The case for a wet, warm climate on early Mars

Arguments are presented in support of the idea that Mars possessed a dense CO2 atmosphere and a wet, warm climate early in its history. The plausibility of a CO2 greenhouse is tested by formulating a simple model of the CO2 geochemical cycle on early Mars. By scaling the rate of silicate weathering on Earth, researchers estimated a weathering time constant of the order of several times 10 to the 7th power years for early Mars. Thus, a dense atmosphere could have existed for a geologically significant time period (approx. 10 to the 9th power years) only if atmospheric CO2 was being continuously resupplied. The most likely mechanism by which this could have been accomplished is the thermal decomposition of carbonate rocks induced directly or indirectly by intense, global scale volcanism

Continuous N-alkylation reactions of amino alcohols using γ-Al2O3 and supercritical CO2: unexpected formation of cyclic ureas and urethanes by reaction with CO2

The use of γ-Al2O3 as a heterogeneous catalyst in scCO2, has be successfully applied to the amination of alcohols for the synthesis of N-alkylated heterocycles. The optimal reaction conditions (temperature and substrate flow rate) were determined using an automated self-optimising reactor, resulting in moderate to high yields of the target products. Carrying out the reaction in scCO2 was shown to be beneficial, as higher yields were obtained in the presence of CO2 than in its absence. A surprising discovery is that, in addition to cyclic amines, cyclic ureas and urethanes could be synthesised by incorporation of CO2 from the supercritical solvent into the product

Photooxidation of Fulvenes in a Continuous Flow Photoreactor using Carbon Dioxide as a Solvent

A range of 3‐substituted oxepinones have been synthesised by the photooxidation of fulvenes with photochemically generated singlet oxygen (1O2) using carbon dioxide (CO2) as a solvent and a CO2‐soluble porphyrin photosensitizer. The reactive intermediates generated in this reaction decompose to yield a range of useful and underutilized building blocks that are not easily accessible using more traditional reaction setups. Fulvenes containing an exocyclic allylic hydrogen are shown to form three products through potentially competing intramolecular pathways, which can be tuned to some extent by adjusting the conditions in the flow reactor. A range of substrates containing a variety of functional groups was examined; this led to lower yields of the desired lactones being observed in the case of compounds containing polar electron‐donating groups. We also demonstrate that one of the lactones can be further hydrogenated over a Pd/C catalyst to the unsaturated 7‐membered ring in high yield

Psychosocial therapy for Parkinson's-related dementia: intervention development.

Background: Group-based psychosocial therapy, such as group Cognitive Stimulation Therapy, improves cognition and quality of life in people living with dementia. Neuropsychiatric symptoms and restricted mobility are common complications for people with Parkinson's-related dementia (PRD) and may limit access to, and participation in, group activities. This study describes the development of a condition-specific, home-based psychosocial therapy for people with PRD ready to be trialled in a clinical population. Methods: By means of a multistage process, a draft therapy manual was developed in an iterative manner through collaboration with medical experts, researchers and Patient and Public Involvement (PPI) representatives. In stage 1, an extensive literature search of psychosocial therapies for dementia with potential relevance for Parkinson's disease (PD) was undertaken to select a candidate therapy for adaptation. In stage 2, qualitative feedback from stakeholders and intelligence regarding existing nonpharmacological therapies for cognitive impairment in PD was combined to produce a prototype therapy manual. In stage 3, the manual was field tested in: 1) a home-setting using a 25-item assessment tool; and 2) at a local PD support group with PPI representatives. Based on the feedback from this phase, final design modifications were implemented and a draft therapy manual produced. Results: The manual was developed in an iterative manner. Interview and focus group transcripts identified three enduring themes: manual form and content, therapy acceptability by people with PRD, and companion guidance and support. Major adaptations included: removal of discrete levels of task complexity, removal of images that were potentially hallucinogenic or lacked clarity, and updating of the content. Conclusion: We have successfully developed a Cognitive Stimulation Therapy-based psychosocial therapy specifically adapted for people with PRD. The therapy is ready to trial in a pilot randomized controlled study

Continuous photo-oxidation in a vortex reactor: efficient operations using air drawn from the laboratory

