bluuebunny/crossref_metadata_2025 huggingface dataset:
Is Mercosur promoting trade? Insights from Argentinean wine exports
Authors: Dal Bianco Andrea , Estrella-Orrego Maria J. , Boatto Vasco L. , Gennari Alejandro J.
Published: April 2017

As a consequence of the rapid and significative decrease in domestic demand, to avoid structural surplus traditional wine producing countries have been forced to export a growing share of their wine production. This article empirically investigates Argentinean trade policy on the wine sector over the last years, in order to understand its effect on export flows. An expanded gravity model was estimated through a Poisson pseudo-maximum likelihood estimator, in order to account for heteroskedasticity. The data used refer to Argentinean exports of bottled wine to all main world importers during the period 1997-2010, and account for more than 90% of total trade flows. Our results show that Mercosur membership has promoted Argentinean wine exports to other Latin American countries, but may as a whole have been counter-productive. A more open trade policy could increase Argentinean bottled wine exports by more than 5.8%. In addition, given the rise in wine importation and consumption in countries with high tariff barriers, such as China, the small number of free trade agreements could penalize Argentinean exports even more in the future.
Risk factors associated with honey bee colony loss in apiaries in Galicia, NW Spain
Authors: Meana Aranzazu , Llorens-Picher Miguel , Euba Amaia , Bernal José L. , Bernal José , García-Chao María , Dagnac Tierry , Castro-Hermida Jose A. , Gonzalez-Porto Amelia V. , Higes Mariano , Martín-Hernández Raquel
Published: April 2017

A cross-sectional study was carried out in Galicia, NW Spain, in order to estimate the magnitude of honey bee colony losses and to identify potential risk factors involved. A total of 99 samples from 99 apiaries were collected in spring using simple random sampling. According to international guidelines, the apiaries were classified as affected by colony loss or asymptomatic. Each sample consisted of worker bees, brood and comb-stored pollen. All worker bees and brood samples were analysed individually in order to detect the main honey bee pathogens. Moreover, the presence of residues of the most prevalent agrotoxic insecticides and acaricides was assessed in comb-stored pollen. The general characteristics of the apiaries and sanitary information regarding previous years was evaluated through questionnaires, while the vegetation surrounding the apiaries sampled was assessed by palynological analysis of comb-stored pollen. The colony loss prevalence was 53.5% (CI95%=43.2-63.9) and Nosema ceranae was found to be the only risk factor strongly associated with colony loss. The decision tree also pointed out the impact of the Varroa mite presence while variables such as apiary size, the incorrect application of Varroa mite treatments, and the presence of Acarapis woodi and Kashmir bee virus (KBV) were identified as possible co-factors.
School Governance, Accountability and Performance Management
Authors: Salvioni Daniela M. , Cassano Raffaella
Published: April 2017

Limited resources, recent reforms of educational system that impose rapid changes in the governance system, high demand for managerial skill and operational autonomy, impose the capability to optimize performance, transparency of behaviour, dialogue with stakeholder to grow results in the school system. It therefore draws attention to the importance of activate long-term positive relations between schools, students, families, governmental authority and other structures of public Administration to improve quality and performance in school management. So is critical an effectiveness accountability system as starting point to develop the quality of relations between the schools and their stakeholders. In this regard, this article proposes the Network Governance as lever to improve an effectiveness stakeholder engagement and to optimize performance in the School System. This study represents a dissertation that aims to raise awareness about the cycle of performance management in schools and for the optimization of the use of public resources.
Simultaneous Analysis of Simple Coumarins and Furocoumarines in Cigarettes by Solid-Phase Extraction with Gas Chromatography-Mass Spectrometry
Authors: Zheng Yang , Xu Xiuli , Yuan Fei , Yao Meiyi , Ji Shunli , Huang Zhiqiang , Zhang Feng
Published: April 2017

A sensitive, high-throughput analytical method based on a GC-MS method was established for the simultaneous quantitative determination of two categories of harmful coumarins: simple coumarins (coumarin, 6-methylcoumarin, 7-methoxycoumarin, 3,4-dihydrocoumarin, and 7-ethoxy-4-methylcoumarin) and furocoumarines (psoralen, 8-methoxypsoralen, 5-methoxypsoralen, and trioxysalen). The nine analytes were extracted with ethyl acetate, purified with Oasis HLB solid-phase extraction (SPE) cartridges, and identified and quantitatively determined by GC-MS in selected-ion monitoring mode. The LODs and LOQs of these compounds were in the ranges of 12.5–21.2 and 41.6–70.0 μg/kg, respectively. Average recoveries for the nine analytes ranged from 72.7 to 86.6% atLOQ, 1.5× LOQ, and 2× LOQ spike levels, with RSDs that were typically lower than 5.1%. TheSPE-GC-MS method developed in this study was initially applied to research coumarins in cigarette samples; it proved to be accurate, sensitive, convenient, and practical.
Development and Single-Laboratory Validation of a Liquid Chromatography Tandem Mass Spectrometry Method for Quantitation of Tetrodotoxin in Mussels and Oysters
Authors: Turner Andrew D , Boundy Michael J , Rapkova Monika Dhanji
Published: April 2017

