bluuebunny/crossref_metadata_2025 huggingface dataset:
О «Флотилии плавучих университетов», "Природа"
Authors: Комаров В.Н. , Самохвалов С.А.
Published: March 2022

Впрошлом году из печати вышла книга «Экспедиции по Поволжью и Прикаспию. Этюды половины тысячелетия. От первых путешественников до “Флотилии плавучих университетов”». Авторами выступили научный руководитель экспедиции «Флотилия плавучих университетов» А.В.Иванов (Институт географии РАН, Музей землеведения Московского государственного университета имени М.В.Ломоносова), начальник штаба экспедиции И.А.Яшков (Музей геологии, нефти и газа, г.Ханты-Мансийск) и руководитель проекта «Плавучая школа телевидения» Е.Е.Захаров (Саратовский государственный технический университет имени Ю.А.Гагарина, ГТУ). Издание иллюстрировано серией черно-белых изображений исторического плана, а также крупным блоком цветных фотографий о деятельности экспедиции в 2015–2021 гг. — работами фотохудожников А.В.Сочивко, М.П.Игнатовой, А.М.Паничева, Е.Г.Романовой и др.
КЛИРИКИ И МИРЯНЕ В РИМЕ IV–VI вв. ПО «КНИГЕ ПАП», "Средние века"
Authors: Аникьев И.И.
Published: March 2022

В статье поднимается вопрос о существовании в Риме в VI в. городского духовенства как особой общности, отличной от папского окружения. Автор доказывает, что сборник папских биографий, известных как «Книга пап» (Liber Pontificalis), отражает взгляды и особенности социальных представлений этой общности. Среди них: противопоставление себя не только мирянам, но и другим общностям, таким как монашество; защита своих прав и привилегий посредством создания системы ритуалов, соблюдение внутренней иерархии духовенства и конструирования собственной картины церковной истории.
ТЕНЬ ИМПЕРАТОРА: РОЛЬ КАРЛА IV ЛЮКСЕМБУРГА В СУДЬБЕ КОРОЛЯ ФРАНЦИИ КАРЛА V МУДРОГО (ФАКТЫ, КОНТЕКСТЫ, ИНТЕРПРЕТАЦИИ), "Средние века"
Authors: Цатурова С.К.
Published: March 2022

Взаимоотношения французских монархов с императорами Священной Римской Империи всегда были сложными. Однако избрание на императорский престол отпрыска Люксембургского дома, Карла IV, положило начало периоду наиболее тесных, близких и доверительных отношений между Империей и Французским королевством. В статье детально исследуются два важных эпизода этих контактов, относящихся к жизни будущего короля Франции Карла V Мудрого, в бытность его еще наследником престола. В его сложных отношениях с отцом королем Иоанном II Добрым, в ситуации политического кризиса, разразившегося в стране в связи с поражением французской армии и пленением короля, дофин Карл неизменно прибегал к помощи дяди, императора Карла IV Люксембурга. Конечные успехи короля Франции Карла V Мудрого свидетельствуют, что он получил от императора хорошие советы и сумел ими правильно воспользоваться.
ПРЕЦЕССИОННАЯ, ЦИКЛИЧНАЯ, ГЛОБАЛЬНАЯ СМЕНА КЛИМАТА НА ЗЕМЛЕ, "Энергия: экономика, техника, экология"
Authors: Гарматюк В.
Published: March 2022

Увеличение средней температуры на планете вызвано прецессией Земли (изменением наклона планеты к Солнцу). При прецессии на Земле циклично меняются площади, интенсивность и время нагрева лучами Солнца суши и воды.
ОСВОЕНИЕ АРКТИКИ, ДАЛЬНЕГО ВОСТОКА И СИБИРИ КАК ЭКОНОМИЧЕСКАЯ СТРАТЕГИЯ РФ, "Энергия: экономика, техника, экология"
Authors: Ранцев-Картинов В.А.
Published: March 2022

Данная статья представляет только некоторые энергетические аспекты большого общенационального проекта по освоению Арктики, Дальнего Востока и Сибири. В 2019 г. после обращения в правительство РФ о рассмотрении предложений по проекту получен ответ из Министерства РФ по развитию Дальнего Востока и Арктики: “…предложения будут учитываться при подготовке новой редакции стратегии развития Арктической зоны РФ”. Предварительные оценки автора показали, что претворение в жизнь этого проекта на федеральном уровне может дать дополнительный вклад в доходную часть бюджета страны, вплоть до её удвоения. Это обусловлено применением разработанных и запатентованных новых высокоэффективных нанотехнологий в различных областях промышленного производства.
Detection of setup errors with a body‐surface laser‐scanning system for whole‐breast irradiation after breast‐conserving surgery
Authors: Jiang Ping , Liu Ziyi , Jiang Weijuan , Qu Ang , Sun Haitao , Wang Junjie
Published: March 2022

Purpose

We compared the setup errors determined by an optical imaging system (OSIS) in women who received breast‐conserving surgery (BCS) followed by whole‐breast radiotherapy (WBRT) with those from cone‐beam computed tomography (CBCT) carried out routinely.

Methods

We compared 130 setup errors in 10 patients undergoing WBRT following BCS by analyzing the translational and rotational couch shifts via CBCT and OSIS. Patients were treated with intensity‐modulated radiotherapy (IMRT). The patient outline extracted from the planning reference Computed tomography (CT) was used as the reference for OSIS and CBCT alignment during treatment. We detected the setup uncertainty using CBCT and OSIS at the first five fractionations of RT and then twice a week.

Results

The absolute translational setup error (mean ± Standard deviation (SD)) in x (lateral), y (longitudinal), and z (vertical) axes detected by the OSIS was 0.14 ± 0.18, 0.15 ± 0.14, and 0.13 ± 0.13 cm, respectively. The rotational setup error (mean ± SD) in Rx (pitch), Ry (roll), and Rz (yaw) axes was 0.77 ± 0.54, 0.76 ± 0.61, and 1.23 ± 0.95, respectively. Significant difference is observed only in one direction (Rx, p = 0.03) in the paired setup errors obtaining from OSIS and CBCT, without significant differences in five directions.

