bluuebunny/crossref_metadata_2025 huggingface dataset:
Deciphering the Influence of Effective Shear Modulus on Neuronal Network Directionality and Growth Cones’ Morphology via Laser‐Assisted 3D‐Printed Nanostructured Arrays
Authors: Flamourakis George , Dong Qiangrui , Kromm Dimitri , Teurlings Selina , van Haren Jeffrey , Allertz Tim , Smeenk Hilde , de Vrij Femke M. S. , Tas Roderick P. , Smith Carlas S. , Brinks Daan , Accardo Angelo
Published: October 2024

In the present study, the influence of topographic and mechanical cues on neuronal growth cones (NGCs) and network directionality in 3D‐engineered cell culture models is explored. Two‐photon polymerization (2PP) is employed to fabricate nanopillar arrays featuring tunable effective shear modulus. Large variations in mechanical properties are obtained by altering the aspect ratio of the nanostructures. The nanopillar arrays are seeded with different neuronal cell lines, including neural progenitor cells (NPCs) derived from human induced pluripotent stem cells (iPSCs), I3Neurons, and primary hippocampal neurons. All cell types exhibit preferential orientations according to the nanopillar topology, as shown by neurites creating a high number of oriented orthogonal networks. Furthermore, the differentiation and maturation of NPCs are affected by the topographic and mechanical properties of the nanopillars, as shown by the expression of the mature neuronal marker Synapsin I. Lastly, NGCs are influenced by effective shear modulus in terms of spreading area, and stochastic optical reconstruction microscopy (STORM) is employed to assess the cytoskeleton organization at nanometric resolution. The developed approach, involving laser‐assisted 3D microfabrication, neuro‐mechanobiology, and super‐resolution microscopy, paves the way for prospective comparative studies on the evolution of neuronal networks and NGCs in healthy and diseased (e.g., neurodegenerative) conditions.
Effective Upcycling of Degraded NCM Cathode Materials Assisted by Surface Engineering for High‐Performance Lithium‐Ion Batteries
Authors: Chen Long , Xing Chunxian , Yang Zhuoli , Tao Shuqiang , Zhang Yucheng , Wang Guangren , Yang Peng , Song Jiapeng , Chen Jiaqi , Fei Linfeng
Published: October 2024

Lithium‐ion batteries (LIBs) with ternary oxide cathode materials are the prevalent energy storage devices for electric vehicles, and the huge amounts of spent LIBs pose severe challenges in terms of environmental impact and resource management. Particularly, the proper handling of degraded cathode materials is of central importance for the sustainable and closed‐loop development of LIBs industry. In this context, direct regeneration of degraded ternary oxides toward reusable high‐performance cathode materials is environmentally and economically favorable in contrast to present metallurgical recycling methods. In this work, a simple and effective two‐step method is demonstrated to regenerate the degraded NCM 622 (LiNi0.6Co0.2Mn0.2O2) materials by elemental compensation and structural restoration. Moreover, a multi‐functional LTO (Li4Ti5O12) surface coating is simultaneously designed to guarantee rapid Li+ diffusion and stable surface of the regenerated product. Therefore, the regenerated LTO‐coated NCM materials show excellent electrochemical performance; specifically, the initial discharge capacity (183.0 mAh g−1 at 0.1 C), rate capability (90.0 mAh g−1 at 10 C), and cycling stability (79.3% capacity retention after 200 cycles) are even comparable with those of fresh materials. The as‐established upcycling strategy may shed light on the value‐added recycling of degraded cathode materials and thereby a virtuous cycle of LIBs.
Stability‐Enhanced Variable Stiffness Metamaterial with Controllable Force‐Transferring Path
Authors: Yi Jixuan , Lyu Ronghao , Li Yiwen , Wan Chao , Zhang Kai
Published: October 2024

Self‐contact variable stiffness (SVS) metamaterial offers specific patterns of elastic strain energy storage by changing its force‐transferring path. The change of the elastic strain energy storage patterns further influences the stiffness variation of the SVS metamaterials. However, challenges still arise because typically fabricated SVS metamaterials inevitably contain structural irregularities, eccentricities, and defects. These microstructural imperfections impede the stable generation of designed strain energy storage patterns in the metamaterial, implying that the SVS metamaterials cannot achieve expected stiffness variations. To address this burning question, an SVS metamaterial/meta‐structure design paradigm with eccentric unit designs is proposed, which can realize both stable stiffness variations and high load‐bearing. The theoretical, simulation, and experimental results demonstrate that the SVS chain meta‐structure achieves ≈110 times stiffness variation between the low and high loading conditions. Its load‐bearing can reach more than 1500 N when the meta‐structure falls into the high stiffness stage. Furthermore, some typical functions are demonstrated using the stability‐enhanced SVS metamaterial, including customized mechanical protections for human joints and information transformation regulated by remote mechanical input signals. The results can provide a useful solution for generating a more feasible stability‐enhanced SVS metamaterial/meta‐structure and promote their potential applications in aerospace, medical devices, and robotics.
Tuning the Sensitivity of Photonic Sensors Toward Alkanes Through the Textural Properties of Hybrid Xerogel Coatings
Authors: Rosales‐Reina Beatriz , López‐Torres Diego , Cruz‐Quesada Guillermo , Espinal‐Viguri Maialen , Elosúa César , Reinoso Santiago , Garrido Julián J.
Published: October 2024

