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11.
Altieri A Gatti FG Kay ER Leigh DA Martel D Paolucci F Slawin AM Wong JK 《Journal of the American Chemical Society》2003,125(28):8644-8654
A series of [2]rotaxanes containing succinamide and naphthalimide hydrogen-bonding stations for a benzylic amide macrocycle is described. Electrochemical reduction and oxidation of the naphthalimide group alters its ability to form hydrogen bonds to the macrocycle to such a degree that redox processes can be used to switch the relative macrocycle-binding affinities of the two stations in a rotaxane by over 8 orders of magnitude. The structure of the neutral [2]rotaxane in solution is established by (1)H NMR spectroscopy and shows that the macrocycle exhibits remarkable positional integrity for the succinamide station in a variety of solvents. Cyclic voltammetry experiments allow the simultaneous stimulation and observation of a redox-induced dynamic process in the rotaxane which is both reversible and cyclable. Model compounds in which various conformational and co-conformational changes are prohibited demonstrate unequivocally that the redox response is the result of shuttling of the macrocycle between the two stations. At room temperature in tetrahydrofuran the electrochemically induced movement of the macrocycle between the two stations takes approximately 50 micros. 相似文献
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Prema Ranganathan Wilmer K. Fife Martel Zeldin 《Journal of polymer science. Part A, Polymer chemistry》1990,28(10):2711-2717
4-Vinylpyridinium trifluoromethanesulfonate monomers substituted at nitrogen with H, O, CH3, C2H5, C6H13, and C12H25 were synthesized and characterized spectroscopically. Thermal analyses (DSC and TGA) were carried out on all the compounds. The solid monomers (N? H, N? CH3, N? C6H13, and N? C12H25) exhibited endothermic melting followed by exothermic polymerization and exothermic decomposition (>400°C). Liquid N? C2H5 monomer revealed only exothermic polymerization and decomposition. The N? O polymer underwent thermal decomposition below 300°C. The N–C12H25 homopolymer, prepared from monomer in the DSC or in bulk, displayed an unusual thermal transition at 250°C, which has been attributed to a polymer backbone reorientation leading to side-chain ordering of the dodecyl groups. 相似文献
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[reaction: see text] Reported herein is a strategy employing a Mukaiyama reaction in tandem with a hydrogen transfer reaction for the elaboration of 2,3-anti-3,4-anti and 2,3-anti-3,4-syn propionate motifs. The mode of complexation is controlled through monodentate or chelate pathways for the Mukaiyama reaction to give access to either syn or anti aldol products, precursors of the free-radical reduction reaction. Boron Lewis acid is used to control the free-radical reaction through the exocyclic pathway. 相似文献
14.
The influence of using normal-phase and reversed-phase versions of four commercial polysaccharide stationary phases on chiral separations was investigated with capillary electrochromatography (CEC). Both versions of the stationary phases, Chiralcel OD, OJ, and Chiralpak AD, AS were tested for the separation of two basic, two acidic, a bifunctional, and a neutral compound. Different background electrolytes were used, two at low pH for the acid, bifunctional and neutral substances, and three at high pH for the basic, bifunctional and neutral ones. This setup allowed evaluating differences between both stationary-phase versions and between mobile-phase compositions on a chiral separation. Duplicate CEC columns of each stationary phase were in-house prepared and tested, giving information about the intercolumn reproducibility. In general, reversed-phase versions of the current commercial polysaccharide stationary phases are found to be best for reversed-phase CEC, even though at high pH no significant differences were seen between both versions. Most differences were observed at low pH. For acidic compounds, it was seen that an ammonium formate electrolyte performed best, which is also an excellent electrolyte if coupling with mass spectrometry is desired. For basic, bifunctional and neutral compounds, no significant differences between the three tested electrolytes were observed at high pH. Here, a phosphate buffer is preferred as electrolyte because of its buffering capacities. However, if coupling to mass spectrometry is wanted, the more volatile ammonium bicarbonate electrolyte can be used as an alternative. 相似文献
15.
We introduce a new distance measure between two preorders that captures indifference, strict preference, weak preference and incomparability relations. This measure is the first to capture weak preference relations. We illustrate how this distance measure affords decision makers greater modeling power to capture their preferences, or uncertainty and ambiguity around them, by using our proposed distance measure in a multiple criteria aggregation procedure for mixed evaluations. 相似文献
16.
Access to New Endoperoxide Derivatives by Electrochemical Oxidation of Substituted 3‐Azabicyclo[4.1.0]hept‐4‐enes
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Dr. Frédérick Nuter Dr. Abdou Khadre Djily Dimé Dr. Cheng Chen Dr. Lotfi Bounaadja Dr. Elisabeth Mouray Dr. Isabelle Florent Dr. Yvan Six Dr. Olivier Buriez Dr. Angela Marinetti Dr. Arnaud Voituriez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5584-5593
A series of substituted 3‐azabicyclo[4.1.0]hept‐4‐ene derivatives were prepared and analysed by cyclic voltammetry. Preparative aerobic electrochemical oxidation reactions were then carried out. Three original endoperoxides were isolated, characterised and subjected to antimalarial and cytotoxicity activity assays. 相似文献
17.
Cedric Samuel Yvan Chalamet Fernande Boisson Jean‐Charles Majesté Frédéric Becquart Etienne Fleury 《Journal of polymer science. Part A, Polymer chemistry》2014,52(4):493-503
A one‐step process is reported to directly synthesize blends of poly(trimethylene carbonate) (PTMC) with a modified granular starch. Trimethylene Carbonate (TMC) ring‐opening polymerization is performed in the presence of native starch particles in bulk conditions at 150 °C and the efficiency of metal‐free organic catalysts (TBD and phosphazene superbases P1‐t‐Oct, P2‐t‐bu, and P4‐t‐bu) are investigated to replace the organo‐metallic stannous octanoate initiator. TMC monomer is successively converted into PTMC and the robustness of organic catalysts is highlighted with significant activities at very low concentrations (<100 ppm), where stannous octanoate is inefficient. Reactivity of starch toward TMC ROP is deeply investigated by NMR techniques and a starch‐graft‐PTMC is indirectly evidenced. Starch substitution degree reaches 0.9% indicating that PTMC grafting only occurs at the surface of swollen granular starch. PTMC graft length from the starch surface remained low in the range 2–12 and model ROP reactions highlight the role of TMC hydrolysis on PTMC graft length. Despite low PTMC grafts, a fine dispersion of intact starch particles into the PTMC matrix is evidenced. Consequently, metal‐free organic catalysts at low concentrations are promising candidates for synthesizing blends of PTMC with high loadings of surface‐modified starch (32% by weight) in 2 min within a one‐step process. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 493–503 相似文献
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Maria Carmen Florian Eric Condamine loïc Toupet Yvan Ramondenc Gérard Plé 《Supramolecular chemistry》2013,25(6):383-392
The synthesis and the structure of new macrocycles containing semiflexible dispiro-1,3-dioxane units is reported. The structural analysis of the compounds is performed by high field NMR spectra, mass spectrometry investigations (MALDI, ESI-MS) and the solid state molecular structure obtained for two compounds by single crystal X-ray diffractometry. The dynamics of the macrocycles promoted by the flipping of the middle cyclohexane ring of the dispirane units is investigated using low temperature NMR experiments. New macrocycles containing dispiro-1,3-dioxane units were investigated by NMR, X-ray diffractometry and mass spectrometry 相似文献