bluuebunny/crossref_metadata_2025 huggingface dataset:
Extension of Process Limits in High‐Strength Aluminum Forming by Local Contact Heating
Authors: Sellner Erik , Xu Yikai , Groche Peter
Published: May 2023

The aluminum alloy EN AW‐7075 T6 is used in the automotive sector for its favorable strength‐to‐weight ratio. However, the limited cold formability is currently addressed by energy‐ and time‐consuming temperature‐assisted processes. In order to limit the effort to critical forming areas only, the state‐of‐the‐art shows promising results for increasing the blank temperature in the range of warm forming. The design of new processes in an industrial context requires appropriate numerical simulation with inherent complexity due to time‐ and temperature‐dependent effects. Herein, the potential of a newly developed tool setup and process chain with integrated local contact heating of the EN AW‐7075 T6 blank is investigated on the basis of a curved hat profile. A thermomechanically coupled FE model of the process is developed and validated. The influence of the local heating layout is analyzed in experimental forming tests and a corresponding process window is derived. The influence of local heating on the occurring failure mechanisms is discussed based on simulation results. The equivalent plastic strain evolution is successfully used to evaluate the local heating dependent failure behavior. A significant increase in the overall formability of the part is achieved by the proposed process chain.
Graphene Transistors for In Vitro Detection of Health Biomarkers
Authors: Dai Changhao , Kong Derong , Chen Chang , Liu Yunqi , Wei Dacheng
Published: May 2023

Biomarkers are primary indicators for precise diagnosis and treatment. The early identification of health biomarkers has been sustained by the evolutionary success in sensor technologies. Among them, graphene field‐effect transistor (GFET) biosensors have exhibited major advantages such as an ultrashort response time, high sensitivity, easy operation, capability of integration, and label‐free detection. Owing to the atomic thickness, graphene restricts charge carrier flow merely at the material surface and responds to foreign stimuli directly, leading to effective signal acquisition and transmission. Here, this review summarizes the latest advances in GFET biosensors in a comprehensive manner that contains the device design, working principle, surface functionalization, and proof‐of‐concept applications. It provides a comprehensive survey of GFET biosensors with regard to biomarker analysis at the single‐device level and integrated prototypes that include wearable sensors, biomimetic systems, healthcare electronics, and diagnostic platforms. Moreover, there is discussion on the long‐standing research efforts and outlook for the future development of GFET sensor systems from lab to fab.
Surface Li2CO3 Mediated Phosphorization Enables Compatible Interfaces of Composite Polymer Electrolyte for Solid‐State Lithium Batteries
Authors: Yi Xuerui , Guo Yong , Chi Sijia , Pan Siyuan , Geng Chuannan , Li Mengyao , Li Zhenshen , Lv Wei , Wu Shichao , Yang Quan‐Hong
Published: May 2023

Composite polymer electrolytes (CPEs) are subject to interface incompatibilities due to the space charge layer of ceramic and polymer phases. The intensive dehydrofluorination of poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) incorporating Li7La3Zr2O12 (LLZO) significantly compromises electro‐chemo‐mechanical properties and compatibilities with electrodes. Herein, this study addresses the challenges by precisely phosphatizing LLZO surfaces through a surface Li2CO3 mediated chemical reaction. The designed neutral chemical environment of LLZO surfaces ensures high air stability and effective suppression of PVDF‐HFP dehydrofluorination. This greatly facilitates the uniform distribution of ceramic and polymer phases, and fast interfacial Li+ exchange, establishing high‐throughput ion percolation pathways and distinctly enhancing ionic conductivity and transference number. Moreover, the dramatically reduced formation of dehydrofluorination products and an in situ formed interphase layer between phosphatized surface and a Li metal anode stabilize the Li/CPE and cathode/CPE interfaces, which provide a symmetric Li/Li cell and solid‐state Li/LiFePO4 and Li/LiNi0.8Co0.1Mn0.1O2 cells an exceptional cycling performance at room temperature. This study emphasizes the vital importance of achieving electro‐chemo‐mechanical compatibilities for CPEs and provides a new waste to wealth route.
Natural Chlorogenic Acid Planted Nanohybrids with Steerable Hyperthermia for Osteosarcoma Suppression and Bone Regeneration
Authors: Yang Yu‐ying , Zheng Yuan , Liu Jun‐jin , Chang Zhuang‐peng , Wang Yue‐hua , Shao Yun‐yun , Hou Rui‐gang , Zhang Xiao
Published: May 2023

Surgical resection is the most common approach for the treatment of osteosarcoma. However, two major complications, including residual tumor cells and large bone defects, often arise from the surgical resection of osteosarcoma. Discovering new strategies for programmatically solving the two above‐mentioned puzzles has become a worldwide challenge. Herein, a novel one‐step strategy is reported for natural phenolic acid planted nanohybrids with desired physicochemical properties and steerable photothermal effects for efficacious osteosarcoma suppression and bone healing. Nanohybrids are prepared based on the self‐assembly of chlorogenic acid and gold nanorods through robust Au‐catechol interface actions, featuring precise nanostructures, great water solubility, good stability, and adjustable hyperthermia generating capacity. As expected, on the one hand, these integrated nanohybrids can severely trigger apoptosis and suppress tumor growth with strong hyperthermia. On the other hand, with controllable mild NIR irradiation, the nanohybrids promote the expression of heat shock proteins and induce prominent osteogenic differentiation. This work initiates a brand‐new strategy for assisting osteosarcoma surgical excision to resolve the blockage of residual tumor cells elimination and bone regeneration.
Spatial Confinement Modulates Macrophage Response in Microporous Annealed Particle (MAP) Scaffolds
Authors: Liu Yining , Suarez‐Arnedo Alejandra , Riley Lindsay , Miley Tasman , Xia Jingyi , Segura Tatiana
Published: May 2023

