bluuebunny/crossref_metadata_2025_split huggingface dataset:
Cu‐Doping Layered Double Hydroxides Nanozyme Integrated with Nitric Oxide Donor for Enhanced Antioxidant Therapy in Retinopathy
Authors: Xue Bai , Lu Yu , Wang Shuyu , Wu Tingting , Wang Lulu , Xiao Qing , Jiang Wei , Yan Xiyun , Jiang Bing 
Published: July 2024

AbstractThe prevalence of retinal neovascular diseases necessitates novel treatments beyond current therapies like laser surgery or anti‐VEGF treatments, which often carry significant side effects. A novel therapeutic approach is introduced using copper‐containing layered double hydroxides (Cu‐LDH) nanozymes integrated with nitric oxide‐releasing molecules (GSHNO), forming Cu‐LDH@GSHNO aimed at combating oxidative stress within the retinal vascular system. Combination of synthetic chemistry and biological testing, Cu‐LDH@GSHNO are synthesized, characterized, and assessed for curative effect in HUVECs and an oxygen‐induced retinopathy (OIR) mouse model. The results indicate that Cu‐LDH@GSHNO demonstrates SOD‐CAT cascade catalytic ability, accompanied with GSH and nitric oxide‐releasing capabilities, which significantly reduces oxidative cell damage and restores vascular function, presenting a dual‐function strategy that enhances treatment efficacy and safety for retinal vascular diseases. The findings encourage further development and clinical exploration of nanozyme‐based therapies, promising a new horizon in therapeutic approaches for managing retinal diseases driven by oxidative stress.
Rational Design of Color‐Pure Blue Organic Emitters by Poly‐Heteroaromatic Omni‐Delocalization
Authors: Song Sunwu , Feng Siyang , Wang Liangxuan , Jun Jinwon , Milián‐Medina Begoña , Wannemacher Reinhold , Lee Jaesang , Kwon Min Sang , Gierschner Johannes 
Published: July 2024

AbstractCurrent research on organic light emitters which utilize multiple resonance‐induced thermally activated delayed fluorescence (MR‐TADF) materials is gaining significant interest because of the materials’ ability to efficiently generate color‐pure blue emission. However, the underlying reasons for high color purity remain unclear. It is shown here that these emitters share a common electronic basis, which is deduced from resonance structure considerations following Clar's rule, and which is termed as “poly‐heteroaromatic omni‐delocalization” (PHOD). The simple and clear design rules derived from the PHOD concept allow extending the known chemical space by new structural motifs. Based on PHOD, a set of novel high‐efficiency color‐pure emitters with brilliant deep‐blue hue is specifically designed.
Ferroelectric Stochasticity in 2D CuInP2S6 and Its Application for True Random Number Generator
Authors: Kang Seongkweon , Hong Doojin , Das Biswajit , Lee Sang‐Min , Park Ji‐Sang , Lee Yoonmyung , Lee Sungjoo 
Published: July 2024

AbstractTrue random number generators (TRNGs), which create cryptographically secure random bitstreams, hold great promise in addressing security concerns regarding hardware, communication, and authentication in the Internet of Things (IoT) realm. Recently, TRNGs based on nanoscale materials have gained considerable attention for avoiding conventional and predictable hardware circuitry designs that can be vulnerable to machine learning (ML) attacks. In this article, a low‐power and low‐cost TRNG developed by exploiting stochastic ferroelectric polarization switching in 2D ferroelectric CuInP2S6 (CIPS)‐based capacitive structures, is reported. The stochasticity arises from the probabilistic switching of independent electrical dipoles. The TRNG exhibits enhanced stochastic variability with near‐ideal entropy, uniformity, uniqueness, Hamming distance, and independence from autocorrelation variations. Its unclonability is systematically examined using device‐to‐device variations. The generated cryptographic bitstreams pass the National Institute of Standards and Technology (NIST) randomness tests. This nanoscale CIPS‐based TRNG is circuit‐integrable and exhibits potential for hardware security in edge devices with advanced data encryption.
Notch Signaling Hydrogels Enable Rapid Vascularization and Promote Dental Pulp Tissue Regeneration
Authors: Zhang Siyuan , Yu Mei , Li Maojiao , He Min , Xie Li , Huo Fangjun , Tian Weidong 
Published: July 2024

