bluuebunny/crossref_metadata_2025_split huggingface dataset:
Self‐Formation CoO Nanodots Catalyst in Co(TFSI)2‐Modified Electrolyte for High Efficient Li‐O2 Batteries
Authors: Sun Guiru , Gao Rui , Jiao Hailiang , Luo Dan , Wang Yan , Zhang Zexu , Lu Wei , Feng Ming , Chen Zhongwei 
Published: July 2022

AbstractThe major challenges for Li‐O2 batteries are sluggish reaction kinetics and large overpotentials due to the cathode passivation resulting from insulative and insoluble Li2O2. Here, a novel nanodot (ND)‐modified electrolyte is designed by employing cobalt bis(trifluoromethylsulfonyl)imide (Co(TFSI)2) as an electrolyte additive. The Co(TFSI)2 additive can react with discharge intermediate LiO2 and product Li2O2 to form CoO NDs. The generated CoO NDs are well dispersed in electrolyte, which integrates both the high catalytic activity of solid catalyst and the good wettability of soluble catalyst. Under the catalytis of CoO NDs, Li2O2 is produced and deposits on the cathode together with them. At the recharge process, these well dispersed CoO NDs help to decompose solid Li2O2 at a lower overpotential. The Li‐O2 cells with Co(TFSI)2 exhibit a long cycle life of 200 cycles at a current density of 200 mA g−1 under a cutoff capacity of 1000 mAh g−1, as well as a superior reversibility associated with the Li2O2 formation and decomposition. The study is expected to broaden the range of electrolyte additives and provide a new view to developing highly dispersed NDs‐based catalysts for Li‐O2 batteries.
In Situ Characterization of the Protein Corona of Nanoparticles In Vitro and In Vivo
Authors: Latreille Pierre‐Luc , Rabanel Jean‐Michel , Le Goas Marine , Salimi Sina , Arlt Jochen , Patten Shunmoogum A. , Ramassamy Charles , Hildgen Patrice , Martinez Vincent A. , Banquy Xavier 
Published: July 2022

AbstractA new theoretical framework that enables the use of differential dynamic microscopy (DDM) in fluorescence imaging mode to quantify in situ protein adsorption onto nanoparticles (NP) while simultaneously monitoring for NP aggregation is proposed. This methodology is used to elucidate the thermodynamic and kinetic properties of the protein corona (PC) in vitro and in vivo. The results show that protein adsorption triggers particle aggregation over a wide concentration range and that the formed aggregate structures can be quantified using the proposed methodology. Protein affinity for polystyrene (PS) NPs is observed to be dependent on particle concentration. For complex protein mixtures, this methodology identifies that the PC composition changes with the dilution of serum proteins, demonstrating a Vroman effect never quantitatively assessed in situ on NPs. Finally, DDM allows monitoring of the evolution of the PC in vivo. This results show that the PC composition evolves significantly over time in zebrafish larvae, confirming the inherently dynamic nature of the PC. The performance of the developed methodology allows to obtain quantitative insights into nano‐bio interactions in a vast array of physiologically relevant conditions that will serve to further improve the design of nanomedicine.
A Tetrahedral Framework DNA‐Based Bioswitchable miRNA Inhibitor Delivery System: Application to Skin Anti‐Aging
Authors: Li Songhang , Liu Yuhao , Zhang Tao , Lin Shiyu , Shi Sirong , He Jiajun , Xie Yu , Cai Xiaoxiao , Tian Taoran , Lin Yunfeng 
Published: July 2022

AbstractMicroRNA (miR)‐based therapy shows strong potential; however, structural limitations pose a challenge in fully exploiting its biomedical functionality. Tetrahedral framework DNA (tFNA) has proven to be an ideal vehicle for miR therapy. Inspired by the ancient Chinese myth “Sun and Immortal Birds,” a novel bioswitchable miR inhibitor delivery system (BiRDS) is designed with three miR inhibitors (the three immortal birds) and a nucleic acid core (the central sun). The BiRDS fuses miR inhibitors within the framework, maximizing their loading capacity, while allowing the system to retain the characteristics of small‐sized tFNA and avoiding uncertainty associated with RNA exposure in traditional loading protocols. The RNase H‐responsive sequence at the tail of each “immortal bird” enables the BiRDS to transform from a 3D to a 2D structure upon entering cells, promoting the delivery of miR inhibitors. To confirm the application potential, the BiRDS is used to deliver the miR‐31 inhibitor, with antiaging effects on hair follicle stem cells, into a skin aging model. Superior skin penetration ability and RNA delivery are observed with significant anti‐aging effects. These findings demonstrate the capability and editability of the BiRDS to improve the stability and delivery efficacy of miRs for future innovations.
Potassium Ion Mediated Double‐Layered Upright Assembly of Negatively Charged Amyloid‐Like Peptides at Mica/Water Interface
Authors: Li Danni , Huang Jianxiang , Lao Yichong , Zhang Yiling , Song Wei , Song Jie , Liu Cong , Dai Bin , Zhou Ruhong 
Published: July 2022

