bluuebunny/crossref_metadata_2025 huggingface dataset:
Los ciclos de reforma educativa en América Latina: 1960, 1990 y 2000
Authors: Suasnábar Claudio
Published: January 2018

Este artículo focaliza su interés en los ciclos de reforma educativa en América Latina entendidos como los distintos intentos estatales de reestructurar los sistemas educativos latinoamericanos, así como también las tendencias de cambio reciente en el gobierno de la educación y las nuevas formas de regulación a nivel mundial y regional. En esa dirección, la primera parte del texto analiza las reformas educativas de 1960 y los signos de agotamiento del modelo fundacional de los sistemas. La segunda explora los cambios en la matriz socio-política y las reformas educativas desarrolladas durante la década de 1990. La tercera se concentra en el nuevo escenario regional de comienzos del siglo XXI y las principales innovaciones políticas que introducen las reformas educativas de la década de 2000. Hacia el final se presentan una serie de reflexiones que procuran esbozar algunas claves del escenario educativo regional de los próximos años.
RESEÑA de: Marc-Antoine Jullien de Paris (1817): Esbozo de una obra sobre educación comparada y series de preguntas sobre Educación. Edición y estudio introductorio de Luis Mª Naya Garmendia. (Madrid: Delta Publicaciones). ISBN: 978-84-163-8331-3
Authors: Matarranz María
Published: January 2018

---
Las poetas españolas contra la guerra del Vietnam
Authors: Neira Julio
Published: January 2018

Este artículo analiza la contribución de poetas a la antología "Con Vietnam", publicada por la también poeta Angelina Gatell en 1968. Se estudia el contexto de producción y se analizan los poetas de cada una de las 14 mujeres participantes en la antología. El estudio de cada uno de ellas se acompaña de una semblanza crítica y se indaga en los condicionantes históricos-sociales que determinan la valoración de la escritura femenina en el medio-siglo.
María Rosa Lida & Yakov Malkiel, Amor y filología. Correspondencias (1943-1948) [Reseña]
Authors: Conde Juan-Carlos
Published: January 2018

Reseña del mencionado libro.
Visuality in funeral solemnities of the Radvila (Radziwiłł) family in the 18th century
Authors: Paliušytė Aistė
Published: January 2018

The research is focused on the funeral solemnities of the Radvila (Radziwiłł) family, including those to which no proper attention has been paid so far in historiography. Attempts are made to reconstruct and evaluate the visuality of the Radvila’s funeral and compare it to the tradition of other nobility solemnities in the Grand Duchy of Lithuania.
The scenery of the Radvila solemnities changed according to the course and spatial context of the rituals. The most of attention was paid to arrangement of a solemn view in Nesvizh and its approaches. Emblems and other images were applied mostly in church interiors and catafalques. Heraldic motives, insignia were extensively applied, metaphoric and metonymic motives were integrated. Catafalque compositions resounded the virtues of the deceased, expressed their eminent background and status.
After studying the cases of funeral solemnities of the Radvila family, it can be stated that elements of military visualization were more important than it had been witnessed by earlier research. Such often applied military requisites expressed a connection to the nobility ethos of the Grand Duchy of Lithuania, a cultural image of a nobleman-warrior. The importance of the family memory motives in the funeral décor was also noticed. Although images related to a deceased person were used in the décor of solemnity, the general scope of the motives and their application principles reiterated and were in line with the visual rhetoric tradition of funerals in the Grand Duchy of Lithuania.
Although a lot of attention was paid to listing of the décor motives in funeral descriptions, not only their recognisability was considered important. The funeral rhetoric foresaw some visual experience for the viewer, which changed continuously while conducting funeral rituals. The authors of solemnity descriptions noticed and sometimes commented on effects of illumination, shapes and their spatial relations. Dynamic observation, change of a viewer’s position, focused viewing of separate details and the so-called saccadic viewing were foreseen for solemn events. In summary, it can be stated that the research of the Radvila family solemnities revealed the suggestibility of the Baroque culture that was based on a viewer’s visual experience.
Hostages of politics, or once again about the fate of collections of Vilnius Museum of Antiquities
Authors: Mulevičiūtė Jolita
Published: January 2018

After suppression of the Polish-Lithuanian uprising of 1863–1864, the government of the Russian Empire initiated political repressions in the territory of Lithuania. One of such repressive measures was the reorganisation of the Vilnius Museum of Antiquities, which resulted in the loss of its many valuable pieces, when in 1868 the major part of the collection significant to the local history was brought away to the Rumiancev Museum in Moscow. But after a few decades, the tsarist administration decided to get all historical artefacts back. The article provides a research on this unsuccessful attempt at restitution made in 1907–1910. It gives a possibility to trace a tactical turn from forced political methods of Russian ruling to “soft power” strategies based on cultural techniques.
At the beginning of the 20th century, the policy of the Russian Empire in its Western provinces obtained a new quality. According to historians, attempts were made to grow the Russian monarchic nation in the body of the empire and at the same time to respond to self-manifestation of different national groups as to an inevitable fact. This ostensible contradiction was solved by applying the “melting pot” principle. Earlier, the integration of western territories into the imperial structure was implemented by homogenization, i.e. when the cultural phenomena of other nations were simply appropriated (treated as being Russian), ignored or destroyed. Whereas at the beginning of the 20th century it was started to look for the unity in diversity, with the precondition for reshaping and neutralising of the diversity being its own heterogeneity.
While studying the example of the collection of the Vilnius Museum of Antiquities, we face exactly the case of diversity control. The analysis of the subject demonstrates how the historical legacy of other nations becomes incorporated into the Russian imperial body on the basis of treating them as powerless Others. In Western provinces, this direction of cultural appropriation was taken in 1872, after the cancellation of the martial law imposed during the uprising.
A relação de comercialização entre as unidades estaduais escolares urbanas de dourados e os produtores da agricultura familiar
Authors: Bernardo Luciana Virginia Mario , Farinha Maycon Jorge Ulisses Saraiva , Binotto Erlaine
Published: January 2018

