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Cyanoacetylene ( HCCCN), the first member of the cyanopolyyne family (HC n N, where n = 3, 5, 7, ...), is of particular interest in astrochemistry being ubiquitous in space (molecular clouds, solar-type protostars, protoplanetary disks, circumstellar envelopes, and external galaxies) and also relatively abundant. It is also abundant in the upper atmosphere of Titan and comets. Since oxygen is the third most abundant element in space, after hydrogen and helium, the reaction O + HCCCN can be of relevance in the chemistry of extraterrestrial environments. Despite that, scarce information exists not only on the reactions of oxygen atoms with cyanoacetylene but with nitriles in general. Here, we report on a combined experimental and theoretical investigation of the reactions of cyanoacetylene with both ground 3 P and excited 1 D atomic oxygen and provide detailed information on the primary reaction products, their branching fractions (BFs), and the overall reaction mechanisms. More specifically, the reactions of O( 3 P,  1 D) with HCCCN(X 1 Σ + ) have been investigated under single-collision conditions by the crossed molecular beams scattering method with mass spectrometric detection and time-of-flight analysis at the collision energy, E c , of 31.1 kJ/mol. From product angular and time-of-flight distributions, we have identified the primary reaction products and determined their branching fractions (BFs). Theoretical calculations of the relevant triplet and singlet potential energy surfaces (PESs) were performed to assist the interpretation of the experimental results and clarify the reaction mechanism. Adiabatic statistical calculations of product BFs for the decomposition of the main triplet and singlet intermediates have also been carried out. Merging together the experimental and theoretical results, we conclude that the O( 3 P) reaction is characterized by a minor adiabatic channel leading to OCCCN (cyanoketyl) + H (experimental BF = 0.10 ± 0.05), while the dominant channel (BF = 0.90 ± 0.05) occurs via intersystem crossing to the underlying singlet PES and leads to formation of 1 HCCN (cyanomethylene) + CO. The O( 1 D) reaction is characterized by the same two channels, with the relative CO/H yield being slightly larger. Considering the recorded reactive signal and the calculated entrance barrier, we estimate that the rate coefficient for reaction O( 3 P) + HC 3 N at 300 K is in the 10 -12 cm 3 molec -1 s -1 range. Our results are expected to be useful to improve astrochemical and photochemical models. In addition, they are also relevant in combustion chemistry, because the thermal decomposition of pyrrolic and pyridinic structures present in fuel-bound nitrogen generates many nitrogen-bearing compounds, including cyanoacetylene.

The water transport through nanoporous multilayered graphene at 300k is investigated using molecular dynamics (MD) simulation with different water models in this study. We used functionalized and non-functionalized membranes along with five different 3-point rigid water models: SPC (simple point charge), SPC/E (extended simple point charge), TIP3P-FB (transferable intermolecular potential with 3 points-Force Balance), TIP3P-EW (transferable intermolecular potential with 3 points with Ewald summation) and OPC3 (3-point optimal point charge) water models. Based on our simulations with two water reservoirs and a porous multilayered graphene membrane in-between them, it is evident that the water transport varies significantly depending on the water model used, which is in good agreement with previous works. This study contributes to the selection of a water model for molecular dynamics simulations of water transport through multilayered porous graphene.

In the present work, the effects on water transport due to the orientation of the layer in the multilayered porous graphene and the different patterns formed when the layer is oriented to some degrees are studied for both circular and non-circular pore configurations. Interestingly, the five-layered graphene membrane with a layer separation of 3.5 Å used in this study shows that the water transport through multilayered porous graphene can be augmented by introducing an angle to certain layers of the multilayered membrane system.

Background: As new SARS-CoV-2 variants of concern emerge, there is a need to scale up testing to minimize transmission of the Coronavirus disease 2019 (COVID-19). Many countries especially those in the developing world continue to struggle with scaling up reverse transcriptase polymerase reaction (RT-PCR) to detect SARS-CoV-2 due to scarcity of resources. Alternatives such as antigen rapid diagnostics tests (Ag-RDTs) may provide a solution to enable countries scale up testing., Methods: In this study, we evaluated the Panbio™ and STANDARD Q Ag-RDTs in the laboratory using 80 COVID-19 RT-PCR confirmed and 80 negative nasopharyngeal swabs. The STANDARD Q was further evaluated in the field on 112 symptomatic and 61 asymptomatic participants., Results: For the laboratory evaluation, both tests had a sensitivity above 80% (Panbio™ = 86% vs STANDARD Q = 88%). The specificity of the Panbio™ was 100%, while that of the STANDARD Q was 99%. When evaluated in the field, the STANDARD Q maintained a high specificity of 99%, however the sensitivity was reduced to 56%., Conclusion: Using Ag-RDTs in low resource settings will be helpful in scaling-up SARS-CoV-2 testing, however, negative results should be confirmed by RT-PCR where possible to rule out COVID-19 infection., Competing Interests: The authors have declared that no competing interests exist.