AbstractInsight into the surface‐assisted self‐assembly of amyloid‐like peptides is essential to the design and fabrication of novel functional nanomaterials as well as to uncovering the pathogenesis of various neurodegenerative diseases. Despite extensive research, how to control the self‐assembly of amyloid‐like peptides effectively remains challenging. Here, through a combined experimental and theoretical approach, it is demonstrated that cations could modulate the mica/water interface and further induce the self‐assembly of the negatively charged amyloid‐like peptide Ac–VGGAVVAGV–COO− (Ac–GAV–9) into multilayered nanofilaments with a surprising all‐upright parallel β‐sheet conformation. In particular, highly ordered double‐layered nanofilaments are observed on the negatively charged mica surfaces in the presence of 0.5–1.5 m KCl. The molecular dynamics simulations further reveal that the double‐layered nanofilaments have intriguing parallel β‐sheet structures with the C‐termini of the first parallel monolayer pointing to the mica surface and the C‐termini of the second parallel monolayer pointing to the solvent. Moreover, the stability of the nanofilaments could be modulated by peptide and ion concentrations. Further studies show that the growth of double‐layered fibrils at the mica/water interface is a common phenomenon for Ac–GAV–9 in the presence of a variety of salt types.
π‐Extended Zigzag‐Shaped Diphenanthrene‐Based p‐Type Semiconductors Exhibiting Small Effective Masses
Authors: Mitani Masato , Kumagai Shohei , Yu Craig P. , Oi Ayako , Yamagishi Masakazu , Nishinaga Shuhei , Mori Hiroki , Nishihara Yasushi , Hashizume Daisuke , Kurosawa Tadanori , Ishii Hiroyuki , Kobayashi Nobuhiko , Takeya Jun , Okamoto Toshihiro 
Published: July 2022

AbstractMolecular design strategy of the π‐electron core is of importance to enhance the organic semiconducting performance. In this study, diphenanthro[1,2‐b:2′,1′‐d]thiophene (DPT) as a new zigzag‐shaped sulfur‐bridged π‐electron core and its phenyl‐substituted derivative (Ph–DPT) exhibiting unique orbital configurations are reported. The DPT derivatives are readily synthesized through a versatile synthetic scheme in five steps from the commercially available dibenzothiophene. Their single‐crystal structural analyses and band calculations revealed that both DPTs form typical herringbone packing structures, which are favorable for 2D charge carrier transport, along with small effective masses. Single‐crystal‐based field‐effect transistors (FETs) of both DPT and Ph–DPT exhibit p‐type behaviors and charge‐carrier mobility up to 5.5 cm2 V–1 s–1. These results provide information that can broaden the molecular design approaches toward high‐performance organic semiconductors.
Stereoselektive Totalsynthese von (−)‐Thallusin zur Bioaktivitätsprofilierung
Authors: Dhiman Seema , Ulrich Johann F. , Wienecke Paul , Wichard Thomas , Arndt Hans‐Dieter 
Published: July 2022

AbstractChemische Mediatoren sind Schlüsselverbindungen zur Kontrolle von Symbiosen in unserer Umwelt. Hier berichten wir über eine völlig stereoselektive Totalsynthese des Algendifferenzierungsfaktors (−)‐Thallusin, die sich durchdachter 6‐endo‐Zyklisierungschemie und effektiver sp2–sp2‐Kupplungen mittels Zinn‐freier Reagenzien auf späten Stufen bedient. Durch quantitative phänotypische Profilierung wurde für die weit verbreitete Grünalge Ulva mutabilis (Chlorophyta) ein EC50‐Wert von 4.8 pM ermittelt, was die enorme artenübergreifende Bioaktivität dieses von symbiotischen Bakterien produzierten Mediators aufzeigt. SAR‐Untersuchungen weisen darauf hin, dass (−)‐Thallusin mindestens zwei unterschiedliche Signalwege in Ulva auslöst, die durch chemische Editierung der Mediatorstruktur separiert werden können.
Stereoretentive regio‐ und enantioselektive Allylierung von Isoxazolinonen per planar chiralem Palladacyclus‐Katalysator
Authors: Yu Xin , Hu Lingfei , Frey Wolfgang , Lu Gang , Peters René 
Published: July 2022

