bluuebunny/crossref_metadata_2025_split huggingface dataset:
Numerical modeling and experimental verification of ceramic membrane emulsification for stable emulsion production
Authors: Zhou Ke , Wang Yaxin , Yuan Can , Jing Wenheng , Chen Min , Zhong Zhaoxiang , Xing Weihong 
Published: February 2024

AbstractContinuous ceramic membrane emulsification is a promising and scalable technique to prepare water‐in‐heavy oil (W/O) emulsions. The droplet size of W/O emulsions is comprehensively influenced by phase parameters, operational parameters, and membrane parameters, which collectively impact the forces acting on water droplets. In this work, a droplet size prediction model involving multiple factors is established. The forces are analyzed by considering the influence of transmembrane pressure and the viscosity ratio between the dispersed and continuous phases, which are not well considered by current researchers. Additionally, the effects of pore size, crossflow velocity, temperature, and transmembrane pressure were experimentally verified. The experimental results show a high degree of agreement with the predictions. Also, based on the relaxation time difference in oil and water, magnetic resonance imaging was used for the first time to assess the stability of W/O emulsions which was found to be stable for 4 months.
The impact of a virtual mind–body program on symptoms of depression and anxiety among international English‐speaking adults with neurofibromatosis
Authors: McDermott Katherine , Bakhshaie Jafar , Brewer Julie , Vranceanu Ana‐Maria 
Published: February 2024

AbstractThe neurofibromatoses (NFs) are a set of incurable genetic disorders that predispose individuals to nervous system tumors. Although many patients experience anxiety and depression, there is little research on psychosocial interventions in this population. The present study examined the effects of a mind–body intervention on depression and anxiety in adults with NF. This is a secondary analysis of the Relaxation Response Resiliency Program for NF (3RP‐NF), an 8‐week virtual group intervention that teaches mind–body skills (e.g., relaxation, mindfulness) to improve quality of life. Participants were randomized to 3RP‐NF or the Health Enhancement Program for NF (HEP‐NF) consisting of health informational sessions and discussion. We evaluated depression (PHQ‐9) and anxiety (GAD‐7) at posttreatment, 6 months, and 12 months. Both groups improved in depression and anxiety between baseline and posttest, 6 months, and 12 months. The 3RP‐NF group showed greater improvements in depression scores from baseline to 6 months compared with HEP‐NF and with lower rates of clinically significant depressive symptoms. There were no between‐group differences for anxiety. Both interventions reduced distress and anxiety symptoms for individuals with NF. The 3RP‐NF group may be better at sustaining these improvements. Given the rare nature of NF, group connection may facilitate reduced distress.
Epilepsy with faint capillary malformation or reticulated telangiectasia associated with mosaic AKT3 pathogenic variants
Authors: De Bortoli Martina , Ivars Marta , Revencu Nicole , Nassogne Marie‐Cécile , Lavarino Cinzia , Paco Sonia , Lammens Martin , Renders Anne , Dumitriu Dana , Helaers Raphaël , Boon Laurence M. , Baselga Eulalia , Vikkula Miikka 
Published: February 2024

AbstractCapillary malformations (CMs) are the most common type of vascular anomalies, affecting around 0.3% of newborns. They are usually caused by somatic pathogenic variants in GNAQ or GNA11. PIK3CA and PIK3R1, part of the phosphoinositide 3‐kinase–protein kinase B–mammalian target of rapamycin pathway, are mutated in fainter CMs such as diffuse CM with overgrowth and megalencephaly CM. In this study, we present two young patients with a CM‐like phenotype associated with cerebral anomalies and severe epilepsy. Pathogenic variants in PIK3CA and PIK3R1, as well as GNAQ and GNA11, were absent in affected cutaneous tissue biopsies. Instead, we identified two somatic pathogenic variants in the AKT3 gene. Subsequent analysis of the DNA obtained from surgically resected brain tissue of one of the two patients confirmed the presence of the AKT3 variant. Focal cortical dysplasia was also detected in this patient. Genetic analysis thus facilitated workup to reach a precise diagnosis for these patients, associating the vascular anomaly with the neurological symptoms. This study underscores the importance of searching for additional signs and symptoms to guide the diagnostic workup, especially in cases with atypical vascular malformations. In addition, it strongly emphasizes the significance of genotype–phenotype correlation studies in guiding clinicians' informed decision‐making regarding patient care.
Sonographic features of sternal pseudotumour in children
Authors: Gerrie Samantha , Watson Mike , Morreau Phil 
Published: February 2024

