bluuebunny/crossref_metadata_2025_split huggingface dataset:
Exceptional Lithium‐Ion Storage Performance on an Azo‐Bridged Covalent Heptazine Framework
Authors: Yu Yanxin , Jin Qianqian , Zhu Dandan , Ren Yanbiao 
Published: September 2023

AbstractGraphitic carbon nitride (g‐C3N4) possesses rich pyridine nitrogens, which is helpful for facilitating electrochemical capability in Li+ storage; however, its poor conductivity is still the main challenge. Based on the knowledge of its intrinsic merits and defects, here, it is proposed to integrate active heptazine (HEP) species with functional linkers into orderly molecular structures for improved performance. As the first proof‐of‐concept, a unique azo‐linked covalent heptazine framework (Azo‐CHF) where two HEP units are bridged with azo linkages, is ingeniously designed and prepared to enhance the inherent charge conductivity for Li+ storage. Attributing to the deeply extended conjugation along overlapping azo nitrogens and the aromatic π system of HEP cores, Azo‐CHF with the lowest bandgap (2.58 eV) exhibits enhanced Li+/e− transport than g‐C3N4 through density functional theory calculations. Therefore, the Azo‐CHF anode exhibits an unprecedented performance with a large reversible capacity (1723.0 mAh g−1 at 0.1 A g−1), superior rate capability (824.0 mAh g−1 at 10 A g−1), and impressive cyclability (756.5 mAh g−1 undergoing 1000 cycles at 10 A g−1). This study not only demonstrates the great application prospect of Azo‐CHF for Li+ storage, but also opens a fantastic window to further explore high‐performance electrodes by integrating HEP with other active motifs.
A Nano‐Autophagy Inhibitor Triggering Reciprocal Feedback Control of Cholesterol Depletion for Solid Tumor Therapy
Authors: Zhang Pengfei , Shi Yanfeng , Xu Yuanhong , Liang Ye , Huang Chao , Zhong Di , Zhang Zhilei , Yu Yongbo , Zhang Zhao , Zhang Jianfeng , Yu Lei , Zuo Yuhui , Wang Xinsheng , Niu Haitao 
Published: September 2023

AbstractSolid tumors are characterized by enhanced metabolism of lipid, particularly cholesterol, inspiring the exploration of metabolic therapy through cholesterol oxidase (COD)‐mediated cholesterol deprivation. However, the therapeutic efficacy of COD is limited due to the hypoxic tumor microenvironment and the protective autophagy triggered by cholesterol deprivation. Herein, a combination therapy for metabolically treating solid tumors through COD in conjunction with molybdenum oxide nanodots (MONDs), which serve as both potent oxygen generators and autophagy inhibitors, is reported. MONDs convert H2O2 (arising from COD‐mediated cholesterol oxidation) into O2, which is then recycled by COD to form reciprocal feedback for cholesterol depletion. Concurrently, MONDs can overcome autophagy‐induced therapeutic resistance frequently occurring in conventional nutrient deprivation therapy by activating AKT/mTOR pathway phosphorylation. Combination therapy in the xenograft model results in an ≈5‐fold increase in therapeutic efficiency as compared with COD treatment alone. This functionally cooperative metabolic coupling strategy holds great promise as a novel polytherapy approach that will benefit patients with solid tumors.
A Simple and Versatile Approach for the Low‐Temperature Synthesis of Transition Metal Phosphide Nanoparticles from Metal Chloride Complexes and P(SiMe3)3
Authors: Sodreau Alexandre , Zahedi Hooman Ghazi , Dervişoğlu Rıza , Kang Liqun , Menten Julia , Zenner Johannes , Terefenko Nicole , DeBeer Serena , Wiegand Thomas , Bordet Alexis , Leitner Walter 
Published: September 2023

