bluuebunny/crossref_metadata_2025_split huggingface dataset:
Lewis Acid/Oxidant as Rapid Regioselective Halogenating Reagent System for Direct Halogenation of Fused Bi‐/Tri‐cyclic Hetero‐Aromatic Congeners via−H bond Functionalization
Authors: Yadav Ravi Kant , Sharma Richa , Gautam Deepak , Joshi Jyoti , Chaudhary Sandeep 
Published: April 2021

AbstractHerein, we report the identification of new and fast halogenating reagent system consisting of Lewis acid AlX3 [X=Cl, Br, I] as a halogen source in the presence of tert‐butyl hydroperoxide (TBHP) which has been utilized for the direct regioselective halogenation on various fused bi‐/tri‐cyclic hetero‐aromatic congeners 3 a–q, 7 a–d, 8 and 9 via
−H bond functionalization. The operationally simple protocol is quite fast and does not require the external halogenation source at 110 °C in 20–60 minutes and furnished halogenated fused heterocycles 4 a–p, 5 a–k, 6 a–l, 10 a–i, 11 a, 12 a–b in up to 96% yields. The gram‐scale synthesis, wide substrate scope, functional group tolerance, control experiments and application to further derivatization/functionalization for C−C bond formation further highlights the versatility of the developed methodology as well as the compatibility of the new catalyst. The combination of Lewis acid (AlX3) as a halogen source and TBHP (oxidant) as a halogenating reagent system is the first account for the direct regioselective halogenation of several fused bi‐/tri‐cyclic hetero‐aromatic congeners via
−H bond functionalization.
Rotaxane CoII Complexes as Field‐Induced Single‐Ion Magnets
Authors: Cirulli Martina , Salvadori Enrico , Zhang Zhi‐Hui , Dommett Michael , Tuna Floriana , Bamberger Heiko , Lewis James E. M. , Kaur Amanpreet , Tizzard Graham J. , van Slageren Joris , Crespo‐Otero Rachel , Goldup Stephen M. , Roessler Maxie M. 
Published: April 2021

AbstractMechanically chelating ligands have untapped potential for the engineering of metal ion properties. Here we demonstrate this principle in the context of CoII‐based single‐ion magnets. Using multi‐frequency EPR, susceptibility and magnetization measurements we found that these complexes show some of the highest zero field splittings reported for five‐coordinate CoII complexes to date. The predictable coordination behaviour of the interlocked ligands allowed the magnetic properties of their CoII complexes to be evaluated computationally a priori and our combined experimental and theoretical approach enabled us to rationalize the observed trends. The predictable magnetic behaviour of the rotaxane CoII complexes demonstrates that interlocked ligands offer a new strategy to design metal complexes with interesting functionality.
Transition Metal Catalyst‐Free, Base‐Promoted 1,2‐Additions of Polyfluorophenylboronates to Aldehydes and Ketones
Authors: Liu Zhiqiang , Kole Goutam Kumar , Budiman Yudha P. , Tian Ya‐Ming , Friedrich Alexandra , Luo Xiaoling , Westcott Stephen A. , Radius Udo , Marder Todd B. 
Published: April 2021

AbstractA novel protocol for the transition metal‐free 1,2‐addition of polyfluoroaryl boronate esters to aldehydes and ketones is reported, which provides secondary alcohols, tertiary alcohols, and ketones. Control experiments and DFT calculations indicate that both the ortho‐F substituents on the polyfluorophenyl boronates and the counterion K+ in the carbonate base are critical. The distinguishing features of this procedure include the employment of commercially available starting materials and the broad scope of the reaction with a wide variety of carbonyl compounds giving moderate to excellent yields. Intriguing structural features involving O−H⋅⋅⋅O and O−H⋅⋅⋅N hydrogen bonding, as well as arene‐perfluoroarene interactions, in this series of racemic polyfluoroaryl carbinols have also been addressed.
Asymmetric Total Syntheses of 8,9‐Seco‐ent‐kaurane Diterpenoids Enabled by an Electrochemical ODI‐[5+2] Cascade
Authors: Wang Bingnan , Liu Zhaobo , Tong Zhenzhong , Gao Beiling , Ding Hanfeng 
Published: April 2021

