bluuebunny/crossref_metadata_2025_split huggingface dataset:
Yield‐Stress and Creep Control Depot Formation and Persistence of Injectable Hydrogels Following Subcutaneous Administration
Authors: Jons Carolyn K. , Grosskopf Abigail K. , Baillet Julie , Yan Jerry , Klich John H. , Saouaf Olivia M. , Appel Eric A. 
Published: August 2022

AbstractHydrogels that can be injected into the body using standard needles or catheters enable a minimally invasive strategy to prolong local delivery of therapeutic cargo. In particular, physically cross‐linked hydrogels exhibit shear‐thinning and self‐healing behaviors enabling facile injectability and depot formation upon administration. While prior efforts to characterize these systems have focused on injectability and cargo release behaviors, prediction of cargo release in the body often assumes these materials form a depot rather than spreading out upon administration. Here, it is evaluated how hydrogel rheology correlates with depot formation and persistence following subcutaneous administration in mice with two physiochemically distinct, physically cross‐linked hydrogel systems. Calcium‐alginate and polymer‐nanoparticle hydrogel systems exhibit variable mechanical behaviors across several rheological properties (stiffness, viscoelasticity, yield stress, and creep). By relating measured rheological properties to depot formation and persistence time following subcutaneous administration, it is identified that yield stress is predictive of initial depot formation while creep is predictive of depot persistence for these two gel systems. Indeed, only materials with yield stresses >25 Pa form robust depots, and reduced creep correlates with longer depot persistence. These findings provide predictive insights into design considerations for hydrogel technologies capable of extended controlled release of therapeutic cargo.
Mechanically Stable All Flexible Supercapacitors with Fracture and Fatigue Resistance under Harsh Temperatures
Authors: Huang Jianren , Han Songjiu , Zhu Jundong , Wu Qirui , Chen Hongjie , Chen Anbang , Zhang Jiayu , Huang Bing , Yang Xiaoxiang , Guan Lunhui 
Published: August 2022

AbstractFor practical applications in the fields of aerospace and robotic engineering, flexible energy storage devices must be stable under environmental temperatures and different deformed situations. In this work, a mechanically stable supercapacitor (SC) at harsh ambient temperatures is synthesized by in situ polymerization of polyaniline(PANI) onto a double network hydrogel electrolyte from cross‐linked polyvinyl alcohol(PVA) and polyacrylamide/acrylic acid (PAM/AA) networks. The highly integrated structure endows the supercapacitor with unprecedented mechanical performance. The devices can endure 608% tensile strain and be stretched up to 50% without noticeable hysteresis, demonstrating fatigue and fracture resistance under thousands of cyclic loads. Benefiting from an all‐flexible configuration through seamless integration of the PANI electrode, the supercapacitor presents a high specific capacitance of 95.8 mF cm–2. It can also work as an all‐flexible device and maintain its stable output under complex deformations, even physical damages. Furthermore, the device delivers excellent environmental adaptability by steady electrochemical performance after operating at extreme temperatures from −60 to 100 °C. Such a versatile supercapacitor presents a potential application in integrated flexible electronic systems by powering functional devices in harsh environments.
Novel Application of Phosphorescent Material for Non‐Volatile Flash Photomemory and Artificial Photonic Synapse
Authors: Wiyanto Lukius Denny , You Bo‐Ju , Chiang Li‐Jen , Yang Dong‐Lin , Chen Jung‐Yao 
Published: August 2022

AbstractPhosphorescent materials have received considerable attention in organic solar cells (OSCs) due to their long emission lifetime and inhibited geminate recombination. Motivated by its particular photophysical property, herein, the spatially addressable bis(2‐benzo[b]thiophen‐2‐ylpyridine)(acetylacetonate)iridium(III) (Ir(bt)2(acac))/polystyrene‐b‐poly(4‐vinylpyridine) (PS‐b‐P4VP) as a photoactive floating‐gate is first demonstrated to explore the application of phosphorescent material on the photo‐responsive characteristics of photomemory and artificial photonic synapse. By manipulating the interfacial area between Ir(bt)2(acac)/PS‐b‐P4VP and active channel by a solvent annealing process, an ON/OFF current ratio of 103 and a low programming time of 700 ms can be achieved. The current study addresses the exciton lifetime of photoactive material functions in photomemory and highlights the interfacial area between photoactive materials and charge‐carrier transporting materials in reducing photo‐programming time.
Advances in Colloidal Building Blocks: Toward Patchy Colloidal Clusters
Authors: Kim You‐Jin , Moon Jeong‐Bin , Hwang Hyerim , Kim Youn Soo , Yi Gi‐Ra 
Published: August 2022

