 10 and 40 min. Resolution of 1 to 2 mm has been achieved for samples with T(2) values ranging from 38 to 750 mus. There is the possibility of producing image contrast that is determined by the material properties of the sample.