In recent years, evidence has grown for the presence of tetrodotoxin (TTX) in bivalve mollusks, leading to the potential for consumers of contaminated products to be affected by Tetrodotoxin Shellfish Poisoning (TSP). A single-laboratory validation was conducted for the hydrophilic interaction LC (HILIC) tandem MS (MS/MS) analysis of TTX in common mussels andPacific oysters—the bivalve species that havebeen found to contain TTXs in the United Kingdom inrecent years. The method consists of a single-step dispersive extraction in 1% acetic acid, followed by acarbon SPE cleanup step before dilution and instrumental analysis. The full method was developed as a rapid tool for the quantitation of TTX, as well as forthe associated analogs 4-epi-TTX; 5,6,11-trideoxy TTX; 11-nor TTX-6-ol; 5-deoxy TTX; and 4,9-anhydro TTX. The method can also be run as the acquisition of TTX together with paralytic shellfish toxins. Resultsdemonstrated acceptable method performance characteristics for specificity, linearity, recovery, ruggedness, repeatability, matrix variability, and within-laboratory reproducibility for the analysis of TTX. The LOD and LOQ were fit-for-purpose in comparison tothe current action limit for TTX enforced in The Netherlands. In addition, aspects of method performance(LOD, LOQ, and within-laboratory reproducibility) were found to be satisfactory for three other TTX analogs (11-nor TTX-6-ol, 5-deoxy TTX, and 4,9-anhydro TTX). The method was found to be practical and suitable for use in regulatory testing, providing rapid turnaround of sample analysis. Plans currently underway on a full collaborative study to validate a HILIC-MS/MS method for paralytic shellfish poisoning toxins will be extended to include TTX in order to generate international acceptance, ultimately for use as an alternative official control testing method shouldregulatory controls be adopted.
Cristinel Munteanu: Frazeologie româneasca˘ (Ias¸i: Institutul European, 2013. 253 páginas)
Authors:   Universidad de Oviedo (España), Bleortu Cristina ,   Universidad de Zúrich (Suiza), García Rodríguez Alba ,   Universidad de Oviedo (España)
Published: April 2017

NO PRESENTA RESUMEN
Elección gramatical y construcción del discurso: la evolución formal y funcional de los referentes textuales
Authors:   Universidad de Salamanca (España), Aijón Oliva Miguel Ángel
Published: April 2017

Este trabajo propone un acercamiento teórico-analítico a la codificación textual de los referentes de tercera persona en español, entendida como elección simultánea de formas gramaticales y significados en un contexto discursivo. Se tienen en cuenta tres fenómenos de variación: el modo de formulación o indexación de los referentes, su colocación preverbal o posverbal en la cláusula, y la función sintáctica que se les asigna. Estos fenómenos se interpretan como motivados por dos factores discursivo-cognitivos comple-mentarios: la prominencia y la informatividad de los referentes en el contexto. Después de esbozar un modelo de las tendencias prototípicas de codificación a partir de tales factores, se analiza cuantitativa y cualitativamente un texto narrativo para comprobar cómo evolucionan las pautas de elección gramatical a medida que aumenta la prominencia del referente en el contexto. Se concluye que el modo de formulación y la colocación reaccionan a los factores discursivo cognitivos de manera más sistemática que la función sintáctica, la cual depende en parte de las características eventivas de la cláusula específica.
340B Participation and Safety Net Engagement Among Federally Qualified Health Centers
Authors: Watts Elizabeth , McGlave Claire , Quinones Nicole , Bruno John P. , Nikpay Sayeh
Published: October 2024

Importance

The 340B program provides discounts on outpatient drugs to certain hospitals and federally supported clinics (covered entities) that can be used to generate revenue to fund safety net care. While numerous studies have found no association between 340B and safety net care provision for most hospital covered entities, less is known about whether federally qualified health centers (FQHCs), the largest group of covered entities after hospitals, use the program to enhance safety net care.

Objective

To assess whether a proxy for 340B revenue was associated with increased safety net care provision among FQHCs.

Design and Setting

This descriptive, retrospective cohort study examined care provided from 2005 to 2022 by 1468 FQHCs that submitted to the Health Resources and Services Administration Uniform Data System. FQHC and year-level fixed effects were included, as well as a control for differential Medicaid expansion over time. The data were analyzed between March and December 2023.

Exposure

One-year lagged number of locations registered to dispense or administer 340B-discounted drugs (registered locations), which included child sites, in-house pharmacies, and contract pharmacies in the 340B Outpatient Pharmacy Affairs Database.

Main outcomes

Natural logarithm of patient volume by payer, low-income status, and use of enabling services. Natural logarithm of visits in which low-profit preventive services were provided.

Results

An additional registered location was associated with increased patient volume, especially for uninsured (0.4%; 95% CI, 0.3%-0.5%) and privately insured (0.4%; 95% CI, 0.2%-0.5%) patients and low-income (0.4%; 95% CI, 0.2%-0.6%), unhoused (0.3%; 95% CI, 0.1%-0.5%), and non–English-speaking (0.3%; 95% CI, 0.1%-0.5%) patients. An additional registered location was associated with increased visits with an HIV test (0.7%; 95% CI, 0.4%-0.9%), serum lead test (0.8%; 95% CI, 0.6%-1.1%), seasonal influenza shot (0.4%; 95% CI, 0.3%-0.5%), Papanicolaou smear (0.5%; 95% CI, 0.4%-0.7%), and tobacco cessation counseling (1.0%; 95% CI, 0.5%-1.4%). Across the study period, the average annual increase in locations was 1.5.