AbstractSuccessful dental pulp regeneration is closely associated with rapid revascularization and angiogenesis, processes driven by the Jagged1(JAG1)/Notch signaling pathway. However, soluble Notch ligands have proven ineffective in activating this pathway. To overcome this limitation, a Notch signaling hydrogel is developed by indirectly immobilizing JAG1, aimed at precisely directing the regeneration of vascularized pulp tissue. This hydrogel displays favorable mechanical properties and biocompatibility. Cultivating dental pulp stem cells (DPSCs) and endothelial cells (ECs) on this hydrogel significantly upregulate Notch target genes and key proangiogenic markers expression. Three‐dimensional (3D) culture assays demonstrate Notch signaling hydrogels improve effectiveness by facilitating encapsulated cell differentiation, enhancing their paracrine functions, and promoting capillary lumen formation. Furthermore, it effectively communicates with the Wnt signaling pathway, creating an odontoinductive microenvironment for pulp‐dentin complex formation. In vivo studies show that short‐term transplantation of the Notch signaling hydrogel accelerates angiogenesis, stabilizes capillary‐like structures, and improves cell survival. Long‐term transplantation further confirms its capability to promote the formation of pulp‐like tissues rich in blood vessels and peripheral nerve‐like structures. In conclusion, this study introduces a feasible and effective hydrogel tailored to specifically regulate the JAG1/Notch signaling pathway, showing potential in advancing regenerative strategies for dental pulp tissue.
Are plant traits drivers of endophytic communities in seasonally flooded tropical forests?
Authors: Boisseaux Marion , Troispoux Valérie , Bordes Alice , Cazal Jocelyn , Cazal Saint‐Omer , Coste Sabrina , Stahl Clément , Schimann Heidy 
Published: July 2024

AbstractPremiseIn the Amazon basin, seasonally flooded (SF) forests offer varying water constraints, providing an excellent way to investigate the role of habitat selection on microbial communities within plants. However, variations in the microbial community among host plants cannot solely be attributed to environmental factors, and how plant traits contribute to microbial assemblages remains an open question.MethodsWe described leaf‐ and root‐associated microbial communities using ITS2 and 16 S high‐throughput sequencing and investigated the stochastic‐deterministic balance shaping these community assemblies using two null models. Plant ecophysiological functioning was evaluated by focusing on 10 leaf and root traits in 72 seedlings, belonging to seven tropical SF tree species in French Guiana. We then analyzed how root and leaf traits drove the assembly of endophytic communities.ResultsWhile both stochastic and deterministic processes governed the endophyte assembly in the leaves and roots, stochasticity prevailed. Discrepancies were found between fungi and bacteria, highlighting that these microorganisms have distinct ecological strategies within plants. Traits, especially leaf traits, host species and spatial predictors better explained diversity than composition, but they were modest predictors overall.ConclusionsThis study widens our knowledge about tree species in SF forests, a habitat sensitive to climate change, through the combined analyses of their associated microbial communities with functional traits. We emphasize the need to investigate other plant traits to better disentangle the drivers of the relationship between seedlings and their associated microbiomes, ultimately enhancing their adaptive capacities to climate change.
Optical genome mapping with genome sequencing identifies subtelomeric Xq28 deletion and inserted 7p22.3 duplication in a male with multisystem developmental disorder
Authors: Rodriguez‐Gil Jorge L. , Nagy Peter L. , Francke Uta 
Published: July 2024

AbstractWe report a 17‐year‐old male with supravalvular stenosis, initial failure to thrive and delayed early development, short stature, acromelia, dysmorphic facial features, hypertelorism, macrocephaly, syringomyelia, hypertension, and anxiety disorder. Fluorescent in situ hybridization (FISH), chromosomal microarray analysis (CMA), and exome sequencing (ES) were nondiagnostic. Combined optical genome mapping (OGM) and genome sequencing (GS) showed a complex rearrangement including an X chromosome with a 22.5 kb deletion in band Xq28 replaced by a 61.4 kb insertion of duplicated chromosome 7p22.3 material. The deletion removes the distal 3′ untranslated region (UTR) of FUNDC2, the entire CMC4 and MTCP1, and the first five exons of BRCC3. Transcriptome analysis revealed absent expression of CMC4 and MTCP1 and BRCC3 with normal transcript level of FUNDC2. The inserted duplication includes only one known gene: UNCX. Similar overlapping Xq28 deletions have been reported to be associated with Moyamoya disease (MMD), short stature, hypergonadotropic hypogonadism (HH), and facial dysmorphism. Although he has short stature, our patient does not have signs of Moyamoya arteriopathy or hypogonadism. The structurally abnormal X chromosome was present in his mother, but not in his unaffected brother, maternal uncle, or maternal grandparents. We propose that the combination of his absent Xq28 and duplicated 7p22.3 genomic material is responsible for his phenotype. This case highlights the potential of combined OGM and GS for detecting complex structural variants compared with standard of care genetic testing such as CMA and ES.
Ophthalmic manifestations of NAA10‐related and NAA15‐related neurodevelopmental syndromes: Analysis of cortical visual impairment and refractive errors
Authors: Patel Rahi , Park Agnes Y. , Marchi Elaine , Gropman Andrea L. , Whitehead Matthew T. , Lyon Gholson J. 
Published: July 2024

