bluuebunny/crossref_metadata_2025_split huggingface dataset:
Revealing the effect of synergistic interaction between ZnO and ZnCr2O4 on the syngas aromatization
Authors: Ma Zixuan , Tan Minghui , Cao Fenghai , Yang Yuhao , Gong Nana , Wu Yingquan , Zhang Junfeng , Yang Guohui , Tan Yisheng 
Published: November 2022

AbstractZn‐Cr‐based catalysts are widely used as oxide catalysts for syngas aromatization, and it is difficult to study the synergistic effect of ZnO and Zn‐Cr spinel due to the complex system of non‐stoichiometric Zn‐Cr spinels. In order to reveal the synergistic effect, we physically mixed ZnO and ZnCr2O4 with definite structure to avoid ambiguous structure of non‐stoichiometric Zn‐Cr spinels. The results showed that the introduced ZnO affected the oxygen vacancies generation and promoted the activation of CO and H2, leading to an increase of oxygenates compared to the sole ZnCr2O4. Due to the synergy of ZnO and ZnCr2O4, the xZZC catalysts could produce more adsorbed species than the ZnCr2O4 catalyst, while the ZnCr2O4/ZSM‐5 catalyst was more difficult to convert formate species. The ZnO in xZZC/ZSM‐5 decreased the formate adsorption strength, which favored the continued conversion of formate and further realized the enhanced pulling effect on CO conversion.
Design and Manipulation of a Minimalistic Hydrocarbon Nanocar on Au(111)
Authors: Barragán Ana , Nicolás‐García Tomás , Lauwaet Koen , Sánchez‐Grande Ana , Urgel José I. , Björk Jonas , Pérez Emilio M. , Écija David 
Published: November 2022

AbstractNanocars are carbon‐based single‐molecules with a precise design that facilitates their atomic‐scale control on a surface. The rational design of these molecules is important in atomic and molecular‐scale manipulation to advance the development of molecular machines, as well as for a better understanding of self‐assembly, diffusion and desorption processes. Here, we introduce the molecular design and construction of a collection of minimalistic nanocars. They feature an anthracene chassis and four benzene derivatives as wheels. After sublimation and adsorption on an Au(111) surface, we show controlled and fast manipulation of the nanocars along the surface using the tip of a scanning tunneling microscope (STM). The mechanism behind the successful displacement is the induced dipole created over the nanocar by the STM tip. We utilized carbon monoxide functionalized tips both to avoid decomposition and accidentally picking the nanocars up during the manipulation. This strategy allowed thousands of maneuvers to successfully win the Nanocar Race II championship.
Reversible Isomerization Between Silacyclopropyl Cation and Cyclic (Alkyl)(Amino)Silylene
Authors: Nougué Raphaël , Takahashi Shintaro , Baceiredo Antoine , Saffon‐Merceron Nathalie , Branchadell Vicenç , Kato Tsuyoshi 
Published: November 2022

AbstractA phosphine‐stabilized silacyclopropyl cation2has been synthesized and fully characterized. Of particular interest,2reversibly isomerizes into the corresponding seven‐membered cyclic (alkyl)(amino)silylene3at room temperature via a formal migratory ethylene insertion into the Si−P bond. Although silylene3has not been spectroscopically detected, its transient formation has been evidenced by the isolation of the corresponding disilene dimer5as well as by trapping reactions.
Numerical simulation and modeling of viscous fluid residence time distribution in the melt spinning pack
Authors: Zhu Yiwei , Li Xin , Wu Pengfei , Gan Lihua , Hao Haoran , Ma Xin , Cai Ziqi 
Published: November 2022

AbstractMelt spinning is an important method in fiber production. The hydrodynamic performance of fluid in the melt spinning process's core device, spinning pack, can directly affect the quality of fiber products. To guarantee the uniform distribution of flow in the spinning pack, the residence time distribution (RTD) characteristics of high viscosity fluid in the spinning pack were investigated experimentally and numerically in this work. Peak and trailing of RTD curves indicate the existence of short circuit and dead zone in the spinning pack. Results show that the porous media and gland can reduce the dead zone, and baffles could reduce the short circuit. Based on the experiment and numerical simulation results, a one‐dimensional axial diffusion model was established to describe the RTD characteristics of viscous fluid in the spinning pack. This work can be valuable references for the understanding and optimization of the spinning pack in melt spinning process.
Serum cholesterol and the risk of developing hormonally driven cancers: A narrative review
Authors: Murdock Dana J. , Sanchez Robert J. , Mohammadi Kusha A. , Fazio Sergio , Geba Gregory P. 
Published: November 2022