Conclusions and Relevance

The results of this cohort study suggest that there are statistically significant increases in the provision of low-profit but high-value preventive services and care to safety net populations (those who lack insurance, have a low income, or require enabling services) and that, like public hospitals, FQHCs might use 340B revenues to enhance safety net care. This finding may inform debates on the 340B program by supporting differential 340B reforms across hospital and nonhospital covered entities.
NIDA study: Higher doses of buprenorphine beneficial
Authors: Knopf Alison
Published: October 2024

Researchers have found that higher doses of buprenorphine for people with opioid use disorder (OUD) are associated with lower rates of future emergency department (ED) and inpatient care for behavioral health problems.
Ultraviolet Light Causes Skin Cell Senescence: From Mechanism to Prevention Principle
Authors: Song Shujia , Li Fuxing , Zhao Bingxiang , Zhou Min , Wang Xiaobo
Published: October 2024

The skin is an effective protective barrier that significantly protects the body from damage caused by external environmental factors. Furthermore, skin condition significantly affects external beauty. In today's era, which is of material and spiritual prosperity, there is growing attention on skincare and wellness. Ultraviolet radiation is one of the most common external factors that lead to conditions like sunburn, skin cancer, and skin aging. In this review, several mechanisms of UV‐induced skin cell senescence are discussed, including DNA damage, oxidative stress, inflammatory response, and mitochondrial dysfunction, which have their own characteristics and mutual effects. As an illustration, mitochondrial dysfunction triggers electron evasion and the generation of more reactive oxygen species, leading to oxidative stress and the activation of the NLRP3 inflammasome, which in turn causes mitochondrial DNA (mt DNA) damage. Based on the current mechanism, suitable prevention and treatment strategies are proposed from sunscreen, dietary, and experimental medications respectively, aimed at slowing down skin cell aging and providing protection from ultraviolet radiation. The effects of ultraviolet rays on skin is summarized, offering insights and directions for future studies on mechanism of skin cell senescence, with an anticipation of discovering more effective prevention and cure methods.
Investigation into the Mitigation of Crevice Corrosion of Aluminum–Copper Contacts in Seawater by Regulating the Contact Surface Roughness
Authors: Chen Jin , Yin Qiang , Wang Hui‐Ting , Xing Ya‐Zhe
Published: October 2024

Crevice corrosion for dissimilar metal contacts is a key problem in engineering applications. This work has attempted to prevent the ingress of corrosive media into the crevice between aluminum alloy and copper by controlling the roughness (machining accuracy) of the contact surfaces. Both electrochemical and alternating dry/wet immersion tests were used to investigate the corrosion resistance of aluminum alloy–copper contacts with different contact surface roughness. Considering the relationship between the contact surface roughness and the liquid–solid contact angle and the crevice width, a finite element model based on fluid dynamics theory is established to analyze the effect of the contact surface roughness on the seawater infiltration depth in the contact crevice. The distribution of corrosion products on the aluminum alloy and copper surfaces is observed by optical microscope and scanning electron microscope. The phase composition of the corrosion products is analyzed by X‐ray diffraction technique. The results show that the corrosion resistance of the contact improves as the roughness of the contact surface decreases. This is attributed to the fact that the infiltration of seawater is retarded due to the decrease in the crevice width and increase in the contact angle with the decrease in the contact surface roughness.
On the Effect of Cooling Parameters on Solidification Structure in NdFeB Alloys
Authors: Wolz Aymeric , Caniou Romain , Tosoni Olivier , Rado Cyril , Garandet Jean‐Paul
Published: October 2024

The elaboration of suitable NdFeB‐based permanent magnets is essential for high‐performance electrical machines in a number of applications. In this respect, the understanding of the relationship between heat transfer phenomena and the final solidified microstructure is the key to the control of the grain size and the improvement of the magnetic properties. The problem is even more acute with the emergence of new manufacturing processes, such as the laser powder bed fusion, where the cooling rates are much higher than those encountered in the standard strip casting process and where the microstructure can be considered as fixed from the fabrication step. The objective of the present work is to identify correlations between interstructural spacings in the solidified alloys and cooling conditions. This study is based on a methodology coupling experimental and numerical simulation approaches featuring three solidification processes: strip casting, arc melting, and laser fusion. The obtained results cover more than four orders of magnitude in terms of cooling rates R and allow to propose a reliable empirical relationship between the interstructural spacing λ and R of the form λ [μm] = 83 R [K s−1]−0.36. This relation can thus be used to estimate cooling rates from metallographic observations.
Preparation of Porous Si2N2O/SiC Ceramics by Microwave Sintering
Authors: Duan Yuxuan , Guan Li , Min Zhiyu , Fu Ruijie , Li Jiaxin , Fan Lei , Abadikhah Hamidreza , Zhao Biao , Dong Binbin , Zhang Rui
Published: October 2024

Two steps strategy were taken to effectively produce porous Si2N2O/SiC ceramics: 1) direct foaming combined with sol‐gel curing at room temperature to form a green body, and 2) sintering assisted by in‐situ production of Si2N2O fibers under microwave sintering conditions. Non‐toxic silica sol was used to provide silicon source for in‐situ synthesis of Si2N2O, the silica sol could form a gel that stabilizes the bubbles, creating a porous structure. A thorough investigation was conducted into how different sintering temperatures affected the microstructure, flexural strength, and porosity of the porous Si2N2O/SiC composites. The main bonding phase in the porous composites was the Si2N2O with fiber morphology. The optimal microwave sintering temperature for fabricating porous Si2N2O/SiC ceramics, using a combination of sol‐gel and direct foaming techniques, has been determined to be 1200 °C. At this temperature, the porosity can be controlled between 73.32% and 83.16% by proportionally adjusting the ratio of the raw materials. Under the condition of high porosity, the thermal radiation is dominant and the thermal conductivity increases with the increase of temperature. With the decrease of porosity, the heat conduction is dominant, and the thermal conductivity decreases with the increase of temperature.
Being Smarter, Azobenzene‐Containing Biomaterial Showing Triple Stimuli‐Responsive Phase Change Property to Light, Humidity and Force at Room Temperature
Authors: Zhang Lei , Du Qianyao , Zhang Ziying , Chen Jia , Liu Yun , Luo Xiliang , Wang Zhen , Wu Zhongtao
Published: October 2024

