bluuebunny/crossref_metadata_2025 huggingface dataset:
Insight into the Modes of Activation of Pyridinium and Bipyridinium Salts in Non‐Covalent Organocatalysis
Authors: Weiss Robin , Golisano Tamara , Pale Patrick , Mamane Victor
Published: August 2021

A series of pyridinium and bipyridinium salts were prepared and their catalytic properties were evaluated in the aza‐Diels‐Alder reaction between imines and Danishefsky diene. Depending on the substituents of the pyridinium/bipyridinium rings and on the nature of the counterion, two mechanisms of activation were demonstrated. In case of non‐substituted rings, the substrate is activated through charge transfer involving the aryl ring on the C‐side of the imine. When halogen atoms were introduced on the catalysts, the activation mode switched to halogen bond involving the imine nitrogen lone pair. Moreover, alternative activation modes based on hydrogen bonding and radical cation were ruled out. This work allowed us to develop two families of catalysts whose potential was demonstrated in the cycloaddition of various imines with Danishefsky diene. The first family is composed of the simple methyl pyridinium triflate and dioctyl bipyridinium triflate. The former is active only with imines bearing a p‐methoxyphenyl group on the C‐side and the latter was found to be efficient with imines bearing different substituents on both the N‐ and C‐sides of the imines. The second family is based on halogenated pyridinium salts which proved active with almost all considered imines.

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Pharmacological Inhibition of Core Regulatory Circuitry Liquid–liquid Phase Separation Suppresses Metastasis and Chemoresistance in Osteosarcoma
Authors: Lu Bing , Zou Changye , Yang Meiling , He Yangyang , He Jincan , Zhang Chuanxia , Chen Siyun , Yu Jiaming , Liu Kilia Yun , Cao Qi , Zhao Wei
Published: August 2021

Liquid–liquid phase‐separated (LLPS) transcriptional factor assemblies at super‐enhancers (SEs) provide a conceptual framework for underlying transcriptional control in mammal cells. However, the mechanistic understanding of LLPS in aberrant transcription driven by dysregulation of SEs in human malignancies is still elusive. By integrating SE profiling and core regulatory circuitry (CRC) calling algorithm, the CRC of metastatic and chemo‐resistant osteosarcoma is delineated. CRC components, HOXB8 and FOSL1, produce dense and dynamic phase‐separated droplets in vitro and liquid‐like puncta in cell nuclei. Disruption of CRC phase separation decreases the chromatin accessibility in SE regions and inhibits the release of RNA polymerase II from the promoter of SE‐driven genes. Importantly, absence of CRC key component causes a reduction in osteosarcoma tumor growth and metastasis. Moreover, it is shown that CRC condensates can be specifically attenuated by the H3K27 demethylase inhibitor, GSK‐J4. Pharmacological inhibition of the CRC phase separation results in metastasis suppression and re‐sensitivity to chemotherapy drugs in patient‐derived xenograft model. Taken together, this study reveals a previously unknown mechanism that CRC factors formed LLPS condensates, and provides a phase separation‐based pharmacological strategy to target undruggable CRC components for the treatment of metastatic and chemo‐resistant osteosarcoma.
Design Zwitterionic Amorphous Conjugated Micro‐/Mesoporous Polymer Assembled Nanotentacle as Highly Efficient Sulfur Electrocatalyst for Lithium‐Sulfur Batteries
Authors: Liu Jiabing , Li Haipeng , Wang Jiayi , Zhang Yongguang , Luo Dan , Zhao Yan , Li Yebao , Yu Aiping , Wang Xin , Chen Zhongwei
Published: August 2021

The commercial application of lithium‐sulfur (LiS) batteries is seriously hampered by the sluggish redox kinetics and the shuttle effect of lithium polysulfides (LiPSs). In this study, a novel conjugated micro/mesoporous polymer (ST‐CMP) is developed by rational design of the organic condensation reaction of squaric acid and 1,3,5‐Tris(4‐aminophenyl)benzene, which can uniformly wrap onto carbon nanotube (CNT) as assembled nanotentacle, serving as the highly efficient sulfur electrocatalyst for LiS batteries. In this composite, the cross‐linked CNT conductive network significantly improves the electron transfer and reaction kinetics of active materials. In addition, the ST‐CMP assembled nanotentacle prevents the restacking or aggregation of ST‐CMP, favoring the exposure of active sites on ST‐CMP for efficient LiPSs chemical interaction. The abundant polymeric zwitterions in ST‐CMP with uniformly distributed positively polarized N atoms and negatively polarized O atoms can not only empower comprehensive regulation of LiPSs adsorption, but also simultaneously allow accelerated LiPSs catalytic conversion, rendering admirable redox reaction kinetics. With these merits, the obtained S/ST‐CMP@CNT composites exhibit a high initial specific capacity of 1307 mAh g−1 at 0.2 C with an ultralow capacity fading rate of 0.047% per cycle after 500 cycles at 1 C, exhibiting great potential in developing LiS batteries with decent performance.
Fluctuation of particles during funnel flow discharge from flat‐bottomed silos
Authors: Zhang Dancheng , Yang Xiaodong , Zhan Jinhui , Liu Xiaoxing
Published: August 2021