AbstractDie katalytische allylische Substitution ist eines der wichtigsten Werkzeuge in der asymmetrischen Synthese zur enantioselektiven Bildung von C‐C‐Bindungen. Während in vorigen Arbeiten eine hohe Effizienz in Bezug auf Enantio‐ und Regiokontrolle unter Verwendung verschiedener Katalysatortypen erreicht wurde, besteht eine starke allgemeine Einschränkung in einer sehr ausgeprägten Präferenz für die Bildung von allylischen Substitutionsprodukten mit (E)‐konfigurierten C=C‐Doppelbindungen. Hier berichten wir, dass mit einem planar‐chiralen Palladacyclus‐Katalysator unter Verwendung von Isoxazolinonen und Allylimidaten als Substrate ein diastereospezifisches Reaktionsergebnis erzielt wird, wodurch die C=C‐Doppelbindungsgeometrie der Allylsubstrate in den hoch enantiomerenangereicherten Produkten beibehalten wird. DFT‐Rechnungen zeigen, dass die Reaktionen über einen SN2‐Mechanismus und nicht über π‐Allyl‐Pd‐Komplexe ablaufen. Entscheidend für die hohe Kontrolle ist die Stabilisierung des allylischen Fragments im SN2‐Übergangszustand durch π‐Wechselwirkungen mit den Phenylsubstituenten des Pentaphenylferrocen‐Katalysatorkerns.
Exploiting mono‐ and hybrid nanocomposite materials for fused filament fabrication with acrylonitrile butadiene styrene as polymer matrix
Authors: Ceretti Daniel V. A. , Fiorio Rudinei , Van Waeleghem Tom , Desmet Arne , Florizoone Bauke , Cardon Ludwig , D'hooge Dagmar R. 
Published: July 2022

AbstractAcrylonitrile butadiene styrene (ABS) based polymeric composites consisting of mono‐ and hybrid nano‐compounds, that is, graphene nanoplatelets (GNP's), multi‐walled carbon nanotubes (CNT's), and titanium dioxide (TiO2), are studied for fused filament fabrication (FFF). Rheological analysis in a screening step reveals that nanocomposites containing CNT result in a better nano‐filler dispersion within the matrix and enhanced matrix interaction. The addition of GNP and TiO2 leads to a better coalescence between the deposited filaments. For the actual FFF specimens, emphasis is on the tensile, flexural and impact properties as well as the void content. It is shown that the joint addition of GNP, CNT, and TiO2 gives rise to a remarkable synergistic effect, leading to an improved dispersion and an increased tensile modulus and strength of 3D printed ABS by 16 and 20%. Decreasing the layer thickness increases the mechanical properties of the materials, while the printing temperature does not lead to major variations of the mechanical properties, due to a dominant effect of the addition of nanoparticles. It is also shown that for well‐designed composites the slower sintering and higher void content is overruled by the reinforcement effect.
Cation–π interaction assisted facile preparation of graphene/epoxy nanocomposites with superior strength and toughness
Authors: Huang Ying , Yan Xin , Li Xiaobo , Du Mengqi , Li Yicheng , Yuan Rui , Yang Li , Chang Guanjun 
Published: July 2022

AbstractHigh‐performance graphene/epoxy nanocomposites are desired in many fields. However, the performance of graphene/epoxy nanocomposites is far from the actual demand, and many methods reported for the preparation of graphene/epoxy nanocomposites need the participation of environmentally harmful organic solvents. Herein, a novel, facile, and green cation–π interaction assisted phase transfer approach is developed for construction of graphene/epoxy nanocomposites. This strategy includes constructing potassium ion modified reduce graphene oxide (K‐rGO) as nanofiller and choosing 1‐(oxiran‐2‐ylmethyl)‐1H‐indole (IN) as phase transfer agent. The cation–π interaction is formed between K‐rGO and indole group, which not only facilitates the transfer of K‐rGO from water phase to organic phase, but also enhances the dispersion of K‐rGO in epoxy. When the loading of K‐rGO is 0.10 wt%, the tensile strength and elongation at break of epoxy nanocomposites increase by 116.6% and 126.5%, respectively, compared to neat epoxy. The simultaneous improvement in tensile strength and extensibility of graphene/epoxy nanocomposites is achieved. Furthermore, the prepared epoxy nanocomposites exhibit an excellent thermal conductivity owing to the good dispersion of K‐rGO in epoxy matrix.
Light‐driven self‐healing castor oil based polyurethane film with enhanced mechanical properties
Authors: Wang Haoliang , Wang Shiyu , Ren Bibo , Hu Chenggong , Wang Haibo 
Published: July 2022

