bluuebunny/crossref_metadata_2025_split huggingface dataset:
Two‐Dimensional MXene‐Polymer Heterostructure with Ordered In‐Plane Mesochannels for High‐Performance Capacitive Deionization
Authors: Li Qian , Xu Xingtao , Guo Jingru , Hill Jonathan P. , Xu Haishan , Xiang Luoxing , Li Chen , Yamauchi Yusuke , Mai Yiyong 
Published: November 2021

AbstractThe application of traditional electrode materials for high‐performance capacitive deionization (CDI) has been persistently limited by their low charge‐storage capacities, excessive co‐ion expulsion and slow salt removal rates. Here we report a bottom‐up approach to the preparation of a two‐dimensional (2D) Ti3C2Tx MXene‐polydopamine heterostructure having ordered in‐plane mesochannels (denoted as mPDA/MXene). Interfacial self‐assembly of mesoporous polydopamine (mPDA) monolayers on MXene nanosheets leads to the mPDA/MXene heterostructure, which exhibits several unique features: (1) MXene undergoes reversible ion intercalation/deintercalation and possesses high conductivity; (2) mPDA layers establish redox capacitive characteristics and Na+ selectivity, and also help to prevent self‐stacking and oxidation of MXene; (3) in‐plane mesochannels enable the smooth transport of ions at the internal spaces of this stacked 2D material. When applied as an electrode material for CDI, mPDA/MXene nanosheets exhibit top‐level CDI performance and cycling stability compared to those of the so far reported 2D materials. Our study opens an avenue for the rational construction of MXene‐organic hybrid heterostructures, and further motivates the development of high‐performance CDI electrode materials.
Klinische Entwicklung von Metallkomplexen als Photosensibilisatoren für die photodynamische Therapie von Krebs
Authors: Karges Johannes 
Published: November 2021

AbstractKrebs hat sich in den letzten Jahrzehnten zu einer der häufigsten krankheitsbedingten Todesursachen der Welt entwickelt. Neben den am häufigsten angewendeten Techniken (Chirurgie, Immuntherapie, Strahlentherapie oder Chemotherapie) wird der photodynamischen Therapie zunehmend Aufmerksamkeit gewidmet. Die überwiegende Mehrheit der klinisch eingesetzten Photosensibilisatoren ist jedoch nicht ideal und weist mehrere Einschränkungen auf, darunter schlechte Wasserlöslichkeit, schlechte Photostabilität und langsame Ausscheidung aus dem Körper, was zu Photosensibilität führt. In dem Bemühen, diese Nachteile zu überwinden, wird der Einbindung eines Metallions viel Aufmerksamkeit gewidmet. In diesem Kurzaufsatz wird die klinische Entwicklung von metallhaltigen Verbindungen wie Purlytin®, Lutrin®/Antrin®, Photosens®, TOOKAD® soluble oder TLD‐1433 kritisch diskutiert.
Ein unsymmetrisches, cyclisches Diboren basierend auf einem chelatisierenden CAAC‐Liganden sowie dessen Aktivierung kleiner Moleküle und Umlagerungsreaktionen
Authors: Lu Wei , Jayaraman Arumugam , Fantuzzi Felipe , Dewhurst Rian D. , Härterich Marcel , Dietz Maximilian , Hagspiel Stephan , Krummenacher Ivo , Hammond Kai , Cui Jingjing , Braunschweig Holger 
Published: November 2021

AbstractEine Eintopfsynthese eines CAAC‐stabilisierten, unsymmetrischen, cyclischen Diborens wurde mittels Zweielektronenreduktion eines CAAC‐Addukts von B2Br4(SMe2)2 entwickelt. Theoretische Studien offenbarten, dass dieses Diboren einen signifikant geringeren HOMO‐LUMO‐Abstand als bisher beschriebene NHC‐ und Phosphan‐stabilisierte Diborene besitzt. Die Komplexierung des Diborens mit [AuCl(PCy3)] lieferte zwei Diboren‐AuI‐π‐Komplexe, während die Reaktion mit DurBH2, P4 und einem terminalen Alkin zur Spaltung der B‐H‐, P‐P‐ beziehungsweise C‐C‐π‐Bindung führte. Die thermische Umlagerung des Diborens ergab ein elektronenreiches cyclisches Alkylidenboran, welches über die B=C‐Doppelbindung direkt an AgI koordiniert werden konnte.
Photocatalytic Sulfonylcarbocyclization of Alkynes Using SEt as a Traceless Directing Group: Access to Cyclopentenes and Indenes
Authors: Zhou Yulu , Qin Yizhou , Wang Qinggui , Zhang Zuxiao , Zhu Gangguo 
Published: November 2021

