bluuebunny/crossref_metadata_2025 huggingface dataset:
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

Intramolecular 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

Atomic 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

The 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

Mixed 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

Spin 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

A 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.
1H‐Perfluorohexane—An efficient modifier for ethylene tri‐/tetramerization
Authors: Yang Xiaodie , Shao Huijuan , Hao Biaobiao , Fan Haonan , Wang Yating , Jiang Tao
Published: September 2023

Silicon‐bridged/N, P (PNSiP) ligand/Cr (III) catalyst system based on different fluorinated hydrocarbons as modifiers have been explored for ethylene selective tri‐/tetramerization. Modifiers like 1H‐Perfluorohexane (1H‐PFH), Hexafluorobenzene (HFB), and Perfluorobiphenyl (PFB) have been proven to show a significant influence on ethylene oligomerization toward 1‐hexene and 1‐octene of the catalytic system. Among them, 1H‐PFH showed the most significant promotion effect in improving activity from 0.95 × 106 g·(mol Cr·h)−1 to as much as 5.66 × 106 g·(mol Cr·h)−1 at high temperature 90°C. Through the analysis of nuclear magnetic resonance (NMR) spectroscopy and ultraviolet visible diffuse reflectance spectroscopy (UV–vis DRS) results, we concluded that 1H‐PFH can react with an amount of trimethylaluminum (TMA) contained in the cocatalyst modified methylaluminoxane (MMAO) and the solubility of Cr (III) in solvent can be increased after adding 1H‐PFH. Furthermore, the possible reaction routes of 1H‐PFH with TMA and MMAO were proposed.
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

Agudotherium 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

Pterin 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

A 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

Perturbation 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

Der 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

Es 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

Von 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

It 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

An 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.
Spezifische Leitfähigkeit, Strom‐Spannungs‐Kurven, Zersetzungs‐ und Polarisationsspannung geschmolzener berylliumorganischer Komplexsalze
Authors: Strohmeier W. , Haecker W.
Published: September 2023

Berylliumorganische Komplexsalze der allgemeinen Formel MX · n · Be(C2H5)2, wobei M ein Alkalimetall oder eine quartäre Ammoniumgruppe und X ein Halogen oder Pseudohalogen bedeutet, haben bei 80°C eine spezifische Leitfähigkeit von X ∼ 10−2 bis 10−3.

Die spezifische Leitfähigkeit dieser Komplexe in Toluol ist von der gleichen Größenordnung. Die Strom‐Spannungs‐Kurven der meisten dieser Komplexe zeigen eine Art „Anodeneffekt”︁. Die Zersetzungs‐ und Polarisationsspannungen in diesen Elektrolyten wurden gemessen, wobei die Zersetzungs‐spannungen, welche mit zunehmender Temperatur abnehmen, wesentlich größer sind als die Polarisations‐ spannungen
Infrarot‐ und ramanspektroskopische Untersuchungen an homologen und stellungsisomeren n‐Alkanderivaten. 5. Mitteilung: Über die Schwingungsspektren der sekundären Nitroalkane
Authors: Geiseler G. , Kessler H. , Fruwert J.
Published: September 2023

Es wurden die Infrarot‐ und Ramanspektren der sich vom Propan, n‐Butan, n‐Pentan und n‐Octan ableitenden stellungsisomeren sekundären Nitroalkane untersucht und die vermessenen Banden bzw. Streulinien teilweise zugeordnet.
Untersuchung des Verbundverhaltens von CFK‐Spannlitzen in Beton mit faseroptischen Sensoren
Authors: Serrano‐Mesa María , Jesse Frank , Hückler Alex , Schlaich Mike
Published: September 2023

