bluuebunny/crossref_metadata_2025_split huggingface dataset:
Tautomeric Dual‐Site Passivation for Carbon‐Based Printable Mesoscopic Perovskite Solar Cells
Authors: Chen Yan , Ma Dun , Wang Zhiqiang , He Jingshan , Gong Xueqing , Wu Wenjun 
Published: May 2022

AbstractAlthough ionic conjugated passivation systems, such as ionic liquids (ILs), have been used to passivate perovskite in carbon‐based printable mesoscopic perovskite solar cells (FP‐PSCs), their tautomerism process and synergistic effect of multifunctional groups have not yet caused enough attention. In this work, a series of novel ILs including 1‐allyl‐3‐methylimidazole tetrafluoroborate ([AMIm]BF4) and 1‐benzyl‐3‐methylimidazole tetrafluoroborate ([BzMIm]BF4) used as passivants for FP‐PSCs are reported. Combining Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculation, it is found that one of its tautomers (positive ion at the near end N atom of conjugated side chain) plays a key role on dual‐site simultaneous passivation. As the conjugation degree of side chain increases from allyl to benzyl, it not only effectively inhibits the non‐radiative charge recombination, but also reduces the passivation adsorption energy and increases the charge transfer rate. A high efficiency of 16.87% has been achieved with a high FF (>0.7), a Jsc of 23.88 mA cm–2 value and Voc value up to 1.0 V, by using the “tautomeric dual‐site passivation” strategy.
Cyanostilbene‐Based AIEgen Smart Film: Optical Switching by Engineering Molecular Packing Structure and Molecular Conformation Through Thermal and Photoinduced Monotropic Phase Transition
Authors: Koo Jahyeon , Jang Junhwa , Oh Mintaek , Kim Minwook , Hyeong Jaeseok , Lim Seok‐In , Cao Yan , Tran Duy Thanh , Park Sungjune , Jeong Kwang‐Un 
Published: May 2022

AbstractThe optical properties of newly synthesized cyanostilbene‐based AIEgen (D4CS) exhibiting a unique monotropic phase transition are modulated by engineering molecular packing structure and molecular conformation through temperature change and light irradiation. D4CS exhibits only a low‐ordered smectic liquid crystal (SmA) phase over a wide temperature range during cooling and subsequent heating processes, while D4CS crystallizes after a significantly long annealing time at room temperature. Crystallized D4CS exhibits a complex phase transition (SmCr–SmB–SmA–Iso) in the subsequent heating process. In addition, the photoisomerization behavior of D4CS from trans to cis conformer can induce a phase transition to the isotropic (Iso) state, and the reverse isomerization can occur by high‐temperature heat treatment. This unique thermal and photoinduced phase transition of D4CS is accompanied by changes in optical properties including transmittance and luminescence. Based on the optical switching behavior of D4CS, photopatternable temperature and time‐dependent optical films are demonstrated. The newly developed cyanostilbene‐based AIEgen is a smart optical material with great potential for advanced optical sensors, anti‐counterfeiting ink and smart display system.
Recent Advances and Challenges in Ultrafast Photonics Enabled by Metal Nanomaterials
Authors: Wang Gang , Liu Tingyi , Chao Jiale , Jin Hong , Liu Jiayao , Zhang Han , Lyu Wenhao , Yin Peng , Al‐Ghamdi Ahmed , Wageh Swelm , Fu Bo , Zhang Han 
Published: May 2022

