bluuebunny/crossref_metadata_2025_split huggingface dataset:
Controlling Selectivity in Plasmonic Catalysis: Switching Reaction Pathway from Hydrogenation to Homocoupling Under Visible‐Light Irradiation
Authors: Peiris Erandi , Hanauer Sébastien , Le Tien , Wang Jiale , Salavati‐fard Taha , Brasseur Paul , Formo Eric V. , Wang Bin , Camargo Pedro H. C. 
Published: November 2022

AbstractPlasmonic catalysis enables the use of light to accelerate molecular transformations. Its application to the control reaction selectivity is highly attractive but remains challenging. Here, we have found that the plasmonic properties in AgPd nanoparticles allowed different reaction pathways for tunable product formation under visible‐light irradiation. By employing the hydrogenation of phenylacetylene as a model transformation, we demonstrate that visible‐light irradiation can be employed to steer the reaction pathway from hydrogenation to homocoupling. Our data showed that the decrease in the concentration of H species at the surface due to plasmon‐enhanced H2 desorption led to the control in selectivity. These results provide important insights into the understanding of reaction selectivity with light, paving the way for the application of plasmonic catalysis to the synthesis of 1,3‐diynes, and bringing the vision of light‐driven transformations with target selectivity one step closer to reality.
Micromolar Affinity and Higher: Synthetic Host–Guest Complexes with High Stabilities
Authors: Sarkar Sayan , Ballester Pablo , Spektor Mark , Kataev Evgeny A. 
Published: November 2022

AbstractThe design of high‐affinity synthetic host–guest complexes is of paramount importance because they are key elements in constructing unprecedented supramolecular assemblies, functional materials, molecular probes, artificial signal transduction events, and interfaces with the biological world. The present review article collects recent achievements in the design of 1 : 1 host–guest complexes with outstanding stabilities, i.e., exceeding 106 M−1. The relationships between the measured thermodynamic constants and the structural parameters of the interacting species are analyzed. The design features of high‐affinity hosts are discussed in light of their binding properties. Different solvents and different types of noncovalent interactions are considered for the stabilization of the complexes. Finally, some hints are provided for the design of future synthetic receptors displaying high affinity and selectivity.
Electrochemistry Visualization Tool to Support the Electrochemical Analysis of Batteries
Authors: de Souza Matheus Leal , Duquesnoy Marc , Morcrette Mathieu , Franco Alejandro A. 
Published: November 2022

AbstractTo meet the expected performance requirements of lithium‐ion batteries (LIBs), novel electrode materials, coatings and electrolytes have been studied in terms of their degradation mechanisms. Nevertheless, most of the methods used to track these mechanisms are notin operando, i. e., they do not follow them upon the practical LIB cell operation. The differential voltage analysis (DVA) and the incremental capacity analysis (ICA) constitutein operandotechniques that can greatly help in monitoring batteries degradation mechanisms. We report here anin housedeveloped software that allows the visualization of the DVA and the ICA curves of tested cells, with the possibility of rebuilding an experimental full‐cell capacity vs. potential curve through fitting of its electrodes’ half‐cell capacity vs. potential curves. Those features can be applied to multiple charge‐discharge cycles without data pretreatment, offering data exportation. We illustrate the functionalities of our software and indicate perspectives for its further development.
Design of Artificial Enzymes: Insights into Protein Scaffolds
Authors: Hanreich Stefanie , Bonandi Elisa , Drienovská Ivana 
Published: November 2022

AbstractThe design of artificial enzymes has emerged as a promising tool for the generation of potent biocatalysts able to promote new‐to‐nature reactions with improved catalytic performances, providing a powerful platform for wide‐ranging applications and a better understanding of protein functions and structures. The selection of an appropriate protein scaffold plays a key role in the design process. This review aims to give a general overview of the most common protein scaffolds that can be exploited for the generation of artificial enzymes. Several examples are discussed and categorized according to the strategy used for the design of the artificial biocatalyst, namely the functionalization of natural enzymes, the creation of a new catalytic site in a protein scaffold bearing a wide hydrophobic pocket and de novo protein design. The review is concluded by a comparison of these different methods and by our perspective on the topic.
Frequency and outcomes of STEMI patients presenting between 12 and 24 h after symptom onset: Late‐presenting STEMI
Authors: Griffin Anna C. Gonzalez , Yildiz Mehmet , Bradley Steven , Smith Jenna E. , Garcia Santiago , Schmidt Christian W. , Garberich Ross , Walser‐Kuntz Evan , Traverse Jay , Jollis James G. , Sharkey Scott W. , Henry Timothy D. 
Published: November 2022

