bluuebunny/crossref_metadata_2025_split huggingface dataset:
Smart Droplets Stabilized by Designer Surfactants: From Biomimicry to Active Motion to Materials Healing
Authors: Yang Zhefei , Snyder Deborah , Sathyan Ashlin , Balazs Anna , Emrick Todd 
Published: September 2023

AbstractThe science and technologies of emulsion droplets have been a long‐term focus of extensive research endeavors for their practical utility across a breadth of industries, including pharmaceutical products, oil recovery processes, and the food sciences. However, with advances in materials chemistry and characterization tools, new emerging areas are arising with a focus on “smart droplets”. The versatility of emulsion droplets across is based on their ability to partition and create isolated systems with properties defined by the liquid–liquid interface, while preparative routes allow manipulation of droplet size, stability, and encapsulated contents. As described in this article, significant efforts are being devoted to creating new types of droplets by “activating” this interface through the incorporation of reactive structures that trigger droplet response to applied or environmental stimuli (e.g., pH, temperature, salt, or external fields). Moreover, parallels between droplets and live cells inspire efforts to conceive systems that resemble biological motifs or that can produce cellular behaviors that imitate biology (e.g., swarming, communication, or motion). The authors highlight recent advances in smart droplets, with emphasis on organic, polymer, and/or particle surfactants that give rise to inter‐droplet communication (via aggregation, fusion, division, or mass transfer), droplet vehicles for controlled delivery, autonomous droplet motion, and tunable emulsion inversion. Especially emphasized is the macromolecular design to produce reactive and functional surfactants, which are crucial to responsive droplet behavior and their underlying mechanisms. More generally, the exquisite interplay between materials science and biology inspires the review of this research area that provides unique opportunities for insight and inspiration into the capabilities of new droplet designs.
Bioinspired Materials for Immunoengineering of T Cells and Natural Killer Cells
Authors: Sasidharan Sisini , Davis Daniel M. , Dunlop Iain E. 
Published: September 2023

AbstractImmune responses are directed by the complex interactions of different cell types, including T cells and Natural Killer (NK) cells, with a key type of interaction being the formation of close cell‐cell adhesions: immune synapses. Drawing on biophysical characteristics of the immune synapse and the immune cell surface, researchers are developing bioinspired materials for immunoengineering. Here are reviewed key biophysical variables that impact immune cell signaling, and how these have been exploited to develop immunomodulatory biomaterials. Mechanical forces and material properties such as stiffness are sensed by immune cells. This has enabled the modulation of cell activation using mechanically‐controlled biomaterials: hydrogels, micropillars, and nanowire arrays. In parallel, microscopy has revealed micro‐scale and nanoscale molecular patterning at cell surfaces, inspiring the creation of micro‐ and nanopatterned materials using lithography and nanoparticle approaches. The complex 3D structures of immune cells have inspired the creation of topographically patterned substrates and controlled 3D microenvironments. Finally, technologies have been developed to externally modulate biophysical variables, using magnetic and optical fields to stimulate biomaterials and drive immune cell activation. Together, these bioinspired materials are enhancing the understanding of immunology. A challenge is translation to the clinic, e.g., via improved ex vivo cell engineering for adoptive immunotherapies.
All‐Weather Self‐Powered Intelligent Traffic Monitoring System Based on a Conjunction of Self‐Healable Piezoresistive Sensors and Triboelectric Nanogenerators
Authors: Li Yongji , Tian Zhongyuan , Gao Xuan‐Zhi , Zhao Hao‐Yu , Li Xiaofeng , Wang Zhong Lin , Yu Zhong‐Zhen , Yang Dan 
Published: September 2023

