bluuebunny/crossref_metadata_2025_split huggingface dataset:
Appearance of a Photoinduced Hidden State in the Electron Donor–Acceptor Type Metal–Organic Framework (NPr4)2[Fe2(Cl2An)3]
Authors: Banu Samiran , Kato Mone , Takubo Kou , Okimoto Yoichi , Koshihara Shinya , Iwano Kaoru , Kosaka Wataru , Miyasaka Hitoshi , Ishikawa Tadahiko 
Published: September 2023

AbstractElectron donor–acceptor (DA)‐type metal–organic frameworks (MOFs) with valence instability are promising molecular materials for the design of photo‐responsive and electronic/magnetic functional materials. Here, ultrafast photoinduced dynamics in a DA‐type layered MOF that exhibits a charge‐transfer (CT)‐type phase transition are reported: (NPr4)2[Fe2(Cl2An)3], where NPr4+ = tetra‐n‐propylammonium and Cl2An2− = 2,5‐dichloro‐3,6‐dihydroxo‐1,4‐benzoquinonate. At room temperature (300 K: RT), ultrafast photoinduced CT between the Fe and Cl2An ions induces a sensitive change in the state associated with the valence instability from a single‐chain, electron‐correlated state to a new photoinduced, structurally modulated state. In the photoinduced state, two absorption bands are observed, one on the higher‐energy side of the CT band and the other in the mid‐IR range. This strongly implies that the local inversion center on the Cl2An ion that exists in the initial state disappears instantly upon photoexcitation, causing an ultrafast change in the lattice structure due to the softening of rigid bonds. This has never been realized in thermal excitation. These findings demonstrate that a new electronic state with a unique lattice structure—i.e., a photoinduced hidden state—appears in this MOF system at ultra‐high speed (within 110 fs) upon photoexcitation at RT.
Prediction of Piezoelectric Tile Performance in Flat and Mountainous Terrains Through Deep Neural Network
Authors: Adhikari Jitendra , Singh Kamalpreet , Sagar Anjani Kumar , Sharma Vikki Kumar , Kumar Rajeev , Jain Satish Chandra 
Published: September 2023

AbstractPiezoelectric tiles harvest mechanical vibrations and convert them into electrical energy, making them an attractive energy‐harvesting technology. However, their performance is heavily influenced by the terrain where they are installed. Traditional experimental methods for predicting their performance on different terrains are time‐consuming, so a computational approach is necessary to improve efficiency. To address this, a machine learning‐based approach is proposed using Artificial Neural network (ANN) and Deep neural network (DNN) with the Tanh activation function to predict piezoelectric tile performance in diverse terrains. The models are trained on an experimental dataset consisting of four terrains, including Flat terrain (FT) and Hilly Terrain (HT) 1, 2, 3 with road angles of 0, 3, 6, and 10 degrees. A finite element model is also established to optimize the piezoelectric tile and estimate the suitable parameter range to prevent damage to the tile during experiments. The results indicate that the DNN model performs better than the ANN model, achieving high accuracy in predicting piezoelectric tile performance on different terrains. These findings suggest that machine learning can provide a time and cost‐effective way for predicting the performance of piezoelectric tiles in varied terrains, thereby facilitating betters installation and maintenance decisions for piezoelectric tile systems.
Cu‐Catalyzed Enantioselective Reductive Coupling of 1,3‐Dienes and Carboxylic Acid Anhydrides
Authors: Lu Wenxin , Chong Qinglei , Meng Fanke 
Published: September 2023

AbstractCatalytic chemo‐, regio‐ and enantioselective construction of allyl‐Cu complexes generated from a Cu−H addition to trans‐1,3‐dienes followed by in situ addition to anhydrides to construct homoallylic alcohols is presented. This method is distinguished by a characteristic pathway to generate enantiomerically enriched allyl‐Cu species, which react with a wide range of anhydrides in high chemo‐, regio‐ and stereoselectivity. Functionalization of homoallylic alcohol products provides useful building blocks which are otherwise difficult to obtain.
Covariance in human limb joint articular morphology
Authors: Horbaly Haley 
Published: September 2023

