bluuebunny/crossref_metadata_2025_split huggingface dataset:
Phase transfer catalysts shift the pathway to transmetalation in biphasic Suzuki-Miyaura cross-couplings
Authors: Shi Yao , Derasp Joshua S. , Maschmeyer Tristan , Hein Jason E. 
Published: June 2024

AbstractThe Suzuki-Miyaura coupling is a widely used C-C bond forming reaction. Numerous mechanistic studies have enabled the use of low catalyst loadings and broad functional group tolerance. However, the dominant mode of transmetalation remains controversial and likely depends on the conditions employed. Herein we detail a mechanistic study of the palladium-catalyzed Suzuki-Miyaura coupling under biphasic conditions. The use of phase transfer catalysts results in a remarkable 12-fold rate enhancement in the targeted system. A shift from an oxo-palladium based transmetalation to a boronate-based pathway lies at the root of this activity. Furthermore, a study of the impact of different water loadings reveals reducing the proportion of the aqueous phase increases the reaction rate, contrary to reaction conditions typically employed in the literature. The importance of these findings is highlighted by achieving an exceptionally broad substrate scope with benzylic electrophiles using a 10-fold reduction in catalyst loading relative to literature precedent.
Perfect linear optics using silicon photonics
Authors: Moralis-Pegios Miltiadis , Giamougiannis George , Tsakyridis Apostolos , Lazovsky David , Pleros Nikos 
Published: June 2024

AbstractRecently there has been growing interest in using photonics to perform the linear algebra operations of neuromorphic and quantum computing applications, aiming at harnessing silicon photonics’ (SiPho) high-speed and energy-efficiency credentials. Accurately mapping, however, a matrix into optics remains challenging, since state-of-the-art optical architectures are sensitive to fabrication imperfections. This leads to reduced fidelity that degrades as the insertion losses of the optical matrix nodes or the matrix dimensions increase. In this work, we present the experimental deployment of a 4 × 4 coherent crossbar (Xbar) as a silicon chip and validate experimentally its theoretically predicted fidelity restoration credentials. We demonstrate the experimental implementation of 10,000 arbitrary linear transformations achieving a record-high fidelity of 99.997% ± 0.002, limited mainly by the measurement equipment. Our work represents an integrated optical circuit providing almost unity and loss-independent fidelity in the realization of arbitrary matrices, highlighting light’s credentials in resolving complex computations.
Storing and managing water for the environment is more efficient than mimicking natural flows
Authors: Null Sarah E. , Zeff Harrison , Mount Jeffrey , Gray Brian , Sturrock Anna M. , Sencan Gokce , Dybala Kristen , Thompson Barton 
Published: June 2024

AbstractDams and reservoirs are often needed to provide environmental water and maintain suitable water temperatures for downstream ecosystems. Here, we evaluate if water allocated to the environment, with storage to manage it, might allow environmental water to more reliably meet ecosystem objectives than a proportion of natural flow. We use a priority-based water balance operations model and a reservoir temperature model to evaluate 1) pass-through of a portion of reservoir inflow versus 2) allocating a portion of storage capacity and inflow for downstream flow and stream temperature objectives. We compare trade-offs to other senior and junior priority water demands. In many months, pass-through flows exceed the volumes needed to meet environmental demands. Storage provides the ability to manage release timing to use water efficiently for environmental benefit, with a co-benefit of increasing reservoir storage to protect cold-water at depth in the reservoir.
Fe3O4-doped mesoporous carbon cathode with a plumber’s nightmare structure for high-performance Li-S batteries
Authors: Zhang Han , Zhang Mengtian , Liu Ruiyi , He Tengfeng , Xiang Luoxing , Wu Xinru , Piao Zhihong , Jia Yeyang , Zhang Chongyin , Li Hong , Xu Fugui , Zhou Guangmin , Mai Yiyong 
Published: June 2024