AbstractAn electrochemical ODI‐[5+2] cascade reaction was developed which enables the rapid assembly of diversely functionalized bicyclo[3.2.1]octadienones from sensitive ethynylphenols. By combining a directed retro‐aldol/aldol process, a [2,3]‐sigmatropic rearrangement, and an Al(O‐iPr)3‐promoted reductive 1,3‐transposition, the asymmetric total syntheses of five 8,9‐seco‐ent‐kauranoids—(−)‐shikoccin, (−)‐O‐methylshikoccin, (−)‐epoxyshikoccin, (+)‐O‐methylepoxyshikoccin, and (+)‐rabdo‐hakusin—have been achieved in a concise and efficient manner.
Progress and Prospects on the Fabrication of Graphene‐Based Nanostructures for Energy Storage, Energy Conversion and Biomedical Applications
Authors: Immanuel Susan , Ahmad Dar Mushtaq , Sivasubramanian R. , Rezaul Karim Mohammad , Kim Dong‐Wan , Gul Rukshana 
Published: April 2021

AbstractGraphene, a two‐dimensional (2D) layered material has attracted much attention from the scientific community due to its exceptional electrical, thermal, mechanical, biological and optical properties. Hence, numerous applications utilizing graphene‐based materials could be conceived in next‐generation electronics, chemical and biological sensing, energy conversion and storage, and beyond. The interaction between graphene surfaces with other materials plays a vital role in influencing its properties than other bulk materials. In this review, we outline the recent progress in the production of graphene and related 2D materials, and their uses in energy conversion (solar cells, fuel cells), energy storage (batteries, supercapacitors) and biomedical applications.
One‐Step Fabricated and Solution‐Processed Hybrid Gate Dielectrics for Low‐Voltage Organic Thin‐Film Transistors
Authors: Song Youngmin , Ha Young‐Geun 
Published: April 2021

Here, we report the facile one‐step fabrication of rationally designed hybrid gate dielectric films for low‐voltage organic thin‐film transistors. To generate facile one‐step fabricated and solution‐processed organic–inorganic hybrid dielectric films with high dielectric properties, we designed the multicomponent precursor solution by employing high‐k oxide materials to attain a large capacitance and cross‐linkable agents to allow for processability and reducing the surface energy of dielectric films. After spin‐coating with the precursor solution and the subsequent thermal annealing process, we obtained cross‐linked organic–inorganic hybrid dielectric films, exhibiting excellent dielectric properties with a low leakage current density (~10−5 A/cm2) and high capacitance (295 nF/cm2). The effectiveness of the hybrid dielectrics was demonstrated by realizing high‐performance organic thin‐film transistors at low operating voltages, mobility up to 0.31 cm2/V/s, high on/off current ratio (~105), and low threshold voltage (−0.8 V).
Integrated Co‐Electrolysis and Syngas Methanation for the Direct Production of Synthetic Natural Gas from CO2 and H2O
Authors: Mebrahtu Chalachew , Nohl Markus , Dittrich Lucy , Foit Severin R. , de Haart L. G. J. (Bert) , Eichel Rüdiger‐A. , Palkovits Regina 
Published: April 2021