AbstractThe scalable synthetic route to colloidal atoms has significantly advanced over the past two decades. Recently, colloidal clusters with DNA‐coated cores called “patchy colloidal clusters” have been developed, providing a directional bonding with specific angle of rotation due to the shape complementarity between colloidal clusters. Through a DNA‐mediated interlocking process, they are directly assembled into low‐coordination colloidal structures, such as cubic diamond lattices. Herein, the significant progress in recent years in the synthesis of patchy colloidal clusters and their assembly in experiments and simulations is reviewed. Furthermore, an outlook is given on the emerging approaches to the patchy colloidal clusters and their potential applications in photonic crystals, metamaterials, topological photonic insulators, and separation membranes.
Optothermally Programmable Liquids with Spatiotemporal Precision and Functional Complexity
Authors: Chen Xixi , Wu Tianli , Huang Danmin , Zhou Jiajia , Zhou Fengxiang , Tu Mei , Zhang Yao , Li Baojun , Li Yuchao , Jiang Lingxiang 
Published: August 2022

AbstractDue to the intrinsic lack of spatial order and self‐supported shape, liquids are often incompatible with precision manufacturing/processing and are potentially limited for advanced functionality. Herein, an optothermal strategy is developed to fully command phase‐separated liquids with unprecedented spatiotemporal addressability. Specifically, a laser is focused onto an Au film to create a hot spot that locally demixes a temperature‐responsive solution to produce a single optothermal droplet. Spatial precision is assured by the well‐defined thermal field and temporal accuracy guaranteed by the fast heating and response rate. Time‐multiplexed laser foci are deployed to engineer the thermal landscape as desired, which in turn dictates the formation/dissolution, positioning, shaping, and dynamic reconfiguration of the phase‐separated liquids. Further, laser foci are programmed to orchestrate the liquid patterns in a time‐continuous manner to produce liquid animations on the microscale with high fidelity. While focused lasers are routinely used to manipulate solid particles or to microfabricate solid materials, the current strategy embraces the merits of liquids and features functional complexity in information encryption, payload transportation, and reaction localization. The strategy is further applicable in scenarios such as subcellular organization of biomolecular condensates and programmable modulation of non‐equilibrium systems.
Metal‐Free Site‐Selective Direct Oxidative Phosphorylation of Pyrazolones
Authors: Beukeaw Danupat , Rattanasupaponsak Napassawan , Kittikool Tanakorn , Phakdeeyothin Kunita , Phomphrai Khampee , Yotphan Sirilata 
Published: August 2022

AbstractA substrate‐controlled site‐selective phosphorylation of pyrazolin‐5‐ones has been established under metal‐free direct oxidative coupling processes. A reaction between pyrazolones and secondary phosphonates in the presence of TBAI/TBHP combination could result in the N−P bond formation at N2 position. Meanwhile, the C−P bond coupling at C3 position could be obtained from a reaction of N2‐substituted pyrazolone substrates with secondary phosphine oxides using Selectfluor. These chemo‐ and regioselective metal‐free approaches proceed in fair to high yields under mild reaction conditions with good functional group compatibility.magnified image
Furan Synthesis via Triplet Sensitization of Acceptor/Acceptor Diazoalkanes
Authors: Zhu Siqi , Li Fang , Empel Claire , Jana Sripati , Pei Chao , Koenigs Rene M. 
Published: August 2022

AbstractHerein, we report on the photocatalytic reaction of acceptor/acceptor diazoalkanes with terminal alkynes. Experimental and computational studies suggest the formation of a key triplet carbene intermediate that undergoes an addition reaction to the alkyne followed by cyclization to give furan heterocycles (31 to 90% yield). This reaction was studied with a broad range of alkynes and acceptor/acceptor diazoalkanes and now provides access to furans under mild reaction conditions.magnified image
Unraveling Structural Carboxyl Defects in g‐C3N4 for Improved Photocatalytic H2 Evolution via Alternating Hydrogen‐Oxygen‐Plasma Treatment
Authors: Chang Xijiang , Wang Daqian , Xu Shuchang , Zhang Zhihao , Xiong Ziying , Guo Ying , Kang Shifei 
Published: August 2022

