bluuebunny/crossref_metadata_2025_split huggingface dataset:
Quasi‐Solid Electrolyte Design and In Situ Construction of Dual Electrolyte/Electrode Interphases for High‐Stability Zinc Metal Battery
Authors: Guo Shan , Qin Liping , Hu Chao , Li Lanyan , Luo Zhigao , Fang Guozhao , Liang Shuquan 
Published: May 2022

AbstractInterfacial stability and compatibility in rechargeable metal batteries (RMBs) is still made difficult by deterioration under electrochemical dynamic operation due to the activeness of the metallic anodes and their spontaneous reaction with the liquid electrolyte. Herein, robust quasi‐solid zinc metal batteries enabled by in situ formation of stable dual electrolyte/electrode interphases with an electrochemical stability during cycling are reported. The quasi‐solid electrolyte sufficiently transfers the zinc ions due to the construction of the unobstructed ions transportation network composed of intergranular liquid phase migration and interlayer diffusion. The distinctive in situ formation of dual interphases, specially with heterojunction charge aggregation, cleverly settles the issues of interfacial compatibility, which achieves a stable Zn2+ plating/stripping of more than 3000 h and far exceeding the transient 250 h of its liquid counterpart. This design strategy for quasi‐solid electrolytes is expected to advance the development of the quasi‐solid battery field.
Diagnostic distribution and postnatal evaluation of prenatally detected short femur: A single center experience
Authors: Kahraman Ayca Burcu , Simsek‐Kiper Pelin Ozlem , Utine Gulen Eda , Boduroglu Koray 
Published: May 2022

AbstractGenetic skeletal disorders (GSDs) are clinically and etiologically heterogeneous group of disorders caused by abnormal growth and development of bone and/or cartilaginous tissues. Timely and accurate diagnosis is essential for prevention of significant comorbidities. In this study demographic, parental, prenatal and natal characteristics, and postnatal diagnostic distribution along with follow‐up processes of 104 individuals with the finding of “short femur” detected in routine prenatal ultrasonography were evaluated. Of 104 patients, 19 (18.2%) were medically terminated, 12 (11.6%) were deceased during follow‐up and 73 (70.2%) were still under follow‐up. Diagnostic distribution of 104 patients was as follows: 77 (74%) had GSD, eight (7.7%) had chromosomal disorder, seven (6.7%) were completely normal, and 12 (11.5%) had no definite diagnosis. Long‐term follow up evaluation contributed to clinical diagnosis in four patients. When grouped according to Nosology and Classification of GSDs: 2019 revision, the most frequent (n = 30, 38.5%) group was “FGFR3 chondrodysplasia group”, followed by “Type 2 collagen group” (n = 7, 9%), and “Osteogenesis imperfecta and decreased bone density group” (n = 5, 6.4%). The finding of prenatally detected “short femur” represents a group of diverse diagnosis with heterogeneous etiology. GSDs are the most common etiology among fetuses with short extremity.
Engineering Aptamers with Selectively Enhanced Biostability in the Tumor Microenvironment
Authors: Xie Sitao , Wang Zhimin , Fu Ting , Zheng Liyan , Wu Hui , He Lei , Huang Huidong , Yang Cai , Wang Ruowen , Qian Xu , Qiu Liping , Tan Weihong 
Published: May 2022