AbstractMetal chloride complexes react with tris(trimethylsilyl)phosphine under mild condition to produce metal phosphide (TMP) nanoparticles (NPs), and chlorotrimethylsilane as a byproduct. The formation of Si–Cl bonds that are stronger than the starting M‐Cl bonds acts as a driving force for the reaction. The potential of this strategy is illustrated through the preparation of ruthenium phosphide NPs using [RuCl2(cymene)] and tris(trimethylsilyl)phosphine at 35 °C. Characterization with a combination of techniques including electron microscopy (EM), X‐ray absorption spectroscopy (XAS), and solid‐state nuclear magnetic resonance (NMR) spectroscopy, evidences the formation of small (diameter of 1.3 nm) and amorphous NPs with an overall Ru50P50 composition. Interestingly, these NPs can be easily immobilized on functional support materials, which is of great interest for potential applications in catalysis and electrocatalysis. Mo50P50 and Co50P50 NPs can also be synthesized following the same strategy. This approach is simple and versatile and paves the way toward the preparation of a wide range of transition metal phosphide nanoparticles under mild reaction conditions.
Unveiling the TADF Emitters with Apparent Negative Singlet‐Triplet Gaps: Implications for Exciton Harvesting and OLED Performance
Authors: Chen Xinrui , Bagnich Sergey , Pollice Robert , Li Bing , Zhu Yuanyuan , Saxena Rishabh , Yin Yixiao , Zhu Weiguo , Aspuru‐Guzik Alan , Zysman‐Colman Eli , Köhler Anna , Wang Yafei 
Published: September 2023

AbstractIntramolecular through‐space charge transfer thermally activated delayed fluorescence (TSCT‐TADF) has attracted much attention recently as it can achieve both small energy splitting and high emission efficiency. However, the relationship of excited states between TSCT and through‐bond charge transfer (TBCT) remains a challenge in the TSCT‐TADF molecules. Herein, three compounds DPS‐m‐bAc, DPS‐p‐bAc, and DPS‐OAc that possess emissive TSCT and/or TBCT states are prepared. Interestingly, a so‐called inverted energy gap is found for both DPS‐m‐bAc and DPS‐p‐bAc in toluene solution, which results from the different charge transfer states of ICThigh and ICTlow, as proved by the detailed transient photoluminescence and calculated results. Intense emission from blue to yellow associated with high photoluminescence quantum yields of 70–100% are measured in doped polymethyl(methacrylate) (PMMA) films. Notably, compound DPS‐m‐bAc achieves the highest reverse intersystem crossing rate constant (kRISC) of over 107 s−1 in a PMMA film, benefiting from close‐lying TSCT and TBCT states. The solution‐processed device with DPS‐m‐bAc displays a maximum external quantum efficiency of 21.7% and a relatively small efficiency roll‐off (EQE of 20.2% @ 100 cd m−2). Overall, this work demonstrates how with judicious emitter engineering, a synergy between different charge transfer excited states, can be achieved, providing an avenue to achieve highly efficient solution‐processed OLEDs.
Sharp Transformation across Morphotropic Phase Boundary in Sub‐6 nm Wake‐Up‐Free Ferroelectric Films by Atomic Layer Technology
Authors: Chuang Chun‐Ho , Wang Ting‐Yun , Chou Chun‐Yi , Yi Sheng‐Han , Jiang Yu‐Sen , Shyue Jing‐Jong , Chen Miin‐Jang 
Published: September 2023

AbstractAtomic layer engineering is investigated to tailor the morphotropic phase boundary (MPB) between antiferroelectric, ferroelectric, and paraelectric phases. By increasing the HfO2 seeding layer with only 2 monolayers, the overlying ZrO2 layer experiences the dramatic phase transition across the MPB. Conspicuous ferroelectric properties including record‐high remanent polarization (2Pr ≈ 60 µC cm−2), wake‐up‐free operation, and high compatibility with advanced semiconductor technology nodes, are achieved in the sub‐6 nm thin film. The prominent antiferroelectric to ferroelectric phase transformation is ascribed to the in‐plane tensile stress introduced into ZrO2 by the HfO2 seeding layer. Based on the high‐resolution and high‐contrast images of surface grains extracted precisely by helium ion microscopy, the evolution of the MPB between tetragonal, orthorhombic, and monoclinic phases with grain size is demonstrated for the first time. The result indicates that a decrease in the average grain size drives the crystallization from the tetragonal to polar orthorhombic phases.
Fluoropolymer Coated DNA Nanoclews for Volumetric Visualization of Oligonucleotides Delivery and Near Infrared Light Activated Anti‐Angiogenic Oncotherapy
Authors: Zhang Peng , Guo Ranran , Zhang Haiting , Yang Wuli , Tian Ye 
Published: September 2023