Multiple stimuli‐responsiveness is an attractive property that is studied in physical chemistry and materials chemistry. While, multiple stimuli‐responsive phase change in an isothermal way is rarely addressed for functional materials at room temperature. In this study, one azobenzene‐containing surfactant AZO is designed for the fabrication of triple stimuli‐responsive phase change biomaterial (Alg‐AZO) through the electrostatic complexation with natural alginate. Thanks to the photoisomerization ability, molecular flexibility and hydrophilicity of AZO, together with the tailoring effect of alginate on AZO, Alg‐AZO could perform reversible isothermal phase transition between liquid crystalline and isotropic liquid states under the stimuli of either light or humidity at room temperature. Furthermore, the humidity‐induced isotropic state can also fast transit to ordered state under shear force, owing to the π‐π interactions between planar trans‐AZO in Alg‐AZO material. With good biocompatibility, self‐healing property and in vivo wound healing promoting capacity that is promoted by light, humidity and force, Alg‐AZO would be suitable for working as a new smart biomaterial in biological and biomedical areas. This work provides a designing strategy for gaining multiple stimuli‐responsive smart materials based on biomacromolecules, and also opening a new opportunity for gaining self‐healing biomaterials capable of working in various conditions.
Durable Photo‐Pyroelectric Detection in a Diamine‐Constructed Lead‐Free Hybrid Perovskite Ferroelectric
Authors: Wang Yifei , Ye Huang , Wang Peng , Wu Ziyang , Guan Qianwen , Zhang Chengshu , Li Hang , Chen Shuang , Luo Junhua
Published: October 2024

As a subcategory of pyroelectric materials, hybrid perovskite ferroelectrics possess substantial pyroelectric properties and exceptional light absorption characteristics, demonstrating significant potential in the photo‐pyroelectric (PPE) detection field. Despite the significant advantages of hybrid perovskite ferroelectric materials for PPE detection, both the lead issue and the weak stability from van der Waals interactions in monoamines have hindered their further application. Here, 1D lead‐free ferroelectric (BDA)SbBr5 (1, where BDA is 1,4‐butanediammonium) is fabricated to achieve PPE detection. Compound 1 exhibits significant symmetry breaking attributed to the order–disorder transition of organic cations and octahedral distortions. Specifically, compound 1 enables broad‐spectrum PPE detection from UV to near‐infrared (377–980 nm) and further realizes switchable pyroelectric current after polarization. More importantly, the stability of the pyroelectric current is preserved without degradation over three months, attributed to the hydrogen bonding interactions of butanediamide. Further theoretical calculations of compound 1 reveal a more negative energy of formation than its monoamine homologs (BA)2SbBr5 (where BA is n‐butylammonium), which is evidence of its stability. These findings highlight 1 as a promising candidate for high‐stability and environmentally friendly PPE wide‐spectrum detection, representing a noteworthy advancement in the ferroelectric field.
Cu‐Atom Locations in Rocksalt SnTe Thermoelectric Alloy
Authors: Kawami Youichirou , Tran Xuan Quy , Yamamoto Tomokazu , Yoshioka Satoru , Murakami Yasukazu , Matsumura Syo , Nogita Kazuhiro , Zou Jin
Published: October 2024

The development of functional thermoelectric materials requires direct evidence of dopants’ locations to rationally design the electronic and phononic structure of the host matrix. In this study, Cs‐corrected scanning transmission electron microscopy and energy dispersive X‐ray spectroscopy is employed at the atomic scale to identify Cu atoms’ locations in a Cu‐doped SnTe thermoelectric alloy. It is revealed that Cu atoms in the rocksalt SnTe form solid solutions at both Sn and Te sites, contrary to their electronegativity order and the intentional Cu doping at Sn sites. Cu atoms are also located at the tetrahedral and crowdion sites of the face‐centred cubic structure, with varying degrees of correlations. Such high flexibility of Cu atoms in the rocksalt SnTe offers diverse phonon‐scattering mechanisms conducive to the ultra‐low lattice thermal conductivity of singly Cu‐doped SnTe. This study offers atomic‐scale insights for achieving more precise dopant engineering, leading to the accelerated development of functional thermoelectric materials.
Insight into Carrier and Phonon Transports of PbSnS2 Crystals
Authors: Zhan Shaoping , Bai Shulin , Qiu Yuting , Zheng Lei , Wang Sining , Zhu Yingcai , Tan Qing , Zhao Li‐Dong
Published: October 2024

The simultaneous optimization of n‐type and p‐type thermoelectric materials is advantageous to the practical application of the device. As an emerging thermoelectric material, PbSnS2 exhibits highly competitive thermoelectric properties due to its unique carrier and phonon transport characteristics. To promote the utilization of this low‐cost thermoelectric material, p‐type PbSnS2 crystals are synthesized and optimized through Na doping and Se alloying. The resulting thermoelectric transport properties differ significantly from those reported for n‐type crystals, prompting us to compare and analyze both n‐type (Cl‐doped) and p‐type (Na‐doped) PbSnS2 crystals from various perspectives. Cl doping is subject to weaker “Fermi pinning” and lower impurity ionization energy compared with Na doping, leading to higher doping efficiency. The different optimal performance directions in n‐type and p‐type crystals can be attributed to the distinct charge density distributions near the conduction band minimum (CBM) and the valence band maximum (VBM). Additionally, both n‐type and p‐type crystals exhibit ultralow lattice thermal conductivity due to the low symmetry of their twisted NaCl structure combined with the strong anharmonicity. This comprehensive analysis of PbSnS2 crystals provides a solid foundation for further performance optimization and device assembly, while also sheds light on the investigation of layered thermoelectric materials.
Lattice Boundary Enhancement on Thermoelectric Behaviors of Heavily Boron‐Doped Silicon for Energy Harvesting: Electrical versus Thermal Conductivity
Authors: Yu Tsai Shang , Tseng Po‐Hsien , Chen Chun Chi , Huang Cheng‐Ming , Yen Hung‐Wei , Chen Yi‐Sheng , Lin Kun‐Lin , Niu Ranming , Lai Yu‐Sheng , Ko Fu‐Hsiang
Published: October 2024

