bluuebunny/crossref_metadata_2025_split huggingface dataset:
An Atmosphere‐Breathing Refillable Biphasic Device for Cell Replacement Therapy
Authors: An Duo , Wang Long‐Hai , Ernst Alexander Ulrich , Chiu Alan , Lu Yen‐Chun , Flanders James Arthur , Datta Ashim Kumar , Ma Minglin 
Published: November 2019

AbstractCell replacement therapy is emerging as a promising treatment platform for many endocrine disorders and hormone deficiency diseases. The survival of cells within delivery devices is, however, often limited due to low oxygen levels in common transplantation sites. Additionally, replacing implanted devices at the end of the graft lifetime is often unfeasible and, where possible, generally requires invasive surgical procedures. Here, the design and testing of a modular transcutaneous biphasic (BP) cell delivery device that provides enhanced and unlimited oxygen supply by direct contact with the atmosphere is presented. Critically, the cell delivery unit is demountable from the fixed components of the device, allowing for surgery‐free refilling of the therapeutic cells. Mass transfer studies show significantly improved performance of the BP device in comparison to subcutaneous controls. The device is also tested for islet encapsulation in an immunocompetent diabetes rodent model. Robust cell survival and diabetes correction is observed following a rat‐to‐mouse xenograft. Lastly, nonsurgical cell refilling is demonstrated in dogs. These studies show the feasibility of this novel device for cell replacement therapies.
Commencing an Acidic Battery Based on a Copper Anode with Ultrafast Proton‐Regulated Kinetics and Superior Dendrite‐Free Property
Authors: Liang Guojin , Mo Funian , Yang Qi , Huang Zhaodong , Li Xinliang , Wang Donghong , Liu Zhouxin , Li Hongfei , Zhang Qiang , Zhi Chunyi 
Published: November 2019

AbstractBuilding aqueous acidic batteries is in its infancy. There are several sporadic attempts that show desirable electrochemical performance, especially rate stability and high power density. The direct use of a metal anode is regarded as the best protocol for fabricating metal‐based batteries. However, introducing an acid‐tolerant and electrochemically reversible metal anode into an acidic aqueous battery system remains a considerable challenge. In this work, copper (Cu) metal is used as a reversible metal anode to match acidic regimes with a nearly 100% deposition–dissolution efficiency. The reaction kinetics and mechanism of the Cu anode can be regulated by protons with 400% kinetic acceleration compared with a mild electrolyte. In addition, the anode exhibits a dendrite‐free morphology after cycling due to the surface roughening effect, which is different from the morphologies of widely used Zn‐ and Li‐metal anodes. When coupled with the Prussian blue analog as cathodes, the battery delivers ultrafast kinetics of 1830 W kg−1 at 75 C, which is comparable to the power performance of supercapacitors. Long‐term cyclic stability is evaluated, where the capacity retention is 85.6% after 5000 cycles. Finally, flexible fiber‐shaped acidic Cu‐based batteries are demonstrated for potential wearable applications.
Silver Triflate/N‐Fluorobenzenesulfonimide‐Catalyzed Cycloisomerization of Tryptamine‐Ynamide to Spiro[indoline‐3,4′‐piperidine] Induced by Cation‐π‐π Interactions between Substrate and Metal Ligand
Authors: Liang Guoduan , Ji Yanjun , Liu Hairui , Pang Yadong , Zhou Bojun , Cheng Maosheng , Liu Yang , Lin Bin , Liu Yongxiang 
Published: November 2019

AbstractN‐Fluorobenzenesulfonimide (NFSI), one of the most popular fluorinating agents in organic synthesis, was used as a ligand of silver triflate (AgOTf) to assist the trapping of the persistent spiroindoleninium intermediates by forming a weak noncovalent interaction between the substrate and metal ligand. The AgOTf/NFSI catalytic system was identified in the cycloisomerization of tryptamine‐ynamide to spiro[indoline‐3,4′‐piperidine] derivatives. The substrate tolerances were demonstrated by various synthetic substrates and commercially available nucleophiles. A cation‐π‐π model was proposed to elucidate the mechanism of action based on the experimental observations and density functional theory (DFT) calculations.magnified image
Proton‐Mediated Phase Control in Flexible and Transparent Mott Transistors
Authors: Deng Xing , Zhao Yi‐Feng , Zhong Ni , Yue Fang‐Yu , Huang Rong , Peng Hui , Tang Xiao‐Dong , Xiang Ping‐Hua , Chu Ying‐Hao , Duan Chun‐Gang 
Published: November 2019

