bluuebunny/crossref_metadata_2025_split huggingface dataset:
Persistent Radical Tetrathiafulvalene‐Based 2D Metal‐Organic Frameworks and Their Application in Efficient Photothermal Conversion
Authors: Su Jian , Xu Ning , Murase Ryuichi , Yang Zhi‐Mei , D'Alessandro Deanna M. , Zuo Jing‐Lin , Zhu Jia 
Published: November 2020

AbstractA series of stable radical 2D metal‐organic frameworks has been assembled. (m‐TTFTB)3 (m‐Tetrathiafulvalene‐tetrabenzoate) trimer building blocks are beneficial for the stability of the radicals due to delocalization of the unpaired electron. Hexanuclear rare‐earth‐cluster‐based 1D chains further enhance the stability of the frameworks. The radical state of the middle TTF in the trimer has been observed by the change of central C−C and C−S bond distances and the configuration of the TTF by single‐crystal X‐ray diffraction. The radical characteristics are also confirmed by electron paramagnetic resonance, UV/Vis–NIR absorption, and X‐ray photoelectron spectroscopy experiments. Stability tests showed that the radicals are stable even in solutions and under acid/base environments (pH 1–12). Owing to efficient light absorption due to intramolecular charge transfer, low thermal conductivity, and outstanding stability, the radical 2D Dy‐MOF shows excellent photothermal properties, an increase of 34.7 °C within 240 s under one‐sun illumination.
Novel β‐Glucocerebrosidase Activators That Bind to a New Pocket at a Dimer Interface and Induce Dimerization
Authors: Benz Joerg , Rufer Arne C. , Huber Sylwia , Ehler Andreas , Hug Melanie , Topp Andreas , Guba Wolfgang , Hofmann Eva Carolina , Jagasia Ravi , Rodríguez Sarmiento Rosa María 
Published: November 2020

AbstractGenetic, preclinical and clinical data link Parkinson's disease and Gaucher's disease and provide a rational entry point to disease modification therapy via enhancement of β‐Glucocerebrosidase (GCase) activity. We discovered a new class of pyrrolo[2,3‐b]pyrazine activators effecting both Vmax and Km. They bind to human GCase and increase substrate metabolism in the lysosome in a cellular assay. We obtained the first crystal structure for an activator and identified a novel non‐inhibitory binding mode at the interface of a dimer, rationalizing the observed structure–activity relationship (SAR). The compound binds GCase inducing formation of a dimeric state at both endoplasmic reticulum (ER) and lysosomal pHs, as confirmed by analytical ultracentrifugation. Importantly, the pyrrolo[2,3‐b]pyrazines have central nervous system (CNS) drug‐like properties. Our findings are important for future drug discovery efforts in the field of GCase activation and provide a deeper mechanistic understanding of the requirements for enzymatic activation, pointing to the relevance of dimerization.
Impact of Organic Templates on the Selective Formation of Zeolite Oligomers
Authors: Ciantar Marine , Trinh Thuat T. , Michel Carine , Sautet Philippe , Mellot‐Draznieks Caroline , Nieto‐Draghi Carlos 
Published: November 2020

AbstractZeolites are essential materials to industry due to their adsorption and catalytic properties. The best current approach to prepare a targeted zeolite still relies on trial and error's synthetic procedures since a rational understanding of the impact of synthesis variables on the final structures is still missing. To discern the role of a variety of organic templates, we perform simulations of the early stages of condensation of silica oligomers by combining DFT, Brønsted‐Evans‐Polanyi relationships and kinetic Monte Carlo simulations. We investigate an extended reaction path mechanism including 258 equilibrium reactions and 242 chemical species up to silica octamers, comparing the computed concentrations of Si oligomers with 29SI NMR experimental data. The effect of the templating agent is linked to the modification of the intramolecular H‐bond network in the growing oligomer, which produces higher concentration of 4‐membered ring intermediates, precursors of the key double‐four ring building blocks present on more than 39 known zeolite topologies.
Katalytische Synthese von Kaliumacyltrifluoroboraten (KATs) aus Boronsäuren und dem Thioimidat‐KAT‐Transferreagenz
Authors: Schuhmacher Anne , Ryan Sarah J. , Bode Jeffrey W. 
Published: November 2020