Conclusion

OSIS is a repeatable and reliable system that can be used to detect misalignments with accuracy, which is capable of supplementing CBCT for WBRT after BCS. We believe that an OSIS may be easier to use, quicker, and reduce overall dose as this method of patient alignment does not require ionizing radiation.
Self‐Reconfiguring and Stiffening Origami Tube
Authors: Suh Jong-Eun , Miyazawa Yasuhiro , Yang Jinkyu , Han Jae-Hung
Published: March 2022

Reconfigurable structures have attracted increasing attention in numerous fields, such as aerospace, biomechanical, and civil engineering, owing to their nature to reshape and readjust without altering their original architectures. However, one of the most challenging issues in designing a reconfigurable structure is to ensure a load‐bearing capacity after reconfiguration, while keeping the structural flexibility during the transformation process. Here, an origami tube that can be easily reconfigured into multiple shapes, yet offering a stiffening mechanism for load‐bearing purposes is presented. A complete set of possible configurations that a single design can be reconfigured into is mathematically identified and classified. Significant differences in their axial stiffness for various configurations are analytically and experimentally investigated. Lastly, a self‐reconfiguring and stiffening mechanism of the proposed origami tube structure made with shape memory polymer (SMP), which automatically reinforces its axial stiffness about an order of magnitude through kinematic transitions is demonstrated.
Indentation Size Effect Model of Ti6Al4V Alloy by Combining the Macroscopic Power‐Law Constitutive Relation and Strain Gradient Theory
Authors: Cui Weiling , Qiu Ji , Wang Hefeng , Su Buyun
Published: March 2022

Indentation size effect (ISE) is a critical feature for investigating the local properties of materials using the indentation test method. Although there are numerous works on the indentation response, there is a lack of data in the literature on the association between nanoindentation and uniaxial compression. Herein this study, uniaxial compression tests combined with Digital Image Correlation Technique are conducted on Ti6Al4V alloy with a focus on investigating the elastic–plastic properties and obtaining the accurately constitutive relation. Then, an ISE model of Ti6Al4V is established based on this constitutive relation and strain gradient theory. Indentation hardness, predicted by this proposed model, agrees well with the measurement by nanoindentation experimental techniques. This model can be used to bridge the gap between the uniaxial stress–strain and the depth‐dependent hardness, and clarifies the effect of the strain hardening on indentation hardness. The significance of this model is that it provides a direct and reasonable theory foundation to investigate ISE by uniaxial compression, and promotes the potential application of nanoindentation.
Carbon Dots as a Potential Therapeutic Agent for the Treatment of Cancer‐Related Anemia
Authors: Xu Yuanlin , Wang Boyang , Zhang Mingming , Zhang Jingxin , Li Yudong , Jia Peijun , Zhang Huan , Duan Lulu , Li Yan , Li Yating , Qu Xiaoli , Wang Shihui , Liu Donghao , Zhou Wenping , Zhao Huizhi , Zhang Hengchao , Chen Lixiang , An Xiuli , Lu Siyu , Zhang Shijie
Published: March 2022

Due to the adverse effects of erythropoietin (EPO) on cancer patient survival, it is necessary to develop new agents that can be used to efficiently manage and treat cancer‐related anemia. In this study, novel distinctive carbon dots, J‐CDs, derived from jujube are designed, synthesized, and characterized. Based on the obtained results, this material comprises sp2 and sp3 carbon atoms, as well as oxygen/nitrogen‐based groups, and it specifically promotes the proliferation of erythroid cells by stimulating the self‐renewal of erythroid progenitor cells in vitro and in vivo. Moreover, J‐CDs have no discernible effects on tumor proliferation and metastasis, unlike EPO. Transcriptome profiling suggests that J‐CDs upregulate the molecules involved in hypoxia response, and they also significantly increase the phosphorylation levels of STAT5, the major transducer of signals for erythroid progenitor cell proliferation. Overall, this study demonstrates that J‐CDs effectively promote erythrocyte production without affecting tumor proliferation and metastasis; thus, they may be promising agents for the treatment of cancer‐related anemia.
V2O3–Li3PO4 Composite: A New Type of Cathodic Active Material for Li‐Ion Batteries
Authors: Tang Anping , Liang Ziqin , Chen Hezhang , Xu Guorong , Song Haishen
Published: March 2022

A new type of cathodic active material for lithium‐ion batteries based on a composite of Li3PO4 and V2O3 is proposed in this work. Although the V2O3 component is almost inactive in the voltage range of 2–4.5 V versus Li+/Li, the mixture of the two components can deliver a larger reversible specific capacity of ≈190 mA h g−1 in the voltage range of 2–4.5 V at a current density of 15 mA g−1. X‐ray photoelectron spectroscopy data and cyclic voltammetry data suggest that the vanadium ions are probably oxidized and reduced repetitively upon cycling and that the V3+ ions are partially oxidized to V4+ and even V5+ ions during charging to 4.5 V. This distinctive lithium‐ion uptake and release phenomenon, in which Li3PO4 functions as a lithium source of surface conversion reaction, will introduce a new path for designing unique cathodic active materials for lithium‐ion batteries.
Comparative Analysis of the Near‐ and Far‐Field Optical Response of Thin Plasmonic Nanostructures
Authors: Zundel Lauren , Gieri Paul , Sanders Stephen , Manjavacas Alejandro
Published: March 2022