Green energy collection is crucial for achieving future net‐zero carbon emissions, with energy harvesting being a key solution. Silicon, a widely used p‐type semiconductor doped with boron ions, is prevalent in modern electronics. However, the impact of lattice boundaries from ion implantation doping on thermoelectric properties remains underexplored. A heavily boron‐doped silicon layer is used to enhance thermoelectric performance. The layers, formed on silicon, exhibit epitaxial crystal structures under all doping conditions using an ion implantation system. Transmission electron microscopy and atom probe tomography reveal that boron interstitial structures create boundaries in the silicon lattice. These boundaries effectively reduce the thermal conductivity of boron‐doped silicon compared to intrinsic silicon. At 372.76 K, the best power factor of the heavily boron‐doped silicon layer is 3.05 mW/m·K2, obtained at an implant dose of 1016 cm−2. This study demonstrates the raised electrical conductivity is induced by effectively substituting silicon with boron atoms, and the reduced thermal conductivity is caused by boron interstitial‐formed boundaries in silicon. These findings highlight the potential of heavily boron‐doped silicon in improving thermoelectric materials and advancing energy‐efficient technologies.
Spontaneous Formation of Solid Shell Polymeric Multicompartments at All‐Aqueous Interfaces
Authors: Perfeito Francisca G. , Vilabril Sara , Cerqueira Andreia , Oliveira Mariana B. , Mano João F.
Published: October 2024

Multicompartmental capsules have demonstrated value in fields ranging from drug release, mimetics of artificial cells, to energy conversion and storage. However, the fabrication of devices with different compartments usually requires the use of toxic solvents, and/or the adaptation of technically demanding methods, including precision microfluidics and multistep processes. The spontaneous formation of multi‐core capsules resulting from polyelectrolyte complexation at the interface of a prototypic all‐aqueous two‐phase system is described here. The variation of polyelectrolyte concentration and complexation time are described as simple working parameters capable of driving the formation of compartments at different yields, as well as tailoring their morphology. The mild processing technology enables the encapsulation of animal cells, which are capable of invading capsule walls for specific processing conditions.
Surface Optimization of Noble‐Metal‐Free Conductive [Mn1/4Co1/2Ni1/4]O2 Nanosheets for Boosting Their Efficacy as Hybridization Matrices
Authors: Kwon Nam Hee , Kim Se‐Jun , Gu Tae‐Ha , Lee Jang Mee , Kim Myung Hwa , Paik Dooam , Jin Xiaoyan , Kim Hyungjun , Hwang Seong‐Ju
Published: October 2024

Conductive 2D nanosheets have evoked tremendous scientific efforts because of their high efficiency as hybridization matrices for improving diverse functionalities of nanostructured materials. To address the problems posed by previously reported conductive nanosheets like poorly‐interacting graphene and cost‐ineffective RuO2 nanosheets, economically feasible noble‐metal‐free conductive [MnxCo1−2xNix]O2 oxide nanosheets are synthesized with outstanding interfacial interaction capability. The surface‐optimized [Mn1/4Co1/2Ni1/4]O2 nanosheets outperformed RuO2/graphene nanosheets as hybridization matrices in exploring high‐performance visible‐light‐active (λ >420 nm) photocatalysts. The most efficient g‐C3N4–[Mn1/4Co1/2Ni1/4]O2 nanohybrid exhibited unusually high photocatalytic activity (NH4+ formation rate: 1.2 mmol g−1 h−1), i.e., one of the highest N2 reduction efficiencies. The outstanding hybridization effect of the defective [Mn1/4Co1/2Ni1/4]O2 nanosheets is attributed to the optimization of surface bonding character and electronic structure, allowing for improved interfacial coordination bonding with g‐C3N4 at the defect sites. Results from spectroscopic measurements and theoretical calculations reveal that hybridization helps optimize the bandgap energy, and improves charge separation, N2 adsorptivity, and surface reactivity. The universality of the [Mn1/4Co1/2Ni1/4]O2 nanosheet as versatile hybridization matrices is corroborated by the improvement in the electrocatalytic activity of hybridized Co−Fe‐LDH as well as the photocatalytic hydrogen production ability of hybridized CdS.
Orbital Current Boosting Magnetization Switching Efficiency in Metallic Superlattices
Authors: Wei Junwen , Xu Xinkai , Lin Zijin , Qu Yuanjing , Tang Xiaoli , Zhong Zhiyong , Zhang Huaiwu , Jin Lichuan
Published: October 2024

Orbitronics is an emerging domain within spintronics, and it is characterized by a rapid development of methods for utilizing orbital current. Metals with strong spin‐orbit coupling have been effectively used to convert orbital current into orbital torque. This study introduces a metallic [W/Ti]3 superlattice that uses orbital current to significantly enhance the magnetization switching efficiency. The enhancement in torque efficiency is demonstrated via spin‐torque ferromagnetic resonance along with the extraction of damping‐like (ξDL) and field‐like spin‐orbit torque (SOT) efficiencies. ξDL for superlattices is more than 100 times higher than that for Pt. As a result, the critical switching current density of the superlattice becomes two orders of magnitude lower than that of Pt. This is primarily attributed to the orbital current generated by the orbital Rashba–Edelstein effect at the W/Ti interface. The thickness of Ti and W layers is modulated to develop a novel approach to utilize orbital current for augmenting SOT efficiency and magnetization switching efficiency in superlattices. The findings of this study provide a basis for developing low‐power‐consumption memory devices and memory with controllable critical current density in SOT‐magnetic random‐access memory applications.
Promoter Deletion Leading to Allele Specific Expression in a Genetically Unsolved Case of Primary Ciliary Dyskinesia
Authors: Beaman M. Makenzie , Yin Weining , Smith Amanda J. , Sears Patrick R. , Leigh Margaret W. , Ferkol Thomas W. , Kearney Brendan , Olivier Kenneth N. , Kimple Adam J. , Clarke Shannon , Huggins Erin , Nading Erica , Jung Seung‐Hye , Iyengar Apoorva K. , Zou Xue , Dang Hong , Barrera Alejandro , Majoros William H. , Rehder Catherine W. , Reddy Timothy E. , Ostrowski Lawrence E. , Allen Andrew S. , Knowles Michael R. , Zariwala Maimoona A. , Crawford Gregory E.
Published: October 2024