AbstractAptamers are emerging as promising molecular tools in cancer‐targeted theranostics. Improving their in vivo stability has been a critical issue in promoting clinical translation, but such efforts could lead to more serious side effects resulting from prolonged retention in healthy organs. To address this problem, we developed an environment‐responsive stabilization strategy for the selective enhancement of aptamer biostability in the tumor microenvironment (TME). Briefly, by means of the end extension of an ATP‐responsive protection (ARP) module, the designed aptamer could be protected from nuclease degradation through the specific incorporation of ATP. Based on our in vivo results, this ARP‐aptamer probe was effectively accumulated in tumors via aptamer‐based molecular recognition. It showed selectively prolonged tumor retention time, but rapid digestion in healthy organs. Our strategy should provide a new paradigm for the development of organ‐specific nucleic acid‐based imaging and therapeutic agents.
Chiral Multi‐Resonance TADF Emitters Exhibiting Narrowband Circularly Polarized Electroluminescence with an EQE of 37.2 %
Authors: Yang Yiyu , Li Nengquan , Miao Jingsheng , Cao Xiaosong , Ying Ao , Pan Ke , Lv Xialei , Ni Fan , Huang Zhongyan , Gong Shaolong , Yang Chuluo 
Published: May 2022

AbstractHighly efficient circularly polarized luminescence (CPL) emitters with narrowband emission remain a formidable challenge for circularly polarized OLEDs (CP‐OLEDs). Here, a promising strategy for developing chiral emitters concurrently featuring multi‐resonance thermally activated delayed fluorescence (MR‐TADF) and circularly polarized electroluminescence (CPEL) is demonstrated by the integration of molecular rigidity, central chirality and MR effect. A pair of chiral green emitters denoted as (R)‐BN‐MeIAcand (S)‐BN‐MeIAcis designed. Benefited by the rigid and quasi‐planar MR‐framework, the enantiomers not only display mirror‐image CPL spectra, but also exhibit TADF properties with a high photoluminescence quantum yield of 96 %, a narrow FWHM of 30 nm, and a high horizontal dipole orientation of 90 % in the doped film. Consequently, the enantiomer‐based CP‐OLEDs achieved excellent external quantum efficiencies of 37.2 % with very low efficiency roll‐off, representing the highest device efficiency of all the reported CP‐OLEDs.
High‐Performance Zeolitic Hollow‐Fiber Membranes by a Viscosity‐Confined Dry Gel Conversion Process for Gas Separation
Authors: Yang Shaowei , Min Byunghyun , Fu Qiang , Jones Christopher W. , Nair Sankar 
Published: May 2022

AbstractZeolite membranes show great potential for gas and hydrocarbon separations, but high manufacturing cost has been one of the main hurdles in their industrial application. Here we demonstrate a method termed viscosity‐confined dry gel conversion (VCDGC) for zeolite hollow fiber membrane fabrication. We demonstrate in detail the VCDGC synthesis of small‐pore CHA zeolite membranes. Extensive permeation measurements reveal that dry gel‐processed CHA zeolite hollow fiber membranes have excellent gas and hydrocarbon separation characteristics well exceeding or comparable to current membranes. Medium‐pore MFI membranes are also fabricated, and their favorable hydrocarbon separation characteristics indicate the versatility and reliability of the VCDGC method.
Biocatalytic Enantioselective β‐Hydroxylation of Unactivated C−H Bonds in Aliphatic Carboxylic Acids
Authors: Zhang Kun , Yu Aiqin , Chu Xuan , Li Fudong , Liu Juan , Liu Lin , Bai Wen‐Ju , He Chao , Wang Xiqing 
Published: May 2022

AbstractCatalytic selective hydroxylation of unactivated aliphatic (sp3) C−H bonds without a directing group represents a formidable task for synthetic chemists. Through directed evolution of P450BSβ hydroxylase, we realize oxyfunctionalization of unactivated C−H bonds in a broad spectrum of aliphatic carboxylic acids with varied chain lengths, functional groups and (hetero‐)aromatic moieties in a highly chemo‐, regio‐ and enantioselective fashion (>30 examples, Cβ/Cα>20 : 1, >99 % ee). The X‐ray structure of the evolved variant, P450BSβ‐L78I/Q85H/G290I, in complex with palmitic acid well rationalizes the experimentally observed regio‐ and enantioselectivity, and also reveals a reduced catalytic pocket volume that accounts for the increased reactivity with smaller substrates. This work showcases the potential of employing a biocatalyst to enable a chemical transformation that is particularly challenging by chemical methods.
Sigmatrope [1,5]‐Kohlenstoffverschiebung transienter C3‐Ammoniumenolate
Authors: Wicker Garrit , Zhou Rundong , Schoch Roland , Paradies Jan 
Published: May 2022