AbstractTo meet the development of wearable and energy‐efficient flexible electronics, multifunctional oxide film on soft substrate and its versatile phase control are in demand. Here, flexible VO2 film is directly deposited on mica via van der Waals epitaxy, exhibiting pronounced metal‐insulator (MI) transition and infrared (IR) switching properties. Using a rubbery solid ionic gel as gate insulator, a fully flexible and transparent VO2‐channel Mott transistor is successfully demonstrated. The prototype Mott transistor processes excellent mechanical flexibility and giant on/off current ratio of ≈105% even at room temperature. Highly reversible suppression of MI transition is realized by applying small gate voltages and the nonvolatile phase modulation suggests an electrochemical reaction mechanism. X‐ray diffraction and secondary‐ion mass spectroscopy analyses, together with theoretical calculation, confirm that electrically controlled phase transformation is mainly caused by reversible and nonvolatile proton (H+) doping into VO2 lattices. Significant modulation of IR transmittance (>40%) is observed in the VO2 Mott transistor, which is attributed to electrically driven phase transition between insulating VO2 and metallic HxVO2 phases. The flexible and transparent Mott transistor provides a good platform for proton‐mediated Mottronics and realizes novel electric control of optical characteristics, showing a promising application for flexible energy‐saving smart windows.
Efficient Exploration of the Composition Space in Ternary Organic Solar Cells by Combining High‐Throughput Material Libraries and Hyperspectral Imaging
Authors: Harillo‐Baños Albert , Rodríguez‐Martínez Xabier , Campoy‐Quiles Mariano 
Published: November 2019

AbstractOrganic solar cells based on ternary active layers can lead to higher power conversion efficiencies than corresponding binaries, and improved stability. The parameter space for optimization of multicomponent systems is considerably more complex than that of binaries, due to both, a larger number of parameters (e.g., two relative compositions rather than one) and intricate morphology–property correlations. Most experimental reports to date reasonably limit themselves to a relatively narrow subset of compositions (e.g., the 1:1 donor/s:acceptor/s trajectory). This work advances a methodology that allows exploration of a large fraction of the ternary phase space employing only a few (<10) samples. Each sample is produced by a designed sequential deposition of the constituent inks, and results in compositions gradients with ≈5000 points/sample that cover about 15%–25% of the phase space. These effective ternary libraries are then colocally imaged by a combination of photovoltaic techniques (laser and white light photocurrent maps) and spectroscopic techniques (Raman, photoluminescence, absorption). The generality of the methodology is demonstrated by investigating three ternary systems, namely PBDB‐T:ITIC:PC70BM, PTB7‐Th:ITIC:PC70BM, and P3HT:O‐IDFBR:O‐IDTBR. Complex performance‐structure landscapes through the ternary diagram as well as the emergence of several performance maxima are discovered.
Ultrathin, Flexible Polymer Electrolyte for Cost‐Effective Fabrication of All‐Solid‐State Lithium Metal Batteries
Authors: Wu Jingyi , Rao Zhixiang , Cheng Zexiao , Yuan Lixia , Li Zhen , Huang Yunhui 
Published: November 2019

