bluuebunny/crossref_metadata_2025_split huggingface dataset:
Induced Self‐Assembly of Vitamin E‐Spermine/siRNA Nanocomplexes via Spermine/Helix Groove‐Specific Interaction for Efficient siRNA Delivery and Antitumor Therapy
Authors: Zhao Xiaoran , Xu Qi , Wang Qian , Liang Xingxing , Wang Jing , Jin Hongwei , Man Yizhi , Guo Dongyang , Gao Feng , Tang Xinjing 
Published: January 2024

AbstractGene therapy has been one of potential strategies for the treatment of different diseases, where efficient and safe gene delivery systems are also extremely in need. Current lipid nanoparticles (LNP) technology highly depends on the packing and condensation of nucleic acids with amine moieties. Here, an attempt to covalently link two natural compounds, spermine and vitamin E, is made to develop self‐assembled nucleic acid delivery systems. Among them, the spermine moieties specifically interact with the major groove of siRNA helix through salt bridge interaction, while vitamin E moieties are located around siRNA duplex. Such amphiphilic vitamin E‐spermine/siRNA complexes can further self‐assemble into nanocomplexes like multiblade wheels. Further studies indicate that these siRNA nanocomplexes with the neutrally charged surface of vitamin E can enter cells via caveolin/lipid raft mediated endocytosis pathway and bypass lysosome trapping. With these self‐assembled delivery systems, efficient siRNA delivery is successfully achieved for Eg5 and Survivin gene silencing as well as DNA plasmid delivery. Further in vivo study indicates that VE‐Su‐Sper/DSPE‐PEG2000/siSurvivin self‐assembled nanocomplexes can accumulate in cancer cells and gradually release siRNA in tumor tissues and show significant antitumor effect in vivo. The self‐assembled delivery system provides a novel strategy for highly efficient siRNA delivery.
A Holistic Review of C = C Crosslinkable Conjugated Molecules in Solution‐Processed Organic Electronics: Insights into Stability, Processibility, and Mechanical Properties
Authors: Sun Ning , Han Yamin , Huang Wenxin , Xu Man , Wang Jianguo , An Xiang , Lin Jinyi , Huang Wei 
Published: January 2024

AbstractSolution‐processable organic conjugated molecules (OCMs) consist of a series of aromatic units linked by σ‐bonds, which present a relatively freedom intramolecular motion and intermolecular re‐arrangement under external stimulation. The cross‐linked strategy provides an effective platform to obtain OCMs network, which allows for outstanding optoelectronic, excellent physicochemical properties, and substantial improvement in device fabrication. An unsaturated double carbon–carbon bond (C = C) is universal segment to construct crosslinkable OCMs. In this review, the authors will set C = C cross‐linkable units as an example to summarize the development of cross‐linkable OCMs for solution‐processable optoelectronic applications. First, this review provides a comprehensive overview of the distinctive chemical, physical, and optoelectronic properties arising from the cross‐linking strategies employed in OCMs. Second, the methods for probing the C = C cross‐linking reaction are also emphasized based on the perturbations of chemical structure and physicochemical property. Third, a series of model C = C cross‐linkable units, including styrene, trifluoroethylene, and unsaturated acid ester, are further discussed to design and prepare novel OCMs. Furthermore, a concise overview of the optoelectronic applications associated with this approach is presented, including light‐emitting diodes (LEDs), solar cells (SCs), and field‐effect transistors (FETs). Lastly, the authors offer a concluding perspective and outlook for the improvement of OCMs and their optoelectronic application via the cross‐linking strategy.
Capillarity Enabled Large‐Array Liquid Metal Electrodes for Compact and High‐Throughput Dielectrophoretic Microfluidics
Authors: Chai Huichao , Zhu Junwen , Feng Yongxiang , Liang Fei , Wu Qiyan , Ju Zhongjian , Huang Liang , Wang Wenhui 
Published: January 2024

