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91.
Juan-Ramón Jiménez Jana Glatz Amina Benchohra Geoffrey Gontard Lise-Marie Chamoreau Jean-François Meunier Azzedine Bousseksou Rodrigue Lescouëzec 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(21):8166-8170
A mixed-valence {MnII3MnIIIFeII2FeIII2} cyanide-bridged molecular cube hosting a caesium cation, Cs⊂{Mn4Fe4}, was synthesized and structurally characterized by X-ray diffraction. Cyclic-voltammetry measurements show that its electronic state can be switched between five different redox states, which results in a remarkable electrochromic effect. Magnetic measurements on fresh samples point to the occurrence of a spin-state change near room temperature, which could be ascribed to a metal-to-metal electron transfer converting the {FeII−CN−MnIII} pair into a {FeIII−CN−MnII} pair. This feature was only previously observed in the polymeric MnFe Prussian-blue analogues (PBAs). Moreover, this novel switchable molecule proved to be soluble and stable in organic solvents, paving the way for its integration into advanced materials. 相似文献
92.
Jana M. Holthoff Elric Engelage Robert Weiss Stefan M. Huber 《Angewandte Chemie (International ed. in English)》2020,59(27):11150-11157
Halogen bonding is often described as being driven predominantly by electrostatics, and thus adducts between anionic halogen bond (XB) donors (halogen‐based Lewis acids) and anions seem counterintuitive. Such “anti‐electrostatic” XBs have been predicted theoretically but for organic XB donors, there are currently no experimental examples except for a few cases of self‐association. Reported herein is the synthesis of two negatively charged organoiodine derivatives that form anti‐electrostatic XBs with anions. Even though the electrostatic potential is universally negative across the surface of both compounds, DFT calculations indicate kinetic stabilization of their halide complexes in the gas phase and particularly in solution. Experimentally, self‐association of the anionic XB donors was observed in solid‐state structures, resulting in dimers, trimers, and infinite chains. In addition, co‐crystals with halides were obtained, representing the first cases of halogen bonding between an organic anionic XB donor and a different anion. The bond lengths of all observed interactions are 14–21 % shorter than the sum of the van der Waals radii. 相似文献
93.
Sebastian Grieger Beata M. Szydowska Vaishnavi J. Rao Eva Steinmann Marcus Dodds Zahra Gholamvand Georg S. Duesberg Jana Zaumseil Claudia Backes 《Angewandte Chemie (International ed. in English)》2020,59(33):13785-13792
In recent years, various functionalization strategies for transition‐metal dichalcogenides have been explored to tailor the properties of materials and to provide anchor points for the fabrication of hybrid structures. Herein, new insights into the role of the surfactant in functionalization reactions are described. Using the spontaneous reaction of WS2 with chloroauric acid as a model reaction, the regioselective formation of gold nanoparticles on WS2 is shown to be heavily dependent on the surfactant employed. A simple model is developed to explain the role of the chosen surfactant in this heterogeneous functionalization reaction. The surfactant coverage is identified as the crucial element that governs the dominant reaction pathway and therefore can severely alter the reaction outcome. This study shows the general importance of the surfactant choice and how detrimental or beneficial a certain surfactant can be to the desired functionalization. 相似文献
94.
Hualong Song Simon J. Allison Viktor Brabec Hannah E. Bridgewater Jana Kasparkova Hana Kostrhunova Vojtech Novohradsky Roger M. Phillips Jitka Pracharova Nicola J. Rogers Samantha L. Shepherd Peter Scott 《Angewandte Chemie (International ed. in English)》2020,59(34):14677-14685
Monosaccharides are added to the hydrophilic face of a self‐assembled asymmetric FeII metallohelix, using CuAAC chemistry. The sixteen resulting architectures are water‐stable and optically pure, and exhibit improved antiproliferative selectivity against colon cancer cells (HCT116 p53+/+) with respect to the non‐cancerous ARPE‐19 cell line. While the most selective compound is a glucose‐appended enantiomer, its cellular entry is not mainly glucose transporter‐mediated. Glucose conjugation nevertheless increases nuclear delivery ca 2.5‐fold, and a non‐destructive interaction with DNA is indicated. Addition of the glucose units affects the binding orientation of the metallohelix to naked DNA, but does not substantially alter the overall affinity. In a mouse model, the glucose conjugated compound was far better tolerated, and tumour growth delays for the parent compound (2.6 d) were improved to 4.3 d; performance as good as cisplatin but with the advantage of no weight loss in the subjects. 相似文献
95.
