bluuebunny/crossref_metadata_2025_split huggingface dataset:
Can Laminated Carbon Challenge Gold? Toward Universal, Scalable, and Low‐Cost Carbon Electrodes for Perovskite Solar Cells
Authors: Sepalage Gaveshana A. , Weerasinghe Hasitha , Rai Nitish , Duffy Noel W. , Raga Sonia R. , Hora Yvonne , Gao Mei , Vak Doojin , Chesman Anthony S. R. , Bach Udo , Simonov Alexandr N. 
Published: November 2021

AbstractWhile perovskite solar cell (PSC) efficiencies are soaring at a laboratory scale, these are most commonly achieved with evaporated gold electrodes, which would present a significant expense in large‐scale production. This can be remedied through the use of significantly cheaper carbon electrodes that, in contrast to metals, also do not migrate through the device. To this end, the present work investigates simple‐to‐prepare aluminum‐supported carbon electrodes derived from commercially available, inexpensive materials that can be applied onto various hole‐transporting materials and enable photovoltaic performances on par with those provided by gold electrodes. Successful integration of the new carbon‐based electrode into flexible devices produced by a roll‐to‐roll printing technology by both pressing and lamination is demonstrated. However, temperature cycling durability tests reveal that the use of carbon electrodes based on commercial pastes is hindered by incompatibility of adhesive additives with the key components of the PSCs under heating. Resolving this issue, tailor‐made graphite electrodes devoid of damaging additives are introduced, which improve the PSC stability under temperature cycling test protocol to the level provided by benchmark gold electrodes. The study highlights current challenges in developing laminated carbon electrodes in PSCs and proposes strategies toward the resolution thereof.
Integrated metal–organic framework and pressure/vacuum swing adsorption process design: Descriptor optimization
Authors: Zhang Xiang , Zhou Teng , Sundmacher Kai 
Published: November 2021

AbstractAn integrated metal–organic framework (MOF) and pressure/vacuum swing adsorption (P/VSA) process design framework is presented for gas separation. It consists of two steps: adsorbent descriptor optimization, and MOF matching. In the first step, MOFs are represented as a large set of chemical and geometric descriptors from which the most influential ones are selected via a multistep screening method and treated as design variables. The valid design space of the selected descriptors is confined using a tailored classifier model and logic constraints. Based on collected adsorption isotherms of 471 different MOFs, data‐driven isotherm models are developed. Combining the design space, isotherms, and four‐step P/VSA process models, an integrated MOF and P/VSA process design problem is formulated. MOF descriptors and process operating conditions are optimized to maximize the process performance. The obtained optimal descriptors and isotherms can be used to guide the discovery of high‐performance MOFs in a subsequent MOF matching step. This article addresses the first descriptor optimization step exemplified by propene/propane separation.
Passive Harmonic Mode‐Locked Erbium‐Doped Fiber Laser Based on ZrTe3 Nanoparticle‐Based Saturable Absorber
Authors: Hui Zhanqiang , Shen Niping , Wang Yuanhong , Han Dongdong , Li Tiantian , Zhou Hua , Gong Jiamin 
Published: November 2021

Abstract2D layer‐structured nanomaterials have attracted much attention owing to their excellent optical, electrical, and magnetic properties. In this study, a novel 2D zirconium tritelluride (ZrTe3) nanosheet material is prepared. The nonlinear saturated absorption characteristics of the ZrTe3 nanosheets are studied using the double‐equilibrium detection method. The saturation intensity and modulation depth are 100.6 MW cm−2 and 3.3%, respectively. A saturable absorber (SA) based on ZrTe3 is used in a harmonic passive mode‐locking erbium‐doped fiber laser for the first time. The results show that when the pump power is 50 mW, mode‐locking with a fundamental frequency of 5.82 MHz is achieved. The pulse width, center wavelength, 3 dB bandwidth, and signal‐to‐noise ratio (SNR) are 1.44 ps, 1563.7 nm, 2.31 nm, and 76 dB, respectively. With an increase in pump power, a high repetition rate of 483.1 MHz, corresponding to the 83‐order harmonic mode‐locked, is obtained at a pump power of 310 mW. The pulse width, 3 dB optical spectral width, and SNR are 1.302 ps, 3.14 nm, and 67 dB, respectively. This reveals that ZrTe3 nanosheets are excellent photonic materials that can be used to generate high‐repetition‐rate pulse lasers and have great application potential in ultrafast photonics.
Accessing Unsymmetrically Linked Heterocycles through Stereoselective Palladium‐Catalyzed Domino Cyclization
Authors: Arora Ramon , Rodríguez José F. , Whyte Andrew , Lautens Mark 
Published: November 2021

