bluuebunny/crossref_metadata_2025_split huggingface dataset:
Oriente no olhar de Camões
Authors: Nepomuceno Luís André 
Published: March 2023

Leitores de Camões têm observado que, para compor a matéria histórica de seu poema Os Lusíadas, o poeta se apega a uma suposta “verdade” que teria lido nas crônicas e ouvido na tradição oral. Os retratos da África e da Ásia que ele concebeu seriam fruto desse anseio pela “verdade” histórica. O presente artigo propõe, contrariamente, que Camões registrou uma verdade conveniente, atestada pelos interesses da nobreza da casa de Avis, compondo um retrato heroico da missão de Vasco da Gama, ao mesmo tempo em que omitiu práticas desumanas de seu projeto colonialista. Conhecendo de perto o jugo e a escravização dos povos africanos, o poeta ajustou a imagem da África e da Ásia à da figura do antagonista, evidenciando seu povo como gente inculta e inimiga da fé. Esse apagamento da história esconde o anseio de dominação sobre essa gente que se viu colonizada e escravizada nos séculos posteriores.
Estimation of Multiyear Consequences for Abortion Access in Georgia Under a Law Limiting Abortion to Early Pregnancy
Authors: Redd Sara K. , Mosley Elizabeth A. , Narasimhan Suba , Newton-Levinson Anna , AbiSamra Roula , Cwiak Carrie , Hall Kelli Stidham , Hartwig Sophie A. , Pringle Johanna , Rice Whitney S. 
Published: March 2023

ImportanceFollowing the US Supreme Court ruling in Dobbs v Jackson Women’s Health Organization, Georgia’s law limiting abortion to early pregnancy, House Bill 481 (HB481), was allowed to go into effect in July 2022.ObjectivesTo estimate anticipated multiyear effects of HB481, which prohibits abortions after detection of embryonic cardiac activity, on abortion incidence in Georgia, and to examine inequities by race, age, and socioeconomic status.Design, Setting, and ParticipantsThis repeated cross-sectional analysis used abortion surveillance data from January 1, 2007, to December 31, 2017, to estimate future effects of HB481 on abortion care in Georgia, with a focus on the 2 most recent years of data (2016 and 2017). Abortion surveillance data were obtained from the 2007-2017 Georgia Department of Public Health’s Induced Termination of Pregnancy files. Linear regression was used to estimate trends in abortions provided at less than 6 weeks’ gestation and at 6 weeks’ gestation or later in Georgia, and χ2 analyses were used to compare group differences by race, age, and educational attainment. Data were analyzed from July 26 to September 22, 2022.ExposuresHB481, Georgia’s law limiting abortion to early pregnancy.Main Outcome and MeasuresWeeks’ gestation at abortion (&amp;lt;6 vs ≥6 weeks).ResultsFrom January 1, 2007, to December 31, 2017, there were 360 972 reported abortions in Georgia, with an annual mean (SD) of 32 816 (1812) abortions. Estimates from 2016 to 2017 suggest that 3854 abortions in Georgia (11.6%) would likely meet eligibility requirements for abortion care under HB481. Fewer abortions obtained by Black patients (1943 [9.6%] vs 1280 [16.2%] for White patients), patients younger than 20 years (261 [9.1%] vs 168 [15.0%] for those 40 years and older), and patients with fewer years of education (392 [9.2%] with less than a high school diploma and 1065 [9.6%] with a high school diploma vs 2395 [13.5%] for those with some college) would likely meet eligibility requirements under HB481.Conclusions and RelevanceThese findings suggest that Georgia’s law limiting abortion to early pregnancy (HB481) would eliminate access to abortion for nearly 90% of patients in Georgia, and disproportionately harm patients who are Black, younger, and in lower socioeconomic status groups.
Selective de‐implementation of routine in vivo dosimetry
Authors: Mao Serena P. H. , Han‐Oh Sarah , Moore Joseph , Huang Ellen , McNutt Todd R. , Souranis Annette N. , Briner Valerie , Halthore Aditya , Alcorn Sarah R. , Meyer Jeffrey J. , Viswanathan Akila N. , Wright Jean L. 
Published: March 2023