AbstractNanomaterials with outstanding optical properties are widely used in ultrafast photonics. Especially, metal nanomaterials have attracted increasing attention in recent years owing to the surface plasmon resonance that further enhances their nonlinear optical response, making them suitable for generating ultrafast pulses in a wide range of wavebands. Herein, the fabrication and integration processes of typical metal nanomaterials such as gold, silver, and copper, as well as their applications in ultrafast lasers are reviewed. The synthesis methods of metal nanomaterials, which can be divided into dry and wet methods, are first introduced with their characteristics and advantages summarized. Moreover, the integration approaches that are used to incorporate metal nanomaterials into laser cavities are discussed, where sandwich structure based on polymer film and deposition method, as well as evanescent‐wave structure based on D‐shaped and tapered fiber are demonstrated. Besides, the state of the art of typical ultrafast lasers enabled by metal nanoparticles is systematically reviewed. Finally, current challenges and perspectives on the development of ultrafast photonics enabled by metal nanomaterials are proposed.
Macromolecular Viral Entry Inhibitors as Broad‐Spectrum First‐Line Antivirals with Activity against SARS‐CoV‐2
Authors: Groß Rüdiger , Dias Loiola Lívia Mesquita , Issmail Leila , Uhlig Nadja , Eberlein Valentina , Conzelmann Carina , Olari Lia‐Raluca , Rauch Lena , Lawrenz Jan , Weil Tatjana , Müller Janis A. , Cardoso Mateus Borba , Gilg Andrea , Larsson Olivia , Höglund Urban , Pålsson Sandra Axberg , Tvilum Anna Selch , Løvschall Kaja Borup , Kristensen Maria M. , Spetz Anna‐Lena , Hontonnou Fortune , Galloux Marie , Grunwald Thomas , Zelikin Alexander N. , Münch Jan 
Published: May 2022

AbstractInhibitors of viral cell entry based on poly(styrene sulfonate) and its core–shell nanoformulations based on gold nanoparticles are investigated against a panel of viruses, including clinical isolates of SARS‐CoV‐2. Macromolecular inhibitors are shown to exhibit the highly sought‐after broad‐spectrum antiviral activity, which covers most analyzed enveloped viruses and all of the variants of concern for SARS‐CoV‐2 tested. The inhibitory activity is quantified in vitro in appropriate cell culture models and for respiratory viral pathogens (respiratory syncytial virus and SARS‐CoV‐2) in mice. Results of this study comprise a significant step along the translational path of macromolecular inhibitors of virus cell entry, specifically against enveloped respiratory viruses.
Learning From Plants: Lycopene Additive Passivation toward Efficient and “Fresh” Perovskite Solar Cells with Oxygen and Ultraviolet Resistance
Authors: Zhuang Xinmeng , Zhou Donglei , Liu Shuainan , Sun Rui , Shi Zhichong , Liu Le , Wang Tianyuan , Liu Bin , Liu Dali , Song Hongwei 
Published: May 2022

AbstractCurrently, the photovoltaic performance of perovskite solar cells (PSCs) is closely linked to undermined defects in the perovskite, and the correct approach to ensure stability under practical conditions is still in dispute. Therefore, natural, healthy, and low‐cost additives are expected to not only reduce the trap sites but also drastically improve stability. In this work, the natural antioxidant additive lycopene extracted from tomatoes is introduced into PSCs. The results indicate that lycopene can passivate the grain boundaries, improve the crystallinity, reduce trap density, and facilitate the α phase formation of perovskite at room temperature. As a result, the power conversion efficiency (PCE) is considerably improved from 20.57% to 23.62% with vastly enhanced Jsc and Voc. Additionally, lycopene can eliminate the UV‐induced free radicals in the light aging process. The target device displays the enhanced hydrophobic, antioxidative properties, which demonstrates high O2 stability with 91.2% average PCE for 960 h, improved UV stability and long‐term stability with an average PCE of 92.4% after 3500 h. This work provides a strategy to solve the existing efficiency and stability issues in PSC devices through learning from natural plants, which paves the way for the development of environmentally friendly PSCs with high efficiency and stability, on the path toward industrialization.
Benchmarking US consumption and perceptions of beef and plant‐based proteins
Authors: Taylor Hannah , Tonsor Glynn T. , Lusk Jayson L. , Schroeder Ted C. 
Published: May 2022