AbstractA palladium‐catalyzed strategy is presented to synthesize unsymmetrically linked heterocycles within stereoselective tetrasubstituted olefins. This reaction is proposed to occur via a vinyl‐PdII intermediate capable of initiating the cyclization of various alkyne‐tethered nucleophiles. Products are formed in up to 96 % yield and excellent stereoselectivities are obtained using low catalyst loadings. This transformation was scalable up to 1 mmol and mechanistic studies suggest a syn‐carbopalladation of the carbamoyl chloride followed by PdII‐catalyzed cyclization of alkyne‐tethered nucleophiles.
Concurrent Prebiotic Formation of Nucleoside‐Amidophosphates and Nucleoside‐Triphosphates Potentiates Transition from Abiotic to Biotic Polymerization
Authors: Lin Huacan , Jiménez Eddy I. , Arriola Joshua T. , Müller Ulrich F. , Krishnamurthy Ramanarayanan 
Published: November 2021

AbstractPolymerization of nucleic acids in biology utilizes 5′‐nucleoside triphosphates (NTPs) as substrates. The prebiotic availability of NTPs has been unresolved and other derivatives of nucleoside‐monophosphates (NMPs) have been studied. However, this latter approach necessitates a change in chemistries when transitioning to biology. Herein we show that diamidophosphate (DAP), in a one‐pot amidophosphorylation‐hydrolysis setting converts NMPs into the corresponding NTPs via 5′‐nucleoside amidophosphates (NaPs). The resulting crude mixture of NTPs are accepted by proteinaceous‐ and ribozyme‐polymerases as substrates for nucleic acid polymerization. This phosphorylation also operates at the level of oligonucleotides enabling ribozyme‐mediated ligation. This one‐pot protocol for simultaneous generation of NaPs and NTPs suggests that the transition from prebiotic‐phosphorylation and oligomerization to an enzymatic processive‐polymerization can be more continuous than previously anticipated.
Cobalt‐Catalysed Asymmetric Addition and Alkylation of Secondary Phosphine Oxides for the Synthesis of P‐Stereogenic Compounds
Authors: Wu Zeng‐Hua , Cheng An‐Qi , Yuan Meng , Zhao Ya‐Xuan , Yang Huai‐Lan , Wei Li‐Hua , Wang Huai‐Yu , Wang Tao , Zhang Zunting , Duan Wei‐Liang 
Published: November 2021

AbstractThe catalytic asymmetric synthesis of P‐chiral phosphorus compounds is an important way to construct P‐chiral ligands. Herein, we report a new strategy that adopts the pyridinyl moiety as the coordinating group in the cobalt‐catalysed asymmetric nucleophilic addition/alkylation of secondary phosphine oxides. A series of tertiary phosphine oxides were generated with up to 99 % yield and 99.5 % ee, and with broad functional‐group tolerance. Mechanistic studies reveal that (R)‐secondary phosphine oxides preferentially interact with the cobalt catalysts to produce P‐stereogenic compounds.
Solid‐Phase‐Supported Chemoenzymatic Synthesis of a Light‐Activatable tRNA Derivative
Authors: Blümler Anja , Schwalbe Harald , Heckel Alexander 
Published: November 2021

AbstractHerein, we present a multi‐cycle chemoenzymatic synthesis of modified RNA with simplified solid‐phase handling to overcome size limitations of RNA synthesis. It combines the advantages of classical chemical solid‐phase synthesis and enzymatic synthesis using magnetic streptavidin beads and biotinylated RNA. Successful introduction of light‐controllable RNA nucleotides into the tRNAMet sequence was confirmed by gel electrophoresis and mass spectrometry. The methods tolerate modifications in the RNA phosphodiester backbone and allow introductions of photocaged and photoswitchable nucleotides as well as photocleavable strand breaks and fluorophores.
Five‐Fold Symmetric Pentaindolo‐ and Pentakis(benzoindolo)Corannulenes: Unique Structural Dynamics Derived from the Combination of Helical and Bowl Inversions
Authors: Kise Koki , Ooi Shota , Saito Hayate , Yorimitsu Hideki , Osuka Atsuhiro , Tanaka Takayuki 
Published: November 2021

