bluuebunny/crossref_metadata_2025_split huggingface dataset:
Charging Metal‐Organic Framework Membranes by Incorporating Crown Ethers to Capture Cations for Ion Sieving
Authors: Li Jiang , Shi Yayun , Qi Chenyang , Zhang Bowen , Xing Xiwen , Li Yuliang , Chen Tongdan , Mao Xingnuo , Zuo Zhijun , Zhao Xiaoli , Pan Zhenghui , Li Libo , Yang Xiaowei , Li Cheng 
Published: August 2023

AbstractProtein channels on the biofilm conditionally manipulate ion transport via regulating the distribution of charge residues, making analogous processes on artificial membranes a hot spot and challenge. Here, we employ metal–organic frameworks (MOFs) membrane with charge‐adjustable subnano‐channel to selectively govern ion transport. Various valent ions are binded with crown ethers embedded in the MOF cavity, which act as charged guest to regulate the channels’ charge state from the negativity to positivity. Compared with the negatively charged channel, the positive counterpart obviously enhances Li+/Mg2+ selectivity, which benefit from the reinforcement of the electrostatic repulsion between ions and the channel. Meanwhile, theoretical calculations reveal that Mg2+ transport through the more positively charged channel needed to overcome higher entrance energy barrier than that of Li+. This work provides a subtle strategy for ion‐selective transport upon regulating the charge state of insulating membrane, which paves the way for the application like seawater desalination and lithium extraction from salt lakes.
Enzyme‐Compatible Core‐Shell Nanoreactor for in Situ H2‐Driven NAD(P)H Regeneration
Authors: Wang Maodi , Dai Huicong , Yang Qihua 
Published: August 2023

AbstractThe regeneration of the reduced form cofactor NAD(P)H is essential for the extra‐cellular application of bio‐reduction, which necessitates not only the development of efficient artificial NAD(P)H regeneration catalytic system but also its well compatibility with the cascade enzymatic reduction system. In this work, we reported the preparation of a metal nanoparticle (NP) and metal complex integrated core‐shell nanoreactor for H2‐driven NAD(P)H regeneration through the immobilization of a Rh complex on Ni/TiO2 surface via a bipyridine contained 3D porous organic polymer (POP). In comparison with the corresponding single component metal NPs and the immobilized Rh complex, the integrated catalyst presented simultaneously enhanced activity and selectivity in NAD(P)H regeneration thanks to the rapid spillover of activated H species from metal NPs to Rh complex. In addition, the size‐sieving effect of POP precluded the direct interaction of enzyme and Rh complex confined in the pores, enabling the success coupling of core‐shell nanoreactor and aldehyde ketone reductase (AKR) for chemoenzymatic reduction of acetophenone to (R)‐1‐phenylethan‐1‐ol. This work provides a strategy for the rational manipulation of multicomponent cooperation catalysis.
Synthesis of Axially Chiral Biaryls through Cobalt(II)‐Catalyzed Atroposelective C−H Arylation
Authors: Wu Yong‐Jie , Wang Zhen‐Kai , Jia Zhen‐Sheng , Chen Jia‐Hao , Huang Fan‐Rui , Zhan Bei‐Bei , Yao Qi‐Jun , Shi Bing‐Feng 
Published: August 2023

AbstractHighly efficient synthesis of axially chiral biaryl amines through cobalt‐catalyzed atroposelective C−H arylation using easily accessible cobalt(II) salt and salicyloxazoline ligand has been reported. This methodology provides a straightforward and sustainable access to a broad range of enantioenriched biaryl‐2‐amines in good yields (up to 99 %) with excellent enantioselectivities (up to 99 % ee). The synthetic utility of the unprecedented method is highlighted by its scalability and diverse transformations.
Thermally‐Induced Isomerization of Prenucleation Clusters During the Prenucleation Stage of CdTe Quantum Dots
Authors: Wang Tinghui , Wang Zhe , Wang Shanling , Chen Xiaoqin , Luan Chaoran , Yu Kui 
Published: August 2023