Although resonant motion of particles during mass flow discharge from silos has been extensively investigated by earlier researchers, the appearance of such phenomenon during funnel flow discharge has not been emphasized. In this work, the flow behavior of particles during funnel flow discharge from flat‐bottomed silos has been investigated by conducting three‐dimensional Discrete Element Method (DEM) simulations. It is found that particles in the upper part of flowing zone move collectively, manifested by the oscillatory fluctuations of the velocity and the non‐Gaussian characteristics of the fluctuations of individual velocity around the average. Correlation analysis and discrete Fourier transform have been performed to characterize the emission and propagation of velocity fluctuation. It is found that the observed resonant motion of particles is induced by the regular fluctuation of contact force between particles, and there exists an intermediate region in the converging part of the flowing zone. The bottom boundary of this region corresponds to the emission source from which the velocity wave propagates upward and downward. Its upper boundary coincides with that of the converging part of the flowing zone and is featured by the most violent fluctuation of contact force. The simulation results thus suggest that the discharge of granular assembly seems to be determined by the rheological behavior of particles in this intermediate region.
Variations in morphological and epidermal features of shade and sun leaves of two species: Quercus bambusifolia and Q. myrsinifolia
Authors: Maslova Natalia P. , Karasev Eugeny V. , Xu Sheng‐Lan , Spicer Robert A. , Liu Xiao‐Yan , Kodrul Tatiana M. , Spicer Teresa E. V. , Jin Jian‐Hua
Published: August 2021

Premise

Microclimatic differences between the periphery and the interior of tree crowns result in a variety of adaptive leaf macromorphological and anatomical features. Our research was designed to reveal criteria for sun/shade leaf identification in two species of evergreen oaks, applicable to both modern and fossil leaves. We compared our results with those in other species similarly studied.

Methods

For both Quercus bambusifolia and Q. myrsinifolia (section Cyclobalanopsis), leaves from single mature trees with well‐developed crowns were collected in the South China Botanical Garden, Guangzhou, China. We focus on leaf characters often preserved in fossil material. SVGm software was used for macromorphological measurement. Quantitative analyses were performed and box plots generated using R software with IDE Rstudio. Leaf cuticles were prepared using traditional botanical techniques.

Results

Principal characters for distinguishing shade and sun leaves in the studied oaks were identified as leaf lamina length to width ratio (L/W), and the degree of development of venation networks. For Q. myrsinifolia, shade and sun leaves differ in tooth morphology and the ratio of toothed lamina length to overall lamina length. The main epidermal characters are ordinary cell size and anticlinal wall outlines. For both species, plasticity within shade leaves exceeds that of sun leaves.

Conclusions

Morphological responses to sun and shade in the examined oaks are similar to those in other plant genera, pointing to useful generalizations for recognizing common foliar polymorphisms that must be taken into account when determining the taxonomic position of both modern and fossil plants.
Parent B2N2‐Perylenes with Different BN Orientations
Authors: Zhang Peng‐Fei , Zeng Jing‐Cai , Zhuang Fang‐Dong , Zhao Ke‐Xiang , Sun Ze‐Hao , Yao Ze‐Fan , Lu Yang , Wang Xiao‐Ye , Wang Jie‐Yu , Pei Jian
Published: August 2021

Introducing BN units into polycyclic aromatic hydrocarbons expands the chemical space of conjugated materials with novel properties. However, it is challenging to achieve accurate synthesis of BN‐PAHs with specific BN positions and orientations. Here, three new parent B2N2‐perylenes with different BN orientations are synthesized with BN‐naphthalene as the building block, providing systematic insight into the effects of BN incorporation with different orientations on the structure, (anti)aromaticity, crystal packing and photophysical properties. The intermolecular dipole–dipole interaction shortens the π–π stacking distance. The crystal structure, (anti)aromaticity, and photophysical properties vary with the change of BN orientation. The revealed BN doping effects may provide a guideline for the synthesis of BN‐PAHs with specific stacking structures, and the synthetic strategy employed here can be extended toward the synthesis of larger BN‐embedded PAHs with adjustable BN patterns.
Katalytische Carbochlorocarbonylierung von ungesättigten Kohlenwasserstoffen durch C‐COCl‐Bindungsspaltung**
Authors: Denton Elliott H. , Lee Yong Ho , Roediger Sven , Boehm Philip , Fellert Maximilian , Morandi Bill
Published: August 2021

Hier wird über eine Pd‐katalysierte Difunktionalisierung ungesättigter C‐C‐Bindungen mit Säurechloriden berichtet. Formal wird die C‐COCl‐Bindung eines Säurechlorids gespalten und atomökonomisch an gespannte Alkene oder verknüpfte Alkine addiert, um neue Säurechloride zu erzeugen. Die Transformation erfordert kein exogenes CO, läuft unter milden Bedingungen ab, zeigt eine gute Toleranz für funktionelle Gruppen und liefert die isolierten Produkte hoch stereoselektiv. Die intermolekulare Reaktion toleriert dabei sowohl Aryl‐ als auch Alkenyl‐substituierte Säurechloride. Zum Gelingen der Reaktion ist notwendig, die Carbonsäuren in situ in das Säurechlorid umzuwandeln. Die Reaktion dient auch als Beispiel für temperaturabhängige Stereodivergenz, die zusammen mit möglichen Reaktionsmechanismen durch DFT‐Rechnungen untersucht wird. Zudem wird gezeigt, dass Benzofurane in einer intramolekularen Variante der Reaktion gebildet werden können. Die Derivatisierung der Produkte aus der intermolekularen Reaktion bietet einen hoch stereoselektiven Ansatz für die Synthese tetrasubstituierter Cyclopentane.
Intragenomische Decarboxylierung von 5‐Carboxy‐2′‐desoxycytidin
Authors: Kamińska Ewelina , Korytiaková Eva , Reichl Andreas , Müller Markus , Carell Thomas
Published: August 2021

