Minimally invasive resection of heart valve papillary fibroelastoma: two case reports and review of the literature.

BACKGROUND: Cardiac papillary fibroelastomas are rare, accounting for approximately 10% of all cardiac tumors, with 44% of cases located on the aortic valve and only 15% of cases located on the tricuspid valve. However, the optimal management of papillary fibroelastomas remains varied. CASE PRESENTATION: We present two successful instances of treating heart valve papillary fibroelastomas through minimally invasive surgery. These cases involved heart valve papillary fibroelastomas located in two common sites: the aortic valve on the left heart, which was accessed via an upper hemi-sternotomy, and the tricuspid valve on the right heart, which was accessed via beating heart total thoracoscopy. CONCLUSION: The article consistently demonstrates the effectiveness of a minimally invasive surgical approach in managing heart valve papillary fibroelastomas. This study provides further evidence by presenting two cases of heart valve papillary fibroelastomas - one on the aortic valve and the other on the tricuspid valve - that were successfully treated using this approach, resulting in favorable outcomes.

Direct C7-H Arylation of Pyrazolo[1,5-a]azines with Aryl Chlorides.

C7-Arylated pyrazolo[1,5-a]azines are important structural motifs with profound applications in drug and material research. Here, we report a general and straighforward synthesis of these bi(hetero)aryls via palladium-catalyzed direct C-H arylation, employing low-cost and abundant (hetero)aryl chlorides as the aryl source. The catalytic system is robust and covers a wide substrate scope regarding heteroarenes as well as (hetero)aryl chlorides, with possible extension to the C-H arylation of [1,2,4]triazolo[1,5-a]pyrimidines. This study also presents a rare example of using (hetero)aryl chlorides for the direct C-H arylation of six-membered heteroarenes.

Diagnostic performance of MRI perfusion and spectroscopy for brainstem glioma grading.

OBJECTIVE: This study investigated the roles of dynamic susceptibility contrast (DSC) perfusion and multivoxel magnetic resonance spectroscopy (MRS) in grading brainstem glioma (BSG). PATIENTS AND METHODS: Our retrospective study comprised 12 patients, including 6 with pathology verified low-grade BSGs and 6 with high-grade BSGs. We examined differences in age, relative cerebral blood volume (rCBV), regional cerebral blood flow (rCBF), and the metabolite ratios of choline (Cho)/N-acetyl aspartate (NAA) and Cho/creatine (Cr) between these two groups using the Mann-Whitney U test and Chi-square test. Receiver operating characteristic (ROC) curve analysis was used to establish cutoff values and assess their usefulness in grading BSG. RESULTS: The Cho/NAA metabolite ratio had the strongest preoperative predictive performance for identifying the correct histological grade among BSGs, with an area under the ROC curve (AUC) value of 0.944 (cutoff: 3.88, sensitivity [Se]: 83.3%; specificity [Sp]: 100%), followed by the Cho/Cr ratio (cutoff: 3.08; AUC: 0.917; Se: 83.3%; Sp: 100%), rCBF (cutoff: 3.56, AUC: 0.917; Se: 83.3%; Sp: 100%), rCBV (cutoff: 3.16, AUC: 0.889; Se: 100%; Sp: 66.7%), and age (cutoff: 9.5 years, AUC: 0.889; Se: 100%; Sp: 83.3%). CONCLUSIONS: rCBF and rCBV values comparing solid tumors with the normal brain parenchyma and the metabolite ratios for Cho/NAA and Cho/Cre may serve as useful indices for establishing BSG grading and provide important information when determining treatment planning and prognosis in patients with BSG.

Influence of Achiral Phosphine Ligands on a Synergistic Organo- and Palladium-Catalyzed Asymmetric Allylic Alkylation.

An unusual diastereodivergent stereoselective allylation reaction is presented. It consists of a palladium-catalyzed allylation reaction of an organocatalytically generated amino isobenzofulvene, where the diastereoselectivity is controlled by the electronic properties of a monodentate, achiral ligand on palladium. One major diastereoisomer is formed using triarylphosphines substituted with neutral or electron-donating substituents of the aryl group, while those with electron-withdrawing substituents favor the other diastereoisomer. The diastereoselectivity correlates with the Taft inductive parameter of substituents on the triarylphosphine ligand on palladium. The synergistic reaction involves both a catalytic secondary amine catalyst for the indene-aldehyde activation and the monodentate phosphine ligands on palladium, affording a highly enantioselective reaction with up to 98 % enantiomeric excess. Based on computational investigations, the role of the monodentate phosphine ligand on the diastereoselectivity is discussed.