A aquisição da merenda escolar em Mato Grosso do Sul, faz parte das obrigações dos gestores, a mesma tem orientação própria conforme lei federal, na qual, 30% dos recursos devem ser destinados a compra de produtores oriundos da agricultura familiar. Esta política pública destina-se a auxiliar a permanência dos indivíduos no ambiente rural e ao mesmo tempo, proporcionar que a educação básica tenha melhor alimentação em relação aos aspectos nutricionais. O objetivo do artigo é investigar a percepção das escolas estaduais urbanas da cidade de Dourados, estado de Mato Grosso do Sul, sobre o desenvolvimento do Programa de Alimentação Escolar (Pnae), como relação à comercialização. Para a coleta de dados, foram utilizados questionários estruturados, composto por questões abertas e fechadas, aplicadas a 76% das escolas estaduais urbanas. Foi possível identificar dificuldade na comercialização, devido a pouca procura dos produtores familiares no período de Chamada Pública, porém quando um agricultor familiar inicia as atividades de comercialização, tende a se manter uma constante, pois o mesmo atende as necessidades da escola e não há outros produtores que procuram as unidades escolares. Neste cenário, observam-se a necessidade da atuação dos órgãos públicos ou instituições de ensino que proporcionem capacitação aos agricultores familiares sobre práticas de comercialização.
Evaluating the Effectiveness of One-on-One Conversations to Increase Colorectal Cancer Screening in a Community-Based Clinical Setting
Authors: Fleming Tyler J. , Benitez Martha G. , Weintraub Miranda L. Ritterman
Published: January 2018

Context

The American Cancer Society's 80% by 2018 initiative aims to increase at-home colorectal cancer (CRC) screening.

Objective

To assess the effectiveness of one-on-one conversations with patients about CRC screening on compliance with at-home fecal immunochemical tests (FITs).

Setting

Federally funded health care center serving a largely minority, urban, underserved population in Vallejo, California.

Methods

Patients aged 50 to 75 years were divided into 3 main intervention arms: (1) patients who received a one-on-one in-person consultation to discuss the need for CRC screening and the screening process, as well as a FIT; (2) patients who received a telephone call to discuss the need for CRC screening and the screening process before receiving a FIT in the mail; and (3) patients who were mailed a FIT with a letter explaining the importance of completing the FIT and instructions. The FITs were tracked to see if they were returned to the laboratory for processing, and the rates of return were compared in bivariate analyses using t and χ2 tests and in adjusted analyses using logistic regression with bootstrapping.

Results

A total of 3415 patients were included in the study. One-on-one conversations either in person (OR, 24.63; 95% CI, 19.28-31.46) or via telephone (OR, 14.74; 95% CI, 10.96-19.82) were more effective at getting patients to complete the at-home CRC screening than not having one-on-one conversations before receiving the FIT.

Conclusion

Patients may be more likely to complete at-home FITs to screen for CRC if they are first able to discuss the need for screening and the screening process with a health care professional.
Nephroblastoma Arising in a Primary Testicular Teratoma in a Nonatrophic Testis of a 50-Year-Old Man
Authors: Kromka Joseph J. , Turner Kevin , Elisco Anthony , Hale Nathan
Published: January 2018

Extrarenal nephroblastoma is an extremely rare tumor thought to be related to teratoid tumors of germ cell origin. Because few cases have been reported, no standard method for categorizing and managing these tumors exists. To our knowledge, there have only been 3 adult cases of nephroblastoma arising in a germ cell tumor of testicular origin in a nonatrophic testis, all in men aged 19 to 22 years and with aggressive clinical courses. We report a case of nephroblastoma in a nonatrophic testis, with nephroblastoma being the only non–germ cell component, in an older patient and with a more indolent clinical course that was responsive to localized treatment.
Ontogeny reversal and phylogenetic analysis of Turritopsis sp.5 (Cnidaria, Hydrozoa, Oceaniidae), a possible new species endemic to Xiamen, China
Authors: Li Jun-yuan , Guo Dong-hui , Wu Peng-cheng , He Li-sheng
Published: January 2018

Ontogeny reversal, as seen in some cnidarians, is an unprecedented phenomenon in the animal kingdom involving reversal of the ordinary life cycle. Three species of Turritopsis have been shown to be capable of inverted metamorphosis, a process in which the pelagic medusa transforms back into a juvenile benthic polyp stage when faced with adverse conditions. Turritopsis sp.5 is a species of Turritopsis collected from Xiamen, China which presents a similar ability, being able to reverse its life cycle if injured by mechanical stress. Phylogenetic analysis based on both 16S rDNA and cytochrome c oxidase subunit I (COI) genetic barcodes shows that Turritopsis sp.5 is phylogenetically clustered in a clade separate from other species of Turritopsis. The genetic distance between T. sp.5 and the Japanese species T. sp.2 is the shortest, when measured by the Kimura 2-Parameter metric, and the distance to the New Zealand species T. rubra is the largest. An experimental assay on the induction of reverse development in this species was initiated by cutting medusae into upper and lower parts. We show, for the first time, that the two dissected parts have significantly different potentials to transform into polyps. Also, a series of morphological changes of the reversed life cycle can be recognised, including medusa stage, contraction stage I, contraction stage II, cyst, cyst with stolons, and polyp. The discovery of species capable of reverse ontogeny caused by unfavorable conditions adds to the available systems with which to study the cell types that contribute to the developmental reversal and the molecular mechanisms of the directional determination of ontogeny.
Cataracts Associated With Fibroblast Growth Factor Receptor Inhibitors for Cholangiocarcinoma
Authors: Kassaye Isabell , Alyafaie Adam , Zhang Karen , Lifton Jacob , Gordan John D. , Kelley Robin Kate , Yung Madeline
Published: October 2024