We report the construction and use of a vortex reactor which uses a rapidly rotating cylinder to generate Taylor vortices for continuous flow thermal and photochemical reactions. The reactor is designed to operate under conditions required for vortex generation. The flow pattern of the vortices has been represented using computational fluid dynamics, and the presence of the vortices can be easily visualized by observing streams of bubbles within the reactor. This approach presents certain advantages for reactions with added gases. For reactions with oxygen, the reactor offers an alternative to traditional setups as it efficiently draws in air from the lab without the need specifically to pressurize with oxygen. The rapid mixing generated by the vortices enables rapid mass transfer between the gas and the liquid phases allowing for a high efficiency dissolution of gases. The reactor has been applied to several photochemical reactions involving singlet oxygen (1O2) including the photo-oxidations of α-terpinene and furfuryl alcohol and the photodeborylation of phenyl boronic acid. The rotation speed of the cylinder proved to be key for reaction efficiency, and in the operation we found that the uptake of air was highest at 4000 rpm. The reactor has also been successfully applied to the synthesis of artemisinin, a potent antimalarial compound; and this three-step synthesis involving a Schenk-ene reaction with 1O2, Hock cleavage with H+, and an oxidative cyclization cascade with triplet oxygen (3O2), from dihydroartemisinic acid was carried out as a single process in the vortex reactor

Upper- and lower-limb amputees show reduced levels of eeriness for images of prosthetic hands

The uncanny phenomenon describes the feeling of unease associated with seeing an image which is close to appearing human. Prosthetic hands in particular are well-known to induce this effect. Little is known, however, about this phenomenon from the viewpoint of prosthesis users. We studied perceptions of eeriness and human-likeness for images of different types of mechanical, cosmetic, and anatomical hands in upper-limb prosthesis users (n=9), lower-limb prosthesis users (n=10), prosthetists (n=16), control participants with no prosthetic training (n=20), and control participants who were trained to use a myoelectric prosthetic hand simulator (n=23). Both the upper- and lowerlimb prosthesis user groups showed a reduced uncanny phenomenon (i.e., significantly lower levels of eeriness) for cosmetic prosthetic hands compared to the other groups, with no concomitant reduction in how these stimuli were rated in terms of human-likeness. However, a similar effect was found neither for prosthetists with prolonged visual experience of prosthetic hands, nor for the group with short-term training with the simulator. These findings in the prosthesis users therefore seem likely to be related to limb absence or prolonged experience with prostheses

The case for a wet, warm climate on early Mars

Theoretical arguments are presented in support of the idea that Mars possessed a dense CO2 atmosphere and a wet, warm climate early in its history. Calculations with a one-dimensional radiative-convective climate model indicate that CO2 pressures between 1 and 5 bars would have been required to keep the surface temperature above the freezing point of water early in the planet's history. The higher value corresponds to globally and orbitally averaged conditions and a 30% reduction in solar luminosity; the lower value corresponds to conditions at the equator during perihelion at times of high orbital eccentricity and the same reduced solar luminosity. The plausibility of such a COz greenhouse is tested by formulating a simple model of the CO2 geochemical cycle on early Mars. By appropriately scaling the rate of silicate weathering on present Earth, we estimate a weathering time constant of the order of several times 107 years for early Mars. Thus, a dense atmosphere could have persisted for a geologically significant time period (-109 years) only if atmospheric COz was being continuously resupplied. The most likely mechanism by which this might have been accomplished is the thermal decomposition of carbonate rocks induced directly and indirectly (through burial) by intense, global-scale volcanism. For plausible values of the early heat flux, the recycling time constant is also of the order of several times 107 years. The amount of COz dissolved in standing bodies of water was probably small; thus, the total surficiai CO2 inventory required to maintain these conditions was approximately 2 to 10 bars. The amount of CO2 in Mars' atmosphere would eventually have dwindled, and the climate cooled, as the planet's internal heat engine ran down. A test for this theory will be provided by spectroscopic searches for carbonates in Mars' crust

High order harmonic generation from SF6: Deconvolution of macroscopic effects

Citation: Wilson, B. P., Fulfer, K. D., Mondal, S., Ren, X., Tross, J., Poliakoff, E. D., . . . Trallero-Herrero, C. (2016). High order harmonic generation from SF6: Deconvolution of macroscopic effects. Journal of Chemical Physics, 145(22), 11. doi:10.1063/1.4971244We measure high order harmonics from the molecule SF6 over a large range of phase matching conditions and observe several features in the harmonics that are largely independent of such macroscopic conditions. The experimental data are then compared to the quantitative rescattering theory for the generation of harmonics from three orbitals. With this comparison, we are able to assign spectroscopic features in the harmonics to contributions from 1t(1g) (HOMO) and 5t(1u) (HOMO-1) orbitals. Published by AIP Publishing