Investigating the mechanism of Ni-mediated trifluoromethylthiolation of aryl halides using AgSCF3.

The mechanism of the Ni-catalysed trifluoromethylthiolation of aryl chlorides using AgSCF3 is studied herein. A variety of IPr NiII complexes were synthesized via oxidative addition of Ni0 to 2-(2-chloro)phenylpyridines. Their reactivity with AgSCF3 was tested by performing stoichiometric experiments, cyclic voltammetry, and NMR spectroscopic studies. CuSCF3 was shown to behave similarly to AgSCF3, while reactions with NMe4SCF3 revealed a major stoichiometric side reaction that forms a nickel fluoride complex. NMR kinetic studies revealed there is little correlation between the electron-withdrawing/donating nature of the para substituents on either the phenyl or pyridyl groups with the formation of the corresponding products. Cyclic voltammetry (CV) indicated the feasibilty of NiI/NiIII transitions, and an increased rate of formation of product was observed with increased solvent polarity. Evidence suggests that the mechanism proceeds via inner-sphere electron transfer (ET) from AgSCF3 to NiII, ultimately leading to the formation of the trifluoromethylthiolated product.

Routine HbA1c among hematology and oncology inpatients: Diabetes-status and hospital-outcomes.

AIMS: Using routine HbA1c measurement to determine the prevalence of diabetes mellitus (known and previously unrecognized) and their hospital outcomes among hematology and oncology inpatients. METHODS: This was a prospective, observational study. Routine automated HbA1c testing was performed in all hematology and oncology inpatients aged ≥54 years at a tertiary hospital, July 2013-January 2015. The outcome measures were: (i) prevalence of known and previously unrecognized diabetes, and (ii) hospital outcomes: length-of-stay (LOS), intensive-care-unit (ICU) admission, 30-day/18-month readmission, and 18-month mortality. RESULTS: Over the 18-month study period, 1076 inpatients aged ≥54 years were admitted to hematology (n = 298) and oncology (n = 778) units: 21% had known diabetes and 7% had previously unrecognized diabetes. Patients with known diabetes had a longer LOS (IRR: 1.18, 95%CI: 1.02-1.37, p = 0.03), compared to those without diabetes, adjusting for age, hemoglobin level, estimated-glomerular-filtration-rate, admission specialty unit, Charlson's comorbidity index score, and glucocorticoid exposure. No significant differences were observed in ICU admission, 30-day/18-month readmission, and 18-month mortality among patients with known, previously unrecognized and no diabetes (p ≥ 0.05). CONCLUSIONS: Approximately one in five hematology or oncology inpatients aged ≥54 years had known diabetes, and one in fourteen had previously unrecognized diabetes. Those with known diabetes had a longer hospital stay. Routine HbA1c measurement is can be useful for identifying previously unrecognized diabetes, particularly among patients with high glucocorticoid exposure. Further study is required to determine cost-effectiveness in screening for unrecognized diabetes and optimal management of these patients.

The Importance of Ligand-Induced Backdonation in the Stabilization of Square Planar d10 Nickel π-Complexes.

The electronic nature of Ni π-complexes is underexplored even though these complexes have been widely postulated as intermediates in organometallic chemistry. Herein, the geometric and electronic structure of a series of nickel π-complexes, Ni(dtbpe)(X) (dtbpe=1,2-bis(di-tert-butyl)phosphinoethane; X=alkene or carbonyl containing π-ligands), is probed using a combination of 31 P NMR, Ni K-edge XAS, Ni Kß XES, and DFT calculations. These complexes are best described as square planar d10 complexes with π-backbonding acting as the dominant contributor to M-L bonding to the π-ligand. The degree of backbonding correlates with 2 JPP from NMR and the energy of the Ni 1s→4pz pre-edge in the Ni K-edge XAS data, and is determined by the energy of the π*ip ligand acceptor orbital. Thus, unactivated olefinic ligands tend to be poor π-acids whereas ketones, aldehydes, and esters allow for greater backbonding. However, backbonding is still significant even in cases in which metal contributions are minor. In such cases, backbonding is dominated by charge donation from the diphosphine, which allows for strong backdonation, although the metal centre retains a formal d10 electronic configuration. This ligand-induced backbonding can be formally described as a 3-centre-4-electron (3c-4e) interaction, in which the nickel centre mediates charge transfer from the phosphine σ-donors to the π*ip ligand acceptor orbital. The implications of this bonding motif are described with respect to both structure and reactivity.

What Can You Find about Polycystic Ovary Syndrome (PCOS) Online? Assessing Online Information on PCOS: Quality, Content, and User-Friendliness.

BACKGROUND: Polycystic ovary syndrome (PCOS) is a common yet complex condition, where education is vital. It predominantly affects reproductive-aged women, the age group with peak use of the Internet, now a major source of health information. Women with PCOS are dissatisfied with care, and the lack of useful online information is a key concern. METHODS: Using a rigorous and systematic methodology, we examined the quality, information content, and user-friendliness of online information about PCOS. Internet searches were conducted in Australia and the United Kingdom in December 2015 using Google, Bing, and Yahoo with different browsers, operating systems, and domain names. A total of 75 Web sites were evaluated and categorized. RESULTS: The majority of Web sites were commercial (41%) and not-for-profit (76%) and were aimed at women only. Less than a third of the Web sites were externally accredited. Commercial Web sites and Web sites targeting only women had the lowest quality scores, while professional-society Web sites and Web sites targeting only HPs scored the highest in quality. Accredited Web sites had higher quality and user-friendliness scores than nonaccredited Web sites. CONCLUSION: The majority of PCOS Web sites were commercially derived, targeted women, and were not accredited. There is a significant lack of quality, easy-to-read, evidence-based information online for women with PCOS.