AbstractThis article uses two complementary analyses to document consumption of beef and plant‐based proteins along with perceptions held by US consumers. Beef is chosen three times more often than plant‐based proteins and consumers hold a positive image of beef overall. Key differences are outlined between regular meat consumers and those declaring alternative diets. Combined these findings extend understanding in the dynamic situation presented by plant‐based proteins in the US market.
Heterozygous variants in PRPF8 are associated with neurodevelopmental disorders
Authors: O'Grady Lauren , Schrier Vergano Samantha A. , Hoffman Trevor L. , Sarco Dean , Cherny Sara , Bryant Emily , Schultz‐Rogers Laura , Chung Wendy K. , Sacharow Stephanie , Immken Ladonna L. , Holder Susan , Blackwell Rebecca R. , Buchanan Catherine , Yusupov Roman , Lecoquierre François , Guerrot Anne‐Marie , Rodan Lance , de Vries Bert B. A. , Kamsteeg Erik Jan , Santos Simarro Fernando , Palomares‐Bralo Maria , Brown Natasha , Pais Lynn , Ferrer Alejandro , Klee Eric W. , Babovic‐Vuksanovic Dusica , Rhodes Lindsay , Person Richard , Begtrup Amber , Keller‐Ramey Jennifer , Santiago‐Sim Teresa , Schnur Rhonda E. , Sweetser David A. , Gold Nina B. 
Published: May 2022

AbstractThe pre‐mRNA‐processing factor 8, encoded by PRPF8, is a scaffolding component of a spliceosome complex involved in the removal of introns from mRNA precursors. Previously, heterozygous pathogenic variants in PRPF8 have been associated with autosomal dominant retinitis pigmentosa. More recently, PRPF8 was suggested as a candidate gene for autism spectrum disorder due to the enrichment of sequence variants in this gene in individuals with neurodevelopmental disorders. We report 14 individuals with various forms of neurodevelopmental conditions, found to have heterozygous, predominantly de novo, missense, and loss‐of‐function variants in PRPF8. These individuals have clinical features that may represent a new neurodevelopmental syndrome.
Nonsyndromic arteriopathy and aortopathy and vascular Ehlers–Danlos syndrome causing COL3A1 variants
Authors: Yagi Hiroki , Takeda Norifumi , Amiya Eisuke , Akiyama Nana , Chang Hyangri , Ishiura Hiroyuki , Sato Jiro , Akazawa Hiroshi , Morita Hiroyuki , Komuro Issei 
Published: May 2022

AbstractVascular Ehlers–Danlos syndrome (vEDS) is an autosomal dominant genetic disorder characterized by soft connective tissue vulnerability due to dysfunction of Type III collagen and caused by the pathogenic variants in COL3A1 gene. In the era of next‐generation sequencing, multiple genes including COL3A1 can be simultaneously analyzed, and among patients suffering from aortopathy even without any other clinical features suggestive of vEDS, pathogenic COL3A1 variants have been increasingly identified. Here, we briefly summarize the characteristics of 12 Japanese patients from 11 families with arteriopathy and pathogenic or likely pathogenic COL3A1 variants in our hospital. Five patients did not have any extra‐arterial clinical features, however, the multigene panel testing for hereditary thoracic aortic aneurysm and dissection unexpectedly revealed that two had glycine substitutions in the triple‐helical region and three had haploinsufficient type variants in the COL3A1 gene, whose pathogenicities were all classified as pathogenic or likely pathogenic. Further genetic screening and identification of pathogenic variants in patients with nonsyndromic arteriopathy and aortopathy will enable us to develop risk‐stratification and management based on the genetic diagnosis.
Fast and Robust Quantum State Transfer via Optimal Transitionless Quantum Driving
Authors: Zhang Chun‐Ling , Lin Xiu‐Min 
Published: May 2022