AbstractAll‐solid‐state batteries are promising candidates for the next‐generation safer batteries. However, a number of obstacles have limited the practical application of all‐solid‐state Li batteries (ASSLBs), such as moderate ionic conductivity at room temperature. Here, unlike most of the previous approaches, superior performances of ASSLBs are achieved by greatly reducing the thickness of the solid‐state electrolyte (SSE), where ionic conductivity is no longer a limiting factor. The ultrathin SSE (7.5 µm) is developed by integrating the low‐cost polyethylene separator with polyethylene oxide (PEO)/Li‐salt (PPL). The ultrathin PPL shortens Li+ diffusion time and distance within the electrolyte, and provides sufficient Li+ conductance for batteries to operate at room temperature. The robust yet flexible polyethylene offers mechanical support for the soft PEO/Li‐salt, effectively preventing short‐circuits even under mechanical deformation. Various ASSLBs with PPL electrolyte show superior electrochemical performance. An initial capacity of 135 mAh g−1 at room temperature and the high‐rate capacity up to 10 C at 60 °C can be achieved in LiFePO4/PPL/Li batteries. The high‐energy‐density sulfur cathode and MoS2 anode employing PPL electrolyte also realize remarkable performance. Moreover, the ASSLB can be assembled by a facile process, which can be easily scaled up to mass production.
Atomic‐Scale Visualization of Electrochemical Lithiation Processes in Monolayer MoS2 by Cryogenic Electron Microscopy
Authors: Yu Seung‐Ho , Zachman Michael J. , Kang Kibum , Gao Hui , Huang Xin , DiSalvo Francis J. , Park Jiwoong , Kourkoutis Lena F. , Abruña Héctor D. 
Published: November 2019

AbstractWhile lithium ion batteries with electrodes based on intercalation compounds have dominated the portable energy storage market for decades, the energy density of these materials is fundamentally limited. Today, rapidly growing demand for this type of energy storage is driving research into materials that utilize alternative reaction mechanisms to enable higher energy densities. Transition metal compounds are one such class of materials, with storage enabled by “conversion” reactions, where the material is converted to new compound upon lithiation. MoS2 is one example of this type of material that has generated a large amount of interest recently due to its high theoretical lithium storage capacity compared to graphite. Here, cryogenic scanning transmission electron microscopy techniques are used to reveal the atomic‐scale processes that occur during reaction of a model monolayer MoS2 system by enabling the unaltered atomic structure to be determined at various levels of lithiation. It is revealed that monolayer MoS2 can undergo a conversion reaction even with no substrate, and that the resulting particles are smaller than those that form in bulk MoS2, likely due to the more limited 2D diffusion. Additionally, while bilayer MoS2 undergoes intercalation with a corresponding phase transition before conversion, monolayer MoS2 does not.
Heat transfer of dry granular materials in a bladed mixer: Effect of thermal properties and agitation rate
Authors: Hartmanshenn Clara , Khinast Johannes G. , Papageorgiou Charles D. , Mitchell Chris , Quon Justin , Glasser Benjamin J. 
Published: November 2019

AbstractAgitated drying of pharmaceuticals remains a challenging manufacturing step due to the simultaneous heat transfer, mass transfer, and physicochemical changes occurring during the process. This work focuses on the heat transfer component by implementing the discrete element method to model dry particles in a heated bladed mixer. Simulations varying material conductivities and impeller agitation rates were conducted to evaluate the influence on the mean bed temperature and distribution. The results indicated that increasing the agitation rate generally improved heat transfer up until a critical agitation rate where the rate of heat transfer plateaued. The magnitude of this improvement in heat transfer depended on the material's thermal properties. We observed three regimes: a conduction‐dominated regime where particles heated quickly but with an annular temperature gradient, a granular convection‐dominated regime where particles heated slowly but uniformly, and an intermediate regime. The results were nondimensionalized to enable predictions and help inform drying protocols.
Kosaki overgrowth syndrome: A newly identified entity caused by pathogenic variants in platelet‐derived growth factor receptor‐beta
Authors: Takenouchi Toshiki , Okuno Hironobu , Kosaki Kenjiro 
Published: November 2019

