Organic phosphonium salts

Not availabl

The Suess effect in Fiji coral δ13C and its potential as a tracer of anthropogenic CO2 uptake

In the context of increasing anthropogenic CO2 emissions, determining the rate of oceanic CO2 uptake is of high interest. Centennial-scale changes in δ13C of the surface water dissolved inorganic carbon (DIC) reservoir have been shown to be influenced by the carbon isotopic composition of atmospheric CO2. However, the availability of direct oceanic δ13C measurements is limited and methods for reconstructing past δ13C variability of the oceanic DIC are needed. Geochemical reconstructions of DIC variability can help in understanding how the ocean has reacted to historical changes in the carbon cycle. This study explores the potential of using temporal variations in δ13C measured in five Fijian Porites corals for reconstructing oceanic δ13C variability. A centennial-scale decreasing δ13C trend is observed in these Fiji corals. Other studies have linked similar decreasing δ13C trends to anthropogenic changes in the atmospheric carbon reservoir (the “13C Suess effect”). We conclude that solar irradiance is the factor influencing the δ13C cycle on a seasonal scale, however it is not responsible for the centennial-scale decreasing δ13C trend. In addition, variations in skeletal extension rate are not found to account for centennial-scale δ13C variability in these corals. Rather, we found that water depth at which a Fijian Porites colony calcifies influences both δ13C and extension rate mean values. The water depth-δ13C relationship induces a dampening effect on the centennial-scale decreasing δ13C trend. We removed this “water depth effect” from the δ13C composite, resulting in a truer representation of δ13C variability of the Fiji surface water DIC (δ13CFiji-DIC). The centennial-scale trend in this Fiji coral composite δ13CFiji-DIC time-series shares similarities with atmospheric δ13CCO2, implicating the 13C Suess effect as the source of the this coral δ13C trend. Additionally, our study finds that the δ13C variability between the atmosphere and the ocean in this region is not synchronous; the coral δ13C response is delayed by ~ 10 years. This agrees with the previously established model of isotopic disequilibrium between atmospheric δ13CCO2 and oceanic surface water DIC

Fit for purpose? Pattern cutting and seams in wearables development

This paper describes how a group of practitioners and researchers are working across disciplines at Nottingham Trent University in the area of Technical Textiles. It introduces strands of ongoing enquiry centred around the development and application of stretch sensors on the body, focusing on how textile and fashion knowledge are being reflexively revealed in the collaborative development of seamful wearable concepts, and on the tensions between design philosophies as revealed by definitions of purpose. We discuss the current research direction of the Aeolia project, which seeks to exploit the literal gaps found in pattern cutting for fitted stretch garments towards experiential forms and potential interactions. Normative goals of fitness for purpose and seamlessness are interrogated and the potential for more integrated design processes, which may at first appear ‘upside down’, is discussed

Sensitive X-ray Detectors Synthesised from CsPbBr3

The materials used in detection of high energy photons are of primary importance in the construction of efficient, cost effective and sensitive detectors. Current research into Perovskites for solar cell technology has stimulated interest in their potential alternative uses, one of which is in direct photon conversion radiation detectors, owed primarily to their high-Z elemental composition twinned with exceptional charge carrier transport properties. Here, the Perovskite CsPbBr 3 has been synthesised through solution growth. The raw CsPbBr 3 was a granular powder which was formed into disks of 8 mm diameter and 1-2 mm thickness by two methods: 1). the powders were pressed into pellets using a hydraulic press or 2). sealed in a quartz ampoule under vacuum and then melted and quenched to form a polycrystalline solid which was cut to size. Metallic contacts were deposited on the front and back faces to permit charge collection. The results from the pressed devices are promising, particularly given that the production method is cost effective, repeatable and scalable. The solid-from-melt devices show similar performance but further development is required to optimise the production method

Homogeneous gold catalysis using complexes recovered from waste electronic equipment

Despite the greater awareness of elemental sustainability and the benefits of the circular economy concept, much waste electrical and electronic equipment (WEEE) is still destined for landfill. Effective methods for valorizing this waste within our society are therefore imperative. In this contribution, two gold(III) complexes obtained as recovery products from WEEE and their anion metathesis products were investigated as homogenous catalysts. These four recovery products were successfully applied as catalysts for the cyclization of propargylic amides and the condensation of acetylacetone with o-iodoaniline. Impressive activity was also observed in the gold-catalyzed reaction between electron-rich arenes (2-methylfuran, 1,3-dimethoxybenzene, and azulene) and α,β-unsaturated carbonyl compounds (methyl vinyl ketone and cyclohexenone). These recovered compounds were also shown to be effective catalysts for the oxidative cross-coupling reaction of aryl silanes and arenes. When employed as Lewis acid catalysts for carbonyl-containing substrates, the WEEE-derived gold complexes could also be recovered at the end of the reaction and reused without loss in catalytic activity, enhancing still further the sustainability of the process. This is the first direct application in homogeneous catalysis of gold recovery products sourced from e-waste

Photoenzymatic Hydrogenation of Heteroaromatic Olefins using ‘Ene’-Reductases with Photoredox Catalysts

Flavin‐dependent ‘ene’‐reductases (EREDs) are highly selective catalysts for the asymmetric reduction of activated alkenes. This function is, however, limited to enones, enoates, and nitroalkenes using the native hydride transfer mechanism. Here we demonstrate that EREDs can reduce vinyl pyridines when irradiated with visible light in the presence of a photoredox catalyst. Experimental evidence suggests the reaction proceeds via a radical mechanism where the vinyl pyridine is reduced to the corresponding neutral benzylic radical in solution. DFT calculations reveal this radical to be “dynamically stable”, suggesting it is sufficiently long lived to diffuse into the enzyme active site for stereoselective hydrogen atom transfer. This reduction mechanism is distinct from the native one, highlighting the opportunity to expand the synthetic capabilities of existing enzyme platforms by exploiting new mechanistic paradigms