AbstractPeripherally π‐extended corannulenes bearing quintuple azahelicene units, 10 and 11, were prepared and their dynamic behaviors were studied experimentally and theoretically. The fused corannulenes were synthesized from sym‐pentabromocorannulene in three steps. X‐Ray diffraction analysis for 10 displayed a conformer possessing a P(M) bowl chirality and a PPMPM (PMPMM) helical chirality, which was found to be the most stable conformer(s). Variable‐temperature NMR measurements of 10 and 11 revealed that their structural isomers can be interconvertible in solution, depending on the steric congestion around the helical scaffolds. Automated search for conformers in the equilibrium and transition states by Artificial Force Induced Reaction (AFIR) method revealed their interconversion networks, including bowl‐inversion and helical‐inversion. This analysis indicated that the co‐existing corannulene and azahelicene moieties influence the conformational dynamics, which leads to mitigation of the activation energy barriers for isomerization.
A Selective and General Cobalt‐Catalyzed Hydroaminomethylation of Olefins to Amines
Authors: Yang Ji , Delolo Fábio G. , Spannenberg Anke , Jackstell Ralf , Beller Matthias 
Published: November 2021

AbstractA new cobalt catalyst is presented for the domino hydroformylation‐reductive amination reaction of olefins. The optimal Co‐tert‐BuPy‐Xantphos catalyst shows good to excellent linear‐to‐branched (n/iso) regioselectivity for the reactions of aliphatic alkenes with aromatic amines under mild conditions. This system is far more selective than traditional cobalt(I) catalysts and even better than most known rhodium catalysts.
Effective chiral pool synthesis of both enantiomers of the TRPML inhibitor trans‐ML‐SI3
Authors: Kriegler Katharina , Leser Charlotte , Mayer Peter , Bracher Franz 
Published: November 2021

AbstractTwo independent chiral pool syntheses of both enantiomers of the TRPML inhibitor, trans‐ML‐SI3, were developed, starting from commercially available (1S,2R)‐ and (1R,2S)‐configured cis‐2‐aminocyclohexanols. Both routes lead to the target compounds in excellent enantiomeric purity and good overall yields. For the most attractive (−)‐trans‐enantiomer, the R,R‐configuration was identified by these unambiguous syntheses, and the results were confirmed by single‐crystal X‐ray structure analysis. These effective synthetic approaches further allow flexible variation of prominent residues in ML‐SI3 for future in‐depth analysis of structure–activity relationships as both the piperazine and the N‐sulfonyl residues are introduced into the molecule at late stages of the synthesis.
Confined Cobalt on Carbon Nanotubes in Solvent‐free Aerobic Oxidation of Ethylbenzene: Enhanced Interfacial Charge Transfer
Authors: Su Yongzhao , Chen Zhicheng , Huang Jiangnan , Wang Hongjuan , Yu Hao , Zhang Qiao , Cao Yonghai , Peng Feng 
Published: November 2021

AbstractAerobic oxidation of hydrocarbons yielding corresponding oxygenated products is one of the most important chemical processes. In current work, carbon nanotubes supported encapsulated cobalt nanoparticles with carbon layers (Co@C/CNTs) were synthesized and utilized as catalysts in the oxidation of ethylbenzene (EB) in the liquid phase, exhibiting high catalytic performance. The synergistic effect between Co@C and CNTs played the vital role on facilitating the decomposition of peroxides to enhance the overall activity. The inadequate covered Co@C on CNTs surface were considered as catalytic sites. Density functional theory revealed that the exist of Co nanoparticles could improve the interaction between the catalyst and intermediate free radicals, which were significant for EB oxidation. Last but not least, the electron transfer on carbon surface was enhanced by the incorporation of Co@C nanoparticles, which greatly improved the catalytic performance on EB oxidation. This study provides a new insight into the Co‐based catalysts in the aerobic oxidation of hydrocarbons.
Nickel(II)‐Catalyzed Selective(E)‐Olefination of Methyl Heteroarenes Using Benzyl Alcohols via Acceptorless Dehydrogenative Coupling Reaction
Authors: Balamurugan Gunasekaran , Ramesh Rengan 
Published: November 2021