AbstractDielectrophoresis (DEP) particle separation has label‐free, well‐controllable, and low‐damage merits. Sidewall microelectrodes made of liquid metal alloy (LMA) inherits the additional advantage of thick electrodes to generate impactful DEP force. However, existing LMA electrode‐based devices lack the ability to integrate large‐array electrodes in a compact footprint, severely limiting flow rate and thus throughput. Herein, a facile and versatile method is proposed to integrate high‐density thick LMA electrodes in microfluidic devices, taking advantage of the passive control ability of capillary burst valves (CBVs). CBVs with carefully designed burst pressures are co‐designed in microfluidic channels, allowing self‐assembly of LMA electrode array through simple hand‐push injection. The arrayed electrode configuration brings the accumulative DEP deflection effect. Specifically, The fabricated 5000 pairs of sidewall electrodes in a compact chip are demonstrted to achieve ten times higher throughput in DEP deflection. The 5000‐electrode‐pair device is applied to successfully separate four mixed samples, including human peripheral blood mononuclear cells and A549 cells with the flow rate of 70 µL min−1. It is envisioned that this work can greatly facilitate LMA electrode array fabrication and offer a robust and versatile platform for DEP separation applications.
Concurrent Mechanisms of Hot Electrons and Interfacial Water Molecule Ordering in Plasmon‐Enhanced Nitrogen Fixation
Authors: Zhang Shaoce , Chen Dong , Chen Peigang , Zhang Rong , Hou Yue , Guo Ying , Li Pei , Liang Xiu , Xing Tingyang , Chen Jie , Zhao Yuwei , Huang Zhaodong , Lei Dangyuan , Zhi Chunyi 
Published: January 2024

AbstractThe participation of high‐energy hot electrons generated from the non‐radiative decay of localized surface plasmons is an important mechanism for promoting catalytic processes. Herein, another vital mechanism associated with the localized surface plasmon resonance (LSPR) effect, significantly contributing to the nitrogen reduction reaction (NRR), is found. That is to say, the LSPR‐induced strong localized electric fields can weaken the intermolecular hydrogen bonds and regulate the arrangement of water molecules at the solid–liquid interface. The AuCu pentacle nanoparticles with excellent light absorption ability and the capability to generate strong localized electric fields are chosen to demonstrate this effect. The in situ Raman spectra and theoretical calculations are employed to verify the mechanism at the molecular scale in a nitrogen fixation process. Meanwhile, due to the promoted electron transfer at the interface by the well‐ordered interfacial water, as well as the participation of high‐energy hot electrons, the optimal catalyst exhibits excellent performance with an NH3 yield of 52.09 µg h−1 cm−2 and Faradaic efficiency (FE) of 45.82% at ─0.20 V versus RHE. The results are significant for understanding the LSPR effect in catalysis and provide a new approach for regulating the reaction process.
Study on the Photothermal Conversion Performance of TiN Modified Carbon Fiber Fabric
Authors: Wang Lin , Xiong Tiantian , Zou Hantao , Gao Chao , Yan Wu , Liu Xueting 
Published: January 2024

AbstractThe application of solar thermal conversion is an effective means of utilizing solar energy. In this study, plain, honeycomb, and terry cotton fabrics are carbonized into carbon fiber fabrics at high temperatures, with subsequent Titanium nitride (TiN) modification. The dependence of the carbon fabric properties on structure is investigated. Fiber stability, high absorbance, and structural characteristics contribute to efficient performance in solar steam generation. The vertical loop array associated with the surface of the terry structure results in improved absorbance, limiting loss of TiN particles with a consequent enhancement of fiber photothermal conversion. The optimal TiN carbon fiber fabric (TiN CFF) based evaporator can achieve a water evaporation rate of 1.82 kg m−2 h−1 under one sun with up to 93.4% absorbance. Moreover, the fiber exhibits good cycling stability and seawater desalination performance. The synergism due to TiN modification and the terry fabric structure results in an efficient and low‐cost evaporator preparation method, which can be effectively applied in photothermal conversion materials and seawater desalination.
Reaction Space Charting as a Tool in Organic Chemistry Research and Development
Authors: Baró Eloy Lozano , Nadal Rodríguez Pau , Juárez‐Jiménez Jordi , Ghashghaei Ouldouz , Lavilla Rodolfo 
Published: January 2024

AbstractThe chemical and reaction spaces are incredibly vast and special procedures are required to study them. Their complex and multiparametric nature encompass myriads of compounds and interactions and endless modifications involving the distinct impact of relevant variables (temperature, solvent, stoichiometry, etc.). This often calls for the design, collection, and analysis/interpretation of large datasets. Reaction charting, the systematic scanning, description, analysis, and guided modifications of a given process, stands as the most promising approach. It offers fast and accurate solutions as well as expanding the knowledge about the systems. This deeper understanding enables reliable predictions, improvement of the productivity (yields, scope), eventually leading to sustainable, economic, and safe applications. The present review introduces the topic, analyzing selected examples and recent advancements in different organic chemistry‐related fields. The covered methodologies range from classical experimentation modifying one factor at a time, to Design of Experiments and more modern computational approaches involving Machine Learning and Artificial Intelligence. In this way, the impact of charting in process development, biological and medicinal chemistry, catalysis, reaction discovery and computational methods is accounted. Finally, the conclusion/outlook section gives a general appraisal and a prospect on the future implementation of the methodology.
Multi‐ and Gray‐Scale Thermal Lithography of Silk Fibroin as Water‐Developable Resist for Micro and Nanofabrication
Authors: Rostami Mohammadreza , Marković Aleksandra , Wang Ya , Pernollet Joffrey , Zhang Xiaosheng , Liu Xia , Brugger Juergen 
Published: January 2024

