bluuebunny/crossref_metadata_2025_split huggingface dataset:
Pressure‐Tuning Photothermal Synergy to Optimize the Photoelectronic Properties in Amorphous Halide Perovskite Cs3Bi2I9
Authors: Li Zonglun , Jia Binxia , Fang Sixue , Li Quanjun , Tian Fuyu , Li Haiyan , Liu Ran , Liu Yucheng , Zhang Lijun , Liu Shengzhong (Frank) , Liu Bingbing 
Published: December 2022

AbstractEffective modification of the structure and properties of halide perovskites via the pressure engineering strategy has attracted enormous interest in the past decade. However, sufficient effort and insights regarding the potential properties and applications of the high‐pressure amorphous phase are still lacking. Here, the superior and tunable photoelectric properties that occur in the pressure‐induced amorphization process of the halide perovskite Cs3Bi2I9 are demonstrated. With increasing pressure, the photocurrent with xenon lamp illumination exhibits a rapid increase and achieves an almost five orders of magnitude increment compared to its initial value. Impressively, a broadband photoresponse from 520 to 1650 nm with an optimal responsivity of 6.81 mA W−1 and fast response times of 95/96 ms at 1650 nm is achieved upon successive compression. The high‐gain, fast, broadband, and dramatically enhanced photoresponse properties of Cs3Bi2I9 are the result of comprehensive photoconductive and photothermoelectric mechanisms, which are associated with enhanced orbital coupling caused by an increase in BiI interactions in the [BiI6]3− cluster, even in the amorphous state. These findings provide new insights for further exploring the potential properties and applications of amorphous perovskites.
Design of N‐Type Textured Bi2Te3 with Robust Mechanical Properties for Thermoelectric Micro‐Refrigeration Application
Authors: Zhu Yu‐Ke , Jin Yifan , Zhu Jianbo , Dong Xingyan , Liu Ming , Sun Yuxin , Guo Muchun , Li Fushan , Guo Fengkai , Zhang Qian , Liu Zihang , Cai Wei , Sui Jiehe 
Published: December 2022

AbstractThermoelectric refrigeration is one of the mature techniques used for cooling applications, with the great advantage of miniaturization over traditional compression refrigeration. Due to the anisotropic thermoelectric properties of n‐type bismuth telluride (Bi2Te3) alloys, these two common methods, including the liquid phase hot deformation (LPHD) and traditional hot forging (HF) methods, are of considerable importance for texture engineering to enhance performance. However, their effects on thermoelectric and mechanical properties are still controversial and not clear yet. Moreover, there has been little documentation of mechanical properties related to micro‐refrigeration applications. In this work, the above‐mentioned methods are separately employed to control the macroscopic grain orientation for bulk n‐type Bi2Te3 samples. The HF method enabled the stabilization of both composition and carrier concentration, therefore yielding a higher quality factor to compare with that of LPHD samples, supported by DFT calculations. In addition to superior thermoelectric performance, the HF sample also exhibited robust mechanical properties due to the presence of nano‐scale distortion and dense dislocation, which is the prerequisite for realizing ultra‐precision machining. This work helps to pave the way for the utilization of n‐type Bi2Te3 for commercial micro‐refrigeration applications.
Elucidating mechanism of ethylbenzene oxidation catalyzed by carbon‐based catalysts with kinetic modeling
Authors: Su Yongzhao , Huang Jiangnan , Yang Guangxing , Wang Hongjuan , Yu Hao , Zhang Qiao , Cao Yonghai , Peng Feng 
Published: December 2022