This work exemplifies how incorporating organosilane modifiers into silica matrices allows for tuning the optical response of reflection photonic sensors through customizing the textural properties of hybrid xerogel sensing films. Xerogels with propyl molar percentages 0, 5, and 10% are used to construct photonic probes (OFS0pTEOS, OFS5pTEOS and OFS10pTEOS, respectively) by dip‐coating upon optimizing film deposition parameters. The time response of these probes toward a battery of volatile organic compounds (VOCs) comprising species with different functionality, size‐shape, and polarity is systematically analyzed through ON/OFF experiments, revealing that a low propyl content makes the poor‐responding OFS0pTEOS film highly sensitive toward non‐aromatic, large molecules with low‐polar or non‐polar character in OFS5pTEOS. This sensor is particularly sensitive toward alkanes, with globular cyclohexane (cyHex) outperforming elongated n‐hexane. Variable‐temperature calibration curves obtained from step‐by‐step experiments and adsorption–desorption cycles corroborate these observations and allow hysteresis to be quantified. The response to cyHex closely follows VOC concentration changes with the most stable signal among analytes, leading to well‐defined curves with low‐to‐negligible hysteresis. The isosteric enthalpies of cyHex adsorption are obtained for both the bulk material and the sensor, demonstrating labile adsorbate‐adsorbent interactions ruling the sensor response and becoming more exothermic for larger VOC concentrations.
Direct Ink Writing of Cephalopod Skin‐Like Core‐Shell Fibers From Cholesteric Liquid Crystal Elastomers and Dyed Solutions
Authors: Li Shangsong , Yu Kun‐Hao , Garcia Isabel , Nah So Hee , Chui Hiu Ning Tiffany , Tian Ziting , Yang Shu
Published: October 2024

Direct ink writing (DIW) of core‐shell structures allows for patterning hollow or composite structures for shape morphing and color displays. Cholesteric liquid crystal elastomers (CLCEs) with liquid crystal mesogens assembled in a helix superstructure are attractive for generating tunable iridescent structural colors. Here, by fine‐tuning the rheology of the core and shell materials, respectively, this study creates droplets or a continuous filament in the core from the precursors of polydimethylsiloxane (PDMS) or poly(vinyl alcohol), whereas CLCE forms the outer shell. By introducing a dye in the droplets, the skin structures of cephalopods, consisting of chromatophores and iridocytes, are mimicked for enhanced color saturation, lightness, and camouflage. After removal of the core material, a CLCE hollow fiber is obtained, which can switch colors upon mechanical stretching and pneumatic actuation, much like papilla along with iridocytes. Further, liquid crystal mesogens assembled in the bulk of the fiber are in polydomain. Thus, the skin appears opalescent at room temperature, much like how leucophores enhance reflectins. Upon heating above the nematic to isotropic transition temperature, the skin becomes transparent. Lastly, a cephalopod model is constructed, where different parts of the model can change colors independently based on different mechanisms.
Investigation on the Necessity of Low Rates Activation toward Lithium‐Sulfur Batteries
Authors: Li Chen , Wang Su , Wang Zhaokun , Li Zuohang , Zhang Chenchen , Ma Yue , Shi Xixi , Zhang Hongzhou , Song Dawei , Zhang Lianqi
Published: October 2024

Low rate activation process is always used in conventional transition metal oxide cathode and fully activates active substances/electrolyte to achieve stable electrochemical performance. However, the related working mechanism in lithium‐sulfur (Li‐ battery is unclear due to the multiple complex chemical reaction steps including the redox of sulfur and the dissolution of polysulfides intermediate. Hence, the influencing mechanism of activation process on Li‐S battery is explored by adopting different current densities of 0.05, 0.2, and 1 C in initial three cycles before long‐term cycling tests at 0.2 C (denoted by 0.05, 0.2, and 1‐battery). 0.05‐battery presents the highest initial capacity in activation process, while 0.2‐battery presents superior electrochemical performances after 150 cycles. The similar trend can be found in more long‐term cycling rates such as 0.02, 0.1, 0.5, and 1 C. Potentiostatically Li2S precipitation test demonstrates that rapid generation of Li2S is achieved at higher current density, and S8‐Li2Sn‐Li2S conversion is accelerated according to Tafel plots. However, interfacial electrochemical and physical characterizations suggest that serious lithium dendrite growth will be induced under high current density. Therefore, considering the reaction kinetics and interfacial properties, low rate activation process is unnecessary when cycling current lower than 1 C for Li‐S battery.
Synergetic Combination of Bio‐Electrolytes and Bio‐Fluidic Channels as a Novel Resource of Sustainable Energy
Authors: Nath Nabamallika , Bora Barsha Rani , Gogoi Raktim , Raidongia Kalyan
Published: October 2024

Exploration for sustainable energy resources is essential to minimize the dependence on fossil fuels and to improve environmental parameters. Here, the possibility of utilizing bio‐waste‐derived electrolytes as an electrical energy resource by placing them across semipermeable membranes prepared through parallel stacking of coir fibers is examined. The nanofluidic membrane (d‐CF‐V) prepared by modifying the inner walls of the bio‐fluidic channels with atomically thin layers of vanadium pentoxide (VO) shows excellent perm‐selectivity (t+ = 0.87, with 1000‐fold concentration difference) and electricity conversion efficiency (≈ 28.2%). With simulated sea and river water, the d‐CF‐V yields output energy up to 2.4 W m−2, similarly with mineral acid bases (0.5 m HCl and 0.01 m NaOH), the d‐CF‐V shows an energy output of 11.8 W m−2. The sun‐dried Garcinia morella (Kuji thekera), and charred peels of Musa balbisiana (banana) are used as sustainable sources of bio‐electrolytes, which in combination with permselective d‐CF‐V yielded a power density of ≈1.4 W m−2. By replacing standard Ag/AgCl electrodes with nanomaterials exhibiting contrasting charge transfer activities, oxidized carbon nanotube membrane (o‐CNT) and polyaniline (PANI) membrane the output voltage is enhanced from –127 to –568 mV and current output is increased from 10.2 to 51.5 µA.
Tailoring the Charge Transfer‐Driven Oxidation in van der Waals Ferroelectric NbOI2 Through Hetero‐Interface Engineering
Authors: Wang Rui , Yuan XiaoJia , Lin Shui , Wang JiaPeng , Liu Yue , He Wen , Shao WenZhu , Sun ZhaoYuan , Fang YuQiang , Cai Jun , Liu Zhi , Xu Cheng‐Yan , Huang FuQiang , Zhen Liang , Zhang ShengLi , Li Yang
Published: October 2024