Importance

Since fibroblast growth factor receptor inhibitors (FGFRi) are used for treatment of intrahepatic cholangiocarcinoma (iCCA), understanding potential complications following longer-term use in clinical practice settings is warranted. This study describes cataract formation or progression as a complication of FGFRi use for the treatment of iCCA, even after treatment discontinuation.

Objective

To describe cases of cataract formation or worsening in patients with iCCA treated with FGFRi and to characterize the ophthalmologic features, risk factors, and outcomes for FGFRi-associated cataracts.

Design, Setting, and Participants

This retrospective case series study used data from patients with iCCA harboring FGFR2 aberrations who received FGFRi in clinical trials or as standard therapy from the University of California, San Francisco, Hepatobiliary Tissue Bank and Registry. Data were collected from patient visits between February 2015 and October 2021, and this retrospective investigation was conducted from September 6, 2022, to May 4, 2023. Data analysis was conducted from May 5, 2023, to September 6, 2023.

Exposure

Use of an FGFRi for the treatment of iCCA.

Main Outcomes and Measures

The primary outcome was designated as development of a new or worsening cataract after FGFRi initiation. Statistical analysis for the association between cataract formation and clinical covariates was performed using unpaired t tests and Fisher exact tests. A single bivariate logistic regression model was used to examine total duration of FGFRi therapy and age at the conclusion of FGFRi therapy as predictors of cataract development.

Results

A total of 18 patients were included in the study; median (range) patient age was 54 (27-81) years, and 13 patients (72%) were female. Nine patients (50%) developed a cataract or had cataract progression in at least 1 eye after initiation of FGFRi. Of 17 eyes with cataract, 8 eyes (47%) required cataract surgery. One patient rapidly developed a cataract associated with phacomorphic glaucoma, which required urgent surgery. The median (range) time to cataract onset or worsening from initiation of FGFRi was approximately 18 (1-23) months. Five of 9 patients (56%) who developed cataracts or had cataract progression were diagnosed with new or worsening cataracts after discontinuation of FGFRi. Patients who developed cataracts had longer median (range) duration of FGFRi treatment compared with patients who did not develop cataracts (13 months [2-26] vs 5 months [1-11]; odds ratio, 1.01; 95% CI, 1.00-1.02; P = .02).

Conclusions and Relevance

While this retrospective case series study cannot prove cause and effect conclusively due to the study design, study results highlight cataract formation or progression as a potential adverse effect of FGFRi therapy, supporting consideration of periodic eye examinations in patients who have received this treatment.
Dosimetric consequences of adapting the craniocaudal isocenter distance to daily patient position in craniospinal irradiation using volumetric modulated arc therapy
Authors: Heikkilä Annele , Vanhanen Antti , Rossi Maija , Koivumäki Tuomas , Postema Michiel , Boman Eeva
Published: October 2024

Purpose

In craniospinal irradiation, two or three isocenter groups along the craniocaudal axis are required to cover the long treatment target. Adapting the isocenter distance according to daily deviations in patient position is challenging because dosimetric hot or cold spots may occur in the field junction. The aim of this study was to quantify the effect of adapting the isocenter distance to patient position on the dose distribution of the field overlap region in craniospinal irradiation using partial‐arc volumetric modulated arc therapy.

Methods

The magnitude of isocenter distance deviations in craniocaudal direction was quantified by registering the setup images of 204 fractions of 12 patients to the planning images. The dosimetric effect of these deviations was determined by shifting the isocenters of the original treatment plan and calculating the resulting dose distribution.

Results

On fraction‐level, deviations larger than 3 mm caused more than 5 percentage point changes in the doses covering 2% (D2%) and 98% (D98%) of the junction volume in several patients. On treatment course‐level, the changes in D2% and D98% of the junction volume were less than 5 percentage points in all cases except for one patient.

Conclusions

Craniocaudal isocenter distance adaptation can be conducted provided that the mean isocenter distance deviation over the treatment course is within 3 mm.
Advances in Texturing and Thermoelectric Properties of a Calcium Cobaltite Ceramic via Combined Spark Plasma Sintering and Spark Plasma Texturing
Authors: Kruppa Katharina , Karlin Anat , Maor Itzhak I. , Steinbach Frank , Shter Gennady E. , Stobitzer Dorothea , Xie Wenjie , Weidenkaff Anke , Mann‐Lahav Meirav , Grader Gideon S. , Feldhoff Armin
Published: October 2024

