Effect of support of Co-Na-Mo catalysts on the direct conversion of CO<inf>2</inf> to hydrocarbons

This study of the effect of support of Co-Na-Mo based catalysts on the direct hydrogenation of CO$_2$ into hydrocarbons (HC) provides guidelines for the design of catalysts for CO$_2$ conversion. We demonstrate that the surface area of the support and the metal-support interaction have a key role determining the cobalt crystallite size and consequently the activity of the system. Cobalt particles with sizes <2 nm supported on MgO present low reverse water gas shift conversion with negligible Fischer-Tropsch activity. Increasing the cobalt particle size to ~15 nm supported on SiO$_2$ and ZSM-5 supports not only substantially increases the CO$_2$ conversion but it also provides high HC selectivities. Further increase of the cobalt particle size to 25–30 nm has a detrimental effect on the global CO$_2$ conversion with HC:CO ratios below 1, however, lower methane selectivity and enhanced formation of unsaturated HC products are achieved. Additionally, the metal-support interaction potentially also has a strong effect on the growth chain probability of the formed hydrocarbons, increasing as the metal-support interaction increases. These evidences demonstrate that CO$_2$ conversion and hydrocarbon distribution can be tuned towards desired products by controlled catalyst design.University of BathThis is the author accepted manuscript. The final version is available from Elsevier via http://dx.doi.org/10.1016/j.jcou.2016.06.00

Raman scattering studies of order parameters in liquid crystalline dimers exhibiting the nematic and twist-bend nematic phases

Polarized Raman Spectroscopy (PRS) is used to quantify the orientational order in the conventional (N) and twist-bend (NTB) nematic phases of a homologous series of liquid crystalline dimers. The dimers investigated have 7, 8, 9 and 11 methylene groups connecting two cyanobiphenyl mesogens and data for 4-pentyl-4'-cyanobiphenyl (5CB) and 4-octyl-4'-cyanobiphenyl (8CB) are included for comparison. Simulated and measured Raman spectra for the materials are compared. PRS is used to determine both (P2) and (P4) order parameters across the nematic temperature range and immediately below the NTB–N phase transition using a model that takes into account the molecular bend of the odd dimers, which is described in detail. In the nematic phase, the odd dimers are found to exhibit rather low order parameters with hP2i taking values between 0.3 and 0.5 and (P4) about 0.25. In contrast, the even dimer shows extremely high values of the order parameters with (P2) taking values between 0.7 and 0.8 and (P4) between 0.4 and 0.45. For the odd dimers, the values of (P2) in the NTB phase are similar to those of the N phase, whereas (P4) jumps by approximately 5–10% and then decreases with temperature. On comparing the experimental data with the theoretical predictions, we find reasonable qualitative agreement for all materials with molecular field theory. The odd dimers, however, show higher (P4) values than obtained from theoretical models, a factor attributed to the neglect of molecular flexibility and biaxiality in the PRS analysis

An identification and brief advice programme for low-risk alcohol consumption in an acute medical setting: an implementation study.

OBJECTIVES: To implement an identification and brief advice (IBA) intervention to detect low-risk/hazardous alcohol consumption. DESIGN: Implementation was guided through the use of quality improvement tools and training. SETTING: This study was conducted over an 18-month period from April 2010 to September 2011 on a 42-bed acute medical unit at a central London acute hospital. PARTICIPANTS: All medical patients over the age of 18 admitted to the acute assessment unit were eligible; any patient unable to provide a medical history either through language barriers or due to illness was excluded. MAIN OUTCOME MEASURES: Percentage of medical patients admitted each week to the acute assessment unit who were screened for low-risk/hazardous alcohol consumption. RESULTS: Weekly data were analysed in time series run charts and cross-referenced to the date of educational sessions and their effect on the uptake of screening monitored. A demonstrable change in the mean percentage number of patients screened was observed in different time periods, 67.3-80.1%, following targeted teaching on the AAU. CONCLUSIONS: Our study demonstrates the successful use of quality improvement methodology to guide the implementation of Alcohol Use Disorders Identification Test-Consumption (AUDIT-C), an IBA intervention, in the acute medical setting. The incorporation of the AUDIT-C into an admission document has been well accepted by the junior doctors, attaining an average (mean) of 80% of patients being screened using the tool. Targeted teaching of clinical staff involved in admitting patients appears to be the most effective method in improving uptake of IBA by junior doctors

Construction of Chimeric Dual-Chain Avidin by Tandem Fusion of the Related Avidins