AbstractIntroductionSternal pseudotumour is an important but rare entity thought to be an inflammatory, non‐neoplastic lesion that can mimic tumours. The purpose of this paper was to illustrate the imaging features of this lesion to avoid unnecessary investigations.MethodsThe clinical notes and imaging features of four patients with a diagnosis of sternal pseudotumour were reviewed over a period from February 2016 to July 2019.ResultsAll patients were afebrile with no history of trauma. The median age at presentation was 12.5 months. The median length of symptoms prior to presentation was 3.5 days. One patient had a mildly elevated C‐reactive protein. Chest radiographs showed a pre‐sternal soft‐tissue mass, with or without osseous destruction of the subjacent sternum. Ultrasound showed a heterogeneous, hypoechoic pre‐sternal soft‐tissue mass with variable internal vascularity with extension between sternal ossification centres. CT and MRI showed an enhancing dumbbell‐shaped lesion with a pre‐sternal and retro‐sternal soft‐tissue component. The median time to complete resolution was 3 months. One patient had a biopsy that showed chronic inflammation and fibrosis.DiscussionThese lesions present in young children typically with a 1‐ to 2‐week history of a focal 2‐ to 4‐cm swelling over the sternum. The aetiology is unknown but may be on the basis of a yet‐to‐be identified pathogen. Inflammatory markers and cultures are normal or mildly elevated. Important differential considerations include sternal osteomyelitis or neoplastic causes such as Ewing sarcoma, rhabdomyosarcoma, Langerhans cell histiocytosis and infantile fibrosarcoma.ConclusionSternal pseudotumor is a rare but important entity to be aware of to avoid unnecessary invasive biopsy or further investigations. Our suggestion is that this is a ‘Don't touch’ lesion that requires close short‐interval follow‐up at a surgical outpatient clinic and with ultrasound until resolution.
Self‐Assembly of Rod‐Coil Bottlebrush Copolymers into Degradable Nanodiscs with a UV‐Triggered Self‐Immolation Process
Authors: Zeng Haoxiang , Liang Xiaoli , Roberts Derrick A. , Gillies Elizabeth R. , Müllner Markus 
Published: February 2024

AbstractPolymer nanodiscs, especially with stimuli‐responsive features, represent an unexplored frontier in the nanomaterial landscape. Such 2D nanomaterials are considered highly promising for advanced biomedicine applications. Herein, we designed a rod‐coil copolymer architecture based on an amphiphilic, tadpole‐like bottlebrush copolymer, which can directly self‐assemble into core–shell nanodiscs in an aqueous environment. As the bottlebrush side chains are made of amorphous, UV‐responsive poly(ethyl glyoxylate) (PEtG) chains, they can undergo rapid end‐to‐end self‐immolation upon light irradiation. This triggered nanodisc disassembly can be used to boost small molecule release from the nanodisc core, which is further aided by a morphological change from discs to spheres.
Confinement of CsPbBr3 Perovskite Nanocrystals into Extra‐large‐pore Zeolite for Efficient and Stable Photocatalytic Hydrogen Evolution
Authors: Gao Shiqin , Wang Bolun , Chen Feijian , He Guangyuan , Zhang Tianjun , Li Lin , Li Junyan , Zhou Yida , Feng Binyao , Mei Donghai , Yu Jihong 
Published: February 2024

