bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dual‐Phase Aligned Composite Scaffolds Loaded with Tendon‐Derived Stem Cells for Achilles Tendon Repair
Authors: Ning Chao , Gao Cangjian , Li Pinxue , Fu Liwei , Chen Wei , Liao Zhiyao , Xu Zizheng , Yuan Zhiguo , Guo Weimin , Sui Xiang , Liu Shuyun , Guo Quanyi 
Published: July 2022

AbstractTendon injury is one of the most common musculoskeletal disorders, resulting in a significant decrease in the quality of life of patients with tendon injury. With the in‐depth understanding of the anatomical structure and pathological changes that occur during tendon repair, tissue engineering methods using cells and biomaterials are widely studied. However, simulation of the aligned tissue morphology present in natural tendons remains challenging. The design of a well‐aligned scaffold would be appealing to promote better tendon regeneration. Here, a dual‐aligned composite scaffold comprising an outer layer of polycaprolactone/silk fibroin (PCL/SF) copolymer electrospun membrane and an inner layer of tendon extracellular matrix (TECM) loaded with tendon‐derived stem cells (TDSCs) is developed to promote rabbit Achilles tendon repair. As resident, tissue‐specific cells, TDSCs possess stronger tenogenic differentiation abilities. The PCL/SF electrospun membrane with a dense structure provides mechanical support and TECM with a loose porous structure provides bioactive constituents and a microenvironment for tendon repair. As shown here, the engineered scaffold facilitates TDSC proliferation and migration, favors tenogenesis‐associated gene expression, promotes tendon repair with native‐like hierarchically organized collagen fibers, and enhances the mechanical properties, indicating its potential value in the tendon tissue engineering field.
Linking Hydraulic Properties to Hemolytic Performance of Rotodynamic Blood Pumps
Authors: Escher Andreas , Hubmann Emanuel Johannes , Karner Barbara , Messner Barbara , Laufer Günther , Kertzscher Ulrich , Zimpfer Daniel , Granegger Marcus 
Published: July 2022

AbstractIn rotodynamic blood pumps (RBPs) a substantial proportion of input energy is dissipated into the blood. This energy may propel damaging work on blood constituents. To date, the link between this hydraulic energy dissipation and respective hemolytic action in RBPs remains vastly unknown. In this study, computational fluid dynamics is applied to compute the hydraulic energy dissipation at 9 operating conditions in two RBPs (HM3: HeartMate 3; HVAD: HeartWare Ventricular Assist Device). Respective interrelations with hemolytic pump performance are elucidated by comparing these computations with in silico predicted and in vitro measured hemolysis. Despite different pump geometries, hydraulic loss magnitudes, and distributions, global hydraulic energy dissipation shows strong correlation (r > 0.95) to in vitro hemolysis with scaling factors in the same order of magnitude for both devices (φHM3 = 0.599 (mL g) (J 100L)–1; φHVAD = 0.716 (mL g) (J 100L)–1). The analytical description of hydraulic energy dissipation reveals to be a function of shear stresses and exposure time, unmasking its analogy to the power‐law formulation of hemolysis. This hydraulics‐based analysis may denote a step ahead to relate turbomachinery to bioengineering and may provide mechanistic insights into the relation between RBP design, hydraulic properties, and hemolytic performance.
Cross‐Ray Ultrasound Tomography and Photoacoustic Tomography of Cerebral Hemodynamics in Rodents
Authors: Na Shuai , Zhang Yang , Wang Lihong V. 
Published: July 2022