Variation in the non‐coding genome represents an understudied mechanism of disease and it remains challenging to predict if single nucleotide variants, small insertions and deletions, or structural variants in non‐coding genomic regions will be detrimental. Our approach using complementary RNA‐seq and targeted long‐read DNA sequencing can prioritize identification of non‐coding variants that lead to disease via alteration of gene splicing or expression. We have identified a patient with primary ciliary dyskinesia with a pathogenic coding variant on one allele of the SPAG1 gene, while the second allele appears normal by whole exome sequencing despite an autosomal recessive inheritance pattern. RNA sequencing revealed reduced SPAG1 transcript levels and exclusive allele specific expression of the known pathogenic allele, suggesting the presence of a non‐coding variant on the second allele that impacts transcription. Targeted long‐read DNA sequencing identified a heterozygous 3 kilobase deletion of the 5′ untranslated region of SPAG1, overlapping the promoter and first non‐coding exon. This non‐coding deletion was missed by whole exome sequencing and gene‐specific deletion/duplication analysis, highlighting the importance of investigating the non‐coding genome in patients with “missing” disease‐causing variation. This paradigm demonstrates the utility of both RNA and long‐read DNA sequencing in identifying pathogenic non‐coding variants in patients with unexplained genetic disease.
Rhodium‐Catalyzed Asymmetric Cyclopropanation of Indoles with N‐Triftosylhydrazones
Authors: He Caicai , Song Wei , Wei Dandan , Zhao Wei , Yu Qianfei , Tang Jiaqi , Ning Yongquan , Murali Karunanidhi , Sivaguru Paramasivam , de Ruiter Graham , Bi Xihe
Published: October 2024

Herein we report a general rhodium‐catalyzed asymmetric intermolecular dearomative cyclopropanation of indoles using trifluoromethyl N‐triftosylhydrazones as carbene precursors. The reaction enables the rapid construction of diverse cyclopropane‐fused indolines bearing a trifluoromethylated quaternary stereocenter with high enantioselectivity (up to 99 % ee). This mild method exhibits broad substrate scope, tolerating various functional groups, and can even be utilized for the late‐stage diversification of complex bioactive molecules. DFT calculations suggest that the formation of a key zwitterionic intermediate is responsible for the chiral induction. Overall, this approach opens up new possibilities for asymmetric cyclopropanation of challenging aromatic heterocyclic compounds.
Regulating Non‐Equilibrium Solvation Structure in Locally Concentrated Ionic Liquid Electrolytes for Wide‐Temperature and High‐Voltage Lithium Metal Batteries
Authors: Tu Haifeng , Wang Zhicheng , Xue Jiangyan , Tang Zhiyong , Liu Yang , Liu Xiaofang , Liu Lingwang , Lu Suwan , Weng Shixiao , Gao Yiwen , Sun Guochao , Liu Zheng , Peng Keyang , Zhang Xin , Li Dejun , Wu Guangye , Liu Meinan , Hu Jianchen , Li Hong , Xu Jingjing , Wu Xiaodong
Published: October 2024

The development of high‐voltage lithium metal batteries (LMBs) encounters significant challenges due to aggressive electrode chemistry. Recently, locally concentrated ionic liquid electrolytes (LCILEs) have garnered attention for their exceptional stability with both Li anodes and high‐voltage cathodes. However, there remains a limited understanding of how diluents in LCILEs affect the thermodynamic stability of the solvation structure and transportation dynamics of Li+ ions. Herein, we propose a wide‐temperature LCILEs with 1,3‐dichloropropane (DCP13) diluent to construct a non‐equilibrium solvation structure under external electric field, wherein the DCP13 diluent enters the Li+ ion solvation sheath to enhance Li+ ion transport and suppress oxidative side reactions at high‐nickel cathode (LiNi0.9Co0.05Mn0.05O2, NCM90). Consequently, a Li/NCM90 cell utilizing this LCILE achieves a high capacity retention of 94 % after 240 cycles at 4.3 V, also operates stably at high cut‐off voltages from 4.4 V to 4.6 V and over a wide temperature range from −20 °C to 60 °C. Additionally, an Ah‐level pouch cell with this LCILE simultaneously achieves high‐energy‐density and stable cycling, manifesting the practical feasibility. This work redefines the role of diluents in LCILEs, providing inspiration for electrolyte design in developing high‐energy‐density batteries.
A General Hydrotrifluoromethylation of Unactivated Olefins Enabled by Voltage‐Gated Electrosynthesis
Authors: Alvarez Eva M. , Li Jinxiao , Malapit Christian A.
Published: October 2024

