bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Gas Therapy Strategy for Intestinal Flora Regulation and Colitis Treatment by Nanogel‐Based Multistage NO Delivery Microcapsules
Authors: Fu Ya‐Jun , Zhao Xing , Wang Li‐Ya , Li Kai , Jiang Niu , Zhang Shu‐Ting , Wang Rao‐Kaijuan , Zhao Yi‐Fan , Yang Wei 
Published: February 2024

AbstractCurrent approaches to treating inflammatory bowel disease focus on the suppression of overactive immune responses, the removal of reactive intestinal oxygen species, and regulation of the intestinal flora. However, owing to the complex structure of the gastrointestinal tract and the influence of mucus, current small‐molecule and biologic‐based drugs for treating colitis cannot effectively act at the site of colon inflammation, and as a result, they tend to exhibit low efficacies and toxic side effects. In this study, nanogel‐based multistage NO delivery microcapsules are developed to achieve NO release at the inflammation site by targeting the inflammatory tissues using the nanogel. Surprisingly, oral administration of the microcapsules suppresses the growth of pathogenic bacteria and increases the abundance of probiotic bacteria. Metabolomics further show that an increased abundance of intestinal probiotics promotes the production of metabolites, including short‐chain fatty acids and indole derivatives, which modulate the intestinal immunity and restore the intestinal barrier via the interleukin‐17 and PI3K‐Akt signaling pathways. This work reveals that the developed gas therapy strategy based on multistage NO delivery microcapsules modulates the intestinal microbial balance, thereby reducing inflammation and promoting intestinal barrier repair, ultimately providing a new therapeutic approach for the clinical management of colitis.
Programmed Targeting Pyruvate Metabolism Therapy Amplified Single‐Atom Nanozyme‐Activated Pyroptosis for Immunotherapy
Authors: Niu Rui , Liu Yang , Xu Bo , Deng Ruiping , Zhou Shijie , Cao Yue , Li Wanying , Zhang Hao , Zheng Haiyang , Song Shuyan , Wang Yinghui , Zhang Hongjie 
Published: February 2024

AbstractIncreasing cellular immunogenicity and reshaping the immune tumor microenvironment (TME) are crucial for antitumor immunotherapy. Herein, this work develops a novel single‐atom nanozyme pyroptosis initiator: UK5099 and pyruvate oxidase (POx)‐co‐loaded Cu‐NS single‐atom nanozyme (Cu‐NS@UK@POx), that not only trigger pyroptosis through cascade biocatalysis to boost the immunogenicity of tumor cells, but also remodel the immunosuppressive TME by targeting pyruvate metabolism. By replacing N with weakly electronegative S, the original spatial symmetry of the Cu‐N4 electron distribution is changed and the enzyme‐catalyzed process is effectively regulated. Compared to spatially symmetric Cu‐N4 single‐atom nanozymes (Cu‐N4 SA), the S‐doped spatially asymmetric single‐atom nanozymes (Cu‐NS SA) exhibit stronger oxidase activities, including peroxidase (POD), nicotinamide adenine dinucleotide (NADH) oxidase (NOx), L‐cysteine oxidase (LCO), and glutathione oxidase (GSHOx), which can cause enough reactive oxygen species (ROS) storms to trigger pyroptosis. Moreover, the synergistic effect of Cu‐NS SA, UK5099, and POx can target pyruvate metabolism, which not only improves the immune TME but also increases the degree of pyroptosis. This study provides a two‐pronged treatment strategy that can significantly activate antitumor immunotherapy effects via ROS storms, NADH/glutathione/L‐cysteine consumption, pyruvate oxidation, and lactic acid (LA)/ATP depletion, triggering pyroptosis and regulating metabolism. This work provides a broad vision for expanding antitumor immunotherapy.
Improve the Charge Carrier Transporting in Two‐Dimensional Ruddlesden–Popper Perovskite Solar Cells
Authors: Dong Xue , Li Xin , Wang Xiaobo , Zhao Yuzhen , Song Wenqi , Wang Fangmin , Xu Shudong , Miao Zongcheng , Wu Zhongbin 
Published: February 2024