AbstractEthylbenzene (EB) oxidation to oxygenated products catalyzed by carbon nanotubes (CNTs) and CNTs with confined cobalt nanoparticles (Co@C/CNTs) are conducted. Co@C/CNTs with enhanced interfacial charge transfer displays a unique activity. A kinetic model with the simplified network is established, in which seven elementary reactions with prominent features of EB oxidation are selected. The main parameters, reaction rate constant (k) and active energy (Ea) are obtained. Co@C/CNTs could speed up most elementary steps and reduce energy barriers, thus improving the overall activity. The homolytic cleavage of peroxide is confirmed to be the rate‐determining step (RDS). The k ratio (1.55) of acetophenone (AcPO)/1‐phenylethyl alcohol (PEA) is found to be close to the experimental result (rAcPO/rPEA, 1.30). The prediction of EB oxidation is simulated, showing that the synthesis of AcPO dominates the reaction route, while the addition of PEA would prohibit the reaction.
NHC‐Catalyzed Cascade Reactions for the Construction of Fused Cycles via LUMO Activation of α,β‐Unsaturated Carbonyls
Authors: Nie Guihua , Li Tingting 
Published: December 2022

AbstractThe facile syntheses of multicyclic molecules through multi‐step cascade reactions with N‐Heterocyclic carbene (NHC)‐catalyzed LUMO activation strategies are summarized. The reaction mechanisms involved in these cascade catalytic transformations are also provided and discussed. The review article is arranged according to the reaction starting materials that are used for the NHC‐catalytic activation processes.
Dynamics and Proton Conduction of Heterogeneously Confined Imidazole in Porous Coordination Polymers
Authors: Cai Linkun , Yang Junsheng , Lai Yuyan , Liang Yuling , Zhang Rongchun , Gu Cheng , Kitagawa Susumu , Yin Panchao 
Published: December 2022

AbstractThe nanoconfinement of proton carrier molecules may contribute to the lowing of their proton dissociation energy. However, the free proton transportation does not occur as easily as in liquid due to the restricted molecular motion from surface attraction. To resolve the puzzle, herein, imidazole is confined in the channels of porous coordination polymers with tunable geometries, and their electric/structural relaxations are quantified. Imidazole confined in a square‐shape channels exhibits dynamics heterogeneity of core‐shell‐cylinder model. The core and shell layer possess faster and slower structural dynamics, respectively, when compared to the bulk imidazole. The dimensions and geometry of the nanochannels play an important role in both the shielding of the blocking effect from attractive surfaces and the frustration filling of the internal proton carrier molecules, ultimately contributing to the fast dynamics and enhanced proton conductivity.
Propargyl Alcohols as Bifunctional Reagents for Divergent Annulations of Biphenylamines via Dual C−H Functionalization/Dual Oxidative Cyclization
Authors: Dattatri  , Kumar Reddy Singam Maneesh , Vavilapalli Suresh , Babu Nanubolu Jagadeesh , Sridhar Reddy Maddi 
Published: December 2022

AbstractThe C−H functionalization strategy provides access to valuable molecules that previously required convoluted synthetic attempts. Dual C−H unsymmetrical functionalization, with a single bifunctional reagent, is an effective tactic. Propargyl alcohols (PAs), despite containing a reactive C≡C bond, have not been explored as building blocks via oxidative cleavage. Annulations via C−H activation are a versatile and synthetically attractive strategy. We disclose PA as a new bifunctional reagent for unsymmetrical dual C−H functionalization of biphenylamine for regioselectively annulated outcomes. On tuning the conditions, the annulation bifurcated towards an unusual dual oxidative cyclization. This method accommodates a wide range of PAs and showcases late‐stage diversification of some natural products.
C−H‐Funktionalisierung von Tryptophan‐haltigen Peptiden mit Thianthreniumsalzen im späten Synthesestadium: Konjugation und Ligation
Authors: Kaplaneris Nikolaos , Puet Alejandro , Kallert Felix , Pöhlmann Julia , Ackermann Lutz 
Published: December 2022

