bluuebunny/crossref_metadata_2025_split huggingface dataset:
Crosslinked Polymer‐Brush Electrolytes: An Approach to Safe All‐Solid‐State Lithium Metal Batteries at Room Temperature
Authors: Ji Xiaoyu , Li Shimei , Cao Mengxue , Liang Ruiqi , Xiao Lin‐Lin , Yue Kan , Liu Shaohong , Zhou Xingui , Guo Zi‐Hao 
Published: November 2021

AbstractElectric vehicles, intelligent machines, and portable electronics in our daily lives are placing insatiable demand on safe and powerful battery materials that can function at room temperature. Herein, we report an ultrathin and robust solid‐state electrolyte with crosslinked polymer‐brush architecture. On one hand, the highly mobile polymer brushes with a moderate side chain length enable efficient cation solvation and fast ion transport, offering room‐temperature ionic conductivity as high as 0.23 mS cm−1. On the other hand, incorporation of the inorganic core crosslinker endows the material with enhanced mechanical strength, thermal stability, and fire resistance. As a result, the crosslinked polymer‐brush electrolyte films demonstrate stable lithium electrodeposition and great electrochemical performance in Li/LiFePO4 cells at 30 °C, providing a promising pathway to next‐generation safe and high‐energy lithium metal batteries.
Application in photocatalytic degradation of zearalenone based on graphitic carbon nitride
Authors: Li Li , Xiaoxue Shan , Yuchong Zhang , Jin Wang , Zilong Liao , Yuxi Gu , Shuai Chen , Youjun Jiang , Jinying Chen 
Published: November 2021

AbstractA semiconductor nano‐material was prepared, and its degradation efficiency of zearalenone (ZEN) was studied. The photocatalytic material graphitic carbon nitride (g‐C3N4) was synthesized by the traditional method of hot cracking. Its structure was characterized by X‐ray diffraction (XRD), Fourier‐transform infrared (FTIR), X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The photocatalytic degradation experiment showed that under the irradiation of ultraviolet (UV) lamp (254 nm, including 185 nm), g‐C3N4 could induce photocatalytic effect, which provided a new method for the degradation of ZEN in real powder samples. The experimental conditions of photocatalytic degradation of the primary reference material of ZEN and ZEN in real powder samples were explored. And the degradation products of ZEN were analyzed after high‐performance liquid chromatography–mass spectrometry (HPLC–MS). Under each optimal experimental conditions, the degradation rate on primary reference material of ZEN and ZEN in real powder samples was 96.0% and 50.0%, respectively. The results in this work provide a theoretical reference and practical basis for the photocatalytic degradation of mycotoxin in real powder samples by g‐C3N4.
What is the best time for psychosocial counselling from the perspective of cancer patients and their relatives? A multi‐centre qualitative study
Authors: Singer Susanne , Kojima Erika , Deppisch Larissa , Taylor Katherine , Wickert Martin , Riedel Petra , Alt Jürgen , Heß Georg , Hechtner Marlene , Bayer Oliver 
Published: November 2021

AbstractPurposeThe aim of this study was to identify at what time patients with cancer and their relatives want to be informed about and receive psychosocial counselling.MethodsIn a multi‐centre prospective study, both users and non‐users of psychosocial cancer counselling were asked to participate in a qualitative interview about their preferences for psychosocial counselling. A second interview was scheduled 3–6 months thereafter. Interviews were transcribed verbatim and coded according to content analysis.ResultsAltogether, 61 patients and 42 relatives participated, resulting in 183 interviews (103 at t1, 80 at t2). Most often, the optimal time‐point for cancer counselling was defined by the participants according to the treatment trajectory, and the most frequently mentioned preferred time‐point was ‘as early as possible’: at the time of cancer diagnosis (mentioned in 22% of interviews with men and 10% of interviews with women). In particular, men also said that they wanted psychosocial counselling while waiting for test results (5%), at the point of returning to work and/or when under the threat of unemployment (3%). Women especially preferred this support during therapy (4%) and ‘when one has the capacity for it’ (4%), in terms of time and emotional capacity.ConclusionsHealthcare providers should inform their cancer patients and the relatives about the possibilities of professional psychosocial support early on in the disease trajectory (i.e. at the time of diagnosis) and repeatedly thereafter, especially in times of uncertainty, while ensuring the patients’ capacity to process information at each time‐point is taken into consideration.
Optochemical Control of Bacterial Gene Expression: Novel Photocaged Compounds for Different Promoter Systems
Authors: Hogenkamp Fabian , Hilgers Fabienne , Bitzenhofer Nora Lisa , Ophoven Vera , Haase Mona , Bier Claus , Binder Dennis , Jaeger Karl‐Erich , Drepper Thomas , Pietruszka Jörg 
Published: November 2021

