bluuebunny/crossref_metadata_2025_split huggingface dataset:
Progress in Organocatalytic Dearomatization Reactions Catalyzed by N‐Heterocyclic Carbenes
Authors: Zhen Guangjin , Jiang Kai , Yin Biaolin 
Published: April 2022

AbstractDearomative reactions allow for concise assembly of structurally complex, highly functionalized three‐dimensional molecules by breaking the plane of two‐dimensional aromatic starting materials. With the growing interest in N‐heterocyclic carbene (NHC) organocatalysis as a powerful strategy for synthesizing diversiform molecules, mainly by polarity‐reversal (umpolung) approaches, NHC‐catalyzed dearomatization reactions have recently been successfully used for the construction of the skeletons of natural products and drugs. By generating various key intermediates (i. e., Breslow intermediates, acyl azolium intermediates, homoenolate intermediates, enolate intermediates, and azolium dienolate intermediates), NHCs can readily destroy aromaticity by electrophilic or nucleophilic interactions with aromatic compounds. In this overview, progress in NHC‐catalyzed dearomative reactions is summarized; the reactions are grouped according to reaction modes and categories of intermediates, and representative mechanisms are provided. This review aims to serve as a comprehensive reference for work in the emerging field of organocatalytic dearomatization.
Iridium‐Functionalized Metal‐Organic Framework Nanocrystals Interconnected by Carbon Nanotubes Competent for Electrocatalytic Water Oxidation
Authors: Chang Tzu‐En , Chuang Cheng‐Hsun , Chen Yu‐Hsiu , Wang Yi‐Ching , Gu Yu‐Juan , Kung Chung‐Wei 
Published: April 2022

AbstractNanocrystals of a zirconium‐based metal‐organic framework (MOF), UiO‐66, are grown on the surface of the carboxylic acid‐functionalized multi‐walled carbon nanotubes (CNT) at room temperature to synthesize the UiO‐66‐CNT nanocomposites with tunable MOF‐to‐CNT ratios. The porosity, crystallinity, morphology, and electrical conductivity of the nanocomposite are characterized. Spatially dispersed iridium sites are thereafter installed on the defect sites presented within the entire UiO‐66 crystals in these nanocomposites by a self‐limiting solution‐phase approach. The resulting Ir‐functionalized UiO‐66, CNT, and UiO‐66‐CNT nanocomposites are served as the electrocatalysts for water oxidation in acidic aqueous solutions. By utilizing the redox‐hopping pathways to transport electrons within the Ir‐functionalized MOF crystals as well as the electronic conduction between MOF crystals provided by CNT, the nanocomposite with the optimal MOF‐to‐CNT ratio can outperform both the Ir‐functionalized UiO‐66 and CNT. Electrochemical impedance spectroscopy (EIS) is utilized to probe the reaction kinetics occurring on the decorated iridium sites and the transporting behaviors of electrons/ions within these catalytic thin films. For the first time, the electrocatalytic kinetics and the transporting limitations within the MOF‐based thin film can be decoupled with the help of EIS technique. Post‐electrocatalysis characterizations of the nanocomposite after water oxidation are also performed.
Non‐oxidative Dehydrogenation of Methanol to Formaldehyde over Bulk β‐Ga2O3
Authors: Merko Mariia , Busser G. Wilma , Muhler Martin 
Published: April 2022

AbstractThe non‐oxidative dehydrogenation of methanol to formaldehyde is considered a dream reaction compared with the classical oxidative route, because the valuable coupled product hydrogen is formed instead of water, and the produced anhydrous formaldehyde is highly suitable for the further synthesis of oxygenated synthetic fuels. This study reports on the high catalytic performance of pure β‐Ga2O3 in this reaction at temperatures between 500 °C and 650 °C. At 550 °C and a GHSV of 45500 h−1, an initial selectivity to formaldehyde of 77 % was obtained at a methanol conversion of 72 %. Performing the reaction at temperatures beyond this range and lower GHSV resulted in a lower formaldehyde selectivity. The catalyst suffered from deactivation caused by formation of carbon deposits, but it was possible to regenerate its initial activity at 500 °C and 550 °C completely by an oxidative treatment. Irreversible deactivation occurred at 650 °C due to partial volatilization of Ga2O3.
Research Progress on Postoperative Minimal/Molecular Residual Disease Detection in Lung Cancer
Authors: Wu Manqi , Shen Haifeng , Wang Ziyang , Kanu Nnennaya , Chen Kezhong 
Published: April 2022