Misfit‐layered calcium cobaltite [Ca2CoO3‐δ]0.62[CoO2] is an outstanding p‐type semiconducting thermoelectric with strong anisotropic properties. Texture engineering is crucial for enhancing its thermoelectric performance in polycrystalline ceramics. The in‐plane orientation of the grains improves the Seebeck coefficient and electrical conductivity, while the multi‐scale parallel interfaces scatter phonons and reduce thermal conductivity. Here, a tandem process of spark plasma sintering and edge‐free spark plasma texturing is used to produce dense and highly textured calcium cobaltite ceramics. The resulting ceramic shows a high degree of texturization, secondary phases, and enhanced electrical conductivity of 246 S cm−1 together with a strongly improved Seebeck coefficient of 224 µV K−1 at 1073 K. High grain ordering leads to carrier mobility of 0.49 cm2 V−1 s−1, which has a positive effect on both parameters. With a power factor of 12.4 µW cm−1 K−2 at 1073 K in air, previous thermoelectric performances of calcium cobaltite are surpassed, regardless of its form: pristine, doped, or composite. By combining the high power factor with a relatively low thermal conductivity, a remarkable figure‐of‐merit of 0.49 at 1073 K in air is obtained for the textured polycrystalline ceramic, which reaches 60 % of the figure‐of‐merit of a calcium cobaltite single crystal.
A Small Molecular Cathode for High‐Performance Calcium Metal Batteries
Authors: Ma Yiyuan , Qi Qi , Meng Qi , Yi Yuyang , Lin Huijun , Yu Jingya , Cheung Chi Fai , Xu Zheng‐Long
Published: October 2024

Calcium‐ion batteries are emerging as a promising alternative to lithium‐ion batteries by offering potential advantages in cost, affordability, and safety. However, the development of high‐performance calcium batteries has been hindered by the lack of high‐capacity cathodes. Here a small molecular organic cathode, 9,10‐phenanthrenequinone (PQ), is reported which leverages the rapid enolization chemistry of multi‐redox centers (C═O) and the flexible intermolecular structure for high performance. The PQ cathode demonstrates an impressive specific capacity of 250 mAh g−1 at 0.2 C for 200 cycles and superior rate capabilities. The robust performance of PQ cathodes is attributed to the mitigation of small molecule electrode dissolution in the weakly solvating ether electrolytes and the promotion of inter‐and intralayer Ca ion diffusion pathways, which synergistically facilitate the retention of high capacities at elevated current rates. When paired with a Ca metal anode, the full cell achieves remarkable capacities of 214 mAh g−1 at 0.2 C, with an average operating voltage of 2.5 V versus Ca/Ca2+, representing the highest performance among CMBs reported to date. The use of organic cathodes in tailored electrolytes with restricted intermediate dissolutions heralds a new era in the development of multivalent metal batteries.
“Back‐to‐Back” Radial Layered Skeleton Converging Heat Flow to Assist in Thermal Conduction of Aramid Nanofibers/Graphene Phase Change Composite Materials
Authors: Tong Jun , Liu Zhimeng , Liu Yang , Huang Xiubing , Wang Ge
Published: October 2024

Although optimizing the design of thermal conductive frameworks to promote the collection, transportation, and storage of thermal energy in composite phase change materials (CPCMs) is widely studied, the research on oriented layered thermal conductive frameworks is still in the exploratory stage. Taking inspiration from the bidirectional ice template strategy, a new research approach is proposed on the influence of “oriented micro‐unit” in thermal conductivity frameworks on the photothermal mass transfer of CPCMs. Three aramid nanofibers graphene nanosheets aerogels with different “oriented micro‐unit” structures are prepared by the high‐energy ball milling and bidirectional freezing. The enthalpy values of the composite materials are within the range of 146–152 J g−1. Photothermal conversion experiments, hot plate mass transfer experiments, solar‐thermal‐electric energy conversion experiments and multi‐physics field simulation analysis jointly show that the CPCMs with a “back‐to‐back” radial layered structure behaves the most outstanding photothermal conversion ability and heat transfer performance, with an increase in thermal conductivity of 173.3%, a photothermal conversion efficiency of 91.9%, and the maximum solar‐thermal‐electric output voltage of 303.3 mV. The design of “oriented micro‐unit” opens up new ideas for CPCMs in the field where directional heat transfer is required.
Humanized In Vivo Bone Tissue Engineering: In Vitro Preculture Conditions Control the Structural, Cellular, and Matrix Composition of Humanized Bone Organs
Authors: Bessot Agathe , Medeiros Savi Flavia , Gunter Jennifer , Mendhi Jayanti , Amini Shahrouz , Waugh David , McGovern Jacqui , Hutmacher Dietmar W. , Bock Nathalie
Published: October 2024

Bone tissue engineering (BTE) has long sought to elucidate the key factors controlling human/humanized bone formation for regenerative medicine and disease modeling applications, yet with no definitive answers due to the high number and co‐dependency of parameters. This study aims to clarify the relative impacts of in vitro biomimetic ‘preculture composition’ and ‘preculture duration’ before in vivo implantation as key criteria for the optimization of BTE design. These parameters are directly related to in vitro osteogenic differentiation (OD) and mineralization and are being investigated across different osteoprogenitor‐loaded biomaterials, specifically fibrous calcium phosphate‐polycaprolactone (CaP‐mPCL) scaffolds and gelatin methacryloyl (GelMA) hydrogels. The results show that OD and mineralization levels prior to implantation, enhanced by a mineralization medium supplement to the osteogenic medium (OM), significantly improve ectopic BTE outcomes, regardless of the biomaterial type. Specifically, preculture conditions are pivotal in achieving more faithful mimicry of human bone structure, cellular and extracellular matrix composition and organization, and provide control over bone marrow composition. This work emphasizes the potential of using biomimetic culture compositions, specifically the addition of a mineralization medium as a cost‐effective and straightforward approach to enhance BTE outcomes, facilitating rapid development of bone models with superior quality and resemblance to native bone.
Synthetic Periodontal Guided Tissue Regeneration Membrane with Self‐Assembling Biphasic Structure and Temperature‐Sensitive Shape Maintenance
Authors: Swanson W. Benton , Woodbury Seth M. , Dal‐Fabbro Renan , Douglas Lindsey , Albright Jackson , Eberle Miranda , Niemann David , Xu Jinping , Bottino Marco C. , Mishina Yuji
Published: October 2024