AbstractThe potential of microRNA regulation in oncotherapy is limited by the lack of delivery vehicles. Herein, it is shown that fluoropolymer coated DNA nanoclews (FNCs) provide outstanding ability to deliver oligonucleotide through circulation and realize near infrared (NIR) light activated angiogenesis suppression to abrogate tumors. Oligonucleotides are loaded in DNA nanoclews through sequence specific bindings and then a fluorinated zwitterionic polymer is coated onto the surface of nanoclews. Further incorporating quantum dots in the polymer coating endows the vectors with NIR‐IIb (1500–1700 nm) fluorescence and NIR light triggered release ability. The FNC vector can deliver oligonucleotides to cancer cells systemically and realize on‐demand cytosolic release of the cargo with high transfection efficiency. Taking advantage of the NIR‐IIb emission, the whole delivery process of FNCs is visualized volumetrically in vivo with a NIR light sheet microscope. Loaded by FNCs, an oligonucleotide can effectively silence the target miRNA when activated with NIR light, and inhibit angiogenesis inside tumor, leading to complete ablation of cancer. These findings suggest FNCs can be used as an efficient oligonucleotide delivery platform to modulate the expression of endogenous microRNA in gene therapy of cancer.
First Subphthalocyanine Analogue with Fused 6H‐1,4‐diazepine Ring and its Conversion to Aminobenzamide Derivative
Authors: Skvortsov Ivan A. , Chufarin Alexey E. , Zaitsev Mark V. , Kirakosyan Gayane A. , Stuzhin Pavel A. 
Published: September 2023

AbstractMixed cyclization of 5,7‐diphenyl‐6H‐1,4‐diazepine 2,3‐dicarbonitrile and tetrafluorophthalonitrile in the presence of boron trichloride affords along with symmetrical perfluorinated subphthakocyanine, [F12sPc], two novel subporphyrazine‐type products which were isolated by column chromatography and characterized by mass‐sprectometry, NMR, IR, UV‐VIS and fluorescent spectroscopy. It was established that co‐cyclomerization of dinitriles is accompanied by electrophilic chlorination of 1,4‐diazepine ring by evolved Cl2 resulting in formation of dibenzosubporphyrazine [F8sPc1] with fused 6‐chloro‐5,7‐diphenyl‐6H‐1,4‐diazepine fragment. According to DFT modelling and 1H NMR data, a more stable diastereomer with an axial Cl atom is formed and no inversion of the 1,4‐diazepine ring is observed. Hydrolytic cleavage of the 1,4‐diazepine fragment in [F8sPc1] is observed upon chromatography or in the presence of a strong acid (CF3COOH) and leads to 2‐amino‐3‐benzamide substituted dibenzo subporphyrazine [F8sPc2]. Fluorescence of [F8sPc1] (ΦF=0.03) is ca 10 times lower than for [F12sPc] (ΦF=0.28) due to the combined effect of intramolecular charge transfer (ICT) from the donor diazepine ring to the acceptor sPc macrocycle and heavy atom effect of chlorine. Fluorescence of [F8sPc2] is almost completely quenched by ICT from −NH2 group to the electron‐deficient subporphyrazine core (ΦF<0.001), but addition of acid leads to protonation of the amino group and switch‐ON the fluorescence. Therefore, aminobenzamide substituted subporphyrazines can be considered as perspective pH‐sensitive fluorophores.
Spin Frustration in Organic Radicals
Authors: Tang Shuxuan , Wang Xinping 
Published: September 2023