AbstractCyclopentenes and indenes are important structural scaffolds in synthetic, medical, and material chemistry. Cyclization of alkynes via remote C−H functionalization is an appealing approach to construct these motifs due to its high efficiency and step‐economy. Herein, a traceless directing group strategy was designed to reverse the regioselectivity of radical addition which enabled an unprecedented photocatalytic sulfonylcarbocyclization of terminal alkynes by forming C−C bond on inert C(sp3)−H bond. It offers a facile access to decorated cyclopentenes and indenes under mild conditions. The resultant products could be converted into a set of valuable molecular scaffolds, including a key intermediate of AM‐6226. Mechanistic experiments suggest a radical cascade pathway comprising a Markovnikov‐type sulfonylation, 1,5‐hydrogen atom transfer, 5‐endo‐trig cyclization, and β‐elimination. This study lays further groundwork for the use of anti‐Baldwin 5‐endo‐trig radical cyclization in rapidly assembling five‐membered carbocycles.
Cooperative Luminescence and Cooperative Sensitisation Upconversion of Lanthanide Complexes in Solution
Authors: Knighton Richard C. , Soro Lohona K. , Francés‐Soriano Laura , Rodríguez‐Rodríguez Aurora , Pilet Guillaume , Lenertz Marc , Platas‐Iglesias Carlos , Hildebrandt Niko , Charbonnière Loïc J. 
Published: November 2021

AbstractUpconversion materials have led to various breakthrough applications in solar energy conversion, imaging, and biomedicine. One key impediment is the facilitation of such processes at the molecular scale in solution where quenching effects are much more pronounced. In this work, molecular solution‐state cooperative luminescence (CL) upconversion arising from a Yb excited state is explored and the mechanistic origin behind cooperative sensitisation (CS) upconversion in Yb/Tb systems is investigated. Counterintuitively, the best UC performances were obtained for Yb/Tb ratios close to parity, resulting in the brightest molecular upconversion complexes with a quantum yield of 2.8×10−6 at a low laser power density of 2.86 W cm−2.
Dynamic Manipulating Space‐Resolved Persistent Luminescence in Core–Shell MOFs Heterostructures via Reversible Photochromism
Authors: Ma Yu‐Juan , Fang Xiaoyu , Xiao Guowei , Yan Dongpeng 
Published: November 2021

AbstractPhoto‐controllable persistent luminescence at the single crystal level can be achieved by the integration of long‐lived room temperature phosphorescence (RTP) and photochromism within metal–organic frameworks (MOFs) for the first time. Moreover, the multiblock core–shell heterojunctions have been prepared utilizing the isostructural MOFs through an epitaxial growth process, in which the shell exhibits bright yellow afterglow emission that gradually disappears upon further irradiation, but the core does not show such property. Benefitting from combined persistent luminescence and photochromic behavior, a multiple encryption demo can be facilely designed based on the dynamic manipulating RTP via reversible photochromism. This work not only develops new types of dynamically photo‐controllable afterglow switch, but also provides a method to obtain MOFs‐based optical heterojunctions towards potential space/time‐resolved information encryption and anti‐counterfeiting applications.
Hyperbranched poly(ester ether)s as an amplified fluorescence sensor for selective and sensitive Fe3+ detection and bioimaging
Authors: Liang Xue , Li Xiaojie , Tang Yong , Hong Liu , Wei Wei , Liu Xiaoya 
Published: November 2021