AbstractLung cancer is the leading cause of cancer‐related deaths worldwide. Approximately 10%–50% of patients experience relapse after radical surgery, which may be attributed to the persistence of minimal/molecular residual disease (MRD). Circulating tumor DNA (ctDNA), a common liquid biopsy approach, has been demonstrated to have significant clinical merit. In this study, we review the evidence supporting the use of ctDNA for MRD detection and discuss the potential clinical applications of postoperative MRD detection, including monitoring recurrence, guiding adjuvant treatment, and driving clinical trials in lung cancer. We will also discuss the problems that prevent the routine application of ctDNA MRD detection. Multi‐analyte methods and identification of specific genetic and molecular alterations, especially methylation, are effective detection strategies and show considerable prospects for future development. Interventional prospective studies based on ctDNA detection are needed to determine whether the application of postoperative MRD detection can improve the clinical outcomes of lung cancer patients, and the accuracy, sensitivity, specificity, and robustness of different detection methods still require optimization and refinement.
Cyanobacterial metabolites as novel drug candidates in corona viral therapies: A review
Authors: Prabhu Srinivasan , Vijayakumar Subramaniyan , Praseetha Pabakaran 
Published: April 2022

AbstractMost of the medical and nonmedical research labs, all around the world, are racing against time to produce an effective vaccine or an antiviral medicine for coronavirus disease 2019 (COVID‐19). Conventional medicines and novel nano‐materials including chemical and herbal‐based compounds are all into positive trials toward coronaviruses and other pandemic infections. Among them, natural immune boosters have attracted physicians because of their longevity and reliability for fewer side effects. This is a review article with a detailed picture of an unexplored antiviral source with maximum potency in curing viral infections. Cyanobacteriae have been known for centuries and are rich in secondary metabolites of proteins, biopeptides, and polysaccharides for prominent antiviral action against chest infections. But detailed exploratory research is required to purify, scale‐up, and commercialize the pharmacologically active agents from these drug reserves.
On the Fundamental Polymer Chemistry of Inverse Vulcanization for Statistical and Segmented Copolymers from Elemental Sulfur
Authors: Kang Kyung‐Seok , Iyer Krishnan A. , Pyun Jeffrey 
Published: April 2022

AbstractIn this concept review, the fundamental and polymerization chemistry of inverse vulcanization for the preparation of statistical and segmented sulfur copolymers, which have been actively developed and advanced in various applications over the past decade is discussed. This concept review delves into a discussion of step‐growth polymerization constructs to describe the inverse vulcanization process and discuss prepolymer approaches for the synthesis of segmented sulfur polyurethanes. Furthermore, this concept review discusses the advantages of inverse vulcanization in conjunction with dynamic covalent polymerization and post‐polymerization modifications to prepare segmented block copolymers with enhanced thermomechanical and flame retardant properties of these materials.
Superassembled Hierarchical Asymmetric Magnetic Mesoporous Nanorobots Driven by Smart Confined Catalytic Degradation
Authors: Yan Miao , Ma Ding , Qiu Beilei , Liu Tianyi , Xie Lei , Zeng Jie , Liang Kang , Xin Hui , Lian Zhexun , Jiang Lei , Kong Biao 
Published: April 2022

AbstractMicro/nanoscale robotics has received great attention in many important fields. However, it is still a great challenge to construct nanorobots simultaneously possessing multifunctionality, well‐controlled directionality, and fast and durable motion as well as fully compatible and biodegradable components. Here, a hierarchical, asymmetric, hollow, catalytic, magnetic, and mesoporous nanorobot has been fabricated through a multistep interfacial superassembly strategy. The multilayer composites consist of hollow silica nanoflasks sequentially coated with a highly magnetic responsive Fe3O4 layer, a mesoporous silica layer with homogeneous vertical channels, and a layer of catalytic gold nanoparticles on both the inner and outer surfaces. Furthermore, para‐nitrophenol was used as a model pollutant to trigger self‐motility of the nanoflasks by confined catalytic degradation (CCD). We found that the bottleneck morphology and mesoporous surface both improved the catalytic nanoparticle loading capability and CCD effect, thus enabling efficient self‐motility and a durable movement capacity of ∼100 h. In addition, the catalytic performance was improved by 180 % compared with that of solid spherical nanoparticles.
Mesoionic Dithiolates (MIDts) Derived from 1,3‐Imidazole‐Based Anionic Dicarbenes (ADCs)
Authors: Ebeler Falk , Vishnevskiy Yury V. , Neumann Beate , Stammler Hans‐Georg , Ghadwal Rajendra S. 
Published: April 2022