AbstractTo meet the need of alleviating the pressure of petrochemical industry and environmental protection, polyurethane (PU) made from castor oil (CO) as polyols, replacing petrochemical based crude material has attracted a lot of recognition over the past decades. For the sake of prolonging the service life of materials, it is also necessary to endow vegetable oil‐based polymers with self‐healing properties, which is seldom involved in present study. Currently, optically responsive self‐healing system has attracted extensive attention because of its easy control and simple occurrence. However, the problem of low self‐healing efficiency also puzzles the current research of this self‐healing system. In this study, cinnamoyl group was introduced into bio‐based PU as end blocking agent. The photoresponse reversible cycloaddition reaction of cinnamyl groups and the acceptable chain fluidity of CO provided the possibility for the self‐healing properties of polymers. The dimerization degree of [2 + 2] cycloaddition reactions was as high as 58% under UV light for 36 h from UV–vis spectrum. Investigation of the optical healing property indicated that incision on the surface of certain PU sample was completely repaired and healing efficiency enhanced up to 93.1%, with the introduction of cinnamoyl group. What is more, the results from TGA, DMA and tensile tests suggested that the prepared PU samples showed excellent comprehensive performance.
Synthesis and Properties of Nonaromatic Meta‐Benziheptaphyrins and Aromatic Para‐Benziheptaphyrins
Authors: Rawat Nisha , Ojha Belarani , Ravikanth Mangalampalli 
Published: July 2022

AbstractTwo examples of nonaromatic m‐benziheptaphyrins and two examples of aromatic p‐benziheptaphyrins were synthesized by [5+2] condensation of appropriate m‐benzi pentapyrrane and p‐benzi pentapyrrane respectively and bithiophene diol in CH2Cl2 in the presence of one equivalent of TFA under inert conditions for 30 min followed by oxidation with DDQ in open air for 1 h. The 1H NMR studies carried out at room temperature as well as at lower temperature indicated the nonaromatic nature of m‐benziheptaphyrins with inversion of two thiophene rings and aromatic nature of p‐benziheptaphyrins with inversion of one of the thiophene ring. The X‐ray structure obtained for one of the p‐benziheptaphyrins showed a planar conformation with alignment of one of the thiophene ring away from the macrocyclic inner core but maintained its coplanarity with the mean plane and supported the aromatic nature of the macrocycle. The absorption spectra of m‐benziheptaphyrins resembled with the nonaromatic systems and showed two intense bands at 445 nm, 555 nm and a very broad band in the region of 600–1100 nm whereas the p‐benziheptaphyrin showed three sharp intense bands at 534 nm, 585 nm and 832 nm due to their aromatic nature. The protonation of m‐benziheptaphyrins and p‐benziheptaphyrins resulted in significant bathochromic shifts in their absorption maxima and showed strong absorption in NIR region. The electrochemical studies indicated that m‐ & p‐benziheptaphyrins undergo oxidations and reductions easily. DFT and TD‐DFT studies were in agreement with the experimental observations.
Pathways to adaptive functioning in autism from early childhood to adolescence
Authors: Chandler Susie , Carter Leno Virginia , White Philippa , Yorke Isabel , Hollocks Matthew J. , Baird Gillian , Pickles Andrew , Simonoff Emily , Charman Tony 
Published: July 2022

AbstractAdaptive functioning is lower in many autistic individuals to a greater extent than would be expected based on IQ. However, the clinical features associated with these difficulties are less well understood. This study examines longitudinal and contemporaneous associations of adaptive functioning in autistic youth across a wide ability range. Parent‐reported autism symptoms, co‐occurring emotional, behavioral and attention deficit hyperactivity disorder (ADHD) symptoms, and IQ were assessed in early childhood (M age 7 years; T1) and 6 years later in adolescence (M age 13 years; T2) in 179 autistic youth. Adaptive functioning was assessed at T2. Structural equation modeling estimated pathways to adaptive functioning from autism, and psychiatric symptoms at T1 and T2, testing whether associations were driven by continuity of behaviors from T1 to T2 or their contemporaneous effect at T2, or both, controlling for T1 IQ. Lower adaptive functioning at T2 was associated with higher T1 and T2 ADHD symptoms (β = −0.14, and β = −0.21) but not behavioral nor emotional symptoms at either timepoint. Lower adaptive functioning at T2 was also associated with lower T1 IQ (β = 0.43) and higher social communication symptoms (β = −0.37) at T2 but not T1, but the relationship with ADHD symptoms remained. Paths were not moderated by sex or IQ. Increased symptoms of ADHD, both in early childhood and contemporaneously, were associated with reduced adaptive functioning in adolescence. Co‐occurring ADHD may be a modifiable risk factor for adaptive function impairments and should be routinely assessed and when present evidence‐based treatments initiated which may benefit adaptive functioning outcomes.Lay SummaryAdaptive functioning is lower in many autistic individuals to a greater extent than would be expected based on IQ. However, the clinical features associated with these difficulties are less well understood. In a community sample higher attention deficit/hyperactivity disorder (ADHD) symptoms, but not emotional or behavioral symptoms, in both early childhood and contemporaneously were associated with lower adaptive functioning in autistic adolescents. Co‐occurring ADHD may be a modifiable risk factor for adaptive function difficulties in autism.
Gene mutations impede oocyte maturation, fertilization, and early embryonic development
Authors: Fei Cai‐feng , Zhou Li‐quan 
Published: July 2022

