Stereoselective Total Synthesis of Rhodocoranes I and J.

We report the stereoselective total synthesis of rhodocoranes I and J in 10 steps and 16.4% overall yield from ()-limonene. The synthesis was accomplished through the convergent assembly of a highly substituted chiral cyclopentanone and a lithiated furanyl silyl ketene acetal.

Last Glacial Maximum pattern effects reduce climate sensitivity estimates.

Here, we show that the Last Glacial Maximum (LGM) provides a stronger constraint on equilibrium climate sensitivity (ECS), the global warming from increasing greenhouse gases, after accounting for temperature patterns. Feedbacks governing ECS depend on spatial patterns of surface temperature ("pattern effects"); hence, using the LGM to constrain future warming requires quantifying how temperature patterns produce different feedbacks during LGM cooling versus modern-day warming. Combining data assimilation reconstructions with atmospheric models, we show that the climate is more sensitive to LGM forcing because ice sheets amplify extratropical cooling where feedbacks are destabilizing.

Photocatalytic conversion of aryl diazonium salts to sulfonyl fluorides.

Sulfonyl fluorides have emerged as powerful tools in chemical biology for the selective labelling of proteins. A photocatalytic method is described for the conversion of aryl diazonium salts to aryl sulfonyl fluorides. The diazonium substrates are easily obtained in one step from functionalized anilines.

Dendritic cells overcome Cre/Lox induced gene deficiency by siphoning cytosolic material from surrounding cells.

In a previous report, keratinocytes were shown to share their gene expression profile with surrounding Langerhans cells (LCs), influencing LC biology. Here, we investigated whether transferred material could substitute for lost gene products in cells subjected to Cre/Lox conditional gene deletion. We found that in human Langerin-Cre mice, epidermal LCs and CD11b+CD103+ mesenteric DCs overcome gene deletion if the deleted gene was expressed by neighboring cells.

Treatment of effluents from Food Services Establishment (FSEs) by physico-chemical processes: a case study for Trinidad & Tobago.

Background: Effluents from Food Services Establishments (FSEs) contain primarily Fats, Oil and Grease (FOG) which severely impact on sewers and the environment when released in high concentrations. In Trinidad & Tobago, it is estimated that approximately 231,304 kg/day of unaccounted for FOG bearing wastewaters from FSEs, are released into the environment with no viable treatment in the country. This research explored the optimization of physico-chemical processes for the treatment of FOGs for subsequent release into sewers.

Photocatalytic Sulfonyl Fluorination of Alkyl Organoboron Substrates.

Sulfonyl fluorides are highly versatile molecules for click chemistry that have found applications in many areas of chemistry and biology. Recent chemical approaches have focused on the synthesis of alkyl sulfonyl fluorides from readily available starting materials. Here, we report a photocatalytic synthesis of alkyl sulfonyl fluorides from organotrifluoroborates and boronic acid pinacol esters, which are building blocks commonly employed by medicinal chemists in the synthesis of bioactive molecules.

Photosensitized Activation of Diazonium Derivatives for C-B Bond Formation.

Aryl diazonium salts are ubiquitous building blocks in chemistry, as they are useful radical precursors in organic synthesis as well as for the functionalization of solid materials. They can be reduced electrochemically or through a photo-induced electron transfer reaction. Here we provide a detailed picture of the ground and excited-state reactivity of a series of 9 rare and earth abundant photosensitizers with 13 aryl diazonium salts, which also included 3 macrocyclic calix[4]arene tetradiazonium salts.

Risk-based stratified primary care for common musculoskeletal pain presentations: qualitative findings from the STarT MSK cluster randomised controlled trial.

Background: The STarT MSK cluster randomised controlled trial (RCT) investigated the clinical- and cost-effectiveness of risk-based stratified primary care versus usual care for patients with back, neck, shoulder, knee or multi-site pain. Trial quantitative results showed risk-based stratified care was not superior to usual care for patients' clinical outcomes, but the intervention led to some changes in GP clinical decision-making. This paper reports a linked qualitative study exploring how risk-based stratified care was perceived and used in the trial, from the perspectives of clinicians and patients.

Integrating clinician support with intervention design as part of a programme testing stratified care for musculoskeletal pain in general practice.

Background: Stratified care involves subgrouping patients based on key characteristics, e.g. prognostic risk, and matching these subgroups to early treatment options.

Computer-Based Stratified Primary Care for Musculoskeletal Consultations Compared With Usual Care: Study Protocol for the STarT MSK Cluster Randomized Controlled Trial.

Background: Musculoskeletal (MSK) pain is a major cause of pain and disability. We previously developed a prognostic tool (Start Back Tool) with demonstrated effectiveness in guiding primary care low back pain management by supporting decision making using matched treatments. A logical next step is to determine whether prognostic stratified care has benefits for a broader range of common MSK pain presentations.

Sustaining voluntary recycling programmes in a country transitioning to an integrated solid waste management system.

Many developing countries are transitioning to integrated solid waste management systems that will likely have a recycling component for making them sustainable. There are several approaches to recycling, one being waste separation at the household level. Such an approach relies critically on the willingness of households to engage in source-separation.

Correction: Suzuki coupling-based synthesis of VATPase inhibitor archazolid natural product derived fragments.

[This corrects the article DOI: 10.1039/C9RA07050H.].

Suzuki coupling-based synthesis of VATPase inhibitor archazolid natural product derived fragments.

An archazolid natural product fragment that displays dose-dependent inhibition of the vacuolar-type ATPase (VATPase) has been synthesized by a high-yielding Suzuki coupling of two complex subunits. Similarly, a further simplified fragment was prepared and evaluated for VATPase inhibitory activity. This compound did inhibit the VATPase, as evidenced by growth inhibition of etiolated seedlings, however at approximately 10× lower potency than the more complex fragment.

Attitudes and perceptions of rheumatologists regarding consultation skills training for specialist trainees: a qualitative study.

Within rheumatology specialty training, direct observation and formal assessment of consultation skills rarely occur. This study explored the attitudes and perceptions of rheumatology specialist registrars (SpRs) and consultants regarding consultation skills training and potential barriers to its successful implementation in the context of specialist training. Semi-structured interviews with rheumatology consultants and focus groups with rheumatology SpRs were conducted in four UK deanery regions.

Enhancement of intestinal absorption of 2-methyl cytidine prodrugs.

The purpose of this study was to investigate the in vivo absorption enhancement of a nucleoside (phosphoramidate prodrug of 2'-methyl-cytidine) anti-viral agent of proven efficacy by means of intestinal permeation enhancers. Natural nucleosides are hydrophilic molecules that do not rapidly penetrate cell membranes by diffusion and their absorption relies on specialized transporters. Therefore, the oral absorption of nucleoside prodrugs and the target organ concentration of the biologically active nucleotide can be limited due to poor permeation across the intestinal epithelium.

Impact of recreation on recreational water quality of a small tropical stream.

A study was conducted to determine the possible influence of recreation on microbiological water quality of a tropical stream. Microbiological water quality was measured at several recreational sites along the stream and a separate experiment was conducted to look at the effect of sediment resuspension on microbiological water quality. Microbiological quality of the water in the stream was generally poor and varied widely with faecal coliform and Escherichia coli levels ranging from 1 to > 16,000 and 14 to 9615 organisms 100 ml(-1) respectively.