Palladium-catalyzed oxidative C-H/C-H cross-coupling of pyrazolo[1,5-a]azines with five-membered heteroarenes.

The use of Pd(OAc)2 as the catalyst and AgOAc as the oxidant enabled the direct regioselective oxidative C-H/C-H cross-coupling of pyrazolo[1,5-a]pyrimidines or pyrazolo[1,5-a]pyridines with various five-membered heteroarenes without the need of pre-activation and/or directing groups. Successful coupling partners include thiophenes, benzothiophenes, thiazoles, furans, oxazoles, indoles and imidazo[1,2-a]pyridines.

Mechanistic implications of Li-S cell function through modification of organo-sulfur cathode architectures.

Copolymeric organo-sulfur based electrodes provide a unique framework to explore and subsequently improve lithium-sulfur (Li-S) cells. There is a general difference in the way copolymers trap lithium during cell function compared to inorganic carbon-sulfur composites. Using a chain-like polyterpene copolymeric architecture involving the copolymerization of squalene monomer with sulfur (poly(S-r-squalene)), the first evidence for distinguishable differences in the entrapment of lithiated species, when using different copolymeric architectures, is provided. Investigation of poly(S-r-squalene) as an active cathode material via X-ray Absorption Near-Edge Structure (XANES) spectroscopy and high-resolution solid-state Nuclear Magnetic Resonance (NMR) reveal notable differences compared to previously studied poly(S-r-DIB) (proposed to have a less branched architecture) between the lithium environments present during electrochemistry that can be directly linked to the copolymeric structural features. Subtle but pertinent effects based on the copolymeric architecture related to the solid-electrolyte interphase (SEI) formed from the electrolytic components are also uncovered through these techniques. This work offers a comprehensive study on poly(S-r-squalene) and reveals that foundational inverse vulcanisation conditions such as choice of crosslinking monomer can dramatically impact lithium transport and SEI formation for the copolymeric electrode.

[Dialogue between general practitioner and patient regarding tobacco and alcohol consumption, from the patient's standpoint]. / Dialogue entre médecin généraliste et patient : les consommations de tabac et d'alcool en question, du point de vue du patient.

BACKGROUND: General practitioners (GP) are key players in screening and counselling for smokers and alcohol drinkers exceeding French guidelines for low-risk consumption thresholds. Tackling the subject from the patients' perspective, the authors aim at estimating the proportion of the population having discussed their smoking and alcohol consumption with their GPs, and to pinpoint the factors associated with their having done so. METHODS: The data (n=6346) are derived from nationwide representative phone survey in mainland France conducted by the French public health monitoring center Baromètre de Santé publique France. RESULTS: Among the persons aged 18-75 having consulted a GP over the last 12 months (82.5%), 36.7% stated that smoking had been discussed in consultation while 16.8% had talked about alcohol use. For both substances, being a man, a smoker, an excessive alcohol user and having a chronic illness were not only independently associated with being questioned by one's doctor, but also with more frequent patient initiative. About 87% considered it normal to be asked by their GP about their alcohol intake, this proportion being higher among men and people with high incomes. CONCLUSION: Even though a large portion of the population would deem it normal to discuss smoking and alcohol intake in consultation with a GP, the subjects are rarely broached. Our results underline the need to bolster efforts at systematic screening for substance use by GPs.

Variability of radiological grading of blunt cerebrovascular injuries in trauma patients.

CONTEXT: Blunt cerebrovascular injury (BCVI) occurs in 1%-2% of all blunt trauma patients. Computed tomographic angiography of the neck (CTAn) is commonly used for the diagnosis and grading of BCVIs. Grade of injury dictates treatment, and there remains a lack in understanding the inter-reader reliability of these interpretations. AIMS: The aim of this study is to determine the extent of variability in BCVIs among specialized neuroradiologist interpretation of CTAn. SETTINGS AND DESIGN: Retrospective review of trauma patients admitted to a level one trauma center with a BCVI from January 2012 to December 2017. Patients were randomly assigned for CTAn re-evaluation by two of three blinded, neuroradiologists. STATISTICAL ANALYSIS USED: The variability in BCVI grades was measured using the coefficient of unalikeability (u), and inter-reader reliability was calculated using weighted Cohen's kappa (k). RESULTS: Two hundred and twenty-eight BCVIs were analyzed with initial grades of 71 (31%) grade one, 74 (32%) grade two, 26 (11%) grade three, 57 (25%) grade four, and 0 grade five. Variability was present in 93 (41%) of all BCVIs. Grade one injuries had the lowest occurrence of total agreement (31%) followed by grade three (61%), grade two (63%), and grade four (92%). Total variability of grade interpretations (u = 100) occurred most frequently with grade three BCVIs (21%). Weighted Cohen's k calculations had a mean of 0.07, indicating poor reader agreement. CONCLUSIONS: This novel study demonstrated the BCVI variability of radiological grade interpretation occurs in more than a third of patients. The reliability of CTAn interpretation of BCVI grades is not uniform, potentially leading to undertreatment and overtreatment.