AbstractObjectivesLimb synovial joints exhibit complex shapes that must accommodate often‐antagonistic demands of function, mobility, and stability. These demands presumably dictate coordination among joint articular shapes, but the structure of morphological covariance within and among joints is unknown. This study analyzes the human shoulder, elbow, hip, and knee to determine how articular covariance is structured in relation to joint structure, accessory cartilage, and function.Materials and MethodsSurface models were created from the CT scans of 200 modern skeletons from the University of Tennessee Donated Skeletal Collection. Three‐dimensional landmarks were collected on the shoulder, elbow, hip, and knee joints. Two‐block partial least squares were conducted to determine associations between surfaces of conarticular shapes, functionally analogous articulations, and articulations belonging to the same bone.ResultsExcept for the components of the shoulder, all conarticular pairs exhibit covariance, though the strength of these relationships appears unrelated to the amount of accessory cartilage in the joint. Only the analogous articulations of the humerus and femur exhibit significant covariance, but it is unlikely that this pattern is due to function alone. Stronger covariance within the lower limb than the upper limb is consistent broader primate patterns of within‐limb integration.DiscussionWith the exception of the elbow, complementary joint function does not appear to promote strong covariance between articulations. Analogous humeral and femoral surfaces are also serially homologous, which may result in the articular associations observed between these bones. Broadly, these patterns highlight the indirect relationship between joint congruence and covariance.
Variation in human limb joint articular morphology
Authors: Horbaly Haley , Hubbe Mark , Sylvester Adam D. , Steadman Dawnie Wolfe , Auerbach Benjamin M. 
Published: September 2023

AbstractObjectivesSynovial joints in human limbs strike a balance between mobility, stability, and articular fit, yet little is known about how these conflicting demands pattern intraspecific variation in articular shape. In this study, we use geometric morphometrics to establish the apportionment and magnitude of morphological variance of the articular surfaces of the human shoulder, elbow, hip, and knee. We hypothesize that variances will be comparable between articulating surfaces within a joint and will be larger in joints with smaller ranges of motion, given their plurality of functional demands.Materials and MethodsThree‐dimensional landmarks were taken on the articular surfaces of the glenohumeral, humeroulnar, acetabulofemoral, and tibiofemoral joints from CT scans of 200 skeletons from the University of Tennessee Donated Skeletal Collection (84 females, 116 males). Root mean‐squared distances between articulations calculated from Procrustes shape coordinates were used to determine variance distributions.ResultsWe found no difference in variances for each articular surface between the sexes or between left and right articular surfaces. A high range of motion is associated with greater morphological variance; however, this pattern is largely driven by the concave articular surfaces of each joint, which consistently exhibit statistically greater variance than their convex counterparts.DiscussionThe striking pattern of differential variance between articulating morphologies points to potential disparities in development between them. Consistently higher variance in concave surfaces may relate to chondral modeling theory for the formation of joints. Establishing intraspecific morphological variance patterns is a first step in understanding coordinated evolution among articular features.
Mechanisms of Biomolecular Self‐Assembly Investigated Through In Situ Observations of Structures and Dynamics
Authors: Schmid Sakshi Yadav , Lachowski Kacper , Chiang Huat Thart , Pozzo Lilo , De Yoreo Jim , Zhang Shuai 
Published: September 2023

AbstractBiomolecular self‐assembly of hierarchical materials is a precise and adaptable bottom‐up approach to synthesizing across scales with considerable energy, health, environment, sustainability, and information technology applications. To achieve desired functions in biomaterials, it is essential to directly observe assembly dynamics and structural evolutions that reflect the underlying energy landscape and the assembly mechanism. This review will summarize the current understanding of biomolecular assembly mechanisms based on in situ characterization and discuss the broader significance and achievements of newly gained insights. In addition, we will also introduce how emerging deep learning/machine learning‐based approaches, multiparametric characterization, and high‐throughput methods can boost the development of biomolecular self‐assembly. The objective of this review is to accelerate the development of in situ characterization approaches for biomolecular self‐assembly and to inspire the next generation of biomimetic materials.
Einbau von (Bioaktiven) Äquatorialen Liganden in Platin(IV)‐Komplexe
Authors: Kastner Alexander , Schueffl Hemma , Yassemipour Patrick A. , Keppler Bernhard K. , Heffeter Petra , Kowol Christian R. 
Published: September 2023