AbstractSpecific classes of de novo heterozygous gain‐of‐function pathogenic variants of the PDGFRB (platelet‐derived growth factor receptor‐beta) cause a distinctive overgrowth syndrome, named the Kosaki overgrowth syndrome (KOGS) (OMIM #616592). Until now, six patients with this condition have been reported in the literature. In addition to skeletal overgrowth, these patients exhibit hyperelastic, translucent, and fragile skin, scoliosis, progressive loss of subcutaneous adipose tissue, skull deformity, infantile myofibromas, neuropsychiatric symptoms, and arachnoid cysts in the posterior fossa and periventricular white matter signal abnormalities on neuroimaging. This constellation of phenotypes clearly distinguishes KOGS from other PDGFRB‐related disorders, including idiopathic basal ganglia calcification, infantile myofibroma, and Penttinen‐type premature aging syndrome. From a molecular standpoint, PDGFRB is a dimeric receptor tyrosine kinase that plays critical roles in cell growth and tumorigenesis. The two known types of pathogenic variants (p.(Pro584Arg) and p.(Trp566Arg)) of the PDGFRB that cause KOGS are exclusively located in the juxtaglomerular domain that regulates autoactivation/inhibition of PDGFRB. In‐vitro evidence suggests that p.(Pro584Arg) represents a gain‐of‐function pathogenic variant. Inhibition of PDGFRB activity using multi‐kinase inhibitors appears to be a potentially promising therapeutic approach. Investigation of the molecular mechanisms underlying the pathogenesis of this disease using induced pluripotent stem cells is under way. Presence of skeletal overgrowth, distinctive facial features, characteristic hyperelastic and fragile skin, and cerebral white matter lesions with neuropsychiatric symptoms should prompt genetic analysis of the PDGFRB.
Adverse childhood experiences and reproductive strategies in a contemporary U.S. population
Authors: Holdsworth Elizabeth A. , Appleton Allison A. 
Published: November 2019

AbstractObjectivesStressful experiences may initiate developmentally plastic responses toward a faster reproductive strategy. This study tests whether adverse childhood experiences (ACEs) are associated with characteristics of faster reproductive strategies: earlier menarche and reduced prenatal investment in offspring in a well‐nourished, low‐immune system burden population.Materials and MethodsWe analyzed the first 214 enrollees of the prenatal‐birth Albany Infant and Mother Study. Mother's menarcheal age, offspring gestational age at birth, and cephalization index (head circumference/weight, cm/g) were derived from medical records. Linear regression models tested the contribution of self‐reported ACEs from 0 to 18 years of age to menarcheal age and the contribution of menarcheal age to offspring gestational age and cephalization index. Birth outcome models included covariates self‐reported maternal race, education, prenatal smoking, prenatal diet, newborn sex, parity, delivery method, and labor induction derived from medical records.ResultsMore ACEs were associated with earlier age at menarche, controlling for covariates (β= −.18,SE= 0.048,p < .001), though timing of ACEs relative to menarche is unknown. Earlier menarcheal age was associated with offspring higher cephalization index (β= −.01,SE= 0.006,p < .05). Stratified models showed a significant relationship in high (≥2) ACEs group (β= −.02,SE= 0.009,p < .05), not present among low ACEs. Menarcheal age predicted gestational age only among those with high ACEs (β= .22,SE= 0.091,p < .05).DiscussionIn a well‐nourished population, early life stress can result in faster reproductive strategies, initiating sexual maturation earlier, and reducing prenatal investment in individual offspring. Early age at menarche following childhood stress has a stronger relationship with adverse birth outcomes than early menarche without exposure to adverse childhood stress.
A Highly Asymmetric Gold(III) η3‐Allyl Complex
Authors: Holmsen Marte Sofie Martinsen , Nova Ainara , Øien‐Ødegaard Sigurd , Heyn Richard H. , Tilset Mats 
Published: November 2019

AbstractA highly asymmetric AuIII η3‐allyl complex has been generated by treating Au(η1‐allyl)Br(tpy) (tpy=2‐(p‐tolyl)pyridine) with AgNTf2. The resulting η3‐allyl complex has been characterized by NMR spectroscopy and X‐ray crystallography. DFT calculations and variable temperature 1H NMR suggest that the allyl ligand is highly fluxional.
Isolation of a Perfectly Linear Uranium(II) Metallocene
Authors: Guo Fu‐Sheng , Tsoureas Nikolaos , Huang Guo‐Zhang , Tong Ming‐Liang , Mansikkamäki Akseli , Layfield Richard A. 
Published: November 2019