AbstractConventional 3D organic–inorganic halide perovskite materials have shown substantial potential in the field of optoelectronics, enabling the power conversation efficiency of solar cells beyond 26%. A key challenge limiting the further commercial application of 3D perovskite solar cells is their inherent instability over outer oxygen, humidity, light, and heat. By contrast, 2D Ruddlesden–Popper (2DRP) perovskites with bulky organic cations can effectively stabilize the inorganic slabs, yielding excellent environmental stability. However, the efficiencies of 2DRP perovskite solar cells are much lower than those of the 3D counterparts due to poor charge carrier transporting property of insulating bulky organic cations. Their inner structural, dielectric, optical, and excitonic properties remain to be primarily studied. In this review, the main reasons for the low efficiency of 2DRP perovskite solar cells are first analyzed. Next, a detailed description of various strategies for improving the charge carrier transporting of 2DRP perovskites is provided, such as bandgap regulation, perovskite crystal phase orientation and distribution, energy level matching, interfacial modification, etc. Finally, a summary is given, and the possible future research directions and methods to achieve high‐efficiency and stable 2DRP perovskite solar cells are rationalized.
Sculpting Tiered Micro‐Nanogradient Structure by Anisotropic Stepped Anodization for Mediating Water Distribution and Transportation
Authors: Liang Ruiqing , Ma Yingjun , Chen Junlin , Mei Chaoyuan , Xu Wang , Wu Keyu , Li Juan 
Published: February 2024

AbstractTiered micro‐nanogradient structures with custom‐tailored profiles and dimensions can be fabricated by the anisotropic electrochemical anodization of aluminum, where the micro and nanostructures are simultaneously formed. The microgradient structures can be sculpted by the chronological and spatial order of polymer masking followed by step anodization; the nanostructures can be controlled by electrochemical conditions in step anodization. Water spatial distribution and directional transportation abilities of the exemplified micro‐nanogradient structures (i.e., tiered micro symmetric circular structure, microasymmetric circular structure, and microrectangular step structure which are all integrated with nanotip‐capped nanopore structure) are studied under the fogging condition. It is found that despite the directional self‐jumping of the microdroplets caused by the cooperation of asymmetric structure and wind blowing, microdroplets can also be quickly gathered on the topper tier of the gradient structures to form large droplets and then roll away along the descending direction of the structures (also wind blowing direction), which sweep the microdroplets they passed by. These tiered micro‐nanogradient structures not only have potentials to become high efficiency fog collector but also could be a platform for the preparation of tiered micro‐nanogradient structures of various materials with advanced functions.
Enhanced Cyan Photoluminescence and Stability of CsPbBr3 Quantum Dots Via Surface Engineering for White Light‐Emitting Diodes
Authors: He Xingyi , Li Tianfeng , Liang Zifan , Liu Renming , Ran Xia , Wang Xiaojuan , Guo Lijun , Pan Caofeng 
Published: February 2024

AbstractThe emission of cyan light (470‐500 nm) plays a vital role in the visible light spectrum and is essential for applications such as lighting, displays, and optical communication. Inorganic cesium lead bromide perovskite quantum dots (CsPbBr3 PQDs) have made significant progress in the field of luminescence materials and devices, however, the lack of techniques to obtain highly emissive and stable cyan‐emitting CsPbBr3 PQDs has limited their device applications. Here, it is demonstrated that the complete surface passivation by treatment of didodecyldimethylammonium bromide (DDAB) and lead bromide, which can enhance the photoluminescence and stability of cyan emitting CsPbBr3 PQDs. In particular, the photoluminescence quantum yield of CsPbBr3 QDs can be greatly improved from 10.5% to 83.8%. Through an effective PMMA passivation, the obtained stable and bright CsPbBr3 PQDs composite films as the cyan color converters can effectively emit the cyan light to fill the “cyan gap” of white light‐emitting diode (WLED). The color rendering index value of such WLED is remarkably enhanced from 73.6 to 82.5. This study paves the way for the application of PQD color converters in the next generation of full‐visible‐spectrum WLED lighting.
The Birefringence Modulation in Short‐Wave Ultraviolet Sulfates with Functional π‐Conjugated Cations and Polymerized Heteroleptic Tetrahedral Anions
Authors: Shang Yanran , Sha Hongyuan , Wang Zujian , Su Rongbing , He Chao , Yang Xiaoming , Long Xifa 
Published: February 2024