Macrophages are essential in the initiation, maintenance, and transition of inflammatory processes such as foreign body response and wound healing. Mounting evidence suggests that physical factors also modulate macrophage activation. 2D in vitro systems demonstrate that constraining macrophages to small areas or channels modulates their phenotypes and changes their responses to known inflammatory agents such as lipopolysaccharide. However, how dimensionality and pore size affect macrophage phenotype is less explored. In this work, the change in macrophage M1/M2 polarization when confined in microporous annealed particle (MAP) scaffolds is studied. Particles sizes (40, 70, and 130 µm) are selected using outputs from software LOVAMAP that analyzes the characteristics of 3D pores in MAP gels. As the size of building block particle correlates with pore size inside the scaffolds, the three  types of scaffold allow us to study how the degree of spatial confinement modulates the behavior of embedded macrophages. Spatially confining macrophages in scaffolds with pore size on the scale of cells leads to a reduced level of the inflammatory response, which is correlated with a change in cell morphology and motility.
Delocalized Electronic Engineering of Ni5P4 Nanoroses for Durable Li–O2 Batteries
Authors: Han Xue , Zhao Lanling , Wang Jun , Liang Yanjie , Zhang Jintao
Published: May 2023

The sluggish kinetics and issues associated with the parasitic reactions of cathodes are major obstacles to the large‐scale application of Li–O2 batteries (LOBs), despite their large theoretical energy density. Therefore, efficient electrocatalyst design is critical for optimizing their performance. Ni5P4 is analyzed theoretically as a cathode material, and the downshift of the d‐band center is found to enhance electron occupation in antibonding orbits, providing a valuable descriptor for understanding and enhancing the intrinsic electrocatalytic activity. In this study, it is demonstrated that incorporating additional nitrogen atoms into Ni5P4 nanoroses regulates the electronic structure, resulting in superior electrocatalytic performance in LOBs. Further spectroscopic analysis and density functional theory calculations reveal that the incorporated nitrogen sites can effectively induce localized structure polarization, lowering the energy barrier for the production of desirable intermediates and thus enhancing battery capacity and preventing cell degradation. This approach provides a sound basis for developing advanced electrode materials with optimized electronic structures for high‐performance LOBs.
Ordering‐Dependent Hydrogen Evolution and Oxygen Reduction Electrocatalysis of High‐Entropy Intermetallic Pt4FeCoCuNi
Authors: Wang Yong , Gong Na , Liu Hongfei , Ma Wei , Hippalgaonkar Kedar , Liu Zheng , Huang Yizhong
Published: May 2023

Disordered solid‐solution high‐entropy alloys have attracted wide research attention as robust electrocatalysts. In comparison, ordered high‐entropy intermetallics have been hardly explored and the effects of the degree of chemical ordering on catalytic activity remain unknown. In this study, a series of multicomponent intermetallic Pt4FeCoCuNi nanoparticles with tunable ordering degrees is fabricated. The transformation mechanism of the multicomponent nanoparticles from disordered structure into ordered structure is revealed at the single‐particle level, and it agrees with macroscopic analysis by selected‐area electron diffraction and X‐ray diffraction. The electrocatalytic performance of Pt4FeCoCuNi nanoparticles correlates well with their crystal structure and electronic structure. It is found that increasing the degree of ordering promotes electrocatalytic performance. The highly ordered Pt4FeCoCuNi achieves the highest mass activities toward both acidic oxygen reduction reaction (ORR) and alkaline hydrogen evolution reaction (HER) which are 18.9‐fold and 5.6‐fold higher than those of commercial Pt/C, respectively. The experiment also shows that this catalyst demonstrates better long‐term stability than both partially ordered and disordered Pt4FeCoCuNi as well as Pt/C when subject to both HER and ORR. This ordering‐dependent structure–property relationship provides insight into the rational design of catalysts and stimulates the exploration of many other multicomponent intermetallic alloys.
Synergistic Modification of 2D Perovskite with Alternating Cations in the Interlayer Space and Multisite Ligand toward High‐Performance Inverted Solar Cells
Authors: Zhuang Qixin , Li Haiyun , Zhang Cong , Gong Cheng , Yang Hua , Chen Jiangzhao , Zang Zhigang
Published: May 2023

The preparation of high‐quality perovskite films is key to realize efficient and stable inverted perovskite solar cells. The trap‐assisted nonradiative recombination at grain boundary (GB) and surface poses a serious challenge for fabricating high‐quality perovskite films. Here, a synergistic modulation strategy of two‐dimensional (2D) perovskite with alternating cations in the interlayer space (ACI) and multisite ligand 2‐mercapto‐1,3,4‐thiadiazole (MTD) for fabricating high‐quality methylammonium‐free perovskite films is reported. The formation of ACI 2D perovskite promotes the nucleation of three‐dimensional (3D) perovskites, suppresses the generation of yellow phase, and promotes the formation of black phase, leading to increased grain size and crystallinity. Due to the synergistic effect of ACI 2D perovskite and MTD, the defects at GBs and surface are healed simultaneously. The significantly inhibited nonradiative recombination enables realization of high‐efficiency inverted devices with a fascinating power conversion efficiency (PCE) of 24.58%, which is one of the highest PCEs reported for inverted devices. The synergistically modified unsealed device demonstrates an excellent long‐term ambient stability, retaining 90.5% of its initial PCE after 3000 h under a relative humidity of 30–40%. This work provides deep insights into minimizing nonradiative recombination losses through the rational synergistic engineering of GB and surface toward efficient and stable inverted devices.
In Situ Anchoring Ultrafine ZnS Nanodots on 2D MXene Nanosheets for Accelerating Polysulfide Redox and Regulating Li Plating
Authors: Wei Chuanliang , Xi Baojuan , Wang Peng , Liang Yazhan , Wang Zhengran , Tian Kangdong , Feng Jinkui , Xiong Shenglin
Published: May 2023