AbstractShuttling of lithium polysulfides and slow redox kinetics seriously limit the rate and cycling performance of lithium-sulfur batteries. In this study, Fe3O4-dopped carbon cubosomes with a plumber’s nightmare structure (SP-Fe3O4-C) are prepared as sulfur hosts to construct cathodes with high rate capability and long cycling life for Li-S batteries. Their three-dimensional continuous mesochannels and carbon frameworks, along with the uniformly distributed Fe3O4 particles, enable smooth mass/electron transport, strong polysulfides capture capability, and fast catalytic conversion of the sulfur species. Impressively, the SP-Fe3O4-C cathode exhibits top-level comprehensive performance, with high specific capacity (1303.4 mAh g−1 at 0.2 C), high rate capability (691.8 mAh gFe3O41 at 5 C), and long cycling life (over 1200 cycles). This study demonstrates a unique structure for high-performance Li-S batteries and opens a distinctive avenue for developing multifunctional electrode materials for next-generation energy storage devices.
A political economy theory of fossil fuel subsidy reforms in OECD countries
Authors: Droste Nils , Chatterton Benjamin , Skovgaard Jakob 
Published: June 2024

AbstractFossil fuel subsidies continue to be a considerable barrier to meeting the targets of the Paris Agreement. It is thus crucial to understand the political economy of fossil fuel subsidies and their reform. To understand these mechanisms in the developed world, we use a database of different types of fossil fuel subsidy reforms among Organisation for Economic Co-operation and Development (OECD) countries. We find evidence for four intertwined processes i) a market-power mechanism: higher market shares for renewables ease fossil fuel subsidy reforms, and ii) a policy mechanism: reforms reduce the levels of fossil fuel subsidies. Importantly, both effects are contingent on iii) a polity mechanism where institutional quality influences the feasibility and effectiveness of political reforms, and iv) a feedback mechanism where systemic lock-ins determine the effectiveness of market competition. Our results even suggest that reforms carried out by effective governments with low corruption control are associated with increasing subsidies per capita. Renewable energy support can however provide a leverage point to break path-dependencies in fossil fuel-based economies. This turns out to be more effective when coupled with improvements to institutional quality and the insulation of political processes from pro-subsidy interests.
In-situ and wavelength-dependent photocatalytic strain evolution of a single Au nanoparticle on a TiO2 film
Authors: Park Sung Hyun , Kim Sukyoung , Park Jae Whan , Kim Seunghee , Cha Wonsuk , Lee Joonseok 
Published: June 2024

AbstractPhotocatalysis is a promising technique due to its capacity to efficiently harvest solar energy and its potential to address the global energy crisis. However, the structure–activity relationships of photocatalyst during wavelength-dependent photocatalytic reactions remains largely unexplored because it is difficult to measure under operating conditions. Here we show the photocatalytic strain evolution of a single Au nanoparticle (AuNP) supported on a TiO2 film by combining three-dimensional (3D) Bragg coherent X-ray diffraction imaging with an external light source. The wavelength-dependent generation of reactive oxygen species (ROS) has significant effects on the structural deformation of the AuNP, leading to its strain evolution. Density functional theory (DFT) calculations are employed to rationalize the induced strain caused by the adsorption of ROS on the AuNP surface. These observations provide insights of how the photocatalytic activity impacts on the structural deformation of AuNP, contributing to the general understanding of the atomic-level catalytic adsorption process.
Uneven consequences of global climate mitigation pathways on regional water quality in the 21st century
Authors: Lee Minjin , Stock Charles A. , Shevliakova Elena , Malyshev Sergey , Beaudor Maureen , Vuichard Nicolas 
Published: June 2024

AbstractFuture socioeconomic climate pathways have regional water-quality consequences whose severity and equity have not yet been fully understood across geographic and economic spectra. We use a process-based, terrestrial-freshwater ecosystem model to project 21st-century river nitrogen loads under these pathways. We find that fertilizer usage is the primary determinant of future river nitrogen loads, changing precipitation and warming have limited impacts, and CO2 fertilization-induced vegetation growth enhancement leads to modest load reductions. Fertilizer applications to produce bioenergy in climate mitigation scenarios cause larger load increases than in the highest emission scenario. Loads generally increase in low-income regions, yet remain stable or decrease in high-income regions where agricultural advances, low food and feed production and waste, and/or well-enforced air pollution policies balance biofuel-associated fertilizer burdens. Consideration of biofuel production options with low fertilizer demand and rapid transfer of agricultural advances from high- to low-income regions may help avoid inequitable water-quality outcomes from climate mitigation.
Unsupervised learning-enabled pulsed infrared thermographic microscopy of subsurface defects in stainless steel
Authors: Zhang Xin , Fang Tianyang , Saniie Jafar , Bakhtiari Sasan , Heifetz Alexander 
Published: June 2024