AbstractA self‐powered and sustainable traffic monitoring system is highly required for future urban development. Herein, self‐healable piezoresistive sensors and triboelectric nanogenerators (TENGs) are constructed by in situ polymerization of polyvinyl alcohol‐polyacrylamide double network hydrogel in the presence of sodium alginate and tannic acid‐modified cellulose nanocrystals (denoted as PPC) for all‐weather self‐powered intelligent traffic monitoring applications. Because of hydrogen bonding and boron ester bonding, the resultant PPC‐based strain sensor can rapidly self‐heal and restore its sensing ability within 1 min with a self‐healing efficiency of 97.4%. Based on piezoresistive effect, the ions in sodium alginate endow the PPC‐based strain sensor with a relatively high gauge factor of 8.39, which can monitor the motion and fatigue of drivers. Based on triboelectrification effect, the PPC‐based TENG sensor can detect instantaneous vehicle speed, judge traffic accident liability, evaluate vehicle weight, and alert the driver to prevent accidents caused by drowsy driving. After partially replacing water in the PPC with glycerin, the resulting PPC‐based TENG sensor exhibits stable performance at temperatures ranging from ‐30 to 40 °C, ensuring its all‐weather monitoring ability. The all‐weather and self‐powered intelligent traffic monitoring system is promising for ensuring the security of future cities.
Unleashing the Full Potential of Photo‐Driven CO Hydrogenation to Light Olefins over Carbon‐Coated CoMn‐Based Catalysts
Authors: Li Ruizhe , Li Yuan , Li Zhenhua , Ouyang Shuxin , Yuan Hong , Zhang Tierui 
Published: September 2023

AbstractAs a nonpetroleum process, photodriven Fischer–Tropsch synthesis provides a practical approach for the synthesis of light olefins. However, maximizing the solar‐energy conversion efficiency based on the design of the composite catalyst and understanding the catalytic mechanism remain challenging. Herein, a novel carbon‐coated CoMn‐based catalyst, a C‐coated mixture of Co and MnO, is designed for the efficient conversion of syngas to light olefins under light irradiation. The CoMnC‐450 catalyst exhibits a CO conversion of 12.6% with a selectivity to light olefins of 36.5% under light irradiation, showing 5.5‐fold the activity of thermocatalysis. Experimental characterizations as certain the CoMnC‐450 catalyst can be excited to generate photogenerated carriers under light irradiation and then the electron transfer to metallic Co to form electron‐rich active sites with carbon mediation, thereby enhancing the catalytic performance. In situ Fourier transform infrared spectroscopy and theoretical calculation based on density functional theory reveal the unique roles of photogenerated carriers in promoting the adsorption and activation of CO molecules. This study demonstrates a feasible catalyst model to efficiently utilize full‐spectral solar light to produce the value‐added chemical.
Synthesis of Triaminocyclopentadienyl Iron(II) Tricarbonyl Complexes and Application to the Synthesis of Aminophosphines
Authors: Gaignard Gaillard Quentin , Bettoni Léo , Paris Déborah , Lequertier Clémence , Lohier Jean‐François , Gaillard Sylvain , Renaud Jean‐Luc 
Published: September 2023

AbstractA new family of triaminocyclopentadienyl iron(II) tricarbonyl complexes has been synthesized, fully characterized and applied in hydrogenation transfer. These complexes are the first Earth‐abundant metal complexes able to catalyze reductive alkylation of primary and secondary aliphatic amines with 2‐diarylphosphinobenzaldehyde derivatives at room temperature. These non‐pincer type cyclopentadienyl iron(II) complexes demonstrate not only better efficiency than known cyclopentadienone iron carbonyl complexes but also high functionality tolerance. The resulting aminophosphines provide a straightforward and rapid access to potential P−N ligands.
Rotation of the c‐Ring Promotes the Curvature Sorting of Monomeric ATP Synthases
Authors: Valdivieso González David , Makowski Marcin , Lillo M. Pilar , Cao‐García Francisco J. , Melo Manuel N. , Almendro‐Vedia Víctor G. , López‐Montero Iván 
Published: September 2023

AbstractATP synthases are proteins that catalyse the formation of ATP through the rotatory movement of their membrane‐spanning subunit. In mitochondria, ATP synthases are found to arrange as dimers at the high‐curved edges of cristae. Here, a direct link is explored between the rotatory movement of ATP synthases and their preference for curved membranes. An active curvature sorting of ATP synthases in lipid nanotubes pulled from giant vesicles is found. Coarse‐grained simulations confirm the curvature‐seeking behaviour of rotating ATP synthases, promoting reversible and frequent protein‐protein contacts. The formation of transient protein dimers relies on the membrane‐mediated attractive interaction of the order of 1.5 kBT produced by a hydrophobic mismatch upon protein rotation. Transient dimers are sustained by a conic‐like arrangement characterized by a wedge angle of θ ≈ 50°, producing a dynamic coupling between protein shape and membrane curvature. The results suggest a new role of the rotational movement of ATP synthases for their dynamic self‐assembly in biological membranes.
Red Light‐Triggered Anti‐Angiogenic and Photodynamic Combination Therapy of Age‐Related Macular Degeneration
Authors: Xu Shuting , Cui Kaixuan , Long Kaiqi , Li Jia , Fan Ni , Lam Wai‐Ching , Liang Xiaoling , Wang Weiping 
Published: September 2023