AbstractReduction of the uranium(III) metallocene [(η5‐C5iPr5)2UI] (1) with potassium graphite produces the “second‐generation” uranocene [(η5‐C5iPr5)2U] (2), which contains uranium in the formal divalent oxidation state. The geometry of 2 is that of a perfectly linear bis(cyclopentadienyl) sandwich complex, with the ground‐state valence electron configuration of uranium(II) revealed by electronic spectroscopy and density functional theory to be 5f3 6d1. Appreciable covalent contributions to the metal‐ligand bonds were determined from a computational study of 2, including participation from the uranium 5f and 6d orbitals. Whereas three unpaired electrons in 2 occupy orbitals with essentially pure 5f character, the fourth electron resides in an orbital defined by strong 7s‐6d
mixing.
An Ultrasound Activated Vesicle of Janus Au‐MnO Nanoparticles for Promoted Tumor Penetration and Sono‐Chemodynamic Therapy of Orthotopic Liver Cancer
Authors: Lin Xiahui , Liu Shuya , Zhang Xuan , Zhu Rong , Chen Shan , Chen Xiaoyuan , Song Jibin , Yang Huanghao 
Published: November 2019

AbstractSonodynamic therapy (SDT) has the advantages of high penetration, non‐invasiveness, and controllability, and it is suitable for deep‐seated tumors. However, there is still a lack of effective sonosensitizers with high sensitivity, safety, and penetration. Now, ultrasound (US) and glutathione (GSH) dual responsive vesicles of Janus Au‐MnO nanoparticles (JNPs) were coated with PEG and a ROS‐sensitive polymer. Upon US irradiation, the vesicles were disassembled into small Janus Au‐MnO nanoparticles (NPs) with promoted penetration ability. Subsequently, GSH‐triggered MnO degradation simultaneously released smaller Au NPs as numerous cavitation nucleation sites and Mn2+ for chemodynamic therapy (CDT), resulting in enhanced reactive oxygen species (ROS) generation. This also allowed dual‐modality photoacoustic imaging in the second near‐infrared (NIR) window and T1‐MR imaging due to the released Mn2+, and inhibited orthotopic liver tumor growth via synergistic SDT/CDT.
Ti3C2: An Ideal Co‐catalyst?
Authors: Wang Biao , Wang Mengye , Liu Fangyan , Zhang Qian , Yao Shan , Liu Xiaolong , Huang Feng 
Published: November 2019

AbstractHow 2D Ti3C2 enhances photocatalytic efficiency remains unclear. Now, it is shown that it is graphene quantum dots (GQDs) derived from Ti3C2, rather than 2D Ti3C2 itself, that play the role of co‐catalyst for La2Ti2O7/Ti3C2 (LTC) composites during the photocatalytic reaction. After modification of Ti3C2 derivatives, the photocatalytic efficiency of La2Ti2O7 is enhanced 16 times over pure La2Ti2O7. Solid‐state NMR, Raman, and HRTEM results confirm the existence of GQDs in Ti3C2 and LTC composites. The GQDs are formed during the chemical change from Ti3AlC2 to Ti3C2 via HF etching, as Ti atoms are removed and unsaturated carbon bonds are left, which react with each other to form sp2 π‐conjugation GQDs. 2D Ti3C2 is completely oxidized to COx modified TiOx species, causing Ti3C2 to lose its electrical conductivity and the role as co‐catalyst. GQDs largely suppress the photogenerated charge recombination of La2Ti2O7, as revealed by the photoluminescence (PL) and transient photocurrent.
Polymorph‐Dependent Thermally Activated Delayed Fluorescence Emitters: Understanding TADF from a Perspective of Aggregation State
Authors: Zheng Kailu , Ni Fan , Chen Zhanxiang , Zhong Cheng , Yang Chuluo 
Published: November 2019