Periodontal disease poses significant challenges to the long‐term stability of oral health by destroying the supporting structures of teeth. Guided tissue regeneration techniques, particularly barrier membranes, enable local regeneration by providing an isolated, protected compartment for osseous wound healing while excluding epithelial tissue. Here, this study reports on a thermosensitive periodontal membrane (TSPM) technology designed to overcome the mechanical limitations of current membranes through a semi‐interpenetrating network of high molecular weight poly(L‐lactic acid) (PLLA) and in situ‐polymerized mesh of poly(ε‐caprolactone)diacrylate (PCL‐DA), and poly lactide‐co‐glycolide diacrylate (PLGA‐DA). An optimized composition allows facile reshaping at greater than 52 °C and rigid shape maintenance at physiological temperature. Its unique bilayer morphology is achieved through self‐assembly and thermally‐induced phase separation, resulting in distinct yet continuous smooth and nanofibrous compartments adequate for epithelial occlusion and regeneration. Incorporating PLGA‐DA enhances the membrane's hydrophilicity and degradation properties, facilitating a more rapid and controlled degradation and therapeutic delivery. This study demonstrates its ability to promote local regeneration by serving as a barrier membrane and simultaneously as a scaffolding matrix in a rat orthotopic periodontal defect model. The TSPM outperformed a clinically available material (Epi‐Guide) to facilitate robust alveolar bone and periodontal ligament regeneration at 4 and 8 weeks.
Spatially Precise Light‐Activated Dedoping in Wafer‐Scale MoS2 Films
Authors: Ghoshal Debjit , Paul Goutam , Sagar Srikrishna , Shank Cole , Hurley Lauren A. , Hooper Nina , Tan Jeiwan , Burns Kory , Hachtel Jordan A. , Ferguson Andrew J. , Blackburn Jeffrey L. , Lagemaat Jao van de , Miller Elisa M.
Published: October 2024

2D materials, particularly transition metal dichalcogenides (TMDCs), have shown great potential for microelectronics and optoelectronics. However, a major challenge in commercializing these materials is the inability to control their doping at a wafer scale with high spatial fidelity. Interface chemistry is used with the underlying substrate oxide and concomitant exposure to visible light in ambient conditions for photo‐dedoping wafer scale MoS2. It is hypothesized that the oxide layer traps photoexcited holes, leaving behind long‐lived electrons that become available for surface reactions with ambient air at sulfur vacancies (defect sites) resulting in dedoping. Additionally, high fidelity spatial control is showcased over the dedoping process, by laser writing, and fine control achieved over the degree of doping by modulating the illumination time and power density. This localized change in MoS2 doping density is very stable (at least 7 days) and robust to processing conditions like high temperature and vacuum. The scalability and ease of implementation of this approach can address one of the major issues preventing the “Lab to Fab” transition of 2D materials and facilitate its seamless integration for commercial applications in multi‐logic devices, inverters, and other optoelectronic devices.
Metal‐Free Benzothioxanthene Imide Based Dyes for Organic Light‐Emitting Electrochemical Cells
Authors: Leong Kwang Keat , Kim Hee Jung , Morice Korentin , Josse Pierre , Puchán Sánchez Darío , Kim Jinbo , Auh Yanghyun , Kim Donghwan , Blanchard Philippe , Monnereau Cyrille , Cabanetos Clément , Kim Eunkyoung
Published: October 2024

Two synthetic organic dyes of the Benzothioxanthene imide (BTI) family are explored as a promising electroactive material for organic light‐emitting electrochemical cells (LECs). The high thermal stability and ease of thin film processing make BTI‐based compounds suitable for these devices. However, their planar π‐conjugated structure often leads to aggregation‐caused quenching (ACQ), reducing luminescence in the solid state. To overcome this, this study has taken advantage of host‐guest interactions with 4,4′‐bis(9H‐carbazol‐9‐yl) biphenyl (p‐CBP), poly(9‐vinylcarbazole) (PVK), and poly(dioctylfluorene) (PFO) to suppress ACQ. The use of p‐CBP improved the internal electrical double layer (EDL) alignment within the film, resulting in higher luminescence compared to PFO and PVK‐based LECs. The BTI‐F dye, when incorporated into a dual host system with p‐CBP and PFO, achieved an impressive luminescence of up to 3900 cd m−2. Additionally, PFO enhanced charge balance, contributing to a blue shift in maximum absorption wavelength and increasing the device's tolerance. A triple‐host system (p‐CBP, PVK, PFO) further extended the device's half‐life (t1/2) to 54 min, demonstrating the potential of these host‐guest systems in advancing metal‐free LEC technology.
The Role of Host Material in the Design of Ratiometric Optical Density Meters Based on Cr3+ Luminescence in Y3Al5‐xGaxO12:Cr3+
Authors: Jaśkielewicz Julia , Szymczak Maja , Zeler Justyna , Marciniak Lukasz
Published: October 2024

