bluuebunny/crossref_metadata_2025 huggingface dataset:
Screening of ligands for the Ullmann synthesis of electron-rich diaryl ethers
Authors: Otto Nicola , Opatz Till
Published: August 2012

In the search for new ligands for the Ullmann diaryl ether synthesis, permitting the coupling of electron-rich aryl bromides at relatively low temperatures, 56 structurally diverse multidentate ligands were screened in a model system that uses copper iodide in acetonitrile with potassium phosphate as the base. The ligands differed largely in their performance, but no privileged structural class could be identified.
Synthesis of 4” manipulated Lewis X trisaccharide analogues
Authors: Moore Christopher J , Auzanneau France-Isabelle
Published: August 2012

Three analogues of the Lex trisaccharide antigen (β-D-Galp(1→4)[α-L-Fucp(1→3)]-D-GlcNAcp) in which the galactosyl residue is modified at O-4 as a methyloxy, deoxychloro or deoxyfluoro, were synthesized. We first report the preparation of the modified 4-OMe, 4-Cl and 4-F trichloroacetimidate galactosyl donors and then report their use in the glycosylation of an N-acetylglucosamine glycosyl acceptor. Thus, we observed that the reactivity of these donors towards the BF3·OEt2-promoted glycosylation at O-4 of the N-acetylglucosamine glycosyl acceptors followed the ranking 4-F > 4-OAc ≈ 4-OMe > 4-Cl. The resulting disaccharides were deprotected at O-3 of the glucosamine residue and fucosylated, giving access to the desired protected Lex analogues. One-step global deprotection (Na/NH3) of the protected 4”-methoxy analogue, and two-step deprotections (removal of a p-methoxybenzyl with DDQ, then Zemplén deacylation) of the 4”-deoxychloro and 4”-deoxyfluoro protected Lex analogues gave the desired compounds in good yields.
Synthesis of diverse indole libraries on polystyrene resin – Scope and limitations of an organometallic reaction on solid supports
Authors: Knepper Kerstin , Vanderheiden Sylvia , Bräse Stefan
Published: August 2012

The synthesis of diverse substituted indole structures on solid supports is described. The immobilization of nitrobenzoic acid onto Merrifield resin and the subsequent treatment with alkenyl Grignard reagents delivered indole carboxylates bound to solid supports. In contrast to results in the liquid phase, ortho,ortho-unsubstituted nitroarenes also delivered indole moieties in good yields. Subsequent palladium-catalyzed reactions (Suzuki, Heck, Sonogashira, Stille) delivered, after cleavage, the desired molecules in moderate to good yields over four steps. The scope and limitations are presented.
Conformational analysis, stereoelectronic interactions and NMR properties of 2-fluorobicyclo[2.2.1]heptan-7-ols
Authors: de Rezende Fátima M P , Moreira Marilua A , Cormanich Rodrigo A , Freitas Matheus P
Published: August 2012

Four diastereoisomers of 2-fluorobicyclo[2.2.1]heptan-7-ols were computationally investigated by using quantum-chemical calculations, and their relative energies were analyzed on the basis of stereoelectronic interactions, particularly the presence or otherwise of the F∙∙∙HO intramolecular hydrogen bond in thesyn-exoisomer. It was found through NBO and AIM analyses that such an interaction contributes to structural stabilization and that the1hJF,H(O)coupling constant in thesyn-exoisomer is modulated by thenF→σ*OHinteraction, i.e., the quantum nature of the F∙∙∙HO hydrogen bond.
Recyclable fluorous cinchona alkaloid ester as a chiral promoter for asymmetric fluorination of β-ketoesters
Authors: Yi Wen-Bin , Huang Xin , Zhang Zijuan , Zhu Dian-Rong , Cai Chun , Zhang Wei
Published: August 2012

A fluorous cinchona alkaloid ester has been developed as a chiral promoter for the asymmetric fluorination of β-ketoesters. It has comparable reactivity and selectivity to the nonfluorous versions of cinchona alkaloids and can be easily recovered from the reaction mixture by simple fluorous solid-phase extraction (F-SPE) and used for the next round of reaction without further purification.
Muñecas que hablan. Ética y estética de los modelos de belleza en publicidad y moda
Authors: Soley-Beltran Patrícia
Published: August 2012

Partiendo de datos empíricos cualitativos recogidos en entrevistas con ex-modelos de moda, fuentes orales secundarias y material autoetnográfico, se analiza el proceso de incorporación y representación del ideal de belleza como fruto de un trabajo corporal y emocional de las y los modelos. Dado que este colectivo profesional supuestamente incorpora los ideales estéticos e identitarios propuestos por los medios de comunicación y la publicidad, son informantes clave para explorar las actuaciones corporales identitarias de acuerdo con los patrones estéticos hegemónicos, así como para analizar la construcción de dichos ideales. El estudio del trabajo corporal de los modelos muestra sus estrategias de adecuación a las normas de presentación de género, así como la actuación que sostiene la representación de la belleza en los medios de comunicación impresos y audiovisuales. Sus testimonios ponen de relieve sus propias estrategias de adecuación y resistencia a la objetificación, los diferentes grados de autoidentificación corporal según el género, y una visión crítica de las cuestiones éticas relativas a la producción de imagenes. El papel del silencio en la actuación de la belleza, una técnica de despersonalización que facilita la proyección del deseo que sustenta la construcción del glamour, se rompe en esta incursión antropológica a las bambalinas de la moda.
África: Cuerpos colonizados, cuerpos como identidades
Authors: Martí Josep
Published: August 2012