AbstractSpin frustration, which results from geometric frustration and a systematical inability to satisfy all antiferromagnetic (AF) interactions between unpaired spins simultaneously, is under the spotlight for its importance in physics and materials science. Spin frustration is treated as the structural basis of quantum spin liquids (QSLs). Featuring flexible chemical structures, organic radical species exhibit great potential in building spin‐frustrated molecules and lattices. So far, the reported examples of spin‐frustrated organic radical compounds include triradicals, tetrathiafulvalene (TTF) radicals and derivatives, [Pd(dmit)2] compounds (dmit=1,3‐dithiol‐2‐thione‐4,5‐dithiolate), nitronyl nitroxides, fullerenes, polycyclic aromatic hydrocarbons (PAHs), and other heterocyclic compounds where the spin frustration is generated intra‐ or intermolecularly. In this Minireview, we provide a brief summary of the reported radical compounds that possess spin frustration. The related data, including magnetic exchange coupling parameters, spin models, frustration parameters, and crystal lattices, are summarized and discussed.
Stabilization Of The CN35− Anion In Recoverable High‐pressure Ln3O2(CN3) (Ln=La, Eu, Gd, Tb, Ho, Yb) Oxoguanidinates
Authors: Aslandukov Andrey , Jurzick Pascal L. , Bykov Maxim , Aslandukova Alena , Chanyshev Artem , Laniel Dominique , Yin Yuqing , Akbar Fariia I. , Khandarkhaeva Saiana , Fedotenko Timofey , Glazyrin Konstantin , Chariton Stella , Prakapenka Vitali , Wilhelm Fabrice , Rogalev Andrei , Comboni Davide , Hanfland Michael , Dubrovinskaia Natalia , Dubrovinsky Leonid 
Published: September 2023

AbstractA series of isostructural Ln3O2(CN3) (Ln=La, Eu, Gd, Tb, Ho, Yb) oxoguanidinates was synthesized under high‐pressure (25–54 GPa) high‐temperature (2000–3000 K) conditions in laser‐heated diamond anvil cells. The crystal structure of this novel class of compounds was determined via synchrotron single‐crystal X‐ray diffraction (SCXRD) as well as corroborated by X‐ray absorption near edge structure (XANES) measurements and density functional theory (DFT) calculations. The Ln3O2(CN3) solids are composed of the hitherto unknown CN35− guanidinate anion—deprotonated guanidine. Changes in unit cell volumes and compressibility of Ln3O2(CN3) (Ln=La, Eu, Gd, Tb, Ho, Yb) compounds are found to be dictated by the lanthanide contraction phenomenon. Decompression experiments show that Ln3O2(CN3) compounds are recoverable to ambient conditions. The stabilization of the CN35− guanidinate anion at ambient conditions provides new opportunities in inorganic and organic synthetic chemistry.
New information on the mandibular anatomy of Agudotherium gassenae, a Late Triassic non‐mammaliaform probainognathian from Brazil
Authors: Kerber Leonardo , Pretto Flávio A. , Müller Rodrigo T. 
Published: September 2023

AbstractAgudotherium gassenae is a poorly known non‐mammaliaform probainognathian cynodont from the Late Triassic of southern Brazil. It is known only by mandibular remains, and its affinities within Probainognathia are unclear. Furthermore, its phylogenetic affinities were never investigated through computational analyses. In this study, we described new lower jaw remains excavated from the type locality and performed the first phylogenetic investigation of this taxon. The new specimen provides further anatomical information. The rostral region of the lower jaw was poorly preserved in the type series, leading to the interpretation that A. gassenae had three lower incisors. The new specimen demonstrates the presence of four incisors. The phylogenetic analysis positioned A. gassenae as the sister group of Prozostrodontia. This hypothesis differs from that previously presented in the former description of the taxon, in which it was considered a non‐mammaliaform prozostrodont by means of character‐state comparisons.
Construing recombinant ZFP160 from Aspergillus terreus as pterin deaminase enzyme
Authors: Bijukumar Sajitha , Murugesan Thandeeswaran , Dhanapal Anand Raj , Mubarak Shoufia Jabeen , Vedagiri Hemamalini , Jayaraman Angayarkanni 
Published: September 2023