2D transition metal halide oxides (TMHOs) have attracted much interest due to their intriguing ferroelectrics and excellent nonlinear optics, however, their susceptibility to oxidation makes their basic research and practical application a challenge. Therefore, it is crucial to understand the oxidation mechanism and explore effective strategies for protection. Here, taking van der Waals (vdWs) ferroelectric NbOI2 as an example, oxidation mechanisms and tuning the oxidation behaviors of NbOI2 and its heterostructures by a variety of in situ experiments and first‐principles calculations are discovered. The ambient‐pressure X‐ray photoelectron spectra reveal a self‐limiting oxidation in isolated NbOI2, driven by spontaneously formed iodine vacancies that react with oxygen molecules due to their lower formation and adsorption energies. For the heterostructures with a lower Fermi level (such as WSe2) than transition state VI@NbOI2 (NbOI2 rich in I‐vacancies), the charge transfer from NbOI2 to WSe2 drives the continuous and complete oxidation of NbOI2 flakes. Moreover, the heterostructures with a higher Fermi level (such as graphene) than VI@NbOI2 can weaken the oxidation of NbOI2. By linking the energy band structures to oxidation behavior, the work offers a new oxidation mechanism of 2D air‐sensitive materials and a crucial strategy for improving their chemical stability.
Direct and Inverse Photoelectron Spectroscopy Evidence for a Revised Picture of Electronic States of Negative Polarons in n‐Doped C60
Authors: Ren Yutong , Sun Qi , Kuila Suman , Tang Kan , Li Hong , Barlow Stephen , Marder Seth R. , Brédas Jean‐Luc , Kahn Antoine
Published: October 2024

Determining the electronic levels associated with polarons, the fundamental charge carriers in organic semiconductors, is key to understanding the charge transport properties of these materials. Recent findings challenge the traditional view of these electronic levels by highlighting the importance of intra‐molecular Coulomb interactions in polarons. Experimental evidence was previously presented for a revised model of the negative polaron in the case of the polymer semiconductor poly(NDI2OD‐T2); there, the addition of an excess electron was seen to lead to the emergence of a singly occupied state within the energy gap of the undoped material and an unoccupied state above the edge of the conduction states. Here, focus is on a small‐molecule semiconductor, C60, and spectral evidence is provided of a similar picture for the new states appearing upon polaron formation. Specifically, direct and inverse photoemission spectroscopy is used to investigate the density of states in C60 films n‐doped with two dimeric dopants. The Coulomb interaction energy (Hubbard U) of the C60 anion is experimentally determined to be ≈1.1 eV, a value that aligns closely with theoretical predictions.
High‐Accuracy Liquid Flow Monitoring via Triboelectric Nanogenerator Combined with Bionic Design and Common‐Mode Interference Suppression
Authors: He Siyang , Yang Zheng , Wang Jianlong , Wang Xinxian , Zhang Jiacheng , Guo Xin , Li Hengyu , Cheng Tinghai , Wang Zhong Lin , Cheng Xiaojun
Published: October 2024

In the development of smart cities, accurate liquid flow monitoring is essential for the efficient operation of water supply systems. Current flow sensors often face limitations in sensitivity and environmental adaptability, affecting measurement accuracy, and restricting their application in smart city infrastructure. To address these challenges, this study proposes a high‐accuracy flow monitoring method. Specifically, by combining the bionic design with advanced signal processing techniques, the sensitivity and anti‐interference ability are improved, respectively, to enhance the measurement accuracy. Based on this method, a self‐powered flow sensor (SPFS) is developed using noncontact triboelectric nanogenerators (NC‐TENGs) as the sensing unit. The SPFS achieves a sensitivity of 2.07 Hz L−1 min−1 and improves the signal‐to‐noise ratio by more than 13 times over the initial sensing signal. In addition, an intelligent system is developed to accurately measure water resources. The maximum flow rate error rate is less than 0.97% compared to commercial flow sensors. The SPFS demonstrates higher sensitivity and accuracy compared to the existing TENG flow sensors. This study addresses the limitations of existing flow sensors and pioneers a novel solution for enhanced water resource management in smart cities.
Multifunctional Strategies of Advanced Electrocatalysts for Efficient Urea Synthesis
Authors: Ge Riyue , Huo Juanjuan , Lu Peng , Dou Yuhai , Bai Zhongchao , Li Wenxian , Liu Huakun , Fei Bin , Dou Shixue
Published: October 2024