AbstractChromophore‐free fluorescent hyperbranched polymers have attracted widespread attention as fluorescent sensors. However, achieving highly selective and sensitive detection with such sensors remains a major challenge. Herein, two kinds of hyperbranched poly(ester ether) fluorescent sensors (HBPEE1 and HBPEE2) without conventional chromophores were synthesized to provide a simple and effective method for the selective and sensitive detection of Fe3+. Benefiting from the branched structure and the aggregation of numerous oxygen‐rich groups, both hyperbranched poly(ester ether)s emitted strong blue fluorescence in solution, and compared with HBPEE2, HBPEE1 had a higher absolute quantum yield of 14.3% due to its larger molecular weight and denser structure. HBPEE1 exhibited an amplified fluorescence quenching response and superior selectivity and sensitivity in the recognition of Fe3+ among various metal ions. The fluorescence intensity of HBPEE1 at 450 nm showed a good linearity with the Fe3+ concentration in the range of 5–450 μM with the detection limit of 0.04 μM. Multiple Fe3+ detections with high reversibility have been achieved using EDTA‐2Na, which further confirmed the detection mechanism. In addition, the HBPEE1 sensor possessed low toxicity and can be employed for Fe3+ imaging in living cells, making it a potential candidate for biological research and clinical diagnosis.
PA6/PA66/talc composite: Effect of reprocessing on the structure and properties
Authors: Domingo Gustavo D. , Souza Adriana M. C. 
Published: November 2021

AbstractIn this study the effect of repeated injection molding cycles on the structure and properties of polyamide 6/polyamide 66/talc (PA6/PA66/talc ‐ 35/35/30) composite was investigated for samples subjected to one, four, and seven processing cycles. Their morphology (scanning electron microscopy), structure (Fourier transform infrared spectroscopy), melt viscosity (melt flow index [MFI]), mechanical (tensile, flexural, impact, and fatigue tests), and thermal properties (differential scanning calorimetry and thermogravimetric analysis tests) were analyzed. The increase in MFI value and the decrease in the maximum decomposition temperature of PA6, observed by TG analysis, for samples subjected to seven processing cycles, indicated a possible reduction in molar mass of the PA6/PA66 matrix. These samples presented a decrease in degree of crystallinity of PA6 and PA66, which was more pronounced for PA6. The reprocessing of the composite did not present changes in the mechanical properties up to the fourth processing cycle, except for fatigue life which presented a 59% reduction. Samples subjected to seven processing cycles presented a decrease in tensile and flexural strength as well as in tensile and flexural modulus. Charpy impact strength of the samples did not significantly change upon reprocessing. The micrographs of the fatigue fractured surfaces indicated that the weak talc‐matrix interaction and talc‐matrix debonding became more evident with increasing processing cycles.
Breaking the Code: Political Control and the Humanities in 1960 s Bulgaria
Authors: Nikolchina Miglena 
Published: November 2021

AbstractCertain tendencies in Bulgarian academia in the 1960s are explored as constituting a decisive moment in the emancipation of scientific authority from the intrusion of communist political power. With the focus on aesthetics, the major tenet is that, in the face of repression, specific theoretical approaches and currents of thought emerged that proved effective in dismantling dogma and boosting scientific authority vis‐à‐vis ideological control. Although open clashes with the repressive machinery of the communist regime certainly played a role in advancing the autonomy of science while on the other hand networks existed that allowed the clashes to be resolved in favor of science, emphasis here is on the deliberate shaping of an academic ethos and the implementation of modes of thinking, theoretical tools, and stances that were resilient to control and demonstrated their superiority to dogma. In 1960s aesthetics, this process involved battles surrounding the dogmatic conceptualization of reflection by Stalinist philosopher Todor Pavlov. A theorization of art as the production of freedom emerged in the course of these battles—a theorization which might, in fact, be crucial for this production and therefore a necessary condition for an otherwise fragile potentiality.
Imaging flow cytometry data analysis using convolutional neural network for quantitative investigation of phagocytosis
Authors: Mochalova Elizaveta N. , Kotov Ivan A. , Lifanov Dmitry A. , Chakraborti Soumyananda , Nikitin Maxim P. 
Published: November 2021