AbstractAs cone‐beam computed tomography (CBCT) has become the localization method for a majority of cases, the indications for diode‐based confirmation of accurate patient set‐up and treatment are now limited and must be balanced between proper resource allocation and optimizing efficiency without compromising safety. We undertook a de‐implementation quality improvement project to discontinue routine diode use in non‐intensity modulated radiotherapy (IMRT) cases in favor of tailored selection of scenarios where diodes may be useful. After analysis of safety reports from the last 5 years, literature review, and stakeholder discussions, our safety and quality (SAQ) committee introduced a recommendation to limit diode use to specific scenarios in which in vivo verification may add value to standard quality assurance (QA) processes. To assess changes in patterns of use, we reviewed diode use by clinical indication 4 months prior and after the implementation of the revised policy, which includes use of diodes for: 3D conformal photon fields set up without CBCT; total body irradiation (TBI); electron beams; cardiac devices within 10 cm of the treatment field; and unique scenarios on a case‐by‐case basis. We identified 4459 prescriptions and 1038 unique instances of diode use across five clinical sites from 5/2021 to 1/2022. After implementation of the revised policy, we observed an overall decrease in diode use from 32% to 13.2%, with a precipitous drop in 3D cases utilizing CBCT (from 23.2% to 4%), while maintaining diode utilization in the 5 selected scenarios including 100% of TBI and electron cases. By identifying specific indications for diode use and creating a user‐friendly platform for case selection, we have successfully de‐implemented routine diode use in favor of a selective process that identifies cases where the diode is important for patient safety. In doing so, we have streamlined patient care and decreased cost without compromising patient safety.
Functionalized Carbon Dot‐Delivered RNA Nano Fungicides as Superior Tools to Control Phytophthora Pathogens through Plant RdRP1 Mediated Spray‐Induced Gene Silencing
Authors: Wang Zhiwen , Li Yu , Zhang Borui , Gao Xiang , Shi Mengru , Zhang Sicong , Zhong Shan , Zheng Yang , Liu Xili 
Published: March 2023

AbstractSpray‐induced gene silencing (SIGS) represents an attractive avenue for plant protection, but limited uptake efficiency of double‐stranded RNA (dsRNA) has restricted its application against the notorious oomycetes, Phytophthora. To control Phytophthora, dsRNAs targeting two essential genes in Phytophthora are screened for their ability to partially decrease Phytophthora capsici (P. capsici) infection and fecundity. To further facilitate SIGS for Phytophthora control, functionalized carbon dots (CDs) are complexed with the screened dsRNAs (dsRNA‐CDs) through electrostatic interaction. dsRNA‐CDs significantly enhanced the control efficacy of dsRNA against Phytophthora infestans, Phytophthora sojae, and both the wild‐type and fungicide‐resistant P. capsici. The synergism is based on enhancing dsRNA stability and internalization. Dual treatment with dsRNA‐CDs and the corresponding fungicide reduced the amount of fungicide required to achieve the same protective effect by 90%. Plant RdRP1 is the main effector in processing various lengths of small RNAs to induce translation inhibition in Phytophthora. Notably, here the first application of a nano‐delivery system to improve the effect of SIGS against Phytophthora pathogens is reported. Moreover, the elucidation of how CD facilitates dsRNA internalization in recipient cell and the molecular mechanism of SIGS can benefit the application of dsRNA‐CDs in other plant‐pathogen pathosystems through improving dsRNA bioactivity and reducing chemical fungicides application.
Illuminating Trap Density Trends in Amorphous Oxide Semiconductors with Ultrabroadband Photoconduction
Authors: Mattson George W. , Vogt Kyle T. , Wager John F. , Graham Matt W. 
Published: March 2023