AbstractRecent advances in functional ultrasound imaging (fUS) and photoacoustic tomography (PAT) offer powerful tools for studying brain function. Complementing each other, fUS and PAT, respectively, measure the cerebral blood flow (CBF) and hemoglobin concentrations, allowing synergistic characterization of cerebral hemodynamics. Here, cross‐ray ultrasound tomography (CRUST) and its combination with PAT are presented. CRUST employs a virtual point source from a spherically focused ultrasonic transducer (SFUST) to provide widefield excitation at a 4‐kHz pulse repetition frequency. A full‐ring‐shaped ultrasonic transducer array whose imaging plane is orthogonal to the SFUST's acoustic axis receives scattered ultrasonic waves. Superior to conventional fUS, whose sensitivity to blood flow is angle‐dependent and low for perpendicular flow, the crossed transmission and panoramic detection fields of CRUST provide omnidirectional sensitivity to CBF. Using CRUST‐PAT, the CBF, oxygen saturation, and hemoglobin concentration changes of the mouse brain during sensory stimulation are measured, with a field of view of ≈7 mm in diameter, spatial resolution of ≈170 µm, and temporal resolution of 200 Hz. The results demonstrate CRUST‐PAT as a unique tool for studying cerebral hemodynamics.
Dense Coding and Quantum Memory Assisted Entropic Uncertainty Relations in a Two‐Qubit State Influenced by Dipole and Symmetric Cross Interactions
Authors: Abd‐Rabbou Mahmoud Youssef , Khalil Eied Mahmoud 
Published: July 2022

AbstractOptimal dense coding and entropic uncertainty relation of quantum memory (EUR‐QM) of the two‐qubit Heisenberg chain model influenced by atomic dipole and Kaplan–Shekhtman–Entin–Wohlman–Aharony interactions are studied. The temporal evolution of the two functions at the phase decoherence environment with the Werner state as the initial state is discussed. The results imply that the dense coding and EUR‐QM have a contrary relationship, and an increase in the phase decoherence rate reduces the behavior of the two functions. The growth in coupling dipole interaction plays a role in oscillating and increasing the minimum bounds of the dense coding capacity. On the other hand, the effect of a thermal bath on the two functions at finite temperatures is investigated. The coding capacity suffers from sudden death as the temperature increases. The possibility of restraining the sudden death induced by the temperature may be enhanced by increasing the strength of the symmetric cross interaction. As the coupling of dipole increases, the EUR‐QM decreases while the coding capacity rises to its maximum value.
Eisen‐katalysierte Cycloisomerisierung und C−C‐Bindungsaktivierung als Zugang zu nicht‐kanonischen tricyclischen Cyclobutanen
Authors: Kramm Frederik , Ullwer Franziska , Klinnert Benedict , Zheng Min , Plietker Bernd 
Published: July 2022

AbstractCycloisomerisierungen sind leistungsfähige Gerüstumlagerungen, die den atomökonomischen Aufbau komplexer molekularer Architekturen erlauben. Wir präsentieren hier eine ungewöhnliche Art der Cyclopropyl‐Enin‐Cycloisomerisierung, die den Prozess der Cycloisomerisierung mit der Aktivierung einer C−C Bindung in Cyclopropanen verbindet. Es wurde eine Vielzahl substituierter nicht‐kanonischer tricyclischer Cyclobutane unter milden Bedingungen mit [(Ph3P)2Fe(CO)(NO)]BF4 als Katalysator in guten bis exzellenten Ausbeuten und hoher Stereokontrolle synthetisiert.
Reply to the Correspondence on “How Aromatic Are Molecular Nanorings? The Case of a Six‐Porphyrin Nanoring”**
Authors: Casademont‐Reig Irene , Soriano‐Agueda Luis , Ramos‐Cordoba Eloy , Torrent‐Sucarrat Miquel , Matito Eduard 
Published: July 2022

AbstractA recent article by Anderson and co‐workers challenges our conclusions on the aromaticity of the four oxidation states of a butadyine‐linked six‐porphyrin nanoring, based on the experimental 1H‐NMR data and some recent calculations they have performed using the BLYP35 functional. Here, we show that BLYP35 should be taken with caution and demonstrate that the indirect evidence of a ring current from experimental 1H‐NMR data is not a definite proof of aromaticity.
Microenvironment Engineering for the Electrocatalytic CO2 Reduction Reaction
Authors: Lv Jing‐Jing , Yin Ruonan , Zhou Limin , Li Jun , Kikas Reddu , Xu Ting , Wang Zheng‐Jun , Jin Huile , Wang Xin , Wang Shun 
Published: July 2022