The electrochemical reduction of nitrogenous species (such as N2, NO, NO2−, and NO3−) for urea synthesis under ambient conditions has been extensively studied due to their potential to realize carbon/nitrogen neutrality and mitigate environmental pollution, as well as provide a means to store renewable electricity generated from intermittent sources such as wind and solar power. However, the sluggish reaction kinetics and the scarcity of active sites on electrocatalysts have significantly hindered the advancement of their practical applications. Multifunctional engineering of electrocatalysts has been rationally designed and investigated to adjust their electronic structures, increase the density of active sites, and optimize the binding energies to enhance electrocatalytic performance. Here, surface engineering, defect engineering, doping engineering, and heterostructure engineering strategies for efficient nitrogen electro‐reduction are comprehensively summarized. The role of each element in engineered electrocatalysts is elucidated at the atomic level, revealing the intrinsic active site, and understanding the relationship between atomic structure and catalytic performance. This review highlights the state‐of‐the‐art progress of electrocatalytic reactions of waste nitrogenous species into urea. Moreover, this review outlines the challenges and opportunities for urea synthesis and aims to facilitate further research into the development of advanced electrocatalysts for a sustainable future.
Motion‐Adaptive Tessellated Skin Patches With Switchable Adhesion for Wearable Electronics
Authors: Choi Geonjun , Kim Jaeil , Kim Hyunjoong , Bae Haejin , Kim Baek‐Jun , Lee Hee Jin , Jang Hyejin , Seong Minho , Tawfik Salah M. , Kim Jae Joon , Jeong Hoon Eui
Published: October 2024

Skin‐interfaced electronics have emerged as a promising frontier in personalized healthcare. However, existing skin‐interfaced patches often struggle to simultaneously achieve robust skin adhesion, adaptability to dynamic body motions, seamless integration of bulky devices, and on‐demand, damage‐free detachment. Here, a hybrid strategy that synergistically combines these critical features within a thin, flexible patch platform is introduced. This design leverages shape memory polymers (SMPs) arranged in a tessellated array, comprising both rigid and compliant SMPs. This configuration enables exceptional deformability, motion adaptability, and ultra‐strong, repeatable skin adhesion while offering on‐demand adhesion control. Furthermore, the design facilitates the seamless integration of bulky electronics without compromising skin adhesion. By incorporating sizeable electronics including signal acquisition circuits, sensors, and a battery, it is demonstrated that the proposed tessellated patch can be securely mounted on the skin, accommodate dynamic body motions, precisely detect physiological signals with an outstanding signal‐to‐noise ratio (SNR), wirelessly transmit data, and be effortlessly released from the skin.
Balancing Potassiophilicity and Catalytic Activity of Artificial Interface Layer for Dendrite‐Free Sodium/Potassium Metal Batteries
Authors: Deng Wenjie , Yu Zuxi , Yang Hai , Chen Zhihao , Zheng Jiale , He Zixu , Shao Yu , Jiao Shuhong , Tao Xinyong , Shen Yanbin , Wu Xiaojun , Yu Yan
Published: October 2024

Potassium metal batteries (PMBs), with high energy density and low cost, are considered a promising option for grid‐scale energy storage systems. However, challenges such as the uneven nucleation of K and instability of the solid electrolyte interphase (SEI) layer result in dendrite growth and poor cyclic performance, limiting practical application. To address them, constructing an artificial interface layer with rich defects can enhance the potassium affinity and promote the uniform nucleation of potassium, yet this can also catalyze electrolyte to decompose, leading to unstable SEI formation and poor cycle stability. Herein, a carbon layer with a locally ordered structure (SC‐1600) is constructed as the artificial interface to achieve a balance between K affinity and catalytic activity. This optimized design allows for the uniform nucleation of potassium metal and the formation of a dense SEI layer. SC‐1600@K symmetric cell can operate for 2000 h at 0.5 mA cm−2 with a capacity of 0.5 mAh cm−2, and the developed full cell shows a high capacity retention of 78% after 1500 cycles at 1 A g−1. Besides, SC‐1600@Na effectively extend the life of sodium metal batteries. This work provides a new insight for the construction of efficient K metal artificial interface layer.
Iron‐Catalyzed Reductive Coupling of Nitro Compounds with Grignard and Organozinc Reagents for Synthesis of Functionalized Secondary Amines
Authors: Hata Takeshi , Nishi Koki , Goto Daiki , Tatsumi Yuta , Kobayashi Shoma , Shigeta Masayuki , Urabe Hirokazu
Published: October 2024

The treatment of nitro compounds with Grignard reagents in the presence of a catalytic amount of FeCl2/t‐BuMgCl produced various types of secondary amines in good yields. This reductive coupling most likely involves the compatibility of functional groups such as chlorine, benzyl ether, olefin, and acetylene. Moreover, the corresponding poly‐substituted amines were not observed under these conditions. When the Grignard reagents were replaced with organozinc reagents, functionalized secondary amines containing ester and nitrile groups were obtained in good yields.
Assessment of Thermoelectric Properties of Bi2Se3: Insights from Hybrid Functional Studies, Strain Engineering, and Machine Learning Methodology
Authors: Kurian Elavunkel Vipin , Padhan Prahallad
Published: October 2024

Thermoelectric properties in topological insulator Bi2Se3 are explored with multifaceted strategies, i.e., hybrid functional with strain and artificial intelligence methodology. The assessment with the experimental band gap values recognizes the limitations of conventional functional and the effectiveness of screened hybrid functionals. A thorough investigation into the impact of biaxial and uniaxial strain on thermoelectric parameters uncovers distinctive behaviors in n‐type and p‐type Bi2Se3, providing insights into optimal strain conditions for improved performance. Furthermore, the studies on the role of topologically non‐trivial surface states (TNSS) in thermoelectric properties reveal that TNSS significantly dominate electronic transport. Dual scattering time approximation elucidates the segregation of thermoelectric transport contributions from bulk and surface states, highlighting the importance of controlling the relaxation time ratio for enhanced thermoelectric performance. Additionally, the prediction of thermoelectric properties using Random Forest and Neural Networks models showcase impressive agreement with density functional theory predictions across varying temperatures, offering a powerful tool for understanding complex temperature‐dependent trends in thermoelectric properties. In summary, this interdisciplinary study presents a unique approach to advancing the understanding and optimization of thermoelectric properties in Bi2Se3. It provides a comprehensive framework for tailoring material behavior for diverse thermoelectric applications.
Investigation of the Electronic Structure in GaAs/AlxGa1‐xAs Quantum Dots with Four Electrons
Authors: Çakır Bekir , Yakar Yusuf , Özmen Ayhan
Published: October 2024