AbstractStructural defect‐endowed photocatalysts are being increasingly recognized due to the enhanced catalytic activity of multiple defect sites (e.g., vacancies or functional groups). However, because of the excessive destruction effect of conventional chemical oxidation methods toward carboxyl defects engineering, the mechanism is still unclear and practice is rare in developing high‐quality structural carboxyl defect‐involved g‐C3N4. Herein, an alternating hydrogen‐oxygen‐plasma treatment is proposed to endow the g‐C3N4 with enriched vacancy defect sites for the subsequent immobilization of carboxyl groups, thus overcoming the problem of lacking of covalent binding sites in g‐C3N4 in developing carboxyl defective g‐C3N4 photocatalysts. The alternating hydrogen‐oxygen‐plasma treatment does not only influence the defect structure of g‐C3N4, but also changes its morphology, optimizes the electronic distribution, and increases the separation efficiency of photogenerated electrons and holes, thereby increasing photocatalytic H2 evolution by 7.91 times. Density functional calculations and electrochemical characterization suggest that the carboxyl defects generated by the fast H2‐O2 plasma modification lead to a local asymmetric electron environment, which enhances carrier separation capability and significantly improves H2 generation activity. This study provides a new insight into the rational design and fabrication of defect‐containing photocatalysts, carbon materials, and polymers.
Doped Organic Micro‐Thermoelectric Coolers with Rapid Response Time
Authors: Wang Shu‐Jen , Wohlrab Steve , Reith Heiko , Berger Dietmar , Kleemann Hans , Nielsch Kornelius , Leo Karl 
Published: August 2022

AbstractLocal thermal management has important implications regarding comfort, energy consumption, and electronic device performance/lifetime. While organic thermoelectrics have emerged as promising materials for flexible thermoelectric energy harvesting devices, their potential as Peltier cooling element has been largely overlooked. Here, micro‐thermoelectric coolers based on doped small molecule thin‐films with a fast response time (around 25 µs) which is among the fastest micro‐thermoelectric coolers reported are presented. This experimental cooling performance is supported by simulation using the finite‐element method for thermal transport. The results show that organic thermoelectrics offer great potential for flexible and wearable micro‐thermoelectric cooling applications.
Thermodynamic Factor for Facilitating Homogeneous Dendrite Growth in Alkali Metal Batteries
Authors: Choi Gwanghyeon , Kim Youngoh , Choi Joonmyung , Kim Duho 
Published: August 2022

AbstractThis study suggests a critical factor that regulates (in)homogeneous growth based on an in‐depth understanding of three alkali metal ((AM): Li, Na, and K) models using unified‐multiscale atomistic calculations. The importance of AM disordered phases as a transition state is covered with a thermodynamic energy dataset using density functional theory (DFT) calculations, which indicates that the disordered‐phase energy level (DPEL) plays a decisive role in controlling the degree of non‐homogeneity during electrochemical deposition. Using the DFT‐assisted machine learning method, the DPEL‐related cohesive energy is investigated to understand in depth the energy level of disordered phase. Reliable molecular dynamics (MD) simulations systematically compare AM growth during charging. The results illustrate severely fluctuating morphologies including sharp tips in Li metal, whereas Na and K metals showed smooth surfaces. Finally, the transition state thermodynamics are explored using cross‐sectional AM growth models. Metallic Li is preferentially adsorbed on its crystalline phase rather than on grain boundaries comprising disordered phases, resulting in severe dendritic Li growth. However, these characteristics are rarely observed for K metal during the entire deposition process. Based on the growth mechanisms of the three types of AM models, DPEL poses a potentially universal design strategy for facilitating homogeneous lithium‐metal dendrite growth.
Cumulative loneliness and subsequent memory function and rate of decline among adults aged ≥50 in the United States, 1996 to 2016
Authors: Yu Xuexin , Westrick Ashly C. , Kobayashi Lindsay C. 
Published: August 2022