AbstractUnder varying growth and device processing conditions, ultrabroadband photoconduction (UBPC) reveals strongly evolving trends in the defect density of states (DoS) for amorphous oxide semiconductor thin‐film transistors (TFTs). Spanning the wide bandgap of amorphous InGaZnOx(a‐IGZO), UBPC identifies seven oxygen deep donor vacancy peaks that are independently confirmed by energetically matching to photoluminescence emission peaks. The subgap DoS from 15 different types of a‐IGZO TFTs all yield similar DoS, except only back‐channel etch TFTs can have a deep acceptor peak seen at 2.2 eV below the conduction band mobility edge. This deep acceptor is likely a zinc vacancy, evidenced by trap density which becomes 5‐6× larger when TFT wet‐etch methods are employed. Certain DoS peaks are strongly enhanced for TFTs with active channel processing damage caused from plasma exposure. While Ar implantation and He plasma processing damage are similar, Ar plasma yields more disorder showing a ≈2 × larger valence‐band Urbach energy, and two orders of magnitude increase in the deep oxygen vacancy trap density. Changing the growth conditions of a‐IGZO also impacts the DoS, with zinc‐rich TFTs showing much poorer electrical performance compared to 1:1:1 molar ratio a‐IGZO TFTs owing to the former having a ∼10 × larger oxygen vacancy trap density. Finally, hydrogen is found to behave as a donor in amorphous indium tin gallium zinc oxide TFTs.
A Z‐Scheme Heterojunctional Photocatalyst Engineered with Spatially Separated Dual Redox Sites for Selective CO2 Reduction with Water: Insight by In Situ µs‐Transient Absorption Spectra
Authors: Sun Ling , Zhang Ziqing , Bian Ji , Bai Fuquan , Su Hengwei , Li Zhijun , Xie Jijia , Xu Rongping , Sun Jianhui , Bai Linlu , Chen Cailing , Han Yu , Tang Junwang , Jing Liqiang 
Published: March 2023

AbstractSolar‐driven CO2 reduction by water with a Z‐scheme heterojunction affords an avenue to access energy storage and to alleviate greenhouse gas (GHG) emissions, yet the separation of charge carriers and the integrative regulation of water oxidation and CO2 activation sites remain challenging. Here, a BiVO4/g‐C3N4 (BVO/CN) Z‐scheme heterojunction as such a prototype is constructed by spatially separated dual sites with CoOx clusters and imidazolium ionic liquids (IL) toward CO2 photoreduction. The optimized CoOx‐BVO/CN‐IL delivers an ≈80‐fold CO production rate without H2 evolution compared with urea‐C3N4 counterpart, together with nearly stoichiometric O2 gas produced. Experimental results and DFT calculations unveil the cascade Z‐scheme charge transfer and subsequently the prominent redox co‐catalysis by CoOx and IL for holes‐H2O oxidation and electrons‐CO2 reduction, respectively. Moreover, in situ µs‐transient absorption spectra clearly show the function of each cocatalyst and quantitatively reveal that the resulting CoOx‐BVO/CN‐IL reaches up to the electron transfer efficiency of 36.4% for CO2 reduction, far beyond those for BVO/CN (4.0%) and urea‐CN (0.8%), underlining an exceptional synergy of dual reaction sites engineering. This work provides deep insights and guidelines for the rational design of highly efficient Z‐scheme heterojunctions with precise redox catalytic sites toward solar fuel production.
Synthesis of 2,3‐disubstituted Benzofuran via HNTf2/TMSOTf Catalyzed Intermolecular Reaction of o‐alkenyl phenols and Aldehydes
Authors: Tan Jingyao , Wang Rui , Xu Li , Wu Wenli , Deng Meijia , Yuan Wanhong , Li Li , Lin Zhihua 
Published: March 2023

AbstractThe synthetic methods of 2,3‐disubstituted benzofurans have been widely studied, however, the maneuvers of using o‐alkenyl phenols as starting materials are less explored. Herein, we report a general and efficient strategy via HNTf2/TMSOTf catalyzed cascade reaction with readily available o‐alkenyl phenols and aldehydes as starting materials, which provides 2,3‐disubstituted benzofuran derivatives in moderate to good yields. This method features metal‐free circumstances, broad substrate scope, mild reaction conditions, and easy scale preparation.magnified image
Depilatory double‐disc mouse model for evaluation of vesicant dermal injury pharmacotherapy countermeasures
Authors: Roldan Tomas L. , Li Shike , Laskin Jeffrey D. , Gao Dayuan , Sinko Patrick J. 
Published: March 2023