In this paper, a detailed analysis of the electronic structure of four‐electron quantum dots is performed with finite confinement potential by a modified variational optimization approach based mainly on the quantum genetic algorithm and the Hartree‐Fock‐Roothaan method. For the ground and higher excited configurations, our analysis covers a range of parameters like the average energies of ground and excited states, singlet and triplet state energies, orbital energies, and two‐electron Coulomb and exchange interaction energies. One‐electron kinetic energy, the Coulomb potential energy between electrons and impurity, the confinement potential energy for the electrons, and the probability of finding an electron inside or outside the quantum well are also studied. The results demonstrate that both spatial confinement and the height of the potential barrier have a pronounced effect on all energies in the strong and intermediate confinement regions, but this influence weakens significantly in large dot radii. The most substantial difference between singlet and triplet energies occurs in the 1s22s2p configurations, with this difference decreasing in higher configurations. Significant increases in the 1s and 2s orbital energies are observed at the dot radii where the 2p, 3d, and 4f electrons from the outermost orbit begin to penetrate the well.
Homo‐Nuclear Hetero‐Atomic Conjugated Reticular Oligomers for Heterojunction: A Novel “Electron Medium” for Panel Photoelectrocatalysis
Authors: Zhang Ruijuan , Zhang Boying , Liu Haining , Jewell Linda , Liu Xinying , Qiao Shanlin
Published: October 2024

A substantial challenge in employing covalent organic frameworks (COFs) for photoelectrochemical (PEC) water splitting lies in improving their solution‐processability while concurrently facilitating the transfer of charges and mass to the catalytic sites. Herein, we synthesize a solution‐processable conjugated reticular oligomers (CROs), and further embed ruthenium (Ru) into the CRO, forming a CRO‐Ru with homo‐nuclear hetero‐atomic. Thereafter, CRO and CRO‐Ru construct an organic–organic heterojunction membrane at the nanoscale. This design achieves perfect lattice matching, significantly reducing the energy barrier of mass transfer, and effectively lowering the recombination rate of charge carriers. The optimized photocathode, CuI/CRO‐Bpy:CRO‐Bpy‐Ru‐1:1+P3HT/SnO2/Pt, exhibits an efficiency of 111.0 µA cm−2 at 0.4 V versus a reversible hydrogen electrode (RHE). Compared with the original bulk COFs and CROs, the efficiency is significantly improved. The apparent improvements in charge carrier separation and transfer are responsible for the high PEC activity. In the heterojunction, the incorporation of CRO‐Bpy‐Ru with a longer excited‐state lifetime and a substantial built‐in electric field has effectively accelerated the photo‐induced electron transfer from the conduction band (CB) of CRO‐Bpy to the valence band (VB) of CRO‐Bpy‐Ru, effectively suppressing the recombination of charges. These findings offer significant guidance for the design and optimization of high‐performance photoelectrochemical catalysts.
Enhancement of Single‐Molecule Magnet Properties by Manipulating Intramolecular Dipolar Interactions
Authors: Huang Jia‐Qi , Chen Qi‐Wei , Ding You‐Song , Zhu Xiao‐Fei , Wang Bing‐Wu , Pan Feng , Zheng Zhiping
Published: October 2024

A new single‐molecule magnet (SMM) complex [K(18‐crown‐6)][(COT)Er(µ‐Cl)3Er(COT)] (Er2Cl3, COT = cyclooctatetraenide dianion) is obtained by the reaction of [(COT)Er(µ‐Cl)(THF)]2 (Er2Cl2, THF = tetrahydrofuran) with an equivalent of KCl in the presence of 18‐crown‐6. The two COT‐Er units in the newly formed complex are triply bridged by µ‐Cl ligands, leading to the “head‐to‐tail” alignment of the magnetic easy axes distinctly different from the “staggered” arrangement in the precursor complex. This structural transformation has led to significantly enhanced intramolecular dipolar interactions and a reduced transverse component of the crystal fields, increasing the energy barrier from 150(8) K for Er2Cl2 to 264(4) K for Er2Cl3 and extending its magnetic relaxation time at 2 K by 2500 times with respect to Er2Cl2. More importantly, the blocking temperature increased from lower than 2 K for Er2Cl2 to 8 K for Er2Cl3, and the magnetic hysteresis loops at 2 K changed from butterfly‐shaped for Er2Cl2 to open hysteresis loop with coercive force of 7 kOe for Er2Cl3. These results suggest that the properties of SMMs can be effectively tuned and improved by rationally arranging magnetic spins via molecular engineering.
Spontaneous Cooling Enables High‐Quality Perovskite Wafers for High‐Sensitivity X‐Ray Detectors with a Low‐Detection Limit
Authors: Wu Wenyi , Zhang Jianqiang , Liu Ciyu , Zhang Jiankai , Lai Hoajie , Hu Zhongqiang , Zhou Hai
Published: October 2024