DNA besteht aus den vier kanonischen Nukleosiden dA, dC, dG und T. Zudem findet sich auch 5‐Methylcytosin (mdC) in der genomischen DNA. Die Methylierung von dC zu mdC reguliert die Transkriptionsaktivität. Daneben enthält insbesondere das Genom von Stammzellen drei weitere dC‐Derivate, die durch schrittweise Oxidation der Methylgruppe mithilfe von Tet‐Enzymen gebildet werden: 5‐Hydroxymethyl‐dC (hmdC), 5‐Formyl‐dC (fdC) und 5‐Carboxy‐dC (cadC). Es wird angenommen, dass fdC und cadC wieder in dC umgewandelt werden, wodurch ein epigenetischer Kontrollzyklus entsteht, der mit der Methylierung von dC zu mdC beginnt und mit der Oxidation und Entfernung von fdC und cadC endet. Während fdC nachweislich eine intragenomische Deformylierung zu dC durchläuft, wurde eine vergleichbare Decarboxylierung von cadC zwar postuliert, aber bisher nicht beobachtet. Hier zeigen wir mithilfe von Stoffwechselmarkierungen in verschiedenen Zelltypen, dass cadC decarboxyliert, was bestätigt, dass sowohl fdC als auch cadC Nukleoside sind, die im Genom durch Spaltung der C‐C‐Bindung direkt in dC zurückverwandelt werden.
N‐alkyl imidazole‐based homonuclear coordination complex as a neutral organocatalyst for the faster and efficient construction of 3,4‐dihydro‐2H‐1,3‐oxazine scaffold
Authors: Yıldırım Ayhan , Göker Mustafa
Published: August 2021

In the present work, homonuclear coordination complex including Zn (II) andN‐hexadecylimidazole ligand was used for the first time as a highly efficient homogeneous neutral organocatalyst for the synthesis of 3,4‐dihydro‐2H‐1,3‐benzoxazine monomers. Therefore,N‐alkyl orN‐aryl substituted, both mono‐benzoxazine and bis‐benzoxazine, were successfully synthesized (21 examples) via Mannich‐type condensation reactions. Effortlessly obtaining the pure product with high yields and the short reaction time makes this method more useful and advantageous than the common existing benzoxazine synthesis methods.
Effects of networks composed of epoxy/dual thiol‐curing agents on properties of shape memory polymers
Authors: Wang Yanling , Tang Longhao , Li Yongfei , Li Qiang
Published: August 2021

Profound understanding of relationships between molecular networks with properties can make it more convenient for people to prepare and employ shape memory polymers (SMPs). In this paper, a series of epoxy SMPs were developed based on epoxy (E‐51), trimethylolpropane tris(3‐mercaptopropionate) and pentaerythritoltetrakis (3‐mercaptopropionate), and 2‐methylimidazole, through “epoxy‐thiol” click reaction. The effect of networks on key properties (heat resistance and mechanical properties shape recovery performance) was systematically investigated. Experiment results indicated that there were positive correlations between network regularity with both thermal–mechanical properties and heat resistance. In addition, regularity of network structure had an effect to restrict shape recovery speed.
Synthesis and characterization of a novel rigid rod polymer based on 2,6‐dihydroxyterephthalic acid and 2,3,5,6‐tetraminopyridine
Authors: Wang Zhongwen , Deng Yamin , Jia Xin
Published: August 2021

Poly‐p‐phenyleneterephthalamide (PPTA) is widely used in national defense, military industry, and aerospace. However, with weak compression resistance and twist resistance, development of PPTA is greatly impeded. In this work, a novel rigid rod polymer was synthesized by polycondensation of 2,6‐dihydroxyterephthalic acid with 2,3,5,6‐tetraminopyridine which have a large quantity of hydrogen bonds between these polymer chains which provide excellent thermal properties named poly [N‐(2,5‐diamino‐6‐[imino]‐3‐pyridyl)‐4‐formyl‐2,6‐dihydroxybenzamide] (PPDA). The structure of the polymers was characterized by X‐ray diffraction and Fourier transform infrared spectroscopy. The resulting showed that PPDA has good thermal stability and crystallinity, the maximum thermal decomposition temperature close to 900°C under the nitrogen atmosphere. At the same time, PPDA was insoluble in most organic solvents and exhibited good chemical stability. This indicated a superior performance over that of the poly(2,6‐diimidazo(4,5‐b:4′5′‐e)pyridinylene‐1,4(2,5‐dihydroxy)phenylene). In addition, we can foresee that PPDA will play an important role in prospective surgery and aramid areas.
Analyzing clarification in asynchronous information‐seeking conversations
Authors: Tavakoli Leila , Zamani Hamed , Scholer Falk , Croft William Bruce , Sanderson Mark
Published: August 2021

This research analyzes human‐generated clarification questions to provide insights into how they are used to disambiguate and provide a better understanding of information needs. A set of clarification questions is extracted from posts on the Stack Exchange platform. Novel taxonomy is defined for the annotation of the questions and their responses. We investigate the clarification questions in terms of whether they add any information to the post (the initial question posted by the asker) and the accepted answer, which is the answer chosen by the asker. After identifying, which clarification questions are more useful, we investigated the characteristics of these questions in terms of their types and patterns. Non‐useful clarification questions are identified, and their patterns are compared with useful clarifications. Our analysis indicates that the most useful clarification questions have similar patterns, regardless of topic. This research contributes to an understanding of clarification in conversations and can provide insight for clarification dialogues in conversational search scenarios and for the possible system generation of clarification requests in information‐seeking conversations.
Passive sampler designed for per‐ and polyfluoroalkyl substances using polymer‐modified organosilica adsorbent
Authors: Hartmann Heather , Hefner Claire , Carter Erika , Liles David , Divine Craig , Edmiston Paul L.
Published: August 2021

A passive sampler designed to measure per‐ and polyfluoroalkyl substances (PFAS) was evaluated to determine chemical uptake rates under a variety of conditions. The sampler design is simple and robust, using organosilica modified with cross‐linked amine polymer in an high density polyethylene housing retained with polypropylene mesh. The addition of amine groups as a weak ion‐exchange resin in combination with Cu2+ was designed to promote binding of short‐chain PFAS. A five‐fold improvement in perfluorobutanoic acid adsorption was measured when Cu2+ was added to the polyethylenimine polymer. The samplers showed an integrated response to all analytes tested except for short‐chain PFAS. Sampling rates of PFAS analytes from simulated groundwater were on average 10 mL/day at flow rates of 0.038–1.9 cm/min. Relatively low variability in sampling rate was observed over the range of laboratory tested conditions (representing common conditions in environmental waters) including elevated ionic strength, sulfate concentration, and humic acid content.