AbstractThe concept of an integrated power‐to‐gas (P2G) process was demonstrated for renewable energy storage by converting renewable electrical energy to synthetic fuels. Such a dynamically integrated process enables direct production of synthetic natural gas (SNG) from CO2 and H2O. The produced SNG can be stored or directly injected into the existing natural gas network. To study process integration, operating parameters of the high‐temperature solid oxide electrolysis cell (SOEC) producing syngas (H2+CO) mixtures through co‐electrolysis and a fixed bed reactor for syngas methanation of such gas mixtures were first optimized individually. Reactor design, operating conditions, and enhanced SNG selectivity were the main targets of the study. SOEC experiments were performed on state‐of‐the‐art button cells. Varying operating conditions (temperature, flow rate, gas mixture and current density) emphasized the capability of the system to produce tailor‐made syngas mixtures for downstream methanation. Catalytic syngas methanation was performed using hydrotalcite‐derived 20 %Ni‐2 %Fe/(Mg,Al)Ox catalyst and commercial methanation catalyst (Ni/Al2O3) as reference. Despite water in the feed mixture, SNG with high selectivity (≥90 %) was produced at 300 °C and atmospheric pressure. An adequate rate of syngas conversion was obtained with H2O contents up to 30 %, decreasing significantly for 50 % H2O in the feed. Compared to the commercial catalyst, 20 %Ni‐2 %Fe/(Mg,Al)Ox enabled a higher rate of COx conversion.
Mustard Carbonate Analogues as Sustainable Reagents for the Aminoalkylation of Phenols
Authors: Annatelli Mattia , Trapasso Giacomo , Salaris Claudio , Salata Cristiano , Castellano Sabrina , Aricò Fabio 
Published: April 2021

AbstractN,N‐dialkyl ethylamine moiety can be found in numerous scaffolds of macromolecules, catalysts, and especially pharmaceuticals. Common synthetic procedures for its incorporation in a substrate relies on the use of a nitrogen mustard gas or on multistep syntheses featuring chlorine hazardous/toxic chemistry. Reported herein is a one‐pot synthetic approach for the easy introduction of aminoalkyl chain into different phenolic substrates through dialkyl carbonate (β‐aminocarbonate) chemistry. This new direct alcohol substitution avoids the use of chlorine chemistry, and it is efficient on numerous pharmacophore scaffolds with good to quantitative yield. The cytotoxicity via MTT of the β‐aminocarbonate, key intermediate of this synthetic approach, was also evaluated and compared with its alcohol precursor.
Early Permian back‐arc extension in the southeastern Central Asian Orogenic Belt: Evidence from the gabbro–granite complex, Xilinhot, Inner Mongolia, China
Authors: Zhang Xiaofei , Pang Zhenshan , Liu Junlai , Wei Xizhu , Li Shucai , Teng Chao , Huang Fuyong , Wang Biren 
Published: April 2021

Gabbro–granite complexes provide vital constraints on magmatism mechanisms, crust–mantle interaction processes, and regional tectonics. The petrogenesis and tectonic setting of Early Permian igneous rocks in the southeastern Central Asian Orogenic Belt have long been controversial. In this study, the Early Permian Wulajitu gabbro–granite complex in Xilinhot, Inner Mongolia was selected as a research object and an integrated study was conducted using field occurrence, petrology, zircon U–Pb ages, whole‐rock geochemistry, and in situ zircon Hf isotopes. The Wulajitu gabbro–granite complex consists of gabbro and syenogranite with crystallization ages of 277 ± 1 Ma and 274 ± 2 Ma, respectively, belonging to the Early Permian. Their SiO2 contents vary in the range from 43.07–51.60 wt% and 70.30–75.52 wt%, respectively, and exhibit a gap of 51.60–70.30 wt%, displaying a typical bimodal geochemical distribution. The gabbros are low‐K tholeiitic–calc‐alkaline series rocks that are enriched in large‐ion lithophile elements (e.g., Ba, K, and Sr), depleted in high‐field‐strength elements (e.g., Nb and Ta), and have positive εHf (t) values from +9.3 to +13.2, indicating that they likely originated from partial melting of depleted mantle modified by subduction slab fluids. The syenogranites are aluminous A‐type granites characterized by high SiO2 and K2O + Na2O; low Al2O3, CaO, and MgO; depletion in Ba, Nb, Ta, Sr, P, and Ti; enrichment in Rb, Th, U, K, Zr, and Hf; as well as a seagull‐type rare‐earth element distribution pattern with strongly negative Eu anomalies (Eu/Eu* = 0.30–0.52). They show homogeneous zircon Hf isotopic compositions (positive εHf (t) values from +11.4 to +13.7). All these geochemical signatures suggest that the syenogranites were generated from partial melting of juvenile crust under high temperature and low pressure. The Wulajitu gabbro–granite complex most likely formed in a back‐arc spreading basin. Such an extensional regime was closely related to asthenospheric mantle upwelling caused by the rollback of the subducted Palaeo‐Asian Ocean slab in the Early Permian.
Brixenbach research catchment: Quantification of runoff process proportions in a small Alpine catchment depending on soil moisture states and precipitation characteristics
Authors: Meißl Gertraud , Geitner Clemens , Batliner Andreas , Klebinder Klaus , Kohl Bernhard , Markart Gerhard 
Published: April 2021