AbstractBackgroundSulfur mustard (SM) is a chemical warfare vesicant that severely injures exposed eyes, lungs, and skin. Mechlorethamine hydrochloride (NM) is widely used as an SM surrogate. This study aimed to develop a depilatory double‐disc (DDD) NM skin burn model for investigating vesicant pharmacotherapy countermeasures.MethodsHair removal method (clipping only versus clipping followed by a depilatory), the effect of acetone in the vesicant administration vehicle, NM dose (0.5–20 μmol), vehicle volume (5–20 μl), and time course (0.5–21 days) were investigated using male and female CD‐1 mice. Edema, an indicator of burn response, was assessed by biopsy skin weight. The ideal NM dose to induce partial‐thickness burns was assessed by edema and histopathologic evaluation. The optimized DDD model was validated using an established reagent, NDH‐4338, a cyclooxygenase, inducible nitric oxide synthase, and acetylcholinesterase inhibitor prodrug.ResultsClipping/depilatory resulted in a 5‐fold higher skin edematous response and was highly reproducible (18‐fold lower %CV) compared to clipping alone. Acetone did not affect edema formation. Peak edema occurred 24–48 h after NM administration using optimized dosing methods and volume. Ideal partial‐thickness burns were achieved with 5 μmol of NM and responded to treatment with NDH‐4338. No differences in burn edematous responses were observed between males and females.ConclusionA highly reproducible and sensitive partial‐thickness skin burn model was developed for assessing vesicant pharmacotherapy countermeasures. This model provides clinically relevant wound severity and eliminates the need for organic solvents that induce changes to the skin barrier function.
Imaging Amyloid‐β Membrane Interactions: Ion‐Channel Pores and Lipid‐Bilayer Permeability in Alzheimer's Disease
Authors: Viles John H. 
Published: March 2023

AbstractThe accumulation of the amyloid‐β peptides (Aβ) is central to the development of Alzheimer's disease. The mechanism by which Aβ triggers a cascade of events that leads to dementia is a topic of intense investigation. Aβ self‐associates into a series of complex assemblies with different structural and biophysical properties. It is the interaction of these oligomeric, protofibril and fibrillar assemblies with lipid membranes, or with membrane receptors, that results in membrane permeability and loss of cellular homeostasis, a key event in Alzheimer's disease pathology. Aβ can have an array of impacts on lipid membranes, reports have included: a carpeting effect; a detergent effect; and Aβ ion‐channel pore formation. Recent advances imaging these interactions are providing a clearer picture of Aβ induced membrane disruption. Understanding the relationship between different Aβ structures and membrane permeability will inform therapeutics targeting Aβ cytotoxicity.
Multimodale Analyse lichtinduzierter Wasseroxidation in nanoporösen Blockcopolymer‐Membranen**
Authors: Kund Julian , Kruse Jan‐Hendrik , Gruber Andreas , Trentin Ivan , Langer Marcel , Read Clarissa , Neusser Gregor , Blaimer Dominik , Rupp Ulrich , Streb Carsten , Leopold Kerstin , Schacher Felix H. , Kranz Christine 
Published: March 2023

AbstractDie heterogene lichtgetriebene Katalyse ist ein Eckpfeiler nachhaltiger Energieumwandlung. Die meisten katalytischen Studien konzentrieren sich auf die Analyse von Wasserstoff und Sauerstoff, wobei in der Regel über die Gesamtantwort gemittelt wird, und somit eine Korrelation von Heterogenitäten der Matrix mit unterschiedlichen molekularen Aktivitäten limitiert ist. Hier berichten wir von Untersuchungen eines heterogenisierten Katalysator‐Photosensibilisator‐Systems, bei dem ein Polyoxometalat‐Katalysator zur Wasseroxidation und ein molekularer Modell‐Photosensibilisator gemeinsam in einer nanoporösen Blockcopolymer‐Membran immobilisiert wurden. Mittels elektrochemischer Rastersondenmikroskopie (SECM) wurde die lichtinduzierte Sauerstoffentwicklung mit Natriumperoxodisulfat (Na2S2O8) als Opferelektronenakzeptor an den modifizierten Blockcopolymer‐Membranen lokal bestimmt. Ex situ elementspezifische Analysen erzielten räumlich Informationen über die lokale Konzentration und Verteilung der molekularen Komponenten. Untersuchungen der modifizierten Membranen mittels abgeschwächter Infrarot‐Totalreflexion (IR‐ATR) zeigten keinen Abbau des Wasseroxidationskatalysators unter den beschriebenen lichtinduzierten Bedingungen.
Inverse CO2/C2H2 Separation with MFU‐4 and Selectivity Reversal via Postsynthetic Ligand Exchange
Authors: Liu Qiao , Cho Sung Gu , Hilliard Jordon , Wang Ting‐Yuan , Chien Szu‐Chia , Lin Li‐Chiang , Co Anne C. , Wade Casey R. 
Published: March 2023

