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11.
Sunlight‐Driven Formation and Dissociation of a Dynamic Mixed‐Valence Thallium(III)/Thallium(I) Porphyrin Complex 下载免费PDF全文
Victoria Ndoyom Luca Fusaro Vincent Dorcet Bernard Boitrel Stéphane Le Gac 《Angewandte Chemie (International ed. in English)》2015,54(12):3806-3811
Inspired by a Newton’s cradle device and interested in the development of redox‐controllable bimetallic molecular switches, a mixed‐valence thallium(III)/thallium(I) bis‐strap porphyrin complex, with TlIII bound out of the plane of the N core and TlI hung to a strap on the opposite side, was formed by the addition of TlOAc to the free base and exposure to indirect sunlight. In this process, oxygen photosensitization by the porphyrin allows the oxidation of TlI to TlIII. The bimetallic complex is dynamic as the metals exchange their positions symmetrically to the porphyrin plane with TlIII funneling through the macrocycle. Further exposure of the complex to direct sunlight leads to thallium dissociation and to total recovery of the free base. Hence, the porphyrin plays a key role at all stages of the cycle of the complex: It hosts two metal ions, and by absorbing light, it allows the formation and dissociation of TlIII. These results constitute the basis for the further design of innovative light‐driven bimetallic molecular devices. 相似文献
12.
Colette J. Whitfield Andrew T. Turley Dr. Eimer M. Tuite Prof. Bernard A. Connolly Dr. Andrew R. Pike 《Angewandte Chemie (International ed. in English)》2015,54(31):8971-8974
A polymerase chain reaction (PCR) derived method for preparing long DNA, consisting of multiple repeat units of one to ten base pairs, is described. Two seeding oligodeoxynucleotides, so‐called oligoseeds, which encode the repeat unit and produce a duplex with 5′‐overhangs, are extended using a thermostable archaeal DNA polymerase. Multiple rounds of heat–cool extension cycles, akin to PCR, rapidly elongate the oligoseed. Twenty cycles produced long DNA with uniformly repeating sequences to over 20 kilobases (kb) in length. The polynucleotides prepared include [A]n/[T]n, [AG]n/[TC]n, [A2G]n/[T2C]n, [A3G]n/[T3C]n, [A4G]n/[T4C]n, [A9G]n/[T9C]n, [GATC]n/[CTAG]n, and [ACTGATCAGC]n/[TGACTAGTCG]n, indicating that the method is extremely flexible with regard to the repeat length and base sequence of the initial oligoseeds. DNA of this length (20 kb≈7 μm) with strictly defined base reiterations should find use in nanomaterial applications. 相似文献
13.
Cover Picture: The Quest for Polysulfides in Lithium–Sulfur Battery Electrolytes: An Operando Confocal Raman Spectroscopy Study (ChemPhysChem 13/2015) 下载免费PDF全文
14.
The Quest for Polysulfides in Lithium–Sulfur Battery Electrolytes: An Operando Confocal Raman Spectroscopy Study 下载免费PDF全文
Dr. Julien Hannauer Dr. Johan Scheers Julien Fullenwarth Dr. Bernard Fraisse Prof. Dr. Lorenzo Stievano Prof. Dr. Patrik Johansson 《Chemphyschem》2015,16(13):2755-2759
Confocal Raman spectra of a lithium–sulfur battery electrolyte are recorded operando in a depth‐of‐discharge resolved manner for an electrochemical cell with a realistic electrolyte/sulfur loading ratio. The evolution of various possible polysulfides is unambiguously identified by combining Raman spectroscopy data with DFT simulations. 相似文献
15.
Bernard Riss Marion Garreau Prisca Fricero Patricia Podsiadly Nicolas Berton Sophie Buchter 《Tetrahedron》2017,73(23):3202-3212
The absolute configuration of bisabolangelone has been established by an eleven step total synthesis of the corresponding TMS protected antipode starting from (R)-(+)-pulegone. Comparison of the TMS-derivatives by GC on a chiral column, allowed us to assign the absolute configuration of the synthetic compound and thus of the corresponding natural product. The latter has been confirmed by the Mosher's ester analysis of the known secondary carbinol derivative. 相似文献
16.
Raca Todosijević Anis Mjirda Marko Mladenović Saïd Hanafi Bernard Gendron 《Optimization Letters》2017,11(6):1047-1056
In this paper, we present two general variable neighborhood search (GVNS) based variants for solving the traveling salesman problem with draft limits (TSPDL), a recent extension of the traveling salesman problem. TSPDL arises in the context of maritime transportation. It consists of finding optimal Hamiltonian tour for a given ship which has to visit and deliver products to a set of ports while respecting the draft limit constraints. The proposed methods combine ideas in sequential variable neighborhood descent within GVNS. They are tested on a set of benchmarks from the literature as well as on a new one generated by us. Computational experiments show remarkable efficiency and effectiveness of our new approach. Moreover, new set of benchmarks instances is generated. 相似文献
17.