AbstractNAA10‐related (Ogden syndrome) and NAA15‐related neurodevelopmental syndrome are known to present with varying degrees of intellectual disability, hypotonia, congenital cardiac abnormalities, seizures, and delayed speech and motor development. However, the ophthalmic manifestations of NAA10 and NAA15 variants are not yet fully characterized or understood. This study analyzed the prevalence of six ophthalmic conditions (cortical visual impairment, myopia, hyperopia, strabismus, nystagmus, and astigmatism) in 67 patients with pathogenic (P) or likely pathogenic (LP) variants in the NAA10 cohort (54 inherited, 10 de novo; 65 missense, 2 frameshift) and 19 patients with (L)P variants in the NAA15 cohort (18 de novo; 8 frameshift, 4 missense, 4 nonsense, and 1 splice site). Patients were interviewed virtually or in‐person to collect a comprehensive medical history verified by medical records. These records were then analyzed to calculate the prevalence of these ophthalmic manifestations in each cohort. Analysis revealed a higher prevalence of ophthalmic conditions in our NAA10 cohort compared to existing literature (myopia 25.4% vs. 4.7%; astigmatism 37.3% vs. 13.2%; strabismus 28.4% vs. 3.8%; CVI 22.4% vs. 8.5%, respectively). No statistically significant differences were identified in the prevalence of these conditions between the NAA10 and NAA15 variants. Our study includes novel neuroimaging of 13 NAA10 and 5 NAA15 probands, which provides no clear correlation between globe size and severity of comorbid ophthalmic disease. Finally, anecdotal evidence was compiled to underscore the importance of early ophthalmologic evaluations and therapeutic interventions.
Trifluoromethylation Strategies of Alcohols and Phenols
Authors: Pratap Singh Ravi , Ghoshal Tanay , Mishra Vivek 
Published: July 2024

AbstractIn this review, we present a comprehensive update on the latest trifluoromethylation protocols for alcohols, highlighting the significant advancements and innovative strategies in this rapidly evolving field. Given the prevalence of hydroxyl groups in pharmaceutical compounds, there is a heightened interest in synthesizing functionalized organic molecules through the −CF3 functionalization of parent alcohols. Recent developments have introduced intriguing methods such as O‐trifluoromethylation, dehydroxylative trifluoromethoxylation, deoxytrifluoromethylation, and oxytrifluoromethylation of readily available alcohols. These protocols enable the efficient single‐step construction of diverse structures featuring C−CF3 and C−OCF3 bonds. This review aims to encapsulate the significant progress, structural diversity, and mechanistic insights of these transformative reactions, emphasizing their substrate scope and the underlying reaction pathways that drive these advancements.
Fluorierte Dialkyl Chloronium Salze: Synthese und Reaktivität für CH2CF3‐Übertragungs‐ und Hydridabstraktions‐Reaktionen
Authors: Fischer Lukas , Lee Michael H. , Kim Isaac , Wiesner Anja , Hoffmann Kurt F. , Riedel Sebastian 
Published: July 2024