A heterogeneous reusable palladium(II)-bis(N-heterocyclic carbene) catalyst was prepared and shown to catalyze the intramolecular C(sp 3 )-H activation/cyclization of N-alkyl-2-bromoanilines furnishing indolines. This new catalytic system was based on a bis-imidazolium ligand immobilized on a spaced cross-linked polystyrene support. The iodide ligands on the catalyst played a central role in the efficiency of the process occurring through a "release and catch" mechanism. The heterogeneous nature of the catalyst was further exploited in the design of a continuous-flow protocol that allowed a more efficient recovery and reuse of the catalyst, as well as a very fast and safe procedure., (© 2022 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Three different Pd 0 -based heterogeneous catalysts were developed and tested in the Cassar-Heck reaction (i. e., copper-free Sonogashira reaction) aiming at the definition of a waste minimized protocol. The cross-linked polymeric supports used in this investigation were designed to be adequate for different reaction media and were decorated with different pincer-type ionic ligands having the role of stabilizing the formation and dimension of palladium nanoparticles. Among the ionic tags tested, bis-imidazolium showed the best performances in terms of efficiency and durability of the metal catalytic system. Eventually, aqueous acetonitrile azeotrope was selected as the reaction medium as it allowed the best catalytic efficiency combined with easy recovery and reuse. Finally, the synergy between the selected catalyst and reaction medium allowed to obtain highly satisfactory isolated yields of a variety of substrates while using a low amount of metal catalyst. The high performance of the designed POLymeric Ionic TAG (POLITAG)-Pd 0 , along with its good selectivity achieved in a copper-free process, also led to a simplified purification procedure allowing the minimization of the waste generated as also proven by the very low E-factor values (1.4-5) associated., (© 2021 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Background: Anterior drawer test, Lachman test including evaluation of the endpoint, and pivot shift test have been commonly applied clinically in diagnosing anterior cruciate ligament (ACL) injury but how they function in the appraisal of partial ACL tears is less known. The aims of this study were to examine the diagnostic values of the commonly used knee function tests on patients in detecting ACL injury including partial injury patterns, to assess each of the test's predictive values on the specific ACL injury pattern, and to assess if using multiple tests collectively for the diagnosis of the injury could improve diagnostic accuracy., Methods: We evaluated 36 consecutive patients who underwent ACL single bundle augmentation surgery. Those patients were matched by gender and age to 36 patients with a complete rupture of the ACL. Data was obtained from the patients' records. The rupture pattern was confirmed by arthroscopy. An examination under anesthesia was routinely performed by two surgeons who were blinded to the rupture pattern prior to surgery., Results: Collectively using both Lachman test and pivot shift test increases ability to distinguish between partial tears and complete ruptures. When comparing partial PL tears and complete ruptures the pivot shift test is more important than the Lachman test. In diagnosing a complete rupture, the evaluation of the endpoint during the Lachman test is more sensitive than the evaluation of the anterior tibial translation during the Lachman test., Conclusion: Based on the findings of this study, a diagnostic algorithm has been implemented and is presented in this manuscript., Competing Interests: Declaration of competing interest None., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Dehydrogenative C-H arylations of 1,2,3-triazoles were accomplished with the aid of a reusable palladium catalyst in PEG. The widely applicable oxidative palladium catalysis enabled the synthesis of fully decorated 1,2,3-triazoles with a broad functional-group tolerance and ample substrate scope. The sustainability of the aerobic C-H arylation was reflected by the use of PEG as green reaction medium and demonstrated by recycling studies of the catalyst and the reaction medium., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A gold-incorporated SBA-15 catalyst was prepared by a solvent-free ball-milling approach. The catalyst showed high reactivity and selectivity in the reduction of a variety of nitroarenes to anilines operating in absolute EtOH with NaBH 4 as reducing agent. The catalyst was reused in batch conditions over five consecutive runs without any losses of activity or selectivity. Considering the high chemical stability and reusability of the catalytic system, a continuous-flow protocol was also investigated and defined to minimize the generation of waste and optimize the continuous reuse of the catalyst. Benefits of flow conditions were proven by turnover numbers that increased from 47.5 to 1902 and also by the minimization of both leaching (9.5 vs. 1 ppm) and E-factor values (8 vs. 23 in batch)., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

C-H functionalization technologies have progressed enormously in the last decade as testified by the great number of publications that have appeared in the literature, which are receiving great attention from researchers from different areas of expertise. While most of the protocols reported realize the C-H functionalization processes under batch conditions, there is a growing interest in the development of continuous-flow procedures aiming at increasing the performances of established methodologies or the definition of otherwise unfeasible transformations. This review summarizes the application of flow technologies for the realization of C-H functionalization reactions. According to the type of flow reactors necessary, two main general approaches are possible for the application of flow techniques, namely the use of homogeneous or heterogeneous conditions. Each example is discussed and accompanied by the description of the main features and benefits of the use of flow compared to batch conditions.