AbstractSilk fibroin (SF) is a natural material with polymorphic structures that determine its water solubility and biodegradability, which can be altered by exposing it to heat. Here, a hybrid thermal lithography method combining scalable microscale laser‐based patterning with nanoscale patterning based on thermal scanning probe lithography is developed. The latter enables in addition grayscale patterns to be made. The resolution limit of the writing in silk fibroin is studied by using a nanoscale heat source from a scanned nanoprobe. The heat thereby induces local water solubility change in the film, which can subsequently be developed in deionized water. Nanopatterns and grayscale patterns down to 50 nm lateral resolution are successfully written in the silk fibroin that behaves like a positive tone resist. The resulting patterned silk fibroin is then applied as a mask for dry etching of SiO2 to form a hard mask for further nano‐processing. A very high selectivity of 42:1 between SiO2 and silk fibroin is obtained allowing for high‐aspect ratio structure to be fabricated. The fabricated nanostructures have very low line edge roughness of 5 ± 2 nm. The results demonstrate the potential of silk fibroin as a water‐soluble resist for hybrid thermal lithography and precise micro/nanofabrication.
Magnetic Tactile Sensor with Bionic Hair Array for Sliding Sensing and Object Recognition
Authors: Man Jiandong , Jin Zhenhu , Chen Jiamin 
Published: January 2024

AbstractDue to the high application value in intelligent robots, tactile sensors with large sensing area and multi‐dimensional sensing ability have attracted the attention of researchers in recent years. Inspired by bionics of hairs on human skin, a flexible tactile sensor based on magnetic cilia array is developed, showing extremely high sensitivity and stability. The upper layers of the sensor are multiple magnetic cilia containing magnetic particles, while the lower layer is a serpentine flexible circuit board with a magnetic sensor array. When magnetic cilia are bent under force, the magnetic sensor array can detect changes in the magnetic field, thereby the magnitude and direction of external force can be obtained. The proposed sensor has a resolution of 0.2 mN with a working range of 0–19.5 mN and can distinguish the direction of external force. The large sensing area and short response time make this sensor suitable for sliding tactile detection, and experiments show that the sensor can be also applied in object recognition with a success accuracy of 97%. In addition to the shape of objects, the sensor can identify whether there is magnetism inside objects, making it of significant value in intelligent robots and modern medicine.
The Development of Carbon/Silicon Heterojunction Solar Cells through Interface Passivation
Authors: Chen Bingbing , Zhang Xuning , Gao Qing , Yang Dehua , Chen Jingwei , Chang Xuan , Zhang Cuili , Bai Yuhua , Cui Mengnan , Wang Shufang , Li Han , Flavel Benjamin S. , Chen Jianhui 
Published: January 2024

AbstractPassivating contactsin heterojunction (HJ) solar cells have shown great potential in reducing recombination losses, and thereby achieving high power conversion efficiencies in photovoltaic devices. In this direction, carbon nanomaterials have emerged as a promising option for carbon/silicon (C/Si) HJsolar cells due to their tunable band structure, wide spectral absorption, high carrier mobility, and properties such as multiple exciton generation. However, the current limitations in efficiency and active area have hindered the industrialization of these devices. In this review, they examine the progress made in overcoming these constraints and discuss the prospect of achieving high power conversion efficiency (PCE) C/Si HJ devices. A C/Si HJ solar cell is also designed by introducing an innovative interface passivation strategy to further boost the PCE and accelerate the large area preparationof C/Si devices. The physical principle, device design scheme, and performanceoptimization approaches of this passivated C/Si HJ cells are discussed. Additionally, they outline potential future pathways and directions for C/Si HJ devices, including a reduction in their cost to manufacture and their incorporation intotandem solar cells. As such, this review aims to facilitate a deeperunderstanding of C/Si HJ solar cells and provide guidance for their further development.
Direct Construction of C‐Alkyl Glycosides from Non‐Activated Olefins via Nickel‐Catalyzed C(sp3)─C(sp3) Coupling Reaction
Authors: Yu Changyue , Xu Yinghuan , Zeng Mingjie , Wang Jingjing , Dai Wenhao , Wang Jiang , Liu Hong 
Published: January 2024