Dada la gran importancia que toda sociedad otorga al cuerpo, tanto a su conceptualización como a los criterios para su presentación social, no es de extrañar que el cuerpo ocupe un lugar central en los procesos de colonización y las políticas coloniales. En este artículo se analiza la relación que podemos establecer entre colonialidad y presentación social del cuerpo, sirviéndonos para ello de los nuevos enfoques de los estudios postcoloniales, así como de la teoría antropológica y sociológica sobre el cuerpo en general. A partir de casos concretos de la colonización europea en África, el artículo se centra especialmente en las prácticas relativas al uso de indumentaria, así como a las modificaciones corporales. Si el establecimiento de identidades es crucial para construir un orden social jerarquizado, estos aspectos concretos de la presentación social del cuerpo han tenido un papel relevante en los procesos de subalternización, siendo la misma noción de salvaje uno de los ejemplos más claros para ello.
Antecedentes de los epígrafes de la poesía de Quevedo en la literatura clásica y del Siglo de Oro. Con una hipótesis sobre su autoría
Authors: Alonso Veloso María José
Published: August 2012

Muchos de los autores griegos y latinos redactaron epígrafes a sus poemas, como también lo hicieron escritores italianos y españoles del Siglo de Oro imitados por Francisco de Quevedo. Sus autógrafos y numerosas composiciones tempranas, recogidas en antologías de principios del siglo XVII, contienen también estos títulos, que figuran tanto en la edición póstuma de la poesía quevediana de 1648, debida a González de Salas, como en la de 1670, supervisada por Pedro Aldrete. El presente artículo tiene el propósito de revisar el problema de la autoría de tales epígrafes, atribuidos mayoritariamente por la crítica a su primer editor.
How does deposition of gas phase species affect pH at frozen salty interfaces?
Authors: Wren S. N. , Donaldson D. J.
Published: August 2012

Abstract. Chemical processes occurring on snow and ice surfaces play an important role in controlling the oxidative capacity of the overlying atmosphere. However, efforts to gain a better, mechanistic understanding of such processes are impeded by our poor understanding of the chemical nature of the air-ice interface. Here we use a surface-sensitive spectroscopic technique to investigate how the nature of the ice, whether frozen freshwater, salt water or seawater, influences pH changes at the surface. Deposition of HCl(g) leads to a very different pH response at the frozen freshwater surface than at the frozen salt water surface indicating that these two surfaces present different chemical environments. Importantly, the sea ice surface is buffered against pH changes arising from deposition of gas phase species. These results have important implications for understanding pH-sensitive processes occurring at the air-ice boundary, such as bromine activation.
Particulate sulfate ion concentration and SO2 emission trends in the United States from the early 1990s through 2010
Authors: Hand J. L. , Schichtel B. A. , Malm W. C. , Pitchford M. L.
Published: August 2012

Abstract. We examined particulate sulfate ion concentrations across the United States from the early 1990s through 2010 using remote/rural data from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network and from early 2000 through 2010 using data from the Environmental Protection Agency's (EPA) urban Chemical Speciation Network (CSN). We also examined measured sulfur dioxide (SO2) emissions from power plants from 1995 through 2010 from the EPA's Acid Rain Program. The 1992–2010 annual mean sulfate concentrations at long-term sites in the United States have decreased significantly and fairly consistently across the United States at a rate of −2.7% yr−1 (p < 0.01). Short-term annual mean trends at rural and urban sites were −4.6% yr−1 (p < 0.01) from 2001 to 2010 and −6.2% yr−1 (p < 0.01) from 2002 to 2010, respectively. Annual total SO2 emissions from power plants across the United States have decreased at a similar rate as sulfate concentrations from 2000 to 2010 (−4.9% yr−1, p < 0.01), suggesting a linear relationship between SO2 emissions and average sulfate concentrations. This linearity was strongest in the eastern United States and weakest in the West where power plant SO2 emissions were lowest and sulfate concentrations were more influenced by non-power-plant and international SO2 emissions. In addition, annual mean, short-term sulfate concentrations decreased more rapidly in the East relative to the West due to differences in seasonal behavior at certain regions in the West. Specifically, increased wintertime concentrations in the central and northern Great Plains and increased springtime concentrations in the western United States were observed. These seasonal and regional increased concentrations could not be explained by changes in local and regional SO2 emissions, suggesting other contributing influences. This work implies that on an annual mean basis across the United States, air quality mitigation strategies have been successful in reducing the particulate loading of sulfate in the atmosphere; however, for certain seasons and regions, especially in the West, current mitigation strategies appear insufficient.
Carbon fluxes forced by anticyclonic mesoscale eddies generated by islands at the subtropical NE Atlantic Ocean
Authors: Lasternas S. , Piedeleu M. , Sangrà P. , Duarte C. M. , Agustí S.
Published: August 2012