AbstractMetal halide perovskites (MHPs), renowned for their outstanding optoelectronic properties, hold significant promise as photocatalysts for hydrogen evolution reaction (HER). However, the low stability and insufficient exposure of catalytically active sites of bulky MHPs seriously impair their catalytic efficiency. Herein, we utilized an extra‐large‐pore zeolite ZEO‐1 (JZO) as a host to confine and stabilize the CsPbBr3 nanocrystals (3.4 nm) for boosting hydrogen iodide (HI) splitting. The as‐prepared CsPbBr3@ZEO‐1 featured sufficiently exposed active sites, superior stability in acidic media, along with intrinsic extra‐large pores of ZEO‐1 that were favorable for molecule/ion adsorption and diffusion. Most importantly, the unique nanoconfinement effect of ZEO‐1 led to the narrowing of the band gap of CsPbBr3, allowing for more efficient light utilization. As a result, the photocatalytic HER rate of the as‐prepared CsPbBr3@ZEO‐1 photocatalyst was increased to 1734 μmol ⋅ h−1 ⋅ g−1(CsPbBr3) under visible light irradiation compared with bulk CsPbBr3 (11 μmol ⋅ h−1 ⋅ g−1(CsPbBr3)), and the long‐term durability (36 h) can be achieved. Furthermore, Pt was incorporated with well‐dispersed CsPbBr3 nanocrystals into ZEO‐1, resulting in a significant enhancement in activity (4826 μmol ⋅ h−1 ⋅ g−1(CsPbBr3)), surpassing most of the Pt‐integrated perovskite‐based photocatalysts. Density functional theory (DFT) calculations and charge‐carrier dynamics investigation revealed that the dramatically boosted photocatalytic performance of Pt/CsPbBr3@ZEO‐1 could be attributed to the promotion of charge separation and transfer, as well as to the substantially lowered energy barrier for HER. This work highlights the advantage of extra‐large‐pore zeolites as the nanoscale platform to accommodate multiple photoactive components, opening up promising prospects in the design and exploitation of novel zeolite‐confined photocatalysts for energy harvesting and storage.
Transient Metallo‐Lipidoid Assemblies Amplify Covalent Catalysis of Aqueous and Non‐Aqueous Reactions
Authors: Solra Manju , Kapila Rohit , Das Sourav , Bhatt Preeti , Rana Subinoy 
Published: February 2024

AbstractDissipative supramolecular assemblies are hallmarks of living systems, contributing to their complex, dynamic structures and emerging functions. Living cells can spatiotemporally control diverse biochemical reactions in membrane compartments and condensates, regulating metabolite levels, signal transduction or remodeling of the cytoskeleton. Herein, we constructed membranous compartments using self‐assembly of lipid‐like amphiphiles (lipidoid) in aqueous medium. The new double‐tailed lipidoid features Cu(II) coordinated with a tetravalent chelator that dictates the binding of two amphiphilic ligands in cis‐orientation. Hydrophobic interactions between the lipidoids coupled with intermolecular hydrogen bonding led to a well‐defined bilayer vesicle structure. Oil‐soluble SNAr reaction is efficiently upregulated in the hydrophobic cavity, acting as a catalytic crucible. The modular system allows easy incorporation of exposed primary amine groups, which augments the catalysis of retro aldol and C−N bond formation reactions. Moreover, a higher‐affinity chelator enables consumption of the Cu(II) template leveraging the differential thermodynamic stability, which allows a controllable lifetime of the vesicular assemblies. Concomitant temporal upregulation of the catalytic reactions could be tuned by the metal ion concentration. This work offers new possibilities for metal ion‐mediated dynamic supramolecular systems, opening up a massive repertoire of functionally active dynamic “life‐like” materials.
Isolierte Rhodium(II)‐Metallradikalzentren Katalysieren die Hydrofunktionalisierung von Olefinen
Authors: Qiu Zihang , Deng Hao , Neumann Constanze N. 
Published: February 2024

AbstractRh(II)‐Porphyrinkomplexe weisen einen ausgeprägten metallzentrierten Radikalcharakter auf, und die Fähigkeit kleine Moleküle unter milden Bedingungen zu aktivieren. Katalyse mit Rh(II)‐Porphyrinen ist jedoch äußerst selten. Zusätzlich zu Dimerisierung gehen Rh(II)‐Porphyrine leicht kinetisch und thermodynamisch einfache Reaktionen ein, an denen zwei Rh(II)‐Zentren beteiligt sind, um stabile Rh(III)‐X Zwischenprodukte zu erzeugen, die den Umsatz in der thermischen Katalyse behindern. Hier berichten wir über die geometrische Isolierung von Rh(II)‐Metallradikalen in einem MOF‐Wirt, die Rh(II)‐Metallradikale nicht nur vor Dimerisierung schützt, sondern ihnen auch die Teilnahme an der thermischen Katalyse ermöglicht. Der Zugang zu PCN‐224 oder PCN‐222, bei denen die Porphyrin‐Linker vollständig durch Rh(II) metalliert sind, aber keine begleitenden Rh(0)‐Nanopartikel erzeugt werden, gelang durch die erste direkte MOF‐Synthese mit einem Linker der ein Übergangsmetall‐Alkyl Motiv enthält, gefolgt von Photolyse der Rh(III)−C Bindung.
Selective Construction and Structural Transformation of Homogeneous Linear Metalla[4]catenane and Metalla[2]catenane Assemblies
Authors: Shan Wei‐Long , Hou Huan‐Huan , Si Nian , Wang Cai‐Xia , Yuan Guozan , Gao Xiang , Jin Guo‐Xin 
Published: February 2024