AbstractWir berichten über die Synthese von Kaliumacyltrifluoroboraten (KATs) mittels Palladium‐katalysierter Kreuzkupplung von Boronsäuren mit dem Thioimidat‐KAT‐Transferreagenz. Die Kombination von breit erhältlichen Aryl‐ und Vinylboronsäuren mit kommerziellem Thioimidat 1 unter Verwendung von katalytischem PdII und CuII als Additiv erlaubt die Herstellung von KATs in hohen Ausbeuten und mit guter Verträglichkeit für verschiedene funktionelle Gruppen. Das formale Einfügen von CO in Organoboronsäuren kann unter Verwendung eines geringfügig veränderten Vorgehens auch für Boronsäurepinakolester und Kaliumorganotrifluoroborate angewendet werden. Durch die einzigartige Chemie von KATs und Trifluoroboratiminiumionen (TIMs) lassen sich Kreuzkupplungen auch auf die Synthese von Amiden und α‐Aminotrifluoroboraten als Eintopfvariante ausweiten.
Improving the Overall Properties of Circularly Polarized Luminescent Materials Through Arene–Perfluoroarene Interactions
Authors: Zhang Haowen , Han Jianlei , Jin Xue , Duan Pengfei 
Published: November 2020

AbstractA major trade‐off in the field of circularly polarized luminescence (CPL) of pure organic materials is that the large luminescence dissymmetry factor (glum) usually gives rise to the suppression of luminescence efficiency (ΦPL). Here, a supramolecular self‐assembled system, driven by arene–perfluoroarene (AP) interactions of chiral polycyclic aromatic hydrocarbons (PAHs) and octafluoronaphthalene (OFN), is reported to provide a solution to this problem. Two kinds of chiral PAHs based on pyrene and anthracene could co‐assemble with OFN in hybrid solvents to form long‐range‐ordered AP assemblies. The detailed process of AP interaction driving self‐assembly was verified by morphological measurements and fluorescence spectra. The AP assemblies exhibited chirality amplification not only in the excited state but also in the ground state. In addition, the AP assemblies showed an enhanced luminescence efficiency compared with the individual chiral PAHs due to the energy‐barrier effect of OFN. The present strategy based on AP interactions could be applied to boost the development of highly efficient CPL‐active materials.
Coupling of Cu(100) and (110) Facets Promotes Carbon Dioxide Conversion to Hydrocarbons and Alcohols
Authors: Zhong Dazhong , Zhao Zhi‐Jian , Zhao Qiang , Cheng Dongfang , Liu Bin , Zhang Gong , Deng Wanyu , Dong Hao , Zhang Lei , Li Jingkun , Li Jinping , Gong Jinlong 
Published: November 2020

AbstractCopper can efficiently electro‐catalyze carbon dioxide reduction to C2+ products (C2H4, C2H5OH, n‐propanol). However, the correlation between the activity and active sites remains ambiguous, impeding further improvements in their performance. The facet effect of copper crystals to promote CO adsorption and C−C coupling and consequently yield a superior selectivity for C2+ products is described. We achieve a high Faradaic efficiency (FE) of 87 % and a large partial current density of 217 mA cm−2 toward C2+ products on Cu(OH)2‐D at only −0.54 V versus the reversible hydrogen electrode in a flow‐cell electrolyzer. With further coupled to a Si solar cell, record‐high solar conversion efficiencies of 4.47 % and 6.4 % are achieved for C2H4 and C2+ products, respectively. This study provides an in‐depth understanding of the selective formation of C2+ products on Cu and paves the way for the practical application of electrocatalytic or solar‐driven CO2 reduction.
A Biomimetic DNA‐Based Membrane Gate for Protein‐Controlled Transport of Cytotoxic Drugs
Authors: Lanphere Conor , Arnott Patrick M. , Jones Sioned Fôn , Korlova Katarina , Howorka Stefan 
Published: November 2020

AbstractChemistry is ideally placed to replicate biomolecular structures with tuneable building materials. Of particular interest are molecular nanopores, which transport cargo across membranes, as in DNA sequencing. Advanced nanopores control transport in response to triggers, but this cannot be easily replicated with biogenic proteins. Here we use DNA nanotechnology to build a synthetic molecular gate that opens in response to a specific protein. The gate self‐assembles from six DNA strands to form a bilayer‐spanning pore, and a lid strand comprising a protein‐binding DNA aptamer to block the channel entrance. Addition of the trigger protein, thrombin, selectively opens the gate and enables a 330‐fold increase inw the transport rate of small‐molecule cargo. The molecular gate incorporates in delivery vesicles to controllably release enclosed cytotoxic drugs and kill eukaryotic cells. The generically designed gate may be applied in biomedicine, biosensing or for building synthetic cells.
Water Mobility in the Interfacial Liquid Layer of Ice/Clay Nanocomposites
Authors: Li Hailong , Mars Julian , Lohstroh Wiebke , Koza Michael Marek , Butt Hans‐Jürgen , Mezger Markus 
Published: November 2020