Abstract. The carbon fluxes mediated by planktonic communities in two cyclonic eddies (CEs) and two anticyclonic eddies (AEs) at the Canary Eddy Corridor were studied and compared with the dynamics in two far-field (FF) stations located outside the eddies. We observed favorable conditions and signs for upwelling at the center of CEs and for downwelling and mixing at the centers of AEs. CEs were characterized by higher nutrients concentration and highest chlorophyll a concentration, associated with highest microphytoplankton and diatoms abundance. AEs displayed similar chlorophyll a values and nutrients concentration (except highest ammonium concentration) to those of the FF stations and were characterized by increasing abundance of picophytoplankton and heterotrophic bacteria. While primary production was similar between the systems, the production of dissolved organic carbon (PDOC) was significantly higher at AEs. Phytoplankton cell mortality was lowest in CEs and we found higher cell mortality in AE than FF, despite similar chl a concentration. Environmental changes at the AEs presented significant prejudicial effects on the phytoplankton health as indicated by higher phytoplankton mortality (e.g. 60% of dead diatoms cells) and higher cell lysis rates observed at AEs than at two other systems. The adverse conditions associated to the early-stage anticyclonic systems, mainly triggered by active downwelling, resulted in higher consequent PDOC production, corresponding to forcing of the carbon flux to the dissolved pool and a weakness of the carbon pump.
The influence of dynamic vegetation on the present-day simulation and future projections of the South Asian summer monsoon in the HadGEM2 family
Authors: Martin G. M. , Levine R. C.
Published: August 2012

Abstract. Various studies have shown the importance of Earth System feedbacks in the climate system and the necessity of including these in models used for making climate change projections. The HadGEM2 family of Met Office Unified Model configurations combines model components which facilitate the representation of many different processes within the climate system, including atmosphere, ocean and sea ice, and Earth System components including the terrestrial and oceanic carbon cycle and tropospheric chemistry. We examine the climatology of the Asian summer monsoon in present-day simulations and in idealised climate change experiments in which a quadrupling of CO2 is applied as a step change. Members of the HadGEM2 family are used, with a common physical framework, one of which includes tropospheric chemistry and an interactive terrestrial and oceanic carbon cycle, to investigate whether such components affect the way in which the monsoon changes. We focus particularly on the role of interactive vegetation in the simulations from these model configurations. Using an atmosphere-only HadGEM2 configuration, we investigate how the changes in land cover which result from the interaction between the dynamic vegetation and the model systematic rainfall biases affect the Asian summer monsoon, both in the present-day and in future climate projections. We demonstrate that the response of the dynamic vegetation to biases in regional climate, such as lack of rainfall over tropical dust-producing regions, can affect both the present-day simulation and the response to climate change forcing scenarios.
Analyzing numerics of bulk microphysics schemes in community models: warm rain processes
Authors: Sednev I. , Menon S.
Published: August 2012

Abstract. Implementation of bulk cloud microphysics (BLK) parameterizations in atmospheric models of different scales has gained momentum in the last two decades. Utilization of these parameterizations in cloud-resolving models when timesteps used for the host model integration are a few seconds or less is justified from the point of view of cloud physics. However, mechanistic extrapolation of the applicability of BLK schemes to the regional or global scales and the utilization of timesteps of hundreds up to thousands of seconds affect both physics and numerics. We focus on the mathematical aspects of BLK schemes, such as stability and positive-definiteness. We provide a strict mathematical definition for the problem of warm rain formation. We also derive a general analytical condition (SM-criterion) that remains valid regardless of parameterizations for warm rain processes in an explicit Eulerian time integration framework used to advanced finite-difference equations, which govern warm rain formation processes in microphysics packages in the Community Atmosphere Model and the Weather Research and Forecasting model. The SM-criterion allows for the existence of a unique positive-definite stable mass-conserving numerical solution, imposes an additional constraint on the timestep permitted due to the microphysics (like the Courant-Friedrichs-Lewy condition for the advection equation), and prohibits use of any additional assumptions not included in the strict mathematical definition of the problem under consideration. By analyzing the numerics of warm rain processes in source codes of BLK schemes implemented in community models we provide general guidelines regarding the appropriate choice of time steps in these models.
Weather model performance on extreme rainfall events simulation's over Western Iberian Peninsula
Authors: Pereira S. C. , Carvalho A. C. , Ferreira J. , Nunes J. P. , Kaiser J. J. , Rocha A.
Published: August 2012

Abstract. This study evaluates the performance of the WRF-ARW numerical weather model in simulating the spatial and temporal patterns of an extreme rainfall period over a complex orographic region in north-central Portugal. The analysis was performed for the December month of 2009, during the Portugal Mainland rainy season. The heavy rainfall to extreme heavy rainfall periods were due to several low surface pressure's systems associated with frontal surfaces. The total amount of precipitation for December exceeded, in average, the climatological mean for the 1971–2000 time period in +89 mm, varying from 190 mm (south part of the country) to 1175 mm (north part of the country). Three model runs were conducted to assess possible improvements in model performance: (1) the WRF-ARW is forced with the initial fields from a global domain model (RunRef); (2) data assimilation for a specific location (RunObsN) is included; (3) nudging is used to adjust the analysis field (RunGridN). Model performance was evaluated against an observed hourly precipitation dataset of 15 rainfall stations using several statistical parameters. The WRF-ARW model reproduced well the temporal rainfall patterns but tended to overestimate precipitation amounts. The RunGridN simulation provided the best results but model performance of the other two runs was good too, so that the selected extreme rainfall episode was successfully reproduced.
How will climate change modify river flow regimes in Europe?
Authors: Schneider C. , Laizé C. L. R. , Acreman M. C. , Flörke M.
Published: August 2012