AbstractDie stereospezifische [1,5]‐Kohlenstoffverschiebung der C3‐Ammoniumenolate wird beschrieben. Gemäß mechanistischen, kinetischen und rechnergestützten Experimenten verläuft die neuartige Umlagerung über ein transientes C3‐Ammoniumenolat. Dies wird durch eine katalysierte intramolekulare Aza‐Michael‐Addition erzeugt. Die anschließende [1,5]‐sigmatrope Kohlenstoffmigration bildet die entsprechenden Tetrahydrochinolin‐4‐one in 61–98 % Ausbeute und mit exzellenten Diastereoselektivitäten von d.r. >99 : 1.
Total Synthesis of Parameritannin A2, a Branched Epicatechin Tetramer with Two Double Linkages
Authors: Betkekar Vipul V. , Suzuki Keisuke , Ohmori Ken 
Published: May 2022

AbstractThe first total synthesis of parameritannin A2 (1), a branched epicatechin (EC) tetramer is reported. The “phloroglucinol trick” was used to circumvent two synthetic issues encountered when assembling four EC units, namely, the steric constraint and the formation of the C4−C6 interflavan linkage. As a substructure of the middle EC unit, phloroglucinol enabled the single‐step assembly of two EC units (top and side) through A‐type linkages. The middle EC unit was constructed by conducting a newly developed three‐carbon flavan annulation via a Pummerer/Friedel–Crafts cascade reaction to furnish a trimeric intermediate bearing a thio‐leaving group at C4 position, which allowed the final installation of the bottom EC unit.
Cobalt Silylenes as Platforms for Catalytic Nitrene‐Group Transfer by Metal–Ligand Cooperation.
Authors: Whited Matthew T. , Han Wenlai , Jin‐Lee Helen J. , DiNardo Zach , Watson Emma , Zhang Jia , Kohen Daniela 
Published: May 2022

AbstractA cobalt silylene (Co=Si) linkage enables a distinct metal/ligand cooperative activation of an organic azide, where nitrene transfer occurs to and from the Co⋅⋅⋅Si linkage without ligand dissociation from the 18‐electron cobalt center. This process utilizes the orthogonal binding affinities of the silicon and cobalt sites to avoid CO poisoning that would otherwise inhibit reactivity, leading to significantly improved catalytic isocyanate generation compared with related systems. The dual‐site approach demonstrates the potential of metal/main‐group bonds to access new and efficient catalytic pathways.
Structural Origin of Enhanced Circularly Polarized Luminescence in Hybrid Manganese Bromides
Authors: Chen Jian , Zhang Shuai , Pan Xin , Li Ruiqian , Ye Shi , Cheetham Anthony K. , Mao Lingling 
Published: May 2022

AbstractChiral hybrid metal halides with a high dissymmetry factor (glum) and a superior photoluminescence quantum yield (PLQY) are promising candidates for circularly polarized luminescence (CPL) light sources. Here, we report eight new chiral hybrid manganese halides, crystallizing in the non‐centrosymmetric space group P212121 and showing intense CPL emissions. Oppositely‐signed circular dichroism (CD) and CPL signals are detected according to the R‐ and S‐configurations of the chiral alkanolammonium cations. Time‐resolved PL spectra show long averaged decay lifetimes up to 1 ms for (R‐3‐quinuclidinol)MnBr3 (R‐1). The glum of polycrystalline samples for coordinated structures (23×10−3) is more than doubled compared with the non‐coordinated ones (8.5×10−3), due to the structural variations. R‐1 exhibit both a high glum and a high PLQY (50.2 %). The effective chirality transfer mechanism through coordination bonds, with strongly emissive MnII centers, enables a new class of high‐performance CPL materials.
Extending the π‐Skeleton of Multi‐Resonance TADF Materials towards High‐Efficiency Narrowband Deep‐Blue Emission
Authors: Lv Xialei , Miao Jingsheng , Liu Meihui , Peng Qian , Zhong Cheng , Hu Yuxuan , Cao Xiaosong , Wu Han , Yang Yiyu , Zhou Changjiang , Ma Jiazhi , Zou Yang , Yang Chuluo 
Published: May 2022