AbstractPhotocaged compounds are applied for implementing precise, optochemical control of gene expression in bacteria. To broaden the scope of UV‐light‐responsive inducer molecules, six photocaged carbohydrates were synthesized and photochemically characterized, with the absorption exhibiting a red‐shift. Their differing linkage through ether, carbonate, and carbamate bonds revealed that carbonate and carbamate bonds are convenient. Subsequently, those compounds were successfully applied in vivo for controlling gene expression in E. coli via blue light illumination. Furthermore, benzoate‐based expression systems were subjected to light control by establishing a novel photocaged salicylic acid derivative. Besides its synthesis and in vitro characterization, we demonstrate the challenging choice of a suitable promoter system for light‐controlled gene expression in E. coli. We illustrate various bottlenecks during both photocaged inducer synthesis and in vivo application and possibilities to overcome them. These findings pave the way towards novel caged inducer‐dependent systems for wavelength‐selective gene expression.
Effects of Ethene Pressure on the Deactivation of Ni‐Zeolites During Ethene Oligomerization at Sub‐ambient Temperatures
Authors: Caulkins Richard , Joshi Ravi , Gounder Rajamani , Ribeiro Fabio H. 
Published: November 2021

AbstractNi cation sites exchanged onto microporous materials catalyze ethene oligomerization to butenes and heavier oligomers but also undergo rapid deactivation. The use of mesoporous supports has been reported previously to alleviate deactivation in regimes of high ethene pressures and low temperatures that cause capillary condensation of ethene within mesoporous voids. Here, we reproduce these prior findings on mesoporous Ni‐MCM‐41 and report that, in sharp contrast, reaction conditions that nominally correspond to ethene capillary condensation in microporous Ni‐Beta or Ni‐FAU zeolites do not mitigate deactivation, likely because confinement within microporous voids restricts the formation of condensed phases of ethene that are effective at solvating and desorbing heavier intermediates that are precursors to deactivation. Deactivation rates are found to transition from a first‐order to a second‐order dependence on Ni site density in Ni‐FAU zeolites with increasing ethene pressure, suggesting a transition in the dominant deactivation mechanism involving a single Ni site to one involving two Ni sites, reminiscent of the effects of increasing H2 pressure on changing the kinetic order of deactivation in our prior work on Ni‐Beta zeolites.
Analysis of NH3‐TPD Profiles for CuSSZ‐13 SCR Catalyst of Controlled Al Distribution – Complexity Resolved by First Principles Thermodynamics of NH3Desorption, IR and EPR Insight into Cu Speciation**
Authors: Mozgawa Bartosz , Zasada Filip , Fedyna Monika , Góra‐Marek Kinga , Tabor Edyta , Mlekodaj Kinga , Dědeček Jiří , Zhao Zhen , Pietrzyk Piotr , Sojka Zbigniew 
Published: November 2021

AbstractNH3temperature‐programmed desorption (NH3‐TPD) is frequently used for probing the nature of the active sites in CuSSZ‐13 zeolite for selective catalytic reduction (SCR) of NOx. Herein, we propose an interpretation of NH3‐TPD results, which takes into account the temperature‐induced dynamics of NH3interaction with the active centers. It is based on a comprehensive DFT/GGA+D and first‐principles thermodynamic (FPT) modeling of NH3adsorption on single Cu2+, Cu+, [CuOH]+centers, dimeric [Cu‐O‐Cu]2+, [Cu‐O22−‐Cu]2species, segregated CuO nanocrystals and Brønsted acid sites (BAS). Theoretical TPD profiles are compared with the experimental data measured for samples of various Si/Al ratios and distribution of Al within the zeolite framework. Copper reduction, its relocation, followed by the intrazeolite olation/oxolation processes, which are concomitant with NH3desorption, were revealed by electron paramagnetic resonance (EPR) and IR. DFT/FPT results show that the peaks in the desorption profiles cannot be assigned univocally to the particular Cu and BAS centers, since the observed low‐, medium‐ and high‐temperature desorption bands have contributions coming from several species, which dynamically change their speciation and redox states during NH3‐TPD experiment. Thus, a rigorous interpretation of the NH3‐TPD profiles of CuSSZ‐13 in terms of the strength and concentration of the active centers of a particular type is problematic. Nonetheless, useful connections for molecular interpretation of TPD profiles can be established between the individual component peaks and the corresponding ensembles of the adsorption centers.
Narrowly‐Distributed Conjugated Polymers Synthesized through Suzuki Polymerization with Palladium(II) N‐Heterocyclic Carbene Complex Confined in Dendritic Mesoporous Silica Nanoparticles
Authors: Wu Yusen , Zhu Yanchao , Wang Jie , Shang Zhikun , Jin Huixian , Ding Yun , Hu Aiguo 
Published: November 2021