AbstractAt solid/ice interfaces, a premelting layer is formed at temperatures below the melting point of bulk water. However, the structural and dynamic properties within the premelting layer have been a topic of intense debate. Herein, we determined the translational diffusion coefficient Dt of water in ice/clay nanocomposites serving as model systems for permafrost by quasi‐elastic neutron scattering. Below the bulk melting point, a rapid decrease of Dt is found for charged hydrophilic vermiculite, uncharged hydrophilic kaolin, and more hydrophobic talc, reaching plateau values below −4 °C. At this temperature, Dt in the premelting layer is reduced up to a factor of two compared to supercooled bulk water. Adjacent to charged vermiculite the lowest water mobility was observed, followed by kaolin and the more hydrophobic talc. Results are explained by the intermolecular water interactions with different clay surfaces and interfacial segregation of the low‐density liquid water (LDL) component.
Acceptor Engineering for Optimized ROS Generation Facilitates Reprogramming Macrophages to M1 Phenotype in Photodynamic Immunotherapy
Authors: Yang Guang , Ni Jen‐Shyang , Li Yaxi , Zha Menglei , Tu Yao , Li Kai 
Published: November 2020

AbstractReprogramming tumor‐associated macrophages to an antitumor M1 phenotype by photodynamic therapy is a promising strategy to overcome the immunosuppression of tumor microenvironment for boosted immunotherapy. However, it remains unclear how the reactive oxygen species (ROS) generated from type I and II mechanisms, relate to the macrophage polarization efficacy. Herein, we design and synthesize three donor–acceptor structured photosensitizers with varied ROS‐generating efficiencies. Surprisingly, we discovered that the extracellular ROS generated from type I mechanism are mainly responsible for reprogramming the macrophages from a pro‐tumor type (M2) to an anti‐tumor state (M1). In vivo experiments prove that the photosensitizer can trigger photodynamic immunotherapy for effective suppression of the tumor growth, while the therapeutic outcome is abolished with depleted macrophages. Overall, our strategy highlights the designing guideline of macrophage‐activatable photosensitizers.
Racemic Monomer‐Based One‐Handed Helical Polymer Recognizes Enantiomers through Auto‐Evolution of Its Helical Handedness Excess
Authors: Ikai Tomoyuki , Kurake Tomoyuki , Okuda Shogo , Maeda Katsuhiro , Yashima Eiji 
Published: November 2020

AbstractA racemic monomer‐based optically inactive polyacetylene folds into a one‐handed helix assisted by a nonracemic alcohol, which can separate various enantiomers as a chiral stationary phase in chromatography. The chiral‐resolving power is virtually identical to that of the enantiopure monomer‐based one‐handed helical polyacetylene. Because of its unique static memory of the induced helicity, the original racemic polyacetylene expresses an auto‐evolution of its helical handedness over time, and at the same time, chirality of the nonracemic alcohol is discriminated accompanied by successive enhancement of its optical purity enantioselectively adsorbed on the helical polyacetylene owing to the chiral filter effect as directly monitored by NMR, which contributes to further enhancing the helix‐sense‐excess of the helical polyacetylene.
Preparation of Hierarchical Porous Activated Carbon from Banana Leaves for High‐performance Supercapacitor: Effect of Type of Electrolytes on Performance
Authors: Roy Chanchal Kumar , Shah Syed Shaheen , Reaz Akter H. , Sultana Sharmin , Chowdhury Al‐Nakib , Firoz Shakhawat H. , Zahir Md. Hasan , Ahmed Qasem Mohammed Ameen , Aziz Md. Abdul 
Published: November 2020