AbstractThe evolution of prenucleation clusters in the prenucleation stage of colloidal semiconductor quantum dots (QDs) has remained unexplored. With CdTe as a model system, we show that substances form and isomerize prior to the nucleation and growth of QDs. Called precursor compounds (PCs), the prenucleation clusters are relatively optically transparent and can transform to absorbing magic‐size clusters (MSCs). When a prenucleation‐stage sample at 25, 45, or 80 °C is dispersed in a mixture of cyclohexane (CH) and octylamine (OTA) at room temperature, either MSC‐371, MSC‐417, or MSC‐448 evolves with absorption peaking at 371, 417, or 448 nm, respectively. We propose that PC‐371 forms at 25 °C, and isomerizes to PC‐417 at 45 °C and to PC‐448 at 80 °C. The PCs and MSCs are quasi isomers. Relatively large and small amounts of OTA favor PC‐371 and PC‐448 in dispersion, respectively. The present findings suggest the existence of PC‐to‐PC isomerization in the QD prenucleation stage.
Asymmetric Allylic Substitution‐Isomerization for the Modular Synthesis of Axially Chiral N‐Vinylquinazolinones
Authors: Zou Jia‐Yu , Yang Yu‐Ying , Gu Jun , Liu Fei , Ye Zhiwen , Yi Wenbin , He Ying 
Published: August 2023

AbstractAxially chiral N‐substituted quinazolinones are important bioactive molecules, which are presented in many synthetic drugs. However, most strategies toward their atroposelective synthesis are mainly limited to the axially chiral arylquinazolinone frameworks. The development of modular synthetic methods to access diverse quinazolinone‐based atropisomers remains scarce and challenging. Herein, we report the regio‐ and atroposelective synthesis of axially chiral N‐vinylquinazolinones via the strategy of asymmetric allylic substitution‐isomerization. The catalysis system utilized both asymmetric transition‐metal catalysis and organocatalysis to efficiently afford trisubstituted and tetrasubstituted N‐vinylquinazolinone atropisomers, respectively. With the meticulous design of β‐substituted allylic substrates, both Z‐ and E‐tetrasubstituted axially chiral N‐vinylquinazolinones were obtained in good yields and high enantioselectivities.
Zeolite Synthesis in the Presence of Metallosiloxanes for the Quantitative Encapsulation of Metal Species for the Selective Catalytic Reduction (SCR) of NOx
Authors: Khairova Rushana , Komaty Sarah , Dikhtiarenko Alla , Cerrillo Jose Luis , Veeranmaril Sudheesh Kumar , Telalović Selvedin , Tapia Antonio Aguilar , Hazemann Jean‐Louis , Ruiz‐Martinez Javier , Gascon Jorge 
Published: August 2023

AbstractMetal encapsulation in zeolitic materials through one‐pot hydrothermal synthesis (HTS) is an attractive technique to prepare zeolites with a high metal dispersion. Due to its simplicity and the excellent catalytic performance observed for several catalytic systems, this method has gained a great deal of attention over the last few years. While most studies apply synthetic methods involving different organic ligands to stabilize the metal under synthesis conditions, here we report the use of metallosiloxanes as an alternative metal precursor. Metallosiloxanes can be synthesized from simple and cost‐affordable chemicals and, when used in combination with zeolite building blocks under standard synthesis conditions, lead to quantitative metal loading and high dispersion. Thanks to the structural analogy of siloxane with TEOS, the synthesis gel stabilizes by forming siloxane bridges that prevent metal precipitation and clustering. When focusing on Fe‐encapsulation, we demonstrate that Fe‐MFI zeolites obtained by this method exhibit high catalytic activity in the NH3‐mediated selective catalytic reduction (SCR) of NOx along with a good H2O/SO2 tolerance. This synthetic approach opens a new synthetic route for the encapsulation of transition metals within zeolite structures.
Self‐quenched Fluorophore Dimers for DNA‐PAINT and STED Microscopy
Authors: Kessler Laurell F. , Balakrishnan Ashwin , Deußner‐Helfmann Nina S. , Li Yunqing , Mantel Maximilian , Glogger Marius , Barth Hans‐Dieter , Dietz Marina S. , Heilemann Mike 
Published: August 2023

AbstractSuper‐resolution techniques like single‐molecule localisation microscopy (SMLM) and stimulated emission depletion (STED) microscopy have been extended by the use of non‐covalent, weak affinity‐based transient labelling systems. DNA‐based hybrid systems are a prominent example among these transient labelling systems, offering excellent opportunities for multi‐target fluorescence imaging. However, these techniques suffer from higher background relative to covalently bound fluorophores, originating from unbound fluorophore‐labelled single‐stranded oligonucleotides. Here, we introduce short‐distance self‐quenching in fluorophore dimers as an efficient mechanism to reduce background fluorescence signal, while at the same time increasing the photon budget in the bound state by almost 2‐fold. We characterise the optical and thermodynamic properties of fluorophore‐dimer single‐stranded DNA, and show super‐resolution imaging applications with STED and SMLM with increased spatial resolution and reduced background.
Total Synthesis of (−)‐Batrachotoxin Enabled by a Pd/Ag‐Promoted Suzuki–Miyaura Coupling Reaction
Authors: Watanabe Yuuki , Morozumi Hisahiro , Mutoh Hiroyuki , Hagiwara Koichi , Inoue Masayuki 
Published: August 2023