AbstractA catalytic heterogenous Suzuki polymerization method was developed by confining the Pd(II)‐catalyzed cross coupling reactions to take place exclusively in the nanochannels of dendritic mesoporous silica nanoparticles. Conjugated polymers with various monomer combinations, including donor‐acceptor structures, were obtained in high yields. The molecular weights of the obtained polymers were well controlled with narrow molecular weight distributions (PDI value down to 1.13). All the polymeric products were highly soluble in common organic solvents, granting them with high processability. All the features of this confined Suzuki polymerization method endow the conjugated polymers great potential in optoelectronic applications.
Unfused Nonfullerene Acceptors Based on Simple Dipolar Merocyanines
Authors: Li Yibin , Liu Xin , Liu Hongtao , Yu Jiangsheng , Li Zhong'an 
Published: November 2021

AbstractMerocyanine (MC) dyes exhibit facile synthesis and attractive optical properties, making them widely studied as the donor materials in organic solar cells (OSCs). In this study, for the first time, simple indole‐based MCs are successfully designed as unfused nonfullerene acceptors (NFAs) for OSCs by forming dimers with A−D‐π‐D−A structure, which possess enhanced photostability compared to the well‐known ITIC acceptor and high electron mobility in blend films. When blended with P3HT donor, one of the dimers, i. e. Z2, shows a good cell efficiency of 3.53 %, which outperforms the performance of most of P3HT/NFA blends, particularly for unfused systems, and thus indicates good potential of simple MCs as NFAs.
Molecular Modelling and Simulations of Light‐Harvesting Decanuclear Ru‐Based Dendrimers for Artificial Photosynthesis
Authors: Rogati Giovanna M. A. , Capecci Chiara , Fazio Enza , Serroni Scolastica , Puntoriero Fausto , Campagna Sebastiano , Guidoni Leonardo 
Published: November 2021

AbstractThe structure of a decanuclear photo‐ and redox‐active dendrimer based on Ru(II) polypyridine subunits, suitable as a light‐harvesting multicomponent species for artificial photosynthesis, has been investigated by means of computer modelling. The compound has the general formula [Ru{(μ‐dpp)Ru[(μ‐dpp)Ru(bpy)2]2}3](PF6)20 (Ru10; bpy=2,2′‐bipyridine; dpp=2,3‐bis(2′‐pyridyl)pyrazine). The stability of possible isomers of each monomer was investigated by performing classical molecular dynamics (MD) and quantum mechanics (QM) simulations on each monomer and comparing the results. The number of stable isomers is reduced to 36 with a prevalence of MER isomerism in the central core, as previously observed by NMR experiments. The simulations on decanuclear dendrimers suggest that the stability of the dendrimer is not linked to the stability of the individual monomers composing the dendrimer but rather governed by the steric constrains originated by the multimetallic assembly. Finally, the self‐aggregation of Ru10 and the distribution of the counterions around the complexes is investigated using Molecular Dynamics both in implicit and explicit acetonitrile solution. In representative examples, with nine and four dendrimers, the calculated pair distribution function for the ruthenium centers suggests a self‐aggregation mechanism in which the dendrimers are approaching in small blocks and then aggregate all together. Scanning transmission electron microscopy complements the investigation, supporting the formation of different aggregates at various concentrations.
Thiophene‐Fused 1,4‐Diazapentalene: A Stable C=N‐Containing π‐Conjugated System with Restored Antiaromaticity
Authors: Usuba Junichi , Fukazawa Aiko 
Published: November 2021

AbstractInvited for the cover of this issue are Junichi Usuba and Aiko Fukazawa at Kyoto and Nagoya Universities. The image depicts the strength of the antiaromaticity of the title compounds as the power of a phoenix. Read the full text of the article at 10.1002/chem.202103122.
Multifunctional Nanoaggregates Composed of Active CPUL1 and a Triphenylphosphine Derivative for Mitochondria‐Targeted Drug Delivery and Cell Imaging
Authors: Liu Jing , Ji Fei , Xia Zhuolu , Zhang Chunhua , Zhao Changshun , Li Yanfei , Zhou Xiang , Huang Dechun , Chen Wei , Jiang Feng 
Published: November 2021