AbstractAn efficient catalytic protocol for the synthesis of selective(E)‐olefins by the newly synthesized nickel complexes via greener acceptorless dehydrogenative coupling methodology is presented. Two nickel(II) N, S chelating complexes were structurally characterized with the aid of spectral and single crystal X‐ray diffraction methods. Olefination of 2‐methylheteroarenes with benzyl alcohols via acceptorless dehydrogenative coupling is achieved by inexpensive nickel(II) catalysts. The present olefination protocol is simple and furnishes the desired 2‐alkenylheteroarenes in 35 h and yields in the range of 40–93 %. The dehydrogenative coupling reaction proceeds via the generation of an aldehyde intermediate and produces water and hydrogen as sole by‐products. The wide substrate scope of this catalytic reaction covered the synthesis of drug intermediates.
Ring Size Determines the Conformation, Global Aromaticity and Photophysical Properties of Macrocyclic Oligofurans
Authors: Dishi Or , Malakar Partha , Shimon Linda J. W. , Ruhman Sanford , Gidron Ori 
Published: November 2021

AbstractIn π‐conjugated macrocycles, there is a trade‐off between the global and local expression of effects such as aromaticity, with the outcome of the trade‐off determined by the geometry and aromaticity of the constituent units. Compared with other aromatic rings, the aromatic character of furan is relatively small, and therefore global effects in macrocyclic furans are expected to be more pronounced. Following our introduction of macrocyclic oligofuran, we present the first synthesis of a series of π‐conjugated bifuran macrocycles of various ring sizes, from trimer to hexamer, and characterize them using both computational and experimental methods. The properties of macrocyclic oligofurans change considerably with size: The smaller trimer is rigid, weakly emissive and planar as revealed by its single crystal structure, and displays global antiaromaticity. In contrast, the larger pentamer and hexamer are flexible, emissive, have non‐planar structures, and exhibit local aromaticity. The results are supported by NICS and ACID calculations that indicate the global antiaromaticity of planar furan macrocycles, and by transient absorption measurements showing sharp absorption band for the trimer and only the internal conversion decay pathway.
Les rapports de responsabilité sociétale: Une étude des pratiques Canadiennes
Authors: Coulmont Michel , Berthelot Sylvie , Martineau Félix 
Published: November 2021

AbstractThe aim of this study is to identify the performance indicators that Canadian corporations voluntarily disclose based on the Global Reporting Initiative (GRI) and to examine their comparability. The results tend to show that all the companies studied disclose few indicators and that the format of these indicators makes comparisons impossible. Additional analyses revealed that while a minority of companies publish some indicators, the vast majority (91%) disclose poor quality information. Accordingly, the companies' strategy appears to be to muddy the waters than actually account for their performance.
Regioselective β‐Trifluoromethylation of β‐Silylporphyrins by Using a Trifluoromethyl Copper Complex
Authors: Hayashi Satoshi , Okamoto Akari , Nabekura Ryoto , Noji Masahiro , Takanami Toshikatsu 
Published: November 2021

AbstractWe developed a method for the regioselective β‐trifluoromethylation of β‐silylated Zn(II) porphyrins by using a phenanthroline and triphenylphosphine‐ligated trifluoromethyl–copper complex [(phen)(Ph3P)CuCF3]. The regioselective porphyrin trifluoromethylation, which occurs under mild conditions, exhibits excellent substrate generality and functional group compatibility.
N‐Thiocyanato‐2,10‐camphorsultam Derivatives: Design and Applications of Original Electrophilic Thiocyanating Reagents
Authors: Gao Mélissa , Vuagnat Martin , Jubault Philippe , Besset Tatiana 
Published: November 2021

AbstractThe synthesis of bench‐stable electrophilic thiocyanating reagents was depicted in two steps from readily available starting materials in good yields. These newly designed electrophilic reagents were successfully applied for the thiocyanation of different nucleophiles under mild and transition metal‐free conditions. Preliminary experiments for the asymmetric C3‐thiocyanation of an oxindole derivative were also conducted leading to the expected product with no induction of chirality, although opening possibilities for accessing chiral compounds.
Specific age‐correlated activation of top hierarchical motor control areas during gait‐like plantar stimulation: An fMRI study
Authors: Jeanvoine Henry , Labriffe Matthieu , Tannou Thomas , Navasiolava Nastassia , Ter Minassian Aram , Girot Jean‐Baptiste , Leiber Louis‐Marie , Custaud Marc‐Antoine , Annweiler Cédric , Dinomais Mickaël 
Published: November 2021