Carbonfaserverstärkte Kunststoffe (CFK) eignen sich aufgrund ihrer hohen Zugfestigkeit und Korrosionsbeständigkeit als Bewehrung von Betonbauteilen, insbesondere als Spannglieder. Untersuchungen an der TU Berlin mit vorgespannten CFK‐Litzen im sofortigen Verbund zeigten, dass trotz Einhaltung einschlägiger Empfehlungen für die Betondeckung bereits bei moderaten Vordehnungen Spaltzugrisse im Beton auftreten können. In diesem Zusammenhang wurde das Verbundverhalten von vorgespannten Stahl‐ und CFK‐Litzen in Beton anhand von Spannkrafteinleitungsversuchen untersucht. Um die Übertragungslängen zuverlässig bestimmen zu können, wurden erstmals verteilte faseroptische Sensoren (Distributed Fibre Optic Sensors, DFOS) eingesetzt, die eine hoch ortsaufgelöste Dehnungsmessung liefern. Die Ergebnisse zeigen, dass in CFK‐Litzen aufgrund der hohen Zugfestigkeit signifikant höhere Verbundspannungen aktiviert werden, die zwar kürzere Übertragungslängen ermöglichen, aber zu vermehrter Spaltzugrissbildung führen können. Als wesentliche Einflussgrößen für Spaltrisse wurde neben der Betondeckung die Höhe der Vordehnung ermittelt. In diesem Aufsatz werden die durchgeführten Versuche detailliert beschrieben und die Versuchsergebnisse sowie die durch DFOS gewonnenen Erkenntnisse vorgestellt und diskutiert.
Insights into the antiosteoporotic mechanism of the soy‐derived isoflavone genistein: Modulation of the Wnt/beta‐catenin signaling
Authors: Mannino Federica , Imbesi Chiara , Irrera Natasha , Pallio Giovanni , Squadrito Francesco , Bitto Alessandra
Published: September 2023

Bone remodeling is a process that involves osteoblasts, osteoclasts, and osteocytes, and different intracellular signaling, such as the canonical Wnt/β‐catenin pathway. Dysregulations of this pathway may also occur during secondary osteoporosis, as in the case of glucocorticoid‐induced osteoporosis (GIO), which accelerates osteoblast and osteocyte apoptosis by reducing bone formation, osteoblast differentiation and function, accelerates in turn osteoblast, and osteocyte apoptosis. Genistein is a soy‐derived nutrient belonging to the class of isoflavones that reduces bone loss in osteopenic menopausal women, inhibiting bone resorption; however, genistein may also favor bone formation. The aim of this study was to investigate whether estrogen receptor stimulation by genistein might promote osteoblast and osteocyte function during glucocorticoid challenge. Primary osteoblasts, collected from C57BL6/J mice, and MLO‐A5 osteocyte cell line were used to reproduce an in vitro model of GIO by adding dexamethasone (1 μM) for 24 h. Cells were then treated with genistein for 24 h and quantitative Polymerase Chain Reaction (qPCR) and western blot were performed to study whether genistein activated the Wnt/β‐catenin pathway. Dexamethasone challenge reduced bone formation in primary osteoblasts and bone mineralization in osteocytes; moreover, canonical Wnt/β‐catenin pathway was reduced following incubation with dexamethasone in both osteoblasts and osteocytes. Genistein reverted these changes and this effect was mediated by both estrogen receptors α and β. These data suggest that genistein could induce bone remodeling through Wnt/β‐catenin pathway activation.
Synthesis, Theoretical, in Silico and in Vitro Biological Evaluation Studies of New Thiosemicarbazones as Enzyme Inhibitors
Authors: Erdoğan Musa , Serdar Çavuş M. , Muğlu Halit , Yakan Hasan , Türkeş Cüneyt , Demir Yeliz , Beydemir Şükrü
Published: September 2023