Herein we report the use of Rhodiasolv © Polarclean as a novel polar aprotic solvent for the synthesis of decorated heterocycles via dipolar cycloaddition (isooxazoles) or intramolecular C-H functionalization processes (benzo-fused chromenes). The use of Polarclean allowed to isolate the final products in good yields by simple solid filtration or liquid-liquid phase separation, avoiding the need for chromatographic purification. Moreover, since in the synthesis of benzo-fused chromenes, the metal catalyst is retained in Polarclean, the catalyst/reaction medium can be easily reused for consecutive reaction runs, without any apparent loss in efficiency. This methodology is associated with a limited waste production. These results extend the applicability of Polarclean as a promising reaction medium for the replacement of toxic petrol-based solvent.

Herein, we report the use of γ-valerolactone as a new biomass-derived reaction medium for microwave assisted organic synthesis. The interaction of this solvent with microwaves and its heating profile under microwave irradiation has been fully characterized for the first time, demonstrating its stability and the applicability in microwave assisted Pd/C catalysed reactions avoiding the arcing phenomena frequently observed in these conditions. The use of γ-valerolactone demonstrated to be compatible with aliphatic and aromatic amines in the hydrogen transfer Pd/C mediated synthesis of benzimidazoles.

C-H arylations were accomplished with a user-friendly heterogeneous palladium catalyst in the biomass-derived γ-valerolactone (GVL) as an environmentally-benign reaction medium. The user-friendly protocol was characterized by ample substrate scope and high functional group tolerance in the C-H arylation of 1,2,3-triazoles, and the palladium catalyst could be recycled and reused in the C-H activation process.

A heterogeneous fluoride catalyst was found to enable the straightforward formation of alkenyl nitriles from the reaction of aldehydes and simple or substituted acetonitriles, in the presence of commercially available silazanes and in solvent-free conditions. The protocol afforded the products in good to excellent yields with selectivity values dependent on the nature of the substrates. It represents an alternative to classic approaches using stoichiometric strong bases, and the catalyst can be easily recovered and reused for consecutive cycles.

Objective: The aim of this study was to evaluate the approaches and procedures used by Brazilian orthopedic surgeons for treating osteoarthrosis by means of unicompartmental knee arthroplasty and high tibial osteotomy of the knee., Methods: A questionnaire with 14 closed questions was developed and applied to Brazilian knee surgeons during the three days of the 43(rd) Brazilian Congress of Orthopedics and Traumatology., Results: A total of 113 surgeons filled out the questionnaire completely and became part of the sample analyzed. In this study, the majority of the surgeons performed fewer than five unicompartmental knee arthroplasty procedures/year (61.1%) and between 5 and 15 high tibial osteotomy procedures/year (37.2%). Use of computerized navigation systems during surgery remains uncommon in our environment, since only 0.9% of the specialists were using it. 65.5% of the surgeons reported that they had chosen to use total knee arthroplasty rather than partial arthroplasty due to lack of familiarity with the surgical technique. When asked about the possibility that the number of unicompartmental prostheses used in Brazil would grow as surgeons in this country become increasingly familiar with the technique, 80.5% of the respondents believed in this hypothesis. In this sample, we found that the greater the surgeon's experience was, the greater the numbers of unicompartmental prostheses and tibial osteotomies performed annually were (r = 0.550 and r = 0.465, respectively; p < 0.05)., Conclusions: There is a clear evolutional trend towards treatment of unicompartmental osteoarthritis using partial knee arthroplasty in Brazil. However, further prospective controlled studies are needed in order to evaluate the clinical and scientific benefits of these trends.

Objective: To verify the influence of pharyngeal flap surgery on the management of velopharyngeal insufficiency on nasality and speech nasalance on nasal sound production in individuals with cleft lip and palate., Methods: Prospective study in 159 individuals with repaired cleft palate ± lip, of both genders, aged 6 to 57 years old. All the participants presented residual velopharyngeal insufficiency and were submitted to pharyngeal flap surgery. Perceptual speech evaluation and nasometric assessment were performed before and after (14 months on average) the pharyngeal flap surgery. Hyponasality was rated as absent or present, and nasalance scores were determined by means of nasometer using nasal stimuli, with a cutoff score of 43% used as the lowest limit of normality. Nasality and nasalance were compared before and after surgery (p < 0.05)., Results: On the basis of correlation between both the methods used, perceptual hyponasality was observed in 14% of the individuals, whereas nasalance scores indicating hyponasality (< 43%) were obtained in 25% of the patients after surgery., Conclusion: Pharyngeal flap surgery influenced the production of nasal sounds, causing hyponasality in a significant proportion of individuals. The presence of this speech symptom can also be an indicator of upper airway obstruction caused by pharyngeal flap, which should be investigated objectively and prudently postoperatively.