AbstractMulti‐resonance TADF (MR‐TADF) emitters are promising for high‐resolution OLEDs, but the concurrent optimization of excited‐state dynamics and color purity remains a tough challenge. Herein, three deep‐blue MR‐TADF compounds (BN1–BN3) featuring gradually enlarged ring‐fused structures and increased rigidity are accessed by lithium‐free borylation in high yields from the same precursor, with all the emitters possessing CIEy coordinates below 0.08. Structure–property investigations demonstrate a strategic improvement of the oscillator strength (fosc) and acceleration of the reverse intersystem crossing (RISC) process by extending the π‐skeleton, where BN3 realizes a maximum external quantum efficiency (EQE) of 37.6 % and reduced roll‐off, thus showing the best efficiency reported for deep‐blue TADF OLEDs. The internal regulation of the efficiency and color purity of these compounds validate the general effectiveness to achieve advanced deep‐blue narrowband emitters with higher‐order boron/nitrogen‐based MR motifs.
Enhancement of Plasmon‐Induced Photoelectrocatalytic Water Oxidation over Au/TiO2 with Lithium Intercalation
Authors: Li Hao , Wang Shengyang , Wang Mingtan , Gao Yuying , Tang Jianbo , Zhao Shengli , Chi Haibo , Zhang Pengfei , Qu Jiangshan , Fan Fengtao , Li Can 
Published: May 2022

AbstractPlasmon‐induced chemical reaction is an emerging field but its development faces huge challenges because of low quantum efficiency. Herein, we report that the solar energy conversion efficiency of Au/TiO2 in plasmon‐induced water oxidation is greatly enhanced by intercalating Li+ into TiO2. An incident photon‐to‐current efficiency as high as 2.0 %@520 nm is achieved by Au/Li0.2TiO2 in photoelectrocatalytic water oxidation, realizing a 33‐fold enhancement in photocurrent density compared with Au/TiO2. The superior photoelectrocatalytic performance is mainly ascribed to the enhanced electric conductivity and higher catalytic activity of Li0.2TiO2. Furthermore, the ultrafast transient absorption spectroscopy suggests that lithium intercalation into TiO2 could change the dynamics of hot electron relaxation in Au nanoparticles. This work demonstrates that intercalation of alkaline ions into semiconductors can promote the charge separation efficiency of the plasmonic effect of Au/TiO2.
Sigmatropic [1,5] Carbon Shift of Transient C3 Ammonium Enolates
Authors: Wicker Garrit , Zhou Rundong , Schoch Roland , Paradies Jan 
Published: May 2022

AbstractThe stereospecific sigmatropic [1,5] carbon shift of C3 ammonium enolates is discovered. According to mechanistic, kinetic and computational experiments, this new rearrangement proceeds via the catalytic generation of a transient C3 ammonium enolate by intramolecular aza‐Michael addition. This intermediate rapidly undergoes [1,5] sigmatropic carbon migration to furnish the respective tetrahydroquinoline‐4‐ones with excellent diastereoselectivities of d.r. >99 : 1 and in 61–98 % yield.
Electrical stimulation therapy and rotary jet‐spinning scaffold to treat bone defects
Authors: Meneghetti Damaris Helena , Bagne Leonardo , de Andrade Pinto Stella Aparecida , de Carvalho Zavaglia Cecilia Amelia , Amaral Maria Esméria Corezola , Esquisatto Marcelo Augusto Maretto , dos Santos Gláucia Maria Tech , de Andrade Thiago Antônio Moretti , Santamaria Milton , Caetano Guilherme Ferreira , de Aro Andrea Aparecida , Mendonça Fernanda Aparecida Sampaio 
Published: May 2022