AbstractAlthough cholesterol has been hypothesized to promote cancer development through several potential pathways, its role in the risk of developing hormonally driven cancer is controversial. This literature review summarizes evidence from the highest quality studies to examine the consistency and strength of the relationship between serum cholesterol parameters and incidence of hormonally driven cancer. Articles were identified using EMBASE. Longitudinal observational studies published between January 2000 and December 2020 were considered for inclusion. The endpoint of interest was incident prostate, ovary, breast, endometrium, and uterine cancers. In total, 2732 reports were identified and screened; 41 studies were included in the review. No associations were found for ovarian cancer. Most endometrial cancer studies were null. The majority (76.9%) of studies reported no association between cholesterol and prostate cancer. Data on breast cancer were conflicting, associations limited, and effect sizes modest. Our results do not provide evidence for a clear association between cholesterol and different types of incident, hormonally driven reproductive cancers. Future studies should investigate the impact of lipid‐lowering therapy.
Data are data: Do we need a randomized trial of transcatheter aortic valve replacement for bicuspid valves?
Authors: Ueyama Hiroki , Block Peter C. 
Published: November 2022

Key Points
No randomized trials have been done for TAVR in bicuspid aortic valve (BAV) and probably will never be done.
TAVR for BAV has a similar risk profile to tricuspid aortic valve patients except for a higher risk of permanent pacemaker implantation at 30 and 180 days after the index procedure.
Further real‐world data are needed to refine patient selection, procedural technique, and lifetime planning of intervention.
“Does gender equality also apply to chronic total occlusion management?”
Authors: Di Mario Carlo , Di Muro Francesca Maria 
Published: November 2022

Key Points
Women are less frequently referred to CTO recanalizations according to their ambiguous presentation
Gender has a great impact on technical procedural success and also on procedural complication rate
It is important to adopt tricks to avoid the most common complications in women such as cardiac tamponade, access problems, and contrast nephropathy
A new method for detecting proanthocyanidin content in wheat reveals the relationship between R‐1 gene to grain color deepness
Authors: Himi Eiko , Matsuura Takakazu , Miura Hideho , Yoshihara Naoya , Maekawa Masahiko 
Published: November 2022

AbstractBackground and ObjectivesGrain color of wheat is one of the important quality parameters that affect the flour color and its product such as bread and noodles. R‐1 gene, a regulator of grain color, is located on chromosomes 3A, 3B, and 3D, and at least one dominant allele is responsible for the red color of the grain. It has been thought that the number of dominant R‐1 allele relates to the deepness of the red color of grain; however, methods to quantify grain pigments have not been established yet. The aim of this work was to establish a method for quantifying pigments using 4‐dimethylaminocinnamaldehyde (DMACA), which reacts with precursors of which constitute major pigments of wheat grain.FindingsWheat proanthocyanidins were detectable in immature seeds by the DMACA method but became undetectable as the grains matured. Comparison between lines with the same flowering time and genetic background revealed that the amount of pigment was determined by the number of dominant R‐1 alleles.ConclusionsWe established the DMACA method for quantifying wheat seed pigments and used that to clarify the relationship between the number of R‐1 alleles and pigment content.Significance and NoveltySince the method developed in this study is not affected by other pigments such as chlorophyll, it can be universally applied to other plants and tissues in addition to wheat grains.
Revisiting the Reaction of IPr with Tritylium: An Alternative Mechanistic Pathway**
Authors: Song Hayoung , Lee Eunsung 
Published: November 2022