AbstractMetallic structures produced with laser powder bed fusion (LPBF) additive manufacturing method (AM) frequently contain microscopic porosity defects, with typical approximate size distribution from one to 100 microns. Presence of such defects could lead to premature failure of the structure. In principle, structural integrity assessment of LPBF metals can be accomplished with nondestructive evaluation (NDE). Pulsed infrared thermography (PIT) is a non-contact, one-sided NDE method that allows for imaging of internal defects in arbitrary size and shape metallic structures using heat transfer. PIT imaging is performed using compact instrumentation consisting of a flash lamp for deposition of a heat pulse, and a fast frame infrared (IR) camera for measuring surface temperature transients. However, limitations of imaging resolution with PIT include blurring due to heat diffusion, sensitivity limit of the IR camera. We demonstrate enhancement of PIT imaging capability with unsupervised learning (UL), which enables PIT microscopy of subsurface defects in high strength corrosion resistant stainless steel 316 alloy. PIT images were processed with UL spatial–temporal separation-based clustering segmentation (STSCS) algorithm, refined by morphology image processing methods to enhance visibility of defects. The STSCS algorithm starts with wavelet decomposition to spatially de-noise thermograms, followed by UL principal component analysis (PCA), fine-tuning optimization, and neural learning-based independent component analysis (ICA) algorithms to temporally compress de-noised thermograms. The compressed thermograms were further processed with UL-based graph thresholding K-means clustering algorithm for defects segmentation. The STSCS algorithm also includes online learning feature for efficient re-training of the model with new data. For this study, metallic specimens with calibrated microscopic flat bottom hole defects, with diameters in the range from 203 to 76 µm, were produced using electro discharge machining (EDM) drilling. While the raw thermograms do not show any material defects, using STSCS algorithm to process PIT images reveals defects as small as 101 µm in diameter. To the best of our knowledge, this is the smallest reported size of a sub-surface defect in a metal imaged with PIT, which demonstrates the PIT capability of detecting defects in the size range relevant to quality control requirements of LPBF-printed high-strength metals.
ECMO is associated with decreased hospital mortality in COVID-19 ARDS
Authors: Kim Won-Young , Jung Sun-Young , Kim Jeong-Yeon , Chae Ganghee , Kim Junghyun , Joh Joon-Sung , Park Tae Yun , Baek Ae-Rin , Jegal Yangjin , Chung Chi Ryang , Lee Jinwoo , Cho Young-Jae , Park Joo Hun , Hwang Jung Hwa , Song Jin Woo 
Published: June 2024

AbstractThis study determined whether compared to conventional mechanical ventilation (MV), extracorporeal membrane oxygenation (ECMO) is associated with decreased hospital mortality or fibrotic changes in patients with COVID-19 acute respiratory distress syndrome. A cohort of 72 patients treated with ECMO and 390 with conventional MV were analyzed (February 2020–December 2021). A target trial was emulated comparing the treatment strategies of initiating ECMO vs no ECMO within 7 days of MV in patients with a PaO2/FiO2 < 80 or a PaCO2 ≥ 60 mmHg. A total of 222 patients met the eligibility criteria for the emulated trial, among whom 42 initiated ECMO. ECMO was associated with a lower risk of hospital mortality (hazard ratio [HR], 0.56; 95% confidence interval [CI] 0.36–0.96). The risk was lower in patients who were younger (age < 70 years), had less comorbidities (Charlson comorbidity index < 2), underwent prone positioning before ECMO, and had driving pressures ≥ 15 cmH2O at inclusion. Furthermore, ECMO was associated with a lower risk of fibrotic changes (HR, 0.30; 95% CI 0.11–0.70). However, the finding was limited due to relatively small number of patients and differences in observability between the ECMO and conventional MV groups.
Fruit quality, antioxidant, and mineral attributes of pomegranate cv. Ghojagh, influenced by shading and spray applications of potassium sulfate and sodium silicate
Authors: Moradi Samira , Zamani Zabihollah , Fatahi Reza , Saba Mahmoud Koushesh , Paliaga Sara , Laudicina Vito Armando , Inglese Paolo , Liguori Giorgia 
Published: June 2024