Abstract. Worldwide, flow regimes are being modified by various anthropogenic impacts and climate change induces an additional risk. Rising evapotranspiration rates, declining snow cover and changing precipitation patterns will interact differently at different locations. Consequently, in distinct climate zones, unequal consequences can be expected in matters of water stress, flood risk, water quality, and food security. In particular, river ecosystems and their vital ecosystem services will be compromised as their species richness and composition have evolved over long time under natural flow conditions. This study aims at evaluating the exclusive impacts of climate change on river flow regimes in Europe. Various flow characteristics are taken into consideration and diverse dynamics are identified for each distinct climate zone in Europe. In order to simulate natural and modified flow regimes, the global hydrology model WaterGAP3 is applied. All calculations for current and future conditions (2050s) are carried out on a 5' × 5' European grid. To address uncertainty, climate forcing data of three different global climate models are used to drive WaterGAP3. Finally, the hydrological alterations of different flow characteristics are quantified by the Indicators of Hydrological Alteration approach. Results of our analysis indicate that on European scale, climate change can be expected to modify flow regimes significantly. This is especially the case in the Mediterranean climate zone (due to drier conditions with reduced precipitation across the year) and in the continental climate zone (due to reduced snowmelt and drier summers). Regarding single flow characteristics, strongest impacts on timing were found for the boreal climate zone. This applies for both, high and low flows. While low flow magnitudes are likely to be stronger influenced in the Mediterranean climate, high flow magnitudes will be mainly altered in snow climates with warmer summers. At the end of this study, typical future flow regimes under climate change are illustrated for each climate zone including a validation on robustness.
Seawater capacitance – a promising proxy for mapping and characterizing drifting hydrocarbon plumes in the deep ocean
Authors: Wynn J. C. , Fleming J. A.
Published: August 2012

Abstract. Hydrocarbons released into the deep ocean are an inevitable consequence of natural seep, seafloor drilling, and leaking wellhead-to-collection-point pipelines. The Macondo 252 (Deepwater Horizon) well blowout of 2010 was even larger than the Ixtoc event in the Gulf of Campeche in 1979. History suggests it will not be the last accidental release, as deepwater drilling expands to meet an ever-growing demand. For those who must respond to these sorts of disasters, the first line of action should be to know what is going on. This includes knowing where an oil plume is at any given time, where and how fast it is moving, and how it is evolving. We have experimented in the laboratory with induced polarization as a method to track hydrocarbons in the seawater column and find that finely dispersed oil in seawater gives rise to a large distributed capacitance. This potentially could be used to both map and characterize oil plumes, down to less than 0.1%, drifting and evolving in the deep ocean. A side benefit demonstrated in some earlier sea-trials is that this same approach in modified form can also map certain heavy placer minerals, as well as communication cables, pipelines, and wrecks buried beneath the seafloor.
Atopaxar
Authors: Wurster T. , May A. E.
Published: August 2012

Atopaxar, also known as E 5555 is a novel reversible protease-activated receptor-1 (PAR-1) thrombin receptor antagonist. To date, Atopaxar has been investigated in phase II trials with focus on safety and tolerability in patients with acute coronary syndromes or stable coronary artery disease on top of standard antiplatelet therapy. Atopaxar was generally well tolerated, however a rise in liver enzymes and prolongation of the QTcF interval were observed. The data suggest, that atopaxar administration may promote some minor bleeding complications, but does not seem to significantly increase the risk of major bleeding. Although not powered for efficacy, the currently available data suggest potential benefits in patients at high risk for recurrent ischemic events on top of standard antiplatelet therapy. In conclusion, more studies (e.g. phase III) are needed to evaluate efficacy and safety of atopaxar.
Investigation on the pollen morphology of traditional cultivars of Prunus species in Sicily
Authors: Geraci Anna , Polizzano Vincenza , Marino Pasquale , Schicchi Rosario
Published: August 2012

In this study pollen grains of 13 cultivars and 3 rootstocks belonging to 5 species (P. armeniaca, P. domestica, P. dulcis, P. persica, P. avium) of the genus Prunus collected from North-East Sicily were examined for the micromorphological characterization through the scanning electron microscopy (SEM). The length of polar axis (P) and the equatorial diameter (E) of grain, P/E ratio, the length of colpi (C), diameter of perforations (DP) and the number of perforations in 25 μm2 (PN), the width of muri (WM), the distance between muri (DM) and their number in 25 μm2 (MN), the width of grooves (WG) were measured and their variation was compared among studied taxa. Moreover multivariate statistical analysis was carried out to distinguish morphometric information from measured parameters. All pollen grains are trizonocolpate, isopolar, medium-large sized and their shape varies from prolate to perprolate. Regarding outline pollen grains are subtriangular in polar view and elliptic in equatorial view. Exine sculpturing is striate with perforations on grain surface. The arrangement of ridges appears roughly parallel but too sloped (sometimes curved) compared to polar axis, or branched and oriented in different directions, or perfectly parallel or more irregular with bifurcated ridges often sinuous. The analyses showed a great variability (particularly in P. domestica cultivars) related in some cases to the diversity in the morphological features of the leaves and the fruits of the investigated entities.
Health Status and Mental Health of Transgender and Gender-Diverse Adults
Authors: Liu Michael , Patel Vishal R. , Reisner Sari L. , Keuroghlian Alex S.
Published: June 2024

This cross-sectional study examines self-reported poor or fair health status, frequent mental distress, and depression among transgender and gender-diverse respondents compared with cisgender respondents to the 2014 to 2022 Behavioral Risk Factor Surveillance System.
Initial Oxygen Concentration for the Resuscitation of Infants Born at Less Than 32 Weeks’ Gestation
Authors: Sotiropoulos James X. , Oei Ju Lee , Schmölzer Georg M. , Libesman Sol , Hunter Kylie E. , Williams Jonathan G. , Webster Angela C. , Vento Maximo , Kapadia Vishal , Rabi Yacov , Dekker Janneke , Vermeulen Marijn J. , Sundaram Venkataseshan , Kumar Praveen , Kaban Risma K. , Rohsiswatmo Rinawati , Saugstad Ola D. , Seidler Anna Lene
Published: June 2024

Importance

Resuscitation with lower fractional inspired oxygen (FiO2) reduces mortality in term and near-term infants but the impact of this practice on very preterm infants is unclear.