AbstractMacrophages play an important role in the adaptive immune system. Their ability to neutralize cellular targets through Fc receptor‐mediated phagocytosis has relied upon immunotherapy that has become of particular interest for the treatment of cancer and autoimmune diseases. A detailed investigation of phagocytosis is the key to the improvement of the therapeutic efficiency of existing medications and the creation of new ones. A promising method for studying the process is imaging flow cytometry (IFC) that acquires thousands of cell images per second in up to 12 optical channels and allows multiparametric fluorescent and morphological analysis of samples in the flow. However, conventional IFC data analysis approaches are based on a highly subjective manual choice of masks and other processing parameters that can lead to the loss of valuable information embedded in the original image. Here, we show the application of a Faster region‐based convolutional neural network (CNN) for accurate quantitative analysis of phagocytosis using imaging flow cytometry data. Phagocytosis of erythrocytes by peritoneal macrophages was chosen as a model system. CNN performed automatic high‐throughput processing of datasets and demonstrated impressive results in the identification and classification of macrophages and erythrocytes, despite the variety of shapes, sizes, intensities, and textures of cells in images. The developed procedure allows determining the number of phagocytosed cells, disregarding cases with a low probability of correct classification. We believe that CNN‐based approaches will enable powerful in‐depth investigation of a wide range of biological processes and will reveal the intricate nature of heterogeneous objects in images, leading to completely new capabilities in diagnostics and therapy.
Recent advances in ensemble density functional theory and linear response theory for strong correlation
Authors: Lee Seunghoon , Park Woojin , Nakata Hiroya , Filatov Michael , Choi Cheol Ho 
Published: November 2021

AbstractThe formulations and performances of spin‐restricted ensemble‐referenced KS and mixed‐reference spin‐flip time‐dependent density functional theory incorporating strong correlations into density functional theories are documented. As a result of balanced dynamic and nondynamic correlation, they are capable of describing strongly correlated challenging systems including diradicals, bond dissociation, conical intersections, doubly excited states, and so on, overcoming the limitations of current density functional theories.
Tailoring the Electrocatalytic Properties of sp2‐Hybridized Carbon Nanomaterials with Molecule Doping
Authors: Li Wenhao , He Wenya , Chen Xijie , Chen Tianxiao , Wu Yun , Li Chuan , Zhang Xin , Yu Le , Yang Fengchun 
Published: November 2021

AbstractFor electrocatalytic processes, the electronic structure especially the density of states (DOS) of electrode materials plays a dominant role in process of electron transfer kinetics for redox reactions. The unusual electronic properties of sp2‐hybridized carbon nanomaterials with adjustable DOS offer great promise in constructing high performance electrodes for electrochemical applications. However, researchers are still confronted with challenges such as how the electronic properties influence the kinetics of electron transfer and how to modulate the electronic structure appropriate strategy for achieving efficient electrochemical reactions of different sp2 carbon nanomaterials. With the aim of understanding the impacts of electronic structures on electrocatalytic properties, we selected several typical 0D to 3D carbon nanomaterials, and tailored the electrocatalytic performance of carbon nanomaterials by doping electron donor and electron acceptor. The results demonstrate that different molecular doping give rise to entirely different modifications in electronic structure of the sp2‐hybridized carbon nanomaterials, endowing modulation of the electrocatalytic properties for the appropriate redox reaction. When doped with electron acceptor, it is more conducive to the oxidation reaction. Conversely, doping with electron donors is more conducive to the occurrence of reduction reactions. This strategy reveals electronic structure effects on the electron transfer of electrocatalytic redox reaction and provides an efficient approach on tailoring the electrocatalytic performance of sp2‐hybridized carbon nanomaterials. For further electrochemical applications, that can ultimately provide rational guidance toward the development of improved catalysts.
How 5 f Electron Polarisability Drives Covalency and Selectivity in Actinide N‐Donor Complexes
Authors: Köhler Luisa , Patzschke Michael , Schmidt Moritz , Stumpf Thorsten , März Juliane 
Published: November 2021

AbstractWe report a series of isostructural tetravalent actinide (Th, U−Pu) complexes with the N‐donor ligand N,N’‐ethylene‐bis((pyrrole‐2‐yl)methanimine) (H2L, H2pyren). Structural data from SC‐XRD analysis reveal [An(pyren)2] complexes with different An−Nimine versus An−Npyrrolide bond lengths. Quantum chemical calculations elucidated the bonding situation, including differences in the covalent character of the coordinative bonds. A comparison to the intensely studied analogous N,N′‐ethylene‐bis(salicylideneimine) (H2salen)‐based complexes [An(salen)2] displays, on average, almost equal electron sharing of pyren or salen with the AnIV, pointing to a potential ligand‐cage‐driven complex stabilisation. This is shown in the fixed ligand arrangement of pyren and salen in the respective AnIV complexes. The overall bond strength of the pure N‐donor ligand pyren to AnIV (An=Th, U, Np, Pu) is slightly weaker than to salen, with the exception of the PaIV complex, which exhibits extraordinarily high electron sharing of pyren with PaIV. Such an altered ligand preference within the early AnIV series points to a specificity of the 5f1 configuration, which can be explained by polarisation effects of the 5 f electrons, allowing the strongest f electron backbonding from PaIV (5f1) to the N donors of pyren.
Insights into Proton Dynamics in a Photofunctional Salt‐Cocrystal Continuum: Single‐Crystal X‐ray, Neutron Diffraction, and Hirshfeld Atom Refinement
Authors: Yano Yoshio , Ono Toshikazu , Ohhara Takashi , Hisaeda Yoshio 
Published: November 2021