AbstractPomegranate (Punica granatum L.) fruit quality depends on many traits including visual, biochemical and mineral characteristics. One of the negative traits is aril whitening (AW) which is a frequently observed disorder in hot and dry climates, that leads to decline in desirable fruit quality. Color, antioxidant, and mineral contents of the arils are of prime importance as quality traits. Therefore, this study aims to investigate the effect of shading and foliar minerals on fruit quality during the fruit development stages of pomegranate. Treatments included shaded (50% green net) and unshaded trees and foliar application of trees with potassium sulfate (K, 1% and 2%) or sodium silicate (Si, 0.05, 0.1 and 0.15%) during two growing seasons. Results showed that the severity of AW at harvest decreased significantly when trees were covered with shading compared to control. The color values of L* and ⁰hue for arils were lower in fruits grown under shading conditions indicating darker red arils. Shading significantly reduced chilling injury in cold storage compared to open field fruits. Shading and Si 0.15% increased superoxide dismutase, and catalase enzymes activity while decreased Polyphenol oxidase and peroxidase. Covering trees with shading and Si 0.15% spray resulted in the highest total anthocyanin, antioxidant activity, and total phenolics content in the arils. Shading as well as Si 0.15% increased macronutrients content of the arils. The study concluded that covering pomegranate trees and spraying with Si in hot climate reduced AW, increased antioxidant traits, and led to higher fruit quality.
The relationship between muscle thickness and pennation angle is mediated by fascicle length in the muscles of the lower extremities
Authors: Martin-Rodriguez Saul , Gonzalez-Henriquez Juan Jose , Diaz-Conde Juan Carlos , Calbet Jose A. L. , Sanchis-Moysi Joaquin 
Published: June 2024

AbstractMuscle morphological architecture, a crucial determinant of muscle function, has fascinated researchers since the Renaissance. Imaging techniques enable the assessment of parameters such as muscle thickness (MT), pennation angle (PA), and fascicle length (FL), which may vary with growth, sex, and physical activity. Despite known interrelationships, robust mathematical models like causal mediation analysis have not been extensively applied to large population samples. We recruited 109 males and females, measuring knee flexor and extensor, and plantar flexor MT, PA, and FL using real-time ultrasound imaging at rest. A mixed-effects model explored sex, leg (dominant vs. non-dominant), and muscle region differences. Males exhibited greater MT in all muscles (0.1 to 2.1 cm, p < 0.01), with no sex differences in FL. Dominant legs showed greater rectus femoris (RF) MT (0.1 cm, p = 0.01) and PA (1.5°, p = 0.01), while vastus lateralis (VL) had greater FL (1.2 cm, p < 0.001) and PA (0.6°, p = 0.02). Regional differences were observed in VL, RF, and biceps femoris long head (BFlh). Causal mediation analyses highlighted MT’s influence on PA, mediated by FL. Moderated mediation occurred in BFlh, with FL differences. Gastrocnemius medialis and lateralis exhibited FL-mediated MT and PA relationships. This study unveils the intricate interplay of MT, FL, and PA in muscle architecture.
First in vitro cell co-culture experiments using laser-induced high-energy electron FLASH irradiation for the development of anti-cancer therapeutic strategies
Authors: Orobeti Stefana , Sima Livia Elena , Porosnicu Ioana , Diplasu Constantin , Giubega Georgiana , Cojocaru Gabriel , Ungureanu Razvan , Dobrea Cosmin , Serbanescu Mihai , Mihalcea Alexandru , Stancu Elena , Staicu Cristina Elena , Jipa Florin , Bran Alexandra , Axente Emanuel , Sandel Simion , Zamfirescu Marian , Tiseanu Ion , Sima Felix 
Published: June 2024