AbstractWe report that active substance (CPUL1) and triphenylphosphine (TPP) derivative could self‐assemble into multifunctional nanoaggregates (CPUL1−TPP NAs) through electrostatic and π‐π stacking interactions. CPUL1 was wrapped tightly inside the nanoparticles as well as CPUL1 and TPP derivative self‐assembled into stable and compact nanoparticles in water. The positive surface charge of CPUL1−TPP NAs made them much easier to be endocytosed to enter cytoplasm, accumulate in the mitochondria and induce cell apoptosis based on their mitochondria targeting ability, fluorescence property and fast cell uptake characteristic, which showed better antitumor efficacy on HUH7 hepatoma cells in vitro than that of free CPUL1.
Nickel‐Catalyzed Allylic Substitution Reactions: An Evolving Alternative
Authors: Ghorai Debasish , Cristòfol Àlex , Kleij Arjan W. 
Published: November 2021

AbstractTransition metal‐catalyzed allylic substitution reactions represent versatile transformations in organic synthesis forging C−C and C‐heteroatom bonds. Despite major contributions realized with precious transition metals, earth‐abundant nickel catalysis over the years has emerged as a relative sustainable and efficient alternative in the area of allylic substitution reactions. During the last two decades, the field has witnessed successful accomplishments of chemo‐, regio‐ and enantioselective conversions affording a plethora of products through the employment of Ni‐based methodologies. In this Minireview, the most imperative contributions will be discussed with special attention for the more sustainable character and unique reactivity of Ni, the overall process selectivity features and the functional group tolerance and product scope.
Protic Ferrocenyl Acyclic Diamino Carbene Gold(I) Complexes
Authors: Waniek Sven D. , Förster Christoph , Heinze Katja 
Published: November 2021

AbstractTwo mononuclear protic ferrocenyl acyclic diamino carbene gold(I) complexes AuCl[C(NHFc)(NR2)] were prepared by nucleophilic attack of diethylamine (R = Et) and diisopropylamine (R = iPr) at the ferrocenyl substituted isocyanide complex chlorido(isocyanoferrocene)gold(I) AuCl(CN−Fc). In the solid state, the multifunctional protic carbene gold(I) complexes display intermolecular aurophilic interactions or intermolecular NH⋅⋅⋅Cl hydrogen bonding in addition to intramolecular non‐classical NH⋅⋅⋅Fe hydrogen bonds. Oxidation of the AuCl[C(NHFc)(NR2)] complexes initially takes place at the iron centres giving highly coloured ferrocenium ions, which subsequently likely undergo electron transfer from gold(I) to iron(III) yielding putative EPR‐active gold(II) species.
Monosubstituted 3,3‐Difluorocyclopropenes as Bench‐Stable Reagents: Scope and Limitations
Authors: Nosik Pavel S. , Pashko Mykola O. , Poturai Andrii S. , Kvasha Denys A. , Pashenko Alexander E. , Rozhenko Alexander B. , Suikov Sergiy , Volochnyuk Dmitriy M. , Ryabukhin Sergey V. , Yagupolskii Yurii L. 
Published: November 2021

AbstractA general approach to gem‐difluorocyclopropenes synthesis based on the reaction of alkynes with Ruppert‐Prakash reagent is reported. The proposed method is evaluated for the synthesis of a wide difluorocyclopropenes scope based on their bench lifespan and hydrolytic stability. The tolerance of the method for common functional groups was shown. Previously unavailable difluorocyclopropenes substituted with aliphatic were prepared using the proposed procedure. The retain of stability was proven by the multigram scale synthesis and further storage in the temperature interval −78 to −4 °C over a year. This makes them attractive building blocks and intermediates for organic synthesis. The reasons for dropping stability were defined. The relations between the structure of the substituents and the stability of the difluorocyclopropene ring were determined and discussed.
A Hexagonal Shape‐Persistent Nanobelt of Elongated Rhombic Symmetry with Orthogonal π‐Planes by a One‐Pot Reaction
Authors: Lauer Jochen C. , Kohl Bernd , Braun Felix , Rominger Frank , Mastalerz Michael 
Published: November 2021

AbstractTriptycenes with their predefined D3h‐symmetry are excellent molecular building blocks to construct shape‐persistent nanobelts having π‐orbitals orthogonal to the ring plane. However, up to now, there are only a very few examples of fused and rigid iptycene nanobelts synthesized in several consecutive steps in overall yields below 1 %. Here we present the simple one‐step one‐pot approach to an iptycene nanobelt, which forms in >2 % and can readily be isolated from the polymeric by‐product by gel‐permeation chromatography.
Depositional history of a talus cone in an arid intermontane basin in Central Asia: An interdisciplinary study at the Late Pleistocene–Late Holocene Obishir‐I site, Kyrgyzstan
Authors: Brancaleoni Greta , Shnaider Svetlana , Osipova Evgeniya , Danukalova Guzel , Kurbanov Redzhep , Deput Ewa , Alisher kyzy Saltanat , Abdykanova Aida , Krajcarz Maciej T. 
Published: November 2021