AbstractMesoionic dithiolates [(MIDtAr)Li(LiBr)2(THF)3] (MIDtAr={SC(NDipp)}2CAr; Dipp=2,6‐iPr2C6H3; Ar=Ph 3 a, 3‐MeC6H4 (3‐Tol) 3 b, 4‐Me2NC6H4 (DMP) 3 c) and [(MIDtPh)Li(THF)2] (4) are readily accessible (in≥90 % yields) as crystalline solids on treatments of anionic dicarbenes Li(ADCAr) (2 a‐c) (ADCAr={C(NDipp)2}2CAr) with elemental sulfur. 3 a‐c and 4 are monoanionic ditopic ligands with both the sulfur atoms formally negatively charged, while the 1,3‐imidazole unit bears a formal positive charge. Treatment of 4 with (L)GeCl2 (L=1,4‐dioxane) affords the germylene (MIDtPh)GeCl (5) featuring a three‐coordinated Ge atom. 5 reacts with (L)GeCl2 to give the Ge−Ge catenation product (MIDtPh)GeGeCl3 (6). KC8 reduction of 5 yields the homoleptic germylene (MIDtPh)2Ge (7). Compounds 3 a‐c and 4–7 have been characterized by spectroscopic studies and single‐crystal X‐ray diffraction. The electronic structures of 4–7 have been analyzed by DFT calculations.
Spatially Resolved Measurements of HNCO Hydrolysis over SCR Catalysts
Authors: Eck Mario , Lott Patrick , Schweigert David , Börnhorst Marion , Deutschmann Olaf 
Published: April 2022

AbstractIn order to understand deposit formation during urea selective catalytic reduction (SCR) resulting from isocyanic acid (HNCO) formation, the present study investigates the potential of HNCO hydrolysis by spatially resolved gas phase concentration profiles along a single catalyst channel of commercial Cu‐zeolite and V‐based SCR catalysts. The spatially resolved profiles, obtained in a special hot gas test rig via capillary technique, provide information on reaction rates of HNCO hydrolysis, NH3 adsorption and NO conversion, hereby revealing a better performance of the standard V‐based catalyst regarding the HNCO hydrolysis, which is attributed to the TiO2 support.
Heart Team risk assessment with angiography‐derived fractional flow reserve determining the optimal revascularization strategy in patients with multivessel disease: Trial design and rationale for the DECISION QFR randomized trial
Authors: Miyata Kotaro , Asano Taku , Saito Akira , Abe Kohei , Tanigaki Toru , Hoshino Masahiro , Kobayashi Tomoaki , Takaoka Yoshimitsu , Kanie Takayoshi , Yamasaki Manabu , Yoshino Kunihiko , Wakabayashi Naoki , Ouchi Koki , Kodama Hiroyuki , Shiina Yumi , Tamaki Rihito , Nishihata Yosuke , Masuda Keita , Suzuki Takahiro , Nonaka Hideaki , Emori Hiroki , Katagiri Yuki , Miyazaki Yosuke , Sotomi Yohei , Yasunaga Motoki , Kogame Norihiro , Kuramitsu Shoichi , Reiber Johan H. C. , Okamura Takayuki , Higuchi Yoshiharu , Kakuta Tsunekazu , Misumi Hiroyasu , Komiyama Nobuyuki , Matsuo Hitoshi , Tanabe Kengo ,   DECISION QFR investigators
Published: April 2022

AbstractIn patients with multivessel disease (MVD), functional information on lesions improves the prognostic capability of the SYNTAX score. Quantitative flow ratio (QFR®) is an angiography‐derived fractional flow reserve (FFR) that does not require a pressure wire or pharmacological hyperemia. We aimed to investigate the feasibility of QFR‐based patient information in Heart Teams' discussions to determine the optimal revascularization strategy for patients with MVD. We hypothesized that there is an acceptable agreement between treatment recommendations based on the QFR approach and recommendation based on the FFR approach. The DECISION QFR study is a prospective, multicenter, randomized controlled trial that will include patients with MVD who require revascularization. Two Heart Teams comprising cardiologists and cardiac surgeons will be randomized to select a revascularization strategy (percutaneous coronary intervention or coronary artery bypass graft) according to patient information either based on QFR or on FFR. All 260 patients will be assessed by both teams with reference to the anatomical and functional SYNTAX score/SYNTAX score II 2020 derived from the allocated physiological index (QFR or FFR). The primary endpoint of the trial is the level of agreement between the treatment recommendations of both teams, assessed using Cohen's κ. As of March 2022, the patient enrollment has been completed and 230 patients have been discussed in both Heart Teams. The current trial will indicate the usefulness of QFR, which enables a wireless multivessel physiological interrogation, in the discussions of Heart Teams to determine the optimal revascularization strategy for MVD.
Strongly Bound π‐Hole Tetrel Bonded Complexes between H2SiO and Substituted Pyridines. Influence of Substituents
Authors: Bhattarai Sumitra , Sutradhar Dipankar , Chandra Asit K. 
Published: April 2022