AbstractSulfates with a large bandgap are always promising optical candidates. However, due to insufficient birefringence, their applications are restricted. Here, in terms of this deficiency, two strategies are proposed to rationally modulate the optical anisotropy of sulfates by cations and anions, respectively. For the cation modulation, the [C(NH2)3]Al(SO4)2·6H2O crystal is investigated, which exhibits an unprecedented birefringence (0.098 @ 546 nm) compared with other deep‐ultraviolet transparent sulfates, resulting from the synergy of π‐conjugated [C(NH2)3]+ and non‐π‐conjugated [SO4]2− groups. For the anion modulation, a novel functional group, [S3O6]2−, with a large polarizability anisotropy, is designed. Thus, a new crystal, NaKS3O6, is obtained, which exhibits a large birefringence of 0.130 @ 546 nm with a short ultraviolet absorption cutoff edge of 215 nm. These results confirm the validity of the strategies. Therefore, the strategies play an important role in improving sulfate's birefringence and then promoting their potential applications in advanced optical systems.
Circularly Polarized Room Temperature Phosphorescence of Chiral Bromoxanthone Using a Chiral Self‐Assembled Liquid Crystal Polymer Frameworks
Authors: Xu Dan , Liu Chao , Li Hang , Cheng Yixiang , Zheng Wen‐Hua 
Published: February 2024

AbstractChiral self‐assembly has often been found to be an efficient strategy for the development of high‐performance circularly polarized luminescent (CPL) materials, through the regulation of the ordered helical superstructure blocks in liquid crystal media. Here, the design and synthesis of two pairs of axially chiral emitters (BBXT‐3‐Br and BOHXT‐3‐Br) are reported based on bromoxanthone. And the chiral self‐assembled liquid crystal polymer (LCP) framework (PRM257) is demonstrated by mixing of the emitters with liquid crystal monomer (RM257) through thermal annealing and photoinitiated polymerization. Both BBXT‐3‐Br@PRM257 and BOHXT‐3‐Br@PRM257 exhibited excellent room temperature phosphorescence (RTP) properties. In addition, BBXT‐3‐Br@PRM257 enantiomers showed afterglow with an average lifetime (τ) of 162.41 ms and emitted blue CPL (λem = 450 nm, ΦFL = 1.3%, |gFL| = 0.071), although weak circularly polarized RTP (CP‐RTP) is observed. Interestingly, BOHXT‐3‐Br@PRM257 with a less conjugated system emits red RTP (τ = 98.83 ms) and also intense CP‐RTP (λem = 612 nm, ΦPhos = 0.45%, |gRTP| = 0.057).
tert‐Butyl Nitrite Promoted Visible‐Light‐Induced Steric‐Hindrance‐Regulated Concurrent Cross‐Coupling and Regioselective Nitration of 3‐Alkylidene‐2‐oxindoles
Authors: Sarkar Prabhat , Rana Soumitra , Jana Debashis , Mandal Subham , Mukhopadhyay Chhanda 
Published: February 2024