AbstractRadiation delivery at ultrahigh dose rates (UHDRs) has potential for use as a new anticancer therapeutic strategy. The FLASH effect induced by UHDR irradiation has been shown to maintain antitumour efficacy with a reduction in normal tissue toxicity; however, the FLASH effect has been difficult to demonstrate in vitro. The objective to demonstrate the FLASH effect in vitro is challenging, aiming to reveal a differential response between cancer and normal cells to further identify cell molecular mechanisms. New high-intensity petawatt laser-driven accelerators can deliver very high-energy electrons (VHEEs) at dose rates as high as 1013 Gy/s in very short pulses (10–13 s). Here, we present the first in vitro experiments carried out on cancer cells and normal non-transformed cells concurrently exposed to laser-plasma accelerated (LPA) electrons. Specifically, melanoma cancer cells and normal melanocyte co-cultures grown on chamber slides were simultaneously irradiated with LPA electrons. A non-uniform dose distribution on the cell cultures was revealed by Gafchromic films placed behind the chamber slide supporting the cells. In parallel experiments, cell co-cultures were exposed to pulsed X-ray irradiation, which served as positive controls for radiation-induced nuclear DNA double-strand breaks. By measuring the impact on discrete areas of the cell monolayers, the greatest proportion of the damaged DNA-containing nuclei was attained by the LPA electrons at a cumulative dose one order of magnitude lower than the dose obtained by pulsed X-ray irradiation. Interestingly, in certain discrete areas, we observed that LPA electron exposure had a different effect on the DNA damage in healthy normal human epidermal melanocyte (NHEM) cells than in A375 melanoma cells; here, the normal cells were less affected by the LPA exposure than cancer cells. This result is the first in vitro demonstration of a differential response of tumour and normal cells exposed to FLASH irradiation and may contribute to the development of new cell culture strategies to explore fundamental understanding of FLASH-induced cell effect.
The small hive beetle’s capacity to disperse over long distances by flight
Authors: Cornelissen Bram , Ellis James D. , Gort Gerrit , Hendriks Marc , van Loon Joop J. A. , Stuhl Charles J. , Neumann Peter 
Published: June 2024

AbstractThe spread of invasive species often follows a jump-dispersal pattern. While jumps are typically fostered by humans, local dispersal can occur due to the specific traits of a species, which are often poorly understood. This holds true for small hive beetles (Aethina tumida), which are parasites of social bee colonies native to sub-Saharan Africa. They have become a widespread invasive species. In 2017, a mark-release-recapture experiment was conducted in six replicates (A–F) using laboratory reared, dye-fed adults (N = 15,690). Honey bee colonies were used to attract flying small hive beetles at fixed spatial intervals from a central release point. Small hive beetles were recaptured (N = 770) at a maximum distance of 3.2 km after 24 h and 12 km after 1 week. Most small hive beetles were collected closest to the release point at 0 m (76%, replicate A) and 50 m (52%, replicates B to F). Temperature and wind deviation had significant effects on dispersal, with more small hive beetles being recaptured when temperatures were high (GLMM: slope = 0.99, SE = 0.17, Z = 5.72, P < 0.001) and confirming the role of wind for odour modulated dispersal of flying insects (GLMM: slope = − 0.39, SE = 0.14, Z = − 2.90, P = 0.004). Our findings show that the small hive beetles is capable of long-distance flights, and highlights the need to understand species specific traits to be considered for monitoring and mitigation efforts regarding invasive alien species.
Frequency and clinical impact of viraemia in paediatric patients undergoing therapy for cancer
Authors: Barnbrock Anke , Berger Annemarie , Lauten Melchior , Demmert Martin , Klusmann Jan-Henning , Ciesek Sandra , Bochennek Konrad , Lehrnbecher Thomas 
Published: June 2024

AbstractIn contrast to transplant recipients, there is a paucity of data regarding frequency and clinical significance of viraemia in children receiving conventional chemotherapy. In a prospective observational study, we assessed the frequency of and clinical impact of viraemia with cytomegalovirus (CMV), Epstein-Barr virus (EBV), adenovirus, human herpesvirus-6 (HHV6) and herpes-simplex virus 1/2 (HSV1/2) in paediatric cancer patients at diagnosis, at a routine examination during intensive chemotherapy, and during febrile neutropenia (FN). Seventy-nine patients (median age 6 years; 66 children with haematological malignancies) were included in the study. Overall, 362 blood samples were analysed, 72 from the time at diagnosis (11.1% with positive PCR result), 118 during a regular control after chemotherapy (11.0% positive), and 159 during FN (8.8% positive). The overall positivity rate was 9.6% (CMV 3.3%, HHV6 2.7%, HSV 2.2%, EBV 0.8% and adenovirus 0.3%). There were no significant differences between FN episodes with and without viraemia in terms of duration of fever or neutropenia/lymphopenia, severity of mucositis (> II0), incidence of diarrhea and ICU admission. Our results indicate that viraemia in paediatric cancer patients generally does not have a major clinical impact, and may help in the decision regarding the indication of routine evaluation for viraemia in febrile neutropenic, but otherwise asymptomatic children.