AbstractDie bioorthogonale Diversifizierung strukturell komplexer Peptide im späten Stadium der Synthese besitzt ein großes Potenzial für die Entdeckung von neuen Arzneimitteln und die molekulare Bildgebung. Wir berichten über eine Palladium‐katalysierte C−H‐Arylierung von Tryptophan‐haltigen Peptiden mit leicht zugänglichen und modularen Arylthianthrenium‐Salzen. Unter äußerst milden Reaktionsbedingungen konnte die Diversifizierung im späten Stadium der Synthese von strukturell komplexen Peptiden erreicht werden. Die Abstimmbarkeit und einfache Herstellung von Arylthianthrenium‐Salzen ermöglichte die zweckmäßige Verknüpfung von Tryptophan‐haltigen Peptiden mit Arzneimittel‐, Naturstoff‐ und Peptidgerüsten, durch das Bilden sterisch anspruchsvoller Biaryl‐Bindungen. Die Robustheit des Palladiumkatalyseregimes spiegelte sich in der vollständigen Toleranz gegenüber einer Vielzahl empfindlicher und koordinierender funktioneller Gruppen wieder. Somit ermöglichte die Vielseitigkeit unserer Methode den effizienten Zugang zu stark substituierten, markierten, konjugierten und ligierten linearen und zyklischen Peptiden.
Ein neuer Thiolat‐gebundener Dimangan‐Cluster als strukturelles und funktionales Modell der Class Ib Ribonukleotidreduktasen
Authors: Battistella Beatrice , Lohmiller Thomas , Cula Beatrice , Hildebrandt Peter , Kuhlmann Uwe , Dau Holger , Mebs Stefan , Ray Kallol 
Published: December 2022

AbstractIn Class Ib Ribonukleotidreduktasen (RNRs) aktiviert ein Dimangan(II)‐Cluster Superoxid (O2⋅−) anstelle von molekularem Sauerstoff (O2), um eine hochvalente MnIII‐O2‐MnIV‐Spezies zu bilden, die für die Oxidation von Tyrosin zum Tyrosyl‐Radikal verantwortlich ist. Im vorliegenden biomimetischen Ansatz wird ein Thiolat‐gebundener Dimangan‐Komplex [MnII2(BPMT)(OAc)2](ClO)4 (BPMT=(2,6‐Bis{[bis(2‐pyridylmethyl)amino]methyl}‐4‐methylthiophenolat) (1) synthetisiert und dessen Reaktion mit O2⋅− zur Bildung des [(BPMT)MnO2Mn]2+‐Komplexes 2 gezeigt. Resonanz‐Raman‐Untersuchungen zeigen das Vorliegen einer O‐O‐Bindung in 2, während die ESR‐Analyse ein Signal bei g=2 mit 16 Linien für St=
aufzeigt, das typischerweise mit einem MnIIIMnIV‐Kern assoziiert wird, wie es auch in Class Ib RNR detektiert wurde. Anders als zuvor publizierte Mn‐O2‐Mn‐Komplexe, die durch O2⋅−‐Aktivierung an Mn2‐Zentren gebildet wurden, ist 2 ein geeignetes elektrophiles Oxidationsmittel für Aldehyd‐Deformylierungsreaktionen und Phenol‐Oxidationsreaktionen, sodass es eines der besten strukturellen und funktionalen Modelle der Class Ib RNRs darstellt.
Engineering a Highly Regioselective Fungal Peroxygenase for the Synthesis of Hydroxy Fatty Acids
Authors: Gomez de Santos Patricia , González‐Benjumea Alejandro , Fernandez‐Garcia Angela , Aranda Carmen , Wu Yinqi , But Andrada , Molina‐Espeja Patricia , Maté Diana M. , Gonzalez‐Perez David , Zhang Wuyuan , Kiebist Jan , Scheibner Katrin , Hofrichter Martin , Świderek Katarzyna , Moliner Vicent , Sanz‐Aparicio Julia , Hollmann Frank , Gutiérrez Ana , Alcalde Miguel 
Published: December 2022

