(p -Cymene)thioglycollatoruthenium(II) dimer; a complex with an ambi-basic S,O-donor ligand

The title compound was prepared from the (p-cymene)ruthenium chloride dimer and thioglycollic acid. The structure is a centrosymmetric dimer bridged by the soft-base S atoms, with the hard-base O atoms of the carboxylate group chelating to form a five-membered twisted-ring. The coordination of the ruthenium atoms is completed by a η6-p-cymene ligand, giving an 18-electron count. The Ru–S bonds are essentially equal at 2.396(1) Å

Platinum(II), palladium(II), nickel(II), and gold(I) complexes of the “electrospray-friendly” thiolate ligands 4-SC₅H₄N- and 4-SC₆H₄OMe-

The series of platinum(II), palladium(II), and nickel(II) complexes [ML₂(dppe)] [M = Ni, Pd, Pt; L = 4-SC₅H₄N or 4-SC₆H₄OMe; dppe = Ph₂PCH₂CH₂PPh₂] containing pyridine-4-thiolate or 4-methoxybenzenethiolate ligands, together with the corresponding gold(I) complexes [AuL(PPh3)], were prepared and their electrospray ionization mass spectrometric behavior compared with that of the thiophenolate complexes [M(SPh)₂(dppe)] (M = Ni, Pd, Pt) and [Au(SPh)(PPh₃)]. While the pyridine-4-thiolate complexes yielded protonated ions of the type [M + H]+ and [M + 2H]²+ ions in the Ni, Pd, and Pt complexes, an [M + H]+ ion was only observed for the platinum derivative of 4-methoxybenzenethiolate. Other ions, which dominated the spectra of the thiophenolate complexes, were formed by thiolate loss and aggregate formation. The X-ray crystal structure of [Pt(SC₆H₄OMe-4)₂(dppe)] is also reported

Modification of kraft wood-pulp fibre with silica for surface functionalisation

A new science strategy for natural fibre modification was devised in which glass surface properties would be imparted to wood-derived fibre. The enhancements known from addition of silane reagents to glass fibre–polymer composites could therefore be realised for modified cellulose fibre–polymer composites. A process is described whereby the internal void spaces and micropores of never-dried Kraft pulp fibre walls were impregnated with silica. This was achieved by initial dehydration of never-dried fibre through azeotropic distillation to achieve substitution of fibre water with the silicon chemical solution over a range of concentrations. Kraft fibres were stiffened and made resistant to collapse from the effect of the azeotrope drying. Specific chemical reaction of azeotrope-dried fibre with the reagent ClSi(OEt)3 followed by base-catalysed hydrolysis of the ester groups formed a fibre-bound silica composite. The physico-chemical substitution of water from micropores and internal voids of never-dried fibre with property-modifying chemicals offers possibilities in the development of new fibre characteristics, including fibres which may be hardened, plasticised, and/or stabilised against moisture, biodegradation or fire. The embedded silica may also be used as sites of attachment for coupling agents to modify the hydrophilic character of the fibre or to functionalise the fibre surface

Evolution of Mid-Atlantic coastal and back-barrier estuary environments in response to a hurricane : implications for barrier-estuary connectivity

This paper is not subject to U.S. copyright. The definitive version was published in Estuaries and Coasts 39 (2016): 916-934, doi:10.1007/s12237-015-0057-x.Assessments of coupled barrier island-estuary storm response are rare. Hurricane Sandy made landfall during an investigation in Barnegat Bay-Little Egg Harbor estuary that included water quality monitoring, geomorphologic characterization, and numerical modeling; this provided an opportunity to characterize the storm response of the barrier island-estuary system. Barrier island morphologic response was characterized by significant changes in shoreline position, dune elevation, and beach volume; morphologic changes within the estuary were less dramatic with a net gain of only 200,000 m3 of sediment. When observed, estuarine deposition was adjacent to the back-barrier shoreline or collocated with maximum estuary depths. Estuarine sedimentologic changes correlated well with bed shear stresses derived from numerically simulated storm conditions, suggesting that change is linked to winnowing from elevated storm-related wave-current interactions rather than deposition. Rapid storm-related changes in estuarine water level, turbidity, and salinity were coincident with minima in island and estuarine widths, which may have influenced the location of two barrier island breaches. Barrier-estuary connectivity, or the transport of sediment from barrier island to estuary, was influenced by barrier island land use and width. Coupled assessments like this one provide critical information about storm-related coastal and estuarine sediment transport that may not be evident from investigations that consider only one component of the coastal system.Funding for this project was provided by the New Jersey Department of Environmental Protection and the US Geological Survey (USGS) Coastal and Marine Geology Program

High-dose chemotherapy as initial salvage chemotherapy in patients with relapsed or refractory testicular cancer: a systematic review and meta-analysis