AbstractObjectivesTo assess the characteristics and prognosis of ST‐elevation myocardial infarction (STEMI) patients, presenting between 12 and 24 h after symptom onset, in contemporary regional STEMI systems of care in the United States.BackgroundPrevious observational studies have been inconsistent regarding the benefit of primary percutaneous coronary intervention (PCI) compared with conservative management for late‐presenting STEMI patients and the majority of randomized trials are from the fibrinolytic era.MethodsUsing a two‐center registry‐based cohort from March 2003 to December 2020, we evaluated the frequency, clinical characteristics, and outcomes of STEMI patients, stratified by symptom onset to balloon time: <3, 3−6, 6−12, and 12−24 h (late presenters).ResultsAmong 5427 STEMI patients with available symptom onset time, 6.2% were late presenters, which increased to 11% during the early phase of the Covid‐19 pandemic. As symptom onset to balloon time increased, patients were more likely to be older, female, and have a history of hypertension and diabetes mellitus. Late presenters with an identifiable culprit lesion were less likely to be revascularized with PCI (96%, 96%, 95%, and 92%; p for trend = 0.004) and had a longer median door‐to‐balloon time (82, 109, 107, and 117 min; p for trend < 0.001). In‐hospital and 1‐year death risks were comparable between late and earlier presenters.ConclusionDespite the unfavorable risk profile and longer door‐to‐balloon time, clinical outcomes of late presenters were similar to those presenting within 12 h of symptom onset.
Incorporating Pd into Cu‐Coordinated Metal‐Organic Frameworks to Promote N2 Electrochemical Reduction into Ammonia
Authors: Huang Hao , Liu Qiaoxi , Cheng Qingpeng , Zhang Maolin , Liu Jialei 
Published: November 2022

AbstractFixation nitrogen using renewable energy has attracted much attention recently. However, the performance is limited by the competing hydrogen evolution reaction (HER) and the difficulty in activating N2. Here, an attractive strategy was proposed to enhance the electrochemical nitrogen reduction reaction (NRR) activity by introducing Pd into the HKUST‐1 framework. After thermal treatment, the obtained Pd/HKUST‐1 (250 °C) catalyst exhibited an ammonia production rate of 42.0 mg/gcat ⋅ h at −0.4 V vs. RHE with Faradaic efficiency of 4.6 %. The ammonia production reached as high as 415 mg/gcat in a 10‐hours stability test. With the assistance of density functional theory (DFT) calculations, the incorporated Pd was revealed to have the unique property to react with adsorbed H (Had) atom from HER and form α‐PdH species. Compared with other metals such as Ag, Au, and Pt, the in situ formed α‐PdH species could reduce the energy barrier of the rate‐limiting *N2H step, resulting in an enhanced NRR activity.
Selective Radical Oxidation of Cyclohexane to Adipic Acid at Electrochemical Interfaces
Authors: Tian Hao , Zhang Yujun , Zhang Ziyang , Lv Tingting , Bian Lei , Wang Hong , Li Jianxin , Yamauchi Yusuke , Wang Zhong‐Li 
Published: November 2022

AbstractDirect conversion of cyclohexane to adipic acid (AA) under mild conditions is an attractive technology in response to the increasing industrial demand of chemical intermediate AA. Exploring advanced free radical oxidation systems is the key to converting cyclohexane in a direct and mild manner. This study demonstrates that electrocatalytic water oxidation can quantitatively generate hydroxyl radicals (⋅OH) to selectively oxidize cyclohexane to AA by a vanadium oxide (VOx)‐platinum (Pt) composite catalyst coupled with persulfate (PS) redox mediator at the electrode/electrolyte interface under ambient temperature and pressure. The three active components of VOx, Pt, and PS can produce different concentrations of ⋅OH radicals alone or in combination, resulting in different AA selectivity and cyclohexane conversion, and the activity increased with the increase of free radical concentration before AA peroxidation. The optimized ternary oxidation system of VOx‐Pt‐PS achieved a cyclohexane conversion of 85 % with 95 % AA selectivity and the corresponding yield was 81 %, better than most traditional oxidation systems. Electrochemical interfaces‐driven radical oxidation provides opportunities to oxidatively convert many other inexpensive hydrocarbons to value‐added chemicals.
Facile Formation of Stable Neutral Radicals and Cations from [22]Smaragdyrin BF2Complexes
Authors: Deng Weikang , Liu Yang , Shimizu Daiki , Tanaka Takayuki , Nakai Akito , Rao Yutao , Xu Ling , Zhou Mingbo , Osuka Atsuhiro , Song Jianxin 
Published: November 2022