AbstractEs wird ein neuer Ansatz für die Synthese von Dialkylchloronium‐Kationen [R−Cl−R]+ beschrieben (R=CH3, CH2CF3), der die Herstellung von fluorierten Derivaten ermöglicht. Unter Verwendung des Xenonium‐Salzes [XeOTeF5][M(OTeF5)n] (M=Sb, n=6; M=Al, n=4) werden Chloratome von Chloralkanen oder dem deaktivierten Chlorfluoralkan CH2ClCF3 oxidiert und als ClOTeF5 abgespalten, wodurch die Isolierung des entsprechenden Chloronium‐Salzes möglich ist. Da das resultierende stark elektrophile Kation [Cl(CH2CF3)2]+ in der Lage ist, schwache Nukleophile zu alkylieren, kann diese Verbindung für die Einführung einer fluorierten Alkylgruppe verwendet werden. Darüber hinaus weist das fluorierte Alkylchloronium‐Kation eine hohe Hydrid‐Ionen‐Affinität auf, sodass lineare Kohlenwasserstoffe auch bei niedrigen Temperaturen durch Hydridabstraktion aktiviert werden und so verzweigte Carbokationen bilden.
Photoinduced Cu(II)‐Mediated Decarboxylative Thianthrenation of Aryl and Heteroaryl Carboxylic Acids
Authors: He Zhen , Dydio Paweł 
Published: July 2024

AbstractGiven that (hetero)aryl carboxylic acids are inexpensive materials available in a great variety from commercial and natural resources or synthesis, the strategies enabling their use as starting materials for preparing fine chemicals are highly sought after. Here we report a photoinduced Cu(II)‐mediated protocol converting (hetero)aryl carboxylic acids into (hetero)aryl thianthrenium salts, high value‐added building blocks that can undergo various subsequent transformations, creating an attractive two‐step pathway for the divergent functionalization of these ubiquitous starting materials. The excellent compatibility of the method is shown by preparing a broad range of sterically and electronically varied (hetero)aryl thianthrenium salts, including derivatives of pharmaceuticals, such as ataluren, celecoxib, flavoxate, probenecid, repaglinide, and tamibarotene. The syntheses of 13 C‐labeled probenecid and bioisosteres of ataluren as well as the unconventional modifications of celecoxib and flavoxate, illustrate the synthetic potential of the strategy. Mechanistic studies are in line with a reaction occurring through a photoinduced ligand‐to‐metal charge transfer (LMCT) of Cu(II)‐arylcarboxylates, enabling radical decarboxylative carbometallation to form arylcopper(II) intermediates that in turn react with thianthrene to form the product. Noteworthy, the susceptibility of aryl thianthrenium salts to photodegradation is overcome by a Cu(I)‐driven salvage loop, which continuously intercepts the transiently formed radicals and regenerates the products.
Copper(I) Catalysed Diboron(4) Reduction of Nitrous Oxide
Authors: Hood Thomas M. , Charman Rex S. C. , Liptrot David J. , Chaplin Adrian B. 
Published: July 2024

AbstractA process for the catalytic reduction of nitrous oxide using NHC‐ligated copper(I) tert‐butoxide precatalysts and B2pin2 as the reductant is reported. These reactions proceed under mild conditions via copper(I)‐boryl intermediates which react with N2O by facile O‐atom insertion into the Cu−B bond and liberate N2. Turnover numbers >800 can be achieved at 80 °C under 1 bar N2O.
Photoinduced Cu(II)‐Mediated Decarboxylative Thianthrenation ofAryl and Heteroaryl Carboxylic Acids
Authors: He Zhen , Dydio Paweł 
Published: July 2024

AbstractGiven that (hetero)aryl carboxylic acids are inexpensive materials available in a great variety from commercial and natural resources or synthesis, the strategies enabling their use as starting materials for preparing fine chemicals are highly sought after. Here we report a photoinduced Cu(II)‐mediated protocol converting (hetero)aryl carboxylic acids into (hetero)aryl thianthrenium salts, high value‐added building blocks that can undergo various subsequent transformations, creating an attractive two‐step pathway for the divergent functionalization of these ubiquitous starting materials. The excellent compatibility of the method is shown by preparing a broad range of sterically and electronically varied (hetero)aryl thianthrenium salts, including derivatives of pharmaceuticals, such as ataluren, celecoxib, flavoxate, probenecid, repaglinide, and tamibarotene. The syntheses of 13 C‐labeled probenecid and bioisosteres of ataluren as well as the unconventional modifications of celecoxib and flavoxate, illustrate the synthetic potential of the strategy. Mechanistic studies are in line with a reaction occurring through a photoinduced ligand‐to‐metal charge transfer (LMCT) of Cu(II)‐arylcarboxylates, enabling radical decarboxylative carbometallation to form arylcopper(II) intermediates that in turn react with thianthrene to form the product. Noteworthy, the susceptibility of aryl thianthrenium salts to photodegradation is overcome by a Cu(I)‐driven salvage loop, which continuously intercepts the transiently formed radicals and regenerates the products.
Near‐Full‐Spectrum Emission Realized in a Single Lead Halide Perovskite across the Visible‐Light Region
Authors: An Lian‐Cai , Li Zi‐Ying , Azeem Muhammad , Li Wei , Qin Yan , Gao Fei‐Fei , Han Song‐De , Wang Guo‐Ming , Bu Xian‐He 
Published: July 2024