Lithium−sulfur (Li−S) battery is a promising energy storage system due to its cost effectiveness and high energy density. However, formation of Li dendrites from Li metal anode and shuttle effect of lithium polysulfides (LiPSs) from S cathode impede its practical application. Herein, ultrafine ZnS nanodots are uniformly grown on 2D MXene nanosheets by a low‐temperature (60 °C) hydrothermal method for the first time. Distinctively, the ZnS nanodot‐decorated MXene nanosheets (ZnS/MXene) can be easily filtered to be a flexible and freestanding film in several minutes. The ZnS/MXene film can be used as a current collector for Li‐metal anode to promote uniform Li deposition due to the superior lithiophilicity of ZnS nanodots. ZnS/MXene powders obtained by freeze drying can be used as separator decorator to address the shuttle effect of LiPSs due to their excellent adsorbability. Theoretical calculation proves that the existence of ZnS nanodots on MXene can obviously improve the adsorption ability of ZnS/MXene with Li+ and LiPSs. Li−S full cells with composite Li‐metal anode and modified separator exhibit remarkable rate and cycling performance. Other transition metal sulfides (CdS, CuS, etc.) can be also grown on 2D MXene nanosheets by the low‐temperature hydrothermal strategy.
DeDoc2 Identifies and Characterizes the Hierarchy and Dynamics of Chromatin TAD‐Like Domains in the Single Cells
Authors: Li Angsheng , Zeng Guangjie , Wang Haoyu , Li Xiao , Zhang Zhihua
Published: May 2023

Topologically associating domains (TADs) are functional chromatin units with hierarchical structure. However, the existence, prevalence, and dynamics of such hierarchy in single cells remain unexplored. Here, a new generation TAD‐like domain (TLD) detection algorithm, named deDoc2, to decode the hierarchy of TLDs in single cells, is reported. With dynamic programming, deDoc2 seeks genome partitions with global minimal structure entropy for both whole and local contact matrix. Notably, deDoc2 outperforms state‐of‐the‐art tools and is one of only two tools able to identify the hierarchy of TLDs in single cells. By applying deDoc2, it is showed that the hierarchy of TLDs in single cells is highly dynamic during cell cycle, as well as among human brain cortex cells, and that it is associated with cellular identity and functions. Thus, the results demonstrate the abundance of information potentially encoded by TLD hierarchy for functional regulation. The deDoc2 can be freely accessed at https://github.com/zengguangjie/deDoc2.
Recent Advances in Ultralow‐Pt‐Loading Electrocatalysts for the Efficient Hydrogen Evolution
Authors: Guo Fei , Macdonald Thomas J. , Sobrido Ana Jorge , Liu Longxiang , Feng Jianrui , He Guanjie
Published: May 2023

Hydrogen production from water electrolysis provides a green and sustainable route. Platinum (Pt)‐based materials have been regarded as efficient electrocatalysts for the hydrogen evolution reaction (HER). However, the large‐scale commercialization of Pt‐based catalysts suffers from the high cost. Therefore, ultralow‐Pt‐loading electrocatalysts, which can reach the balance of low cost and high HER performance, have attracted much attention. In this review, representative promising synthetic strategies, including wet chemistry, annealing, electrochemistry, photochemistry, and atomic layer deposition are summarized. Further, the interaction between different electrocatalyst components (transition metals and their derivatives) and Pt is discussed. Notably, this interaction can effectively accelerate the kinetics of the HER, enhancing the catalytic activity. At last, current challenges and future perspectives are briefly discussed.
Plastic Shavings by Laser: Peeling Porous Graphene Springs for Multifunctional All‐Carbon Applications
Authors: Kim Chanwoo , Hwang Eunseung , Kwon Jinhyeong , Jang Tae Hwan , Lee Won Chul , Kim Shi Hyeong , Park Jongmin , Lee Ming‐Tsang , Kim Hyun , Hong Sukjoon , Lee Habeom
Published: May 2023