AbstractRather than just focusing on the catalyst itself in the electrocatalytic CO2 reduction reaction (eCO2RR), as previously reviewed elsewhere, we herein extend the discussion to the special topic of the microenvironment around the electrocatalytic center and present a comprehensive overview of recent research progress. We categorize the microenvironment based on the components relevant to electrocatalytic active sites, i.e., the catalyst surface, substrate, co‐reactants, electrolyte, membrane, and reactor. Supported by most of the reported articles, the relevant factors affecting the catalytic performance of eCO2RR are then discussed in detail, and existing challenges and potential solutions are mentioned. Perspectives for the future research on eCO2RR, including the integration of different microenvironment factors, the extension to industrial application by coupling with carbon capture and conversion, and separation of products, are also discussed.
Methyl Substitution Destabilizes Alkyl Radicals
Authors: Blokker Eva , van Zeist Willem‐Jan , Sun Xiaobo , Poater Jordi , van der Schuur J. Martijn , Hamlin Trevor A. , Bickelhaupt F. Matthias 
Published: July 2022

AbstractWe have quantum chemically investigated how methyl substituents affect the stability of alkyl radicals MemH3−mC⋅ and the corresponding MemH3−mC−X bonds (X = H, CH3, OH; m = 0 – 3) using density functional theory at M06‐2X/TZ2P. The state‐of‐the‐art in physical organic chemistry is that alkyl radicals are stabilized upon an increase in their degree of substitution from methyl<primary<secondary<tertiary, and that this is the underlying cause for the decrease in C−H bond strength along this series. Here, we provide evidence that falsifies this model and show that, on the contrary, the MemH3−mC⋅ radical isdestabilizedwith increasing substitution. The reason that the corresponding C−H bond nevertheless becomes weaker is that substitution destabilizes the sterically more congested MemH3−mC−H molecule even more.
Tridecacyclene Tetraimide: An Easily Reduced Cyclooctatetraene Derivative
Authors: Kumar Rakesh , Chmielewski Piotr J. , Lis Tadeusz , Volkmer Dirk , Stępień Marcin 
Published: July 2022

AbstractTridecacyclene tetraimide, TCTI, an electron‐deficient non‐benzenoid nanocarbon with a C56N4 polycyclic framework was obtained in a concise synthesis. TCTI has a non‐planar structure and forms π‐stacked dimers in the solid state. In solution, it undergoes eight single‐electron reductions, yielding a range of negatively charged states up to an octaanion. Except for the latter species, which has a remarkably large electronic gap, the anions feature extended near‐infrared absorptions, with a particularly strong band at 1692 nm observed for the dianion. A computational analysis of the TCTI anions shows that their stability originates from the combined effects of electron‐deficient imide groups and the local aromaticity of reduced acenaphthylene units. The properties of TCTI make it potentially useful in electrochromic and charge storage applications.
Nickel‐Catalyzed Enantioselective Reductive Alkyl‐Carbamoylation of Internal Alkenes
Authors: Wu Xianqing , Turlik Aneta , Luan Baixue , He Feng , Qu Jingping , Houk K. N. , Chen Yifeng 
Published: July 2022