Here we present the first successful hydrotrifluoromethylation of unactivated olefins under electrochemical conditions. Commercially available trifluoromethyl thianthrenium salt (TT+−CF3BF4−, Ep/2=−0.85 V vs Fc/Fc+) undergoes electrochemical reduction to generate CF3 radicals which add to olefins with exclusive chemoselectivity. The resulting carbon centered radical undergoes a second cathodic reduction, instead of a classical HAT process, to generate a carbanion that can be terminated by protonation from solvent. The use of MgBr2 (+0.20 V onset oxidation potential) plays a key role as an enabling sacrificial reductant for the reaction to operate in an undivided cell. Guided by cyclic voltammetry (CV) studies, fine‐tuning the solvent system, trifluoromethylating reagent's counteranion and careful selection of redox processes, this work led to the development of a voltage‐gated electrosynthesis by pairing two redox processes with a narrow potential difference (ΔE≈1.00 V) allowing the reaction to proceed with two important advances: (a) high reactivity and selectivity towards hydrotrifluoromethylation over undesired dibromination, and (b) an unprecedented functional group tolerance, including aniline, phenols, unprotected alcohol, epoxide, trialkyl amine, and several redox sensitive heterocycles.
Perylene‐Embedded Helical Nanographenes with Emission up to 1010 nm: Synthesis, Structures, and Chiroptical Properties
Authors: Huo Gui‐Fei , Xu Wei‐Tao , Hu Jinlian , Han Yi , Fan Wei , Wang Wei , Sun Zhe , Yang Hai‐Bo , Wu Jishan
Published: October 2024

Near‐infrared (NIR) circularly polarized absorbing or emitting materials offer distinct advantages over their visible‐light counterparts and have attracted considerable interest across various fields. Materials exhibiting NIR chiroptical properties with high fluorescence quantum yields (ΦF) are particularly rare. In this study, we report the synthesis of a series of helical nanographenes (1, 2, 3, and 4), where perylene is fused with one to four hexa‐peri‐hexabenzocoronene (sub) units by a strategy involving Diels–Alder cycloaddition followed by a Scholl reaction. X‐ray crystallographic analysis confirmed their structures, revealing helicene moieties integrated into a highly contorted framework. Benefiting from a similar distribution pattern of frontier molecular orbitals to perylene and extended π‐conjugation, compounds 1–4 demonstrate respectable ΦF values of 31.9 %, 15.0 %, 13.7 %, and 6.5 %, respectively, with emission maxima reaching up to 1010 nm. Their enantiopure forms, isolated by preparative chiral HPLC, exhibit distinct circular dichroism signals and circularly polarized luminescence across a broad spectral range, extending from the ultraviolet to the NIR.
Photo‐Amplified Plasma Membrane Rupture by Membrane‐Anchoring NIR‐II Small Molecule Design for Improved Cancer Photoimmunotherapy
Authors: Chen Pengfei , Rong Jie , Chen Kai , Huang Tian , Shen Qingming , Sun Pengfei , Tang Weiwei , Fan Quli
Published: October 2024

Immunotherapy is a promising cancer treatment method for eradicating tumor cells by enhancing the immune response. However, there are several major obstacles to conventional phototherapy‐mediated immune responses, including inadequate immunogenicity and immunosuppressive environment. Here, we present a novel photoimmunotherapy modality—the development of membrane‐anchoring small molecule inducing plasma membrane rupture (PMR) by NIR‐II photo‐stimulation, thus evoking cell necrotic death and enhancing antitumor immunotherapy. Our top‐performing membrane‐anchoring small molecule (CBT‐3) exhibits temperature‐tunable PMR efficiency, allowing rapid necrotic death in cancer cells at 50 μM dose by using exogenous NIR‐II light‐mediated mild photothermal effect (1064 nm, 0.6 W cm−2). Further evidence indicated that this gentle therapeutic approach activated inflammatory signaling pathways in cells, enhanced immunogenic cell death, and reshaped the immunosuppressive tumor microenvironment, ultimately promoting systemic antitumor immune responses in vivo. This study represents the first instance of utilizing NIR‐II photo‐amplified PMR effect based on membrane‐anchoring small molecule, providing a novel avenue for advancing cancer photoimmunotherapy.
Germylene Mediated Reductive C−C and C−N Coupling of an Isocyanide and its Device Application
Authors: Gour Kritika , Pramanik Debjit , Dash Soumya Ranjan , Shinde Dipak Dattatray , Venugopal Geethu , Vanka Kumar , Rath Arup K. , Sen Sakya S.
Published: October 2024

We have demonstrated a unique reductive coupling of 4‐iodophenyl isocyanide, facilitated by a perimidine‐based N‐heterocyclic germylene (NHGe), which yields a bis‐spirogerma compound featuring simultaneous C−C and C−N bond formation. This reaction, which leads to the oxidation of germanium from +2 to +4, represents a significant departure from previously documented isocyanide‐germylene interactions. The product exhibits extensive conjugation across its bicyclic C4Ge2N2 framework, conferring distinct photophysical properties, including prominent orange luminescence in both solution and solid states. The photophysical properties are supported by the TD‐DFT calculations confirming an n→π* transition. The potential application of this compound in optoelectronic devices, particularly as a hole transport layer in PbS quantum dot solar cells, is also explored, with promising preliminary results.
Synthesis, Characterization, Molecular Docking, Cytotoxicity, and Antimicrobial Activity of Schiff Base Ligand and Its Metal Complexes
Authors: Tawfiq K. M. , Al Naymi Hanan Adnan Shaker , Obaid Shatha M. H. , Jarad Amer J. , Al‐Noor Taghreed H. , Al‐Sarray Ali J.
Published: October 2024