Manufacturing strategies to create three‐dimensional (3D) structures with multifunctional nanomaterials are of intense interest for fabricating building blocks in many electromechanical applications. A coil spring composed of graphene provides an important step toward the realization of all‐carbon devices, as it is one of the essential elements for a wide range of systems. In this connection, here an unprecedented fabrication strategy to create a new type of 3D coil spring composed of laser‐induced graphene springs (LIG‐S) which is spontaneously produced via the pyrolytic jetting technique, is presented. Similar to wood or metal shavings observed in traditional machining processes, a pair of LIG‐S with two opposite chiralities and controllable macroscopic dimensions is produced by a single scanning of a focused continuous‐wave (CW) laser on a polyimide (PI) substrate. The resulting LIG‐S, plastic shavings by laser, exhibits sufficient mechanical and electrical properties to enable many applications including strain‐tolerant spring electrodes, antennas, supercapacitors, gas sensors, and luminescent filaments under extreme conditions. Without using any conventional fabrication techniques or other labor‐intensive, time‐consuming, and expensive processes, this novel approach enables a high‐throughput mass production of macro‐, micro‐, and nanoscale featured LIG‐S that can be manufactured within seconds to realize many open opportunities in all‐carbon electromechanical systems.
N‐Containing Carbon‐Coated β‐Si3N4 Enhances Si Anodes for High‐Performance Li‐Ion Batteries
Authors: Hernandha Rahmandhika Firdauzha Hary , Umesh Bharath , Rath Purna Chandra , Trang Le Thi Thu , Wei Ju‐Chao , Chuang Yu‐Chun , Li Ju , Chang Jeng‐Kuei
Published: May 2023

The lithiation/delithiation properties of α‐Si3N4 and β‐Si3N4 are compared and the carbon coating effects are examined. Then, β‐Si3N4 at various fractions is used as the secondary phase in a Si anode to modify the electrode properties. The incorporated β‐Si3N4 decreases the crystal size of Si and introduces a new NSiO species at the β‐Si3N4/Si interface. The nitrogen from the milled β‐Si3N4 diffuses into the surface carbon coating during the carbonization heat treatment, forming pyrrolic nitrogen and CNO species. The synergistic effects of combining β‐Si3N4 and Si phases on the specific capacity are confirmed. The operando X‐ray diffraction and X‐ray photoelectron spectroscopy data indicate that β‐Si3N4 is partially consumed during lithiation to form a favorable Li3N species at the electrode. However, the crystalline structure of the hexagonal β‐Si3N4 is preserved after prolonged cycling, which prevents electrode agglomeration and performance deterioration. The carbon‐coated β‐Si3N4/Si composite anode shows specific capacities of 1068 and 480 mAh g−1 at 0.2 and 5 A g−1, respectively. A full cell consisting of the carbon‐coated β‐Si3N4/Si anode and a LiNi0.8Co0.1Mn0.1O2 cathode is constructed and its properties are evaluated. The potential of the proposed composite anodes for Li‐ion battery applications is demonstrated.
Superconductivity at Interfaces in Cuprate‐Manganite Superlattices
Authors: Bonmassar Nicolas , Christiani Georg , Heil Tobias , Logvenov Gennady , Suyolcu Y. Eren , van Aken Peter A.
Published: May 2023

One of the unsolved problems for using high‐Tc superconducting cuprates for spintronic applications are the short coherence lengths of Cooper pairs in oxides (a few Å), which requires atomically sharp and defect‐free interfaces. This research demonstrates the presence of high‐Tc superconducting La1.84Sr0.16CuO4 in direct proximity to SrLaMnO4 and provides evidence for the sharpness of interfaces between the cuprate and the manganite layers at the atomic scale. These findings shed light on the impact of the chemical potential at the interface of distinct materials on highly sensitive physical properties, such as superconductivity. Additionally, this results show the high stability of ultrathin layers from the same K2NiF4‐type family, specifically one unit cell of Sr2−xLaxMnO4 and three unit cells of La1.84Sr0.16CuO4. This work advances both the fundamental understanding of the proximity region between superconducting cuprates and manganite phases and the potential use of oxide‐based materials in quantum computing.
Polyaniline‐Coated Mesoporous Carbon Nanosheets with Fast Capacitive Energy Storage in Symmetric Supercapacitors
Authors: Noh Jungchul , Jekal Suk , Yoon Chang‐Min
Published: May 2023

Polyaniline‐capped mesoporous carbon nanosheets with high conductivity and porosity are synthesized by vapor deposition polymerization. The mesoporous carbon template is prepared by removing ordered cubic iron oxide nanocrystals embedded in the carbon matrix obtained by thermal decomposition of an iron‐oleate complex in a sodium chloride matrix. The evaporated aniline monomers are slowly polymerized on the carbon surface pretreated with FeCl3as an initiator, partially filling the carbon pores to improve conductivity. The resulting products exhibit efficient hybrid energy storage mechanisms of electric double‐layer capacitance and pseudocapacitance. When the nanosheets are assembled for a symmetric supercapacitor, the device capacitance reaches 107.8 F g−1, at a current density of 0.5 A g−1, and a capacitance retention of 69.6% is achieved at a ten times higher current density of 5 A g−1. Electrochemical impedance spectroscopy reveals that the transition from resistive to capacitive behavior occurs within 0.63 s, indicating that fast ion and charge transport results in high capacitance and rate capability. The corresponding energy and power densities are 9.59 Wh kg−1and 200.1 W kg−1at a current density of 0.5 A g−1, demonstrating efficient energy storage in a symmetric supercapacitor.
Individual bee foragers are less‐efficient transporters of pollen for plants from which they collect the most pollen in their scopae
Authors: Weinman Lucia R. , Ress Trent , Gardner Joel , Winfree Rachael
Published: May 2023

Premise

Bees provision most of the pollen removed from anthers to their larvae and transport only a small proportion to stigmas, which can negatively affect plant fitness. Though most bee species collect pollen from multiple plant species, we know little about how the efficiency of bees' pollen transport varies among host plant species or how it relates to other aspects of generalist bee foraging behavior that benefit plant fitness, such as specialization on individual foraging bouts.