Eleven new thiosemicarbazone derivatives (1–11) were designed from nine different biologically and pharmacologically important isothiocyanate derivatives containing functional groups such as fluorine, chlorine, methoxy, methyl, and nitro at various positions of the phenyl ring, in addition to the benzyl unit in the molecular skeletal structure. First, their substituted‐thiosemicarbazide derivatives were synthesized from the treatment of isothiocyanate with hydrazine to synthesize the designed compounds. Through a one‐step easy synthesis and an eco‐friendly process, the designed compounds were synthesized with yields of up to 95 % from the treatment of the thiosemicarbazides with aldehyde derivatives having methoxy and hydroxy groups. The structures of the synthesized molecules were elucidated with elemental analysis and FT–IR, 1H‐NMR, and 13C‐NMR spectroscopic methods. The electronic and spectroscopic properties of the compounds were determined by the DFT calculations performed at the B3LYP/6‐311++G(2d,2p) level of theory, and the experimental findings were supported. The effects of some global reactivity parameters and nucleophilic‐electrophilic attack abilities of the compounds on the enzyme inhibition properties were also investigated. They exhibited a highly potent inhibition effect on acetylcholinesterase (AChE) and carbonic anhydrases (hCAs) (KI values are in the range of 23.54±4.34 to 185.90±26.16 nM, 103.90±23.49 to 325.90±77.99 nM, and 86.15±18.58 to 287.70±43.09 nM for AChE, hCA I, and hCA II, respectively). Furthermore, molecular docking simulations were performed to explain each enzyme‐ligand complex's interaction.
Amino Acid Residues Controlling Domain Interaction and Interdomain Electron Transfer in Cellobiose Dehydrogenase
Authors: Motycka Bettina , Csarman Florian , Rupp Melanie , Schnabel Karoline , Nagy Gabor , Karnpakdee Kwankao , Scheiblbrandner Stefan , Tscheliessnig Rupert , Oostenbrink Chris , Hammel Michal , Ludwig Roland
Published: September 2023

The function of cellobiose dehydrogenase (CDH) in biosensors, biofuel cells, and as a physiological redox partner of lytic polysaccharide monooxygenase (LPMO) is based on its role as an electron donor. Before donating electrons to LPMO or electrodes, an interdomain electron transfer from the catalytic FAD‐containing dehydrogenase domain to the electron shuttling cytochrome domain of CDH is required. This study investigates the role of two crucial amino acids located at the dehydrogenase domain on domain interaction and interdomain electron transfer by structure‐based engineering. The electron transfer kinetics of wild‐type Myriococcum thermophilum CDH and its variants M309A, R698S, and M309A/R698S were analyzed by stopped‐flow spectrophotometry and structural effects were studied by small‐angle X‐ray scattering. The data show that R698 is essential to pull the cytochrome domain close to the dehydrogenase domain and orient the heme propionate group towards the FAD, while M309 is an integral part of the electron transfer pathway – its mutation reducing the interdomain electron transfer 10‐fold. Structural models and molecular dynamics simulations pinpoint the action of these two residues on the domain interaction and interdomain electron transfer.
Small Molecules Targeting Human UDP‐GlcNAc 2‐Epimerase
Authors: Gorenflos López Jacob L. , Dornan Gillian L. , Boback Nico , Neuenschwander Martin , Oder Andreas , Kemnitz‐Hassanin Kristin , Schmieder Peter , Specker Edgar , Asikoglu Hatice Ceyda , Oberdanner Christian , Seyffarth Carola , von Kries Jens Peter , Lauster Daniel , Hinderlich Stephan , Hackenberger Christian P. R.
Published: September 2023