AbstractThe combination of electrical stimulation (ES) and bone tissue engineering (BTE) has been successful in treatments of bone regeneration. This study evaluated the effects of ES combined with PCL + β‐TCP 5% scaffolds obtained by rotary jet spinning (RJS) in the regeneration of bone defects in the calvaria of Wistar rats. We used 120 animals with induced bone defects divided into 4 groups (n = 30): (C) without treatment; (S) with PCL+ β‐TCP 5% scaffold; (ES) treated with ES (10 μA/5 min); (ES + S) with PCL + β‐TCP 5% scaffold. The ES occurred twice a week during the entire experimental period. Cell viability (in vitro: Days 3 and 7) and histomorphometric, histochemical, and immunohistochemical (in vivo; Days 30, 60, and 90) analysis were performed. In vitro, ES + S increased cell viability after Day 7 of incubation. In vivo, it was observed modulation of inflammatory cells in ES therapy, which also promoted blood vessels proliferation, and increase of collagen. Moreover, ES therapy played a role in osteogenesis by decreasing ligand kappa B nuclear factor‐TNFSF11 (RANKL), increasing alkaline phosphatase (ALP), and decreasing the tartarate‐resistant acid phosphatase. The combination of ES with RJS scaffolds may be a promising strategy for bone defects regeneration, since the therapy controlled inflammation, favored blood vessels proliferation, and osteogenesis, which are important processes in bone remodeling.
Competitive Oxygen Reduction Pathways to Superoxide and Peroxide during Sodium‐Oxygen Battery Discharge
Authors: Jovanov Zarko P. , Lutz Lukas , Lozano Juan G. , Holc Conrad , Gao Xiangwen , Grimaud Alexis , Tarascon Jean‐Marie , Chen Yuhui , Johnson Lee R. , Bruce Peter G. 
Published: May 2022

AbstractThe sodium‐air battery offers a sustainable, high‐energy alternative to lithium‐ion batteries. Discharge in the cell containing glyme‐based electrolytes can lead to formation of large cubic NaO2 particles via a solution‐precipitation mechanism. While promising, high rates result in sudden death. The exact nature of the discharge product has been a matter of contention, and Na2O2 has never been directly detected in a dry glyme Na−O2 cell. If Na2O2 were to form during discharge in the Na−O2 cell it would have a detrimental impact on cell performance. Here we show that Na2O2 forms during discharge at high overpotential in the glyme‐based Na−O2 batteries. Na2O2 formation is confirmed by spectroscopic and electrochemical analysis and electron microscopy demonstrates that it results in thin insulating films at the electrode surface. The formation of these thin films results in rapid cell death during discharge, introducing an inherent chemical limitation to the Na−O2 battery.
The Dynamic Range of Acidity: Tracking Rules for the Unidirectional Penetration of Cellular Compartments
Authors: Assies Lea , Mercier Vincent , López‐Andarias Javier , Roux Aurelien , Sakai Naomi , Matile Stefan 
Published: May 2022