Methods

We compared the pollen collected and transported by three bee species for 46 co‐occurring plant species. Specifically, we compared the relative abundance of pollen taxa in the individual bees' scopae, structures where bees store pollen to provision larvae, with the relative abundance of pollen taxa on the rest of bees' bodies, which is more likely to be transferred to stigmas.

Results

Bees carried five times more pollen grains in their scopae than elsewhere on their bodies. Within foraging bouts, bees were relatively specialized in their pollen collection, but transported proportionally less pollen for the host plants on which they specialized. Across foraging bouts, two bee species transported proportionally less pollen for some of their host plants than for others, though differences didn't consistently follow the same trend as at the foraging bout scale.

Conclusions

Our results suggest that foraging‐bout specialization, which is known to reduce heterospecific pollen transfer, also results in less‐efficient pollen transport. Thus, bee foragers that visit predominantly one plant species may have contrasting effects on that plant's fitness.
Alzheimer's disease heterogeneity explained by polygenic risk scores derived from brain transcriptomic profiles
Authors: Chung Jaeyoon , Sahelijo Nathan , Maruyama Toru , Hu Junming , Panitch Rebecca , Xia Weiming , Mez Jesse , Stein Thor D. ,   the Alzheimer's Disease Neuroimaging Initiative, Saykin Andrew J. , Takeyama Haruko , Farrer Lindsay A. , Crane Paul K. , Nho Kwangsik , Jun Gyungah R.
Published: May 2023

Introduction

Alzheimer's disease (AD) is heterogeneous, both clinically and neuropathologically. We investigated whether polygenic risk scores (PRSs) integrated with transcriptome profiles from AD brains can explain AD clinical heterogeneity.

Methods

We conducted co‐expression network analysis and identified gene sets (modules) that were preserved in three AD transcriptome datasets and associated with AD‐related neuropathological traits including neuritic plaques (NPs) and neurofibrillary tangles (NFTs). We computed the module‐based PRSs (mbPRSs) for each module and tested associations with mbPRSs for cognitive test scores, cognitively defined AD subgroups, and brain imaging data.

Results

Of the modules significantly associated with NPs and/or NFTs, the mbPRSs from two modules (M6 and M9) showed distinct associations with language and visuospatial functioning, respectively. They matched clinical subtypes and brain atrophy at specific regions.

Discussion

Our findings demonstrate that polygenic profiling based on co‐expressed gene sets can explain heterogeneity in AD patients, enabling genetically informed patient stratification and precision medicine in AD.

HIGHLIGHTS

Co‐expression gene‐network analysis in Alzheimer's disease (AD) brains identified gene sets (modules) associated with AD heterogeneity.

AD‐associated modules were selected when genes in each module were enriched for neuritic plaques and neurofibrillary tangles.

Polygenic risk scores from two selected modules were linked to the matching cognitively defined AD subgroups (language and visuospatial subgroups).

Polygenic risk scores from the two modules were associated with cognitive performance in language and visuospatial domains and the associations were confirmed in regional‐specific brain atrophy data.
Peptide Cyclization by the Use of Acylammonium Species
Authors: Shamoto Otoka , Komuro Keiji , Sugisawa Naoto , Chen Ting‐Ho , Nakamura Hiroyuki , Fuse Shinichiro
Published: May 2023

Although cyclic peptides have become increasingly important as drugs, the most conventional peptide cyclization method using moderately active coupling agents suffers from a lot of waste and high cost as well as long reaction times and burdensome purification. Herein, we report an unconventional approach to peptide cyclization that uses acylammonium species generated from inexpensive and less wasteful Me2NBn and ClCO2i‐Pr. Using this approach, we observed the desired rapid activation of the C‐terminus of cyclization precursors by an acylammonium ion for rapid and epimerization/dimerization‐free cyclization of synthetically challenging peptides, including a difficult cyclization involving N‐methyl amide bond formation. The ease of purification, productivities, and reaction mass efficiencies of our approach were significantly superior to those in previous reports. We synthesized a previously reported versicotide D analogue, and our data indicated that its assigned stereostructure should be revised.
Bioorthogonally Assisted Phototherapy: Recent Advances and Prospects
Authors: Kozma Eszter , Bojtár Márton , Kele Péter
Published: May 2023

Photoresponsive materials offer excellent spatiotemporal control over biological processes and the emerging phototherapeutic methods are expected to have significant effects on targeted cancer therapies. Recent examples show that combination of photoactivatable approaches with bioorthogonal chemistry enhances the precision of targeted phototherapies and profound implications are foreseen particularly in the treatment of disperse/diffuse tumors. The extra level of on‐target selectivity and improved spatial/temporal control considerably intensified related bioorthogonally assisted phototherapy research. The anticipated growth of further developments in the field justifies the timeliness of a brief summary of the state of the art.
Stabilizing Interfaces in High‐Temperature NCM811‐Li Batteries via Tuning Terminal Alkyl Chains of Ether Solvents
Authors: Wang Zhijie , Chen Changsheng , Wang Danni , Zhu Ye , Zhang Biao
Published: May 2023