AbstractA tert‐butyl nitrite (TBN) promoted visible‐light‐induced one‐pot C−N cross coupling reaction of 3‐alkylidene‐2‐oxindoles with benzene‐1,2‐diamine was explored. Simultaneously, the indoline motif of 3‐alkylidene‐2‐oxindoles as well as 3‐ylidene oxindoles are regioselectively nitrated at the C‐6 position by in‐situ formed NO2 radical. (E)‐3‐(2‐(aryl)‐2‐oxoethylidene)oxindole and (E)‐3‐ylidene oxindole produce distinct nitrated diastereomeric coupling products, a phenomenon influenced by the steric bulk of the functional group. The experimental findings suggest the potential involvement of a radical pathway in this reaction.
Nickel‐Catalyzed Sonogashira Couplings: Extending the Reaction Scope to Aryl Bromides and Chlorides
Authors: Braconi Elena , Godineau Edouard , Smejkal Tomas , Jäckh Simon 
Published: February 2024

AbstractThe alkyne motif is present in several naturally occurring molecules and specialty chemicals. The Sonogashira reaction is recognized as one of the most exploited methods for the synthesis of substituted alkynes. While palladium catalysts have been traditionally employed, recent efforts have been directed towards developing alternatives based on Earth‐abundant metals such as nickel. However, nickel‐catalyzed Sonogashira couplings still present important substrate limitations. While more reactive aryl iodides have been well documented, the coupling of more challenging yet cost‐effective aryl bromides and chlorides lags significantly behind. Herein, we present a method for the nickel‐catalyzed Sonogashira coupling of aryl bromides and chlorides, whose discovery was accelerated thanks to high‐throughput experimentation. Fine‐tuning of the bipyridine ligand was essential to activate chemoselectively C(sp2)−Br or C(sp2)−Cl bonds. A wide range of functionally diverse alkynes, including examples of active ingredients and their intermediates, were accessed in a single step and with yields up to 98%. The developed methodology is expected to be widely adopted by academia and industry, marking a step forward in the field of base metal catalysis.
Synthesis of Chiral Vicinal Amino Alcohol Derivatives via Lewis Acid‐Catalyzed Asymmetric Ring Opening of Aziridines with Alcohols and Carboxylic Acids
Authors: Ma Chen‐Xue , Hu Qi , Qin Hai‐Lin , Yang Gaosheng , Chai Zhuo 
Published: February 2024

AbstractUnder the catalysis of a Cu(I) or Ag(I) salt with a chiral diphosphine ligand, the enantioselective nucleophilic ring opening of racemic 2‐styrenylaziridines via kinetic resolution or dynamic kinetic asymmetric transformation (DyKAT) and of meso aziridines via desymmetrization with alcohols was realized. The reaction provided a range of chiral vicinal amino ether derivatives in 47%‐98% yields and with 50%–98% ee. The reaction could be extended to aliphatic carboxylic acids as nucleophiles. The synthetic utility was demonstrated in a four‐step formal synthesis of a diastereomer of the antirythmetic agent vernakalant.
Pathway Evolution Through a Bottlenecking‐Debottlenecking Strategy and Machine Learning‐Aided Flux Balancing
Authors: Deng Huaxiang , Yu Han , Deng Yanwu , Qiu Yulan , Li Feifei , Wang Xinran , He Jiahui , Liang Weiyue , Lan Yunquan , Qiao Longjiang , Zhang Zhiyu , Zhang Yunfeng , Keasling Jay D. , Luo Xiaozhou 
Published: February 2024