AbstractPlatin(IV)‐Prodrugs sind aufgrund ihrer erhöhten Tumorselektivität und geringeren Nebenwirkungen äußerst interessante Alternativen zu Platin(II)‐Antitumortherapeutika. Im Gegensatz zur gängigen Theorie haben wir kürzlich beobachtet, dass äquatoriale Liganden von z. B. Oxaliplatin(IV)‐Komplexen unter Bildung von [(DACH)Pt(OHeq)2(OAcax)2] hydrolysiert werden können. In der hier vorgestellten Arbeit untersuchten wir die Reaktivität und synthetische Verwendbarkeit dieses Komplexes, als Vorstufe für die Entwicklung neuartiger Platin(IV)‐Komplexe, welche mit herkömmlichen Methoden nicht zugänglich sind. Tatsächlich war es möglich die äquatorialen Hydroxidoliganden z. B. durch ein oder zwei monodentate Biotin‐Liganden, die unter Standardmethoden oxidiert werden würden, zu ersetzen. Die gebildeten Komplexe erwiesen sich als sehr stabil und zeigten auch nach der Reduktion eine langsame Ligandenfreisetzung, eine ideale Eigenschaft für lang zirkulierende zielgerichtete Strategien. Daraufhin wurden zwei Platin(IV)‐Komplexe mit äquatorialen Maleimiden, für die Bindung an Serumalbumin als natürlichen Nanocarrier, synthetisiert. Die Komplexe zeigten im Vergleich zu Oxaliplatin eine stark verlängerte Plasmahalbwertszeit und eine deutlich verbesserte Antitumoraktivität in vivo. Zusammenfassend ermöglicht diese neu entwickelte Syntheseplattform den einfachen und gezielten Einbau äquatorialer Liganden in Platin(IV)‐Komplexe. Des Weiteren können verschiedene (bioaktive) Einheiten koordiniert werden, wodurch sogar zielgerichtete dreifach‐wirksame Platin(IV)‐Prodrugs mit nur einem Platinzentrum möglich wären.
Enhanced Metal‐Support Interactions Boost the Electrocatalytic Water Splitting of Supported Ruthenium Nanoparticles on a Ni3N/NiO Heterojunction at Industrial Current Density
Authors: Liu Rui , Sun Mingzi , Liu Xiangjian , Lv Zunhang , Yu Xinyu , Wang Jinming , Liu Yarong , Li Liuhua , Feng Xiao , Yang Wenxiu , Huang Bolong , Wang Bo 
Published: September 2023

AbstractDeveloping highly efficient and stable hydrogen production catalysts for electrochemical water splitting (EWS) at industrial current densities remains a great challenge. Herein, we proposed a heterostructure‐induced‐strategy to optimize the metal‐support interaction (MSI) and the EWS activity of Ru‐Ni3N/NiO. Density functional theory (DFT) calculations firstly predicted that the Ni3N/NiO‐heterostructures can improve the structural stability, electronic distributions, and orbital coupling of Ru‐Ni3N/NiO compared to Ru‐Ni3N and Ru‐NiO, which accordingly decreases energy barriers and increases the electroactivity for EWS. As a proof‐of‐concept, the Ru‐Ni3N/NiO catalyst with a 2D Ni3N/NiO‐heterostructures nanosheet array, uniformly dispersed Ru nanoparticles, and strong MSI, was successfully constructed in the experiment, which exhibited excellent HER and OER activity with overpotentials of 190 mV and 385 mV at 1000 mA cm−2, respectively. Furthermore, the Ru‐Ni3N/NiO‐based EWS device can realize an industrial current density (1000 mA cm−2) at 1.74 V and 1.80 V under alkaline pure water and seawater conditions, respectively. Additionally, it also achieves a high durability of 1000 h (@ 500 mA cm−2) in alkaline pure water.
Sulfur Changes the Electrochemical CO2 Reduction Pathway over Cu Electrocatalysts
Authors: Liang Shuyu , Xiao Jiewen , Zhang Tianyu , Zheng Yue , Wang Qiang , Liu Bin 
Published: September 2023

AbstractElectrochemical CO2 reduction to value‐added chemicals or fuels offers a promising approach to reduce carbon emissions and alleviate energy shortage. Cu‐based electrocatalysts have been widely reported as capable of reducing CO2 to produce a variety of multicarbon products (e.g., ethylene and ethanol). In this work, we develop sulfur‐doped Cu2O electrocatalysts, which instead can electrochemically reduce CO2 to almost exclusively formate. We show that a dynamic equilibrium of S exists at the Cu2O‐electrolyte interface, and S‐doped Cu2O undergoes in situ surface reconstruction to generate active S‐adsorbed metallic Cu sites during the CO2 reduction reaction (CO2RR). Density functional theory (DFT) calculations together with in situ infrared absorption spectroscopy measurements show that the S‐adsorbed metallic Cu surface can not only promote the formation of the *OCHO intermediate but also greatly suppress *H and *COOH adsorption, thus facilitating CO2‐to‐formate conversion during the electrochemical CO2RR.
Dithienoazepine‐Based Near‐Infrared Dyes: Janus‐Faced Effects of a Thiophene‐Fused Structure on Antiaromatic Azepines
Authors: Murai Masahito , Enoki Takahiro , Yamaguchi Shigehiro 
Published: September 2023