AbstractAb initio calculation at the MP2/aug‐cc‐pVTZ level has been performed on the π‐hole based N…Si tetrel bonded complexes between substituted pyridines and H2SiO. The primary aim of the study is to find out the effect of substitution on the strength and nature of this tetrel bond, and its similarity/difference with the N…C tetrel bond. Correlation between the strength of the N…Si bond and several molecular properties of the Lewis acid (H2SiO) and base (pyridines) are explored. The properties of the tetrel bond are analyzed using AIM, NBO, and symmetry‐adapted perturbation theory calculations. The complexes are characterized with short N…Si intermolecular distances and high binding energies ranging between −142.72 and −115.37 kJ/mol. The high value of deformation energy indicates significant geometrical distortion of the monomer units. The AIM and NBO analysis reveal significant coordinate covalent bond character of the N⋅⋅⋅Si π‐hole bond. Sharp differences are also noticed in the orbital interactions present in the N⋅⋅⋅Si and N⋅⋅⋅C tetrel bonds.
Selective Conversion of HMF into 3‐Hydroxymethylcyclopentylamine through a One‐Pot Cascade Process in Aqueous Phase over Bimetallic NiCo Nanoparticles as Catalyst
Authors: Hurtado Beatriz , Arias Karen S. , Climent Maria J. , Concepción Patricia , Corma Avelino , Iborra Sara 
Published: April 2022

Abstract5‐hydroxymethylfurfural (HMF) has been successfully valorized into 3‐hydroxymethylcyclopentylamine through a one‐pot cascade process in aqueous phase by coupling the hydrogenative ring‐rearrangement of HMF into 3‐hydroxymethylcyclopentanone (HCPN) with a subsequent reductive amination with ammonia. Mono‐ (Ni@C, Co@C) and bimetallic (NiCo@C) nanoparticles with different Ni/Co ratios partially covered by a thin carbon layer were prepared and characterized. Results showed that a NiCo catalyst, (molar ratio Ni/Co=1, Ni0.5Co0.5@C), displayed excellent performance in the hydrogenative ring‐rearrangement of HMF into HCPN (>90 % yield). The high selectivity of the catalyst was attributed to the formation of NiCo alloy structures as hydrogenating sites that limited competitive reactions such as the hydrogenation of furan ring and the over‐reduction of the formed HPCN. The subsequent reductive amination of HPCN with aqueous ammonia was performed giving the target cyclopentylaminoalcohol in 97 % yield. Moreover, the catalyst exhibited high stability maintaining its activity and selectivity for repeated reaction cycles.
Catalytic Transfer Hydrogenation of 5‐Hydroxymethylfurfural with Primary Alcohols over Skeletal CuZnAl Catalysts
Authors: Huang Yao‐Bing , Zhang Xuan , Zhang Jilong , Chen Haoze , Wang Tipeng , Lu Qiang 
Published: April 2022

AbstractCatalytic transfer hydrogenation (CTH) with alcohols has been increasingly employed as effective tool for biomass upgrading, however, relying predominantly on secondary alcohols. Herein, for the first time skeletal CuZnAl catalysts were employed for the activation of a primary alcohol, ethanol, for the hydrogenation 5‐hydroxymethylfurfual (HMF) to 2,5‐bis(hydroxymethyl)furan (BHMF) under a mild condition. The catalysts were extensively characterized to reveal the structure characteristics and surface compositions. Over 90 % yield of BHMF were obtained over the optimal CuZnAl‐0.5 catalyst at the reaction temperatures of 100–120 °C. Reaction kinetics indicated a competitive adsorption between HMF and ethanol on the catalyst surface, with the activation of ethanol being the rate‐determining step (apparent activation energy Ea=70.9 kJ mol−1). Preliminary adsorption investigation using combined attenuated total reflectance infrared spectroscopy and density functional theory calculation proposed a η2‐(O,O)‐aldehyde, furoxy perpendicular configuration of HMF on catalyst surface. The catalyst was further applied to the CTH of various aldehydes to the corresponding alcohols with high yields, demonstrating the broad applicability of the current system.
Lignin as Polymer Electrolyte Precursor for Stable and Sustainable Potassium Batteries
Authors: Trano Sabrina , Corsini Francesca , Pascuzzi Giuseppe , Giove Elisabetta , Fagiolari Lucia , Amici Julia , Francia Carlotta , Turri Stefano , Bodoardo Silvia , Griffini Gianmarco , Bella Federico 
Published: April 2022