The skillful combination of luminescent thermometry and optical heating has enabled the development of luminescent optical density meters. However, developing such sensing materials with predefined sensing performance requires an understanding of which material parameters play a dominant role in the optical response of the system. In this study, a systematic investigation is conducted on the influence of host material composition and crystal field strength affecting the Cr3+ ions on the sensing performance of the ratiometric optical density meter based on the 2E→4A2 to 4T2→4A2 luminescence intensity ratio (LIR) in Y3Al5‐xGaxO12:Cr3+. As shown, the LIR reveals thermal variation according to the Boltzmann distribution in these materials over the 160 to 500 K range. However, at higher temperatures, monotonic changes in LIR are still observed. This has enabled the development of optical density meters with high sensitivity, operating over a wide range of power densities (<5500 W cm−2). The maximum sensitivity is found for Y3Al3Ga2O12:Cr3+, reaching 0.086% W−1 cm2 at 2 W cm−2, which is the highest value reported to date among all ratiometric Cr3+‐based optical density meters. It is demonstrated that a strong crystal field favorably influences the thermal sensitivity of the analyzed systems, thereby achieving high sensitivity in the low optical power density range (<1000 W cm−2). However, it also limits the operating range of the sensing material. Conversely, to extend the operating range of the optical density meter, materials with intermediate or low crystal field strengths are preferred.
Super‐Absorber, Super‐Bright, Nearly‐Non‐Blinking CsPbI3 Perovskite Nanocrystal
Authors: Mukherjee Soumen , Ghosh Swarnali , Ghosal Mainak , Dey Sourav , Mandal Saptarshi , De Chayan K. , Debnath Rahul , Karmakar Manobina , Karmakar Ayon Jyoti , Datta Prasanta K. , Mandal Prasun K.
Published: October 2024

Gigantic magnitude of molar extinction coefficient (ɛ) (≈2 × 108 m−1 cm−1) and PLQY (0.98) through Zn‐alloying and surface‐passivating ligand variation, make the CsPbI3 based perovskite nanocrystal (PNC) the most super‐absorbing and most super‐bright among quantum dot‐PNC family. Radiative rate got enhanced 9 times and non‐radiative rate decreased 13 times. Moreover, very high (detrapping rate/trapping rate) of electron and 90% peak of ON fraction make this PNC a nearly‐non‐blinking one. Ultrafast and comparatively shorter hot exciton/electron cooling time (536 fs) and hot exciton/electron trapping time (516 fs) can explain why this PNC exhibits hitherto unobserved excellent optical properties.
Cocktail Polyplexes With Synchronous Flightless I siRNA and Nitric Oxide Release for Potential Chronic Wound Healing
Authors: Kharaziha Mahshid , Salehi Sahar , Scheibel Thomas
Published: October 2024

Chronic wounds are one of the health challenges threatening human life. In these wounds, overexpression of some types of cytoskeletal actin‐remodeling proteins including Flightless I (Flii) can often lead to severe skin scarring. Herein, arginine functionalized poly(β‐amino ester)s are synthesized to develop polyplexes with alginate for delivery of Flii siRNA. This approach results in forming polyplexes with distinct features, such as tunable zeta potential, particle size, polydispersity, and arginine conjugation level. It is demonstrated that the uptake of arginine functionalized poly(β‐amino ester)/alginate particles is composition‐dependent for various cell types including J774.1 macrophages and BJ fibroblasts. Such polyplexes trigger nitric oxide release by macrophages enhancing the expression of anti‐inflammatory genes while diminishing the expression of pro‐inflammatory markers and demonstrating its immunomodulatory properties. Flii siRNA loaded particles provide condensed siRNA into the core‐shell polyplex and exhibit controlled release of Flii siRNA over 24 h. The uptake rate of this polyplex by macrophages and fibroblasts is higher than that of a commercial gene carrier (Lipofectamine 2000), knocking down the in vitro Flii gene expression (1.3‐fold). The increased BJ fibroblast proliferation and higher expression of collagen I (COL I) show the suitability of these polyplexes for wound healing.
Covalent Carbide Interconnects Enable Robust Interfaces and Thin SEI for Graphite Anode Stability under Extreme Fast Charging
Authors: Rangom Yverick , Sherepenko Oleksii , Shafiee Ahad , Cholewinski Alek , Gundegowda Kalligowdanadoddi Kiran , Bastug Azer Bersu , Jafarzadeh Parisa , Zhao Boxin , Biro Elliot , Kleinke Holger , Pope Michael A.
Published: October 2024

Carbonaceous and carbon‐coated electrodes are ubiquitous in electrochemical energy storage and conversion technologies due to their electrochemical stability, lightweight nature, and relatively low cost. However, traditional reliance on conductive additives and binders leads to impermanent electrical pathways. Here, a general approach is presented to fabricate robust electrodes with a progressive failure mechanism by introducing carbide‐based interconnects grown via carbothermal conversion of (5 wt%) titanium hydride nanoparticles. This method concurrently enhances both electrical and mechanical properties within the electrode architecture. The resulting chemical bonding between active materials establishes a novel mechanism to maintain stable electrical pathways during cycling. Employed as Li‐ion battery anodes, these electrodes exhibit improved cyclability, achieving 80% capacity retention after 800 fast‐charge cycles at moderate loading (1 mAh cm−2). High loading cells with areal capacity of 3 mAh cm−2 show significantly improved cycle life over the same number of cycles. This performance improvement is attributed to the absence of significant impedance growth and a thinner solid electrolyte interphase (SEI) layer formed at high current densities (4C) as demonstrated by X‐ray photoelectron spectroscopy and transmission electron microscopy studies. The enhanced conductivity facilitates SEI formation, lowering ionic impedance and mitigating lithium plating, ultimately leading to the reported extended cycle life.
Regulating Chlorine and Hydrogen Atom Transfer for Selective Photoelectrochemical C─C Coupling by Cu‐coordination Effect at Semiconductor/Electrolyte Interfaces
Authors: Li Qiaozhen , Dang Kun , Wu Lei , Liu Siqin , Zhang Yuchao , Zhao Jincai
Published: October 2024