Article Impact Statement

Measuring per‐ and polyfluoroalkyl substances in environmental samples is important for monitoring. Passive samplers can offer practical advantages for making measurements.
Systematizing the different notions of growth‐coupled product synthesis and a single framework for computing corresponding strain designs
Authors: Schneider Philipp , Mahadevan Radhakrishnan , Klamt Steffen
Published: August 2021

A widely used design principle for metabolic engineering of microorganisms aims to introduce interventions that enforce growth‐coupled product synthesis such that the product of interest becomes a (mandatory) by‐product of growth. However, different variants and partially contradicting notions of growth‐coupled production (GCP) exist. Herein, we propose an ontology for the different degrees of GCP and clarify their relationships. Ordered by coupling degree, we distinguish four major classes: potentially, weakly, and directionally growth‐coupled production (pGCP, wGCP, dGCP) as well as substrate‐uptake coupled production (SUCP). We then extend the framework of Minimal Cut Sets (MCS), previously used to compute dGCP and SUCP strain designs, to allow inclusion of implicit optimality constraints, a feature required to compute pGCP and wGCP designs. This extension closes the gap between MCS‐based and bilevel‐based strain design approaches and enables computation (and comparison) of designs for all GCP classes within a single framework. By computing GCP strain designs for a range of products, we illustrate the hierarchical relationships between the different coupling degrees. We find that feasibility of coupling is not affected by the chosen GCP degree and that strongest coupling (SUCP) requires often only one or two more interventions than wGCP and dGCP. Finally, we show that the principle of coupling can be generalized to couple product synthesis with other cellular functions than growth, for example, with net ATP formation. This work provides important theoretical results and algorithmic developments and a unified terminology for computational strain design based on GCP.
Engineered Human Induced Pluripotent Cells Enable Genetic Code Expansion in Brain Organoids
Authors: van Husen Lea S. , Katsori Anna‐Maria , Meineke Birthe , Tjernberg Lars O. , Schedin‐Weiss Sophia , Elsässer Simon J.
Published: August 2021

Human induced pluripotent stem cell (hiPSC) technology has revolutionized studies on human biology. A wide range of cell types and tissue models can be derived from hiPSCs to study complex human diseases. Here, we use PiggyBac‐mediated transgenesis to engineer hiPSCs with an expanded genetic code. We demonstrate that genomic integration of expression cassettes for a pyrrolysyl‐tRNA synthetase (PylRS), pyrrolysyl‐tRNA (PylT) and the target protein of interest enables site‐specific incorporation of a non‐canonical amino acid (ncAA) in response to an amber stop codon. Neural stem cells, neurons and brain organoids derived from the engineered hiPSCs continue to express the amber suppression machinery and produce ncAA‐bearing reporter. The incorporated ncAA can serve as a minimal bioorthogonal handle for further modifications by labeling with fluorescent dyes. Site‐directed ncAA mutagenesis will open a wide range of applications to probe and manipulate proteins in brain organoids and other hiPSC‐derived cell types and complex tissue models.
Aberrant expression of lncRNAs SNHG6, TRPM2‐AS1, MIR4435‐2HG, and hypomethylation of TRPM2‐AS1 promoter in colorectal cancer
Authors: Ghasemi Tayyebeh , Khalaj‐Kondori Mohammad , Hosseinpour feizi Mohammad Ali , Asadi Parviz
Published: August 2021

Accumulating evidence has indicated that deregulation of lncRNAs plays essential roles in colorectal cancer (CRC) carcinogenesis. The goal of this study was to analyze the expression of lncRNAs in colorectal cancer and their association with clinicopathological variables. Bioinformatics analysis of published CRC microarray data was performed to identify the important lncRNAs. The expression levels of candidate genes were assessed in the human colon cancer/normal cell lines, CRC, adenomatous colorectal polyps, and their marginal tissues by qRT‐PCR. Moreover, the methylation status of the TRPM2‐AS1 promoter was studied using qMSP assay. Furthermore, we investigated the molecular mechanisms of these lncRNAs in CRC progression using in silico analysis. Microarray analysis revealed that lncRNAs SNHG6, MIR4435‐2HG, and TRPM2‐AS1 were upregulated in CRC. These results were validated in colon cell lines. Moreover, qRT‐PCR showed that the expression levels of SNHG6 and TRPM2‐AS1 were upregulated in the colorectal tumor tissues compared with their paired tissues. Nonetheless, there was no significant increase in MIR4435‐2HG expression in CRC samples. Furthermore, we observed a significant hypomethylation of TRPM2‐AS1 promoter and its activation in CRC tissues. By in silico analysis, we found that the lncRNAs upregulation could promote proliferation and drug resistance of colorectal cancer cells via miRNAs sponging and modulation of their targets expression. In conclusion, based on our results upregulation of SNHG6 and TRPM2‐AS1, and hypomethylation of TRPM2‐AS1 promoter might be considered as potential diagnostic biomarkers for CRC initiation and development.
Endodontic management of a rare case of the geminated maxillary second molar tooth using CBCT
Authors: Ramezani Masoumeh , Asgari Shima , Adel Mamak
Published: August 2021