Developing high‐quality perovskite wafers is essential for integrating perovskite technology throughout the chip industry chain. In this article, a spontaneous cooling strategy with a hot‐pressing technique is presented to develop high‐purity, wafer‐scale, pinhole‐free perovskite wafers with a reflective surface. This method can be extended to a variety of perovskite wafers, including organic–inorganic, 2D, and lead‐free perovskites. Besides, the size of the wafer with diameters of 10, 15, and 20 mm can be tailored by changing the mold. Furthermore, the mechanism of spontaneous cooling for improving the quality of perovskite wafers is revealed. Finally, the high‐quality lead‐free Cs3Cu2I5 perovskite wafers demonstrate excellent X‐ray detection performances with a high sensitivity of 3433.6 µC Gyair−1 cm−2 and a low detection limit of 33.17 nGyair s−1. Moreover, the Cs3Cu2I5 wafers exhibit outstanding environmental and operational stability even without encapsulation. These research presents a spontaneous cooling strategy to achieve wafer‐scale, high‐quality perovskites with mirror‐like surfaces for X‐ray detection, paving the way for integrating perovskites into electronic and optoelectronic devices and promoting the practical application of perovskite X‐ray detectors.
Scalable Metal–Organic Chemical Vapor Deposition of High Quality PtSe2
Authors: Prechtl Maximilian , Heiserer Stefan , Busch Marc , Hartwig Oliver , Ó Coileáin Cormac , Stimpel‐Lindner Tanja , Zhussupbekov Kuanysh , Lee Kangho , Zhussupbekova Ainur , Berman Samuel , Shvets Igor V. , Duesberg Georg S.
Published: October 2024

Platinum diselenide (PtSe2), a 2D noble metal dichalcogenide, has recently received significant attention due to its outstanding properties. It undergoes a semimetal to semiconductor transition when thinned, offers a bandgap in the infrared range, and exhibits excellent stability in ambient conditions. These properties make it a prime active material in optoelectronic and chemical sensing devices. However, there is a high demand for a synthesis method that can produce large‐scale and reliable high‐quality PtSe2. In this study, the growth of PtSe2 is presented by metal–organic vapor deposition on a variety of substrates. Comprehensive Raman, X‐ray photoelectron, and X‐ray diffraction spectroscopy, as well as scanning tunneling microscopy characterization reveals the high quality of the deposited PtSe2. Domains within the films are found to be up to several hundreds of nanometers in size, and their highly ordered crystalline structure is evident from atomic‐scale measurements. Electrical characterization demonstrates improved conductivity relative to conventional synthesis methods. This study provides fundamental guidance for the scalable synthesis and implementation of high quality PtSe2 layers with controllable thickness, offering a key requirement for the implementation of PtSe2 in future applications.
Stable LCO Cathodes Charged at 4.6 V for High Energy Secondary Li‐ion Batteries by One‐Pot Dual Metal Fluorides Coating
Authors: Harika Villa Krishna , Penki Tirupathi Rao , Fan Tianju , Elumalai Perumal , Shpigel Netanel , Aurbach Doron
Published: October 2024

LiCoO2 (LCO) has been the cathode material of choice for three decades for durable, lightweight Li‐ion storage systems. Being charged up to 4.2 V versus Li/Li+, LCO provides excellent cycling stability with a specific capacity of ≈140 mAh g−1. Raising the cut‐off voltage to 4.6 V improves capacity by up to 60% however, it leads to rapid degradation of the cathode structure. Here, a one‐pot dual coating of MgF2 and AlF3 with fluorinated electrolyte additives achieves 190 mAh g−1 at a 0.5 C rate after 400 cycles with a capacity retention of 93%. Various analytical tools are used to follow the structural and morphological changes during cycling. Synergistically, ion transport is improved, and detrimental interfacial side reactions with the electrolyte solutions are fully mitigated. Structural stability is thus improved by using this coating, with only a little loss of the active material. This work provides a brief guideline for designing dual metal‐ion‐based surface coatings in various electrolytes to develop high‐voltage cathode systems for Li and maybe also Na batteries.
Strategically Modified Ligand Incorporating Mixed Phosphonate and Carboxylate Groups to Enhance Performance in All‐Iron Redox Flow Batteries
Authors: Nambafu Gabriel S. , Hollas Aaron M. , Rice Peter S. , Weller Jon Mark , Boglaienko Daria , Reed David M. , Sprenkle Vincent L. , Li Guosheng
Published: October 2024

Iron redox flow batteries (Fe‐RFBs) hold significant promise for achieving cost‐effectiveness and utilizing abundant materials for stationary energy storage applications. Here, a design of a novel Fe complex utilizing a nitrogenous phosphonate/carboxylate mixed ligand, N,N‐Bis(phosphonomethyl)glycine (BMPG), is presented to achieve high performance Fe anolyte. Compared to its all‐phosphonate form, nitrilotri(methylphosphonic acid) (NTMPA), the new complex Fe(BPMG)2 demonstrates a negatively shifted redox potential, resulting in ≈0.07 V (≈10%) increase in battery output voltage. Full battery testing paired with ferrocyanide catholyte demonstrates stable cycling (capacity degradation <0.0001%/cycle) over 730 consecutive charge/discharge cycles with Coulombic Efficiency of 100% at a current density of 20 mA cm−2 under near neutral pH (≈8). Of particular interest, density functional theory (DFT) studies and operando Raman measurements provide strong evidence supporting a molecular structure in BPMG, which reveals the mixed phosphonate/carboxylate groups in BPMG maintain the octahedral coordination of the Fe ion center with phosphonates exclusively, while leaving the carboxylate unbound for both Fe(II) and Fe(III) complexes. This structural similarity between BPMG‐based Fe(II) and Fe(III) complexes effectively mitigates the slow redox reaction kinetics observed in Fe(NTMPA)2 anolyte, where significant ligand reorientation occurs between Fe(II) and Fe(III) complexes.
Portable Machine Tools by Small Piezoelectric Robots for Scalable and Waviness‐Adaptive Fabrication of Surface Microstructures
Authors: Ding Peiyuan , Zhang Jianfu , Feng Pingfa , Zhang Xiangyu , Wang Jianjian
Published: October 2024