AbstractThe Brixenbach valley is a small Alpine torrent catchment (9.2 km2, 820–1950 m a.s.l., 47.45°, 12.26°) in Tyrol, Austria. Intensive hydrological research in the catchment since more than 12 years, including a hydrogeological survey, pedological and land use mapping, measurements of precipitation, runoff, soil moisture and infiltration as well as the conduction of rainfall simulations, has contributed to understand the hydrological response of the catchment, its subcatchments and specific sites. The paper presents a synthesis of the research in form of runoff process maps for different soil moisture states and precipitation characteristics, derived with the aid of a newly developed Soil‐hydrological model. These maps clearly visualize the differing runoff reaction of different subcatchments. The pasture dominated areas produce high surface flow rates during short precipitation events (1 h, 86 mm) with high rainfall intensity, whilst the forested areas often develop shallow subsurface flow. Dry preconditions lead to a slight reduction of surface flow, long rainfall events (24 h, 170 mm) to a dominance of deep subsurface flow and percolation.
Natural revegetation and afforestation in abandoned cropland areas: Hydrological trends and changes in Mediterranean mountains
Authors: Khorchani Makki , Nadal‐Romero Estela , Lasanta Teodoro , Tague Christina 
Published: April 2021

AbstractWater resources availability is one of the main concerns for policy makers around the world in present and future management plans. In the Mediterranean basin, this concern is increased given the extreme variability in climate and the intrinsic aridity conditions. Water resources in the Mediterranean region depend mainly on surface and subsurface supply from mountain areas. Because evapotranspiration comprises a substantial portion of the water budget, recent land cover changes due to cropland abandonment may change transpiration (TRANS) and water supply. Therefore, land management plans must account for these potential hydrologic changes to guarantee water availability in the upcoming decades. Short‐term changes to water yield have been shown to follow afforestation or natural revegetation, the main management strategies in abandoned cropland areas. Studies comparing long‐term trends of these management practices, however, are scarce due to the lack of long‐term hydrological data. In this study, we use the regional hydro‐ecological simulation system (RHESSys), to analyse long‐term changes and annual and seasonal trends in streamflow (STR) and transpiration following management of abandoned cropland areas. Annual mean values show significant differences between the three management scenarios for both streamflow and transpiration, while differences between climate scenarios are not significant. The Mann Kendall trend analysis shows significant changes to water yield compared to the situation before management. Depending on the total afforested area, afforestation could significantly decrease annual streamflow between 2.3%·decade−1 and 5.9%·decade−1 and increase annual transpiration between 1.1%·decade−1 and 3.5%·decade−1. These trends are attributed to changes during the first 30 years after management, while during the fourth and fifth decade, changes to water yield tend to stabilize or decrease. These results are substantial to optimize land management plans, ensuring sustainable hydrological and ecological ecosystem services.
Dietary intake of advanced glycation endproducts and risk of hepatobiliary cancers: A multinational cohort study
Authors: Mayén Ana‐Lucia , Aglago Elom K. , Knaze Viktoria , Cordova Reynalda , Schalkwijk Casper G. , Wagner Karl‐Heinz , Aleksandrova Krasimira , Fedirko Veronika , Keski‐Rahkonen Pekka , Leitzmann Michael F. , Katzke Verena , Srour Bernard , Schulze Matthias B. , Masala Giovanna , Krogh Vittorio , Panico Salvatore , Tumino Rosario , Bueno‐de‐Mesquita Bas , Brustad Magritt , Agudo Antonio , Chirlaque López María Dolores , Amiano Pilar , Ohlsson Bodil , Ramne Stina , Aune Dagfinn , Weiderpass Elisabete , Jenab Mazda , Freisling Heinz 
Published: April 2021