AbstractThe hydroxylation of fatty acids is an appealing reaction in synthetic chemistry, although the lack of selective catalysts hampers its industrial implementation. In this study, we have engineered a highly regioselective fungal peroxygenase for the ω‐1 hydroxylation of fatty acids with quenched stepwise over‐oxidation. One single mutation near the Phe catalytic tripod narrowed the heme cavity, promoting a dramatic shift toward subterminal hydroxylation with a drop in the over‐oxidation activity. While crystallographic soaking experiments and molecular dynamic simulations shed light on this unique oxidation pattern, the selective biocatalyst was produced by Pichia pastoris at 0.4 g L−1 in a fed‐batch bioreactor and used in the preparative synthesis of 1.4 g of (ω‐1)‐hydroxytetradecanoic acid with 95 % regioselectivity and 83 % ee for the S enantiomer.
Alkynyl‐Protected Chiral Bimetallic Ag22Cu7 Superatom with Multiple Chirality Origins
Authors: Deng Guocheng , Lee Kangjae , Deng Hongwen , Malola Sami , Bootharaju Megalamane S. , Häkkinen Hannu , Zheng Nanfeng , Hyeon Taeghwan 
Published: December 2022

AbstractUnderstanding the origin of chirality in the nanostructured materials is essential for chiroptical and catalytic applications. Here we report a chiral AgCu superatomic cluster, [Ag22Cu7(C≡CR)16(PPh3)5Cl6](PPh4), Ag22Cu7, protected by an achiral alkynyl ligand (HC≡CR: 3,5‐bis(trifluoromethyl)phenylacetylene). Its crystal structure comprises a rare interpenetrating biicosahedral Ag17Cu2 core, which is stabilized by four different types of motifs: one Cu(C≡CR)2, four −C≡CR, two chlorides and one helical Ag5Cu4(C≡CR)10(PPh3)5Cl4. Structural analysis reveals that Ag22Cu7 exhibits multiple chirality origins, including the metal core, the metal‐ligand interface and the ligand layer. Furthermore, the circular dichroism spectra of R/S‐Ag22Cu7 are obtained by employing appropriate chiral molecules as optical enrichment agents. DFT calculations show that Ag22Cu7 is an eight‐electron superatom, confirm that the cluster is chirally active, and help to analyze the origins of the circular dichroism.
Diethylzinc‐Mediated Cross‐Coupling Reactions between Dibromoketones and Monobromo Carbonyl Compounds
Authors: Takeshima Aika , Kano Taichi 
Published: December 2022

AbstractA novel route to synthesize 1,4‐dicarbonyl compounds is described. α,α‐Dibromoketones generate zinc enolates through a diethylzinc‐mediated halogen‐metal exchange and react with α‐bromocarbonyl compounds to furnish 1,4‐dicarbonyl compounds via a second generation of zinc enolates. This cross‐coupling reaction is enabled by the chemoselective formation of zinc enolates from α,α‐dibromoketones in the presence of α‐bromocarbonyl compounds. Chiral 1,4‐dicarbonyl compounds can be obtained via the enantioselective bromination of aldehydes using a chiral secondary amine catalyst and a subsequent cross‐coupling reaction between the resulting chiral α‐bromoaldehydes and α,α‐dibromoacetophenones.
Rational Design of Ferroelectric 2D Perovskite for Improving the Efficiency of Flexible Perovskite Solar Cells Over 23 %
Authors: Han Bin , Wang Yaohua , Liu Chang , Sun Kexuan , Yang Mengjin , Xie Lisha , Yang Shuncheng , Meng Yuanyuan , Lin Shuyuan , Xu Peng , Li Jun , Qiu Qingqing , Ge Ziyi 
Published: December 2022

AbstractDespite the great progress of flexible perovskite solar cells (f‐PSCs), it still faces several challenges during the homogeneous fabrication of high‐quality perovskite thin films, and overcoming the insufficient exciton dissociation. To the ends, we rationally design the ferroelectric two‐dimensional (2D) perovskite based on pyridine heterocyclic ring as the organic interlayer. We uncover that incorporation of the ferroelectric 2D material into 3D perovskite induces an increased built‐in electric field (BEF), which enhances the exciton dissociation efficiency in the device. Moreover, the 2D seeds could assist the 3D crystallization by forming more homogeneous and highly‐oriented perovskite crystals. As a result, an impressive power conversion efficiency (PCE) over 23 % has been achieved by the f‐PSCs with outstanding ambient stability. Moreover, the piezo/ferroelectric 2D perovskite intrigues a decreased hole transport barriers at the ITO/perovskite interface under tensile stress, which opens new possibilities for developing highly‐efficient f‐PSCs.
High‐Precision Mapping of Membrane Proteins on Synaptic Vesicles using Spectrally Encoded Super‐Resolution Imaging
Authors: Jiang Yifei , Zhang Jicheng , Jung Seung‐Ryoung , Chen Haobin , Xu Shihan , Chiu Daniel T. 
Published: December 2022