Surface functional microstructures exhibit extensive application requirements in an array of breakthrough areas. One critical problem that restricts their industrial application is the lack of scalable fabrication techniques due to the limitation of conventional machine tools. This study proposes a scalable surface texturing technique using a portable small (30 × 19 × 22 mm) three‐leg robot that walks and works on the workpiece surface. Due to the elliptical tool vibration, microgrooves can be created on the workpiece surface periodically; meanwhile, the machining force drives the robot to walk forward. Surface texturing experiments are conducted on aluminum and copper workpieces to explore the machining performance of the small robot. The robot can reach a maximum moving velocity of 6.3 mm s−1 and can produce microstructures with a spacing of 4–14 μm on workpiece surfaces. Owing to its unique working principle, the small robot can maintain a constant depth of cut, demonstrating its capacity to adapt to the surface waviness of the workpiece. Finally, the motion straightness of the robot is greatly improved by combining it with the auxiliary track, and multiline microstructures are obtained. In short, the developed small robot presents a promising solution to the challenge of scalable surface texturing.
Clinical Features of a Japanese Girl With Radio‐Tartaglia Syndrome due to a SPEN Truncating Variant
Authors: Nishi Eriko , Yanagi Kumiko , Okamoto Nobuhiko , Kaname Tadashi
Published: October 2024

Radio‐Tartaglia syndrome (RATARS) (MIM#619312) is a genetic disorder caused by heterozygous truncating variants of SPEN on chromosome 1p36. This syndrome is extremely rare, with only 34 cases reported to date. RATARS is characterized by developmental delay, hypotonia, and intellectual disability. In this study, we report a Japanese girl with psychomotor delay, hypotonia, and facial features resembling Down syndrome (DS). We identified a de novo heterozygous pathogenic variant of SPEN and diagnosed her with RATARS. The patient was born at 38 weeks and 1 day of gestational age, weighing 2598 g, without respiratory or feeding difficulties. We first considered DS as a differential diagnosis based on the developmental delay with hypotonia and facial features, including an upslanted palpebral fissure, hypertelorism, epicanthus folds, and a low nose; however, it was ruled out after cytogenetic testing. Microarray analysis revealed no pathogenic aberrations. We performed trio‐based whole exome sequencing and identified a recurrent pathogenic variant of SPEN:NM_015001.3:c.6223_6227del, p.(Ser2075GlufsTer46). Although some features of RATARS have been reported to be similar to those of 1p36 deletion syndrome, facial similarity to DS was a characteristic of our case. Whether this feature is unique to the patient or relatively common in individuals with RATARS should be discussed further as more cases of individuals with RATARS are reported.
Family Lore, a Variant of Uncertain Significance, and CADASIL
Authors: Duarte Rhys , Vossaert Liesbeth , Darilek Sandra A. , Rose Chelsi , Schauer Evan , Parobek Christian , Bland Emily , Machol Keren , Mizerik Elizabeth , Murali Chaya N.
Published: October 2024

An infant presents in extremis. After the medical team stabilizes him, the race is on to figure out why he got so sick in the first place. The consulting genetics team thinks that it is unlikely his problems are due to a genetic cause, but his extreme, confounding presentation is enough to justify trio exome sequencing. When the results reveal an unexpected, paternally inherited variant of uncertain significance (VUS) in NOTCH3, fresh questions arise. The infant's presenting symptoms and descriptive diagnoses, including hematemesis, epistaxis, and gastric ulcers, certainly do not fit the mold of CADASIL. However, closer inspection of his family history yields tantalizing clues: a father and paternal grandfather with seizures, and a paternal grandfather with unexplained mood disturbances in middle age. Combining details gleaned from the family history and medical literature, the clinical genetics and laboratory genetics team collaborated, reclassified the VUS as likely pathogenic, and offered a new unifying diagnosis to explain much of the family's lore.
Recent Progress on Organic Electron Donors (OEDs) Enabled Radical Reactions
Authors: Shao Yu , Jia Xiaodong
Published: October 2024

Over the past few decades, organic transformations facilitated by small organic molecules have witnessed considerable advancements. Small organic molecules have been widely applied to the construction of various skeletons. However, reduction as one of the fundamental reactions is generally initiated by metal‐containing reducing agents, although the initial progress of organic electron donors (OEDs) enabled reductive cleavage of some chemical bonds had been achieved in 1990s. Due to their structural diversity and tunability, OEDs can overcome the limitations of metal‐based reducing agents, such as low selectivity and poor functional group tolerance as well as the environmental problems caused by substantial inorganic waste after reactions. Building on a brief historical overview of OED research, this review focuses on the rencent advancements of the OEDs promoted radical reactions. It covers the reduction of C−X (X=C, O, N etc.) single bonds, radical cyclization, intermolecular radical addition to unsaturated bonds, radical coupling, functionalization of aromatics, and C−H bond activation. Additionally, the mechanistic insights of the typical reactions are highlighted for well understanding of the reaction mode involving OEDs.
Biomarkers of endothelial dysfunction and cognition: A two‐step IPD meta‐analysis
Authors: Beran Magdalena , Jansen Willemijn J. , Oomens Julie E. , Moonen Justine E. F. , Slagboom P. Eline , Huisman Martijn , Kok Almar A. L. , Nooyens Astrid C. J. , Verschuren Wilhelmina Maria Monique , Stehouwer Coen D. A. , Schalkwijk Casper , Köhler Sebastian , Beekman Marian , Slagboom Pieternella Eline , Wolters Frank J. , Ikram M. Arfan , Vallerga Costanza L. , van Meurs Joyce B. J. , Ghanbari Mohsen , Vonk Jet M. J. , Geerlings Mirjam I. , van Sloten Thomas T. , Schram Miranda T. ,   the NCDC Consortium
Published: October 2024

INTRODUCTION

This study assessed the association of plasma biomarkers of endothelial dysfunction with cognitive performance and decline.