Immobilized Carbodiimide Assisted Flow Combinatorial Protocol to Facilitate Amide Coupling and Lactamization.

Through a screen of over one hundred and 30 permutations of reaction temperatures, solvents, carbodiimide resins, and carbodiimide molar equivalences, in the presence, absence, or combination of diisopropylamine and benzotriazole additives, a convenient and first reported carbodiimide polymer-assisted flow approach to effect amide coupling and lactamization was developed. The protocol entails injecting a single solution (1:9 dimethylformamide: dichloromethane) containing a carboxylic acid and an amine or linear peptide sequence into a continuous stream of dichloromethane. The protocol remained viable in the absence of base, did not require carboxylate preactivation which, and in concert with minimal workup requirements, enabled the isolation of products in high yields. Compared to the utilization of untethered carbodiimide reagents, the flow procedure was also observed to provide a degree of racemization safety.

One-Pot Synthesis of α,ß-Unsaturated γ-Lactones and Lactams via a Sequential trans-Hydroalumination and Catalytic Carboxylation of Propargyl Alcohols and Amines with Carbon Dioxide.

A one-pot, sequential process that combines a trans-selective hydroalumination of propargyl alcohols and amines with a copper- or silver-catalyzed carboxylation reaction using carbon dioxide, followed by an acid-mediated intramolecular condensation step, led to the formation of a wide range of α,ß-unsaturated γ-butyrolactones and lactams.

Halide Anion Triggered Reactions of Michael Acceptors with Tropylium Ion.

Tropylium bromide undergoes noncatalyzed, regioselective additions to a large variety of Michael acceptors. In this way, acrylic esters are converted into ß-bromo-α-cycloheptatrienylpropionic esters. The reactions are interpreted as nucleophilic attack of bromide ions at the electron-deficient olefins and the approach of the tropylium ion to the incipient carbanion. Quantum chemical calculations were performed to elucidate the analogy to the amine- or phosphine-catalyzed Rauhut-Currier reactions. Subsequent synthetic transformations of the bromo-cycloheptatrienylated adducts are reported.

Catalytic Synthesis of Trifluoromethyl Cyclopropenes and Oligo-Cyclopropenes.

The synthesis of trifluoromethylated cyclopropenes is often associated with important applications in drug discovery and functional materials. In this report, we describe the use of readily available chiral rhodium(II) catalysts for a highly efficient asymmetric cyclopropenation reaction of fluorinated donor-acceptor diazoalkanes with a broad variety of aliphatic and aromatic alkynes. Further studies highlight the unique reactivity of fluorinated donor-acceptor diazoalkanes in the synthesis of oligo-cyclopropenes. Subsequent C-H functionalization of trifluoromethyl cyclopropenes furnishes densely substituted cyclopropene frameworks and also allows the alternative synthesis of bis-cyclopropenes.

Tetrabenzo[5.7]fulvalene: a forgotten aggregation induced-emission luminogen.

Tetrabenzo[5.7]fulvalene, one of the first recognized stable members of mixed fulvalenes, has attracted widespread interest for its remarkable structure. However, little has been known about its photoactivity, most likely owing to its very weak luminescence in the solution state. Here we show for the first time that this compound exhibits aggregation-induced emission (AIE) properties. Its photoluminescence and X-ray crystal structure reveal an interesting mechanism of the AIE phenomenon.

Elucidation of structures and lithium environments for an organo-sulfur cathode.

Composite organo-sulfur cathodes provide a unique platform for the realization of lithium-sulfur (Li-S) cells. However, difficulties arise in the interpretation of the function of these electrodes in Li-S cells and the role they play in suppressing the so-called 'shuttle effect'. This work focuses on monitoring in detail the structural evolution and lithium environments during charge-discharge cycles in a lithium half-cell of an organo-sulfur cathode, which was synthesised by inverse vulcanisation with 1,3-diisopropenylbenzene. For the first-time in organo-sulfur materials, high resolution solid state 7Li-1H and 13C-1H double resonance NMR spectroscopy coupled with X-ray absorption near-edge structure (XANES) and X-ray diffraction (XRD) are used to develop a detailed structural model of the cathode material and its lithium environments as a function of cycle number. This work provides the first experimental evidence via 2D NMR spectroscopy of distinct molecular proximities of the lithium species with respect to the sulfur, the organic skeleton and the electrolyte in the cathode material. This approach enables us to develop unparalleled understanding of the mechanisms of the high charge capacity of 607 mA h g-1, rationalising initial capacity drop and suppression of capacity fade with cycling. These results also show new possibilities on how to better understand electrode function to further increase the lithium capacities of organo-sulfur cathode materials, which can in turn lead to performance-enhanced Li-S cells.