Nanostructures made of metallic materials support collective oscillations of their conduction electrons, commonly known as surface plasmons. These modes, whose characteristics are determined by the material and morphology of the nanostructure, couple strongly to light and confine it into subwavelength volumes. Of particular interest are metallic nanostructures for which the size along one dimension approaches the nanometer or even the subnanometer scale, since such morphologies can lead to stronger light–matter interactions and higher degrees of confinement than regular three‐dimensional nanostructures. Here, the plasmonic response of metallic nanodisks of varying thicknesses and aspect ratios is investigated under far‐ and near‐field excitation conditions. It is found that, for far‐field excitation, the strength of the plasmonic response of the nanodisk increases with its thickness, as expected from the increase in the number of conduction electrons in the system. However, for near‐field excitation, the plasmonic response becomes stronger as the thickness of the nanodisk is reduced. This behavior is attributed to the higher efficiency with which a near‐field source couples to the plasmons supported by thinner nanodisks. The results of this work advance the understanding of the plasmonic response of thin metallic nanostructures, thus increasing their potential for the development of novel applications.
Geminate and Nongeminate Pathways for Triplet Exciton Formation in Organic Solar Cells
Authors: Privitera Alberto , Grüne Jeannine , Karki Akchheta , Myers William K. , Dyakonov Vladimir , Nguyen Thuc‐Quyen , Riede Moritz K. , Friend Richard H. , Sperlich Andreas , Gillett Alexander J.
Published: March 2022

Organic solar cells (OSCs) have recently shown a rapid improvement in their performance, bringing power conversion efficiencies to above 18%. However, the open‐circuit voltage of OSCs remains low relative to their optical gap and this currently limits efficiency. Recombination to spin‐triplet excitons is a key contributing factor, and is widely, but not universally, observed in donor–acceptor blends using both fullerene and nonfullerenes as electron acceptors. Here, an experimental framework that combines time‐resolved optical and magnetic resonance spectroscopies to detect triplet excitons and identify their formation mechanisms, is reported. The methodology is applied to two well‐studied polymer:fullerene systems, PM6:PC60BM and PTB7‐Th:PC60BM. In contrast to the more efficient nonfullerene acceptor systems that show only triplet states formed via nongeminate recombination, the fullerene systems also show significant triplet formation via geminate processes. This requires that geminate electron–hole pairs be trapped long enough to allow intersystem crossing. It is proposed that this is a general feature of fullerene acceptor systems, where isolated fullerenes are known to intercalate within the alkyl sidechains of the donor polymers. Thus, the study demonstrates that engineering good donor and acceptor domain purity is key for suppressing losses via triplet excitons in OSCs.
Electrochemically Driven Interfacial Transformation For High‐Performing Solar‐To‐Fuel Electrocatalytic Conversion
Authors: Wulan Bari , Zhao Lanling , Tan Dongxing , Cao Xueying , Ma Jizhen , Zhang Jintao
Published: March 2022

The carbon dioxide reduction reaction (CO2RR) suffers from poor selectivity with low Faradaic efficiency and limited current density due to the lack of advanced electrocatalysts. Herein, it is demonstrated that the electrochemically driven interfacial transformation of bismuth sulfide (Bi2S3) nanorods enables the in situ formation of a 3D bismuth nanosheet network (BiNN) on functionalized carbon fibers (BiNN‐CFs). Notably, the formation of an ideal heterojunction with self‐driven charge migration facilitates the composition conversion with rapid reduction of Bi2S3 nanorods in seconds. The functionalization of CFs via Joule heating of the polytetrafluoroethylene coating induces an interfacial interaction for the simultaneous morphology evolution into the hierarchical BiNN via the recrystallization process. More importantly, the hierarchical BiNN‐CFs display improved performance for the CO2RR, including reasonable selectivity for formate generation (≈92%) in the broad potential range, a large partial current density of 419 mA cm–2, and good long‐term stability. Theoretical understanding elucidates that the lattice distortion tunes the p‐band center for optimizing the intermediate adsorption, and thus improving the electrocatalytic activity. Of particular note, the solar‐driven CO2–H2O full cell also demonstrates a promising energy conversion efficiency of 13.3%. These advances demonstrate the large space to optimize electrocatalysis that stems from the rational regulation of interfacial structure and properties.
“One Stone Two Birds” Design for Dual‐Functional TiO2‐TiN Heterostructures Enabled Dendrite‐Free and Kinetics‐Enhanced Lithium–Sulfur Batteries
Authors: Xue Pan , Zhu Kaiping , Gong Wenbin , Pu Jun , Li Xiyao , Guo Can , Wu Liyun , Wang Ran , Li Hongpeng , Sun Jingyu , Hong Guo , Zhang Qiang , Yao Yagang
Published: March 2022

Lithium–sulfur batteries (LSBs) are regarded as promising next‐generation energy storage systems owing to their remarkable theoretical energy density (2600 Wh kg‐1) and low cost. However, sluggish electrochemical kinetics, lithium polysulfides (LiPS) shuttling, and uncontrollable Li dendrite growth seriously hamper the commercial application of LSBs. Herein, dual‐functional 3D interconnected free‐standing fibers embedded with TiO2‐TiN heterostructures as an advanced skeleton are designed for concurrently regulating both the sulfur cathode (S/hollow TiO2‐TiN) and Li anode (Li/solid TiO2‐TiN). As a cathode skeleton, the hollow TiO2‐TiN fibers afford synergistic functions of chemical anchoring, physical confinement, and excellent electrocatalysis for LiPS. Meanwhile, the multifunctional skeleton with remarkable lithiophilicity and high conductivity can accomplish uniform Li deposition and homogeneous Li ion flux for inhibiting the growth of dendrites. Benefiting from these advantages, the full battery (S/hollow TiO2‐TiN || Li/solid TiO2‐TiN) exhibits excellent electrochemical performance, including high cycling stability (988.8 mAh g−1 after 200 cycles at 0.5 C) and impressive rate properties (639.3 mAh g−1 at 2 C). This work inaugurates a novel strategy from experimental and theoretical aspects for fabricating LSBs with robust electrochemical performance.
Cu2O−CD nanosuperstructures as a Biomimetic Catalyst for Oxidation of Benzylic sp3 C−H bonds and Secondary Amines using Molecular Oxygen: First Total Synthesis of proposed Swerilactone O
Authors: Pawar Shweta A. , Poojari Sandhya V. , Vijay Kumar A.
Published: March 2022