AbstractAmong C‐glycosides, C‐alkyl glycosides are significant building blocks for natural products and glycopeptides. However, research on efficient construction methods for C‐alkyl glycosides remains relatively limited. Compared with Michael acceptors, non‐activated olefins are more challenging substrates and have rarely been employed in the construction of C‐glycosides. Here, a highly efficient and convenient approach for the synthesis of C‐alkyl glycosides through a nickel‐catalyzed C(sp3)‐C(sp3) coupling reaction is presented. A distinctive feature of this method is its utilization of non‐activated olefins as the anomeric radical acceptors for hydroalkylation, allowing for the direct formation of C‐glycoside bonds in a single step. Furthermore, this method demonstrates excellent compatibility with a broad scope of highly reactive functional groups. Mechanistic investigations suggest that the reaction proceeds via a free radical pathway, leading predominantly to the formation of products with α‐configuration. Overall, this innovative methodology offers a versatile and practical approach for the synthesis of C‐alkyl glycosides, offering new avenues for the production of intricate glycosides with potential applications in drug discovery and chemical biology.
Precisely Activating cGAS‐STING Pathway with a Novel Peptide‐Based Nanoagonist to Potentiate Immune Checkpoint Blockade Cancer Immunotherapy
Authors: Xing Yumeng , Peng Ao , Yang Jianhui , Cheng Zhifei , Yue Yi , Liu Feilong , Li Fenghe , Liu Yang , Liu Qi 
Published: January 2024

AbstractAs an essential intracellular immune activation pathway, the cGAS‐STING pathway has attracted broad attention in cancer treatment. However, low bioavailability, nonspecificity, and adverse effects of small molecule STING agonists severely limit their therapeutic efficacy and in vivo application. In this study, a peptide‐based STING agonist is first proposed, and KLA is screened out to activate the cGAS‐STING pathway by promoting mitochondrial DNA (mtDNA) leakage. To precisely activate the cGAS‐STING pathway and block the PD‐1/PD‐L1 pathway, a multi‐stimuli activatable peptide nanodrug (MAPN) is developed for the effective delivery of KLA and PD‐L1 antagonist peptide (CVR). With rational design, MAPN achieved the site‐specific release of KLA and CVR in response to multiple endogenous stimuli, simultaneously activating the cGAS‐STING pathway and blocking PD‐1/PD‐L1 pathway, ultimately initiating robust and durable T cell anti‐tumor immunity with a tumor growth inhibition rate of 78% and extending the median survival time of B16F10 tumor‐bearing mice to 40 days. Overall, antimicrobial peptides, which can promote mtDNA leakage through damaging mitochondrial membranes, may be potential alternatives for small molecule STING agonists and giving a new insight for the design of novel STING agonists. Furthermore, MAPN presents a universal delivery platform for the effective synergy of multiple peptides.
Impact of Non‐Stoichiometric Phases and Grain Boundaries on the Nanoscale Forming and Switching of HfOx Thin Films
Authors: Schmidt Niclas , Kaiser Nico , Vogel Tobias , Piros Eszter , Karthäuser Silvia , Waser Rainer , Alff Lambert , Dittmann Regina 
Published: January 2024

AbstractHfO2 is one of the most common memristive materials and it is widely accepted that oxygen vacancies are prerequisite to reduce the forming voltage of the respective memristive devices. Here, a series of six oxygen engineered substoichiometric HfO2 − x thin films with varying oxygen deficiency is investigated by conductive atomic force microscopy (c‐AFM) and the switching process of substoichiometric films is observed on the nanoscale. X‐ray diffractometry (XRD) exhibits a phase transition from stoichiometric, monoclinic HfO2 toward oxygen deficient, rhombohedral HfO1.7. The conductance of HfO2 − x is increasing with increasing oxygen deficiency, which is consistent with the increasing prevalence of the highly conductive rhombohedral phase. Simultaneously, c‐AFM reveals significant local conductivity differences between grains and grain boundaries, regardless of the level of oxygen deficiency. Single grains of highly oxygen deficient samples are formed at significant lower voltages. The mean forming voltage is reduced from (7.0 ± 0.6) V for HfO2 to (1.9 ± 0.8) V for HfO1.7. Resistive switching on the nanoscale is established for single grains for the highest deficient thin film samples. The final resistance state is thereby dependent on the initial conductivity of the grains. These studies offer valuable insights into the switching behavior of memristive polycrystalline HfO2.
Kinetic Asymmetry and Directionality of Nonequilibrium Molecular Systems
Authors: Astumian Raymond Dean 
Published: January 2024