AbstractPotassium batteries show interesting peculiarities as large‐scale energy storage systems and, in this scenario, the formulation of polymer electrolytes obtained from sustainable resources or waste‐derived products represents a milestone activity. In this study, a lignin‐based membrane is designed by crosslinking a pre‐oxidized Kraft lignin matrix with an ethoxylated difunctional oligomer, leading to self‐standing membranes that are able to incorporate solvated potassium salts. The in‐depth electrochemical characterization highlights a wide stability window (up to 4 V) and an ionic conductivity exceeding 10−3 S cm−1 at ambient temperature. When potassium metal cell prototypes are assembled, the lignin‐based electrolyte attains significant electrochemical performances, with an initial specific capacity of 168 mAh g−1 at 0.05 A g−1 and an excellent operation for more than 200 cycles, which is an unprecedented outcome for biosourced systems in potassium batteries.
Cortical atrophy and amyloid and tau deposition in Down syndrome: A longitudinal study
Authors: Padilla Concepcion , Montal Victor , Walpert Madeleine J. , Hong Young T. , Fryer Tim D. , Coles Jonathan P. , Aigbirhio Franklin I. , Hartley Sigan L. , Cohen Ann D. , Tudorascu Dana L , Christian Bradley T. , Handen Benjamin L. , Klunk William E. , Holland Anthony J. , Zaman Shahid H. 
Published: April 2022

AbstractIntroduction: The Down syndrome population has a high prevalence for dementia, often showing their first clinical symptoms in their 40s. Methods: In a longitudinal cohort, we investigate whether amyloid deposition at time point 1 (TP1) could predict cortical thickness change at time point 2 (TP2). The association between tau burden and cortical thickness was also examined at time point 3 (TP3). Results: Between TP1 and TP2 there was pronounced cortical thinning in temporo‐parietal cortices and cortical thickening in the frontal cortex. Baseline amyloid burden was strongly associated to cortical thinning progression, especially in the temporo‐parietal regions. At TP3, tau deposition negatively correlated with cortical atrophy in regions where tau usually accumulates at later Braak stages. Discussion: A higher amount of amyloid accumulation triggers a cascade of changes of disease‐causing processes that eventually lead to dementia. As expected, we found that regions where tau usually accumulates were those also displaying high levels of cortical atrophy.
Phenology and production of pollen, nectar, and sugar in 1612 plant species from various environments
Authors: Filipiak Michał , Walczyńska Aleksandra , Denisow Bożena , Petanidou Theodora , Ziółkowska Elżbieta 
Published: April 2022

AbstractTo predict the quantity and quality of food available to pollinators in various landscapes over time, it is necessary to collect detailed data on the pollen, nectar, and sugar production per unit area and the flowering phenology of plants. Similar data are needed to estimate the contribution of plants to the functioning of food webs via the flow of energy and nutrients through the soil–plant‐nectar/pollen‐consumer pathway. Current knowledge on this topic is fragmented. This database represents the first compilation of data on the various food resources produced by 1612 plant species belonging to 755 genera and 133 families, including crop plants and wild plants, annuals and perennials, animal‐ and wind‐pollinated plants, and weeds and trees growing in different ecosystems under various environmental conditions. The data set consists of 103 parameters related to the traits of plant species and geographical and environmental factors, allowing for precise calculations of the amounts of nectar, pollen, and energy provided by plants and available to consumers in the considered flora or ecosystem on a daily basis throughout the year. These parameters, gathered by us and extracted from the available literature, describe pollen, nectar, and sugar production (where applicable, in mass, volume, and concentration units), honey yield, the timing and duration of flowering, flower longevity, number of plants and flowers per unit area, weather conditions (temperature and precipitation), geographical location, landscape, and syntaxonomy. The data were obtained from various, mostly European, pedoclimatic zones, and the majority of the data were available for plant species and communities present in Central Europe, especially in Poland, where research on floral resources has a long tradition. These data are representative of the whole continent and may be used as a reference for plant communities occurring on continents other than Europe since the database allows for the consideration of differences in the production of resources by a single plant species growing in different communities. This data set provides a unique opportunity to test hypotheses related to the functioning of food webs, nutrient cycling, plant ecology, and pollinator ecology and conservation. The data are released under a CC‐BY‐NC‐SA license, and this paper must be properly cited when using the database.