AbstractLabeled ammonium cations with pKa∼7.4 accumulate in acidic organelles because they can be neutralized transiently to cross the membrane at cytosolic pH 7.2 but not at their internal pH<5.5. Retention in early endosomes with less acidic internal pH was achieved recently using weaker acids of up to pKa9.8. We report here that primary ammonium cations with higher pKa10.6, label early endosomes more efficiently. This maximized early endosome tracking coincides with increasing labeling of Golgi networks with similarly weak internal acidity. Guanidinium cations with pKa13.5 cannot cross the plasma membrane in monomeric form and label the plasma membrane with selectivity for vesicles embarking into endocytosis. Self‐assembled into micelles, guanidinium cations enter cells like arginine‐rich cell‐penetrating peptides and, driven by their membrane potential, penetrate mitochondria unidirectionally despite their high inner pH. The resulting tracking rules with an approximated dynamic range of pKachange ∼3.5 are expected to be generally valid, thus enabling the design of chemistry tools for biology research in the broadest sense. From a practical point of view, most relevant are two complementary fluorescent flipper probes that can be used to image the mechanics at the very beginning of endocytosis.
Triangular Arrangement of Ferromagnetic Iron Chains in the High‐TC Ferromagnet TiFe1−xOs2+xB2
Authors: Scheifers Jan P. , Flores Justin H. , Janka Oliver , Pöttgen Rainer , Fokwa Boniface P. T. 
Published: May 2022

AbstractTransition‐metal borides (TMBs) containing Bn‐fragment (n>3) have recently gained interest for their ability to enable exciting magnetic materials. Herein, we show that the B4‐containing TiFe0.64(1)Os2.36(1)B2 is a new ferromagnetic TMB with a Curie temperature of 523(2) K and a Weiss constant of 554(3) K, originating from the chain of M3‐triangles (M=64 %Fe+36 %Os). The new phase was synthesized from the elements by arc‐melting, and its structure was elucidated by single‐crystal X‐ray diffraction. It belongs to the Ti1+xOs2−xRuB2‐type structure (space group P
2 m, no. 189) and contains trigonal‐planar B4 boron fragments [B−B distance of 1.87(4) Å] interacting with M3‐triangles [M–M distances of 2.637(8) Å and 3.0199(2) Å]. The experimental results were supported by computational calculations based on the ideal TiFeOs2B2 composition, which revealed strong ferromagnetic interactions within and between the Fe3‐triangles. This discovery represents the first magnetically ordered Os‐rich TMB, thus it will help expand our knowledge of the role of Os in low‐dimensional magnetism of intermetallics and enable the design of such materials in the future.
Sleep‐disordered breathing in heart failure patients with different etiologies
Authors: Wang Tao , Yu Fu‐Chao , Wei Qin , Xu Xuan , Xie Liang , Ding Ning , Tong Jia‐Yi 
Published: May 2022

AbstractBackgroundThe prevalence of sleep‐disordered breathing (SDB) is closely related to the severity of heart failure (HF), and the severity of HF is different in patients with HF of different etiologies.Hypothesis: This study aimed to explore the prevalence of SDB in patients with HFof different etiologies.MethodsHospitalized HF patients were consecutively enrolled. All patients underwent portable overnight cardiorespiratory polygraphy. Patients were divided into five groups according to the etiology of HF: ischemic, hypertensive, myocardial, valvular, and arrhythmic. The prevalence of SDB and clinical data was compared among the five groups.ResultsIn total, 248 patients were enrolled in this study. The prevalence of SDB in HF was 70.6%, with the prevalence of obstructive sleep apnea (OSA) at 47.6% and central sleep apnea (CSA) at 23.0%. Patients were divided into five groups: ischemic, hypertensive, myocardial, valvular, and arrhythmic. The prevalence of SDB among the five groups was 75.3%, 81.4%, 77.8%, 51.9%, and 58.5% (p = .014), respectively. The prevalence of OSA among the five groups was 42.7%, 72.1%, 36.1%, 37.0%, and 49.1% (p = .009), whereas the CSA was 32.6%, 9.3%, 41.7%, 14.8%, and 9.4% (p < .001), respectively.ConclusionsSDB is common in HF patients. The prevalence and types of SDB varied in HF with different etiologies, which may be related to the different severities of HF. SDB was highly prevalent in patients with ischemic, hypertensive, and myocardial HF. Hypertensive HF patients were mainly complicated with OSA, while myocardial HF patients were mainly complicated with CSA. Both conditions were highly prevalent in ischemic HF patients. The prevalence of SDB was relatively low in valvular and arrhythmic HF patients, and OSA was the main type.