Cu2O−cyclodextrin (Cu2O−CD) nanosuperstructures catalyzed oxidation of benzylic sp3 C−H bonds and secondary amines via C−H bond activation is demonstrated in this protocol. Cu2O−CD nanosuperstructures displayed excellent catalytic activity for the oxidative transformation of substrates in combination with a radical promoter N‐hydroxyphthalimide (NHPI) and molecular oxygen as the green oxidant to afford the corresponding oxidized products with high selectivity and excellent yields. Moreover, the nanosuperstructures were found to be stable during the reaction, easy to recover, and recyclable up to three cycles to afford the products consistently with no loss of catalytic activity. The remarkable feature of this protocol is that the catalyst Cu2O−CD remained intact even after three cycles without undergoing over‐oxidation or any phase changes. The phase purity of Cu2O was ascertained by various characterization techniques such as X‐ray diffraction (XRD), Scanning electron microscopy (SEM), High‐resolution transmission electron microscopy (HRTEM), X‐ray photoelectron spectroscopy (XPS), Thermogravimetric analysis (TGA), and Inductively coupled plasma atomic emission spectroscopy (ICP‐AES) analysis. Furthermore, to gain more detailed insights into the reaction mechanism, oxygen labelled catalyst i. e., Cu218O−CD nanosuperstructures were synthesized using H218O (18‐labelled water) to determine any possible dioxygen exchange mechanism operative by Cu218O oxide thereby ascribing the source of oxygen in the reaction. Several other control experiments such as Electron Spin Resonance (ESR) and radical quenching studies established the mechanism to traverse a radical pathway. Additionally, the developed Cu2O−CD catalyst was also showcased to efficiently mimic the activity of the enzyme (S)‐tetrahydroprotoberberine oxidase (STOX) for the biomimetic synthetic transformation of tetrahydropalmatine to palmatine hydroxide. Interestingly, the developed Cu2O−CD mediated benzylic oxidation was used as a key step for the first total synthesis of the natural product Swerilactone O, an unusual secoiridoid with unprecedented C13 skeleton wherein aldol condensation reaction followed by oxidation afforded the natural product in 69% yield for overall steps. The utility of benign, supramolecular, and recyclable catalyst Cu2O−CD for oxidative transformations under aerobic conditions endorses the sustainability of the developed protocol.
A comparison of rectal and oral cultivable microbiota in wild and captive black lion tamarins (Leontopithecus chrysopygus, Mikan 1823)
Authors: Fatoretto Bruna T. , Gonzalez Irys H. L. , Lima Caio F. d. M. , Monticelli Cauê , Ramos Patrícia L.
Published: March 2022

The black lion tamarin (Leontopithecus chrysopygus) is an endangered primate species, restricted to the Atlantic Forest fragments of São Paulo state, Brazil, with an estimated wild population of ~1600 individuals. Integrative studies between zoo (ex situ) and wild (in situ) animals are crucial to modern conservation programs. They can demonstrate a substantial impact with the One Health concept, an interdisciplinary research frontier regarding the relations between human, animal, and environmental health. Studies of wild populations ofLeontopithecusspp. are scarce and should be encouraged to provide baseline information to develop preventive and curative medicine in zoos and other conservation programs. Studying these animals in the wild can offer important reference parameters for the species. Comparing bacterial communities between in situ and ex situ populations can help us understand both conditions and the dynamics of potentially pathogenic microorganisms. To increase our understanding of resident microorganisms among these groups, we collected oral and rectal samples from captive (zoo) and wild black lion tamarins. We employed a culture method for the identification of aerobic bacteria. Thirty‐three specimens were sampled (24 zoo and 8 wild animals) and 18 bacterial genera were identified. We found primarily Gram‐positive bacteria in wild animals, whereas in zoo animals, Gram‐negative bacteria were dominant. Some of the bacterial species we identified are potentially pathogenic, whereas several others are being reported here for the first time in this host species. Our results reinforce the importance of integrative studies for the future management and conservation of this endangered primate species.
Ultrafast Electrothermal Flow‐Enhanced Magneto Biosensor for Highly Sensitive Protein Detection in Whole Blood
Authors: Li Jiran , Lillehoj Peter B.
Published: March 2022

Current diagnostic tests for sensitive protein detection rely on immunological techniques, such as ELISA, which require sample purification, multiple washing steps and lengthy incubation, hindering their use for rapid testing. Here, we report a simple electrothermal flow‐enhanced biosensor for ultrafast, high sensitivity measurements of protein biomarkers in whole blood. Magnetic nanobeads dually‐labeled with a detection antibody and enzyme reporter are used to form immunocomplexes with the target protein, which are readily transported to the sensor via magnetic concentration. The incorporation of electrothermal flows enhances immunocomplex formation, allowing for rapid and sensitive detection without requiring blood purification or lengthy incubation. Proof of concept was carried out using Plasmodium falciparum histidine‐rich protein 2 (PfHRP2), a malaria parasite biomarker, which could be detected at concentrations as low as 5.7 pg mL−1 (95 fM) in whole blood in 7 min. The speed, sensitivity and simplicity of this device make it attractive for rapid diagnostic testing.
Enantioselective Synthesis of Planar‐Chiral Macrocycles through Asymmetric Electrophilic Aromatic Amination
Authors: Wang Donglei , Shao Ying‐Bo , Chen Yunrong , Xue Xiao‐Song , Yang Xiaoyu
Published: March 2022

An efficient approach for asymmetric synthesis of planar‐chiral macrocycles (paracyclophanes) has been disclosed through enantioselective electrophilic aromatic aminations with azodicarboxylates enabled by chiral phosphoric acid catalysis. A wide range of chiral macrocycles bearing varied ring sizes (16 to 23‐membered) and functional group‐containingansachains were readily afforded using this method, with excellent yields and high enantioselectivities (23 examples, up to 99.5 : 0.5 er). Experimental studies and DFT calculations were performed to elucidate the mechanism and origin of stereoselectivities of these reactions. Preliminary utilization of the planar‐chiral macrocycle as chiral organocatalyst showcased the potential applications of these novel chiral skeletons.
A Bis‐(carbone) Pincer Ligand and Its Coordinative Behavior toward Multi‐Metallic Configurations
Authors: Aweke Bamlaku Semagne , Yu Cheng‐Han , Zhi Minna , Chen Wen‐Ching , Yap Glenn P. A. , Zhao Lili , Ong Tiow‐Gan
Published: March 2022