AbstractHerein, we leverage the Ni‐catalyzed enantioselective reductive dicarbofunctionalization of internal alkenes with alkyl iodides to enable the synthesis of chiral pyrrolidinones bearing vicinal stereogenic centers. The application of newly developed1‐NapQuinim is critical for formation of two contiguous stereocenters in high yield, enantioselectivity, and diastereoselectivity. This catalytic system also improves both the yield and enantioselectivity in the synthesis of α,α‐dialkylated γ‐lactams. Computational studies reveal that the enantiodetermining step proceeds with a carbamoyl‐NiIintermediate that is reduced by the Mn reductant prior to intramolecular migratory insertion. The presence of thet‐butyl group of the Quinim ligand leads to an unfavorable distortion of the substrate in the TS that leads to the minor enantiomer. Calculations also support an improvement in enantioselectivity with1‐NapQuinim compared top‐tolQuinim.
Scalable, Chemoselective Nickel Electrocatalytic Sulfinylation of Aryl Halides with SO2
Authors: Lou Terry Shing‐Bong , Kawamata Yu , Ewing Tamara , Correa‐Otero Guillermo A. , Collins Michael R. , Baran Phil S. 
Published: July 2022

AbstractSimple access to aryl sulfinates from aryl iodides and bromides is reported using an inexpensive Ni‐electrocatalytic protocol. The reaction exhibits a broad scope, uses stock solution of simple SO2 as sulfur source, and can be scaled up in batch and recycle flow settings. The limitations of this reaction are clearly shown and put into context by benchmarking with state‐of‐the‐art Pd‐based methods.
One‐Step Ethylene Purification from Ternary Mixtures in a Metal–Organic Framework with Customized Pore Chemistry and Shape
Authors: Ding Qi , Zhang Zhaoqiang , Liu Yulong , Chai Kungang , Krishna Rajamani , Zhang Sui 
Published: July 2022

AbstractAdsorptive separation is an energy‐efficient technology for the separation of C2 hydrocarbons. However, it remains a critical problem to directly produce high‐purity C2H4 from ternary C2H2/C2H4/C2H6 mixtures by simultaneously trapping C2H2 and C2H6. Herein, we report the one‐step C2H4 purification from the ternary mixture by a metal–organic framework Zn(ad)(int) (ad=adeninate; int=isonicotinate). The material combines dense heterocyclic rings and accessible uncoordinated O atoms as strong binding sites for C2H6 and C2H2. Its spindle‐like cage exhibits an interesting shape matching with the targeted molecules, affording Zn(ad)(int) not only high separation selectivity for C2H6/C2H4 and C2H2/C2H4, but also excellent gas capacity. Breakthrough experiments show that polymer‐grade C2H4 can be separated from the ternary mixtures with a record productivity of 1.43 mmol g−1. In situ powder X‐ray diffraction and Fourier transform infrared spectrum analyses further provide deep insights into the separation mechanism.
Thermoelectric Zintl Compound In1−xGaxTe: Pure Acoustic Phonon Scattering and Dopant‐Induced Deformation Potential Reduction and Lattice Shrink
Authors: Li Fan , Liu Xin , Ma Ni , Chen Ling , Wu Li‐Ming 
Published: July 2022

AbstractWe report a Zintl phase thermoelectric material, coarse grain‐In0.99Ga0.01Te, achieving a ZT peak of 1.2 at 648 K and an average ZT=0.8 in 300–650 K, which outperforms all the known InTe‐based materials to date. The synergistic optimization of electronic property and phonon transport are achieved by the purification of grain boundary scattering, together with the Ga‐doping‐induced weak phonon‐electron coupling, which enhances the carrier mobility and carrier concentration simultaneously and consequently gives a remarkably increased power factor of 8.9 μW cm−1 K−2. The DFT phonon calculations indicate the dopant reduces the deformation potential coefficient and induces the lattice shrink, which reduces significantly the acoustic cutoff frequency, and enhances the scattering phase space. Moreover, the bonding hierarchy leads to the dense intragranular dislocation arrays, which suppresses the lattice thermal conductivity further and induces an ultralow lattice thermal conductivity (0.21 Wm−1 K−1).
Additive‐Triggered Polar Polymorph Formation: β‐Sc(IO3)3, a Promising Next‐Generation Mid‐Infrared Nonlinear Optical Material
Authors: Wu Chao , Wei Guangfeng , Jiang Xingxing , Xu Qinke , Lin Zheshuai , Huang Zhipeng , Humphrey Mark G. , Zhang Chi 
Published: July 2022