The radical telomerisation of vinylidene fluoride (VDF) with 2-mercaptoethanol as chain transfer agent (CTA) was studied to synthesise fluorinated telomers which bear a hydroxy end-group, such as H(VDF)nS(CH2)2OH, under thermal (di-tert-butyl peroxide as the initiator) or photochemical initiations. A careful structural study of a typical H-VDF-S(CH2)2OH telomer was performed by 1H and 19F NMR spectroscopy. These analytical methods allowed us to explore the selective addition of the thiyl radical onto the hydrogenated side of VDF, and the telomer containing one VDF unit was obtained selectively. Surprisingly, for higher [VDF]o initial concentrations, a monoadduct telomer was produced as well as PVDF homopolymer. This feature was related to the fast consumption of the CTA. The kinetics of radical telomerisation led to a quite high transfer constant of the CTA (40 at 140 °C) that evidences the formation of a monoadduct as the only telomer formed. 相似文献
18.
Adesola A. Adeleke Sizwe J. Zamisa Md. Shahidul Islam Kolawole Olofinsan Veronica F. Salau Chunderika Mocktar Bernard Omondi 《Molecules (Basel, Switzerland)》2021,26(5)
A series of fifteen silver (I) quinoline complexes Q1–Q15 have been synthesized and studied for their biological activities. Q1–Q15 were synthesized from the reactions of quinolinyl Schiff base derivatives L1–L5 (obtained by condensing 2-quinolinecarboxaldehyde with various aniline derivatives) with AgNO3, AgClO4 and AgCF3SO3. Q1–Q15 were characterized by various spectroscopic techniques and the structures of [Ag(L1)2]NO3 Q1, [Ag(L1)2]ClO4 Q6, [Ag(L2)2]ClO4 Q7, [Ag(L2)2]CF3SO3 Q12 and [Ag(L4)2]CF3SO3 Q14 were unequivocally determined by single crystal X-ray diffraction analysis. In vitro antimicrobial tests against Gram-positive and Gram-negative bacteria revealed the influence of structure and anion on the complexes′ moderate to excellent antibacterial activity. In vitro antioxidant activities of the complexes showed their good radical scavenging activity in ferric reducing antioxidant power (FRAP). Complexes with the fluorine substituent or the thiophene or benzothiazole moieties are more potent with IC50 between 0.95 and 2.22 mg/mL than the standard used, ascorbic acid (2.68 mg/mL). The compounds showed a strong binding affinity with calf thymus-DNA via an intercalation mode and protein through a static quenching mechanism. Cytotoxicity activity was examined against three carcinoma cell lines (HELA, MDA-MB231, and SHSY5Y). [Ag(L2)2]ClO4 Q7 with a benzothiazole moiety and [Ag(L4)2]ClO4 Q9 with a methyl substituent had excellent cytotoxicity against HELA cells. 相似文献
19.
Several studies of jets impinging on a plane surface have already been made. This paper suggests a new approach to studying
impingements of jets. Comparisons have been made between visualisation results and wall pressure measurements. It is shown
that only one of these two techniques is sufficient for characterising the flow nature near the wall. Visualisations can be
sufficient for determining the location of wall pressure maxima and minima. Detachments and reattachments of the flow are
thus located, and the main characteristics of a jet impinging on a plane wall can be shown by simpler experiments such as
the spreading over method.
Received: 15 October 1998/Accepted: 27 July 1999 相似文献
20.
Subgrid-modelling in LES of compressible flow 总被引:1,自引:0,他引:1
Subgrid-models for Large Eddy Simulation (LES) of compressible turbulent flow are tested for the three-dimensional mixing layer. For the turbulent stress tensor the recently developed dynamic mixed model yields reasonable results.A priori estimates of the subgrid-terms in the filtered energy equation show that the usually neglected pressure-dilatation and turbulent dissipation rate are as large as the commonly retained pressure-velocity subgrid-term. Models for all these terms are proposed: a similarity model for the pressure-dilatation, similarity andk-dependent models for the turbulent dissipation rate and a dynamic mixed model for the pressure-velocity subgrid-term. Actual LES demonstrates that for a low Mach number all subgrid-terms in the energy equation can be neglected, while for a moderate Mach number the effect of the modelled turbulent dissipation rate is larger than the combined effect of the other modelled subgrid-terms in the filtered energy equation. 相似文献