Semiconductor‐based photoelectrochemical (PEC) organic transformations usually show radical characteristics, in which the reaction selectivity is often difficult to precisely control due to the nonselectivity of radicals. Accordingly, several simple organic reactions (e.g., oxidations of alcohols, aldehydes, and other small molecules) have been widely studied, while more complicated processes like C─C coupling remain challenging. Herein, a synergistic heterogeneous/homogeneous PEC strategy is developed to achieve a controllable radical‐induced C─C coupling reaction mediated by the copper‐coordination effect at the semiconductor/electrolyte interfaces, which additionally exerts a significant impact on the product regioselectivity. Through experimental studies and theoretical simulations, this study reveals that the copper‐chloride complex effectively regulates the formation of chloride radicals, a typical hydrogen atom transfer agent, on semiconductor surfaces and stabilizes the heterogeneous interfaces by suppressing the radical‐induced surface passivation. Taking the Minisci reaction (the coupling between 2‐phenylquinoline and cyclohexane) as a model, the yield of the target C─C coupling product reaches up to 90% on TiO2 photoanodes with a selectivity of 95% and long‐term stability over 100 h. Moreover, such a strategy exhibits a broad scope and can be used for the functionalization of various heteroaromatic hydrocarbons.
Optimized Preparation and Potential Range for Spinel Lithium Titanate Anode for High‐Rate Performance Lithium‐Ion Batteries
Authors: Haghipour Amir , Arnold Stefanie , Oehm Jonas , Schmidt Dominik , Gonzalez‐Garcia Lola , Nakamura Hitoshi , Kraus Tobias , Knoblauch Volker , Presser Volker
Published: October 2024

The significant demand for energy storage systems has spurred innovative designs and extensive research on lithium‐ion batteries (LIBs). To that end, an in‐depth examination of utilized materials and relevant methods in conjunction with comparing electrochemical mechanisms is required. Lithium titanate (LTO) anode materials have received substantial interest in high‐performance LIBs for numerous applications. Nevertheless, LTO is limited due to capacity fading at high rates, especially in the extended potential range of 0.01–3.00 V versus Li+/Li, while delivering the theoretical capacity of 293 mAh g−1. This study demonstrates how the performance of the LTO anode can be improved by modifying the manufacturing process. Altering the dry and wet mixing duration and speeds throughout the manufacturing process leads to differences in particle sizes and homogeneity of dispersion and structure. The optimized anode at 5 A g−1 (≈17C) and 10 A g−1 (≈34C) yielded 188 and 153 mAh g−1 and retained 73% and 68% of their initial capacity after 1000 cycles, respectively. The following findings offer valuable information regarding the empirical modifications required during electrode fabrication. Additionally, it sheds light on the potential to produce efficient anodes using commercial LTO powder.
Self‐assembled small molecule spherulites under mild conditions: High solid‐state quantum yield and unique interconnected structural and fluorescent colors
Authors: Li Cheng , Arteaga Oriol , Ehlers Florian , Krüsmann Marcel , Sun Bianjing , Poisson Jade , Karg Matthias , Vana Philipp , Zhang Kai
Published: October 2024

Spherulites are generally fabricated from cooling polymer melts, while their fabrication under mild conditions or from small molecule materials has been barely reported. Besides, organic luminescent molecules typically suffer from low quantum yields in a solid state. Moreover, preparing material with interconnected and simultaneous changes in structural and fluorescent colors is challenging. Here, we present the first solution‐derived spherulites with unique interconnected structural and fluorescent colors, self‐assembled from stearoylated monosaccharides at room temperature. D‐galactose stearoyl ester self‐assembled into banded spherulites, containing twisted nanoplates and interconnected simultaneously changing structural and fluorescent colors. In comparison, D‐mannose stearoyl ester can only form non‐banded spherulites, which contain oriented nanoplates and uniform structural and fluorescent colors. Such materials revealed a novel negative correlation between fluorescence and birefringence, termed alignment‐promoted quenching propensity. Remarkably, the solid‐state fluorescence quantum yields of galactose and mannose‐derived spherulites are as high as 49 ± 2% and 51 ± 2% respectively, approximately ten times higher than those of unmodified monosaccharides. These quantum yield values are among the highest of reported organic nonconventional fluorophores and even comparable to those of conventional aromatic chromophores. Moreover, these spherulites manifested an unexpected excitation‐dependent multicolor photoluminescence with a broad‐spectrum emission (410−620 nm). They show multiple peaks in the photoluminescent emission spectra and broad fluorescence lifetime distributions, which should be attributed to the clustering of a variety of oxygen‐containing functional groups as emissive moieties.
Mechanical Ventilator Settings Estimation From an AI Model
Authors: Moghadam Ali , Pidaparti Ramana M.
Published: October 2024