Carbones are divalent carbon(0) species that contain two lone pairs of electrons. Herein, we have prepared the first known stable and isolable free bis‐(carbone) pincer framework with a well‐defined solid‐state structure. This bis‐(carbone) ligand is an effective scaffold for forming monometallic (Ni and Pd) and trinuclear heterometallic complexes with Au−Pd−Au, Au−Ni−Au, and Cu−Ni−Cu configurations. Sophisticated quantum‐theoretical analyses found that the metal–metal interactions are too weak to play a significant role in upholding these multi‐metallic configurations; rather, the four lone pairs of electrons within the bis‐(carbone) framework are the main contributors to the stability of the complexes.
Synthesis of Cyclic Allylborates from 1,3‐Dienes and a Diboron Reagent
Authors: Sakuragi Seiya , Akiba Tomofumi , Tanahashi Takumi , Fujihara Tetsuaki
Published: March 2022

The synthesis of cyclic allylborates was achieved by the reaction of 1,3‐dienes and B2pin2 using a copper catalyst. Several 1,3‐dienes were converted to the corresponding cyclic allylborates in moderate to high yields. The cyclic allylborate obtained could be used in several organic transformations such as allylation of electrophiles and Suzuki–Miyaura coupling.
Counterion‐Paired Bright Heptamethine Fluorophores with NIR‐II Excitation and Emission Enable Multiplexed Biomedical Imaging
Authors: Yang Yang , Sun Caixia , Wang Shangfeng , Yan Kui , Zhao Mengyao , Wu Bin , Zhang Fan
Published: March 2022

Photon excitation and emission at the NIR‐II spectral window enable high‐contrast deep‐tissue bioimaging. However, multiplexed imaging with NIR‐II excitation and emission has been hampered by the limited chemical strategies to develop bright fluorophores with tunable absorption in this spectral regime. Herein, we developed a series of heptamethine cyanines (HCs) with varied absorption/emission maxima spanning from 1100 to 1600 nm through a physical organic approach. A bulky counterion paired to HCs was found to elicit substantial improvements in absorptivity (7‐fold), brightness (14‐fold), and spectral profiles in water, addressing a notorious quenching problem of NIR‐II cyanines due to aggregation and polarization. We demonstrated the utilities of HC1222 and HC1342 for high‐contrast dual‐color imaging of circulatory system, lymphatic structures, tumor, and organ function in living mice under 1120 nm and 1319 nm excitation, showing HCs as a promising platform for non‐invasive bioimaging.
Light‐Triggered High‐Affinity Binding of Tetramethylammonium over Potassium Ions by [18]crown‐6 in a Tetrahedral Anion Cage
Authors: Wang Yue , Li Boyang , Zhu Jiajia , Zhang Wenyao , Zheng Bo , Zhao Wei , Tang Juan , Yang Xiao‐Juan , Wu Biao
Published: March 2022

An azobenzene‐functionalized bis‐bis(urea) ligand (Lazo) and phosphate anion assemble to give the first photoactive “aniono” constructs, tetrahedron (A4L6) and helicate (A2L3), which readily undergo interconversion through cis‐trans isomerization of the azo group under irradiation/heating. Most strikingly, the tetrahedral cage can accommodate an [18]crown‐6 molecule, which can capture two tetramethylammonium (TMA+) ions with an unusually high affinity, even capable of replacing K+ in [K([18]crown‐6)]+ to form a {(TMA)2
([18]crown‐6)}
cage “Russian doll” structure. Thus, the current work may provide a model for the light‐driven binding and exchange of the biologically important K+ and TMA+ ions.
Triazoloquinazoline derived classical DNA intercalators: Design, synthesis, in silico ADME profile, docking, and antiproliferative evaluations
Authors: El‐Adl Khaled , Ibrahim Mohamed‐Kamal , Alesawy Mohamed S. , Eissa Ibrahim H.
Published: March 2022

Thirteen novel [1,2,4]triazolo[4,3‐c]quinazoline derivatives as DNA intercalators were synthesized and their anticancer activities evaluated against HepG2 and HCT‐116 cells. A docking study was carried out to explore how the new derivatives bind to active sites of DNA. The docking data were highly interrelated with that of biological testing. The HCT‐116 cell line was the most sensitive one to the effect of the new derivatives. Compound 7c exhibited the highest anticancer activities against both the HepG2 and HCT116 cancer cell lines. Despite this compound displaying less activity than doxorubicin, it could be useful as a template for future manipulation, optimization, and investigation to produce other analogs with potential activity. The most active derivatives, 7c, 7b, and 7a were evaluated as DNA binders. Compound 7c displayed the highest binding affinity. Furthermore, the absorption, distribution, metabolism, excretion, and toxicity (ADMET) profile was calculated for the four most active compounds in comparison to doxorubicin as reference drug. Our derivatives 7a, 7b, and 7c displayed a very good calculated ADMET profile in comparison to doxorubicin.
Androgen‐targeting therapeutics mitigate the adverse effect of GnRH agonist on the risk of neurodegenerative disease in men treated for prostate cancer
Authors: Branigan Gregory L. , Torrandell‐Haro Georgina , Soto Maira , Gelmann Edward P. , Vitali Francesca , Rodgers Kathleen E. , Brinton Roberta Diaz
Published: March 2022

Background

Prostate cancer and multiple neurodegenerative diseases (NDD) share an age‐associated pattern of onset. Therapy of prostate cancer is known to impact cognitive function. The objective of this study was to determine the impact of multiple classes of androgen‐targeting therapeutics (ATT) on the risk of NDD.