AbstractPterin deaminase stands as a metalloenzyme and exhibits both antitumor and anticancer activities. Therefore, this study aimed to explore the molecular function of zinc finger protein‐160 (zfp160) from Aspergillus terreus with its enzyme mechanism in detail. Subsequently, preliminary molecular docking studies on zfp160 from A. terreus were done. Next, the cloning and expression of zfp160 protein were carried out. Following, protein expression was induced and purified through nickel NTA column with imidazole gradient elution. Through the Mascot search engine tool, the expressed protein of MALDI‐TOF was confirmed by 32 kDa bands of SDS–PAGE. Furthermore, its enzymatic characterization and biochemical categorization were also explored. The optimum conditions for enzyme were determined to be pH 8, temperature 35°C, km 50 μm with folic acid as substrate, and Vmax of 24.16 (IU/mL). Further, in silico analysis tried to explore the interactions and binding affinity of various substrates to the modeled pterin deaminase from A. terreus. Our results revealed the binding mode of different substrate molecules with pterin deaminase using the approximate scoring functions that possibly correlate with actual experimental binding affinities. Following this, molecular dynamic simulations provided the in‐depth knowledge on deciphering functional mechanisms of pterin deaminase over other drugs.
Beobachtungen über den Einfluß der Oberflächendiffusion beim Wachstum von Kaliumkristallen im übersättigten Dampf
Authors: Dittmar Werner , Neumann Kurt 
Published: September 2023

AbstractA drop‐like single crystal of potassium was formed by condensation of potassium on a silver wire. The potassium atmosphere was supersaturated and the velocity of growth of the crystal was investigated. Vigorous surface diffusion influences the velocity of condensation on different surface areas of a potassium crystal. The diffusion takes place from the crystal faces towards the round regions. Therefore the condensation coefficient becomes smaller than 1 for the faces and larger than 1 for the round regions. More extended round regions show a coefficient of condensation which is practically 1.A tangential growth of the faces is caused by diffusion too. This is an important fact for the development of a perfect crystal: Considering the applied supersaturation the normal velocities of growth for faces and round regions are not different enough to create corners and edges. Considering the velocity of formation of a corner it is possible to calculate the product D Co (D is the surface diffusion coefficient and co is the adsorption density).This product is some orders of magnitude higher than the result calculated using standard theories for the calculation of D and co. Some possible explanations are given.
Störungslinien und Störungsbänder in innerlich oxydierten Kupfer‐ und Silberlegierungen
Authors: Meijering J. L. 
Published: September 2023

AbstractPerturbation of the reaction balance, e.g. of Be + O → BeO, at the subscale boundary gives rise to local variations in the BeO concentration. The perturbations may be brought about by changes in gas atmosphere or in temperature, and also by a special geometry of the specimen.
Der Einfluß des pH auf die elektrischen und chemischen Eigenschaften von Zinkoxidelektroden
Authors: Lohmann F. 
Published: September 2023

AbstractDer Einfluß des pH auf das Potential in der Doppelschicht von Zinkoxideinkristallelektroden wird durch Messung der pH‐Abhängigkeit des Flachbandpotentials bestimmt. Die Ergebnisse lassen sich mit der amphoteren Dissoziation auf der Grenzfläche gebildeter ‐ZnOH‐Gruppen deuten. Nach dem Vergleich des Flachbandpotentials eines Oxidhalbleiters am isoelektrischen Punkt mit dem Potential einer ladungsfreien Metall‐elektrode wird die Lage der Energiebänder im Zinkoxid abgeschätzt.
Die Löslichkeit von Wasserdampf und Wasserstoff in festen Oxiden
Authors: Stotz Siegfried , Wagner Carl 
Published: September 2023