AbstractScientists have long been fascinated by the biomolecular machines in living systems that process energy and information to sustain life. The first synthetic molecular rotor capable of performing repeated 360° rotations due to a combination of photo‐ and thermally activated processes was reported in 1999. The progress in designing different molecular machines in the intervening years has been remarkable, with several outstanding examples appearing in the last few years. Despite the synthetic accomplishments, there remains confusion regarding the fundamental design principles by which the motions of molecules can be controlled, with significant intellectual tension between mechanical and chemical ways of thinking about and describing molecular machines. A thermodynamically consistent analysis of the kinetics of several molecular rotors and pumps shows that while light driven rotors operate by a power‐stroke mechanism, kinetic asymmetry—the relative heights of energy barriers—is the sole determinant of the directionality of catalysis driven machines. Power‐strokes—the relative depths of energy wells—play no role whatsoever in determining the sign of the directionality. These results, elaborated using trajectory thermodynamics and the nonequilibrium pump equality, show that kinetic asymmetry governs the response of many non‐equilibrium chemical phenomena.
Trifluoromethyl Rhodium‐Carbynoid in [2+1+2] Cycloadditions
Authors: Zhao Wen‐Wen , Tian Meng‐Yang , Zhou Yi‐Lin , Liu Lu‐Jie , Tian Shao‐Fang , He Chun‐Yang , Yang Xing‐Zhi , Chen Yong‐Zheng , Han Wen‐Yong 
Published: January 2024

AbstractTrifluoromethyl cationic carbyne (CF3C+:) possessing dual carbene‐carbocation behavior emulated as trifluoromethyl metal‐carbynoid (CF3C+=M) has not been explored yet, and its reaction characteristics are unknown. Herein, a novel α‐diazotrifluoroethyl sulfonium salt was prepared and used in Rh‐catalyzed three‐component [2+1+2] cycloadditions for the first time with commercially available N‐fused heteroarenes and nitriles, yielding a series of imidazo[1,5‐a] N‐heterocycles that are of interest in medicinal chemistry, in which the insertion of trifluoromethyl Rh‐carbynoid (CF3C+=Rh) into C=N bonds of N‐fused heteroarenes was involved. This strategy demonstrates synthetic applications in late‐stage modification of pharmaceuticals, construction of CD3‐containing N‐heterocycles, gram‐scale experiments, and synthesis of phosphodiesterase 10A inhibitor analog. These highly valuable and modifiable imidazo[1,5‐a] N‐heterocycles exhibit good antitumor activity in vitro, thus demonstrating their potential applications in medicinal chemistry.
Solid State Machinery of Multiple Dynamic Elements in a Metal–Organic Framework
Authors: Perego Jacopo , Daolio Andrea , Bezuidenhout Charl X. , Piva Sergio , Prando Giacomo , Costarella Benjamin , Carretta Pietro , Marchiò Luciano , Kubicki Dominik , Sozzani Piero , Bracco Silvia , Comotti Angiolina 
Published: January 2024

AbstractEngineering coordinated rotational motion in porous architectures enables the fabrication of molecular machines in solids. A flexible two‐fold interpenetrated pillared Metal‐Organic Framework precisely organizes fast mobile elements such as bicyclopentane (BCP) (107 Hz regime at 85 K), two distinct pyridyl rotors and E‐azo group involved in pedal‐like motion. Reciprocal sliding of the two sub‐networks, switched by chemical stimuli, modulated the sizes of the channels and finally the overall dynamical machinery. Actually, iodine‐vapor adsorption drives a dramatic structural rearrangement, displacing the two distinct subnets in a concerted piston‐like motion. Unconventionally, BCP mobility increases, exploring ultra‐fast dynamics (107 Hz) at temperatures as low as 44 K, while the pyridyl rotors diverge into a faster and slower dynamical regime by symmetry lowering. Indeed, one pillar ring gained greater rotary freedom as carried by the azo‐group in a crank‐like motion. A peculiar behavior was stimulated by pressurized CO2, which regulates BCP dynamics upon incremental site occupation. The rotary dynamics is intrinsically coupled to the framework flexibility as demonstrated by complementary experimental evidence (multinuclear solid‐state NMR down to very low temperatures, synchrotron radiation XRD, gas sorption) and computational modelling, which helps elucidate the highly sophisticated rotor‐structure interplay.