This report illustrates a rare case of a geminated maxillary right second molar tooth using CBCT in a 23‐year‐old man with severe pain. Nonsurgical endodontic treatment was performed, which gave rise to an asymptomatic tooth at the 12‐month follow‐up.
Case series: New‐onset freezing of gait in combined use of deep brain stimulation and Levodopa
Authors: Salari Mehri , Aminzade Zahra , Jalili khoshnood Reza , Tehrani Fateh Sepand
Published: August 2021

Concurrent use of DBS and levodopa in Parkinson's disease patients can lead to freezing of gait. This phenomenon may be due to an inverted‐U‐Shaped function of dopamine.
A case of catastrophic epistaxis from the internal carotid artery due to multiple surgeries and irradiations for pituitary tumor: Rescued utilizing high‐flow bypass and simultaneous skull base reconstruction
Authors: Takabayashi Kosuke , Takebayashi Seiji , Sakurai Juro , Gotoh Shuho , Takizawa Katsumi
Published: August 2021

Revascularization for internal carotid artery rupture should be considered immediately under the situation where endovascular treatment is not indicated. Revascularization can prevent the risk of hemorrhage during skull base reconstruction.
A case report of mediastinal cavernous hemangioma
Authors: Ouladdameshghi Davoud , Eshraghi Mohsen , Shahhamzeh Alireza , Riyah Mohammad Mehdi , Fatemi Maedeh Alsadat , Fazilat‐Panah Danial , Dehghani Mansoureh
Published: August 2021

When faced with a hypervascular mediastinal tumor, mediastinal hemangioma should be taken into consideration. Although it is uncommon, considering this important diagnosis may avoid a possible extensive surgery that is not necessary.
Failed endocarditis prophylaxis before a dental procedure in a high‐risk single‐lung patient with a bioprosthetic heart valve: A rare case report
Authors: Pinter‐Högerle Anabel , von Oehsen Hartwig H. C. , Högerle Benjamin A. , Breit Rainer
Published: August 2021

Regarding endocarditis prophylaxis, there is an increasing burden of enterococci related to antibiotic resistances. The testing of the bacterial milieu of the oral cavity before dental procedures may be promising to adjust the antibiotics.
Zn‐Vacancy Engineered S‐Scheme ZnCdS/ZnS Photocatalyst for Highly Efficient Photocatalytic H2 Evolution
Authors: Hao Xuqiang , Xiang Dingzhou , Jin Zhiliang
Published: August 2021

Vacancy defects engineering is a valid strategy to enhance the separation efficiency of photo‐generated charges. Herein, a zinc vacancy mediated S‐scheme ZnCdS/ZnS composite derived from ZnCdS/MOF‐5 was constructed in‐situ through the sacrificial reagent of Na2S/Na2SO3 aqueous solution in visible‐light irradiation. The MOF‐5 converted to ZnS (ZnS−VZn) with abundant zinc vacancies which were proved by the XPS and PL results. ZnS−VZn has two‐photon absorption performance, which immensely enhanced the visible light absorption capacity for the photocatalysts. The photo‐generated electrons of ZnS−VZn on the Zn‐vacancy defect would regroup with the holes in the valence band (VB) of ZnCdS via ohmic contact which is induced by Zn‐vacancy defects. Therefore, the photoexciton of ZnCdS can be able to separate effectively and eliminate the useless electrons and holes. The ZnCdS/ZnS(20) sample revealed an outstanding photocatalytic hydrogen generation rate of 12.31 mmol h−1g−1 with a turnover number (TON) of 64.61, which is about 82.06 and 21.98 times greater than that of neat ZnS−VZn and ZnCdS. This work gives an insight into the design of the zinc vacancy‐engineered S‐scheme photocatalyst of ZnCdS/ZnS for highly efficient photocatalysis.
Numerical and Experimental Analysis of the Daughter Distribution in Liquid‐Liquid Stirred Tanks
Authors: Maluta Francesco , Buffo Antonio , Marchisio Daniele , Montante Giuseppina , Paglianti Alessandro , Vanni Marco
Published: August 2021

The drop size distributions (DSDs) of a dilute immiscible liquid‐liquid mixture were measured in a fully turbulent stirred tank operating at different impeller speeds. The results were used to infer the best daughter distribution function (DDF) leading to the best reproduction of the shape of the DSD. Bell‐shaped, U‐shaped, M‐shaped, and uniform statistical DDFs were studied, producing from two to four daughters from each breakup event. A simplified approach from the literature was adopted to solve the population balance equation that considers the spectrum of the turbulence inside the tank obtained from computational fluid dynamics simulations. The U‐shaped distribution producing four fragments better reproduces the shape of the experimental DSD in the studied system.
Species selection tool: Soil‐specific forage species selection for New York State
Authors: Post Christopher , Cherney Jerome , Reid Shaw
Published: August 2021

Selection of forage species that are best suited to a particular soil type and forage use provide the most efficient land use. This program was developed to provide recommendations for perennial forage species in New York State, based on soil type and intended forage use through a web interface (http://www.forages.org). Forage species uses include both pasture and stored feed for different livestock classes as well as soil conservation uses. A database was developed that contains potential yields for more than 30 species and more than 40 species mixtures on each of 612 agricultural soil types in New York State. The database has potential forage yields based on native soil drainage as well as yields for optimal artificial drainage. Potential yields are modified by the program based on soil pH and the optimal pH range for each forage species. Species are recommended based on potential yield, intended forage use, and soil type. The program also provides pasture yield distributions, a summary of species traits, and potential corn grain and silage yields for a selected soil type. Computer‐based species recommendations agree with current published recommendations. The program has been used successfully by the National Resources Conservation Service and New York extension personnel for more than 20 years. Although the soil type/species yield relationships will not apply directly to other regions of the world, the method utilized to develop the database could be used to create similar species selection programs for other regions.
Ternary Hybrid Perovskite Solid Solution Single Crystals: Growth, Composition Determination and Phase Stability in Highly Moist Atmosphere
Authors: Tao Kezheng , Gao Lei , Yan Qingfeng
Published: August 2021