Ether electrolytes are promising for lithium metal batteries. Despite the intensive research in recent years, most state‐of‐the‐art ether electrolytes still cannot form reliable electrode‐electrolyte interfaces in NCM811‐Li batteries at diluted concentrations, especially in those operating at elevated temperatures. We report a simple but effective strategy to break this bottleneck and stabilize interfaces in high‐temperature NCM811‐Li batteries in ether electrolytes. We propose that by gradually extending the terminal groups of glycol diethers from methyl groups to n‐butyl groups, the comprehensive stability of ether electrolytes is improved. An anion‐dominated solvation structure is realized at a concentration of 1 M. Accordingly, the electrode‐electrolyte interactions are suppressed, and a thinner, denser, and more inorganic‐rich solid‐ /cathode‐electrolyte interface is achieved. Additionally, the surface phase transition and structural degradation of NCM811 cathode are alleviated. Consequently, in the ethylene glycol dibutyl ether‐based electrolyte, the Coulombic efficiency for Li−Cu cells working at 60 °C is boosted to 99.41 % with a cycling life of over 200 cycles. The lifespan of high‐temperature NCM811‐Li cells is prolonged by more than 400 % with a stable average Coulombic efficiency of 99.77 % at quasi‐practical conditions of 50 μm Li, lean electrolyte of 10 μL mAh−1, and medium‐high cathode loading of >2.2 mAh cm−2.
A Hydrogen Bonded Supramolecular Framework Birefringent Crystal
Authors: Li Yanqiang , Zhang Xu , Zheng Jieyu , Zhou Yang , Huang Weiqi , Song Yipeng , Wang Han , Song Xianyu , Luo Junhua , Zhao Sangen
Published: May 2023

Birefringent crystals could modulate the polarization of light and are widely used as polarizers, waveplates, optical isolators, etc. To date, commercial birefringent crystals have been exclusively limited to purely inorganic compounds such as α‐BaB2O4 with birefringence of about 0.12. Herein, we report a new hydrogen bonded supramolecular framework, namely, Cd(H2C6N7O3)2⋅8 H2O, which exhibits exceptionally large birefringence up to about 0.60. To the best of our knowledge, the birefringence of Cd(H2C6N7O3)2⋅8 H2O is significantly larger than those of all commercial birefringent crystals and is the largest among hydrogen bonded supramolecular framework crystals. First‐principles calculations and structural analyses reveal that the exceptional birefringence is mainly ascribed to strong covalent interactions within (H2C6N7O3)− organic ligands and the perfect coplanarity between them. Given the rich structural diversity and tunability, hydrogen bonded supramolecular frameworks would offer unprecedented opportunities beyond the traditional purely inorganic oxides for birefringent crystals.
Structural Switching of a Distorted Trigonal Metal‐Organic Cage to a Tetragonal Cage and Singlet Oxygen Mediated Oxidations
Authors: Banerjee Ranit , Chakraborty Debsena , Jhang Wei‐Ting , Chan Yi‐Tsu , Mukherjee Partha Sarathi
Published: May 2023

Construction of metal–organic cages with unique architecture and guest binding abilities is highly desirable. Herein, we report the synthesis of a distorted trigonal cage (1) from a twisted tetratopic ligand (L) and a PdII acceptor. Surprisingly, 1 exhibited a complete structural reorganization of its building units in the presence of C70 and C60 to form guest‐encapsulated tetragonal cages, (C70)2@2 and (C60)2@2, respectively. These guest‐bound cages were found to be potential 1O2 generators, with the former effectively catalyzing two different varieties of 1O2‐mediated oxidation reactions.
High‐throughput Synthesis of Solution‐Processable van der Waals Heterostructures through Electrochemistry
Authors: Shi Huanhuan , Li Mengmeng , Fu Shuai , Neumann Christof , Li Xiaodong , Niu Wenhui , Lee Yunji , Bonn Mischa , Wang Hai I. , Turchanin Andrey , Shaygan Nia Ali , Yang Sheng , Feng Xinliang
Published: May 2023

Two‐dimensional van der Waals heterostructures (2D vdWHs) have recently gained widespread attention because of their abundant and exotic properties, which open up many new possibilities for next‐generation nanoelectronics. However, practical applications remain challenging due to the lack of high‐throughput techniques for fabricating high‐quality vdWHs. Here, we demonstrate a general electrochemical strategy to prepare solution‐processable high‐quality vdWHs, in which electrostatic forces drive the stacking of electrochemically exfoliated individual assemblies with intact structures and clean interfaces into vdWHs with strong interlayer interactions. Thanks to the excellent combination of strong light absorption, interfacial charge transfer, and decent charge transport properties in individual layers, thin‐film photodetectors based on graphene/In2Se3 vdWHs exhibit great promise for near‐infrared (NIR) photodetection, owing to a high responsivity (267 mA W−1), fast rise (72 ms) and decay (426 ms) times under NIR illumination. This approach enables various hybrid systems, including graphene/In2Se3, graphene/MoS2 and graphene/MoSe2 vdWHs, providing a broad avenue for exploring emerging electronic, photonic, and exotic quantum phenomena.
Catalytic Photoinduced Intramolecular Decarboxylative and Desulfonylative sp3 Allylation Enabled by Sulfinate Salts
Authors: Haut Franz‐Lucas , Mega Riccardo S. , Estornell Joan V. , Martin Ruben
Published: May 2023

Herein, we describe a catalytic intramolecular decarboxylative/desulfonylative sp3 allylation triggered by sulfinate salts under light irradiation. The reaction is likely enabled by a non‐classical, radical‐polar crossover mechanism, allowing rapid and reliable access to valuable allyl architectures from readily accessible precursors. The protocol is characterized by its operational simplicity and scalability, employing abundant, commercially available catalysts.
Rh/Cr2O3 and CoOx Cocatalysts for Efficient Photocatalytic Water Splitting by Poly (Triazine Imide) Crystals
Authors: Liu Minghui , Zhang Guigang , Liang Xiaocong , Pan Zhiming , Zheng Dandan , Wang Sibo , Yu Zhiyang , Hou Yidong , Wang Xinchen
Published: May 2023