AbstractAlthough many porous materials, including metal–organic frameworks (MOFs), have been reported to selectively adsorb C2H2 in C2H2/CO2 separation processes, CO2‐selective sorbents are much less common. Here, we report the remarkable performance of MFU‐4 (Zn5Cl4(bbta)3, bbta=benzo‐1,2,4,5‐bistriazolate) toward inverse CO2/C2H2 separation. The MOF facilitates kinetic separation of CO2 from C2H2, enabling the generation of high purity C2H2 (>98 %) with good productivity in dynamic breakthrough experiments. Adsorption kinetics measurements and computational studies show C2H2 is excluded from MFU‐4 by narrow pore windows formed by Zn−Cl groups. Postsynthetic F−/Cl− ligand exchange was used to synthesize an analogue (MFU‐4‐F) with expanded pore apertures, resulting in equilibrium C2H2/CO2 separation with reversed selectivity compared to MFU‐4. MFU‐4‐F also exhibits a remarkably high C2H2 adsorption capacity (6.7 mmol g−1), allowing fuel grade C2H2 (98 % purity) to be harvested from C2H2/CO2 mixtures by room temperature desorption.
Photokatalytische Ringöffnung von Methylencyclobutanen zur Synthese von γ,δ‐ungesättigten Aldehyden
Authors: Zhang Yan , Zhao Chunhang , Ma Chanchan , Cai Zhenzhi , Trienes Sven , Ackermann Lutz 
Published: March 2023

AbstractRadikalische Additionsreaktionen an Olefine haben sich als eine zunehmend leistungsfähige Strategie für die Synthese von difunktionalisierten Verbindungen entwickelt. Trotz signifikanter Fortschritte sind die bekannten Methoden weitgehend auf zwei Ansätze beschränkt, welche entweder die 1,2‐Difunktionalisierung von Alkenen oder die distale Funktionalisierung mittels Wasserstoffatomtransfer (HAT) verfolgen. In dieser Arbeit wird nun die photoinduzierte Kohlenstoff‐Kohlenstoff (C−C)‐Aktivierung/Ringöffnung als ein anderer Ansatz beschrieben, welcher Zugang zu γ,δ‐ungesättigten Aldehyden aus Methylencyclobutanolen und Sulfonylchloriden unter Freisetzung der Ringspannungsenergie ermöglicht. Bemerkenswerterweise konnte das Sulfonyl‐Motiv der erhaltenen Produkte durch einen weiteren photokatalytischen Prozess leicht entfernt werden, was den effizienten Aufbau des Naturprodukts Alatanon A ermöglichte. Die synthetische Anwendbarkeit unseres Ansatzes spiegelte sich außerdem in der hohen Toleranz gegenüber vielfältigen funktionellen Gruppen und damit großen Anwendungsbreite sowie der Skalierbarkeit der Reaktion wider. Die Photokatalyse stellt eine konzeptionell eigenständige Alternative zu bestehenden Ansätzen für die distale 1,4‐Difunktionalisierung dar, welche die Doppelbindung in den so erhaltenen Produkten beibehält.
Circumcoronenes
Authors: Zou Ya , Hou Xudong , Wei Haipeng , Shao Jiawei , Jiang Qing , Ren Longbin , Wu Jishan 
Published: March 2023