(±)-Polysiphenol and other Analogues via Symmetrical Intermolecular Dimerizations: a Synthetic, Spectroscopic, Structural and Computational Study

We report an improved total synthesis of 4,5-dibromo-9,10-dihydrophenanthrene-2,3,6,7-tetraol, (±)-polysiphenol, via intermolecular McMurray dimerization of 5-bromovanillin and subsequent intramolecular oxidative coupling as the key steps. The synthetic route is applicable to 4,5-dichloro- and 4,5-difluoro-halologues (as well as a 4,5-dialkyl-analogue). Distinctive AA′BB′ multiplets in their 1H NMR spectra for the dimethylene bridges of the dibromo and dichloro compounds reveal them to be room-temperature stable atropisomers, while for the difluoro compound they present as a singlet. X-ray crystal structure determinations of their tetramethylated synthetic precursors show atropisomeric twist angles of 48°, 46°, and 32°, respectively, with the former representing the largest yet observed in any 4,5-disubstituted-9,10-dihydrophenanthrene. DFT computational studies reveal an unprecedented two-stage atropisomeric interconversion process involving time-independent asynchronous rotations of the dimethylene bridge and the biaryl axis for halologues containing chlorine or bromine, but a more synchronous rotation for the difluoro analogue

Recent Decisions

Recent Decisions ADMIRALTY--COGSA--BILL OF LADING CARGO DESCRIPTION AND PACKER IDENTITY DETERMINE WHEN A CONTAINER IS A PACKAGE IN COGSA LIABILITY PROCEEDINGS Alan L. Marchisotto ============================ ADMIRALTY--JURISDICTION OVER AVIATION TORT CLAIMS--ADMIRALTY JURISDICTION DOES NOT EXTEND TO AVIATION TORT CLAIMS IN THE ABSENCE OF A SIGNIFICANT RELATIONSHIP BETWEEN THE TORT AND TRADITIONAL MARITIME ACTIVITIES W. H. Schwarzschild III ============================ ALIENS--ALIENS MAY MAINTAIN A CAUSE OF ACTION FOR PRIVATE EMPLOYMENT DISCRIMINATION UNDER 42 U.S.C. § 1981 (1970) Mark M. Greisberger ============================ ANTITRUST--ARTICLE 86 OF THE EEC TREATY APPLIES TO CERTAIN CHANGES IN INTERNAL CORPORATE STRUCTURE Richard P. Granfield =========================== CONSTITUTIONAL LAW--EXECUTIVE POWER--PRESIDENTIAL AUTHORITY TO NEGOTIATE FOREIGN COMMERCIAL AGREEMENTS PURSUANT TO FOREIGN AFFAIRS POWER IS NOT CIRCUMSCRIBED ABSENT EX-PLICIT LEGISLATION Donald B. Cameron, Jr. ========================== JURISDICTION--SECURITIES EXCHANGE ACT OF 1934--SECTION 10(b) APPLIES TO A TRANSACTION IN UNLISTED FOREIGN SECURITIES WHEN SIGNIFICANT FRAUDULENT CONDUCT OCCURS IN THE UNITED STATES Isaac H. Braddock ========================= TARIFFS--TRADE AGREEMENT CONCESSIONS MAY BE SUSPENDED ON A MOST-FAVORED-NATION BASIS WHEN SUCH TREATMENT IS REQUIRED BY INTERNATIONAL AGREEMENTS OF THE UNITED STATES David A. Boillo

Improving procedural fidelity of behavioural interventions for people with intellectual and developmental disabilities: A systematic review

Background: Despite its importance within behavioural intervention, it remains unclear how best to achieve high procedural fidelity. This paper reviewed studies on improving procedural fidelity of behavioural interventions for individuals with intellectual and developmental disabilities (IDD). Method: A systematic literature search was conducted, which identified 20 studies meeting inclusion criteria. Data were extracted on study design, participant characteristics, intervention, target behaviours, effect sizes, maintenance, generalisation, and social validity. A quality rating was also applied. Results: A total of 100 participants took part in the included studies. Most participants were teachers working with children in school settings. There was a significant positive correlation between level of procedural fidelity and client outcomes. Feedback was the most commonly employed intervention to improve procedural fidelity. Conclusions: More research should be conducted in environments with high levels of variability such as community homes to determine how to reach and maintain high levels of procedural fidelity

Deconstructing patient centred communication and uncovering shared decision making: an observational study

BACKGROUND: Patient centred communication (PCC) has been described as a method for doctor-patient communication. The principles of shared decision making (SDM) have been proposed more recently. AIMS: This study aimed to examine PCC and SDM empirically with respect to their mutual association, the variation in practitioners' working styles, and the associations with patient characteristics. METHODS: Sixty general practitioners recruited 596 adult patients who gave written consent to have their consultations videotaped. The tapes were assessed by two researchers, using a standardised instrument for global communication. For the purpose of this exploratory study, scales for PCC and SDM were based on subsamples of items in the MAAS. RESULTS: The scales for PCC and SDM were weakly associated (Pearson correlation: 0.25). Physicians varied more on SDM than on PCC. The intracluster correlation of the PCC and SDM scales were, respectively, 0.34 and 0.19. However, hypotheses regarding associations with patient characteristics were not confirmed. Neither PCC nor SDM scores were related to patient gender, education, age, functional health status or existence of chronic conditions. CONCLUSION: The study provides evidence that PCC and SDM can be differentiated and comprise approaches to communication between clinicians and patients which may be more clearly distinguished by further focused research and training developments