Methods

A retrospective cohort study of men aged 45 and older with prostate within the US‐based Mariner claims data set between January 1 and 27, 2021. A propensity score approach was used to minimize measured and unmeasured selection bias. Disease risk was determined using Kaplan–Meier survival analyses.

Results

Of the 1,798,648 men with prostate cancer, 209,722 met inclusion criteria. Mean (SD) follow‐up was 6.4 (1.8) years. In the propensity score‐matched population, exposure to ATT was associated with a minimal increase in NDD incidence (relative risk [RR], 1.07; 95% CI, 1.05–1.10; p < 0.001). However, GnRH agonists alone were associated with significantly increased NDD risk (RR, 1.47; 95% CI, 1.30–1.66; p <0.001). Abiraterone, commonly administered with GnRH agonists and low‐dose prednisone, was associated with a significantly decreased risk (RR, 0.77; 95% CI, 0.68–0.87; p < 0.001) of any NDD.

Conclusions

Among patients with prostate cancer, GnRH agonist exposure was associated with an increased NDD risk. Abiraterone acetate reduced the risks of Alzheimer's disease and Parkinson's disease conferred by GnRH agonists, whereas the risk for ALS was reduced by androgen receptor inhibitors. Outcomes of these analyses contribute to addressing controversies in the field and indicate that GnRH agonism may be a predictable instigator of risk for NDD with opportunities for risk mitigation in combination with another ATT.
Blood donation motivation in the United States and Russia: What keeps donors coming back?
Authors: Sheldon Kennon M. , Osin Evgeny , Lapka Samantha , Rasskazova Elena , Titova Liudmila , Khrushev Sergei , Vybornykh Dmitry , Gaponova Tatiana
Published: March 2022

What keeps regular blood donors coming back, despite the inconvenience and discomfort, thereby maintaining the community's blood supply? We approached 494 people waiting to give blood, 229 Americans and 265 Russians, with a survey that assessed their motivations to donate, their contextual emotions, and their future donation intentions. The Russian sample was older, and many were regulars at the donation centre. The U.S. sample was younger, attending a 3‐day college blood drive. Multigroup path analysis results showed that, as hypothesised, in both samples, autonomous donation motivations predicted contextual emotions and future donation intentions. Furthermore, contextual emotions partially mediated the motivation‐to‐future intentions effect. Small differences in results for the two samples, as well as differences in the two national systems for maintaining blood supplies, are discussed.
Hexavalent chromium induces centrosome amplification through ROS‐ATF6‐PLK4 pathway in colon cancer cells
Authors: Bian Xue K. , Guo Jia L. , Xu Si X. , Han Ya W. , Lee Shao C. , Zhao Ji Z.
Published: March 2022

Centrosome amplification (CA) refers to a numerical increase in centrosomes resulting in cells with more than two centrosomes. CA has been shown to initiate tumorigenesis and increase the invasive potential of cancer cells in genetically modified experimental models. Hexavalent chromium is a recognized carcinogen that causes CA and tumorigenesis as well as promotes cancer metastasis. Thus, CA appears to be a biological link between chromium and cancer. In the present study, we investigated how chromium triggers CA. Our results showed that a subtoxic concentration of chromium‐induced CA in HCT116 colon cancer cells, resulted in the production of reactive oxygen species (ROS), activated ATF6 without causing endoplasmic reticulum stress, and upregulated the protein level of PLK4. Inhibition of ROS production, ATF6 activation, or PLK4 upregulation attenuated CA. Inhibition of ROS using N‐acetyl‐l‐cysteine (NAC) inhibited chromium‐induced activation of ATF6 and upregulation of PLK4. ATF6‐specific siRNA knocked down the protein level and activation of ATF6, and upregulated PLK4, with no effect on ROS production. Knockdown of PLK4 protein had no effect on chromium‐induced ROS production or activation of ATF6. In conclusion, our results suggest that hexavalent chromium induces CA via the ROS‐ATF6‐PLK4 pathway and provides molecular targets for inhibiting chromium‐mediated CA, which may be useful for the assessment of CA in chromium‐promoted tumorigenesis and cancer cell metastasis.
KLF11 promotes the progression of glioma via regulating Holliday junction recognition protein
Authors: Li Jian , Wang Chunhong , Cheng Rui , Su Haiyang , Wang Lijun , Ji Lei , Ji Hongming
Published: March 2022

Understanding the molecular mechanism of glioma is very important for the diagnosis and treatment of glioma. Recently, a new study illustrated that KLF11 could be a potential prognostic and diagnostic biomarker in glioma, but the critical role is not illustrated. In this study, we found that KLF11 was highly expressed in glioma cancer tissues and cells, and KLF11 high expression of glioblastoma (GBM) and lower‐grade glioma (LGG) were correlated with poorer overall survival and disease‐free survival percentages. KLF11 knockdown inhibited glioma cell proliferation and migration, while KLF11 overexpression enhanced cell proliferation and migration. In vivo, knockdown of KLF11 reduced the tumor size of glioma. With regard to the molecular regulatory mechanism, we clarified that the Holliday junction recognition protein (HJURP) was positively regulated by KLF11. Meanwhile, we demonstrated that HJURP knockdown also inhibited glioma carcinoma progression. Overexpression of HJURP rescued the suppressed proliferation and migration function of glioma cells with depletion of KLF11. Therefore, our study demonstrated the function of KLF11 in glioma and showed KLF11 and HJURP could be prognostic and diagnostic markers in glioma, which provides a new insight of glioma therapy.
Apaf‐1 interacting protein, a new target of microRNA‐146a‐3p, promotes prostate cancer cell development via the ERK1/2 pathway
Authors: Wang Nan , Li Rou , Jia Huizhen , Xie Hui , Liu Chi , Jiang Shan , Zhang Ke , Lin Ping , Yu Xiaoguang
Published: March 2022