AbstractCliff‐related talus accumulations are often highly affected by post‐depositional processes, and the sedimentological characteristics are poorly documented, especially in arid settings. In the southern margin of the Fergana Valley, Kyrgyzstan, the Obishir‐I is an archaeological site of the Epipaleolithic Obishirian industry, located within a talus cone. Archaeological excavations have allowed us to study the internal structure, chronology, and depositional history of the cone as well as the relationship between the slope processes and the archaeological assemblage. We applied a multiproxy approach, including sedimentological studies supported by the basic geochemistry of sediments, luminescence dating, paleoecology of fossil mollusks, and archaeological analyses. The Obishir‐I rockfall talus accumulated from the Last Glacial Maximum to the early part of the Middle Holocene. The talus onlaps the bedrock at the foot of a limestone cliff, and its chronology is coherent, spanning from ca. 19–8 ka B.P. The material is an unconsolidated, poorly sorted mixture of angular rock fragments accumulated by rockfall and fine‐grained materials accumulated by aeolian processes, illuviation, and in situ weathering. The sequence bears an archaeological collection attributed to two settlement phases: unidentified Upper Paleolithic and the Obishirian. Both assemblages are affected by post‐depositional relocation within the slope.
Proposal and Validation of a Novel Scoring System for Hepatocellular Carcinomas Beyond Curability Borders
Authors: Demirtas Coskun Ozer , Ricco Gabrielle , Ozdogan Osman Cavit , Baltacioglu Feyyaz , Ones Tunc , Yumuk Perran Fulden , Dulundu Ender , Uzun Sinan , Colombatto Pierro , Oliveri Filippo , Brunetto Maurizia Rosanna , Gunduz Feyza 
Published: November 2021

Optimal scoring system for clinical prognostic factors in patients with unresectable hepatocellular carcinoma (HCC) is currently uncertain. We aimed to develop and externally validate an easy to use tool, particularly for this population, and named it the “unresectable hepatocellular carcinoma prognostic index” (UHPI). We evaluated the data of patients with treatment‐naive unresectable HCC who were diagnosed in the training center from 2010 to 2019 (n = 209). A simple prognostic model was developed by assigning points for each covariate in proportion to the beta coefficients in the Cox multivariable model. Predictive performance and distinction ability of the UHPI were further evaluated in an independent European validation cohort (n = 147) and compared with 11 other available models. A simple scoring system was derived, assigning 0.5/1/2 scores for six independent covariates including, the Child‐Pugh score, Eastern Cooperative Oncology Group performance status, maximum tumor size, vascular invasion or extrahepatic metastasis, lymph node involvement, and alpha‐fetoprotein. The UHPI score, ranging from 0 to 6, showed superior performance in prognosis prediction and outperformed 11 other staging or prognostic models, giving the highest homogeneity (c‐index, 6‐month and 1‐year area under the receiver operator characteristic curves), lowest Akaike information criterion, and –2 log‐likelihood ratio values. The UHPI score allocated well the risk of patients with unresectable HCC for mortality within the first year, using two cut‐off values (low‐risk, <0.5; intermediate‐risk, 0.5‐2; high‐risk, >2). Conclusion: The UHPI score can predict prognosis better than other systems in subjects with unresectable HCC and can be used in clinical practice or trials to estimate the 6‐month and 1‐year survival probabilities for this group.
Pilot decision‐making during a dual engine failure on take‐off: Insights from three different decision‐making models
Authors: Parnell Katie J. , Wynne Rachael A. , Plant Katherine L. , Banks Victoria A. , Griffin Thomas, G.C. , Stanton Neville A. 
Published: November 2021

AbstractCommercial airline pilots are required to make efficient, justifiable, and safety‐critical decisions when faced with adverse events such as engine failures. Although these are rare events, the consequences are severe, and the pilot response is critical. This paper reviews pilot decision‐making when faced with a dual engine failure on take‐off using three different decision models; the Recognition Primed Decision Model, Decision Ladders and the Perceptual Cycle Model. In‐depth interviews with eight experienced airline pilots were conducted to capture their decision‐making processes in response to a dual engine failure on take‐off event. The analysis of these interviews using the three different decision models provide recommendations for a proposed decision assistant. The different decision models are discussed in relation to the insight they can bring to developing a future decision assistant tool within the flight deck of commercial aircraft.