Informing Translation: The Accuracy of Information on Websites for Lifestyle Management of Polycystic Ovary Syndrome.

Lifestyle (diet, physical activity [PA], and/or behavioral) interventions are recommended for all women with polycystic ovary syndrome (PCOS) in international guidelines. The internet is a widely used health information resource. However, the accuracy of lifestyle information on PCOS websites is unknown and is reviewed here to inform translation of the international guideline on PCOS. An internet search was conducted with three search engines across different web browsers and countries. Accuracy was assessed through a checklist of 29 questions based on international guidelines for diet, PA, or weight management for the general population and for PCOS with higher scores indicating greater accuracy. Fifteen websites were eligible out of 72 (20%). The total accuracy score was 56 ± 13 (mean ± standard deviation; potential range: -29 to 87) comprising 23 ± 6 for diet (-11 to 33), 15 ± 5 for PA (-9 to 27), and 14 ± 3 for weight management (-8 to 24). A moderate proportion of websites provided general information on appropriate diet (40-80%) or weight management strategies (47-60%), but only 10 to 40% of websites provided information on core foods, discretionary foods, exercise quantity/intensity, energy deficits, or behavioral strategies. Limited websites on PCOS contain information on lifestyle management. The majority provided information on general diet, PA, and weight recommendations but less information on practical implementation of lifestyle change as an identified translation gap for the international guideline on PCOS.

Oxaziridine cleavage with a low-valent nickel complex: competing C-O and C-N fragmentation from oxazanickela(ii)cyclobutanes.

Reacting the low-valent nickel complex [(dtbpe)Ni]2(µ-η2:η2-C6H6) with oxaziridines was found to form mixtures of imine, amide and aldehyde products. If the N-substituent of the oxaziridine is sufficiently bulky, a short-lived intermediate can be isolated and characterized by X-ray diffraction studies as an oxazanickela(ii)cyclobutane. This is the first well-defined example of N-O oxidative addition of an oxaziridine to a transition metal. Subsequent fragmentation of this oxazanickelacyclobutane forms a complex mixture of products, including a nickel(ii) imido complex, demonstrating that oxaziridines can serve as nitrene precursors. Preliminary mechanistic analysis is consistent with a bimetallic mechanism of fragmentation of the oxazanickelacyclobutane to form the nickel imido and η2-aldehyde complexes.

An Investigation of the Use of Traditional Chinese Medicine and Complementary and Alternative Medicine in Stroke Patients.

This study aimed to investigate the use of traditional Chinese medicine and complementary and alternative medicine in stroke patients in Taiwan. Chinese herbal medicine, massage, acupuncture, natural products, and exercise were widely used among stroke patients. Integrating safe and effective traditional Chinese medicine and complementary and alternative medicine into conventional therapies is suggested.

Cardiometabolic Risks in Polycystic Ovary Syndrome: Non-Traditional Risk Factors and the Impact of Obesity.

Polycystic ovary syndrome (PCOS) is a common and complex endocrinopathy with reproductive, metabolic, and psychological features and significantly increased cardiometabolic risks. PCOS is underpinned by inherent insulin resistance and hyperandrogenism. Obesity, more common in PCOS, plays an important role in the pathophysiology, exacerbating hyperinsulinaemia and hyperandrogenism, leading to recommended first-line lifestyle intervention. Significant traditional and non-traditional risk factors are implicated in PCOS in addition to obesity-exacerbated cardiometabolic risks and are explored in this review to promote the understanding of this common metabolic and reproductive condition.

Ligandless Nickel-Catalyzed Ortho-Selective Directed Trifluoromethylthiolation of Aryl Chlorides and Bromides Using AgSCF3.

A mild protocol for Ni-catalyzed trifluoromethylthiolation of aryl chlorides and bromides is described herein. The method utilizes AgSCF3 as an easily accessible nucleophilic trifluoromethylthiolating reagent and does not require any ligands or additives. Ortho-selectivity is achieved using a variety of directing groups such as imines, pyridines, and oxazolines for 24 examples in up to 95% yield.

Exploring Regioselective Bond Cleavage and Cross-Coupling Reactions using a Low-Valent Nickel Complex.

Recently, esters have received much attention as transmetalation partners for cross-coupling reactions. Herein, we report a systematic study of the reactivity of a series of esters and thioesters with [{(dtbpe)Ni}2(µ-η(2):η(2)-C6H6)] (dtbpe=1,2-bis(di-tert-butyl)phosphinoethane), which is a source of (dtbpe)nickel(0). Trifluoromethylthioesters were found to form η(2)-carbonyl complexes. In contrast, acetylthioesters underwent rapid Cacyl-S bond cleavage followed by decarbonylation to generate methylnickel complexes. This decarbonylation could be pushed backwards by the addition of CO, allowing for regeneration of the thioester. Most of the thioester complexes were found to undergo stoichiometric cross-coupling with phenylboronic acid to yield sulfides. While ethyl trifluoroacetate was also found to form an η(2)-carbonyl complex, phenyl esters were found to predominantly undergo Caryl-O bond cleavage to yield arylnickel complexes. These could also undergo transmetalation to yield biaryls. Attempts to render the reactions catalytic were hindered by ligand scrambling to yield nickel bis(acetate) complexes, the formation of which was supported by independent syntheses. Finally, 2-naphthyl acetate was also found to undergo clean Caryl-O bond cleavage, and although stoichiometric cross-coupling with phenylboronic acid proceeded with good yield, catalytic turnover has so far proven elusive.