AbstractWe demonstrate a facile efficient way to fabricate activated carbon nanosheets (ACNSs) consisting of hierarchical porous carbon materials. Simply heating banana leaves with K2CO3 produce ACNSs having a unique combination of macro‐, meso‐ and micropores with a high specific surface area of ∼1459 m2 g−1. The effects of different electrolytes on the electrochemical supercapacitor performance and stability of the ACNSs are tested using a two‐electrode system. The specific capacitance (Csp) values are 55, 114, and 190 F g−1 in aqueous 0.5 M sodium sulfate, organic 1 M tetraethylammonium tetrafluoroborate in acetonitrile, and pure ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([BMIM][PF6]) electrolytes, respectively. The ACNSs also shows the largest potential window of 3.0 V, the highest specific energy (59 Wh kg−1) and specific power (750 W kg−1) in [BMIM][PF6]. A mini‐prototype device is prepared to demonstrate the practicality of the ACNSs.
Lignin valorization beyond energy use: has lignin's time finally come?
Authors: Xu Chunbao Charles , Dessbesell Luana , Zhang Yongsheng , Yuan Zhongshun 
Published: November 2020

AbstractAccording to an old proverb, ‘you can make anything out of lignin, except money’. The complexity of lignin's structure and many inferior characteristics of lignin, such as its insolubility in organic solvent and poor reactivity related to it large molecular weight, have posed significant challenges to lignin valorization. Driven mainly by the commercial availability of large amounts of kraft lignin and hydrolysis lignin in kraft pulp mills and cellulosic ethanol plants, there is a pressing need to valorize lignin for high‐value chemical and material products for better overall profitability for the plants, and for the emerging bioeconomy. To this end, we have developed, over 10 years and in several publications, an engineering approach to lignin valorization. This perspective paper provides an overview of this process and concretizes the research achieved in support of lignin valorization. In the method presented, lignin is first de‐polymerized into de‐polymerized lignin (DL) at a high yield and with a tunable Mw (weight average molecular weight). The DL is then utilized as a mixture (no separation needed) to substitute directly petroleum‐based phenol (up to 75% substitution), polyols (up to 50% substitution), and bis‐phenol A (100 substitution) in preparation of bio‐based phenolic resins, polyurethane foams, and epoxy resins. The DL products were also used to replace petroleum‐based antioxidants resulting in enhanced thermo‐oxidative and thermal stability of polyethylene in the synthesis of bio‐based resins / plastic composites. This approach has demonstrated both technical and economic feasibility, generating a payback period of approximately 3 years for a commercial capacity of 40 000 t/y. Thus, Lignin valorization beyond energy use can be profitable, and the old proverb may prove wrong. Lignin's time might have finally come! © 2020 Society of Industrial Chemistry and John Wiley & Sons Ltd
Intranasal administration of perillyl alcohol–loaded nanoemulsion and pharmacokinetic study of its metabolite perillic acid in plasma and brain of rats using ultra‐performance liquid chromatography/tandem mass spectrometry
Authors: da Silva Santos Juliane , Diedrich Camila , Machado Christiane Schineider , da Fonseca Clovis Orlando , Khalil Najeh Maissar , Mainardes Rubiana Mara 
Published: November 2020

AbstractPerillyl alcohol (POH) is a monocyclic terpene that has strong antitumor activity. Brain tumors are particularly difficult to treat with therapeutic agents, and clinical trials have shown their low tolerance through oral administration. We proposed the entrapment of POH into an oil‐in‐water chitosan nanoemulsion aiming its intranasal administration for brain targeting. An ultra‐performance liquid chromatography/tandem mass spectrometry (UPLC–MS/MS) method was developed and validated for the quantitation of total metabolite perillic acid (PA) in plasma and brain of rats. The rat samples containing the metabolite were treated by liquid–liquid extraction with acetonitrile. The mobile phase was 0.1% formic acid in water (solvent A) and 0.1% formic acid in methanol (solvent B), at a flow rate of 0.3 mL min−1 in gradient elution. The chromatography was run for 10 min, and analytical curves were built in acetonitrile, plasma, and brain. The PA was detected in positive ion mode with multiple reaction monitoring. The method has shown high selectivity, sensitivity, and throughput. The low quantification limits of 162, 178, and 121 ng mL−1 for acetonitrile, brain, and plasma, respectively, indicate a good detectability of the method. The repeatability and precision observed were within the limits recommended in the literature. The accuracy of the method was verified through high recovery rates (106–118%). The validated method was successfully applied to the pharmacokinetic study of the metabolite PA after the intranasal administration of free or POH‐loaded nanoemulsion in rats. The results showed that chitosan nanoemulsion improved the plasma and brain bioavailability of POH, representing a promising alternative to free POH treatment.
Minimally invasive surgery vs laparotomy for early stage cervical cancer: A propensity score‐matched cohort study
Authors: Dai Danian , Huang He , Feng Yanling , Wan Ting , Liu Zhimin , Tong Chongjie , Liu Jihong 
Published: November 2020