Ternary hybrid perovskite solid solutions have shown superior optoelectronic properties and better stability than their ABX3 simple perovskite counterparts under ambient conditions. However, crystal growth and identification of the accurate composition of these complex crystalline compounds remain challenging, and their stability under extreme conditions such as in highly moist atmosphere is unknown. Herein, large‐size (up to 2 cm) single crystals of ternary perovskite 0.80FAPbI3 ⋅ x′FAPbBr3 ⋅ y′CsPbI3 (x′+y′=0.20) are grown. An elemental analysis method based on wavelength dispersive X‐ray fluorescence is proposed to determine their accurate compositions. Among these single crystals, the composition with y′=0.12 shows the best moisture stability at 90 % relative humidity for 15 days. Other components with richer or poorer Cs+ ions undergo different phase segregation behaviours. The performance and stability of photodetectors based on these single crystals are tested. This work offers a deeper insight into phase stability of ternary hybrid perovskite solid solution crystals in highly moist atmosphere.
Quenched Lewis Acidity: Studies on the Medium Dependent Fluorescence of Zinc(II) Complexes
Authors: Kurz Hannah , Hörner Gerald , Weser Oskar , Li Manni Giovanni , Weber Birgit
Published: August 2021

Three new zinc(II) coordination units [Zn(1–3)] based on planar‐directing tetradentate Schiff base‐like ligands H2(1–3) were synthesized. Their solid‐state structures were investigated by single crystal X‐ray diffraction, showing the tendency to overcome the square‐planar coordination sphere by axial ligation. Affinity in solution towards axial ligation has been tested by extended spectroscopic studies, both in the absorption and emission mode. The electronic spectrum of the pyridine complex [Zn(1)(py)] has been characterized by MC‐PDFT to validate the results of extended TD‐DFT studies. Green emission of non‐emissive solutions of [Zn(1–3)] in chloroform could be switched on in the presence of potent Lewis‐bases. While interpretation in terms of an equilibrium of stacked/non‐fluorescent and destacked/fluorescent species is in line with precedents from literature, the sensitivity of [Zn(1–3)] was greatly reduced. Results of a computation‐based structure search allow to trace the hidden Lewis acidity of [Zn(1–3)] to a new stacking motif, resulting in a strongly enhanced stability of the dimers.
Giant Shape‐Persistent Tetrahedral Porphyrin System: Light‐Induced Charge Separation
Authors: Marchini Marianna , Luisa Alessandra , Bergamini Giacomo , Armaroli Nicola , Ventura Barbara , Baroncini Massimo , Demitri Nicola , Iengo Elisabetta , Ceroni Paola
Published: August 2021

Tetraphenylmethane appended with four pyridylpyridinium units works as a scaffold to self‐assemble four ruthenium porphyrins in a tetrahedral shape‐persistent giant architecture. The resulting supramolecular structure has been characterised in the solid state by X‐ray single crystal analysis and in solution by various techniques. Multinuclear NMR spectroscopy confirms the 1 : 4 stoichiometry with the formation of a highly symmetric structure. The self‐assembly process can be monitored by changes of the redox potentials, as well as by modifications in the visible absorption spectrum of the ruthenium porphyrin and by a complete quenching of both the bright fluorescence of the tetracationic scaffold and the weak phosphorescence of the ruthenium porphyrin. An ultrafast photoinduced electron transfer is responsible for this quenching process. The lifetime of the resulting charge separated state (800 ps) is about four times longer in the giant supramolecular structure compared to the model 1 : 1 complex formed by the ruthenium porphyrin and a single pyridylpyridinium unit. Electron delocalization over the tetrameric pyridinium structure is likely to be responsible for this effect.
Fabrication of ZnSe/C Hollow Polyhedrons for Lithium Storage
Authors: Yuan Jujun , Li Xiaofan , Li Haixia , Lai Weidong , Gan Yunfei , Yang Jianwen , Zhang Xianke , Liu Jun , Zhu Xiurong , Li Xiaokang
Published: August 2021

ZnSe has got extensive attention for high‐performance LIBs anode due to its remarkable theoretical capacity and environmental friendliness. Nevertheless, the large volume variation for the ZnSe in the discharge/charge processes brings about rapid capacity fading and poor rate performance. Herein, ZnSe/C hollow polyhedrons are successfully synthesized by selenization of zeolitic imidazolate framework‐8 (ZIF‐8) with resorcinol‐formaldehyde (RF) coating. The protection of C layer derived from RF coating layer and Ostwald ripening during the process of selenization play important roles in promoting formation of ZnSe/C hollow polyhedrons. The ZnSe/C hollow polyhedrons exhibit good rate performance and long‐term cycle stability (345 mAh g−1 up to 1000 cycles at 1 A g−1) for lithium ion batteries (LIBs) anode. The improved electrochemical performance is benefit from the unique ZnSe/C hollow structure, in which the hollow structure can effectively avoid terrible volume expansion, and the thin ZnSe/C shell can not only provide adequate diffusion paths of lithium ions and but also enhance the electronic conductivity.
Prolonging the Triplet State Lifetimes of Rhenium Complexes with Imidazole‐Pyridine Framework for Efficient CO2 Photoreduction
Authors: Qiu Li‐Qi , Chen Kai‐Hong , Yang Zhi‐Wen , Ren Fang‐Yu , He Liang‐Nian
Published: August 2021