BACKGROUND: Avidin is a chicken egg-white protein with high affinity to vitamin H, also known as D-biotin. Many applications in life science research are based on this strong interaction. Avidin is a homotetrameric protein, which promotes its modification to symmetrical entities. Dual-chain avidin, a genetically engineered avidin form, has two circularly permuted chicken avidin monomers that are tandem-fused into one polypeptide chain. This form of avidin enables independent modification of the two domains, including the two biotin-binding pockets; however, decreased yields in protein production, compared to wt avidin, and complicated genetic manipulation of two highly similar DNA sequences in the tandem gene have limited the use of dual-chain avidin in biotechnological applications. PRINCIPAL FINDINGS: To overcome challenges associated with the original dual-chain avidin, we developed chimeric dual-chain avidin, which is a tandem fusion of avidin and avidin-related protein 4 (AVR4), another member of the chicken avidin gene family. We observed an increase in protein production and better thermal stability, compared with the original dual-chain avidin. Additionally, PCR amplification of the hybrid gene was more efficient, thus enabling more convenient and straightforward modification of the dual-chain avidin. When studied closer, the generated chimeric dual-chain avidin showed biphasic biotin dissociation. SIGNIFICANCE: The improved dual-chain avidin introduced here increases its potential for future applications. This molecule offers a valuable base for developing bi-functional avidin tools for bioseparation, carrier proteins, and nanoscale adapters. Additionally, this strategy could be helpful when generating hetero-oligomers from other oligomeric proteins with high structural similarity

Complex hybrid origin of genetic caste determination in harvester ants

Caste differentiation and division of labour are the hallmarks of insect societies and at the root of their ecological success. Kin selection predicts that caste determination should result from environmentally induced differences in gene expression, a prediction largely supported by empirical data. However, two exceptional cases of genetically determined caste differentiation have recently been found in harvester ants. Here we show that genetic caste determination evolved in these populations after complex hybridization events. We identified four distinct genetic lineages, each consisting of unique blends of the genomes of the parental species, presumably Pogonomyrmex barbatus and P. rugosus. Crosses between lineages H1 and H2 and between J1 and J2 give rise to workers, whereas queens develop from within-lineage matings. Although historical gene flow is evident, genetic exchange among lineages and between lineages and the parental species no longer occurs. This unusual system of caste determination seems to be evolutionarily stable

Effect of support of Co-Na-Mo catalysts on the direct conversion of CO2 to hydrocarbons

This study of the effect of support of Co-Na-Mo based catalysts on the direct hydrogenation of CO2 into hydrocarbons (HC) provides guidelines for the design of catalysts for CO2 conversion. We demonstrate that the surface area of the support and the metal-support interaction have a key role determining the cobalt crystallite size and consequently the activity of the system. Cobalt particles with sizes <2 nm supported on MgO present low reverse water gas shift conversion with negligible Fischer-Tropsch activity. Increasing the cobalt particle size to ∼15 nm supported on SiO2 and ZSM-5 supports not only substantially increases the CO2 conversion but it also provides high HC selectivities. Further increase of the cobalt particle size to 25–30 nm has a detrimental effect on the global CO2 conversion with HC:CO ratios below 1, however, lower methane selectivity and enhanced formation of unsaturated HC products are achieved. Additionally, the metal-support interaction potentially also has a strong effect on the growth chain probability of the formed hydrocarbons, increasing as the metal-support interaction increases. These evidences demonstrate that CO2 conversion and hydrocarbon distribution can be tuned towards desired products by controlled catalyst design

Bifunctional Avidin with Covalently Modifiable Ligand Binding Site

The extensive use of avidin and streptavidin in life sciences originates from the extraordinary tight biotin-binding affinity of these tetrameric proteins. Numerous studies have been performed to modify the biotin-binding affinity of (strept)avidin to improve the existing applications. Even so, (strept)avidin greatly favours its natural ligand, biotin. Here we engineered the biotin-binding pocket of avidin with a single point mutation S16C and thus introduced a chemically active thiol group, which could be covalently coupled with thiol-reactive molecules. This approach was applied to the previously reported bivalent dual chain avidin by modifying one binding site while preserving the other one intact. Maleimide was then coupled to the modified binding site resulting in a decrease in biotin affinity. Furthermore, we showed that this thiol could be covalently coupled to other maleimide derivatives, for instance fluorescent labels, allowing intratetrameric FRET. The bifunctional avidins described here provide improved and novel tools for applications such as the biofunctionalization of surfaces

Fungi in the Marine Environment: Open Questions and Unsolved Problems.

Terrestrial fungi play critical roles in nutrient cycling and food webs and can shape macroorganism communities as parasites and mutualists. Although estimates for the number of fungal species on the planet range from 1.5 to over 5 million, likely fewer than 10% of fungi have been identified so far. To date, a relatively small percentage of described species are associated with marine environments, with ∼1,100 species retrieved exclusively from the marine environment. Nevertheless, fungi have been found in nearly every marine habitat explored, from the surface of the ocean to kilometers below ocean sediments. Fungi are hypothesized to contribute to phytoplankton population cycles and the biological carbon pump and are active in the chemistry of marine sediments. Many fungi have been identified as commensals or pathogens of marine animals (e.g., corals and sponges), plants, and algae. Despite their varied roles, remarkably little is known about the diversity of this major branch of eukaryotic life in marine ecosystems or their ecological functions. This perspective emerges from a Marine Fungi Workshop held in May 2018 at the Marine Biological Laboratory in Woods Hole, MA. We present the state of knowledge as well as the multitude of open questions regarding the diversity and function of fungi in the marine biosphere and geochemical cycles