Uridine diphosphate N‐acetylglucosamine 2‐epimerase (GNE) is a key enzyme in the sialic acid biosynthesis pathway. Sialic acids are primarily terminal carbohydrates on glycans and play fundamental roles in health and disease. In search of effective GNE inhibitors not based on a carbohydrate scaffold, we performed a high‐throughput screening campaign of 68,640 drug‐like small molecules against recombinant GNE using a UDP detection assay. We validated nine of the primary actives with an orthogonal real‐time NMR assay and verified their IC50 values in the low micromolar to nanomolar range manually. Stability and solubility studies revealed three compounds for further evaluation. Thermal shift assays, analytical size exclusion, and interferometric scattering microscopy demonstrated that the GNE inhibitors acted on the oligomeric state of the protein. Finally, hydrogen‐deuterium exchange mass spectrometry (HDX‐MS) revealed which sections of GNE were shifted upon the addition of the inhibitors. In summary, we have identified three small molecules as GNE inhibitors with high potency in vitro, which serve as promising candidates to modulate sialic acid biosynthesis in more complex systems.
Acute fibrinous constrictive pericarditis and large pericardial effusion as the first manifestation of systemic lupus erythematsous disease in an adult male patient
Authors: Yousefi‐Koma Hannaneh , Jalalian Rozita , Bagheri Babak
Published: September 2023

Key Clinical Message

Systemic lupus erythematosus (SLE) can have various manifestations. Although cardiac involvement is very common in SLE patients, a severe acute pericarditis as the first manifestation of SLE in a male patient is relatively rare. A 36‐year‐old male was admitted to our hospital with acute pericarditis, large circumferential fibrinous pericarditis, and major criteria of a high‐risk case of acute pericarditis. After a complete investigation, the underlying disease was revealed to be SLE. All of his symptoms were completely resolved after 6 weeks of treatment with non‐steroidal anti‐inflammatory drugs and corticosteroids with no need for a pericardiocentesis. Patients with acute fibrinous pericarditis should be considered and precisely investigated for multiorgan autoimmune process such as SLE, to avoid unnecessary intervention, and minimize the risk of recurrence and chronicity of the condition.
Thrombocytopenia and hyperthyroidism: A case report and literature review
Authors: Yingchoncharoen Pitchaporn , Abdelnabi Mahmoud , Thongpiya Jerapas , Hoffman Alexandra , Tariq Hira , Mittal Neha
Published: September 2023

Key Clinical Message

Immune thrombocytopenic purpura (ITP) is very challenging to diagnose with concurrent comorbidities affecting platelet count including PAH and autoimmune thyroid disease. ITP resolution can be achieved with tailored treatment of the underlying conditions to avoid adverse events.

Immune thrombocytopenic purpura (ITP) is an autoimmune disorder characterized by a platelet count of <100 × 109/L in the absence of other causes of thrombocytopenia. It is classified as primary or idiopathic and secondary due to various coexisting conditions, including autoimmune thyroid diseases. It is especially challenging when the patient has comorbidities that affect platelet count easily, leading to anchoring bias. The first‐line treatment of ITP is corticosteroids, and it is also recommended to treat the primary causes of secondary ITP. Here, the authors report a case of secondary ITP in a patient with a recent diagnosis of Grave's disease and a history of idiopathic pulmonary hypertension with baseline chronic thrombocytopenia, possible mechanisms, and treatment strategies with a multidisciplinary approach.
Idiopathic high‐flow priapism in a 4‐month‐old infant: A case report and review of literature
Authors: Ahmed Faisal , Badheeb Mohamed , Al‐wageeh Saleh , Alyhari Qasem , Altam Abdulfattah , Ghabisha Saif
Published: September 2023

Key Clinical Message

High‐flow priapism in pediatric population is rare, yet comprehensive clinical evaluation, along with penile Doppler ultrasound, and cavernosal blood analysis are crucial for accurate diagnosis. Conservative therapy is effective as an initial treatment.

High‐flow priapism is considerably rare in the pediatric age group. We report a four‐month‐old infant presented with a prolonged penile erection. Diagnostic confirmation was achieved through the utilization of Doppler ultrasound and cavernous blood gas analysis. We also review published data on the management of this condition.
Presumed first episode of nonconvulsive status epilepticus as the cause of postoperative disorder of consciousness following the completion of general anesthesia: A case report
Authors: Tsuzuki Yumi , Ishida Yusuke , Tomino Mikiko
Published: September 2023

Key Clinical Message

Disorder of consciousness can lead to irreversible sequelae without proper intervention. Consequently, early diagnosis and treatment are of paramount importance in patients with disorder of consciousness.