The photocatalytic reduction of CO2 into fuels offers the prospect for creating a new CO2 economy. Harnessing visible light‐driven CO2‐to‐CO reduction mediated by the long‐lived triplet excited state of rhenium(I) tricarbonyl complexes is a challenging approach. We here develop a series of new mononuclear rhenium(I) tricarbonyl complexes (Re‐1−Re‐4) based on the imidazole‐pyridine skeleton for photo‐driven CO2 reduction. These catalysts are featured by combining pyridyl‐imidazole with the aromatic ring and different pendant organic groups onto the N1 position of 1,3‐imidazole unit, which display phosphorescence under Ar‐saturated solution even at ambient conditions. By contrast, {Re[9‐(pyren‐1‐yl)‐10‐(pyridin‐2‐yl)‐9H‐pyreno[4,5‐d]imidazole)](CO)3Cl} (Re‐4) by introducing pyrene ring at the N1 position of pyrene‐fused imidazole unit exhibits superior catalytic performance with a higher turnover number for CO (TONCO=124) and >99.9 % selectivity, primarily ascribed to the strong visible light‐harvesting ability, long‐lived triplet lifetimes (164.2 μs) and large reductive quenching constant. Moreover, the rhenium(I) tricarbonyl complexes derived from π‐extended pyrene chromophore exhibit a long lifetime corresponding to its ligand‐localized triplet state (3IL) evidenced from spectroscopic investigations and DFT calculations.
Rational Design and Synthesis of Interlocked [2]Catenanes Featuring Half‐Sandwich Cp*Rh/Ir Units and Pyrene‐Based Ligands†
Authors: Shen Yue‐Rong , Gao Xiang , Cui Zheng , Jin Guo‐Xin
Published: August 2021

Main observation and conclusion

The construction of interlocked topologies by metal‐cation‐template methods has been extensively explored. However, construction of these species using template‐free chemical self‐assembly methods is hard to rationally achieve due to the inherent unpredictability of self‐assembly processes. In this work, a strategy to construct interlocked [2]catenanes by coordination‐driven template‐free self‐assembly is demonstrated, whereby combining rigid bidentate ligands with large conjugated‐π area units and building blocks with appropriate lengths facilitated construction of interlocked [2]catenane compounds. Two rigid bidentate ligands, L1 and L2, were chosen to self‐assemble with three dinuclear building blocks B1, B2 and B3. Ultimately, the successful construction of three [2]catenanes demonstrated the validity of the strategy. Although [2]catenanes are the simplest of all interlocked topologies, this motif is the basis for constructing more intricate topologies. This successful strategy may therefore lead to construction of other, more intricate topologies in the future.
Personalized sedation goal for agitated delirium in patients with cancer: Balancing comfort and communication
Authors: Hui David , De La Rosa Allison , Urbauer Diana L. , Nguyen Thuc , Bruera Eduardo
Published: August 2021

Background

Agitated delirium is common and highly distressing. Medications are often needed to reduce agitation, but it is unclear what the desired level of sedation is. This study assessed personalized sedation goals (PSGs) and their predictors for patients in a delirium clinical trial and in clinical vignettes.

Methods

This was a preplanned secondary analysis of a double‐blind randomized clinical trial examining the sedative effect of chlorpromazine and/or haloperidol in patients with agitated delirium. At the baseline, caregivers and nurses were independently asked to select the PSG for the trial patient from 5 choices corresponding to Richmond Agitation Sedation Scale (RASS) scores of 0 or higher (no sedation), –1 to –2, –3, –4, and –5 (deep sedation). Respondents also selected a PSG for 6 vignettes that differed by the level of agitation, ability to communicate, and survival.

Results

Forty‐two caregivers and 39 nurses answered questions regarding PSGs. For the trial patient, caregivers preferred RASS scores of –1 to –2 most often (36%), whereas nurses preferred an RASS score of –3 most often (51 %). Caregivers were significantly more likely than nurses to choose lighter sedation (odds ratio [OR], 4.8; P = .01) despite reporting greater delirium‐related distress (P = .0006). Patients were undersedated 33% to 53% of the time and oversedated 0% to 15% of the time according to the PSG response criteria. In the case vignettes, deeper sedation was preferred by nurses (P < .0001) and for patients who were unable to communicate (OR, 3.1‐4.4; P < .0001) and had a shorter life expectancy (OR, 1.7; P = .002).

Conclusions

Caregivers often preferred lighter sedation than nurses. Many patients were undersedated in comparison with caregivers' PSGs, and this highlights room for improvement.

Lay Summary

In the last days of life, many patients with cancer develop delirium and become restless/agitated; this can be highly distressing.

Caregivers and physicians alike are often concerned about the use of sedatives for agitated delirium and try to find a balance between maximizing comfort and maintaining communication.

This study examined the concept of a personalized sedation goal for setting an individualized target for the level of sedation.