Objective

To evaluate the relative effectiveness of initial FiO2 on reducing mortality, severe morbidities, and oxygen saturations (SpO2) in preterm infants born at less than 32 weeks’ gestation using network meta-analysis (NMA) of individual participant data (IPD).

Data Sources

MEDLINE, Embase, CENTRAL, CINAHL, ClinicalTrials.gov, and WHO ICTRP from 1980 to October 10, 2023.

Study Selection

Eligible studies were randomized clinical trials enrolling infants born at less than 32 weeks’ gestation comparing at least 2 initial oxygen concentrations for delivery room resuscitation, defined as either low (≤0.3), intermediate (0.5-0.65), or high (≥0.90) FiO2.

Data Extraction and Synthesis

Investigators from eligible studies were invited to provide IPD. Data were processed and checked for quality and integrity. One-stage contrast-based bayesian IPD-NMA was performed with noninformative priors and random effects and adjusted for key covariates.

Main Outcomes and Measures

The primary outcome was all-cause mortality at hospital discharge. Secondary outcomes were morbidities of prematurity and SpO2 at 5 minutes.

Results

IPD were provided for 1055 infants from 12 of the 13 eligible studies (2005-2019). Resuscitation with high (≥0.90) initial FiO2 was associated with significantly reduced mortality compared to low (≤0.3) (odds ratio [OR], 0.45; 95% credible interval [CrI], 0.23-0.86; low certainty) and intermediate (0.5-0.65) FiO2 (OR, 0.34; 95% CrI, 0.11-0.99; very low certainty). High initial FiO2 had a 97% probability of ranking first to reduce mortality. The effects on other morbidities were inconclusive.

Conclusions and Relevance

High initial FiO2 (≥0.90) may be associated with reduced mortality in preterm infants born at less than 32 weeks’ gestation compared to low initial FiO2 (low certainty). High initial FiO2 is possibly associated with reduced mortality compared to intermediate initial FiO2 (very low certainty) but more evidence is required.
Nonmetal Substitution in Interstitial Site of O3‐NaNi0.5Mn0.5O2 Induces the Generation of a Nearly Zero Strain P2&O3 Biphasic Structure as Ultrastable Sodium‐Ion Cathode
Authors: Yu Lai , He Xiaoyue , Peng Bo , Wang Feng , Ahmad Nazir , Shen Yongkuan , Ma Xinyi , Tao Zongzhi , Liang Jiacheng , Jiang Zixuan , Diao Zhidan , He Bowen , Xie Yuhu , Qing Bing , Wang Chao , Wang Yifei , Zhang Genqiang
Published: June 2024

Co‐free O3‐type NaNi0.5Mn0.5O2 cathode material for sodium‐ion batteries has shown great promise due to its high theoretical capacity and plentiful Na reservoir. However, the rapid capacity recession caused by harmful phase transition and large volume strain severely restricts their practical application. Herein, the obstacle is well addressed by constructing a P2&O3 biphasic structure via a customized boron‐doping strategy. The light‐weight boron doping in the interstitial position reduces the energy gap of the formation energy of P2 and O3 structure, which induces the formation of P2&O3 biphase in high Na state. In addition, the biphasic structure exhibits near zero volume strain due to the lattice interlocking effect of P2&O3, as identified by in situ X‐ray diffraction measurement. As a result, it presents a remarkable cyclability with a capacity retention of 85.2% over 1000 cycles at a high rate of 5 C. More importantly, a pouch‐type full‐cell device can exhibit a long cycling life with 70.8% capacity retention over 150 cycles at 0.1 C. This work can offer a new inspiration for designing advanced high sodium electrode materials via light element doping for future energy storage devices.
Solving the Annealing of Mo Interconnects for Next‐Gen Integrated Circuits
Authors: Erofeev Ivan , Hartanto Antony Winata , Saidov Khakimjon , Aabdin Zainul , Pacco Antoine , Philipsen Harold , Tjiu Weng Weei , Hui Hui Kim , Holsteyns Frank , Mirsaidov Utkur
Published: June 2024

Recent surge in demand for computational power combined with strict constraints on energy consumption requires persistent increase in the density of transistors and memory cells in integrated circuits. Metal interconnects in their current form struggle to follow the size downscaling due to materials limitations at the nanoscale, causing severe performance losses. Next‐generation interconnects need new materials, and molybdenum (Mo) is considered the best choice, offering low resistivity, good scalability, and barrierless integration at a low cost. However, it requires annealing at temperatures far exceeding the currently accepted limit. In this work, the challenges of high‐temperature annealing of patterned Mo nanowires are looked into, and a new approach is presented to overcome them. It is demonstrated that while a conventional annealing process improves the average grain size, it can also reduce the cross‐section area, thus increasing the resistivity. Using high‐resolution transmission electron microscopy (TEM) with in situ heating, the evolution of structural features in real time is directly observed. Using insights from these experiments, a cyclic pulsed annealing method is developed, and it is shown that the desired grain structure is achieved in only a few seconds, without forming the surface grooves. These findings can radically facilitate Mo integration, boosting the efficiency of future integrated circuits.
Contemporary Impedance Analyses of Archetypical PM6:Y6 Bulk‐Heterojunction Blend
Authors: Tokmoldin Nurlan , Deibel Carsten , Neher Dieter , Shoaee Safa
Published: June 2024