Disorder of consciousness (DOC) has various etiologies. Here, we report a case in which DOC following general anesthesia was suspected as being due to the first episode of nonconvulsive status epilepticus (NCSE). An elderly man in his 80s underwent uneventful tumor resection surgery under general anesthesia for extramammary Paget's disease. After the procedure, he regained consciousness following anesthesia discontinuation and was extubated. Soon after extubation, however, although his respiratory status remained stable, his level of consciousness deteriorated to a Glasgow Coma Scale (GCS) score of E1V1M1. Head computed tomography and magnetic resonance imaging scans indicated no abnormal findings. Subsequently, involuntary movements were noted in his left upper limb. Suspecting an epilepsy episode, diazepam was administered, leading to an improvement in the level of consciousness (GCS: E4V5M6). Based on the improvement in consciousness after diazepam administration, we strongly suspected NCSE.
Sigmoid volvulus secondary to undescended testicle: Report of first case in the literatures
Authors: Ahmadinejad Mojtaba , Mammohammadi Alireza , Hajialigol Amirhossein , Tajik Armin , Maleki Hadi , Pak Haleh , Zebarjadi Bagherpour Javad
Published: September 2023

Sigmoid volvulus accounts for 20%–50% of colonic obstructions in Eastern countries. This occurs mostly in patients with a lack of mobility and a history of chronic constipation. There are some very known complications of a undescended intra‐abdominal testicle such as cancer, ischemia, and infertility; But the rotation of the colon around the spermatic cord of one UDT is a very rare phenomenon that there is no similar report. A 67‐year‐old man came to the emergency department with a complaint of abdominal pain and obstipation. On examination, patient was febrile (T: 38.5) and had mild general tenderness. According to the appearance of coffee beans in the X‐ray, the diagnosis of sigmoid volvulus was made. In the requested tests, leukocytosis was observed. Rectosigmoidoscopy was unsuccessful. The patient underwent laparotomy. After manual untwisting, a tubular structure at the base of the meso‐sigmoid was noticed. With further exploration, the testis was observed intra‐abdominally. Orchidectomy and sigmoidectomy were performed by Hartmann's method. Sigmoid volvulus is one of the common cases that surgeons frequently encounter. The case scenarios are often the same, and from experience, most cases result from a long meso and an elongated sigmoid secondary to prolonged constipation. Therefore, it is clear that a scrotal examination would not be part of the routine examination of a patient with sigmoid volvulus. In this article, by reporting a very rare etiology for a very common pathology, we tried to point out the importance of head‐to‐toe examination in all patients.
B(C6F5)3‐Catalyzed [2+3]‐Cyclative o,m‐diC‐H Functionalization of Phenols
Authors: Luo Jingyan , Luo Zhou , Zhang Biqi , Zhao Qiuyu , Liu Lu , Liu Yuanyuan
Published: September 2023

Metal‐free catalytic C−H functionalization is highly desired for the construction of C−C bonds. We herein report a highly chemoselective consecutive C−H [2+3]‐cyclative functionalization for the simultaneous formation of two C−C bonds with construction of polycyclic phenols catalyzed by commercially available and low‐cost B(C6F5)3. This catalytic system tolerates a wide range of substrate scope, providing a series of 2,6,7,8‐tetrahydroacenaphthylen‐3‐ol‐type polycyclic compounds efficiently. Several derivatizations of the catalytic products have also been conducted to show the potential application of this method in synthesis of polycyclic compounds.
The role of temperature‐enhanced fault closure in promoting postinjection pressure diffusion and seismicity in enhanced geothermal systems
Authors: Ji Yinlin , Chen Yuedu , Hofmann Hannes , Zhang Yuan , Zang Arno , Zimmermann Günter
Published: September 2023