AbstractFor the past few years, shortcuts to adiabaticity have attracted great attention since they can avoid the necessity of slow driving for adiabatic method while inheriting the partial robustness of the adiabatic dynamics. In this paper, a universal approach to implement quantum state transfer in a three‐state system via optimal transitionless quantum driving is presented. The fast path is optimized for great robustness against uncontrolled systematic error by selecting appropriate experimental parameters. The robustness of the protocol is discussed via numerical simulations. Compared with conventional transitionless quantum driving and adiabatic passage, the protocol via optimized transitionless quantum driving possesses more robustness against the systematic error. Furthermore, decoherence arising from atomic spontaneous emission and dephasing only has a slight impact on the fidelity of quantum state transfer. This work opens up a new avenue for high‐fidelity quantum state transfer in the case of the uncontrolled errors.
Copper‐Bridged Tetrakis(4‐ethynylphenyl)ethene Aggregates with Photo‐Regulated 1O2 and O2.− Generation for Selective Photocatalytic Aerobic Oxidation
Authors: Sun Huiying , Lang Zhongling , Zhao Yingnan , Zhao Xinyu , Qiu Tianyu , Hong Qiang , Wei Kaiqiang , Tan Huaqiao , Kang Zhenhui , Li Yangguang 
Published: May 2022

AbstractActive species regulation is a key scientific issue that essentially determines the selectivity and activity of a photocatalyst. Herein, CuI‐bridged tetrakis(4‐ethynylphenyl)ethene aggregates (T4EPE‐Cu) with photo‐regulated 1O2 and O2.− generation were demonstrated for selective photocatalytic aerobic oxidation. In this system, transient photovoltage combined with the density functional theory calculations confirmed that Cu‐alkynyl was the main oxygen activation site. The adsorbed O2 tends to produce O2.− because of the potential well effect of Cu‐alkynyl under high‐energy light excitation. But under low‐energy light, O2 tends to produce 1O2 via resonance energy transfer with Cu‐alkynyl. For α‐terpinene oxidation, the ratios of 1O2 products to O2.− products can be controlled from 1.3 (380 nm) to 10.7 (600 nm). Furthermore, T4EPE‐Cu exhibited ultrahigh photocatalytic performance for Glaser coupling and benzylamine oxidation, with a conversion and selectivity of over 99 %.
Synthesis and Characterization of Stable Iron Pentacarbonyl Radical Cation Salts
Authors: Rall Jan M. , Schorpp Marcel , Keilwerth Martin , Mayländer Maximilian , Friedmann Christian , Daub Michael , Richert Sabine , Meyer Karsten , Krossing Ingo 
Published: May 2022

AbstractThe open‐shell iron pentacarbonyl cation [Fe(CO)5].+ was isolated by deelectronation, i.e., the single‐electron oxidation of the parent neutral Fe(CO)5 using [phenazineF].+ as the [Al(ORF)4]− and [F‐{Al(ORF)3}2]− salt (RF=C(CF3)3; phenazineF=perfluoro‐5,10‐bis(perfluorophenyl)‐5,10‐dihydrophenazine). [Fe(CO)5].+[Al(ORF)4]− was fully characterized (scXRD analysis, IR, NMR, EPR, 57Fe spectroscopy, CV and SQUID magnetization study) and, apart from being a compound of fundamental interest, may serve as a precursor for low‐valent iron coordination chemistry.
Metathesis between E−C(spn) and H−C(sp3) σ‐Bonds (E=Si, Ge; n=2, 3) on an Osmium‐Polyhydride
Authors: Esteruelas Miguel A. , López Ana M. , Oñate Enrique , Raga Esther 
Published: May 2022

AbstractThe silylation of a phosphine of OsH6(PiPr3)2 is performed via net‐metathesis between Si−C(spn) and H−C(sp3) σ‐bonds (n=2, 3). Complex OsH6(PiPr3)2 activates the Si−H bond of Et3SiH and Ph3SiH to give OsH5(SiR3)(PiPr3)2, which yield OsH4{κ1‐P,η2‐SiH‐[iPr2PCH(Me)CH2SiR2H]}(PiPr3) and R−H (R=Et, Ph), by displacement of a silyl substituent with a methyl group of a phosphine. Such displacement is a first‐order process, with activation entropy consistent with a rate determining step occurring via a highly ordered transition state. It displays selectivity, releasing the hydrocarbon resulting from the rupture of the weakest Si‐substituent bond, when the silyl ligand bears different substituents. Accordingly, reactions of OsH6(PiPr3)2 with dimethylphenylsilane, and 1,1,1,3,5,5,5‐heptamethyltrisiloxane afford OsH5(SiR2R′)(PiPr3)2, which evolve into OsH4{κ1‐P,η2‐GeH‐[iPr2PCH(Me)CH2SiR2H]}(PiPr3) (R=Me, OSiMe3) and R′−H (R′=Ph, Me). Exchange reaction is extended to Et3GeH. The latter reacts with OsH6(PiPr3)2 to give OsH5(GeEt3)(PiPr3)2, which loses ethane to form OsH4{κ1‐P,η2‐GeH‐[iPr2PCH(Me)CH2GeEt2H]}(PiPr3).
Iridium‐Catalyzed Asymmetric Hydrogenation of 2,3‐Diarylallyl Amines with a Threonine‐Derived P‐Stereogenic Ligand for the Synthesis of Tetrahydroquinolines and Tetrahydroisoquinolines
Authors: Rojo Pep , Molinari Medea , Cabré Albert , García‐Mateos Clara , Riera Antoni , Verdaguer Xavier 
Published: May 2022