A Schiff base ligand (L) was synthesized via condensation of N‐(1‐naphthyl)ethylenediamine dihydrochloride with phthalaldehyde. The ligand was characterized by FT‐IR, UV–Vis, 1H NMR, mass spectrometry, and elemental analysis (C, H, N). Five metal complexes (Co(II), Ni(II), Cu(II), Zn(II), and Cd(II)) were prepared with the ligand in a 1:1 (M:L) ratio using an aqueous ethanol solution. The complexes were characterized by FT‐IR, UV–Vis, mass spectrometry, and elemental analysis (C, H, N). Additionally, 1H NMR spectroscopy was employed for Cd(II) complex. Antimicrobial activity of the ligand and its metal complexes against pathogenic bacteria (K. pneumoniae, E. coli, S. aureus, and S. epidermidis) and fungus (C. albicans) were evaluated using the agar well diffusion method. All compounds exhibited inhibitory effects with zone diameters ranging from 8 to 16 mm. The ligand and complexes also displayed significant anticancer activity against a mammary carcinoma cell line. Among them, Zn(II) and Cu(II) complexes demonstrated the highest inhibitory effects (70.68% and 70.57%, respectively), followed by the ligand (61.35%) and Co(II), Cd(II), and Ni(II) complexes (60.34%, 58.96%, and 41.63%, respectively). IC50 values followed a similar trend, ranging from 31.69% (Co(II)) to 165.7% (Cd(II)). Molecular docking studies indicated strong binding affinities of the ligand and the Zn(II) complex to the estrogen receptor.
A Cd (II)‐based Metal–Organic Framework as Switch‐Off Fluorescence Sensors for Antibiotic Detection
Authors: Yin Zhi‐Chao , Ray Manaswini , Liu Cai‐Yang , Dakua Trilochan , Parvez Mohammad Khalid , Al‐Dosari Mohammed S. , Mohanty Aurobinda , Jin Jun‐Cheng
Published: October 2024

Detecting antibiotic residues is crucial for monitoring their excessive use in healthcare and agricultural practices. Herein, a new 3D metal–organic framework (MOF) containing {[Cd (bpyp)(sdba)]·DMF·2H2O}n (1) (bpyp = 2,5‐bis (pyrid‐4‐yl)pyridine and H2sdba = 4,4′‐sulfonyldibenzoic acid) has been designed and synthesized. MOF 1 displays sensitive detection tetracycline (TCY) with a limit of detection below 7.67 × 10−6 M in an aqueous solution. The detection mechanism involves competitive absorption between MOF 1 and antibiotics, supported by UV–vis spectroscopy and fluorescence lifetime measurements. MOF 1 exhibits a visible fluorescence response to TCY under a 254 nm UV lamp. MOF 1 is applied in the quantitative detection of TCY in lake water with the recovery based on the sensing platform was 92.26–107.54% with RSD (%) less than 4.38%, indicating outstanding reliability.
Topological Insulator Nanowires Made by AFM Nanopatterning: Fabrication Process and Ultra Low‐Temperature Transport Properties
Authors: Yakovlev Dmitry S. , Frolov Aleksei V. , Nazhestkin Ivan A. , Temiryazev Alexei G. , Orlov Andrey P. , Shvartzberg Jonathan , Dizhur Sergey E. , Gurtovoi Vladimir L. , Hovhannisyan Razmik , Stolyarov Vasily S.
Published: October 2024

Topological insulator nanostructures became an essential platform for studying novel fundamental effects emerging at the nanoscale. However, conventional nanopatterning techniques, based on electron beam lithography and reactive ion etching of films, have inherent limitations of edge precision, resolution, and modification of surface properties, all of which are critical factors for topological insulator materials. In this study, an alternative approach for the fabrication of ultrathin Bi2Se3 nanoribbons is introduced by utilizing a diamond tip of an atomic force microscope (AFM) to cut atomically thin exfoliated films. This study includes an investigation of the magnetotransport properties of ultrathin Bi2Se3 topological insulator nanoribbons with controlled cross‐sections at ultra‐low 14 mK) temperatures. Current‐dependent magnetoresistance oscillations are observed with the weak antilocalization effect, confirming the coherent propagation of 2D electrons around the nanoribbon surface's perimeter and the robustness of topologically protected surface states. In contrast to conventional lithography methods, this approach does not require a highly controlled clean room environment and can be executed under ambient conditions. Importantly, this method facilitates the precise patterning and can be applied to a wide range of 2D materials.
Citrus wastewater as a source of value‐added products: Quali‐quantitative analysis and in vitro screening on breast cancer cell lines
Authors: Raimondi Maria Valeria , Rigogliuso Salvatrice , Saiano Filippo , Poma Paola , Labbozzetta Manuela , Barreca Marilia , Barbera Marcella , Bivacqua Roberta , Li Petri Giovanna , Buscemi Silvestre , Sardo Ignazio , Spanò Virginia , Palumbo Piccionello Antonio , Montalbano Alessandra , Barraja Paola , Notarbartolo Monica
Published: October 2024

Citrus wastewater from industries is a source of bioactive compounds whose recovery could be a useful approach to convert processing waste into potential resources to be exploited in food, pharmaceutical, and chemical companies. Citrus wastewater, obtained from the industrial processing of Citrus sinensis, was freeze‐dried and qualitative/quantitative evaluated using HPLC/MS Q‐TOF analysis. Antiproliferative activity was investigated on MDA‐MB‐231 (triple‐negative breast cancer cell line), MCF‐7 (breast cancer cell line), and its multidrug‐resistant variant MCF‐7R. Fraction 8 emerged for its cytotoxicity toward MCF‐7R cells. Its main component, the polymethoxylated flavone nobiletin (80%), is likely involved in increasing the number of G1‐phase MCF‐7R cells without inducing cell death. Notably, fraction 8 sensitizes MCF7‐R cells to the antiproliferative effects of doxorubicin, thus contributing to overcoming MCF7‐R multidrug resistance. Our studies highlighted the possibility of applying a sustainable strategy for citrus wastewater recycling to recover functional compounds as useful adjuvants for the prevention and treatment of malignancies.