AbstractDespite a recent proposal on the mechanism of a single‐electron transfer (SET) process between tritylium and 2,6‐bis(diisopropylphenyl)imidazol‐2‐ylidene (IPr) based on evidence of transient IPr radical cation intermediate ([IPr]⋅+) formation, such oxidation is still contentious because of the high oxidation potential of N‐heterocyclic carbenes. Our experimental analysis indicates that the appearance of deep purple color, previously considered to be from transient [IPr]⋅+, originates from a zwitterionic intermediate (3 a), not a radical cation. Here, we propose an alternative mechanism for the reaction involving tritylium and IPr. This mechanism is noteworthy for explaining how [NHC−H]+ can be generated without the formation of transient [NHC]⋅+, which has been frequently proposed as an intermediate for the reaction between NHC and oxidants. These results also show that a transient strong single‐electron donor (3 a) could be generated by the alternative mechanism for oxidants using NHCs, which is a more feasible explanation for the reactivity of NHCs with oxidants.
Construction of TiO2/SrTiO3Heterojunction Derived from Monolayer Ti3C2MXene for Efficient Photocatalytic Overall Water Splitting
Authors: Zhuo Zhenzhen , Wang Xue , Shen Cheng , Cai Mengdie , Jiang Yong , Xue Zhaoming , Fu Zhiyuan , Wang Qi , Wei Yuxue , Sun Song 
Published: November 2022

AbstractConstruction of heterojunction at the atomic scale to ensure efficient charge separation for improvement of photocatalytic water splitting is challenging. Herein, a facile hydrothermal method has been applied for the in situ fabrication of TiO2/SrTiO3heterojunction, using the monolayer Ti3C2MXene as the template and reactant. It is found that the sample with the hydrothermal reaction time of 60 min exhibits the highest H2evolution rate with the sacrificial reagent, due to the efficient charge separation of TiO2/SrTiO3heterojunction as Ti3C2derivative. In addition, the sample shows the best overall water splitting performance at a hydrothermal reaction time of 120 min, where TiO2is nearly converted to SrTiO3, due to the fast kinetic process and low structural defects of SrTiO3. This work not only provides a simple strategy for the fabrication of heterojunction photocatalysts but also demonstrates the difference in optimization of half‐reaction and overall water splitting reaction.
Disentangling the Effect of Pressure and Mixing on a Mechanochemical Bromination Reaction by Solid‐State NMR Spectroscopy**
Authors: Bartalucci Ettore , Schumacher Christian , Hendrickx Leeroy , Puccetti Francesco , d'Anciães Almeida Silva Igor , Dervişoğlu Rıza , Puttreddy Rakesh , Bolm Carsten , Wiegand Thomas 
Published: November 2022

AbstractMechanical forces, including compressive stresses, have a significant impact on chemical reactions. Besides the preparative opportunities, mechanochemical conditions benefit from the absence of any organic solvent, the possibility of a significant synthetic acceleration and unique reaction pathways. Together with an accurate characterization of ball‐milling products, the development of a deeper mechanistic understanding of the occurring transformations at a molecular level is critical for fully grasping the potential of organic mechanosynthesis. We herein studied a bromination of a cyclic sulfoximine in a mixer mill and used solid‐state nuclear magnetic resonance (NMR) spectroscopy for structural characterization of the reaction products. Magic‐angle spinning (MAS) was applied for elucidating the product mixtures taken from the milling jar without introducing any further post‐processing on the sample. Ex situ13C‐detected NMR spectra of ball‐milling products showed the formation of a crystalline solid phase with the regioselective bromination of theS‐aryl group of the heterocycle in position 4. Completion is reached in less than 30 minutes as deduced from the NMR spectra. The bromination can also be achieved by magnetic stirring, but then, a longer reaction time is required. Mixing the solid educts in the NMR rotor allows to get in situ insights into the reaction and enables the detection of a reaction intermediate. The pressure alone induced in the rotor by MAS is not sufficient to lead to full conversion and the reaction occurs on slower time scales than in the ball mill, which is crucial for analysing mixtures taken from the milling jar by solid‐state NMR. Our data suggest that on top of centrifugal forces, an efficient mixing of the starting materials is required for reaching a complete reaction.
C−C Coupling through Nitrogen Deletion: Application to Library Synthesis
Authors: Holovach Serhii , Melnykov Kostiantyn P. , Poroshyn Illia , Iminov Rustam T. , Dudenko Dmytro , Kondratov Ivan , Levin Mark , Grygorenko Oleksandr O. 
Published: November 2022

AbstractA protocol for parallel C(sp3)−C(sp3) coupling of (hetero)aromatic aldehydes and (hetero)arylmethyl amines based on a reductive amination – “nitrogen deletion” reaction sequence has been developed. After preliminary validation experiments, an illustrative compound library of 25 members was prepared with 76 % synthetic efficiency. The estimated chemical space accessible by the proposed approach covers almost 600 000 representatives that are scarcely represented in current compound databases.
Intermolecular n→π* Interactions Based on a Tailored Multicarbonyl‐Containing Macrocycle
Authors: Zhu Jun , Wang Xu‐Dong , Ao Yu‐Fei , Wang Qi‐Qiang , Wang De‐Xian 
Published: November 2022