Background: The role of high-dose chemotherapy followed by autologous hematopoietic cell transplantation in the management of patients with relapsed/refractory germ-cell tumors has not been established in prospective studies. Our aim was to estimate the benefits and harm of this treatment in men with relapsed/refractory germ-cell tumors. Methods: Electronic databases, conference proceedings, and trial registers until April 30, 2023, were searched. Randomized and non-randomized prospective controlled trials were included. Risk of bias assessments were performed using either RoB2 or ROBINS-I tools. The certainty of evidence was assessed using the Grading of Recommendations, Assessment, Development, and Evaluations (GRADE) approach. Time-to-event data were analyzed using the hazard ratio. The primary outcome was overall survival, and a meta-analysis was not conducted to assess it because non-randomized trials were judged to have a critical risk of bias. Categorical data were analyzed using a risk ratio. All results are presented with the corresponding 95% confidence interval. Results: Four out of 3,824 records met the inclusion criteria, and three out of four were used to assess primary and secondary outcomes. Based on the IT94 study (N = 263 participants), single high-dose chemotherapy followed by autologous hematopoietic cell transplantation may have little to no effect on overall survival [hazard ratio (HR) 0.98, 95%CI 0.68 to 1.42; p = 0.916]. Non-randomized trials (N = 43 participants) showed contrasting results, which may be explained by the number of cycles of high-dose chemotherapy administered in each study. Regarding secondary outcomes, information was only provided for event-free survival, response rate, and acute toxicities. Conclusions: Based on prospective data, there is insufficient evidence to support or refute the proposal that high-dose chemotherapy with autologous hematopoietic cell transplantation improves survival in men with relapsed/refractory germ-cell tumors. If this treatment is considered essential, the choice should be made by experienced clinicians at high-volume cancer centers

A review of methods for the analysis of diagnostic tests performed in sequence

Background: Many clinical pathways for the diagnosis of disease are based on diagnostic tests that are performed in sequence. The performance of the full diagnostic sequence is dictated by the diagnostic performance of each test in the sequence as well as the conditional dependence between them, given true disease status. Resulting estimates of performance, such as the sensitivity and specificity of the test sequence, are key parameters in health-economic evaluations. We conducted a methodological review of statistical methods for assessing the performance of diagnostic tests performed in sequence, with the aim of guiding data analysts towards classes of methods that may be suitable given the design and objectives of the testing sequence. Methods: We searched PubMed, Scopus and Web of Science for relevant papers describing methodology for analysing sequences of diagnostic tests. Papers were classified by the characteristics of the method used, and these were used to group methods into themes. We illustrate some of the methods using data from a cohort study of repeat faecal immunochemical testing for colorectal cancer in symptomatic patients, to highlight the importance of allowing for conditional dependence in test sequences and adjustment for an imperfect reference standard. Results: Five overall themes were identified, detailing methods for combining multiple tests in sequence, estimating conditional dependence, analysing sequences of diagnostic tests used for risk assessment, analysing test sequences in conjunction with an imperfect or incomplete reference standard, and meta-analysis of test sequences. Conclusions: This methodological review can be used to help researchers identify suitable analytic methods for studies that use diagnostic tests performed in sequence

Experience of adopting faecal immunochemical testing to meet the NICE colorectal cancer referral criteria for low-risk symptomatic primary care patients in Oxfordshire, UK

Objective To compare the diagnostic performance of guaiac faecal occult blood (gFOB) testing with faecal immunochemical test (FIT) in a low-risk symptomatic primary care population to provide objective data on which to base local referral guidelines. Design Stool samples from routine primary care practice sent for faecal occult blood testing were analysed by a standard gFOB method and the HM-JACKarc FIT between January and March 2016. Symptoms described on the test request were recorded. Patients were followed up over 21 months for evidence of serious gastrointestinal pathology including colorectal adenocarcinoma. Results In 238 patients, the sensitivity and specificity for colorectal adenocarcinoma detection using gFOB were 85.7% and 65.8%, respectively, compared with 85.7% and 89.2% for FIT. The positive predictive value (PPV) for gFOB was 7.1% and negative predictive value (NPV) was 99.3%. Comparatively, the PPV for FIT was 19.4% and NPV 99.5%. The improved performance of FIT over gFOB was due to a lower false positive rate (10.8 vs 34.2, p≤0.01) with no increase in the false negatives rate. For any significant colorectal disease, the PPV for FIT increased to 35.5% with a reduction in NPV to 95.7%. Conclusion In this low-risk symptomatic patient group, the proportion of samples considered positive by FIT was considerably lower than gFOB with the same rate of colorectal adenocarcinoma detection. One in three of those with positive FIT had a significant colorectal disease. This supports National Institute of Health and Care Excellence recommendation that FIT can be reliably used as a triage test in primary care without overburdening endoscopy resources

Harnessing the electronic health care record to optimise patient safety in primary care: a framework for evaluating “electronic safety netting” tools

The management of diagnostic uncertainty is part of every primary care physician’s role. e–Safety-netting tools help health care professionals to manage diagnostic uncertainty. Using software in addition to verbal or paper based safety-netting methods could make diagnostic delays and errors less likely. There are an increasing number of software products that have been identified as e–safety-netting tools, particularly since the start of the COVID-19 pandemic. e–Safety-netting tools can have a variety of functions, such as sending clinician alerts, facilitating administrative tasking, providing decision support, and sending reminder text messages to patients. However, these tools have not been evaluated by using robust research designs for patient safety interventions. We present an emergent framework of criteria for effective e–safety-netting tools that can be used to support the development of software. The framework is based on validated frameworks for electronic health record development and patient safety. There are currently no tools available that meet all of the criteria in the framework. We hope that the framework will stimulate clinical and public conversations about e–safety-netting tools. In the future, a validated framework would drive audits and improvements. We outline key areas for future research both in primary care and within integrated care systems