Abstractmeso‐Trimesityl‐substituted [20]smaragdyrin freebase was synthesized byp‐toluenesulfonic acid catalyzed reaction of 5‐mesityldipyrromethane and 2,14‐dibromodipyrrin in an improved yield of 63 %. Unexpectedly, treatment of the [20]smaragdyrin freebase with BF3 ⋅ OEt2and triethylamine (TEA) gave a stable radical species, in which the BF2unit is coordinated at the tripyrrin site, probably by ready release of a hydrogen atom of a [22]smaragdyrin BF2complex. Similar treatment of [22]smaragdyrin free base produced another [22]smaragdyrin BF2complex, in which the BF2unit is coordinated at the dipyrrin site. The tripyrrin site coordinated neutral radical was oxidized with AgSbF6to give a stable antiaromatic cation; this was reduced with NaBH4to its 22π congener, which was easily oxidized back to the neutral radical in the air and rearranged to thermodynamically stable dipyrrin site coordinated [22]smaragdyrin BF2complex upon treatment with BF3 ⋅ OEt2and TEA. Further, the dipyrrin site coordinated [22]smaragdyrin BF2complex was similarly oxidized to a stable neutral radical and a stable cation in a stepwise manner. This work demonstrates a rare ability of smaragdyrin BF2complexes to exist in multiple redox states, particularly forming a stable neutral radical by facile release of a hydrogen atom.
Clearing an ESKAPE Pathogen in a Model Organism; A Polypyridyl Ruthenium(II) Complex Theranostic that Treats a Resistant Acinetobacter baumannii Infection in Galleria mellonella
Authors: Smitten Kirsty , Southam Hannah M , Fairbanks Simon , Graf Arthur , Chauvet Adrien , Thomas Jim A 
Published: November 2022

AbstractIn previous studies we have described the therapeutic action of luminescent dinuclear ruthenium(II) complexes based on the tetrapyridylphenazine, tpphz, bridging ligand on pathogenic strains of Escherichia coli and Enterococcus faecalis. Herein, the antimicrobial activity of the complex against pernicious Gram‐negative ESKAPE pathogenic strains of Acinetobacter baumannii (AB12, AB16, AB184 and AB210) and Pseudomonas aeruginosa (PA2017, PA_ 007_ IMP and PA_ 004_ CRCN) are reported. Estimated minimum inhibitory concentrations and minimum bactericidal concentrations for the complexes revealed the complex shows potent activity against all A. baumannii strains, in both glucose defined minimal media and standard nutrient rich Mueller‐Hinton‐II. Although the activity was lower in P. aureginosa, a moderately high potency was observed and retained in carbapenem‐resistant strains. Optical microscopy showed that the compound is rapidly internalized by A. baumannii. As previous reports had revealed the complex exhibited no toxicity in Galleria Mellonella up to concentrations of 80 mg/kg, the ability to clear pathogenic infection within this model was explored. The pathogenic concentrations to the larvae for each bacterium were determined to be≥105 for AB184 and≥103 CFU/mL for PA2017. It was found a single dose of the compound totally cleared a pathogenic A. baumannii infection from all treated G. mellonella within 96 h. Uniquely, in these conditions thanks to the imaging properties of the complex the clearance of the bacteria within the hemolymph of G. mellonella could be directly visualized through both optical and transmission electron microscopy.
Self Cycloaddition of o‐Naphthoquinone Nitrosomethide to (±) Spiro{naphthalene(naphthopyranofurazan)}‐one Oxide: An Insight into its Formation
Authors: Tzeli Demeter , Gerontitis Ioannis E. , Petsalakis Ioannis D. , Tsoungas Petros G. , Varvounis George 
Published: November 2022