Post shut‐in seismic events in enhanced geothermal systems (EGSs) occur predominantly at the outer rim of the co‐injection seismic cloud. The concept of postinjection fracture and fault closure near the injection well has been proposed and validated as a mechanism for enhancing post shut‐in pressure diffusion that promotes seismic hazard. This phenomenon is primarily attributed to the poro‐elastic closure of fractures resulting from the reduction of wellbore pressure after injection termination. However, the thermal effects in EGSs, mainly including heat transfer and thermal stress, may not be trivial and their role in postinjection fault closure and pressure evolution needs to be explored. In this study, we performed numerical simulations to analyze the relative importance of poro‐elasticity, heat transfer, and thermo‐elasticity in promoting postinjection fault closure and pressure diffusion. The numerical model was first validated against analytical solutions in terms of fluid pressure diffusion and against heated flow‐through experiments in terms of thermal processes. We then quantified and distinguished the contribution of each individual mechanism by comparing four different shut‐in scenarios simulated under different coupled conditions. Our results highlight the importance of poro‐elastic fault closure in promoting postinjection pressure buildup and seismicity, and suggest that heat transfer can further augment the fault closure‐induced pressure increase and thus potentially intensify the postinjection seismic hazard, with minimal contribution from thermo‐elasticity.
Disentangling dyslexia from typical L2‐learning in emergent literacy
Authors: Helland Turid , Morken Frøydis , Helland Wenche A.
Published: September 2023

The present paper assessed how dyslexia can be identified in school children with another language than their first language. Participants were school children with Norwegian as their second language (L2), and two groups of children with Norwegian as their first language (L1): a control group (L1‐Con), and a dyslexia group (L1‐Dys). All were 2nd and 3rd graders who had attended Norwegian schools from 1st grade on. None of the individuals in L1‐Con or the L2 group were identified with any learning disability. However, slow literacy progress was seen in some L2‐children. The children were tested individually within the symptomatic and cognitive levels. Results were analysed in two steps: (1) group comparisons; (2) L2 individual profiles and tentative L2 subgrouping. An unexpected L2 profile showed language scores below norm, coupled with some scores within and some scores above norm within the cognitive domain. Case assessment of the L2 group resulted in three subgroups: one comparable to L1‐Con, one comparable to L1‐Dys, and one with a result in between these two groups. Low linguistic scores cannot be considered valid markers of dyslexia in L2. Within the cognitive domain, a variety of low scores can indicate dyslexia, while high scores can be compensatory.
Multiscale landscape genetic analysis identifies major waterways as a barrier to dispersal of feral pigs in north Queensland, Australia
Authors: Ryan James , Prentis Peter J. , Fuller Susan
Published: September 2023

Feral pigs (Sus scrofa) are a destructive and widespread invasive pest in Australia. An understanding of feral pig movement is required to develop management strategies to control feral pigs in Australia. Because landscape structure can have a strong influence on animal movement, it is important to determine how landscape features facilitate or impede the movement of feral pigs. Consequently, we conducted a landscape genetic analysis of feral pig populations in the Herbert region of far north Queensland, Australia, to determine management units and provide recommendations to better inform feral pig population control strategies. Using microsatellite data obtained from 256 feral pig samples from 44 sites, we examined feral pig population structure at multiple spatial scales for univariate and multivariate landscape resistance surfaces to determine the optimal spatial scale and to identify which of the nine landscape features tested impede or facilitate feral pig gene flow. Only weak genetic structure was found among the 44 sampling sites, but major waterways were identified as a minor barrier to gene flow, and an isolation by distance model was supported. We also found that highways facilitated gene flow across the study area, and this suggests that they may act as movement corridors or indicate translocation of feral pigs. Additionally, incorporating a second spatial scale enhanced the ability of our landscape genetics analysis to detect the influence of landscape structure on gene flow. We identified three management units based on natural barriers to gene flow and future targeted control should be undertaken in these management units to deliver sustained reduction of feral pig populations in the Herbert region. This study demonstrates how a landscape genetic approach can be used to gain insight into the ecology of an invasive pest species and be used to develop population control strategies which utilise natural barriers to movement.
Synthesis of bioethanol from mixed vegetable wastes: Experimental methodology and characterization
Authors: González‐Guerra Guillermo Manuel , Garate Ruiz José Ramón , Santos Tanamachi Kazuhiro , Restrepo‐Elorza María del Pilar , Gómez‐Castro Fernando Israel , Hernández Salvador , García‐García Juan Cristóbal , Gamiño‐Arroyo Zeferino
Published: September 2023