AbstractThe engineering of tunable photoluminescence (PL) in single materials with a full‐spectrum emission represents a highly coveted objective but poses a formidable challenge. In this context, the realization of near‐full‐spectrum PL emission, spanning the visible light range from 424 to 620 nm, in a single‐component two‐dimensional (2D) hybrid lead halide perovskite, (ETA)2PbBr4 (ETA+=(HO)(CH2)2NH3+), is reported, achieved through high‐pressure treatment. A pressure‐induced phase transition occurs upon compression, transforming the crystal structure from an orthorhombic phase under ambient conditions to a monoclinic structure at high pressure. This phase transition driven by the adaptive and dynamic configuration changes of organic amine cations enables an effective and continuous narrowing of the band gap in this halide crystal. The hydrogen bonding interactions between inorganic layers and organic amine cations (N−H⋅⋅⋅Br and O−H⋅⋅⋅Br hydrogen bonds) efficiently modulate the organic amine cations penetration and the octahedral distortion. Consequently, this phenomenon induces a phase transition and results in red‐shifted PL emissions, leading to the near‐full‐spectrum emission. This work opens a possibility for achieving wide PL emissions with coverage across the visible light spectrum by employing high pressure in single halide perovskites.
Achieving Record C2H2 Packing Density for Highly Efficient C2H2/C2H4 Separation with a Metal–Organic Framework Prepared by a Scalable Synthesis in Water
Authors: Zhang Xin , Chen Qiancheng , Bai Xuefeng , Zhao Yan‐Long , Li Jian‐Rong 
Published: July 2024

AbstractAdsorptive C2H2/C2H4 separation using metal–organic frameworks (MOFs) has emerged as a promising technology for the removal of C2H2 (acetylene) impurity (1 %) from C2H4 (ethylene). The practical application of these materials involves the optimization of separation performance as well as development of scalable and green production protocols. Herein, we report the efficient C2H2/C2H4 separation in a MOF, Cu(OH)INA (INA: isonicotinate) which achieves a record C2H2 packing density of 351 mg cm−3 at 0.01 bar through high affinity towards C2H2. DFT (density functional theory) calculations reveal the synergistic binding mechanism through pore confinement and the oxygen sites in pore wall. The weakly basic nature of binding sites leads to a relatively low heat of adsorption (Qst) of approximately 36 kJ/mol, which is beneficial for material regeneration and thermal management. Furthermore, a scalable and environmentally friendly synthesis protocol with a high space‐time yield of 544 kg m−3 day−1 has been developed without using any modulating agents. This material also demonstrates enduring separation performance for multiple cycles, maintaining its efficacy after exposure to water or air for three months.
Air‐laid and foam‐laid nonwoven composites: The effect of carrier medium on mechanical properties
Authors: Paunonen Sara , Keränen Janne T. , Kamppuri Taina 
Published: July 2024

AbstractThermoplastic nonwoven composites were produced with the air‐laying and foam‐forming processes from cellulosic and plastic fibers. The two raw material combinations were (1) PP/PE (fiber length 3 mm), PP/PE (12 mm), fluff pulp fibers (2 mm) and (2) PP/PE (3 mm), fluff pulp fibers, viscose (10 mm). After forming, the fibrous sheets (400 gsm) were bonded with heat pressing (145°C). The effect of the carrier medium, air or aqueous foam, on the tensile and impact properties and sheet structure was explored. The air‐laids differed from the foam‐laids by sheet anisotropy, density, and the lack of an additional bonding regime between wood fibers due to the dry forming process. The PP/PE bonding fibers gave the air‐laids a good capacity to elongate compared to the foam‐laids. The advantage was lost when nonbonding viscose was added. The impact strength was dependent on the PP/PE dosage and the sheet density, rather than the moisture‐induced bonding between wood fibers. The changing long/short fiber ratios caused gradual shifts in sheet properties, usually a reduction in a mechanical property as the share of short fiber increased in the mix. Economic analysis revealed that increasing fluff content can reduce raw material costs, providing a possibility for cost optimization in total production costs.