Abstract2‐Hydroxy‐1‐naphthaldehyde oxime was oxidized by AgO (or Ag2O), in presence of N‐methyl morpholine N‐oxide (NMMO), to the title spiro adduct‐dimer (±)‐Spiro{naphthalene‐1(2H),4′‐(naphtho[2′,1′:2,3]pyrano[4,5‐c]furazan)}‐2‐one‐11′‐oxide by a Diels‐Alder(D−A) type self‐cycloaddition, through the agency of an o‐naphthoquinone nitrosomethide (o‐NQM). Moreover, 2‐hydroxy‐8‐methoxy‐1‐naphthaldehyde oxime was prepared and subjected to the same oxidation conditions. Its sterically guided result, 9‐methoxynaphtho[1,2‐d]isoxazole, was isolated, instead of the expected spiro adduct. The peri intramolecular H bonding in the oxime is considered to have a key contribution to the outcome. Geometry and energy features of the oxidant‐ and stereo‐guided selectivity of both oxidation outcomes have been explored by DFT, perturbation theory and coupled cluster calculations. The reaction free energy of the D−A intermolecular cycloaddition is calculated at −82.0 kcal/mol, indicating its predominance over the intramolecular cyclization of ca. −37.6 kcal/mol. The cycloaddition is facilitated by NMMO through dipolar interactions and hydrogen bonding with both metal complexes and o‐NQM. The 8(peri)‐OMe substitution of the reactant oxime sterically impedes formation of the spiro adduct, instead it undergoes a more facile cyclodehydration to the isoxazole structure by ca. 4.9 kcal/mol.
Validation of the French version of the ICHOM adult oral health standard set
Authors: Nicolas‐Boluda Alba , Simon Stephane 
Published: November 2022

AbstractIntroductionThe ICHOM Adult Oral Health Standard Set (AOHSS) recently developed by the ICHOM Oral Adult Health Working Group is a standard set of outcomes designed for its collection in clinical practice in dental health. The outcome standard set is made up of clinical‐reported outcome measures (CROMs) and patient‐reported outcome measures (PROMs). The purpose of this study was to translate and cross‐culturally adapt the PROM section of the Standard Set in French for France to enable comprehensive evaluation of the patients' oral health quality of life in a French population.MethodsThe questionnaire was translated following the guidelines of the International Society for Pharmacoeconomics and Outcome Research (ISPOR). We included patients consulting in a dentistry clinic (n = 127) and seeking dental care. The PROM and CROM data were collected from all patients. Both reliability and the internal consistency were evaluated.ResultsThe ICHOM AOHSS was successfully translated into French. We sampled and surveyed 126 patients in a dentistry clinic in France using the French translation of the ICHOM AOHSS. Cronbach's α was calculated to measure the internal consistency. The resulting Cronbach's α was 0.8, indicating acceptable homogeneity.ConclusionsThe French version of the ICHOM AOHSS shows acceptable psychometric properties in terms of reliability and internal consistency. This translation is suitable for its implementation in a French‐speaking patient population.
Novel Vanillin‐based hybrids inhibit quorum sensing and silences phenotypical expressions in Pseudomonas aeruginosa
Authors: Dua Tamanna , Mangal Surabhi , Akshita Goel , Harshdeep  , Atri Ankit K. , Sharma Purshotam , Harjai Kusum , Singh Vasundhara 
Published: November 2022

AbstractIn this study, we report the chemical synthesis, computational analysis, and anti‐virulent studies of five Vanillin‐based hybrids employing phytochemicals. Vanillin (V) is known to have substantial anti‐quorum sensing activity against the gram‐negative pathogen Pseudomonas aeruginosa. Therefore, with the aim to further enhance the potency of Vanillin, it was chemically conjugated via a triazole (T) linker with five phytochemicals‐ Zingerone (Z), Eugenol (E), Guaiacol (G), Cinnamaldehyde (C), and Ferulic acid (F) to form the hybrids named as VTZ (1), VTE (2), VTG (3), VTC (4), and VTF (5), respectively. Molecular docking studies revealed the strong binding affinity of the designed hybrids with quorum‐sensing receptors (LasR, Rh1R, and PqsR). The synthesized hybrids were also evaluated for anti‐quorum sensing activities to examine the efficacy against P. aeruginosa bacterial strains PAO1. The hybrids VTE (2), VTG (3), and VTC (4) displayed improved anti‐quorum activity relative to Vanillin. Furthermore, the attenuation of virulence factors of P. aeruginosa (Las‐A protease, Las‐B elastase, pyocyanin pigmentation, and motility) in the presence of VTE (2), VTG (3), and VTC (4) further authenticated the anti‐virulent activity of the hybrids. The new design strategy of the phytochemical–phytochemical scaffolds and their biological evaluation provides a proof of concept for the simultaneous perturbation of well‐established anti‐virulent targets. This appears to be highly promising and effective strategy to ameliorate the enigma of antimicrobial resistance.
1,8‐Diarylnaphthalenes: Synthesis, Properties, and Applications
Authors: Gulevskaya Anna V. , Ermolenko Eugeny A. 
Published: November 2022