An organic bulk heterojunction based on a blend of a conjugated polymer PBDB‐T‐2F (PM6) and a non‐fullerene acceptor BTP‐4F (Y6) has come forward in recent years as an archetypical system for the study of the operating principles of organic photovoltaic devices. One of the experimental techniques that has shown immense value in the study of this blend is impedance spectroscopy (IS). In spite of its relative simplicity, this method and its derivatives offer the possibility of diverse, all‐round characterization of materials and devices of interest. This Perspective summarizes recent research demonstrating the application of IS as a powerful method to obtain multifaceted information on PM6:Y6 and presents a current understanding of the experimental results. A description of general approaches employed in the processing of experimental data, including the Nyquist plots, capacitance spectra, and energy‐resolved electrochemical IS data, is supplemented by additional analysis, notably on characterization of non‐geminate recombination of free charge carriers and their transport in this groundbreaking organic blend. Finally, this work outlines the perspectives and limitations of IS in the study of future promising materials and devices.
Gas Diffusion Electrodes for Electrocatalytic Oxidation of Gaseous Ammonia: Stepping Over the Nitrogen Energy Canyon
Authors: Cechanaviciute Ieva A. , Kumari Bhawana , Alfes Lars M. , Andronescu Corina , Schuhmann Wolfgang
Published: June 2024

As ammonia continues to gain more and more interest as a promising hydrogen carrier compound, so does the electrochemical ammonia oxidation reaction (AmOR). To avoid the liberation of H2 in a reverse Haber–Bosch reaction under release of the energetically more favorable N2, we propose the oxidation of ammonia to value‐added nitrite (NO2−), which is usually obtained during the Ostwald process. We investigated the anodic oxidation of gaseous ammonia directly supplied to a gas diffusion electrode (GDE) using a variety of compositionally different multi‐metal catalysts coated on Ni foam under the simultaneous formation of H2 at the cathode. This will double the amount of H2 per ammonia molecule while applying a lower overpotential than that required for water electrolysis (1.4–1.8 V vs. RHE at 50 mA ⋅ cm−2). A selectivity study demonstrated that some of the catalyst compositions were able to produce significant amounts of NO2−, and further investigations using the most promising catalyst composition Nif_AlCoCrCuFe integrated within a GDE demonstrated up to 88 % Faradaic efficiency for NO2− at the anode coupled to close to 100 % Faradaic efficiency for the cathodic H2 production.
Anodic H2O2 Generation in Carbonate‐Based Electrolytes—Mechanistic Insight from Scanning Electrochemical Microscopy
Authors: Li Lejing , Antony Rajini P. , Santos Carla Santana , Limani Ndrina , Dieckhöfer Stefan , Schuhmann Wolfgang
Published: June 2024

For the anodic H2O2 generation, it has been shown that the electrolyte composition can steer the reaction pathway toward increased H2O2 generation. Previous efforts made on composition optimization found that the impact of the molar fraction of carbonate species varies for different anodes, and therefore, controversies remain concerning the reaction pathways as well as the species involved in H2O2 formation. Considering that water oxidation results in the liberation of protons within the anode microenvironment, the corresponding acidification would cause an equilibrium shift between carbonate species, which in turn may modulate the reaction pathway. We determined the changes in the fraction of carbonate species in the vicinity of an anode by performing local pH measurements using a Au nanoelectrode positioned in close proximity to an operating anode by shear‐force scanning electrochemical microscopy (SECM). It could be confirmed that the main anionic species at the interface is HCO3−, at potentials where H2O2 is preferentially formed, regardless of the pH value in the bulk. The simultaneous use of a Au−Pt double barrel microelectrode in generator‐collector SECM measurements demonstrates that the local HCO3− concentration is collectively determined by the oxidation current, buffer capacity, and bulk pH of the electrolyte.
Perovskite‐Like Liquid‐Crystalline Materials Based on Polyfluorinated Imidazolium Cations
Authors: Stergiou Anastasios , Leccioli Leonardo , Ricci Davide , Zaffalon Matteo L. , Brovelli Sergio , Bombelli Francesca Baldelli , Terraneo Giancarlo , Metrangolo Pierangelo , Cavallo Gabriella
Published: June 2024

Hybrid Organic‐Inorganic Halide Perovskites (HOIHPs) represent an emerging class of semiconducting materials, widely employed in a variety of optoelectronic applications. Despite their skyrocket growth in the last decade, a detailed understanding on their structure–property relationships is still missing. In this communication, we report two unprecedented perovskite‐like materials based on polyfluorinated imidazolium cations. The two materials show thermotropic liquid crystalline behavior resulting in the emergence of stable mesophases. The manifold intermolecular F ⋅ ⋅ ⋅ F interactions are shown to be meaningful for the stabilization of both the solid‐ and liquid‐crystalline orders of these perovskite‐like materials. Moreover, the structure of the incorporated imidazolium cation was found to tune the properties of the liquid crystalline phase. Collectively, these results may pave the way for the design of a new class of halide perovskite‐based soft materials.
The “Pull Effect” of a Hanging ZnII on Improving the Four‐Electron Oxygen Reduction Selectivity with Co Porphyrin
Authors: Han Jinxiu , Tan Huang , Guo Kai , Lv Haoyuan , Peng Xinyang , Zhang Wei , Lin Haiping , Apfel Ulf‐Peter , Cao Rui
Published: June 2024