Mechanical ventilation (MV) is used in subjects with respiratory problems for assistance in breathing. Various MV settings are adjusted at the clinician's discretion based on the patient's respiratory condition. In this study, an AI (artificial intelligence) model using artificial neural networks (ANNs) along with Bayesian Optimization (BO) was developed to estimate the desired MV settings for various subject scenarios. The ANN model with two hidden layers was trained with experimental data collected from subjects (canines and felines) in our previous work. Inverse mapping of the trained ANNs was conducted using BO to predict the acceptable MV settings for specific subject outcomes. Our results suggest that the model can support veterinarians in estimating the proper MV parameters for optimal subject outcome.
SOS1‐Related Noonan Syndrome and Sudden Cardiac Arrest in the Absence of Cardiomyopathy—An Arrhythmia Phenotype?
Authors: Cirelli Michael A. , Wackel Philip , Javed Rabia , Gavrilova Ralitza , Qureshi M. Yasir , Dearani Joseph A. , Boucher Lauren M. , Niaz Talha
Published: October 2024

Noonan syndrome (NS) is a predominantly autosomal dominant condition with various cardiac and extra‐cardiac manifestations. Although it has been linked with atrial arrhythmias, ventricular arrhythmias are extremely rare in the absence of underlying structural cardiac abnormalities. We report an instance of aborted sudden cardiac arrest in a 7‐year‐old male with a confirmed SOS1 variant and a lack of evidence to support a structural cardiac, metabolic, or infectious etiology. This is the second reported instance of sudden cardiac arrest related to ventricular fibrillation in a child with SOS1‐related NS in the absence of any structural cardiac defects. Although no definitive correlation can be ascertained from a limited existing body of knowledge surrounding SOS1 and ventricular fibrillation unrelated to structural heart defects, it provokes the idea of an arrhythmia phenotype and future research is warranted to guide proper clinical treatment, monitoring, and management of such individuals.
Ruthenium Catalysed Transfer Deuteration of Heteroaromatics in D2O
Authors: Gonzalo‐Navarro Carlos , Ruiz‐Castañeda Margarita , Fidalgo Jairo , Espino Gustavo , Jalón Félix A. , Manzano Blanca R.
Published: October 2024

There is a growing interest in deuterated derivatives in various fields, including the pharmaceutical industry. In this industry, partially hydrogenated heterocycles are also a target. Combining these two concepts, it was studied the reduction of heterocycles with simultaneous deuterium incorporation by transfer deuteration, a process of introducing two deuterium atoms into an organic molecule using non‐D2 sources, avoiding the use of a gas or harmful reagents. Formic acid/sodium formate and D2O as the sole deuterium source were used under mild conditions. The precatalyst was [RuCl(p‐cym)(dmbpy)]BF4, (p‐cym=p‐cymene, dmbpy=4,4’‐dimethyl‐2,2’‐bipyridine), which is able to generate the “Ru−D” fragment from D+ by a polarity inversion process (“umpolung”). A wide range of heterocycles were tested. Selective reduction in the nitrogen‐containing ring with deuterium incorporation into the same ring was achieved. The experiments were carried out in a biphasic D2O/toluene medium, which allowed excellent catalyst recycling with a simple work‐up. Through detailed studies for 3‐methylquinoline using DCOOD/DCOONa, the reaction mechanism that involves D+ incorporation at the nitrogen atom and an initial 1,2‐type addition was elucidated. In single‐phase D2O experiments, a distinct selectivity with deuterium incorporation in the non‐hydrogenated ring was observed thus enabling to modulate it by the choice of the medium.
Associations of semaglutide with first‐time diagnosis of Alzheimer's disease in patients with type 2 diabetes: Target trial emulation using nationwide real‐world data in the US
Authors: Wang William , Wang QuangQiu , Qi Xin , Gurney Mark , Perry George , Volkow Nora D. , Davis Pamela B. , Kaelber David C. , Xu Rong
Published: October 2024

INTRODUCTION

Emerging preclinical evidence suggests that semaglutide, a glucagon‐like peptide receptor agonist (GLP‐1RA) for type 2 diabetes mellitus (T2DM) and obesity, protects against neurodegeneration and neuroinflammation. However, real‐world evidence for its ability to protect against Alzheimer's disease (AD) is lacking.

METHODS

We conducted emulation target trials based on a nationwide database of electronic health records (EHRs) of 116 million US patients. Seven target trials were emulated among 1,094,761 eligible patients with T2DM who had no prior AD diagnosis by comparing semaglutide with seven other antidiabetic medications. First‐ever diagnosis of AD occurred within a 3‐year follow‐up period and was examined using Cox proportional hazards and Kaplan–Meier survival analyses.

RESULTS

Semaglutide was associated with significantly reduced risk for first‐time AD diagnosis, most strongly compared with insulin (hazard ratio [HR], 0.33 [95% CI: 0.21 to 0.51]) and most weakly compared with other GLP‐1RAs (HR, 0.59 [95% CI: 0.37 to 0.95]). Similar results were seen across obesity status, gender, and age groups.

DISCUSSION

These findings support further studies to assess semaglutide's potential in preventing AD.

Highlights

Semaglutide was associated with 40% to 70% reduced risks of first‐time AD diagnosis in T2DM patients compared to other antidiabetic medications, including other GLP‐1RAs.

Semaglutide was associated with significantly lower AD‐related medication prescriptions.

Similar reductions were seen across obesity status, gender, and age groups.

Our findings provide real‐world evidence supporting the potential clinical benefits of semaglutide in mitigating AD initiation and development in patients with T2DM.

These findings support further clinical trials to assess semaglutide's potential in delaying or preventing AD.