AbstractEs werden Gleichungen für die Löslichkeit von Wasserdampf und Wasserstoff in festen Oxiden unter Berücksichtigung der jeweils beteiligten Fehlordnungsstellen abgeleitet. Aus Messungen der Änderung des elektrischen Widerstandes von Cu2O, CoO und NiO durch die Gegenwart von Wasserdampf werden obere Grenzwerte für den Gehalt an interstitiellen Protonen in diesen Oxiden bei 1000 °C und pH2O = 18 Torr erhalten.
Die Elektronenspektren 2,2′‐verknüpfter Diphenyle; Polarisationsgradspektren und Modellrechnungen. Teil I: Phenanthren, 9,10‐Diazaphenanthren‐Base und ‐Kation
Authors: Dörr Friedrich , Hohlneicher Georg , Schneider Siegfried 
Published: September 2023

AbstractVon einer größeren Zahl von Verbindungen, die alle der Klasse der 2,2'‐verknüpften Diphenyle angehören, wurden die Absorptionsübergänge mit Hilfe der Polarisationsgradspektroskopie klassifiziert und die Ergebnisse mit Modellrechnungen nach Pariser, Parr und Pople (PPP‐Modell) verglichen. Im vorliegenden Teil I werden die Auswahlregeln für die Schwingungskopplung und für die Spin‐Bahn‐Wechselwirkung diskutiert; die Wahl der Parameter für die Rechnung wird begründet. Zur Klassifizierung der angeregten Zustände werden Beziehungen zwischen dem Plattschen Perimetermodell und dem Anteil bestimmter Konfigurationen an diesen Zuständen herangezogen. Dann werden die Spektren des Phenanthrens sowie des 9,10‐Diazaphenanthrens und seines Kations eingehend diskutiert. Es zeigt sich, daß das PPP‐Modell die Übergänge, auch im kurzwelligen Bereich, sowie für die Azaverbindungen auch die Lösungsmitteleffekte gut beschreibt.
The mathematical description of two‐phase separation processes
Authors: Arkenbout C. J. , Los J. , Smit W. M. 
Published: September 2023

AbstractIt was shown by Cohen, that for a large number of separation methods the multiplication of the elementary effect by means of a column or a cascade may be described by one basic column equation.In Cohen's treatment of two phase separation processes like distillation and chemical exchange, however, the axial dispersion effects have been neglected. Unfortunately the axial mixing may be rather large in two phase processes, especially when packed columns are applied.In this paper an improved derivation of the column equation for two phase processes is given. In this column equation the axial dispersion effects are included.The derivation starts from a mass balance holding for the entire cross‐section of the column. Into this mass balance the contribution of the interfacial mass transfer to the concentration distribution is introduced. In order to avoid superfluous mathematics the equation representing the interfacial mass transfer is simplified. As a consequence the application of the column equation derived is limited to systems of very closely related compounds like isotopes. Although the adverse effect of the axial dispersion on the separation results cannot yet be calculated, the theory presented may give good guidance, when investigating the conditions for obtaining optimal separations.
Untersuchungen über die Nichtadditivität der scheinbaren Äquivalentleitfähigkeit binärer Elektrolytgemische in Lösungsmitteln sehr niedriger Dielektrizitätskonstanten
Authors: Eicke Hans Friedrich 
Published: September 2023

AbstractAn einigen ausgewählten binären Gemischen mono‐ bzw. mono‐ und divalenter Elektrolyte in nichtwäßrigen organischen Lösungsmitteln sehr niedriger Dk (C6H6, C6H12) wird die Nichtadditivität der scheinbaren Äquivalentleitfähigkeit Λ = 103 (i/E)E→0/(ao + co) (i = Stromdichte, E = Feldstärke, ao, co = Anfangskonzentration der Gemischkomponenten) untersucht. Unter der Annahme einfacher doppelter Umsetzungen werden für Mischungen 1,1‐ bzw. 1,1‐ und 2,1 wertiger Elektrolyte theoretische Beziehungen für Λ abgeleitet, die eine befriedigende Deutung der experimentellen Resultate erlauben. Im besonderen wird experimentell und theoretisch gezeigt, daß auch in Lösungen niedriger Dk 1,1 wertiger binärer Elektrolytgemische Abweichungen von der Additivität der scheinbaren Äquivalentleitfähigkeit beobachtet werden können.