Due to the challenge of cleaving O−O bonds at single Co sites, mononuclear Co complexes typically show poor selectivity for the four‐electron (4e−) oxygen reduction reaction (ORR). Herein, we report on selective 4e− ORR catalyzed by a Co porphyrin with a hanged ZnII ion. Inspired by Cu/Zn‐superoxide dismutase, we designed and synthesized 1‐CoZn with a hanging ZnII at the second sphere of a Co porphyrin. Complex 1‐CoZn is much more effective than its Zn‐lacking analogues to catalyze the 4e− ORR in neutral aqueous solutions, giving an electron number of 3.91 per O2 reduction. With spectroscopic studies, the hanging ZnII was demonstrated to be able to facilitate the electron transfer from CoII to O2, through an electronic “pull effect”, to give CoIII‐superoxo. Theoretical studies further suggested that this “pull effect” plays crucial roles in assisting O−O bond cleavage. This work is significant to present a new strategy of hanging a ZnII to improve O2 activation and O−O bond cleavage.
Highly efficient catalytic reduction of organic dyes, Cr (VI) and 4‐nitrophenol, and photocatalytic degradation of MB by an inorganic–organic hybrid polyoxometalate
Authors: Liu Zi‐Qing , Kong Ling‐Yan , Fei Bao‐Li
Published: June 2024

It is urgent to remove various pollutants from the water environment. Therefore, an inorganic–organic hybrid polyoxometalate (POM) [PMoVI6MoV2VIV8O44{Co(2,2′‐bipy)2(H2O)}4]‐[PMoVI4MoV4VIV8O44{Co(2,2′‐bipy)2(H2O)}2]·4H2O (PMoVCo) was fully characterized by XRD, XPS, FTIR, SEM, BET and zeta potential techniques, and applied for the catalytic reduction of hazardous methylene blue (MB), methyl orange (MO), rhodamine B (RhB), Cr (VI) and 4‐nitrophenol (4‐NP) in aqueous media over NaBH4 under mild condition. The removal ratios were 99.6% (MB, 2.5 min), 97.0% (MO, 3.0 min), 92.5% (RhB, 2.0 min), 89.2% (Cr (VI), 2.0 min) and 89.6% (4‐NP, 2.5 min), respectively. The pseudo‐first‐order rate constants of the reactions were 1.992 min−1 (MB), 0.810 min−1 (MO), 1.768 min−1 (RhB), 1.186 min−1 (Cr (VI)) and 0.934 min−1 (4‐NP), respectively. Additionally, PMoVCo exhibited satisfactory catalytic activity for the photo‐Fenton‐like degradation of MB at neutral pH under visible light irradiation with a degradation rate up to 99.9% in 480 min. The results of the recycling experiment prove that PMoVCo has high catalytic reusability. Moreover, the possible mechanisms of the catalytic reduction and degradation processes were proposed. The catalytic activities of PMoVCo are better than other inorganic–organic hybrid POMs. All the results of this study indicate that PMoVCo has the potential to be a satisfactory catalyst for wastewater remediation via reduction or photocatalytic degradation.
Enzymatic conversion of camellia seed oil into glycerol esters: Synthesis and characterization
Authors: Wu Jingzhi , Xiao Jingjing , Nie Suli , Chao Yan , Li Peiwang , Li Changzhu , Xiao Zhihong , Wu Hongmei
Published: June 2024

The conversion of triacylglycerols in edible oils into diacylglycerols (DAGs) is of great significance for obtaining products with health benefits. Camellia seed oil (C‐oil), which is rich in oleic acid and linoleic acid, is an excellent raw material for the production of DAGs. In this study, single factor optimization experiments were carried out for hydrolysis and esterification respectively. Using Lipozyme® RM IM as catalyst, the maximum percent of C‐oil hydrolysis reached 87.14% at the reaction temperature of 60°C, reaction time of 24 h, water content of 30% and enzyme addition amount of 4%. The maximum content of camellia seed oil diacylglycerol (C‐DAG) reached 62.49% under the conditions of Lipozyme® RM IM as catalyst, vacuum system, 3% enzyme addition, 2% water addition, reaction temperature of 50°C and substrate molar ratio of free fatty acid to glycerol of 1:1. The high content of DAG was obtained by a coupled method, which eliminated the purification steps and reduced production costs. C‐oil and C‐DAG have been characterized by GC, TG, DSC, and GC‐IMS. Our results showed that the enzymatic coupling method did not affect the structural of the substances, but did affect the crystallization and melting properties of the oils. Moreover, the taste of C‐DAG was more delicate than C‐oil. Finally, the reaction mechanism was analyzed using FTIR spectroscopy, revealing that C‐oil was primarily hydrolyzed into free fatty acids. C‐DAG exhibited ester C‐O stretching vibrations in the range 1280–1030 cm−1, indicating successful esterification reaction between camellia seed oil free fatty acids (C‐FFAs) and glycerol catalyzed by lipases.
Small‐ and medium‐sized enterprises' carbon footprint reduction initiatives as a catalyst for green jobs: A systematic review and comprehensive business strategy agenda
Authors: Olekanma Obafemi , Rodrigo Liyanage S. , Adu Douglas A. , Gahir Bruce
Published: June 2024