The Apaf‐1 interacting protein (APIP), a ubiquitously expressed antiapoptotic molecule, is aberrantly expressed and of great significance in various cancers. However, little is known regarding the potential value and underlying mechanisms of APIP in prostate cancer. Here, we demonstrated that APIP expression is significantly upregulated in prostate cancer cell lines. APIP overexpression promoted tumor cell proliferation and migration and induced extracellular regulated protein kinases 1/2 (ERK1/2) activation. Pharmacological inhibition of ERK1/2 signaling reversed APIP‐induced increase in cell proliferation and migration induced by APIP overexpression. Expression of APIP was hampered by miR‐146a‐3p. A dual luciferase reporter gene assay identified the regulatory relationship between APIP and miR‐146a‐3p in prostate cancer, suggesting that APIP is a direct target of miR‐146a‐3p. miR‐146a‐3p reduced cell proliferation and migration in prostate cancer. Furthermore, miR‐146a‐3p inhibited ERK1/2 activation. Application of an ERK1/2 inhibitor reversed the increase in cell proliferation and migration induced by miR‐146a‐3p inhibition. In summary, this study focused on the role of APIP in regulating cell growth and migration and proposes a theoretical basis for APIP as a promising biomarker in prostate cancer development.
Rare case of umbilical urachal sinus mimicking infected umbilical abscess: A case report
Authors: Torabi Hossein , Shirini Kasra , Ghaffari Rona
Published: March 2022

Incomplete obliteration of urachus during the fetal period can lead to urachal abnormalities. One of these abnormalities is the urachal sinus that can be asymptomatic, or it can be symptomatic by becoming infected or being malignant, and it can mimic other diseases' symptoms. Although it is rare in adults, it should be considered a significant differential diagnosis in patients with abdominal pain or umbilical discharge. This article presents a young patient with urachal sinus mimicking umbilical pilonidal sinus symptoms.
First report of emerged pulmonary lophomoniasis in two Afghanian medical tourists
Authors: Sharifpour Ali , Zarrinfar Hossein , Fakhar Mahdi , Zakariaei Zakaria , Soleymani Mostafa , Banimostafavi Elham Sadat , Nakhaei Maryam
Published: March 2022

Lophomonas is a neglected and emerging protozoan that infects the lower and upper respiratory tracts of humans. Here, we present two cases of lophomoniasis from Afghanistan that include symptoms such as fever, cough, hemoptysis, and pleural effusion.
Mixing Characteristics for Scale‐up of an Orbital Shaken Bioreactor
Authors: Lee Hyunwoo , Lee Joon-Chul , Seo Youngjin
Published: March 2022

Two types of culture bags are typically used. Among the criteria for evaluating the bioreactor performance, mixing time and shear stress are important indicators. Experiments and numerical analyses are conducted to evaluate and predict the performance of an orbital shaken bioreactor by analyzing mixing time and shear stress. Reliability is ensured by performing numerical analysis under the same conditions using FLUENT. The error between the experimental and numerical analysis results is within the error range of the experiments. For two different working fluid volumes the mixing time and shear stress are predicted using validated numerical models.
Hollow Co‐Based Layered Double Hydroxide Decorated with Ag Nanoparticles for the Oxygen Evolution Reaction
Authors: Gan Xingyu , Guo Xinjie , Li Suozhu , Wang Yun , Wang Fengxiang , Lv Xiaoxia
Published: March 2022

Developing cost‐effective and efficient oxygen evolution reaction (OER) catalysts is very important for electrochemical water splitting devices. Herein, hollow Co‐based layered double hydroxide (LDH) decorated with Ag nanoparticles (Ag@H−Co‐−LDH) was constructed using ion etching of zeolitic imidazolate frameworks‐67 (ZIF‐67), followed by simple stirring with Ag salts. Hollow double layered structure could expose rich active centers and improve electron transfer and mass transport. Meanwhile, the introduction of Ag species greatly increases the electrical conductivity and enhances cobalt species to form highly catalytically active Co4+. Therefore, the as‐obtained Ag@H−Co−LDH exhibits a distinguished OER activity with a low overpotential of 298 mV to provide an oxygen evolution current density of 10 mA cm−2, which is superior to that of Co−LDH and even commercial RuO2.
Fully Bridged Triphenylamines Comprising Five‐ and Seven‐Membered Rings
Authors: Michalsky Ina , Gensch Viktoria , Walla Christian , Hoffmann Marvin , Rominger Frank , Oeser Thomas , Tegeder Petra , Dreuw Andreas , Kivala Milan
Published: March 2022

A family of fully bridged triphenylamines with embedded 5‐ and 7‐membered rings is presented. The compounds are potent electron donors capable to undergo donor/acceptor interactions with strong cyano‐based acceptors both in the solid state and solution. These interactions were evaluated by IR and UV/vis spectroscopy as well as X‐ray crystallography. The vinylene‐bridged compound was oxidized to the corresponding 1,2‐diketone which readily underwent acid‐catalyzed condensation with selected 1,2‐phenylenediamines. The resulting π‐extended quinoxaline derivatives represent valuable building blocks for the development of functional chromophores upon appropriate functionalization.
Diarylcuprates for Selective Syntheses of Multifunctionalized Ketones from Thioesters under Mild Conditions
Authors: Kato Daiki , Murase Tomoya , Talode Jalindar , Nagae Haruki , Tsurugi Hayato , Seki Masahiko , Mashima Kazushi
Published: March 2022

Ketones were selectively synthesized from thioesters by using diarylcuprates(I) generated in situ from copper(I) salts and aryl Grignard reagents in a 1 : 1.3–1.5 ratio under ambient temperature. During the ketone synthesis, various functional groups, such as carbonyl (ketones, esters, and amides), O‐protecting groups, halogens, and heteroarenes, were tolerated to afford multifunctionalized ketones in excellent yields. This copper‐mediated ketone synthesis could be applied to the synthesis of not only gluconolactone‐derived ketone 6, a synthetic intermediate in the transformation to the SGLT2 inhibitor canagliflozin, but also thiolactol 8, a valuable synthetic intermediate for (+)‐biotin. Control experiments on an isolated diphenylcuprate(I), [CuPh2]− (12), and DFT calculations revealed that this ketone synthesis proceeded by oxidative addition of the C−S bond of thioesters to [CuPh2]−, while reductive elimination from the CuIII intermediate produced the corresponding ketone and an inactive species [(RS)CuPh]−, the latter reacted with [CuPh]4 (11) to regenerate the reactive diphenylcuprate(I).
Fast selection of compiler optimizations using performance prediction with graph neural networks
Authors: do Rosario Vanderson Martins , da Silva Anderson Faustino , Zanella André Felipe , Napoli Otávio O. , Borin Edson
Published: March 2022