Caregivers often preferred lighter sedation than nurses. Many patients were undersedated in comparison with caregivers' stated goals, and this highlights room for improvement.
The Effect of Food on the Pharmacokinetics of the Potassium‐Competitive Acid Blocker Vonoprazan
Authors: Mulford Darcy J. , Leifke Eckhard , Hibberd Mark , Howden Colin W.
Published: August 2021

Herein, we report a food‐effect study of vonoprazan, an oral potassium‐competitive acid blocker. In a phase 1, randomized, open‐label, crossover study, healthy subjects received a single 20‐mg dose of vonoprazan either following an overnight fast or 30 minutes after a high‐fat breakfast. Plasma vonoprazan levels were determined at 0 hour and at 17 subsequent assessment points up to 48 hours after dosing. After a 5‐day washout, subjects received a second 20‐mg vonoprazan dose in the alternative fed/fasted state (identical process repeated). Twenty‐four subjects completed the study. Vonoprazan exposure was not meaningfully affected by food. Geometric mean ratios for maximum concentration, area under the concentration‐time curve from time 0 to 24 hours, and area under the plasma concentration–time curve extrapolated to infinity obtained under fed and fasting conditions were 1.05 (90% confidence interval, 0.98‐1.12), 1.13 (1.09‐1.18), and 1.15 (1.11‐1.19), respectively. Four subjects experienced 6 adverse events that were all mild and considered unrelated to the study drug. Vonoprazan can be administered without regard to food intake.
The role of attachment, coping style and reasons for substance use in substance users with psychosis
Authors: Berry Katherine , Haddock Gillian , Barrowclough Christine , Gregg Lynsey
Published: August 2021

Seventy substance users with psychosis who were participating in a clinical trial of a psychological therapy for psychosis were additionally assessed for attachment, coping styles and self‐reported reasons for substance use in order to test a hypothesized sequential mediation model. In this model the relationship between insecure attachment and problematic substance use was assumed to be sequentially mediated by dysfunctional coping and the use of substances to cope with distress. Hypothesized associations between insecure‐avoidant attachment and substance use were not supported, but the relationship between insecure‐anxious attachment and problematic substance use was confirmed and found to be fully mediated by dysfunctional coping and coping reasons for use. Findings suggest that fostering secure attachments in people with psychosis might promote more successful coping and could prevent or reduce substance use related problems in this group.
Enantiopure Double ortho‐Oligophenylethynylene‐Based Helical Structures with Circularly Polarized Luminescence Activity
Authors: Reiné Pablo , Ortuño Ana M. , Resa Sandra , Álvarez de Cienfuegos Luis , Ribagorda María , Mota Antonio J. , Abbate Sergio , Longhi Giovanna , Miguel Delia , Cuerva Juan M.
Published: August 2021

In this paper, we describe the optical and chiroptical properties of an enantiopure multipodal ortho‐oligophenylethynylene (S,S,S,S)‐1 presenting four chiral sulfoxide groups at the extremes. The presence of these groups together with alkynes allows the coordination with carbophilic Ag(I), and/or oxophilic Zn(II) cations, yielding double helical structures in an enantiopure way. In this sense, different behaviors in absorption, fluorescence, ECD and CPL spectra have been found depending on the stoichiometry and nature of the metal. We have observed that Zn(II) coordination favors an intensity increase of the electronic circular dichroism (ECD) spectra of compound (S,S,S,S)‐1 yielding an M‐helicity in the ortho‐oligophenylene ethynylene (o‐OPE) backbone. On the other hand, ECD spectra of final Ag(I) complex shows two different bands with an opposite sign to the free ligand, thus giving the P‐helical isomer. In addition, circularly polarized luminescence (CPL) exhibit an enhanced intensity and negative sign in both complexes. Computational studies were also carried out, supporting the experimental results.
The evolution of “atypia” in thyroid fine‐needle aspiration specimens
Authors: Kim Teresa H. , Krane Jeffrey F.
Published: August 2021

The Bethesda System for Reporting Thyroid Cytopathology (TBSRTC) provided a standardized framework for resulting thyroid fine‐needle aspiration (FNA) specimens and introduced the low‐risk category of atypia of undetermined significance/follicular lesion of undetermined significance (AUS/FLUS). This indeterminate category has significantly evolved over time with the incorporation of molecular testing, reclassification of noninvasive follicular thyroid neoplasm with papillary‐like nuclear features (NIFTP), and a shift toward more conservative management. Despite these refinements, AUS/FLUS remains a challenge, at both the diagnostic and therapeutic level. We review the criteria for AUS/FLUS and the associated controversies in rendering this diagnosis, while highlighting the importance of a multidisciplinary approach to managing atypical thyroid nodules.
Fine‐scale foraging habitat selection by two diving central place foragers in the Northeast Atlantic
Authors: Huon Mathilde , Planque Yann , Jessopp Mark John , Cronin Michelle , Caurant Florence , Vincent Cécile
Published: August 2021

Habitat selection and spatial usage are important components of animal behavior influencing fitness and population dynamic. Understanding the animal–habitat relationship is crucial in ecology, particularly in developing strategies for wildlife management and conservation. As this relationship is governed by environmental features and intra‐ and interspecific interactions, habitat selection of a population may vary locally between its core and edges. This is particularly true for central place foragers such as gray and harbor seals, where, in the Northeast Atlantic, the availability of habitat and prey around colonies vary at local scale. Here, we study how foraging habitat selection may vary locally under the influence of physical habitat features. Using GPS/GSM tags deployed at different gray and harbor seals’ colonies, we investigated spatial patterns and foraging habitat selection by comparing trip characteristics and home‐range similarities and fitting GAMMs to seal foraging locations and environmental data. To highlight the importance of modeling habitat selection at local scale, we fitted individual models to colonies as well as a global model. The global model suffered from issues of homogenization, while colony models showed that foraging habitat selection differed markedly between regions for both species. Despite being capable of undertaking far‐ranging trips, both gray and harbor seals selected their foraging habitat depending on local availability, mainly based on distance from the last haul‐out and bathymetry. Distance from shore and tidal current also influenced habitat preferences. Results suggest that local conditions have a strong influence on population spatial ecology, highlighting the relevance of processes occurring at fine geographical scale consistent with management within regional units.