AbstractNoncentrosymmetric (NCS) solids have attracted interest for their potential in ferroelectric, piezoelectric, and nonlinear optical (NLO) devices, but their synthesis remains a major challenge. In this study, the additive Li2CO3 triggers formation of an NCS precursor at an early nucleation stage, and plays a crucial role in the successful polymorphism transformation. The resultant metastable β‐Sc(IO3)3 is a promising mid‐infrared NLO crystal, with the strongest second‐harmonic generation responses (2.2×KTiOPO4 @ 2100 nm, 16×KH2PO4 @ 1064 nm) and the largest optical band gap (4.52 eV) for a rare‐earth iodate, as well as sufficient birefringence (Δn=0.219 @ 546 nm) for type I phase‐matching, and wide optical transparency, which are induced by optimal alignment of the iodate anions. This study reveals the key role of additives in the growth of polar NCS solids, a discovery with implications for the strategic design of new NCS polymorphism materials with exceptional NLO properties.
Highly Efficient and Direct Ultralong All‐Phosphorescence from Metal–Organic Framework Photonic Glasses
Authors: Zhou Bo , Qi Zhenhong , Yan Dongpeng 
Published: July 2022

AbstractRealizing efficient and ultralong room‐temperature phosphorescence (RTP) is highly desirable but remains a challenge due to the inherent competition between excited state lifetime and photoluminescence quantum yield (PLQY). Herein, we report the bottom‐up self‐assembly of transparent metal–organic framework (MOF) bulk glasses exhibiting direct ultralong all‐phosphorescence (lifetime: 630.15 ms) with a PLQY of up to 75 % at ambient conditions. These macroscopic MOF glasses have high Young's modulus and hardness, which provide a rigid environment to reduce non‐radiative transitions and boost triplet excitons. Spectral technologies and theoretical calculations demonstrate the photoluminescence of MOF glasses is directly derived from the different triplet excited states, indicating the great capability for color‐tunable afterglow emission. We further developed information storage and light‐emitting devices based on the efficient and pure RTP of the fabricated MOF photonic glasses.
Kristallstrukturbasierte Mutagenese der Cattleyene‐Synthase führt zur Bildung umgelagerter polycyclischer Diterpene
Authors: Xing Baiying , Xu Houchao , Li Annan , Lou Tingting , Xu Meng , Wang Kaibiao , Xu Zhengren , Dickschat Jeroen S. , Yang Donghui , Ma Ming 
Published: July 2022

AbstractDie Kristallstrukturen der Cattleyen‐Synthase (apo‐CyS) und der mit Geranylgeranylpyrophosphat (GGPP) komplexierten CyS wurden gelöst. Die CySC59A‐Variante zeigte eine erhöhte Produktion von Cattleyen und weiteren Diterpenen mit unterschiedlichen Skeletten. Ihre Struktur zeigte ein vergrößertes aktives Zentrum, was die relaxierte Selektivität erklärt. Isotopenmarkierungsexperimente offenbarten einen bemerkenswerten Cyclisierungsmechanismus, der mehrere Gerüstumlagerungen für eines der neuen Diterpene umfasst.
From Ensemble Electrochemistry to Nano‐Impact Electrochemistry: Altered Reaction Selectivity
Authors: Zhong Rui , Wang Xiaoyu , Tao Qianqian , Zhang Jianhua , Lin Chuhong , Wei Hui , Zhou Yi‐Ge 
Published: July 2022