AbstractReproductive diseases are a long‐standing problem and have become more common in the world. Currently, 15% of the world's population suffers from infertility, and half of them are women. Maturation of oocytes, successful fertilization, and high‐quality embryos are prerequisites for pregnancy. With the development of assisted reproductive technology and advanced genetic assays, we have found that infertility in many young female patients is caused by mutations in various developmental regulators. These pathogenic factors may result in impediment of oocyte maturation, failure of fertilization or early embryonic development arrest. In this review, we categorize these clinically‐identified, mutated genetic factors by their molecular characteristics: nuclear factors (PALT2, TRIP13, WEE2, TBPL2, REC114, MEI1 and CDC20), cytoplasmic factors (TLE6, PADI6, NLRP2/5, FBXO43, MOS and BTG4), a factor unique to primates (TUBB8), cell membrane factor (PANX1), and zona pellucida factors (ZP1‐3). We compared discrepancies observed in phenotypes between human and mouse models to provide clues for clinical diagnosis and treatment of related reproductive diseases.
Cellular self‐organization: An overdrive in Cambrian diversity?
Authors: Vujovic Filip , Hunter Neil , Farahani Ramin M. 
Published: July 2022

AbstractDuring the early Cambrian period metazoan life forms diverged at an accelerated rate to occupy multiple ecological niches on earth. A variety of explanations have been proposed to address this major evolutionary phenomenon termed the “Cambrian explosion.” While most hypotheses address environmental, developmental, and ecological factors that facilitated evolutionary innovations, the biological basis for accelerated emergence of species diversity in the Cambrian period remains largely conjectural. Herein, we posit that morphogenesis by self‐organization enables the uncoupling of genomic mutational landscape from phenotypic diversification. Evidence is provided for a two‐tiered interpretation of genomic changes in metazoan animals wherein mutations not only impact upon function of individual cells, but also alter the self‐organization outcome during developmental morphogenesis. We provide evidence that the morphological impacts of mutations on self‐organization could remain repressed if associated with an unmet negative energetic cost. We posit that accelerated morphological diversification in transition to the Cambrian period has occurred by emergence of dormant (i.e., reserved) morphological novelties whose molecular underpinnings were seeded in the Precambrian period.
Low recognition of attention deficit hyperactivity disorder in adult patients admitted to the Epilepsy Monitoring Unit
Authors: Pham Caitlynn , Roy Cayla , Tang Christine , Maheshwari Atul 
Published: July 2022

AbstractIntroductionAdult patients with epilepsy (PWE) have an 18% prevalence of comorbid attention deficit hyperactivity disorder (ADHD) compared to a prevalence of 2%–5% in the general population. Recognition of this dual diagnosis is important since stimulant therapy is both safe and effective in this population.MethodsHere, we aim to determine if PWE have adequate documentation for comorbid ADHD when being admitted to the Epilepsy Monitoring Unit (EMU). A retrospective review was conducted at the Baylor St. Luke's Medical Center EMU for patients presenting between July 2017 and November 2020. Patients were divided into two groups: Group I—patients without a documented ADHD diagnosis or ADHD medications and Group II—patients with a documented ADHD diagnosis and/or taking medications indicated specifically for ADHD.ResultsOf 524 individual patients who presented to the EMU, only 25 patients (4.8%) had documentation of a diagnosis of ADHD and/or ADHD medications (Group II). The proportion of patients in Group II did not significantly differ based on the EMU diagnosis. However, there was a significantly greater number of other psychiatric diagnoses (p = .005) and a greater number of psychiatric medications prescribed (p < .001) in patients in Group II.ConclusionOur study suggests that ADHD is underrecognized and underdiagnosed in patients presenting to the EMU, and screening tools may be useful to help clinicians address seizure comorbidities such as ADHD.