AbstractCurrent research on thermally activated fluorescence (TADF) emitters is mainly based on the molecular levels, while the aggregation states of TADF emitters are to be explored deeply. Now two multifunctional emitters are reported with simultaneous TADF, aggregation induced emission (AIE), and multicolor mechanochromic luminescence (MCL) features. Both emitters also show polymorph‐dependent TADF emission. Crystal structure analysis reveals that the polymorphism is ascribed to the mutable conformations in different aggregation states. This work brings new insight to TADF emitters from a perspective of aggregation states.
N‐Confused Phlorin‐Prodigiosin Chimera: meso‐Aryl Oxidation and π‐Extension Triggered by Peripheral Coordination
Authors: Su Guangxian , Li Qizhao , Ishida Masatoshi , Li Chengjie , Sha Feng , Wu Xin‐Yan , Wang Lu , Baryshnikov Glib , Li Dawei , Ågren Hans , Furuta Hiroyuki , Xie Yongshu 
Published: November 2019

AbstractAn N‐confused phlorin isomer bearing a dipyrrin moiety at the α‐position of the confused pyrrole ring (1) was synthesized. PdII and BIII coordination at the peripheral prodigiosin‐like moiety of 1 afforded the corresponding complexes 2 and 3. Reflux of 2 in triethylamine (TEA) converted the meso‐phenyl into the PdII‐coordinating phenoxy group to afford 4. Under the same reaction conditions, TEA was linked to the α‐position of the dipyrrin unit in 3 as an N,N‐diethylaminovinyl group to afford 5. Furthermore, peripheral coordination of BIII in 3 and 5 improved the planarity of the phlorin macrocycle and thus facilitated the coordination of AgIII at the inner cavity to afford 3‐Ag and 5‐Ag, respectively. These results provide an effective approach for developing unique porphyrinoids through peripheral coordination.
Cobalt‐Catalyzed E‐Selective Cross‐Dimerization of Terminal Alkynes: A Mechanism Involving Cobalt(0/II) Redox Cycles
Authors: Ueda Yohei , Tsurugi Hayato , Mashima Kazushi 
Published: November 2019

AbstractA highly E‐selective cross‐dimerization of terminal alkynes with either terminal silylacetylenes, tert‐butylacetylene, or 1‐trimethylsilyloxy‐1,1‐diphenyl‐2‐propyne in the presence of a dichlorocobalt(II) complex bearing a sterically demanding 2,9‐bis(2,4,6‐triisopropylphenyl)‐1,10‐phenanthroline, activated with two equivalents of EtMgBr, gives a variety of (E)‐1,3‐enynes. A well‐characterized diolefin/cobalt(0) complex, with divinyltetramethyldisiloxane, acted as a catalytically active species without any activation, clearly indicating that a cobalt(0) species is involved in the catalytic cycle.
Zeise, Liebig, Jensen, Hückel, Dewar und die Olefin‐π‐Komplex‐Bindung
Authors: Wentrup Curt 
Published: November 2019

AbstractZeises Salz, KPt(C2H4)Cl3, war die erste charakterisierte metallorganische Verbindung; es war auch der erste Olefin‐π‐Komplex. Es wurde 1825–1830 publiziert, inmitten eines Streites zwischen Dumas auf der einen Seite und Berzelius und Liebig auf der anderen, die jeweils die Etherin‐(Ethylen‐)Theorie bzw. die Radikaltheorie verteidigten. Obwohl Zeises Auffassung, dass die Verbindung Ethylen enthält, bestätigt wurde, wurde der Streit viele Jahre fortgesetzt. Dies geschah zu einer Zeit, als die Theorien der organischen Chemie in rasanter Entwicklung waren, lange bevor ein klares Verständnis der Natur der Moleküle, Bindung und Struktur vorhanden war. Zeise sah die Struktur seines Salzes als das Produkt einer Addition von PtCl2 an Ethylen. Jensen vermutete eine zentrale Bindung an Ethylen, aber benötigte theoretische Hilfe, um sie zu erklären. Sein Versuch, eine theoretische Erläuterung von Hückel zu bekommen, schlug fehl, und es war schließlich Dewar, der 1951 die Natur der π‐Komplexe im Sinne der Molekülorbitaltheorie deutlich machte.