AbstractIntroductionThe study objective was to investigate the association between loneliness duration and memory function over a 20‐year period.MethodsData were from 9032 adults aged ≥50 in the Health and Retirement Study. Loneliness status (yes vs. no) was assessed biennially from 1996 to 2004 and its duration was categorized as never, 1 time point, 2 time points, and ≥3 time points. Episodic memory was assessed from 2004 to 2016 as a composite of immediate and delayed recall trials combined with proxy‐reported memory. Mixed‐effects linear regression models were fitted.ResultsA longer duration of loneliness was associated with lower memory scores (P < 0.001) and a faster rate of decline (P < 0.001). The association was stronger among adults aged ≥65 than those aged <65 (three‐way interaction P = 0.013) and was stronger among women than men (three‐way interaction P = 0.002).DiscussionCumulative loneliness may be a salient risk factor for accelerated memory aging, especially among women aged ≥65.Highlight
A longer duration of loneliness was associated with accelerated memory aging.
The association was stronger among women than men and among older adults than the younger.
Reducing loneliness in mid‐ to late life may help maintain memory function.
Phosphorylated tau sites that are elevated in Alzheimer's disease fluid biomarkers are visualized in early neurofibrillary tangle maturity levels in the post mortem brain
Authors: Moloney Christina M. , Labuzan Sydney A. , Crook Julia E. , Siddiqui Habeeba , Castanedes‐Casey Monica , Lachner Christian , Petersen Ronald C. , Duara Ranjan , Graff‐Radford Neill R. , Dickson Dennis W. , Mielke Michelle M. , Murray Melissa E. 
Published: August 2022

AbstractIntroductionAlzheimer's disease (AD) biomarkers are increasingly more reliable in predicting neuropathology. To facilitate interpretation of phosphorylated tau sites as an early fluid biomarker, we sought to characterize which neurofibrillary tangle maturity levels (pretangle, intermediary 1, mature tangle, intermediary 2, and ghost tangle) are recognized.MethodsWe queried the Florida Autopsied Multi‐Ethnic (FLAME) cohort for cases ranging from Braak stages I through VI, excluding non‐AD neuropathologies and tauopathies. Thioflavin‐S staining was compared to immunohistochemical measures of phosphorylated threonine (pT) 181, pT205, pT217, and pT231 in two hippocampal subsectors across n = 24 cases.ResultsEach phosphorylated tau site immunohistochemically labeled early neurofibrillary tangle maturity levels compared to advanced levels recognized by thioflavin‐S. Hippocampal burden generally increased with each Braak stage.DiscussionThese results provide neurobiologic evidence that these phosphorylated tau fluid biomarker sites are present during early neurofibrillary tangle maturity levels and may explain why these fluid biomarker measures are observed before symptom onset.Highlights
Immunohistochemical evaluation of four phosphorylated tau fluid biomarker sites.
Earlier neurofibrillary tangle maturity levels recognized by phosphorylated tau in proline‐rich region.
Advanced tangle pathology is elevated in the subiculum compared to the cornu ammonis 1 of the hippocampus.
Novel semi‐quantitative frequency to calculate tangle maturity frequency.
Pyridine‐oxazoline ligated iron complexes: Synthesis, characterization, and catalytic activity for isoprene polymerization
Authors: Zhao Mengmeng , Zhang Xianhui , Wang Ledong , Wang Liang , Zhu Guangqian , Wang Qinggang 
Published: August 2022

A series of iron(II) dichloride complexes (Fe1–Fe3) bearing 2‐(pyridin‐2‐yl)‐4,5‐dihydrooxazole (L1), 4‐isopropyl‐2‐(pyridin‐2‐yl)‐4,5‐dihydrooxazole (L2), and 4‐(t‐butyl)‐2‐(pyridin‐2‐yl)‐4,5‐dihydrooxazole (L3) and iron(II) acetylacetonate complex (Fe4) bearing L1 were synthesized and characterized by elemental and spectroscopic analyses. Determined by single‐crystal X‐ray crystallography, complex Fe3 adopts an unusual unsymmetrical binuclear core. Upon activation with methylaluminoxane (MAO), the pyridine‐oxazoline (Py‐ox) ligated iron complexes (Fe1–Fe4) showed excellent activity towards isoprene polymerization. Complex Fe1 displayed the highest activity of 8160 kg (mol·h)−1 with 54% of 3,4‐polyisoprene. The ligand environment and counter anion on iron center all displayed significant effects on polymerization activity and selectivity, which reflected the special performance compared with pyridine‐imine. And we propose the possible mechanism through cis‐η4 mode following the σ bond rotation because of the steric effect of t‐butyl substituent of Fe4 to give high trans‐1,4‐polymers. Furthermore, the effects of reaction parameters on the catalytic activity and selectivity were investigated in detail.
Synergistic effect of silicon‐containing groups on the self‐healing performance of polyurethanes based on disulfide bonds
Authors: Lou Jiankun , Yang Lide , Wei Tao , Yuan Jianmin , Deng Jianru 
Published: August 2022