AbstractAlthough the synthesis of mechanically interlocked molecules has been extensively researched, selectively constructing homogeneous linear [4]catenanes remains a formidable challenge. Here, we selectively constructed a homogeneous linear metalla[4]catenane in a one‐step process through the coordination‐driven self‐assembly of a bidentate benzothiadiazole derivative ligand and a binuclear half‐sandwich rhodium precursor. The formation of metalla[4]catenanes was facilitated by cooperative interactions between strong sandwich‐type π‐π stacking and non‐classical hydrogen bonds between the components. Moreover, by modulating the aromatic substituents on the binuclear precursor, two homogeneous metalla[2]catenanes were obtained. The molecular structures of these metallacatenanes were unambiguously characterized by single‐crystal X‐ray diffraction analysis. Additionally, reversible structural transformation between metal‐catenanes and the corresponding metallarectangles could be achieved by altering their concentration, as confirmed by mass spectrometry and NMR spectroscopy studies.
Tuning the Absorption, Fluorescence, Intramolecular Charge Transfer, and Intersystem Crossing in Spiro[fluorene]acridinone
Authors: Bo Yifan , Zhang He , Li Yue , Reva Yana , Xie Linghai , Guldi Dirk M. 
Published: February 2024

AbstractIn this work, we prepared a series of electron donor‐acceptor systems based on spiro[fluorene‐9,7’‐dibenzo[c,h]acridine]‐5’‐one (SFDBAO). Our SFDBAOs consist of orthogonally positioned fluorenes and aromatic ketones. By fine‐tuning the substitution of electron‐donating pyrenes, the complex interplay among different excited‐state decay channels and the overall impact of solvents on these decay channels were uncovered. Placing pyrene, for example, at the aromatic ketones resulted in a profound solvatochromism in the form of a bright charge‐transfer (CT) emission spanning from yellow to red‐NIR. In contrast, a dark non‐emissive CT was noted upon pyrene substitution at the fluorenes. In apolar solvents, efficient triplet‐excited state generation was observed for all SFDBAOs. Either charge transfer was concluded to mediate the intersystem crossing (ISC) in the case of pyrene substitution or the El‐Sayed rule was applicable when lacking pyrene substitution as in the case of SFABAO. In polar solvents, charge separation is the sole decay upon pyrene substitution. Moreover, competition between ISC and CT lowered the triplet‐excited state generation in SFDBAO.
Enzymatic Synthesis of TNA Protects DNA Nanostructures
Authors: Qin Bohe , Wang Qi , Wang Yuang , Han Feng , Wang Haiyan , Jiang Shuoxing , Yu Hanyang 
Published: February 2024

AbstractXeno‐nucleic acids (XNAs) are synthetic genetic polymers with improved biological stabilities and offer powerful molecular tools such as aptamers and catalysts. However, XNA application has been hindered by a very limited repertoire of tool enzymes, particularly those that enable de novo XNA synthesis. Here we report that terminal deoxynucleotide transferase (TdT) catalyzes untemplated threose nucleic acid (TNA) synthesis at the 3’ terminus of DNA oligonucleotide, resulting in DNA‐TNA chimera resistant to exonuclease digestion. Moreover, TdT‐catalyzed TNA extension supports one‐pot batch preparation of biostable chimeric oligonucleotides, which can be used directly as staple strands during self‐assembly of DNA origami nanostructures (DONs). Such TNA‐protected DONs show enhanced biological stability in the presence of exonuclease I, DNase I and fetal bovine serum. This work not only expands the available enzyme toolbox for XNA synthesis and manipulation, but also provides a promising approach to fabricate DONs with improved stability under the physiological condition.
Photocatalytic CO2 Reduction Using CO2‐Binding Enzymes
Authors: Terholsen Henrik , Huerta‐Zerón Hilario Diego , Möller Christina , Junge Henrik , Beller Matthias , Bornscheuer Uwe T. 
Published: February 2024