METHODS

Data from 9414 individuals from eight Dutch cohorts were included (Ø  age‐range: 57–93 years). Plasma biomarkers of endothelial dysfunction (soluble intercellular adhesion molecule‐1 (sICAM‐1), soluble vascular cell adhesion molecule‐1 (sVCAM‐1), soluble E‐selectin) were combined into a standardized composite score. Cognitive outcomes included executive function, processing speed, immediate and delayed memory, attention, and language. Linear regressions and linear mixed models were run in the individual cohorts and standardized coefficients were subsequently pooled using random‐effects meta‐analyses.

RESULTS

A higher endothelial dysfunction composite score was cross‐sectionally associated with worse performance on executive function, processing speed, delayed memory, and attention, but not immediate memory or language (pooled β‐range: −0.04, −0.02). We found no association with change in cognition over time.

DISCUSSION

This comprehensive two‐step, individual participant data (IPD) meta‐analysis showed a small, consistent cross‐sectional association between endothelial dysfunction and worse cognitive performance across multiple domains but no support for a longitudinal association.

Highlights

Prior evidence on endothelial dysfunction (ED) biomarkers and cognition is conflicting.

This two‐step, individual participant data (IPD) meta‐analysis used data from eight Dutch cohorts.

ED was consistently associated with concurrent cognition.

ED was not associated with a change in cognition over time.

The association of ED with current cognition may be generic.
Association of common and rare variants with Alzheimer's disease in more than 13,000 diverse individuals with whole‐genome sequencing from the Alzheimer's Disease Sequencing Project
Authors: Lee Wan‐Ping , Choi Seung Hoan , Shea Margaret G. , Cheng Po‐Liang , Dombroski Beth A. , Pitsillides Achilleas N. , Heard‐Costa Nancy L. , Wang Hui , Bulekova Katia , Kuzma Amanda B. , Leung Yuk Yee , Farrell John J. , Lin Honghuang , Kunkle Brian W. , Naj Adam , Blue Elizabeth E. , Nusetor Frederick , Wang Dongyu , Boerwinkle Eric , Bush William S. , Zhang Xiaoling , De Jager Philip L. , Dupuis Josée , Farrer Lindsay A. , Fornage Myriam , Martin Eden , Pericak‐Vance Margaret , Seshadri Sudha , Wijsman Ellen M. , Wang Li‐San ,   The Alzheimer's Disease Sequencing Project, Schellenberg Gerard D. , Destefano Anita L. , Haines Jonathan L. , Peloso Gina M.
Published: October 2024

INTRODUCTION

Alzheimer's disease (AD) is a common disorder of the elderly that is both highly heritable and genetically heterogeneous.

METHODS

We investigated the association of AD with both common variants and aggregates of rare coding and non‐coding variants in 13,371 individuals of diverse ancestry with whole genome sequencing (WGS) data.

RESULTS

Pooled‐population analyses of all individuals identified genetic variants at apolipoprotein E (APOE) and BIN1 associated with AD (p < 5 × 10−8). Subgroup‐specific analyses identified a haplotype on chromosome 14 including PSEN1 associated with AD in Hispanics, further supported by aggregate testing of rare coding and non‐coding variants in the region. Common variants in LINC00320 were observed associated with AD in Black individuals (p = 1.9 × 10−9). Finally, we observed rare non‐coding variants in the promoter of TOMM40 distinct of APOE in pooled‐population analyses (p = 7.2 × 10−8).

DISCUSSION

We observed that complementary pooled‐population and subgroup‐specific analyses offered unique insights into the genetic architecture of AD.

Highlights

We determine the association of genetic variants with Alzheimer's disease (AD) using 13,371 individuals of diverse ancestry with whole genome sequencing (WGS) data.

We identified genetic variants at apolipoprotein E (APOE), BIN1, PSEN1, and LINC00320 associated with AD.

We observed rare non‐coding variants in the promoter of TOMM40 distinct of APOE.
Development and workflow of a separation process for optimum design: A case of phenylenediamine
Authors: O'Young Lionel , Wang Zeping , Fu Weisong , Ye Peng , Chen Weihong
Published: October 2024

An industrial project based upon the multi‐scale objective‐oriented process development (MOPD) method for developing an optimum process for separating phenylenediamine (PDA) isomers was executed. This article reports the first four (4) steps of that project. In the first step, the solution for this separation problem was conceptualized. It is a distillation‐crystallization‐hybrid process. The second step is to validate the concept experimentally from the thermodynamic point of view followed by kinetic considerations. It was found that a 2‐stage crystallization is required to purify the main product isomers to the desirable specification that is higher than 99.5 mol%. A heat and material balance model was then constructed for analyzing and optimizing various design variables, also used to understand the operability of the process. Finally, with proper HAZOP analysis and detailed engineering, the pilot unit was designed. Throughout the project, all exercises and efforts are well focused with clear objectives, hence there are minimum detours on the execution; furthermore, the clear objectives enhanced the communications among various disciplines tremendously. It is a valuable asset for senior management in the allocation of resources and budgets.