AbstractThe evolution of pathway enzymes enhances the biosynthesis of high‐value chemicals, crucial for pharmaceutical, and agrochemical applications. However, unpredictable evolutionary landscapes of pathway genes often hinder successful evolution. Here, the presence of complex epistasis is identifued within the representative naringenin biosynthetic pathway enzymes, hampering straightforward directed evolution. Subsequently, a biofoundry‐assisted strategy is developed for pathway bottlenecking and debottlenecking, enabling the parallel evolution of all pathway enzymes along a predictable evolutionary trajectory in six weeks. This study then utilizes a machine learning model, ProEnsemble, to further balance the pathway by optimizing the transcription of individual genes. The broad applicability of this strategy is demonstrated by constructing an Escherichia coli chassis with evolved and balanced pathway genes, resulting in 3.65 g L−1 naringenin. The optimized naringenin chassis also demonstrates enhanced production of other flavonoids. This approach can be readily adapted for any given number of enzymes in the specific metabolic pathway, paving the way for automated chassis construction in contemporary biofoundries.
Dynamic Chemistry Toolbox for Advanced Sustainable Materials
Authors: Deng Yuanxin , Zhang Qi , Feringa Ben L. 
Published: February 2024

AbstractDeveloping dynamic chemistry for polymeric materials offers chemical solutions to solve key problems associated with current plastics. Mechanical performance and dynamic function are equally important in material design because the former determines the application scope and the latter enables chemical recycling and hence sustainability. However, it is a long‐term challenge to balance the subtle trade‐off between mechanical robustness and dynamic properties in a single material. The rise of dynamic chemistry, including supramolecular and dynamic covalent chemistry, provides many opportunities and versatile molecular tools for designing constitutionally dynamic materials that can adapt, repair, and recycle. Facing the growing social need for developing advanced sustainable materials without compromising properties, recent progress showing how the toolbox of dynamic chemistry can be explored to enable high‐performance sustainable materials by molecular engineering strategies is discussed here. The state of the art and recent milestones are summarized and discussed, followed by an outlook toward future opportunities and challenges present in this field.
Unveiling the Impact of the Electrolyte's Counter Ions on Organic Electrochemical Transistor Performance
Authors: Bitton Sapir , Tessler Nir 
Published: February 2024

AbstractThe effect of the electrolyte's counter‐ion in organic electrochemical transistors is often neglected. the influence of anions (i.e., counter ions) is investigated on organic electrochemical transistors (OECTs) with a PEDOT:PSS‐like semiconductor through device simulations. The study examined the effects of mobile anions on OECT performance under two scenarios: when anions are blocked by the semiconductor and when they can penetrate it. In each case, the OECT's ON and OFF states are analyzed. The findings show that when anions can penetrate the semiconductor, the ON/OFF ratio of the OECT remains unchanged while the transconductance significantly increases. In the ON state, the case of blocked anions is observed that the current is predominantly surface‐current, whereas it becomes volumetric only when anions can penetrate the semiconductor. Furthermore, the extreme case is explored in which anions remain stationary within the electrolyte. In this scenario, achieving a reasonable ON/OFF ratio necessitates an ion density within the electrolyte that is two orders of magnitude higher than the dopant density of the semiconductor. This work underscores the substantial influence of counter anions on OECT performance, highlighting their critical role in shaping device behavior.
Understanding Piezoionic Effects in Chemo–Mechanical Energy Harvesting by Carbon Nanotube Yarn Twists
Authors: Kim Keon Jung , Oh Seongjae , Kim Youngoh , Park Chae‐Lin , Song Young‐Chul , Lee Habeom , Kim Eun Sung , Suh Dongseok , Lim Seong Chu , Kim Hyun , Choi Joonmyung , Kim Shi Hyeong 
Published: February 2024