AbstractChiral compounds containing nitrogen heteroatoms are fundamental substances for the chemical, pharmaceutical and agrochemical industries. However, the preparation of some of these interesting scaffolds is still underdeveloped. Herein we present the synthesis of a family of P‐stereogenic phosphinooxazoline iridium catalysts from L‐threonine methyl ester and their use in the asymmetric hydrogenation of N‐Boc‐2,3‐diarylallyl amines, achieving very high enantioselectivity. Furthermore, the synthetic utility of the 2,3‐diarylpropyl amines obtained is demonstrated by their transformation to 3‐aryl‐tetrahydroquinolines and 4‐benzyl‐tetrahydroisoquinolines, which have not yet been obtained in an enantioselective manner by direct reduction of the corresponding aromatic heterocycles. This strategy allows the preparation of these types of alkaloids with the highest enantioselectivity reported up to date.
Molecular Motion and Nonradiative Decay: Towards Efficient Photothermal and Photoacoustic Systems
Authors: Xu Changhuo , Ye Ruquan , Shen Hanchen , Lam Jacky W. Y. , Zhao Zheng , Zhong Tang Ben 
Published: May 2022

AbstractNonradiative decay invariably competes with radiative decay during the deexcitation process of matter. In the community of luminescence research, nonradiative decay has been deemed less attractive than radiative decay. However, all things in their being are good for something and so is nonradiative decay. As the molecular motion‐facilitated nonradiative decay (MMFND) effect is inevitable in photophysical processes, it provides a new avenue to convert the harvested light energy into exploitable forms by harnessing molecular motion. In many cases, active molecular motion enables thermal deactivation from excited states. In this Minireview, recent advances in photothermal and photoacoustic systems with MMFND character are summarized. We believe that this presentation of the rational engineering of molecular motion for efficient photothermal generation will deepen the understanding of the relationship between molecular motion and nonradiative decay and navigate people to rethink the positive aspects of nonradiative decay for the establishment of new light‐controllable techniques.
Organocatalytic Enantioselective Synthesis of Bicyclo[2.2.2]octenones via Oxaziridinium Catalysed ortho‐Hydroxylative Phenol Dearomatization**
Authors: D'Arcy Tom D. , Elsegood Mark R. J. , Buckley Benjamin R. 
Published: May 2022

AbstractHydroxylative dearomatization reactions of phenols (HPD) offer an efficient way to assemble complex, biologically relevant scaffolds. Despite this, enantioselective hydroxylative phenol dearomatizations for the construction of bicyclo[2.2.2]octenones are classically limited to stoichiometric chiral reagents, and a practical, enantioselective catalytic method has remained elusive. Herein, we describe a highly enantioselective, organocatalytic tandem o‐HPD‐[4+2] reaction. Our methodology utilizes a chiral oxaziridinium organocatalyst, that is available in both enantiomeric forms, to afford dearomatized products in high enantioselectivity over a range of phenol substitution patterns. This approach was applied to the highly enantioselective synthesis of (+)‐biscarvacrol (99 : 1 e.r.) and (−)‐bis(2,6‐xylenol) (94 : 6 e.r.). The practicality of our conditions was demonstrated at gram‐scale, using an amine precatalyst, accessible in a single synthetic step.
Ligand Fluorination to Mitigate the Raman Relaxation of DyIII Single‐Molecule Magnets: A Combined Terahertz, Far‐IR and Vibronic Barrier Model Study
Authors: Ma Yan , Zhai Yuan‐Qi , Luo Qian‐Cheng , Ding You‐Song , Zheng Yan‐Zhen 
Published: May 2022