AbstractAdvanced glycation endproducts (AGEs) may contribute to liver carcinogenesis because of their proinflammatory and prooxidative properties. Diet is a major source of AGEs, but there is sparse human evidence on the role of AGEs intake in liver cancer etiology. We examined the association between dietary AGEs and the risk of hepatobiliary cancers in the European Prospective Investigation into Cancer and Nutrition prospective cohort (n = 450 111). Dietary intake of three AGEs, Nε‐[carboxymethyl]lysine (CML), Nε‐[1‐carboxyethyl]lysine (CEL) and Nδ‐[5‐hydro‐5‐methyl‐4‐imidazolon‐2‐yl]‐ornithine (MG‐H1), was estimated using country‐specific dietary questionnaires linked to an AGEs database. Cause‐specific hazard ratios (HR) and their 95% confidence intervals (CI) for associations between dietary AGEs and risk of hepatocellular carcinoma (HCC), gallbladder and biliary tract cancers were estimated using multivariable Cox proportional hazard regression. After a median follow‐up time of 14.9 years, 255 cases of HCC, 100 cases of gallbladder cancer and 173 biliary tract cancers were ascertained. Higher intakes of dietary AGEs were inversely associated with the risk of HCC (per 1 SD increment, HR‐CML = 0.87, 95% CI: 0.76‐0.99, HR‐CEL = 0.84, 95% CI: 0.74‐0.96 and HR‐MH‐G1 = 0.84, 95% CI: 0.74‐0.97). In contrast, positive associations were observed with risk of gallbladder cancer (per 1 SD, HR‐CML = 1.28, 95% CI: 1.05‐1.56, HR‐CEL = 1.17; 95% CI: 0.96‐1.40, HR‐MH‐G1 = 1.27, 95% CI: 1.06‐1.54). No associations were observed for cancers of the intra and extrahepatic bile ducts. Our findings suggest that higher intakes of dietary AGEs are inversely associated with the risk of HCC and positively associated with the risk of gallbladder cancer.
Care to female adolescents victims of sexual violence at a referral service in Brazil from 2011 to 2018
Authors: Becerra Torres Alejandra Suyapa , Duarte Caroline Alves , Wittmann Barbara Zantut , Côrtes Maria Teresa Ferreira , Alves Ândria Cléia , Teixeira Ana Luiza , de Azevedo Renata Cruz Soares , Fernandes Arlete Maria dos Santos 
Published: April 2021

AbstractObjectiveTo evaluate the characteristics of aggression, care, and follow‐up of sexual violence in adolescent women at a university service in Campinas, São Paulo, Brazil.MethodsIn a retrospective cohort study from 2011 to 2018, we assessed sociodemographic characteristics, type and form of sexual violence perpetration, background and perception of the victim about violence, and characteristics of care and social/legal support during follow‐up.ResultsOf 521 adolescents 242 (46.5%) were aged 10–14 years, 354 (68%) had not started sexual life, 465 (89%) perceived the violence and they had low prevalence of alcohol (71, 16%) and other psychoactive substance consumption (25, 6%), and 24 (4.6%) had an intellectual disability. Intimidation through physical force, acute abuse, vaginal penetration, acquaintance aggressor, being approached in a public place, and family/acquaintance residence were the most prevalent characteristics of aggression. In the 2017–2018 biennium, we observed a decrease in the prevalence of adolescents who were students (P < 0.001), an increase in the number of acquaintance aggressors (P = 0.008), and medical care after 72 hours (P < 0.033).ConclusionAdolescents were victims of severe sexual violence. There was a decrease in prophylactic treatments and half of the adolescents did not complete outpatient follow‐up. The economic worsening over the last decade may have contributed to these results.
Maternal lack of sleep in the first two years after childbirth: Perceived impacts and help‐seeking behaviors
Authors: Simard Valérie , Pilon Mathieu , Blouin Marie‐Michelle 
Published: April 2021