Bioethanol has been identified as a renewable product with high potential for application as biofuel. On the other hand, high volumes of agri‐food residues are generated daily. Such residues have potential as raw materials for industrial bioethanol production. There is a significant advance in the synthesis of biofuels from fruit and vegetable residues; however, most of the studies are focused on the conversion of a single type of raw material, limiting the application of the synthesis routes. This work presents a conversion methodology to produce bioethanol from carrot and broccoli residues and from their mixture; the samples of vegetable wastes has been collected in the municipality of Guanajuato, Mexico. Using the 1H NMR technique, the characteristic signals of bioethanol are identified. On the other hand, using the UV–VIS spectrophotometry technique, a maximum of 25.63 mg of total sugar content has been determined for the mixture. Likewise, a maximum bioethanol concentration of 60.6 g/L is obtained. From a refractometry and HPLC study, a conversion to bioethanol of 34.8% is determined for the mixture of residues. This work analyses the potential of broccoli and carrot residues for bioethanol production, either as isolated or as mixed wastes.
Comparison of magnetic resonance‐guided laser interstitial thermal therapy corpus callosum ablation to open microsurgical corpus callosotomy: A single‐center retrospective cohort study
Authors: Phillips H. Westley , Hect Jasmine L. , Harford Emily , Pan Evelyn , Abel Taylor J.
Published: September 2023

Objective

Corpus callosotomy (CC) is an important treatment for atonic seizures in patients with generalized or multifocal drug‐resistant epilepsy (DRE). Traditionally, CC is performed via an open microsurgical approach, but more recently, MR‐guided stereotactic laser interstitial thermal therapy (LITT) corpus callosum ablation (CCA) has been developed to leverage the safety and minimally invasive nature of LITT. Given the recent adoption of CCA at select centers, how CCA compares to CC is unknown. We aim to compare the clinical seizure outcomes of CCA and CC after extended follow‐up.

Methods

We performed a retrospective cohort study to compare the effectiveness and safety of CC to CCA from 1994 to 2022. The primary outcome was a 50% reduction in target seizure. Secondary outcome measures were postoperative length of stay, adverse events, and other effectiveness metrics. Comparative statistics were executed using Stata. Normality for continuous variables was assessed, and parametric statistics were utilized as needed. Frequency was compared with chi‐squared or Fischer's exact tests, when applicable.

Results

Data from 47 operations performed on 36 patients were included in this study, of which 13 (36%) patients underwent 17 CCA. Patients who received CCA had similar rates of meaningful reduction (>50%) of atonic seizures as their CC counterparts (55% vs 70% P = 0.15). Patients undergoing CCA had significantly shorter hospitalizations than those receiving CC (2.5 vs 6.0 days P < 0.001). There was no significant difference in rates of postoperative complications between the groups, although the magnitude of the complication rates was lower in the CCA cohort (12% vs 28%).

Significance

This early experience suggests CCA has similar outcomes to traditional CC, albeit with a shorter hospital stay. However, future studies are necessary to investigate the noninferiority between these two approaches. Large multicenter studies are necessary to investigate differences in adverse events and whether these findings generalize across other centers.