AbstractWe here disclose that the incorporation of thiophene rings into a seven‐membered 8π azepine in a fused fashion produces a useful antiaromatic core for near‐infrared (NIR) dyes. In contrast to dibenzazepine derivatives with bent structures, dithieno‐fused derivatives with electron‐accepting groups adopt flat conformations in the ground state. The dithieno‐fused derivatives exhibited broad absorption spectra that cover the visible region as well as sharp emission bands in the NIR region, which are considerably red‐shifted relative to those of the dibenzo‐fused congeners. Theoretical study revealed two contradictory effects of the less‐aromatic thiophene‐fused structure, i.e., the enhancement of the antiaromaticity of the adjacent azepine ring and the relief of the antiaromaticity through the contribution of a quinoidal resonance form. The combination of the dithienoazepine core with cationic electron‐accepting groups produced a NIR fluorescent dye with an emission at 878 nm in solution.
Novel core–shell magnetic nanoparticles@Zeolitic imidazolate with glycerol‐nickel for the synthesis of dihydropyrimidinones
Authors: Poursattar Marjani Ahmad , Asadzadeh Fatemeh , Danandeh Asl Aria 
Published: September 2023

The present study reported a novel and eco‐friendly synthesis of Fe3O4@ZIF‐8@Glycerol‐Ni nanocatalyst via a multistep process. The as‐prepared catalyst was used due to its high efficiency, low cost, and biocompatibility for the fabrication of dihydropyrimidinones by Biginelli multicomponent reactions of aryl aldehyde, ethyl acetoacetate, and urea under ambient status. X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR), Brunauer‐Emmet‐Teller (BET), vibrating sample magnetometry (VSM), scanning electron microscopy and energy dispersive X‐ray (SEM‐EDS), inductively coupled plasma (ICP), elemental mapping analysis (EMA), thermogravimetric analysis (TGA), Raman, and transmission electron microscopy (TEM) techniques were successfully utilized to evaluate the nanocatalyst. The advent of the peaks confirmed the presence of nickel on the catalyst's surface due to the oxygen and nickel, and the nanoparticle size is 10–15 nm. Eventually, nano‐heterogeneous catalyst exhibits high performance as well as good selectivity in the synthesis of dihydropyrimidinones. Also, it can be recycled up to multiple fresh runs with no significant loss of catalytic efficiency.
Neurovascular description in the South American plains vizcacha, Lagostomus maximus (Chinchilloidea, Caviomorpha). A study involving evolutionarily related species of Caviomorpha and Muroidea
Authors: Schmidt Alejandro Raúl , Inserra Pablo Ignacio Felipe , Giacchino Mariela , Ferraris Sergio , Lange Fernando , Figueredo Ramiro Vidal , Halperin Julia , Vitullo Alfredo Daniel , Dorfman Verónica Berta 
Published: September 2023

AbstractOxygenated blood is required for the adequate metabolic activity of the brain. This is supplied by the circle of Willis (CoW) and the vertebrobasilar and carotid systems. The CoW ensures blood flow in case of arterial stenosis or occlusion. Different animal models have been explored for the CoW morphological and functional study. This work aims to characterize the vascular architecture of the CoW of the plains vizcacha, Lagostomus maximus (Suborder: Hystricomorpha), and to compare it with evolutionarily related species of Caviomorpha and Muroidea. The blood supply in adult plains vizcachas was studied using latex cerebrovascular casts and angiography. A caudo‐rostral flow direction was determined, beginning in the spinal and vertebral arteries and converging in the basilar artery which bifurcates in the carotid‐basilar communication in the caudal communicating arteries. In the first third of its course, the caudal cerebral arteries project laterally, and the middle and rostral cerebral arteries bifurcate from their rostral terminal segment, supplying the temporo‐parietal and frontal cortex. The CoW architecture is mainly conserved between rodent species. Likewise, the small neurovascular variations observed could be considered phylogenetic morphological variations more than evolutionary adaptations. The absence of the rostral communicating artery that generates the rostral open architecture of the CoW in the vizcacha as in the other analyzed species, supports the need for a revision of the CoW classical function as a security system. Finally, this work supports the importance of expanding our understanding of brain anatomy among species, which may contribute to a better understanding of functional neuroanatomy.
Advances in the extracellular signal‐regulated kinase signaling pathway in silkworms, Bombyx mori (Lepidoptera)
Authors: Lv Jun‐Li , Zheng Kai‐Yi , Wang Xue‐Yang , Li Mu‐Wang 
Published: September 2023