In situ photo‐deposition of both Pt and CoOx cocatalysts on the facets of poly (triazine imide) (PTI) crystals has been developed for photocatalytic overall water splitting. However, the undesired backward reaction (i.e., water formation) on the noble Pt surface is a spontaneously down‐hill process, which restricts their efficiency to run the overall water splitting reaction. Herein, we demonstrate that the efficiency for photocatalytic overall water splitting could be largely promoted by the decoration of Rh/Cr2O3 and CoOx as H2 and O2 evolution cocatalysts, respectively. Results reveal that the dual cocatalysts greatly extract charges from bulk to surface, while the Rh/Cr2O3 cocatalyst dramatically restrains the backward reaction, achieving an apparent quantum efficiency (AQE) of 20.2 % for the photocatalytic overall water splitting reaction.
Introducing Water and Deep Eutectic Solvents in Organosodium Chemistry: Chemoselective Nucleophilic Functionalizations in Air
Authors: Dilauro Giuseppe , Luccarelli Cosimo , Quivelli Andrea F. , Vitale Paola , Perna Filippo M. , Capriati Vito
Published: May 2023

Advancing the development of perfecting the use of polar organometallics in bio‐inspired solvents, we report on the effective generation in batch of organosodium compounds, by the oxidative addition of a C−Cl bond to sodium, a halogen/sodium exchange, or by direct sodiation, when using sodium bricks or neopentylsodium in hexane as sodium sources. C(sp3)‐, C(sp2)‐, and C(sp)‐hybridized alkyl and (hetero)aryl sodiated species have been chemoselectively trapped (in competition with protonolysis), with a variety of electrophiles when working “on water”, or in biodegradable choline chloride/urea or L‐proline/glycerol eutectic mixtures, under hydrous conditions and at room temperature. Additional benefits include a very short reaction time (20 s), a wide substrate scope, and good to excellent yields (up to 98 %) of the desired adducts. The practicality of the proposed protocol was demonstrated by setting up a sodium‐mediated multigram‐scale synthesis of the anticholinergic drug orphenadrine.
Highly Enantio‐ and Diastereoselective Hydrogenation of Cyclic Tetra‐Substituted β‐Enamido Phosphorus Derivatives
Authors: Zhang Jun‐Hao , Xu Hui , Tang Xiaodong , Dang Yanfeng , Zhang Fa‐Guang , Ma Jun‐An
Published: May 2023

Catalytic asymmetric hydrogenation of enamido phosphorus derivatives is one of the most efficient methods for the construction of chiral amino phosphorus products, among which the congested tetra‐substituted substrates remains an unaddressed challenge. In this study, we utilize a commercially available Rh‐Josiphos system for the efficient and stereoselective hydrogenation of a wide set of tetra‐substituted cyclic β‐enamido phosphonates/phosphine oxides, thus enabling access to chiral β‐amino phosphorus compounds featuring two vicinal stereocenters. This protocol was broadly applicable to different ring systems possessing various phosphonate/phosphine oxide groups and further applied in the preparation of amino‐phosphine ligands. DFT mechanistic explorations indicate that the C=C migratory insertion into RhIII−H bond could be the rate‐ and stereo‐determining step. The origins of stereoselectivity are revealed through distortion/interaction analysis, which is primarily regulated by distinguished dispersion interactions and steric repulsions.
Chewing the fat: How lipidomics is changing our understanding of human health and disease in 2022
Authors: Géhin Caroline , Fowler Stephen J. , Trivedi Drupad K.
Published: May 2023

Lipids are biological molecules that play vital roles in all living organisms. They perform many cellular functions, such as 1) forming cellular and subcellular membranes, 2) storing and using energy, and 3) serving as chemical messengers during intra‐ and inter‐cellular signal transduction. The large‐scale study of the pathways and networks of cellular lipids in biological systems is called “lipidomics” and is one of the fastest‐growingomicstechnologies of the last two decades. With state‐of‐the‐art mass spectrometry instrumentation and sophisticated data handling, clinical studies show how human lipid composition changes in health and disease, thereby making it a valuable medium to collect for clinical applications, such as disease diagnostics, therapeutic decision‐making, and drug development. This review gives a comprehensive overview of current workflows used in clinical research, from sample collection and preparation to data and clinical interpretations. This is followed by an appraisal of applications in 2022 and a perspective on the exciting future of clinical lipidomics.
Artificial neural network coupled experimental investigation of tribological behavior of additive manufactured PETG/OMMT nanocomposites
Authors: Mahesh Vinyas
Published: May 2023