Tripathi Jai Prakash Jana Debaldev Vyshnavi Devi N. S. N. V. K. Tiwari Vandana Abbas Syed 《Nonlinear dynamics》2020,102(1):511-535
Nonlinear Dynamics - In this present study, we systematically explore the periodicity (almost periodic nature) of a dynamical system in time-varying environment, which portrays a special case of... 相似文献
96.
A high-pressure microwave digestion was applied for microwave-assisted extraction (MAE) of mercury species from sediments and zoobenthos samples. A mixture containing 3 mol L−1 HCl, 50% aqueous methanol and 0.2 mol L−1 citric acid (for masking co-extracted Fe3+) was selected as the most suitable extraction agent. The efficiency of proposed extraction method was better than 95% with R.S.D. below 6%. A preconcentration method utilizing a “homemade” C18 solid phase extraction (SPE) microcolumns was developed to enhance sensitivity of the mercury species determination using on-column complex formation of mercury-2-mercaptophenol complexes. Methanol was chosen for counter-current elution of the retained mercury complexes achieving a preconcentration factor as much as 1000. The preconcentration method was applied for the speciation analysis of mercury in river water samples. The high-performance liquid chromatography-cold vapour atomic fluorescence spectrometric (HPLC/CV-AFS) method was used for the speciation analysis of mercury. The complete separation of four mercury species was achieved by an isocratic elution of aqueous methanol (65%/35%) on a Zorbax SB-C18 column (4.6 mm × 150 mm, 5 μm) using the same complexation reagent (2-mercaptophenol). The limits of detection were 4.3 μg L−1 for methylmercury (MeHg+), 1.4 μg L−1 for ethylmercury (EtHg+), 0.8 μg L−1 for inorganic mercury (Hg2+), 0.8 μg L−1 for phenylmercury (PhHg+). 相似文献
97.
Quantification of copper and zinc species fractions in legume seeds extracts by SEC/ICP-MS: validation and uncertainty estimation 总被引:1,自引:0,他引:1
Fractions of Cu and Zn species in legume samples (common white bean, pea, chick pea and lentil seeds and defatted soybean flour) were analysed by on-line hyphenation of size exclusion chromatography and inductively coupled plasma-mass spectrometry. Samples were extracted by 0.02 mol l−1 Tris–HCl buffer solution, pH 7.5. The extraction efficiency lay in the region 60–90 and 60–80% for Cu and Zn, respectively. Quantification of elements in the individual chromatographic fractions was carried out by isotope dilution (ID) and external calibration (EC) techniques. For ID analysis the chromatographic effluent was mixed with the flow of 65Cu and 68Zn isotope enriched solution and the isotope ratio values 63Cu/65Cu and (64Zn+66Zn)/68Zn were measured. In the case of EC technique calibration solutions of elements were injected to the flow of mobile phase by the second injector. Prior entering detector the effluent was mixed with the flow of internal standard solution (In, 50 μg l−1). Both methods have similar precision, however the behaviour of both studied elements was not the same. The chromatographic analysis itself was the main source of variability in the case of Cu. For Zn species analysis, the extraction process and the manipulation with the extract, played the significant role too. It was probably caused by lower stability of the present zinc chelates. The total amounts of Zn found in all chromatographic fractions represented 85–95% of Zn in sampled extract whereas those of Cu approached 100%. In case of small peaks the results of ID and EC were not the same. The EC results were lower then ID results. The great deal of results uncertainty accounts for the precision. 相似文献
98.
99.
We establish the well-posedness and thermodynamic consistency of a variational inequality modeling temperature-induced memory
erasure in shape memory materials. It is shown that the input–output operator is continuous with respect to uniform convergence. 相似文献
100.
One of the objectives of the Intergeo project was to provide European mathematics teachers with ??good quality?? pedagogical material supporting the use of dynamic geometry software in classrooms. With this aim in view, an online repository/platform was developed to gather various dynamic geometry resources, based on the idea of a teachers?? community feeding the repository, (re)using available resources and sharing practices related to the use of dynamic geometry in classrooms. The repository is thus open to contributions of any user who can deposit, browse, download and use resources, which naturally raises the question how to handle the resource quality issue in such an open environment. This paper reports on the way we tackled this issue in the Intergeo project. We first explain what we mean by a ??good quality?? dynamic geometry resource. We then provide a rationale behind the design of a questionnaire, the main tool for resource quality reviews, which are at the core of the quality assessment process implemented in the repository. Several experiments carried out with groups of teachers in order to confront our research-based view of the resource quality with the teachers?? one and to observe teachers?? usages of the quality assessment process are also reported in the paper. The outcomes of these experiments highlight strengths and limitations of the resource quality assessment process. They also tend to show that the idea of involving teachers into the resource quality assessment is a promising way of stimulating the use of dynamic geometry in classrooms, provided that teachers benefit from a support to make the quality process their own. 相似文献