Motivated by the growing attention on climate change, this study provides an up‐to‐date and comprehensive systematic literature review (SLR) on small‐ and medium‐sized enterprises (SMEs) carbon footprint reduction initiatives and green jobs. Based on datasets from databases that include Web of Science, Scopus, ProQuest and Google Scholar, we conducted a SLR of 70 published articles spanning 2012 to 2022. Using VOSviewer and InfraNodus, bibliographic cluster analysis revealed the existence of three clusters namely; the role of green job initiatives and green human resource management in SMEs (cluster 1); green innovation, green Initiatives, green strategy and circular economy in SMEs (cluster 2); carbon footprint reduction initiatives, carbon performance, carbon management and carbon emission in SMEs (cluster 3). We found that SMEs adopt green supply chain, employing energy‐saving strategies, eco‐friendly waste reductions and recycling, circular economy, and green office practices. The study results indicate that these carbon footprint initiatives can lead to green job creation since green competences are required to implement green initiatives. However, value propositions relating to carbon reduction initiatives within SMEs need to be integrated with employee engagement. Additionally, the SLR identifies future research areas that include exploring the association among SMEs carbon footprint, green innovation and green jobs, and strategies to enhance climate change initiatives. Consequently, we call for future research to focus on the design of green jobs tracking and carbon footprint reduction reporting framework to support SMEs' green initiatives. The findings have key policy implications for SME owners, policymakers, practitioners and future researchers.
Obesity enhances the response to neoadjuvant anti‐PD1 therapy in oral tongue squamous cell carcinoma
Authors: Tan Xiyan , Li Guoli , Deng Honghao , Xiao Guoming , Wang Yaqin , Zhang Chenzhi , Chen Yanfeng
Published: June 2024

Objectives

Previous studies have demonstrated that obesity may impact the efficacy of anti‐PD1 therapy, but the underlying mechanism remains unclear. In this study, our objective was to determine the prognostic value of obesity in patients with oral tongue squamous cell carcinoma (OTSCC) treated with pembrolizumab and establish a subtype based on fatty acid metabolism‐related genes (FAMRGs) for immunotherapy.

Materials and Methods

We enrolled a total of 56 patients with OTSCC who underwent neoadjuvant anti‐PD1 therapy. Univariate and multivariate Cox regression analyses, Kaplan–Meier survival analysis, and immunohistochemistry staining were performed. Additionally, we acquired the gene expression profiles of pan‐cancer samples and conducted GSEA and KEGG pathway analysis. Moreover, data from TCGA, MSigDB, UALCAN, GEPIA and TIMER were utilized to construct the FAMRGs subtype.

Results

Our findings indicate that high Body Mass Index (BMI) was significantly associated with improved PFS (HR = 0.015; 95% CI, 0.001 to 0.477; p = 0.015), potentially attributed to increased infiltration of PD1 + T cells. A total of 91 differentially expressed FAMRGs were identified between the response and non‐response groups in pan‐cancer patients treated with immunotherapy. Of these, 6 hub FAMRGs (ACSL5, PLA2G2D, PROCA1, IL4I1, UBE2L6 and PSME1) were found to affect PD‐1 expression and T cell infiltration in HNSCC, which may impact the efficacy of anti‐PD1 therapy.

Conclusion

This study demonstrates that obesity serves as a robust prognostic predictor for patients with OTSCC undergoing neoadjuvant anti‐PD1 therapy. Furthermore, the expression of 6 hub FAMRGs (ACSL5, PLA2G2D, PROCA1, IL4I1, UBE2L6 and PSME1) plays a pivotal role in the context of anti‐PD1 therapy and deserves further investigation.
Neutrophilic eccrine hidradenitis from granulocyte‐stimulating factor in a patient with ANCA vasculitis
Authors: Chaisrimaneepan Nattanicha , Saowapa Sakditad , Pangkanon Watsachon , Thongpiya Jerapas , Yingchoncharoen Pitchaporn , Polpichai Natchaya , Siladech Pharit
Published: June 2024

Key Clinical Message

Neutrophilic eccrine hidradenitis (NEH) is one of the cutaneous manifestations of chemotherapy side effects. However, it can arise from other non‐chemotherapy medications. The granulocyte‐colony‐stimulating factor is a medication reported to trigger NEH.
A Pyridine Anchoring Strategy for Dye‐Sensitized Photocatalysis
Authors: Tang Kun , Shao Jiang‐Yang , Zhong Yu‐Wu
Published: June 2024

Anchoring groups play an important role in the assembly of functional molecules onto semiconductor substrates for dye‐sensitized photocatalysis. In addition to directly influencing the adsorption stability, anchoring groups significantly impact the efficiency of electron or hole injection into the substrate, which is a crucial step for photocatalytic reactions. Most reported dye‐sensitized photocatalytic systems, including semiconductor nanoparticles and photoelectrochemical cells, are prepared using the carboxylic or phosphonic acid anchors. The systems prepared with these conventional anchors usually suffer from low adsorption stability in aqueous media. Alternatively, pyridine has emerged as an anchoring group of photosensitizers and molecular catalysts in the construction of photocatalytic systems. The resulting semiconductor nanoparticles and photoelectrodes show superior adsorption stability in aqueous media, providing a simple and efficient way to sensitize the metal or metal oxide substrate. This review focuses on the recent advances of such a pyridine anchoring strategy in the assembly of photosensitizers and molecular catalysts for photocatalytic applications, mainly including photocatalytic water oxidation, reduction, and splitting. The further exploration and understanding of the pyridine‐anchoring method are believed to boost the development of advanced dye‐sensitized photocatalytic devices and technologies.