Oxidative organocatalysed enantioselective coupling of indoles with aldehydes that forms quaternary carbon stereocentres.

The first organocatalysed, metal-free cross-nucleophile coupling of indoles with α-branched aldehydes forming acyclic stereoselective quaternary carbon centres is presented. Applying an amino acid-derived catalyst with suitable organic oxidants affords the desired enantioenriched indole functionalised products with moderate to excellent yield and enantioselectivity. Two metal-free oxidative protocols employing either DDQ or a sequential approach that uses two organocatalysts to facilitate the use of O2 as the terminal oxidant are disclosed. These methods are compatible with various indoles ranging from electron-rich to -deficient substituents at the C-2, -5, -6, and -7-positions reacting with a series of different α-branched aldehydes.

Efficient Synthesis of α-Trifluoromethyl Carboxylic Acids and Esters through Fluorocarboxylation of gem-Difluoroalkenes.

A facile synthetic procedure for the preparation of α-trifluoromethyl carboxylic acids and esters was achieved through multicomponent coupling reactions between gem-difluoroalkenes, cesium fluoride, and carbon dioxide. The products were generated in moderate to excellent yields, and the synthetic utility of this method was demonstrated through the preparation of trifluoromethylated versions of popular nonsteroidal anti-inflammatory drugs (NSAIDs).

Cyanomethyl anion transfer reagents for diastereoselective Corey-Chaykovsky cyclopropanation reactions.

A readily available and bench-stable cyanomethyl sulfonium salt was used in highly diastereoselective Corey-Chaykovsky cyclopropanation reactions of electron-poor olefins. This efficient method provides a rapid route to access densely functionalized cyclopropyl nitriles.

Tropylium-promoted carbonyl-olefin metathesis reactions.

The carbonyl-olefin metathesis (COM) reaction is a highly valuable chemical transformation in a broad range of applications. However, its scope is much less explored compared to analogous olefin-olefin metathesis reactions. Herein we demonstrate the use of tropylium ion as a new effective organic Lewis acid catalyst for both intramolecular and intermolecular COM and new ring-opening metathesis reactions. This represents a significant improvement in substrate scope from recently reported developments in this field.

[Smoking and vaping in France]. / Consommation de tabac et usage de cigarette électronique en France.

INTRODUCTION: The aim of the article is to present a summary of current knowledge on tobacco smoking in France available through representative population surveys. STATE OF ART: Smoking is very common in France as more than a quarter (28.7%) of 15-75years old individuals reported daily smoking in 2016. The rate is also high among 15-year-old (14.6%) and half of them (51.8%) have already smoked one cigarette. Since the 1970s, sex differences in smoking behaviour are narrowing. More recently, since 2000, smoking prevalence has tended to decrease among the most advantaged individuals but to increase among less advantaged ones. These social inequalities, which are becoming more and more pronounced, are being observed from smoking initiation, often before the age of 18. Daily users of E-cigarettes represent 2.5% of individuals from 15-75 years in France. They are also tobacco smokers (58.8%) or former smokers (41.2%). PERSPECTIVES: Taking social inequalities in health into consideration, notably regarding smoking initiation, is a key challenge in the fight against smoking. CONCLUSIONS: It is essential to strengthen efforts to decrease the rate of smoking in France. The 2017 Health Barometer and Escapad surveys will allow evaluation of the public policies implemented in 2016 and determine whether they have had an impact on the image of smoking and on smoking rates.

Tropylium-Promoted Oxidative Functionalization of Tetrahydroisoquinolines.

Structural modification of the tetrahydroisoquinoline (THIQ) framework is of significant interest to organic chemists due to its central role in heterocyclic and medicinal chemistry. Here we demonstrate an efficient metal-free method for the oxidative functionalization of THIQs at the C1 position, which is amenable to a diverse range of C-C coupling reactions. These reactions proceed through a hydride abstraction involving the tropylium ion followed by quenching the generated iminium intermediates with nucleophiles to afford THIQ derivatives with excellent efficiencies and interesting selectivities.