AbstractStrategies for converting mechanical energy into electrical energy hold significant importance in diverse battery‐free and battery‐supported applications. Recent studies have demonstrated promising approaches involving the twisting of carbon nanotube yarns, which alter the intrinsic electrochemical capacitance during mechanical motion, thereby generating electrical energy in various aqueous environments. However, the fundamental mechanism of chemo–mechanical energy harvesters based on the nanoscale piezoionic effect, as well as the kinetics of both cations and anions within the system, remains to be clarified. In this study, experimental and computational approaches aimed at fundamentally understanding the piezoionic effect in nanoscale chemo–mechanical dynamics are presented. This phenomenon is analyzed using in situ Raman scattering, piezoelectrochemical impedance spectroscopy, and molecular dynamics simulations. The findings elucidate the collective contributions of cations and anions under mechanical energy inputs and demonstrate the impact of piezoionic kinetics on electrical energy outputs. By gaining a comprehensive understanding of the fundamental piezoionic effect in chemo–mechanical energy harvesting systems, significant advancements in energy sustainability across numerous practical applications are anticipated.
Non‐Sacrificial Additive Enables a Non‐Passivating Cathode Interface for 4.6 V Li||LiCoO2 Batteries
Authors: Li Wei , Wang Huwei , Zhang Jinkai , Zhang Haodong , Chen Ming , Wang Jiali , Gao Yueteng , Zhao Rongyi , Hu Junyang , Feng Guang , Zhai Dengyun , Kang Feiyu 
Published: February 2024

AbstractVarious electrolyte additives are developed to construct a cathode electrolyte interphase (CEI) layer for high‐voltage LiCoO2 since the cathode suffers severe interfacial degradation when increasing the cut‐off voltage over 4.55 V. However, the CEI derived from the additive sacrificial reaction faces the risk of rupture due to the corrosion reaction and the volumetric variation of the cathode. Herein, a non‐passivating cathode interface is realized for 4.6 V LiCoO2 with a non‐sacrificial electrolyte additive (TBAClO4) by regulating the solvent environment at the interface rather than the preferential decomposition for CEI formation. Owing to the novel protection mechanism, the cell performance shows little dependence on the CEI‐formation process. Therefore, an ultra‐high initial coulombic efficiency (96.63%) and excellent cycling stability (81% capacity retention after 300 cycles) are achieved in Li||LiCoO2 batteries. Moreover, even with the electrolyte containing 1000 ppm H2O, the remarkable water capture ability of the additive together with its interfacial regulation enables the 4.6 V Li||LiCoO2 battery to retain 80% capacity after 200 cycles. This non‐sacrificial strategy provides new insights into high‐voltage electrolyte additive design for high‐energy‐density lithium metal batteries.
Cost‐Effective Transparent N‐Doped Tin Oxide Electrodes with Excellent Thermal and Chemical Stabilities Enabling Stable Perovskite Photovoltaics Based on Tin Oxide Electron Transport Layer
Authors: Seok Hae‐Jun , Kim Su Hyun , Yeom Kyung Mun , Noh Jun Hong , Kim Han‐Ki 
Published: February 2024

AbstractPerovskite solar cells (PSCs) incorporating chemical‐bath‐deposited (CBD) SnO2 layers have garnered considerable attention because they combine high electron mobility and low‐temperature processing, affording remarkable photovoltaic performance. However, the acidic conditions of CBD limit its compatibility with front transparent electrodes (FTEs). Herein, cost‐effective, thermally stable, and highly transparent nitrogen‐doped SnO2 (NTO) FTEs tailored to integrate with CBD‐SnO2‐based PSCs are developed. By precisely controlling the N dopant content in the magnetron sputtering process, a NTO FTE with a sheet resistance of 38.64 Ω/square, an optical transmittance of 86.17%, a smooth surface morphology (1.2 nm), and mechanical flexibility is obtained. Furthermore, doping N in SnO2 imparts thermal and chemical stability superior to those of conventional Sn‐doped In2O3 (ITO) electrodes. Additionally, a well‐matched energy band of NTO with a SnO2 electron transport layer (ETL) and homogeneous interfaces is a critical advantage. By implementing this multifaceted strategy using a novel low‐cost NTO FTE, CBD‐SnO2‐based PSCs with elevated open‐circuit voltages and energy‐barrier‐free characteristics are fabricated. A champion power conversion efficiency of 20.43% is achieved, and 93.30% of the initial efficiency is retained even after 3 000 h without encapsulation. This integration of a NTO FTE with a SnO2 ETL paves the way for robust and long‐lasting high‐performance PSCs.