AbstractBatrachotoxin is an extremely potent cardio‐ and neurotoxic steroidal alkaloid found in certain species of frogs, birds, and beetles. The steroidal 6/6/6/5‐membered carbocycle (ABCD‐ring) is U‐shaped and functionalized with two double bonds, a six‐membered C3‐hemiacetal across the AB‐ring, a seven‐membered oxazepane on the CD‐ring, and a dimethylpyrrolecarboxy group at the D‐ring carbon chain. These structural features present an unusual and formidable synthetic challenge. Herein we report a total synthesis of batrachotoxin based on a newly devised convergent strategy through a 22‐step sequence. Enantiopure AB‐ring and D‐ring fragments were prepared and subjected to a crucial C(sp2)−C(sp2) coupling reaction. Although both C(sp2) centers were sterically encumbered by proximal tetrasubstituted carbon atoms, Ag2O strongly promoted the Pd(PPh3)4‐catalyzed Suzuki–Miyaura coupling reaction at room temperature, thereby connecting the two fragments without damaging their preexisting functionalities. Subsequent treatment with t‐BuOK induced Dieckmann condensation to cyclize the C‐ring. The judiciously optimized functionalizations realized oxazepane formation, carbon chain extension, and pyrrole carboxylic acid condensation to deliver batrachotoxin.
A Fluorescent Probe for Investigating the Role of Biothiols in Signaling Pathways Associated with Cerebral Ischemia‐Reperfusion Injury
Authors: Yang Yutao , Ma Ming , Shen Lei , An Jusung , Kim Eunji , Liu Hongmei , Jin Ming , Wang Shuxiang , Zhang Jinchao , Kim Jong Seung , Yin Caixia 
Published: August 2023

AbstractCerebral ischemia‐reperfusion injury (CIRI) is intimately associated with the redox regulation of biothiol, a crucial antioxidant marker that precludes the onset of ROS. We designed a novel fluorescent probe, DCI‐Ac‐Py, showing various physicochemical properties, such as high selectivity, exceptional signal‐to‐noise ratio, near‐infrared (NIR) optical window, and blood–brain barrier (BBB) penetrability, for detecting biothiols in the brain. The picolinate serves as a specific recognition group that is rapidly activated by biothiol and undergoes nucleophilic substitution with the adjacent acrylic ester to yield the desired NIR probe. Additionally, the probe's lipid solubility is improved through the inclusion of halogen atoms, which aids in penetrating the BBB. Using DCI‐Ac‐Py, we investigated changes of biothiols in vivo in the brains of mice during CIRI. We found that biothiol‐mediated NF‐kB classical (P65‐related) and nonclassical (RelB‐related) pathways contribute to abundant ROS production induced by CIRI and that biothiols are involved in redox regulation. These findings provide new insights into the study of CIRI and shed light on the physiological and pathological mechanisms of biothiols in the brain.
Synthesis, Molecular Packing and Semiconductor Properties of V‐Shaped N‐Heteroacene Dimers
Authors: Xiong Yongming , Gong Qi , Miao Qian 
Published: August 2023

AbstractThis article presents two groups of V‐shaped π‐scaffolds that consist of two N‐heteroacene units fused with either a rigid or flexible eight‐membered ring. These rigid and flexible N‐heteroacene dimers were synthesized through the condensation of tetraphenylenetetraone with the corresponding diamine and the Pd‐catalyzed cross‐coupling of tetrabromodibenzo[a,e]cyclooctatetraene with the corresponding diamine, respectively. A comparison of electronic structures and properties of the two groups of V‐shaped N‐heteroacene dimers shows subtle difference between the rigid and flexible eight‐membered ring linkers in forming extended π‐systems. X‐ray crystallography of these V‐shaped molecules has revealed interesting π‐π interaction modes, which are dependent on the central connecting units and substituting groups. These π‐π interactions between the V‐shaped π‐scaffolds have enabled the molecules to function as organic semiconductors in solution‐processed field effect transistors.
Further examination of behavior during extinction‐based treatment of pediatric food refusal
Authors: Engler Christopher W. , Ibañez Vivian F. , Peterson Kathryn M. , Andersen Ashley S. 
Published: August 2023