AbstractX‐ray diffraction, neutron diffraction, and theoretical calculations were used to investigate the relationship between the optical properties and degree of protonation in acid‐base complexes. We prepared five acid‐base complexes by using a pyridine‐modified pyrrolopyrrole derivative and salicylic acid. Two of the prepared acid‐base complexes were polymorphs of guest‐free crystals with green emission; the other three were guest‐inclusion crystals with yellow emission containing CH2Cl2, CH2Br2, or C2H4Cl2. The presence or absence of guests caused the emission to change color, altering the hydrogen bond strength between the acid‐base complexes. Accurate N⋅⋅⋅H distances between the pyridyl moiety and the carboxy group over the temperature range 123 to 273 K were 1.40 Å for the guest‐free crystals and 1.25 Å for the guest‐inclusion crystals. Our findings contribute to a better understanding of the complex relationship between photofunction and proton dynamics in acid‐base complexes.
PTFE/EP Reinforced MOF/SiO2 Composite as a Superior Mechanically Robust Superhydrophobic Agent towards Corrosion Protection, Self‐Cleaning and Anti‐Icing
Authors: Hussain Muhammad Muzammal , Majeed Muhammad K. , Ma Haitao , Wang Yunpeng , Saleem Adil , Lotfi Mina 
Published: November 2021

AbstractOrganic resin cross‐linking ZIF‐67/SiO2 superhydrophobic (SHPB) multilayer coating was successfully fabricated on metal substrate. The perfluoro‐octyl‐triethoxy silane (POTS) modified ZIF‐67 and SiO2 coating was applied on primary coated polytetrafluoroethylene (PTFE) and epoxy resin (EP) via spray coating method. Here, we present that the robust superhydrophobicity can be realized by structuring surfaces at two different length scales, with a nanostructure design to provide water repellence and a microstructure design to provide durability. The as‐fabricated multilayer coating displayed superior water‐repellence (CA=167.4°), chemical robustness (pH=1–14) and mechanical durability undergoing 120th linear abrasion or 35th rotatory abrasion cycle. By applying different acidic and basic corrosive media and various weathering conditions, it can still maintain superior‐hydrophobicity. To get a better insight of interaction between inhibitor molecules and metal surface, density functional theory (DFT) calculations were performed, showing lower energy gap and increased binding energy of ZPS/SiO2/PTFE/EP (ZPS=ZIF‐67+POTS) multilayer coating compared to the ZIF‐67/SiO2/PTFE/EP, thereby supporting the experimental findings. Additionally, such coatings may be useful for applications such as anti‐corrosion, self‐cleaning, and anti‐icing multi‐functionalities.
Catechol Moiety Integrated Tri‐Aryl Type AIEgen for Visual and Quantitative Boronic Acid Detection
Authors: Hu Renjian , Lin Shiyun , Wang Mengshi , Li Ruoxin , Shuai Zhigang , Wei Yen 
Published: November 2021

AbstractNovel functional AIEgen based on three compact bound aryl skeletons is designed and synthesized. This tri‐aryl type luminogen (TA‐Catechol) embedded with catechol moiety responds rapidly to series of boronic acids. Real‐time visual and quantitative dual‐mode detection method is established for the first time with modest precision and low detection limit (8.0 μM). Detailed mechanistic discussion identifies tetra‐coordinated boronic species as the key intermediate within sensing procedure. Wide range of organic boronic acids compatible with this strategy is displayed which is promising in high throughput screening technology. Furthermore, solid‐state sensing capability of TA‐Catechol is also demonstrated.