AbstractObjectiveTo compare the long‐term oncologic outcomes of minimally invasive surgery (MIS) vs laparotomy for patients with stage IB (2018 FIGO) cervical cancer.MethodsA matched retrospective study of cervical cancer patients who underwent MIS or laparotomy at Sun Yat‐sen University Cancer Center from January 2012 to December 2015 was carried out. Patients were restaged according to the 2018 FIGO staging system for cervical cancer, 700 cases with stage IB cervical cancer were enrolled. Propensity score matching (PSM) was performed by software SPSS version 22.0, and a total of 426 patients were enrolled and analyzed. Oncologic outcomes were compared between patients undergoing MIS vs laparotomy.ResultsAfter PSM, there were no statistical differences in other baseline characteristics between MIS and laparotomy, except for age (p = 0.008). In all stage IB patients, MIS group had significantly lower disease‐free survival (DFS) rate and overall survival (OS) rate compared with laparotomy group (5‐year DFS rate, 87.5% vs 94.1%, hazard ratio for disease recurrence, 2.403; 95% CI, 1.216‐4.744; 5‐year OS rate, 92.3% vs 98.1%, hazard ratio for death, 3.719; 95% CI, 1.370‐10.093). In stage IB1 patients population, MIS was still associated with worse DFS and OS compared to laparotomy (5‐year DFS rate: 89.5% vs 100%, p = 0.012; 5‐year OS rate: 93.4% vs 100%, p = 0.043). Even in stage IB1 patients without lymph vascular space invasion, worse oncologic outcome could be observed in MIS group (DFS: p = 0.021; OS: p = 0.076).ConclusionOur study suggested that laparotomy resulted in better OS and DFS compared with MIS among patients with stage IB cervical cancer. Even in stage IB1 patients without lymph vascular space invasion (2018 FIGO), laparotomy might be still an oncologically safer approach.
Biomass derived Fibers as a Substitute to Synthetic Fibers in Polymer Composites
Authors: Qasim Umair , Ali Muzaffar , Ali Touqeer , Iqbal Rameez , Jamil Farrukh 
Published: November 2020

AbstractAdvancement in science and technology provides the significant opportunities to utilize the plant fibers (unnoticed materials), which are cheap, abundant, sustainable, and biodegradable. A combination of polymer with the untreated and treated fibers, extracted from lignocellulosic biomass, has been getting significant attention because of their low cost, ecofriendly nature, and enhanced mechanical performance. This article delivers an explicit overview of the plant fibers, extraction and pretreatment of the plant fibers, development of the plant fibers reinforced polymeric composites, and the mechanical properties associated with these biocomposites. A special focus is concentrated on the pretreatment of hydrophilic plant fibers for better compatibility with the polymers, to obtain the enhanced composites having desirable properties. Finally, the effects of several pretreatments on the tensile and water absorption properties of the plant fibers reinforced composites has been included in detail for the better understanding of their practical applications.
A Cyanine‐Bridged Somatostatin Hybrid Probe for Multimodal SSTR2 Imaging in Vitro and in Vivo: Synthesis and Evaluation
Authors: Heing‐Becker Isabelle , Grötzinger Carsten , Beindorff Nicola , Prasad Sonal , Erdmann Sarah , Exner Samantha , Haag Rainer , Licha Kai 
Published: November 2020

AbstractMultimodal imaging probes have attracted the interest of ongoing research, for example, for the surgical removal of tumors. Modular synthesis approaches allow the construction of hybrid probes consisting of a radiotracer, a fluorophore and a targeting unit. We present the synthesis of a new asymmetric bifunctional cyanine dye that can be used as a structural and functional linker for the construction of such hybrid probes. 68Ga‐DOTATATE, a well‐characterized radiopeptide targeting the overexpressed somatostatin receptor subtype 2 (SSTR2) in neuroendocrine tumors, was labeled with our cyanine dye, thus providing additional information along with the data obtained from the radiotracer. We tested the SSTR2‐targeting and imaging properties of the resulting probe 68Ga‐DOTA‐ICC‐TATE in vitro and in a tumor xenograft mouse model. Despite the close proximity between dye and pharmacophore, we observed a high binding affinity towards SSTR2 as well as elevated uptake in SSTR2‐overexpressing tumors in the positron emission tomography (PET) scan and histological examination.