AbstractResearchers have demonstrated the effectiveness of extinction‐based treatments to reduce challenging behavior. Although bursts and temporary increases in emotional responding may occur in some basic and applied studies, recent studies on their prevalence have shown that side effects are far from ubiquitous. Woods and Borrero (2019) determined that bursts of inappropriate mealtime behavior and increases in emotional responding occurred in 30% of data sets during extinction‐based treatment of pediatric feeding difficulties. In the current study, we conducted a retrospective consecutive‐controlled case series by evaluating treatment graphs of inappropriate mealtime behavior, negative vocalizations, active acceptance, and mouth clean for 60 children admitted to an intensive day‐treatment feeding disorders program. We discuss the implications of these findings and provide general recommendations for the use of extinction‐based treatment.
Magnetic resonance imaging in the diagnosis of progressive supranuclear palsy: A case report and review of literature
Authors: Alphonce Baraka , Komanya Francisca , Bitesigilwe Mbelwa , Meda John R. , Nyundo Azan 
Published: August 2023

Key Clinical MessageProgressive supranuclear palsy (PSP) has many clinical features overlapping with other Parkinson syndromes and differentiation on clinical ground is difficult. This case highlights how a brain MRI can help diagnose PSP in settings with limited resources where histological diagnosis is difficult.AbstractProgressive supranuclear palsy (PSP) may be challenging to diagnose due to its widely acknowledged clinical complexity and challenges with diagnosis confirmation, particularly in resource‐poor settings where the ability to obtain confirmatory tests is highly complicated, leading to an inaccurate or incomplete diagnosis of PSP. This paper discusses using brain magnetic resonance imaging (MRI) to diagnose PSP, and a review of relevant literature addresses the diagnostic value of MRI in PSP.
The Catalytic Function of Phosphorus Enriched on the Surface of Vanadium‐based Catalysts in Selective Oxidations
Authors: Rüther Frederik , Baumgarten Robert , Gioria Esteban , Knemeyer Kristian , Xie Jingxiu , Kraehnert Ralph , Naumann d'Alnoncourt Raoul , Thomas Arne , Rosowski Frank 
Published: August 2023

AbstractVanadium phosphates are established as the benchmark system for the selective oxidation of n‐butane towards maleic anhydride. By varying the phosphorus content on the surface of three V‐based catalysts with diverse performance, this study experimentally elaborates on the catalytic function of phosphorus. Contact time variation and cofeed studies revealed, that surface phosphates, deposited in sub‐monolayers via atomic layer deposition, significantly contribute to an increased product selectivity. Furthermore, our results suggest that the phosphorus particularly suppresses the consecutive combustion of the (re‐)adsorbed product. The recently introduced solid solution catalyst V1‐xNbxOPO4 with medium maleic anhydride selectivity could be tuned by the surface enrichment with phosphorus towards product selectivities of up to SMAN=60 %, under optimized alkane‐rich feed conditions. Therefore, POx‐V0.3Nb0.7OPO4 is introduced as promising catalyst, which is not based on vanadyl(IV) pyrophosphate, to access significantly higher MAN formation rates at increased alkane partial pressures of cn‐butane>10 %vol in n‐butane oxidation.
Multiply exo‐Methylated Corannulenes
Authors: Miwa Kazuhira , Aoyagi Shinobu , Amaya Toru , Sasamori Takahiro , Morisako Shogo , Kurogi Takashi , Yorimitsu Hideki 
Published: August 2023

AbstractInvited for the cover of this issue are Shinobu Aoyagi (Nagoya City University), Takahiro Sasamori (University of Tsukuba), and Hideki Yorimitsu (Kyoto University). The image depicts multiply exo‐methylated corannulenes (flowers) synthesized from corannulene (central large flower) by the reduction with sodium (soil) to form anionic corannulenes and the subsequent methylation with reduction‐resistant dimethyl sulfate (butterflies). Read the full text of the article at 10.1002/chem.202301557.
Reconstruction of the Late Miocene to Pliocene continental succession of Samos Island: Palaeoenvironmental implications for the Eastern Aegean domain
Authors: Hamon Youri , Deschamps Rémy , Gorini Christian , Sakellariou Dimitris , Bailly Cédric , Kernif Tarik , Christ Alina Bérénice , Adelinet Mathilde , Fortin Jérôme 
Published: August 2023