AbstractSelf‐healing polyurethanes (PUs) with disulfide bonds and diphenyl silicon groups involved in the soft phases were prepared and studied in this work. The self‐healing efficiencies of PUs are greatly improved by the synergistic effect of diphenyl silicon groups with low surface energy—increasing the distance between two polymer chains, enhancing the mobility of polymer chains, and promoting the migration of sulfur‐containing groups to the damaged sites. The analysis of activation energy for the movement of polymer chains based on dynamic mechanical thermal analysis shows that, the higher contents of disulfide bonds and diphenyl silicon groups, the stronger mobility of polymer chains, and the higher self‐healing performance of PUs. The study of temperature and time dependencies for the healing process at damaged sites indicates that it is composed of the recombination of disulfide bonds and the interpenetration and intertwining of polymer chains. The former can be completed in a shorter time, while the latter in a longer time. Sufficient time of heat treatment at relatively high temperature is necessary to get high self‐healing efficiency. This strategy and the relative results are instructive to design and development of self‐healing PUs.
Synthesis and fabrication of biobased thermoplastic polyurethane filament for FDM 3D printing
Authors: Shin Eun Joo , Jung Yang Sook , Choi Hyeong Yeol , Lee Sunhee 
Published: August 2022

AbstractThis study describes a soft‐actuator grade thermoplastic polyurethane (TPU) with 73 ~ 86 shore A, the method of its fabrication and selected properties. The TPU was produced using bio‐based synthesized TPU (HP 2.5, HP 3.0, HB 2.5, and HB 3.0) pellets with bio‐based polyether‐biol (PO3G‐1000), and dicyclohexylmethane diisocyanate (H12MDI) and bio‐based 1,3 propanediol (PDO) and 1,4 butanediol (BDO) as a chain extender. The TPU was formed into a filament for fused deposition modeling (FDM) 3D printers during a melt‐extrusion process at 180 ~ 220°C. The manufactured TPU filaments were characterized by rheological, chemical, thermal, and mechanical analyses. The equivalence ratio 3.0 with a relatively large amount of HS with BDO as a chain extender, more hydrogen‐bonding peaks occurred. The transition temperature and mechanical properties increased depending on the [NCO]:[OH] ratio, and for BDO as the chain extender. However, it was found that when PDO derived from natural material was used, the thermal stability was better. From these results, samples of auxetic re‐entrant TPU were printed with the filaments with reference to the melt flow index. The results showed that the bio‐synthesized HP 3.0 with a hardness of (82 ± 1) shore A was most suitable for FDM 3D printing.
Deportment of cobalt bismuth nanoferrites in Kevlar‐supported cellulose acetatemembranes for heavy metal‐salts rejection profile
Authors: Afzal Amina , Rafique Muhammad Shahid , Iqbal Sadia Sagar , Rafique Muhammad 
Published: August 2022

AbstractThe designed novel hybrid laminate membranes have been synthesized with silane surface functionalized Kevlar fabric packed between two layers of cobalt bismuth nanoferrites (CBF)‐loaded cellulose acetate. Primarily, nanoreinforcement; Co‐Bi nano‐ferrites were synthesized using sol–gel technique and functionalization is carried out using 3‐aminpropyl‐tri‐methoxysilane. Secondarily, thermally assisted evaporation methodology coupled with dip‐coating is adopted to synthesize hybrid Kevlar laminate membranes. Finally, structural, thermal, and flux along rejection studies are done on resultant hybrid membranes. The surface morphology, porosity generation, and homogeneous distribution of nanoincorporation with various concentration are revealed from micrographs of SEM of membranes. Noteworthy, impact of nanoreinforcement has been observed to holdup thermal oxidation of synthesized unique formulations of hybrid membranes employing TGA. Presence of CBF in cellulose acetate (CA)/Kevlar laminate membranes are modified glass transition and crystallization temperatures as cleared in DSC. De‐ionized water for flux and heavy metal salts rejection capabilities of each formulated membrane were tested at applied pressures 60, 120, and 180 psi. The important findings are indicated that, increasing concentration of CBF loading in CA remarkably enhanced efficacy of metal‐nitrates rejection with membranes. It is attributed to sole magneto‐physiochemical behavior of nanoferrites that, facilitate enhanced adsorption in designed hybrid membranes for heavy metal rejection from industrial wastes.