AbstractTowards unexplored intermolecular n→π* interactions, presented herein are the synthesis, structure, self‐assembly and function of a multicarbonyl‐containing macrocycle calix[2]arene[2]barbiturate 1. X‐ray single crystal diffraction reveals the presence of Cl⋅⋅⋅C=O interactions in CH2Cl2⊂1 host‐guest complex and multiple intermolecular C=O⋅⋅⋅C=O interactions between molecules 1 in crystalline state. The intermolecular C=O⋅⋅⋅C=O interactions as attractive driving force led to unprecedented self‐assembly of nanotube with diameter around 1.4 nm and inner surface engineered by aromatic rings. SEM and TEM images of the self‐assembly of 1 demonstrated temperature‐dependent morphologies which allows the observation of spheres at 25 °C and rods at 0 °C, respectively. XRD analysis indicated consistent hexagonal patterns in the self‐assembly and single crystal lattice, indicating the nanotubes driven by C=O⋅⋅⋅C=O interactions constitute the basic structural architectures of both aggregates. The nanoscopic tubes (pores) formed in the rodlike single crystal engendering the separation of moving dyes were preliminarily investigated by a single‐crystal chromatography and crystal‐packed column chromatography.
Incorporation of Conjugated Diynes in Perovskites and their Post‐Synthetic Modification
Authors: Román‐Román Priscila I. , Ortiz‐Cervantes Carmen , Vasquez‐Matias Jessica I. , Vazquez‐Chavez Josué , Hernández‐Rodríguez Marcos , Solis‐Ibarra Diego 
Published: November 2022

AbstractTwo‐dimensional (2D) organic–inorganic hybrid perovskites have rapidly become an attractive alternative to three‐dimensional (3D) perovskites as solar cell absorbers, owing to their improved stability, versatility, and ease of processing. Despite their advantages, the insulating nature of the organic cations makes these materials have lower absorbing and conducting properties, resulting in lower device efficiencies. A way to circumvent these issues is the integration of functional molecules that help mitigate these limitations. In this study, six new perovskites composed of three distinct diynes are synthesized, all of which can be thermally polymerized to form conjugated polymers within the perovskite layers. The incorporation of conjugated polymers results in drastic changes in these materials’ optoelectronic properties and their overall stability. Furthermore, depending on the nature of the diyne and the inorganic layers, the materials show varying polymerization yields, optical bandgaps, and charge carrier densities. These results afford significant insight into the chemical nature of the polymerized species and thus highlight the versatility of this approach to post‐synthetically generate conducting polymers within the layers of 2D perovskites, paving the way toward their use in optoelectronic devices.
Photo‐Activity of Silacyclopropenes and their Application in Metal‐Free Curing of Silicones
Authors: Nobis Matthias , Futter Jonas , Moxter Maximilian , Inoue Shigeyoshi , Rieger Bernhard 
Published: November 2022

AbstractSilicone elastomers are usually produced via addition or condensation curing by means of platinum‐ or tin‐based catalysis. The employed catalysts remain in the final rubber and cannot be recovered, thus creating various economic and environmental challenges. Herein, a light‐mediated curing method using multifunctional silacyclopropenes as crosslinker structures was introduced to create an effective alternative to the conventional industrial crosslinking. To evaluate the potential of the photoreaction a model study with small monofunctional silirenes was conducted. These investigations confirmed the required coupling reactivity upon irradiation and revealed an undesired rearrangement formation. Further optimization showed the reaction selectivity to be strongly influenced by the substitution of the three‐membered ring system and the reaction temperature. The synthesis of multifunctional silirenes was described based on the most suitable model compound to create active crosslinker scaffolds for their application in silicone curing. This photo‐controlled process produces catalyst and additive free elastomers from liquid silicones, including hydride‐, hydroxy‐, or vinyl terminated polydimethylsiloxanes.
Molecular Engineering of Metalloporphyrins for High‐Performance Energy Storage: Central Metal Matters
Authors: Shakouri Shirin , Abouzari‐Lotf Ebrahim , Chen Jie , Diemant Thomas , Klyatskaya Svetlana , Pammer Frank Dieter , Mizuno Asato , Fichtner Maximilian , Ruben Mario 
Published: November 2022