AbstractThe fast Raman relaxation process via a virtual energy level has become a puzzle for how to chemically engineer single‐molecule magnets (SMMs) with better performance. Here, we use the trifluoromethyl group to systematically substitute the methyl groups in the axial position of the parent bis‐butoxide pentapyridyl dysprosium(III) SMM. The resulting complexes—[Dy(OLA)2py5][BPh4] (LA=CH(CF3)2− 1, CH2CF3− 2, CMe2CF3− 3)—show progressively enhanced TBhys (@100 Oe s−1) from 17 K (for 3), 20 K (for 2) to 23 K (for 1). By experimentally identifying the varied under barrier relaxation energy in the 5–500 cm−1 regime, we are able to identify that the C−F bond related vibration energy of the axial ligand ranging from 200 to 350 cm−1 is the key variant for this improvement. Thus, this finding not only reveals a correlation between the structure and the Raman process but also provides a paradigm for how to apply the vibronic barrier model to analyze multi‐phonon relaxation processes in lanthanide SMMs.
A Chain‐Growth Mechanism for Conjugated Polymer Synthesis Facilitated by Dinuclear Complexes with Redox‐Active Ligands
Authors: King Andrew J. , Zhukhovitskiy Aleksandr V. 
Published: May 2022

AbstractConjugated polymers are widely used in energy conversion and sensor applications, but their synthesis relies on imprecise step‐growth or narrow‐scope chain‐growth methods, typically based on transition metal (TM)‐catalyzed cross‐coupling. Here we report that a dinickel complex with a redox‐active naphthyridine diimine ligand accesses new chain‐growth mechanistic manifolds for both donor and acceptor conjugated polymers, represented by poly(3‐hexylthiophene), poly(2,3‐bis(2‐ethylhexyl)thienopyrazine), and poly(2‐(2‐octyldodecyl)benzotriazole). For the latter, our method is particularly effective: we achieve high degrees of polymerization (DP) (>100) with moderate dispersities (Đ) of ≈1.4. Mechanistic analysis supports a radical/radical anion chain‐growth mechanism with organometallic intermediates instead of TM‐catalyzed cross‐couplings. Hence, our work develops new mechanisms for conjugated polymer synthesis and furnishes insights about the elementary reactivity of dinuclear complexes.
Synthesis and application of temperature‐sensitive polymer as a novel plugging agent for water‐based drilling fluids
Authors: Bai Xiaodong , Yong Xuemei , Luo Yumei , Deng Licheng , Li Ke , Zhou Yi 
Published: May 2022

AbstractIn the process of drilling with water‐based drilling fluid, polymer plugging agent is very important to solve the problem of wellbore instability in the formation with micropores and microfractures. In this study, N‐isopropyl acrylamide and 2‐acrylamide‐2‐methylpropanesulfonic acid were grafted onto the surface of SiO2 modified by vinyl trimethoxysilane by reverse suspension polymerization reaction, and a heat‐sensitive polymer plugging agent was synthesized. The structure analysis showed that the synthetic material was the target product, with a particle size of 49.665 μm, high‐temperature resistance and sensitive temperature response behavior. According to laboratory evaluation experiments, it can be seen that the addition of the polymer increased the electrostatic stability of bentonite particles and had a chemical inhibition effect. Under the action of temperature and pressure, the synthesized temperature sensitive plugging agent formed a dense hydrophobic membrane on the surface of mud cake, which physically sealed the microcracks and pores, and reduced the filtration loss, so as to greatly improve the stability of shale. The experimental results showed that the synthesized temperature sensitive plugging agent has excellent high‐temperature resistance and plugging performance.