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101.
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Bruno R.S. de Paula Dávila S. Zampieri J. Augusto R. Rodrigues Paulo J.S. Moran 《Tetrahedron: Asymmetry》2013,24(17):973-981
Enones (Z)-3-methyl-(Z)-3-chloromethyl- and (Z)-3-bromomethyl-4-R-3-buten-2-one (R = n-pentyl, phenyl, 2′- and 4′-chlorophenyl, 3′- and 4′-nitrophenyl, 4′-methoxyphenyl) were synthesized and subjected to reduction by the microorganisms Saccharomyces cerevisiae andGeotrichum candidum. Whereas the bioreduction of 3-methy-4-R-3-buten-2-ones afforded the corresponding (S)-4-R-3-methybutan-2-ones, the bioreduction of 3-chloromethyl- and 3-bromomethyl-4-R-3-buten-2-ones afforded the corresponding (R)-4-R-3-methybutan-2-ones. 相似文献
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To prepare cross‐linked silicone (silicone rubber) particles in an aqueous medium, we investigated two synthesis methods involving a miniemulsion system. The first method was based on cationic ring‐opening polymerization of cyclic siloxane, which is a common synthetic route for linear silicone oil and uses octamethylcyclotetrasiloxane (D4) as the monomer and dimeric D4 (bis‐D4) as the cross‐linker. Although this method produces silicone particles, the particles do not remain in the particulate state after drying because of low cross‐linking density. The polymerization mechanism of this method was also investigated, which proceeds under the ring‐opening reaction of D4 in monomer droplets and upon polycondensation of hydrolyzed D4, which occurs in the water phase (ie, outside the monomer droplets). This mechanism implied that introducing the cross‐linking structure into particles is difficult because of the low solubility of bis‐D4 in water. To overcome these difficulties, we demonstrated a second method of preparing silicone particles based on the thiol‐Michael addition reaction between thiol‐terminated silicone oil and triacrylate in miniemulsion systems. Transmission electron microscopy images indicated that the silicone particles obtained in the particulate state upon drying and the aggregates of these particles showed elasticity. 相似文献
104.
In single‐molecule force spectroscopy (SMFS), many studies have focused on the elasticity and conformation of polymer chains, but little attention has been devoted to the dynamic properties of single polymer chains. In this study, we measured the energy dissipation and elastic properties of single polystyrene (PS) chains in toluene, methanol, and N,N‐dimethylformamide using a homemade piezo‐control and data acquisition system externally coupled to a commercial atomic force microscope (AFM), which provided more accurate information regarding the dynamic properties of the PS chains. We quantitatively measured the chain length‐dependent changes in the stiffness and viscosity of a single chain using a phenomenological model consistent with the theory of viscoelasticity for polymer chains in dilute solution. The effective viscosity of a polymer chain can be determined using the Kirkwood model, which is independent of the intrinsic viscosity of the solvent and dependent on the interaction between the polymer and solvent. The results indicated that the viscosity of a single PS chain is dominated by the interaction between the polymer and solvent. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1736–1743 相似文献
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Jin Tanaka Yu Shibata Anton Joseph Juntaro Nogami Jyunichi Terasawa Ryo Yoshimura Prof. Dr. Ken Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(26):5774-5779
It has been established that a newly developed cyclopentadienyl rhodium(III) [CpARhIII] complex, bearing an acidic secondary amide moiety on the Cp ring, is able to catalyze the ortho-bromination of O-phenyl carbamates with N-bromosuccinimide (NBS) at room temperature. The presence of the acidic secondary amide moiety on the CpA ligand accelerates the bromination by the hydrogen bond between the acidic NH group of the CpA ligand and the carbonyl group of NBS. 相似文献
106.
Enantioselective and Regiodivergent Functionalization of N‐Allylcarbamates by Mechanistically Divergent Multicatalysis
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Dr. Edward Richmond Ismat Ullah Khan Dr. Joseph Moran 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(35):12274-12277
A pair of mechanistically divergent multicatalytic reaction sequences has been developed consisting of nickel‐catalyzed isomerization of N‐allylcarbamates and subsequent phosphoric‐acid‐catalyzed enantioselective functionalization of the resulting intermediates. By appropriate selection of reaction partners, in situ generated imines and ene‐carbamates are mechanistically partitioned to yield opposing functionalized products. Formal α‐functionalization to give protected α‐arylamines is achieved upon enantioselective Friedel–Crafts reaction with arene nucleophiles, whereas formal β‐functionalization is achieved upon reaction with diarylimine electrophiles in an enantioselective Povarov‐[4+2] cycloaddition. 相似文献
107.
A short synthesis of tetramethyltetrathiafulvalene quadruply labeled with carbon-13 is described. 相似文献
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