AbstractSignaling pathways regulate the transmission of signals during organism growth and development, promoting the smooth and accurate completion of numerous physiological and biochemical reactions. The extracellular signal‐regulated kinase (ERK) signaling pathway is an essential pathway involved in regulating various physiological processes, such as cell proliferation, differentiation, adhesion, migration, and more. This pathway also contributes to several important physiological processes in silkworms, including protein synthesis, reproduction, and immune defense against pathogens. Organizing related studies on the ERK signaling pathway in silkworms can provide a better understanding of its mechanism in Lepidopterans and develop a theoretical foundation for improving cocoon production and new strategies for pest biological control.
Jellyfish‐type Dinuclear Hafnium Azido Complexes: Synthesis and Reactivity
Authors: Lin Xin‐Cheng , Cui Yun‐Shu , Xie Si‐Jun , Chen Dong‐Ping , Zhai Dan‐Dan , Shi Zhang‐Jie 
Published: September 2023

AbstractDi‐ and multinuclear hafnium complexes bridged by ligands have been rarely reported. In this article, a novel 3,5‐disubstituted pyrazolate‐bridged ligand LH5 with two [N2N]2−‐type chelating side arms was designed and synthesized, which supported a series of dinuclear hafnium complexes. Dinuclear hafnium azides [LHf2(μ‐1,1‐N3)2(N3)2][Na(THF)4] 3 and [LHf2(μ‐1,1‐N3)2(N3)2][Na(2,2,2‐Kryptofix)] 4 were further synthesized and structurally characterized, featuring two sets of terminal and bridging azido ligands like jellyfishes. The reactivity of 3 under reduction conditions was conducted, leading to a formation of a tetranuclear hafnium imido complex [L1Hf2(μ1‐NH)(N3){μ2‐K}]2 5. DFT calculations revealed that the mixed imido azide 5 was generated via an intramolecular C−H insertion from a putative dinuclear HfIV‐nitridyl intermediate.
Photolysis of Phosphaketenyltetrylenes with a Carbazolyl Substituent
Authors: Li Chenxin , Hinz Alexander 
Published: September 2023

AbstractPhosphaketenes of divalent group 14 compounds can potentially serve as precursors for the synthesis of heavy multiple‐bond systems. We have employed the dtbpCbz substituent (dtbpCbz=1,8‐bis(3,5‐ditertbutylphenyl)‐3,6‐ditertbutylcarbazolyl) to prepare such phosphaketenyltetrylenes [(dtbpCbz)EPCO] (E=Ge, Sn, Pb). While the phosphaketenyltetrylenes are stable at ambient conditions, they can be readily decarbonylated photolytically. For the germylene and stannylene derivatives, dimeric diphosphene‐type products [(dtbpCbz)EP]2 (E=Ge, Sn) were obtained. In contrast, photolysis of the phosphaketenylplumbylene, via isomerisation of the [(dtbpCbz)PbP] intermediate to [(dtbpCbz)PPb], afforded an unsymmetric and incompletely decarbonylated product [(dtbpCbz)2Pb2P2CO] formally comprising a [(dtbpCbz)PPb] and a [(dtbpCbz)PbPCO] moiety.
Exploring the therapeutic potential of naturally occurring piceatannol in non‐communicable diseases
Authors: Gandhi Himanshu , Mahant Shikha , Sharma Abhishek Kumar , Kumar Deepak , Dua Kamal , Chellappan Dinesh Kumar , Singh Sachin Kumar , Gupta Gaurav , Aljabali Alaa A. A. , Tambuwala Murtaza M. , Kapoor Deepak N. 
Published: September 2023

AbstractPiceatannol is a naturally occurring hydroxylated resveratrol analogue that can be found in a variety of fruits and vegetables. It has been documented to have a wide range of beneficial effects, including anti‐inflammatory, antioxidant, anti‐aging, anti‐allergic, antidiabetic, neuroprotective, cardioprotective, and chemopreventive properties. Piceatannol has significantly higher antioxidant activity than resveratrol. Piceatannol has been shown in preclinical studies to have the ability to inhibit or reduce the growth of cancers in various organs such as the brain, breast, lung, colon, cervical, liver, prostate, and skin. However, the bioavailability of Piceatannol is comparatively lower than resveratrol and other stilbenes. Several approaches have been reported in recent years to enhance its bioavailability and biological activity, and clinical trials are required to validate these findings. This review focuses on several aspects of natural stilbene Piceatannol, its chemistry, and its mechanism of action, and its promising therapeutic potential for the prevention and treatment of a wide variety of complex human diseases.