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861.
Miniaturized liquid–liquid interfacial reactors offer enhanced surface area and rapid confinement of compounds of opposite solubility, yet they are unable to provide in situ reaction monitoring at a molecular level at the interface. A picoreactor operative at the liquid–liquid interface is described, comprising plasmonic colloidosomes containing Ag octahedra strategically assembled at the water‐in‐decane emulsion interface. The plasmonic colloidosomes isolate ultrasmall amounts of solutions (<200 pL), allowing parallel monitoring of multiple reactions simultaneously. Using the surface‐enhanced Raman spectroscopy (SERS) technique, in situ monitoring of the interfacial protonation of dimethyl yellow (p‐dimethylaminoazobenzene (DY)) is performed, revealing an apparent rate constant of 0.09 min?1 for the first‐order reaction. The presence of isomeric products with similar physical properties is resolved, which would otherwise be indiscernible by other analytical methods.  相似文献   
862.
Tuning the activity of radicals is crucial for radical reactions and radical‐based materials. Herein, we report a supramolecular strategy to accelerate the Fenton reaction through the construction of supramolecularly activated radical cations. As a proof of the concept, cucurbit[7]uril (CB[7]) was introduced, through host–guest interactions, onto each side of a derivative of 1,4‐diketopyrrolo[3,4‐c]pyrrole (DPP), a model dye for Fenton oxidation. The DPP radical cation, the key intermediate in the oxidation process, was activated by the electrostatically negative carbonyl groups of CB[7]. The activation induced a drastic decrease in the apparent activation energy and greatly increased the reaction rate. This facile supramolecular strategy is a promising method for promoting radical reactions. It may also open up a new route for the catalytic oxidation of organic pollutants for water purification and widen the realm of supramolecular catalysis.  相似文献   
863.
Solvothermal reaction of [MnCl2(terpy)] with elemental As and Se at a 1:1:2 molar ratio in H2O/trien (10:1) at 150 °C affords the linear trimanganese(II) complex [{Mn(terpy)}3(μ‐AsSe4)2] ( 1 ). The tridentate [AsSe2(Se2)]3? anions of 1 chelate the terminal {Mn(terpy)}2+ fragments and bridge these through their remaining Se atom to the central {Mn(terpy)}2+ moiety. Weak interactions of Mn1···Se and Mn3···Se bonds with length 2.914(7) and 3.000(7) Å link the molecules of 1 into infinite chains. Treatment of [MnCl2(cyclam)]Cl with As and Se at a 1:1:2 molar ratio in superheated H2O/CH3OH (1:1) at 150 °C yields the dinuclear complex [{Mn(cyclam)}2 (μ‐As2Se6)] ( 2 ), whose novel [(AsSe2)2(μ‐Se2)]4? ligands bridge the MnII atoms in a μ‐1κ2Se1, Se2: 2κ2Se5,Se6 manner.  相似文献   
864.
Two novel coordination polymers, [Cd(BIM)Cl2]n ( 1 ) and [Pb(BIM)Cl2]n ( 2 ) [wherein BIM = bis(imidazol‐1‐yl)methane], were synthesized by the reactions of the BIM ligand with CdCl2 and PbCl2, respectively. They were characterized by elemental analyses, IR, TGA and X‐ray single‐crystal diffraction techniques. Single‐crystal X‐ray structure analyses showed there is a pseudooctahedral arrangement around the cadmium atom in the complex 1 . It has a three‐dimensional network which contains one‐dimensional inorganic‐organic hybrid chains and μ2‐bridging chloride ligands. A rare pentacoordinate square‐pyramidal arrangement was adopted for the lead(II) atom in the complex 2 , which has an unusual two‐dimensional layer structure of macrometallacycles crosslinked with the bridging Pb2Cl2 units. The metal atoms in both complexes were coordinated with two BIM ligands in cis arrangement and bridged by μ2‐bridging chloride ligands.  相似文献   
865.
The reaction of 2,2′‐Bis(2N‐(1,1′,3,3′‐tetramethyl‐guanidino))diphenylene‐amine (TMG2PA) ( 1 ) with CuI in MeCN results in the formation of [CuII(TMG2PAamid)I] ( 2 ) indicatingthat CuI is the target of an oxidative attack of the N‐H proton of the ligand which itself is converted to molecular hydrogen. In contrast, if [Cu(MeCN)4][PF6] is used as the CuI source, [CuI2(TMGbenz)2][PF6]2 ( 3 ) is obtained instead. The use of the non‐coordinating counterion [PF6] apparently prevents CuI from oxidation but induces itself a cyclisation reaction within the ligand which results in the formation of a benzimidazole‐guanidine ligand.  相似文献   
866.
Enders' N‐heterocyclic carbene (NHC) dehydrogenates ammonia–borane with a relatively low barrier, producing NH2BH2 and NHC–(H)2. The nickel NHC catalyst present in the reaction media can activate the NHC–(H)2 produced to regenerate the free NHC and release H2. The release of free NHC enables further dehydrogenation of ammonia–borane.

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867.
868.
The new approach of kinetically controlled ozone removal suppresses particle formation in laboratory ozonolysis experiments for methylcyclohexene and methylenecyclohexane (MCHa) at excess alkene concentrations (see graph). The results support the hypothesis that peroxy radicals are involved in organic nucleation and particle‐growth mechanisms.

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869.
Inorganic enzyme? Ceria nanoparticles exhibit unique oxidase‐like activity at acidic pH values. These redox catalysts can be used in immunoassays (ELISA) when modified with targeting ligands (see picture; light blue and yellow structures are nanoparticles with attached ligands). This modification allows both for binding and for detection by the catalytic oxidation of sensitive colorimetric dyes (e.g. TMB).

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870.
Radically different : Contrary to previous proposals, the main reaction of the HO. radical with guanosine or 2′‐deoxyguanosine is the hydrogen abstraction from the NH2 moiety to give a guanyl radical. This radical, characterized by a broad band in the visible region (around 610 nm), undergoes tautomerization to the most stable isomer.

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