AbstractPorphyrin derivatives represent an emerging class of redox‐active materials for sustainable electrochemical energy storage. However, their structure–performance relationship is poorly understood, which confines their rational design and thus limits access to their full potential. To gain such understanding, we here focus on the role of the metal ion within porphyrin molecules. The A2B2‐type porphyrin 5,15‐bis(ethynyl)‐10,20‐diphenylporphyrin and its first‐row transition metal complexes from Co to Zn are used as models to investigate the relationships between structure and electrochemical performance. It turned out that the choice of central metal atom has a profound influence on the practical voltage window and discharge capacity. The results of DFT calculations suggest that the choice of central metal atom triggers the degree of planarity of the porphyrin. Single crystal diffraction studies illustrate the consequences on the intramolecular rearrangement and packing of metalloporphyrins. Besides the direct effect of the metal choice on the undesired solubility, efficient packing and crystallinity are found to dictate the rate capability and the ion diffusion along with the porosity. Such findings open up a vast space of compositions and morphologies to accelerate the practical application of resource‐friendly cathode materials to satisfy the rapidly increasing need for efficient electrical energy storage.
Enabling Aqueous Processing of Ni‐Rich Layered Oxide Cathode Materials by Addition of Lithium Sulfate
Authors: Heidbüchel Marcel , Schultz Thorsten , Placke Tobias , Winter Martin , Koch Norbert , Schmuch Richard , Gomez‐Martin Aurora 
Published: November 2022

AbstractAqueous processing of Ni‐rich layered oxide cathode materials is a promising approach to simultaneously decrease electrode manufacturing costs, while bringing environmental benefits by substituting the state‐of‐the‐art (often toxic and costly) organic processing solvents. However, an aqueous environment remains challenging due to the high reactivity of Ni‐rich layered oxides towards moisture, leading to lithium leaching and Al current collector corrosion because of the resulting high pH value of the aqueous electrode paste. Herein, a facile method was developed to enable aqueous processing of LiNi0.8Co0.1Mn0.1O2 (NCM811) by the addition of lithium sulfate (Li2SO4) during electrode paste dispersion. The aqueously processed electrodes retained 80 % of their initial capacity after 400 cycles in NCM811||graphite full cells, while electrodes processed without the addition of Li2SO4 reached 80 % of their capacity after only 200 cycles. Furthermore, with regard to electrochemical performance, aqueously processed electrodes using carbon‐coated Al current collector outperformed reference electrodes based on state‐of‐the‐art production processes involving N‐methyl‐2‐pyrrolidone as processing solvent and fluorinated binders. The positive impact on cycle life by the addition of Li2SO4 stemmed from a formed sulfate coating as well as different surface species, protecting the NCM811 surface against degradation. Results reported herein open a new avenue for the processing of Ni‐rich NCM electrodes using more sustainable aqueous routes.
Energy‐aware redundancy‐aware clustering in wireless sensor networks using Spined Loach Searching Optimization
Authors: N. Sasikala , Sangaiah Pavalarajan 
Published: November 2022

SummaryWireless sensor networks play dominant role in data communication in many engineering applications and faces lot of challenges in its implementation. Energy conservation is also significantly required in these systems as the sensor nodes are battery operated. Hence, the energy efficient‐based technique needs to be implemented in data transmission. The most widely used methods are clustering‐based data transmission and energy efficient routing detection. In clustering, the proper selection of cluster head (CH) node is important to ensure energy balancing. The CH node should have more residual energy as it does many transmissions in the network. Moreover, the location of CH node should be nearer to all member nodes in the cluster. The clustering process must also perform the job of avoiding unnecessary transmissions. By considering these factors, the CH node can be optimally selected using Spined Loach Searching Optimization algorithm. The food searching behavior and environmental suitability for spiny loach fish living are deliberated to develop this bio‐inspired algorithm. In addition, the redundant transmissions inside the clusters can be reduced by employing a new technique called Least Difference Threshold Based Similarity Grouping. This work improves energy efficiency comparing with the conventional low energy adaptive clustering hierarchy protocol, and it is evaluated by setting the network in simulation environment. The network lifetime is increased; energy consumption, delay of transmission and the message cost are reduced.