AbstractChoroidal neovascularization (CNV) is the key pathological event of wet age‐related macular degeneration (wAMD) leading to irreversible vision loss. Currently, anti‐angiogenic therapy with anti‐vascular endothelial growth factor (VEGF) agents has become the standard treatment for wAMD, while it is still subject to several limitations, including the safety concerns of monthly intravitreal administration and insufficient efficacy for neovascular occlusion. Combined therapy with photodynamic therapy (PDT) and anti‐angiogenic agents has emerged as a novel treatment paradigm. Herein, a novel and less‐invasive approach is reported to achieve anti‐angiogenic and photodynamic combination therapy of wAMD by intravenous administration of a photoactivatable nanosystem (Di‐DAS‐VER NPs). The nanosystem is self‐assembled by reactive oxygen species (ROS)‐sensitive dasatinib (DAS) prodrug and photosensitizer verteporfin (VER). After red‐light irradiation to the diseased eyes, intraocular release of anti‐angiogenic DAS is observed, together with selective neo‐vessels occlusion by VER‐generated ROS. Notably, Di‐DAS‐VER NPs demonstrates promising therapeutic efficacy against CNV with minimized systemic toxicity. The study enables an efficient intravenous wAMD therapy by integrating a photoactivation process with combinational therapeutics into one simple nanosystem.
Surface‐Redox Pseudocapacitance‐Dominated Charge Storage Mechanism Enabled by the Reconstructed Cathode/Electrolyte Interface for High‐Rate Magnesium Batteries
Authors: Wu Dongzheng , Kang Yuanhong , Wang Fei , Yang Jin , Xu Yaoqi , Zhuang Yichao , Wu Jiayue , Zeng Jing , Yang Yang , Zhao Jinbao 
Published: September 2023

AbstractTh all phenyl complex (APC) electrolyte is generally accepted to be compatible with Mg metal anodes, offering excellent plating/stripping reversibility. However, the large Cl desolvation penalty of the MgCl+ solvation structure in APC electrolyte causes a high reaction energy barrier at the cathode/electrolyte interface, resulting in unsatisfactory rate performance. Herein, the interface reconstruction strategy of an anatase TiO2 cathode is proposed by the combination of ultrathin carbon coating and oxygen vacancies, which realizes the fast surface‐redox pseudocapacitance charge storage mechanism via MgCl+, circumventing the sluggish solid‐phase migration of Mg2+. Theoretical calculations verify that the introduction of oxygen vacancies in TiO2, not only increases the intrinsic electronic conductivity, but also improves the adsorption capability for MgCl+, which enhances the surface‐redox pseudocapacitance of TiO2. Moreover, in situ Raman measurements, ex situ XPS spectra and XRD patterns demonstrate the structural integrity of TiO2 without undergoing phase change and the rapid reversible storage of MgCl+. Furthermore, in situ electrochemical impedance spectra reveal that the reconstructed cathode/electrolyte interface promotes the kinetics of active cations and induces the less potential‐dependent charge storage process. Consequently, TiO2 exhibits a remarkable rate performance (discharge capacity of 68.9 mAh g−1 at 1 A g−1) and long‐lifespan over 3000 cycles at 0.5 A g−1.
PIDA Mediated Synthesis of Benzopyranoisoxazoles via an Intramolecular Nitrile Oxide Cycloaddition (INOC): Application to the Synthesis 4H‐chromeno[4,3‐c]isoxazol‐4‐ones.
Authors: Maurya Rohit Kumar , Kumar Shubham , Kumar Vikash , Dey Ashutosh , Patlolla Ravinder Reddy , Burra Amarender Goud , Khatravath Mahender 
Published: September 2023

AbstractPresented herein is an approach for the synthesis of highly substituted tricyclic benzopyranoisoxazoles from the corresponding aldoximes via an intramolecular nitrile oxide cycloaddition (INOC) reaction using a hypervalent iodine reagent (Diacetoxyiodo)benzene (PIDA/DIB/(PhI(OAc)2) as the single inexpensive oxidizing agent. The key step involved in this reaction is a sequential intramolecular C−C and C−O bond formation. A variety of benzopyranoisoxazoles were constructed in moderate to high yields. In addition, some of the benzopyranoisoxazoles were converted to 4H‐chromeno[4,3‐c]isoxazol‐4‐ones via allylic oxidation using CrO3 as an oxidant.
Primate field research during a pandemic: Lessons learned from the SARS‐CoV‐2 outbreak
Authors: Jack Katharine M. , Kulick Nelle K. 
Published: September 2023