AbstractNovel concepts to utilize carbon dioxide are required to reach a circular carbon economy and minimize environmental issues. To achieve these goals, photo‐, electro‐, thermal‐, and biocatalysis are key tools to realize this, preferentially in aqueous solutions. Nevertheless, catalytic systems that operate efficiently in water are scarce. Here, we present a general strategy for the identification of enzymes suitable for CO2 reduction based on structural analysis for potential carbon dioxide binding sites and subsequent mutations. We discovered that the phenolic acid decarboxylase from Bacillus subtilis (BsPAD) promotes the aqueous photocatalytic CO2 reduction selectively to carbon monoxide in the presence of a ruthenium photosensitizer and sodium ascorbate. With engineered variants of BsPAD, TONs of up to 978 and selectivities of up to 93 % (favoring the desired CO over H2 generation) were achieved. Mutating the active site region of BsPAD further improved turnover numbers for CO generation. This also revealed that electron transfer is rate‐limiting and occurs via multistep tunneling. The generality of this approach was proven by using eight other enzymes, all showing the desired activity underlining that a range of proteins is capable of photocatalytic CO2 reduction.
Modulating the Electronic Structure of Cobalt in Molecular Catalysts via Coordination Environment Regulation for Highly Efficient Heterogeneous Nitrate Reduction
Authors: Sun Libo , Dai Chencheng , Wang Tianjiao , Jin Xindie , Xu Zhichuan J. , Wang Xin 
Published: February 2024

AbstractAmmonia (NH3) is pivotal in modern industry and represents a promising next‐generation carbon‐free energy carrier. Electrocatalytic nitrate reduction reaction (eNO3RR) presents viable solutions for NH3 production and removal of ambient nitrate pollutants. However, the development of eNO3RR is hindered by lacking the efficient electrocatalysts. To address this challenge, we synthesized a series of macrocyclic molecular catalysts for the heterogeneous eNO3RR. These materials possess different coordination environments around metal centers by surrounding subunits. Consequently, electronic structures of the active centers can be altered, enabling tunable activity towards eNO3RR. Our investigation reveals that metal center with an N2(pyrrole)‐N2(pyridine) configuration demonstrates superior activity over the others and achieves a high NH3 Faradaic efficiency (FE) of over 90 % within the tested range, where the highest FE of approximately 94 % is obtained. Furthermore, it achieves a production rate of 11.28 mg mgcat−1 h−1, and a turnover frequency of up to 3.28 s−1. Further tests disclose that these molecular catalysts with diverse coordination environments showed different magnetic moments. Theoretical calculation results indicate that variated coordination environments can result in a d‐band center variation which eventually affects rate‐determining step energy and calculated magnetic moments, thus establishing a correlation between electronic structure, experimental activity, and computational parameters.
Preparation, characterization, and computational study on transition metal complexes derived from thiophene Schiff base and evaluation of their cytotoxicity against hepatic cell line, antioxidant activities, and ligand's anticorrosive properties
Authors: Sayed Fatma N. , Ashmawy Ashraf M. , Mohamed Gehad G. , Deghadi Reem G. 
Published: February 2024

Novel thiophene Schiff base ligand (L) was synthesized through the condensation of 2‐thiophene‐methylamine and 3‐formyl‐4‐methoxyphenylboronic acid. Transition metal complexes with the formulae [M(L)(H2O)2Cl]Cl2.xH2O (M = Er(III), x = 4 and La(III), x = 5) and [M(L)(H2O)Cl2]Cl.xH2O (M = Yb(III), x = 4 and Ru(III), x = 0) were synthesized. Different spectral and physicochemical methods were used to confirm and identify the stoichiometry, structure, and bonding style of transition metal chelates. The creation of 1:1 molar ratio (M:L) complexes was supported by elemental data. According to IR spectra, the thiophene Schiff base ligand (L) acted as a tridentate ligand that is neutrally coordinated by S‐thiophene, N‐azomethine, and o‐methoxy groups. All chelates formed in octahedral structures according to the findings data. Thermogravimetric analysis (TG and DTG) was employed to examine the heat decomposition of these compounds. DFT/B3LYP method, a molecular modeling methodology, is used to support the expected shape of the produced ligand. Chemical hardness and softness, HOMO and LUMO energy levels, electrophilic index, bond lengths, angles, dipole moment, electronegativity, and other factors were calculated. Against HepG‐2 cell line, the in vitro anticancer activity of all chelates and free ligands was evaluated. These synthesized compounds showed good effectiveness. Additionally, DPPH scavenging was used to assess antioxidant activity, with extremely positive results. Molecular docking with the hepatic protein receptor 3ELJ was used to confirm the anticancer results. Finally, the effectiveness of the current thiophene ligand's ability to block Al‐Si alloys in 1 M HCl solution was examined utilizing electrochemical methods. The high inhibition efficiency was obtained revealing the effectiveness of using this thiophene Schiff base ligand on an industrial scale.