AbstractThe spatial resolution of single‐molecule localization microscopy is limited by the photon number of a single switching event because of the difficulty of correlating switching events dispersed in time. Here we overcome this limitation by developing a new class of photoswitching semiconducting polymer dots (Pdots) with structured and highly dispersed single‐particle spectra. We imaged the Pdots at the first and the second vibronic emission peaks and used the ratio of peak intensities as a spectral coding. By correlating switching events using the spectral coding and performing 4–9 frame binning, we achieved a 2–3 fold experimental resolution improvement versus conventional superresolution imaging. We applied this method to count and map SV2 and proton ATPase proteins on synaptic vesicles (SVs). The results reveal that these proteins are trafficked and organized with high precision, showing unprecedented level of detail about the composition and structure of SVs.
Site‐ and Stereoselective C(sp3)−H Borylation of Strained (Hetero)Cycloalkanols Enabled by Iridium Catalysis
Authors: Gao Qian , Xu Senmiao 
Published: December 2022

AbstractTransition metal‐catalyzed site‐ and stereoselective C−H activation of strained (hetero)cycloalkanes remains a formidable challenge. We herein report a carbamate‐directed iridium‐catalyzed asymmetric β−C(sp3)−H borylation of cyclopropanol derivatives. A variety of densely functionalized cyclopropanols were obtained in good enantioselectivities via desymmetrization and kinetic resolution. In addition, site‐selective C(sp3)−H borylation of methine groups furnished α‐borylated (hetero)cycloalkanols in moderate to good yields. The synthetic utility of the method was further shown in a gram‐scale synthesis and diverse downstream transformations of borylated products.
Machine Learning Informs RNA‐Binding Chemical Space**
Authors: Yazdani Kamyar , Jordan Deondre , Yang Mo , Fullenkamp Christopher R. , Calabrese David R. , Boer Robert , Hilimire Thomas , Allen Timothy E. H. , Khan Rabia T. , Schneekloth John S. 
Published: December 2022

AbstractSmall molecule targeting of RNA has emerged as a new frontier in medicinal chemistry, but compared to the protein targeting literature our understanding of chemical matter that binds to RNA is limited. In this study, we reportedRepositoryOfBInders toNucleic acids (ROBIN), a new library of nucleic acid binders identified by small molecule microarray (SMM) screening. The complete results of 36 individual nucleic acid SMM screens against a library of 24 572 small molecules were reported (including a total of 1 627 072 interactions assayed). A set of 2 003 RNA‐binding small molecules was identified, representing the largest fully public, experimentally derived library of its kind to date. Machine learning was used to develop highly predictive and interpretable models to characterize RNA‐binding molecules. This work demonstrates that machine learning algorithms applied to experimentally derived sets of RNA binders are a powerful method to inform RNA‐targeted chemical space.
Oxidation‐Reduction Molecular Junction Covalent Organic Frameworks for Full Reaction Photosynthesis of H2O2
Authors: Chang Jia‐Nan , Li Qi , Shi Jing‐Wen , Zhang Mi , Zhang Lei , Li Shan , Chen Yifa , Li Shun‐Li , Lan Ya‐Qian 
Published: December 2022