ABSTRACTMost evidence‐based sleep interventions (e.g., graduated extinction of nighttime crying) are in opposition to many parents’ values. This warrants taking a step back and asking the parents about their main concerns regarding their baby's sleep and the type of help they would be likely to use. This study aimed to describe and identify, among mothers of a 0‐ to 24‐month‐old child, the perceived impact of lack of sleep, sleep‐related help‐seeking behaviors as well as the most concerning aspects of the child's sleep, and preferred sleep intervention modalities. Another objective was to identify the factors associated with a negative impact of postpartum sleep, concerns for the child's sleep, and interest in sleep interventions. Canadian mothers (N = 932) were recruited by email snowball sampling and through Facebook to complete an online questionnaire designed for the purposes of the study. Most mothers reported a negative impact of postpartum sleep on their romantic relationship (79.4%) and quality of life (76.7%). Low parental self‐efficacy (PSE) about managing the child's sleep was the best predictor of a negative impact of lack of sleep and sleep‐related concerns, above and beyond any other child's or mother's characteristics. The preferred intervention modalities were reliable websites and online courses on child sleep, with a greater interest in home visits among mothers who need help the most (low self‐efficacy, high concerns). Interventions should aim at increasing PSE about the child's sleep in both parents and include home visits for those who need it the most.
Phosphate restriction impairs mTORC1 signaling leading to increased bone marrow adipose tissue and decreased bone in growing mice
Authors: Ko Frank C. , Kobelski Margaret M. , Zhang Wanlin , Grenga Gina M. , Martins Janaina S. , Demay Marie B. 
Published: April 2021

ABSTRACT
Bone marrow stromal cells (BMSCs) are multipotent cells that differentiate into cells of the osteogenic and adipogenic lineage. A striking inverse relationship between bone marrow adipose tissue (BMAT) and bone volume is seen in several conditions, suggesting that differentiation of BMSCs into bone marrow adipocytes diverts cells from the osteogenic lineage, thereby compromising the structural and mechanical properties of bone. Phosphate restriction of growing mice acutely decreases bone formation, blocks osteoblast differentiation and increases BMAT. Studies performed to evaluate the cellular and molecular basis for the effects of acute phosphate restriction demonstrate that it acutely increases 5′ adenosine monophosphate–activated protein kinase (AMPK) phosphorylation and inhibits mammalian target of rapamycin complex 1 (mTORC1) signaling in osteoblasts. This is accompanied by decreased expression of Wnt10b in BMSCs. Phosphate restriction also promotes expression of the key adipogenic transcription factors, peroxisome proliferator–activated receptor γ (PPARγ) and CCAAT-enhancer binding protein α (CEBPα), in CXCL12 abundant reticular (CAR) cells, which represent undifferentiated BMSCs and are the main source of BMAT and osteoblasts in the adult murine skeleton. Consistent with this, lineage tracing studies reveal that the BMAT observed in phosphate-restricted mice is of CAR cell origin. To determine whether circumventing the decrease in mTORC1 signaling in maturing osteoblasts attenuates the osteoblast and BMAT phenotype, phosphate-restricted mice with OSX-CreERT2–mediated haploinsufficiency of the mTORC1 inhibitor, TSC2, were generated. TSC2 haploinsufficiency in preosteoblasts/osteoblasts normalized bone volume and osteoblast number in phosphate-restricted mice and attenuated the increase in BMAT observed. Thus, acute phosphate restriction leads to decreased bone and increases BMAT by impairing mTORC1 signaling in osterix-expressing cells. © 2021 American Society for Bone and Mineral Research (ASBMR).