AbstractThe COVID‐19 pandemic abruptly halted most primate field research in early 2020. While international travel bans and regional travel restrictions made continuing primate field research impossible early on in the pandemic, ethical concerns of transmitting the virus from researchers to primates and surrounding human communities informed decisions regarding the timing of resuming research. Between June and September 2020, we surveyed field primatologists regarding the impacts of the pandemic on their research. We received 90 completed surveys from respondents residing in 21 countries, though most were from the United States and Canada. These data provide a valuable window into the perspectives and actions taken by researchers during the early stages of the pandemic as events were still unfolding. Only 2.4% of projects reported continuing research as usual, 33.7% continued with some decrease in productivity, 42.2% reported postponing research projects, and 21.7% reported canceling projects or postponing research indefinitely. Respondents most severely impacted by the pandemic were those establishing new field sites and graduate students whose projects were postponed or canceled due to pandemic‐related shutdowns. Fears about increased poaching, the inability to pay local assistants, frozen research funds, declining habituation, disruptions to data collection, and delays in student projects were among the top concerns of respondents. Nearly all the projects able to continue research in any capacity during the early months of the pandemic were run by or employed primate habitat country primatologists. This finding is a major lesson learned from the pandemic; without habitat country scientists, primate research is not sustainable.
It is time for nationally equitable access to assistive technology and home modifications in Australia: An equity benchmarking study
Authors: Layton Natasha , Brusco Natasha , Callaway Libby , Henley Lauren , Wang Rosalie H. 
Published: September 2023

AbstractAustralians with disability have inequitable access to assistive technology (AT) and home modifications (HMs). This is inconsistent with human rights obligations and fails to capitalise on internationally recognised potential return on investment. Co‐designed with a consortium of AT stakeholders, this study quantifies the public provision of AT and HM in Australia by identifying all publicly funded national and state‐/territory‐based schemes and reporting and comparing available data on the spend per person. An environmental scan and data survey identified 88 government funders administering 109 schemes. Data were available for 1/3 of schemes. Economic evaluation of available cost and participant data estimated the annual AT/HM and wrap‐around support spend per person per scheme and organisational costs. Data demonstrated significant AT/HM spend variability across schemes, for example a 50‐fold difference between Aged Care ($51) and National Disability Insurance Scheme (NDIS, $2500). Modelled costs are presented for a $16 billion national scheme where all Australians with disability are funded NDIS‐equivalent. These foundation data demonstrate substantial service provision gaps and an urgent need for change in disability policy. A cost model and policy principles have been proposed to achieve economies of scale and equity in the provision of AT and HM.
Behavioral and Cognitive Outcomes of Rhesus Macaques Following Neonatal Exposure to Antiseizure Medications
Authors: Colman Ricki , Pierre Peter , Adriansjach Julie , Crosno Kristin , Noguchi Kevin K. , Ikonomidou Chrysanthy 
Published: September 2023

ObjectiveExposure of neonatal macaques to the antiseizure medications phenobarbital and midazolam (PbM) causes widespread apoptotic death of neurons and oligodendrocytes. We studied behavior and neurocognitive performance in 12 to 24 month‐old macaques treated as neonates with PbM.MethodsA total of 14 monkeys received phenobarbital and midazolam over 24 hours under normothermia (n = 8) or mild hypothermia (n = 6). Controls (n = 8) received no treatment. Animals underwent testing in the human intruder paradigm at ages 12 and 18 months, and a 3‐step stimulus discrimination task at ages 12, 18, and 24 months.ResultsAnimals treated with PbM displayed lower scores for environmental exploration, and higher scores for locomotion and vocalizations compared with controls. Combined PbM and hypothermia resulted in lower scores for aggression and vigilance at 12 months compared with controls and normothermic PbM animals.A mixed‐effects generalized linear model was used to test for differences in neurocognitive performance between the control and PbM groups in the first step of the stimulus discrimination task battery (shape center baited to shape center non‐baited). The odds of passing this step differed by group (p = 0.044). At any given age, the odds of passing for a control animal were 9.53‐fold (95% CI 1.06–85) the odds for a PbM animal. There was also evidence suggesting a higher learning rate in the shape center non‐baited for the control relative to the PbM group (Cox model HR 2.13, 95% CI 1.02–4.43; p = 0.044).InterpretationThese findings demonstrate that a 24‐hour‐long neonatal treatment with a clinically relevant combination of antiseizure medications can have long‐lasting effects on behavior and cognition in nonhuman primates. ANN NEUROL 2024;95:57–70
Rational Design of Porous Ionic Liquids for Coupling Natural Gas Purification with Waste Gas Conversion
Authors: Ning Hailong , Shi Mingzhen , Yang Qian , Huang Jingwei , Zhang Xiaomin , Wu Youting , Jie Kecheng 
Published: September 2023