AbstractThe full reaction photosynthesis of H2O2 that can combine water‐oxidation and oxygen‐reduction without sacrificial agents is highly demanded to maximize the light‐utilization and overcome the complex reaction‐process of anthraquinone‐oxidation. Here, a kind of oxidation‐reduction molecular junction covalent‐organic‐framework (TTF‐BT‐COF) has been synthesized through the covalent‐coupling of tetrathiafulvalene (photo‐oxidation site) and benzothiazole (photo‐reduction site), which presents visible‐light‐adsorption region, effective electron‐hole separation‐efficiency and photo‐redox sites that enables full reaction generation of H2O2. Specifically, a record‐high yield (TTF‐BT‐COF, ≈276 000 μM h−1 g−1) for H2O2 photosynthesis without sacrificial agents has been achieved among porous crystalline photocatalysts. This is the first work that can design oxidation‐reduction molecular junction COFs for full reaction photosynthesis of H2O2, which might extend the scope of COFs in H2O2 production.
Electron beam assisted recycling of polyurethane (PU) sponge: Turning it into a superabsorbent for wastewater treatment
Authors: Jha Atanu , Shaik Khader Abdul , Bhardwaj Yatender Kumar , Pant Harish Jagat , Chowdhury Subhendu Ray 
Published: December 2022

AbstractPolyurethane (PU) sponge is being used on a large scale now‐a‐days, but that generates environmental pollution as it is not bio‐degradable. Moreover, the PU recycling existing techniques face several problems, which are being addressed sincerely throughout the world. Here, we report an easy, scalable, environment‐friendly, economic, and high throughput technique for converting scrap PU sponge into a superabsorbent for wastewater treatment. This is a new strategy for recycling scrap PU foam. This conversion follows the modification of surface energy of the PU sponge and generation of tiny‐scale roughness by a single‐step electron beam (EB) radiation‐assisted covalent attachment of dodecyl methacrylate (DMA) onto the waste PU sponge. The effect of degree of modification on the surface wettability is studied. Important process parameters namely, total dose, DMA concentration, solvent composition, and so forth are systematically varied and optimized to achieve the required extent of modification (~30 wt%). This desired degree of modification is achieved at 30 kGy total dose and in 15 vol% DMA concentration and 15 vol% water content in the reaction mixture. Grafting yield is measured gravimetrically and successful grafting is further confirmed by Fourier‐transform infrared spectroscopy, surface wettability, and surface morphology. The recycled PU shows superhydrophobicity with very high water contact angle (152°). Now, the recycled sponge can remove major liquid components of wastewater, namely, toxic organic solvents, oily liquids, nonpolar solvent soluble dyes from water media with high absorption capacity (25–30 g/g) successfully.
Anion exchange membranes based on poly (styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) grafted poly (2,6‐dimethyl‐1,4‐phenylene oxide)
Authors: Liu Rui , Nie Yiwen , Chen Junjie , Shen Chunhui , Gao Shanjun 
Published: December 2022

AbstractPoly (styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) (SEBS) has been widely studied in the field of anion exchange membranes (AEMs) due to its superior flexibility and chemical stability, but the poor dimensional stability of functionalized SEBS restricts its further application. Thus, we adopt an effective strategy to reinforce AEMs based on SEBS via grafting poly (2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) using Williamson ether synthesis reaction. With the addition of PPO, grafted membranes exhibit outstanding comprehensive properties, such as mechanical strength, chemical stability, especially dimensional stability. SEBS‐PPO‐QA‐1 grafted membrane with the highest content of PPO showed the best tensile strength (20.54 MPa), and restrained swelling behavior (swelling ratio of 4.81% at 25°C). Moreover, the conductivity retention of SEBS‐PPO‐QA‐1 grafted membrane is up to 92.71% at 80°C after 10 days alkaline treatment. The ion exchange capacity of SEBS‐PPO‐QA‐3 grafted membrane is 1.719 mmol/g, and the ionic conductivity of SEBS‐PPO‐QA‐3 grafted membrane reach 58.27 mS/cm at 80°C and 25.53 mS/cm at 20°C. Therefore, the SEBS‐PPO‐QA‐X grafted membranes, which combine the advantages of PPO and SEBS, are promising in AEM application.