AbstractCircumcoronene, a hexagonal graphene fragment with six zigzag edges, has been the focus of theoretical studies for many years, but its synthesis in solution has remained a challenge. In this study, we present a facile method for synthesizing three derivatives of circumcoronene using Brønsted/Lewis acid‐mediated cyclization of vinyl ether or alkyne. Their structures were confirmed through X‐ray crystallographic analysis. Bond length analysis, NMR measurement, and theoretical calculations showed that circumcoronene mostly follows Clar's bonding model and exhibits dominant local aromaticity. Its absorption and emission spectra are similar to those of the smaller hexagonal coronene due to its six‐fold symmetry.
In Situ Synthesis of AIEgen‐based Porous Organic Polymer Films by Interfacial Amino‐yne Click Polymerization for Efficient Light‐Harvesting
Authors: Song Bo , Zhang Liang , Sun Jianwei , Lam Jacky W. Y. , Tang Ben Zhong 
Published: March 2023

AbstractWe developed a catalyst‐free, atom‐economical interfacial amino‐yne click polymerization to in situ synthesize new aggregation‐induced emission luminogen (AIEgen)‐based free‐standing porous organic polymer films at room temperature. The crystalline properties of POP films were confirmed by powder X‐ray diffraction and high‐resolution transmission electron microscopy. The good porosity of these POP films was proved by their N2uptake experiments. The thickness of POP films can be easily regulated from 16 nm to ≈1 μm by adjusting monomer concentration. More importantly, these AIEgen‐based POP films show bright luminescence with high absolute photoluminescent quantum yields up to 37.8 % and good chemical and thermal stability. The AIEgen‐based POP film can encapsulate an organic dye (e.g., Nile red) to further form an artificial light‐harvesting system with a large red‐shift (Δλ=141 nm), highly efficient energy‐transfer ability (ΦET=91 %), and high antenna effect (11.3).
Photocatalytic C−C Cleavage of Methylenecyclobutanes for γ,δ‐Unsaturated Aldehydes by Strain Release
Authors: Zhang Yan , Zhao Chunhang , Ma Chanchan , Cai Zhenzhi , Trienes Sven , Ackermann Lutz 
Published: March 2023

AbstractRadical additions onto olefins have surfaced as an increasingly powerful strategy for the synthesis of difunctionalized scaffolds. However, despite of major advances, known approaches continue to be largely limited to two manifolds, namely 1,2‐difunctionalization of alkenes and remote difunctionalization via hydrogen atom transfer (HAT). Herein, we describe a mechanistically distinct approach by photoinduced carbon‐carbon (C−C) activation/ring‐opening to access γ,δ‐unsaturated aldehydes from methylenecyclobutanols and sulfonyl chlorides by strain release. Remarkably, the sulfonyl motif on the products was easily removed by another photocatalytic process, which enabled the concise assembly of the natural product alatanone A. The synthetic utility of our approach was reflected by versatile functional group tolerance, ample substrate scope, and scalability. The photocatalysis represents a conceptually distinct alternative to existing approaches for remote 1,4‐diversifications, with a double bond remaining in the thus obtained products.
Selective Preparation of Phosphorus Mononitride (P≡N) from Phosphinoazide and Reversible Oxidation to Phosphinonitrene
Authors: Qian Weiyu , Wende Raffael C. , Schreiner Peter R. , Mardyukov Artur 
Published: March 2023

AbstractThe interstellar candidate phosphorus mononitride PN, a metastable species, was generated through high‐vacuum flash pyrolysis of (o‐phenyldioxyl)phosphinoazide in cryogenic matrices. Although the PN stretching band was not directly detected because of its low infrared intensity and possible overlaps with other strong bands, o‐benzoquinone, carbon monoxide, and cyclopentadienone as additional fragmentation products were clearly identified. Moreover, an elusive o‐benzoquinone‐PN complex formed when (o‐phenyldioxyl)phosphinoazide was exposed to UV irradiation at λ=254 nm. Its recombination to (o‐phenyldioxyl)‐λ5‐phosphinonitrile was observed upon irradiation with the light at λ=523 nm, which demonstrates for the first time the reactivity of PN towards an organic molecule. Energy profile computations at the B3LYP/def2‐TZVP density functional theory level reveal a concerted mechanism. To provide further evidence, UV/Vis spectra of the precursor and the irradiation products were recorded and agree well with time‐dependent DFT computations.