AbstractRemoval of trace impurities for natural gas purification coupled with waste gas conversion is highly desired in industry. We here report a type of porous ionic liquids (PILs) that can realize the continuous flow separation of CH4/CO2/H2S and the conversion of the captured H2S to useful products. The PILs are synthesized through a step‐by‐step surface modification of ionic liquids (ILs) onto UiO‐66‐OH nanocrystals. The introduction of free tertiary amine groups on the nanocrystal surface endows these PILs with an exceptional ability to enrich H2S from CO2 and CH4 with impressive selectivity, while the permanent pores of UiO‐66‐OH act as containers to store an exceptionally higher amount of the selectively captured H2S than the corresponding nonporous ILs. Simultaneously, the tertiary amines as dual functional moieties offer effective catalytic sites for the conversion of the H2S stored in PILs into 3‐mercaptoisobutyric acid, a key intermediate required for the synthesis of Captopril (an antihypertensive drug). Molecular dynamics, density functional theory calculations and Grand Canonical Monte Carlo simulations help understand both the mechanisms of separation and catalysis performance, confirming that the tertiary amines as well as the permanent pores in UiO‐66‐OH play vital roles in the whole procedure.
Electrochemical NiH‐Catalyzed C(sp3)−C(sp3) Coupling of Alkyl Halides and Alkyl Alkenes
Authors: Li Pengfei , Kou Guangsheng , Feng Tian , Wang Minyan , Qiu Youai 
Published: September 2023

AbstractHerein, an electrochemically driven NiH‐catalyzed reductive coupling of alkyl halides and alkyl alkenes for the construction of Csp3−Csp3bonds is firstly reported. Notably, alkyl halides serve dual function as coupling substrates and as hydrogen sources to generate NiH species under electrochemical conditions. The tunable nature of this reaction is realized by introducing an intramolecular coordinating group to the substrate, where the product can be easily adjusted to give the desired branched products. The method proceeds under mild conditions, exhibits a broad substrate scope, and affords moderate to excellent yields with over 70 examples, including late‐stage modification of natural products and drug derivatives. Mechanistic insights offer evidence for an electrochemically driven coupling process. Thesp3‐carbon‐halogen bonds can be activated through single electron transfer (SET) by the nickel catalyst in its low valence state, generated by cathodic reduction, and the generation of NiH species from alkyl halides is pivotal to this transformation.
Tetracopper σ‐Bound μ‐Acetylide and ‐Diyne Units Stabilized by a Naphthyridine‐based Dinucleating Ligand
Authors: Ríos Pablo , See Matthew S. , Handford Rex C. , Cooper Jason K. , Don Tilley T. 
Published: September 2023

AbstractReactions of a dicopper(I) tert‐butoxide complex with alkynes possessing boryl or silyl capping groups resulted in formation of unprecedented tetracopper(I) μ‐acetylide/diyne complexes that were characterized by NMR and UV/Vis spectroscopy, mass spectrometry and single‐crystal X‐ray diffraction. These compounds possess an unusual μ4‐η1:η1:η1:η1 coordination mode for the bridging organic fragment, enforced by the rigid and dinucleating nature of the ligand utilized. Thus, the central π system remains unperturbed and accessible for subsequent reactivity and modification. This has been corroborated by addition of a fifth copper atom, giving rise to a pentacopper acetylide complex. This work may provide a new approach by which metal‐metal cooperativity can be exploited in the transformation of acetylide and diyne groups to a variety of substrates, or as a starting point for the controlled synthesis of copper(I) alkyne‐containing clusters.