Abstract1,8‐Diarylnaphthalenes are a fascinating example of strained organic molecules that have found many practical applications due to unusual parallel face‐to‐face arrangement of two peri‐aryl rings in close proximity almost perpendicular to the central naphthalene backbone. 1,8‐Diarylnaphthalenes show notable potential as photoluminescent and chiral sensors, stereodynamic switches, nonlinear optic chromophores, blue‐transparent frequency doublers, materials for creating high‐performance blue and green OLEDs, chiral ligands and so on. Molecules of this type have also been used as convenient models for studying π‐π, dipole‐π and cation‐π interactions. 1,8‐Diarylnaphthalenes are also interesting as objects to study atropisomeric transformations: if the peri‐aryl rings have ortho‐ or meta‐substituents, then the anti‐conformer becomes C2‐symmetrical (hence chiral), and the syn‐isomer upon symmetrical substitution is achiral. In this review, data on synthetic methods, applications, atropisomerism and structural characteristics of 1,8‐diaryl‐ and 1,8‐dihetarylnaphthalenes are summarized.
Subcritical crack growth behavior of clay‐rich unconventional tight rocks under water‐saturated conditions
Authors: Yan Wei , Huang Xin , Muchiri Nguu Dickson , Cao Han 
Published: November 2022

AbstractHydraulic fracturing is the most widely used primary method for the stimulation of unconventional oil and gas resources. While knowledge of hydraulic fracture parameters is critical to reservoir productivity, predicting the fracture initiation is important for determining the complexity of the fracture network. Subcritical crack growth in reservoir rock plays an important role in forming fracture networks, but the understanding of the influence of fracturing conditions on subcritical crack growth is still lacking. In this paper, the subcritical crack growth behavior of sandstone and shale under ambient air, deionized (DI) water, and slick‐water conditions is studied. X‐ray diffraction analysis is done on the rock samples to determine their mineralogical composition, while tensile strength is measured by the Brazilian test. Then in Load Relaxation mode, a Double‐Torsion test (DT) is carried out under different conditions to study the subcritical crack growth of the samples. To further verify the influence of clay‐rich minerals, a similar analysis is performed on clay‐free granitic rock samples. The results of the tensile strength test and DT test demonstrate that the presence of clay minerals is the main reason for the difference in the subcritical crack growth behavior of shale and sandstone samples. DI water seems to better improve the subcritical crack growth compared with other test conditions. The value of the Subcritical Index (n) is smaller in a slick‐water environment than that in a DI water environment, revealing that slick water can better promote complex fracture propagation.
Derivatives of 3′‐Azidothymidine with 6‐Cyanopyridone as Base or as Phosphoramidate Ester and their Antiretroviral Activity
Authors: Han Jianyang , Arnold Jakob , Pannecouque Christophe , Andrei Graciela , Snoeck Robert , Richert Clemens 
Published: November 2022

AbstractStrongly pairing ethynylpyridone C‐nucleosides are attractive surrogates for thymidine in oligonucleotides. Exploratory work on the antiviral activity of 3′‐azidothymidine (AZT) derivatives with ethynylpyridone as base had identified strong lipophilicity as a limiting factor. Two strategies are being pursued to overcome this issue. In order to make the base more polar, the ethynyl group has been replaced with a cyano group, leading to a cyanopyridone C‐nucleoside, whose eleven‐step synthesis is reported here, together with the synthesis of a 3′‐azido‐2′,3′‐dideoxynucleoside derivative. The base pairing with adenine in a DNA duplex was studied by UV melting analysis of a self‐complementary hexamer containing the 6‐cyano‐2′‐deoxynucleoside instead of thymidine. A melting point increase of 2 °C compared to the unmodified control was found. The other strategy employs a phosphoramidate prodrug design with less lipophilic amino acid esters. Here, anti‐HIV test of the alaninyl and prolinyl methyl esters of AZT gave promising results in cell culture experiments, increasing the selectivity index up to 5.8‐fold for the IIIB strain and up to 5‐fold for the ROD strain of the virus, as compared to the parent nucleoside. These findings help to design the next generation of pyridone C‐nucleosides with potential applications as antivirals.