AbstractSelective electrochemical production of valued chemicals is of significant importance but remains a great challenge in chemistry. Conventional approaches for enhancing reaction selectivity focus on the improvement of the catalysts themselves. In this work, we systematically studied the reaction kinetics and mass transport behavior of LaNiO3 nanocubes (LaNiO3 NCs) catalyzed hydrogen peroxide reduction reaction (HPRR) at ensemble and single nanoparticle levels using nano‐impact electrochemistry (NIE). We find that the selectivity of HPRR was altered at individual random‐walk nanoparticles as compared to their ensemble counterpart without changing the reaction kinetics, due to the significantly enhanced mass transport at single nanoparticles. This discovery offers the scope of new catalytic approaches for engineering electrochemical reactions in general.
Sulfur–Phenolate Exchange: SuFEx‐Derived Dynamic Covalent Reactions and Degradation of SuFEx Polymers
Authors: Chao Yang , Krishna Akash , Subramaniam Muthusamy , Liang Dong‐Dong , Pujari Sidharam P. , Sue Andrew C.‐H. , Li Guanna , Miloserdov Fedor M. , Zuilhof Han 
Published: July 2022

AbstractThe products of the SuFEx reaction between sulfonimidoyl fluorides and phenols, sulfonimidates, are shown to display dynamic covalent chemistry with other phenols. This reaction was shown to be enantiospecific, finished in minutes at room temperature in high yields, and useful for both asymmetric synthesis and sustainable polymer production. Its wide scope further extends the usefulness of SuFEx and related click chemistries.
First report of an egg nursery for the Critically Endangered flapper skate Dipturus intermedius (Rajiformes: Rajidae)
Authors: Dodd Jane , Baxter John M. , Donnan David W. , James Benjamin D. , Lavender Edward , McSorley Claire A. , Mogg Andrew O.M. , Thorburn James A. 
Published: July 2022

Abstract

This study provides the first report of an egg nursery for the Critically Endangered flapper skate Dipturus intermedius and a description of the habitat, thus contributing towards our understanding of essential habitats for the species.
In total, 1,395 flapper skate egg cases were recorded (accounting for overlapping surveys) in two egg case collection dives (n = 67 egg cases), one photogrammetry dive (n = 10 egg cases), 509 drop‐down video (DDV) camera drifts (n = 510 egg cases) and 18 remote operated vehicle (ROV) flights (n = 1,031 egg cases), carried out in the Inner Sound on the west coast of Scotland from 2018 to 2021. All of the egg cases were found on a shallow bedrock plateau between the Isle of Scalpay and a deep (>100 m) water channel between the Isle of Longay and the Crowlin Islands. Egg cases were observed on a cobble/boulder reef between 25 and 58 m depth, with a modelled annual temperature range of 9–12 °C, modelled current speeds up to 0.2 m−1, a rugosity index of 1.7 and low levels of sedimentation.
Flapper skate egg cases are large and the incubation period is protracted (18 months), making them potentially vulnerable to anthropogenic disturbance. A description of the habitat where egg cases were observed in this study will help inform the search for egg nurseries for this Critically Endangered species elsewhere. Targeted DDV, ROV and scuba diving surveys will support this search in areas where suitable bathymetric and hydrodynamic conditions are identified.
Safeguarding egg nurseries is essential for successful conservation. Protection should involve the designation of egg nurseries as Marine Protected Areas where activities that are likely to damage or alter seabed habitats are managed.
The first complete cranium of Homotherium (Machairodontinae, Felidae) from the Nihewan Basin (northern China)
Authors: Jiangzuo Qigao , Zhao Hailong , Chen Xi 
Published: July 2022

AbstractThe Nihewan Basin is famous for producing a rich Early Pleistocene fauna, the most classic and standard for the Early Pleistocene of northern China, as well as rich paleolithic remains, documenting the early presence of humans. Many fossil Carnivora, including the scimitar toothed cat Homotherium, were found from this basin, but no complete material of this cat was known, which hampers a deep study of its taxonomy. Here, we report a complete cranium of Homotherium, found in Shigou, a recently discovered locality in the Nihewan Basin. The morphology of the cranium supports its assignment to Homotherium crenatidens teilhardipiveteaui, a terminal evolutionary stage of the species with a Palearctic distribution. Our analyses suggest that Homotherium evolved largely contemporarily in different regions of Eurasia, suggesting a continuous gene flow within the continent, and the subspecies delimitation should be more chronological than geographical.