AbstractA better understanding of gait disorders that are associated with aging is crucial to prevent adverse outcomes. The functional study of gait remains a thorny issue due to technical constraints inherent to neuroimaging procedures, as most of them require to stay supine and motionless. Using an MRI‐compatible system of boots reproducing gait‐like plantar stimulation, we investigated the correlation between age and brain fMRI activation during simulated gait in healthy adults. Sixty‐seven right‐handed healthy volunteers aged between 20 and 77 years old (49.2 ± 18.0 years; 35 women) were recruited. Two paradigms were assessed consecutively: (a) gait‐like plantar stimulation and (b) chaotic and not gait‐related plantar stimulation. Resulting statistical parametric maps were analyzed with a multiple‐factor regression that included age and a threshold determined by Monte‐Carlo simulation to fulfill a family‐wise error rate correction of p < .05. In the first paradigm, there was an age‐correlated activation of the right pallidum, thalamus and putamen. The second paradigm showed an age‐correlated deactivation of both primary visual areas (V1). The subtraction between results of the first and second paradigms showed age‐correlated activation of the right presupplementary motor area (Brodmann Area [BA] 6) and right mid‐dorsolateral prefrontal cortex (BA9‐10). Our results show age‐correlated activity in areas that have been associated with the control of gait, highlighting the relevance of this simulation model for functional gait study. The specific progressive activation of top hierarchical control areas in simulated gait and advancing age corroborate a progressive loss of automation in healthy older adults.
Inflammatory bowel diseases in Tamil Nadu: A survey of demographics, clinical profile, and practices
Authors: Yewale Rohan V , Natarajan Kartik , Ubal Dhus Jeyaraj , Parameswaran Sarojini Ashok , Ramaswamy Palaniswamy Kallipatti , Babu Vinish Doraisamy , Somasundaram Aravindh , Ramakrishnan Arulraj , Karmegam Sibithooran , Arun Ramaswamy Saraswathy , Manmohan Ujjani Shankaraiah , Mahadevan Balakrishnan , Harri Prasad Baskkaran , Chandrasekar Toguluva Seshadri , Gokul Bollu Janakan , Dutta Amit , Joseph Anjilivelil Joseph , Venkatraman Jayanthi , Ganesh Panchapakesan , Shanmuganathan Subramanyam , Alagammai Palaniappan L , Ramasubramanian Ramalingam , Venkatakrishnan Leelakrishnan , Ganesan Ramamoorthi , Chandrasekaran Arun Arunachalam , Srinivas Sankaranarayanan , Kannan Mariappan , Revathy M Shanmugam , Sathiyasekaran Malathi , Sarangapani Arulprakash , Rajesh Natrajan , Arulselvan Velusamy , Aravind Arumugam , Premkumar Karunakaran , Kavitha Sampath , Varadarajulu Hema Vijayalakshmi , Manimaran Murugesan , Basumani Pandurangan , Murali Ananthavadivelu , Ramakrishna Balakrishnan Siddartha 
Published: November 2021

AbstractBackgroundInflammatory bowel disease (IBD) is increasingly diagnosed in South Asia. This survey by the Tamil Nadu Chapter of the Indian Society of Gastroenterology (TNISG) documents the demography, clinical profile, and therapeutic practices related to IBD in Tamil Nadu.MethodsTNISG members from 32 institutions completed an online cross‐sectional questionnaire on IBD patients from March 2020 to January 2021.ResultsOf 1295 adult IBD patients, 654 had Crohn's disease (CD), 499 ulcerative colitis (UC), and 42 IBD‐unclassified (IBD‐U). CD and UC showed a unimodal age distribution. A total of 55% were graduates or postgraduates. A positive family history was noted in 30, other risk factors were uncommon. In CD, the pattern of involvement was ileocolonic (42.8%), ileal (34.7%), colonic (18.9%), and upper gastrointestinal (3.5%); while in UC, disease was characterized as extensive (44.9%), left‐sided (41.7%), or proctitis (13.4%). Perineal disease, perianal fistulae, and bowel obstruction were noted in 4.3, 14.0, and 23.5%, respectively, of CD. The most widely used drugs were mesalamine, azathioprine, and corticosteroids. Surgery was undertaken in 141 patients with CD and 23 patients with UC. Of the 138 patients with pediatric IBD (≤16 years), 23 were characterized as very early onset IBD (VEO‐IBD), 27 as early‐onset, and 88 as adolescent IBD. VEO‐IBD were more likely to have a positive family history of IBD and were more likely to have perineal disease and to have the IBD‐U phenotype. Among pediatric IBD patients, corticosteroids, mesalamine, and azathioprine were the most commonly used medications, while 25 pediatric patients received biologics.ConclusionThis study provides important information on demography, clinical profile, and treatment practices of IBD in India.