Tuning application performance on modern computing infrastructures involves choices in a vast design space as modern computing architectures can have several complex structures impacting performance. Moreover, different applications use these structures in different ways, leading to a challenging performance function. Consequently, it is hard for compilers or experts to find optimal compilation parameters for an application that maximizes such performance function. One approach to tackle this problem is to evaluate many possible optimization plans and select the best among them. However, executing an application to measure its performance for every plan can be very expensive. To tackle this problem, previous work has investigated the use of Machine Learning techniques to predict the performance of the applications without executing them quickly. In this work, we evaluate the use of graph neural networks (GNN) to make fast predictions without executing the application to guide the selection of good optimization sequences. We propose a GNN architecture to make such predictions. We train and test it using 30 thousand different compilation plans applied to 300 different applications, using ARM64 and LLVM IR code representations as input. Our results indicate that the control and data flow graph can then learn features from the control and data flow graph to outperform nongraph‐aware Machine Learning models. Our GNN architecture achieved 91% accuracy in our dataset compared to 79% when using a nongraph‐aware architecture–taking only 16ms to predict a given input. If the application been optimized took an average of 10 s to execute, and we evaluated 1000 optimization sequences, it would take almost 9 h to assess all pairs, but only 16 s with our GNN .
Ligand‐Induced Tuning of the Electronic Structure of Rhombus Tetraboron Cluster
Authors: Zhao Ya , Wang Tiantong , Wang Chong , Zhang Zhaoyan , Zheng Huijun , Jiang Shuai , Yan Wenhui , Xie Hua , Li Gang , Yang Jiayue , Wu Guorong , Zhang Weiqing , Dai Dongxu , Zheng Xiucheng , Fan Hongjun , Jiang Ling , Yang Xueming , Zhou Mingfei
Published: March 2022

A neutral boron carbonyl complex B4(CO)3 is generated in the gas phase and is characterized by infrared plus vacuum ultraviolet (IR+VUV) two‐color ionization spectroscopy and quantum chemical calculations. The complex is identified to have a planar C2v structure with three CO ligands terminally coordinated to a rhombus B4 core. It has a closed‐shell singlet ground state that correlates to an excited state of B4. Bonding analyses on B4(CO)3 as well as the previously reported B4 and B4(CO)2 indicate that the electronic structure of rhombus tetraboron cluster changes from a close‐shell singlet to an open‐shell singlet in B4(CO)2 and to a close‐shell singlet in B4(CO)3, demonstrating that the electronic structures of boron clusters can be effectively tuned via sequential CO ligand coordination.
Effect of Cyclosporin A and Impact of Dose Staggering on OATP1B1/1B3 Endogenous Substrates and Drug Probes for Assessing Clinical Drug Interactions
Authors: Mochizuki Tatsuki , Zamek‐Gliszczynski Maciej J. , Yoshida Kenta , Mao Jialin , Taskar Kunal , Hirabayashi Hideki , Chu Xiaoyan , Lai Yurong , Takashima Tadayuki , Rockich Kevin , Yamaura Yoshiyuki , Fujiwara Kaku , Mizuno Tadahaya , Maeda Kazuya , Furihata Kenichi , Sugiyama Yuichi , Kusuhara Hiroyuki
Published: March 2022

This study was designed to assess the quantitative performance of endogenous biomarkers for organic anion transporting polypeptide (OATP) 1B1/1B3‐mediated drug‐drug interactions (DDIs). Ten healthy volunteers orally received OATP1B1/1B3 probe cocktail (0.2 mg pitavastatin, 1 mg rosuvastatin, and 2 mg valsartan) and an oral dose of cyclosporin A (CysA, 20 mg and 75 mg) separated by a 1‐hour interval (20 mg (−1 hour), and 75 mg (−1 hour)). CysA 75 mg was also given with a 3‐hour interval (75 mg (−3 hours)) to examine the persistence of OATP1B1/1B3 inhibition. The area under the plasma concentration‐time curve ratios (AUCRs) were 1.63, 3.46, and 2.38 (pitavastatin), 1.39, 2.16, and 1.81 (rosuvastatin), and 1.42, 1.77, and 1.85 (valsartan), at 20 mg, 75 mg (−1 hour) and 75 mg (−3 hours) of CysA, respectively. CysA effect on OATP1B1/1B3 was unlikely to persist at the dose examined. Among 26 putative OATP1B1/1B3 biomarkers evaluated, AUCR and maximum concentration ratio (CmaxR) of CP‐I showed the highest Pearson’s correlation coefficient with CysA AUC (0.94 and 0.93, respectively). Correlation between AUCR of pitavastatin, and CmaxR or AUCR of CP‐I were consistent between this study and our previous study using rifampicin as an OATP1B1/1B3 inhibitor. Nonlinear regression analysis of AUCR−1 of pitavastatin and CP‐I against CysA Cmax yielded Ki,OATP1B1/1B3,app (109 ± 35 and 176 ± 42 nM, respectively), similar to the Ki,OATP1B1/1B3 estimated by our physiologically‐based pharmacokinetic model analysis described previously (107 nM). The endogenous OATP1B1/1B3 biomarkers, particularly CmaxR and AUCR of CP‐I, corroborates OATP1B1/1B3 inhibition and yields valuable information that improve accurate DDI predictions in drug development, and enhance our understanding of interindividual variability in the magnitude of DDIs.