AbstractOn the Island of Samos (East Aegean region, Greece), two sedimentary basins are filled by thick continental series dated to the Late Miocene to Early Pliocene. A multidisciplinary study has been performed including (1) the definition of 21 sedimentary facies, (2) a review of the biological components and (3) carbon, oxygen and strontium stable isotope analyses. The succession is characterised by various depositional settings and hydrochemical compositions. Five main stages of basin evolution have been identified: (1) The Late Serravallian is marked by the development of alluvial fans and fan delta; (2) during the Lower Tortonian, isolated shallow lakes with variable salinity, from fresh to brackish, developed under warm and relatively humid conditions; (3) the Middle to Upper Tortonian is marked by the development of a large and deep lake with saline and alkaline waters, under colder and drier conditions; (4) the Latest Tortonian to Messinian period is represented by an ephemeral alluvial system, developed under a dry climate; (5) during the Zanclean, a palustrine and paludal wetland system, dominated by tufa carbonates, developed under moderately humid conditions. This succession is of particular interest for the reconstruction of the palaeoenvironmental evolution of the transition zone between the Mediterranean domain, and the Paratethys and circum‐Paratethys areas. The geochemical data and the presence of flora (diatoms) and fauna (gastropods) of marine affinity suggest transient ingressions of marine‐related water or groundwater inflows as early as the Lower Tortonian. The Samos succession records the complex interaction between the regional geodynamics and climate. The extensional regime of the Eastern Aegean zone generates subsidence, interrupted in the mid‐Tortonian (9 Ma) by a brief compressive event and a major exposure of the basins. Furthermore, the Late Miocene progressive aridification, followed by a change to a more humid climate (Pliocene) is also a major driver of the sedimentation.
A tandem of GC‐MS and electroanalysis for a rapid chemical profiling of bacterial extracellular matrix
Authors: Silina Y. E. , Zolotukhina E. V. , Koch M. , Fink‐Straube C. 
Published: August 2023

AbstractHerein an assay toward a rapid and reliable profiling of extracellular matrix of Escherichia coli (E. coli) utilizing a tandem of GC‐MS as a tool for definition of the exact chemical nature of low molecular weight compounds and cyclic voltammetry for their high throughput detection is presented.Briefly, during a set of investigations the formation of glycerol in the extracellular matrix (ECM) of E. coli at physiological relevant conditions of cells was revealed. Based on the obtained knowledge, the electrochemical protocol allowing both qualitative and quantitative analyses of glycerol in E. coli ECMs at palladium ink‐modified screen printed electrodes with precision values (RSD) <10 % and recovery rates ranged from 98 % to 102 % was proposed.The provided protocol for a rapid electrochemical profiling of the bacterial ECMs can readily be used as a guideline for the controlled electroanalysis of target electroactive signaling analytes in complex biological samples.
Laser interstitial thermal therapy in pediatric cerebellar epilepsy
Authors: Bicciato Giulio , Gennari Antonio Giulio , Oertel Markus Florian , Dünner Corinne , Krayenbühl Niklaus , Boltshauser Eugen , Toelle Sandra P. , Ramantani Georgia 
Published: August 2023

AbstractCerebellar lesional epilepsy is rare, commonly manifesting in early life and posing diagnostic and treatment challenges. Seizure semiology may be subtle, with repetitive eye blinking, face twitching, and irregular breathing, while EEG commonly remains unremarkable. Pharmacoresistance is the rule, and surgical intervention is the only treatment with the potential for cure. Novel minimally invasive techniques, such as laser interstitial thermal therapy (LITT), are emerging for surgically less accessible, deep‐seated epileptogenic lesions. We report the case of a patient who presented with peculiar eye and face movements occurring episodically and stereotypically since the first weeks of life and was later diagnosed with cerebellar epilepsy related to a hamartoma. Refractory daily seizures, unresponsive to antiseizure medication, were followed by increasingly prominent gait ataxia and delayed speech development. Staged LITT was performed in two consecutive sessions at 3 and 4 years, leading to seizure cessation, neurological improvement, and developmental gains over a postsurgical follow‐up period of 8 months. Our case highlights cerebellar lesional epilepsy as a rare but important differential diagnosis in children with paroxysmal disorders predominantly involving the face. Furthermore, we illustrate the radiological correlates of neurocognitive deficit related to the cerebellar lesion, manifesting as cerebello‐cerebral diaschisis. Most importantly, our observations showcase LITT as a safe and effective therapeutic approach in cerebellar lesional epilepsy and an attractive alternative to open brain surgery, especially for deep‐seated lesions in the pediatric population.