The advent of additive manufacturing has brought a paradigm shift in many engineering applications involving polymer composites. The current study aims at integrating artificial neural network (ANN) with experimentation to assess the wear properties of glycol‐modified polyethylene terephthalate (PETG) composites reinforced with organically modified montmorillonite (OMMT) nanoclay (1%, 3%, and 5% weight percentages). The specimens are fabricated using fused deposition modeling technology. The proposed composites are compounded and developed using a single screw extruder with a diameter of 1.75 mm. As per ASTM G99 standard, the tribological characteristics were investigated using sliding wear with the dry pin on disc arrangement. The data points owing to the wear properties of PETG/OMMT nanocomposites are collected with the aid of the experimentation, which is then used to train the ANN model using Levenberg– Marquardt backward propagation algorithm. The experimental results show that adding OMMT nanoclay at a 3% weight percentage improves the wear properties of the composites compared to virgin PETG. A scanning electron microscope study of the wear mechanism reveals that adding OMMT nanoclay to the proposed composites results in mild wear as opposed to heavy wear in the case of virgin PETG. The ANN model developed to predict the tribological performance of PETG/OMMT facilitates better predictability with 99.6% accuracy, thereby reducing the requirement of expensive experimentation and analysis. The proposed composites may be applicable in the prosthetic, aerospace and automobile industries.
Bidirectional connectivity in fishways: A mitigation for impacts on fish migration of small hydropower facilities
Authors: Bravo‐Córdoba Francisco Javier , García‐Vega Ana , Fuentes‐Pérez Juan Francisco , Fernandes‐Celestino Leandro , Makrakis Sergio , Sanz‐Ronda Francisco Javier
Published: May 2023

Most freshwater fish need to move freely through rivers to complete their life cycles. Thus, river barriers (e.g. dams, culverts and gauging stations) may delay, hinder or even block their longitudinal movements, affecting fish conservation. The most widespread solution to allow upstream fish migration are fishways, whereas downstream migration is basically facilitated through spillways, turbines or specific solutions such as bypass systems.

So far, studies and scientific discussions concerning bidirectional movements through fishways are scarce and focused on large dams and reservoirs, mainly with large migratory species such as salmonids, rather than smaller facilities and lesser known species.

This study investigated bidirectional movements through a small run‐of‐the‐river hydropower plant with a pool‐and‐orifice type fishway, using the Iberian barbel (Luciobarbus bocagei), a potamodromous cyprinid, as the target species. Passive integrated transponder and radio tracking data were collected over 4 years and combined to characterize upstream and downstream movements. The study focused primarily on fish movements through the fishway, but also estimated the multiple associated routes of passage.

The results show diverse fish movements with inter‐ and intra‐annual variability, with several individuals performing bidirectional movements and even some fish returning over the years.

The documented movements and observations indicate that fishways can serve as an effective bidirectional migration corridor for fish, potentially enhancing the conservation efforts for potamodromous species. This study supports the decision to use fishways as an overall mitigation tool to reduce the impact of small hydropower facilities on fish.
3D geometric survey of cultural heritage by UAV in inaccessible coastal or shallow aquatic environments
Authors: Gil‐Docampo Mariluz , Peña‐Villasenín Simón , Bettencourt Ana M. S. , Ortiz‐Sanz Juan , Peraleda‐Vázquez Sara
Published: May 2023

Cultural heritage in coastal or shallow aquatic environments is often located in areas where access is difficult or where accurate survey and documentation may not always be possible with terrestrial or aquatic equipment. The combination of photogrammetry and unmanned aerial vehicles (UAVs) generates a range of possibilities across multiple sectors, including history, ethnography and cultural heritage studies. Additionally, these methods can be used to prospect new archaeological sites. This article presents three case studies that use UAV techniques and Structure from Motion and Multiview Stereo (SfM‐MVS) photogrammetry to conduct topographic and geometric registrations of archaeological, historical and ethnographic sites (some of which are classified as cultural heritage sites). These examples are located in coastal or shallow aquatic environments that are difficult to survey with traditional methods. The results show that it is possible to carry out detailed geometric registration and heritage prospection over large coastal or shallow aquatic environments using a low‐cost UAV. Furthermore, the results of this work show great advantages in terms of cost and quality, even in cases where the seabed is below a shallow water column. Other particularities of SfM‐MVS application in aquatic environments are discussed. From an interdisciplinary perspective, this methodology will offer new possibilities for the study, restoration and conservation of archaeological, historical and ethnographic monuments.
Influence of Additives and Growth Inhibitors in Improving the Physicochemical Properties of Silicoaluminophosphate Molecular Sieve, SAPO‐11
Authors: Manal Arjun K. , Advani Jacky H. , Kanna Narasimharao , Kumar Pramod , Srivastava Rajendra
Published: May 2023

Silicoalumiophosphates (SAPOs) are microporous crystalline materials extensively utilized as adsorbents and catalysts. The present work utilized two strategies to synthesize nanocrystalline SAPO‐11. The first strategy involves a surfactant as a mesoporogen to reduce the crystallite size and increase the surface area for the materials synthesized at 200 °C in 2 days. In the second strategy, the synthesis temperature and time were significantly reduced to 160 °C and 3 h using propylene oxide as a pH accelerator. The reduction in the particle size and the improvement in the surface area were achieved using propyltriethoxysilane, which inhibited the growth of SAPO‐11 particles. The materials were thoroughly characterized using XRD, N2‐sorption, FTIR, pyridine‐adsorbed FTIR, electron microscopy, XPS, and NMR. The surfactant‐assisted synthesis formed a nanorod morphology with a large external and BET surface area. The low‐temperature synthesis involving silane as a growth inhibitor and propylene oxide as a pH modulator demonstrated a rectangular nanoplatelet morphology with a large surface area. The synthesis was scaled up to 10 g with no change in the experimental parameters. A synthesis strategy facilitating nuclei formation and retarding the growth of particle size will attract academia and industrial researchers to utilize these strategies for the manufacturing of zeolites of different frameworks on a large scale.