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171.
172.
Melanie A. Short J. Miles Blackburn Prof. Dr. Jennifer L. Roizen 《Angewandte Chemie (International ed. in English)》2018,57(1):296-299
Masked alcohols are particularly appealing as directing groups because of the ubiquity of hydroxy groups in organic small molecules. Herein, we disclose a general strategy for aliphatic γ‐C(sp3)?H functionalization guided by a masked alcohol. Specifically, we determine that sulfamate ester derived nitrogen‐centered radicals mediate 1,6‐hydrogen‐atom transfer (HAT) processes to guide γ‐C(sp3)?H chlorination. This reaction proceeds through a light‐initiated radical chain‐propagation process and is capable of installing chlorine atoms at primary, secondary, and tertiary centers. 相似文献
173.
A novel method for producing nanosized polymer latex particles doped with fluorescent and phosphorescent solutes is described. Methyl methacrylate monomer (10 wt %) containing either pyrene, 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DMDP), or 1-bromonaphthalene was ultrasonically dispersed in water and simultaneously polymerized to produce approximately 60 nm diameter latex particles. A fluorescence spectroscopic examination of the latex dispersion containing either pyrene or DMDP showed that the solutes were not covalently bound to the polymer and that they were embedded in a highly viscous environment possessing a low polarity (dielectric constant on the order of 2). The fluorescence lifetime of the pyrene in the core of the poly(MMA) latex was found to be 520 ns, irrespective of the oxygen concentration in the dispersion. Room-temperature phosphorescence was observed from 1-bromonaphthalene, with a lifetime of 2.0 ms in an argon atmosphere. In the presence of air, phosphorescence was still observable although with a partially reduced emission intensity. 相似文献
174.
TG and DTA of the compounds Mn(phen)2X2 (where X=CN–,CNO–, NCS– and NCSe–), Mn(phen) (NCS)2, Mn(NCS)2 and Mn(NCSe)2 (wherephen=1,10 phenanthroline) are reported and discussed. Decomposition schemes are proposed based on TG and DTA results and, where possible, the analysis and properties of intermediates formed during thermal breakdown. The decomposition of thiocyanate and selenocyanate ligands is observed to lead to an apparent slight increase in sample weight. This phenomenon is discussed in relation to buoyancy changes resulting from the release of sulphur or selenium vapours.
We wish to express our thanks to Professor S. C. Bevan for helpful advice, particularly in connection with the buoyancy effect noted for thiocyanate and selenocyanate complexes. 相似文献
Zusammenfassung TG und DTA Untersuchungen der Verbindungen Mn(phen)2X2 (X=CN–, CNO–, NCS– und NCSe–), Mn(phen) (NCS)2, Mn(NCS)2 und Mn(NCSe)2 (phen =1.10 Phenantrolin) werden beschrieben. Anhand der TG- und DTA-Ergebnisse werden Zerzetzungsschemata vorgeschlagen und wenn möglich, Analyse und Eigenschaften der im Laufe der thermischen Zersetzung entstandenen Zwischenprodukte angegeben. Es wurde beobachtet, da\ die Zersetzung der Thiocyanat- und Selenocyanatliganden zu einer scheinbaren schwachen Zunahme des Probengewichts führt. Dieses PhÄnomen wird im Zusammenhang mit infolge der Abspaltung von Schwefel- oder SelendÄmpfen auftretenden Änderungen des Auftriebs diskutiert.
Résumé On décrit et discute la TG et l'ATD des composés Mn(phén)2X2 (X=CN–, CNO–, NCS– et NCSe–), Mn(phén) (NCS)2, Mn(NCS)2 et Mn(NCSe)2 (oùphén=1,10 phénantroline). On propose des schémas de décomposition à partir des résultats de TG et d'ATD et, si possible, on donne l'analyse et les propriétés des produits intermédiaires formés lors de la décomposition thermique. On a observé que la décomposition des ligands de thiocyanate et de sélénocyanate entraine une faible augmentation apparante du poids du prélèvement. On explique ce phénomène par les variations de poussée résultant du dégagement de vapeurs de soufre ou de sélénium.
()22, () (NCS)2, Mn(NCS)2 Mn(NCSe)2, X=CN–, CNO–, NCS–, NCSe– =1.10. , , - , . . - , .
We wish to express our thanks to Professor S. C. Bevan for helpful advice, particularly in connection with the buoyancy effect noted for thiocyanate and selenocyanate complexes. 相似文献
175.
Loening NM Rosay M Weis V Griffin RG 《Journal of the American Chemical Society》2002,124(30):8808-8809
The goal of dynamic nuclear polarization (DNP) is to enhance NMR signals by transferring electron spin polarization to the nuclei. Although mechanisms such as the solid effect and thermal mixing can be used for DNP in the solid state, currently, the only practical mechanism in solutions is the Overhauser effect (OE), which usually arises due to dipolar relaxation between electrons and the nuclei. At magnetic fields greater than approximately 1 T, dipolar relaxation does not result in a useful enhancement and therefore the conventional wisdom is that DNP should not work in solutions at high magnetic fields. However, scalar relaxation due to time-dependent scalar couplings has a different magnetic field dependence and can lead to substantial OE enhancements. At room temperature and at a magnetic field of 5 T (211 MHz for protons, 140 GHz for electrons), we have observed that scalar relaxation between electrons and nuclei results in NMR signal enhancements of 180, 42, -36, and 8, for 31P, 13C, 15N, and 19F, respectively. 相似文献
176.
Martin Bröring Prof. Dr. Christian Hell Melanie Steiner Carsten D. Brandt 《无机化学与普通化学杂志》2007,633(7):1082-1086
A set of porphyrinoid manganese(IV) complexes with the 2,3,7,8,12,13,17,18‐octaethyl‐5,15‐di‐p‐tolylcorrolato ligand [(oedtc)MnIVX] (X = Cl, Br, I) was prepared by oxidation of a manganese(III) precursor. The most unexpected complex in this series, [(oedtc)MnIVI], was found to display significant thermal stability despite the unusual MnIV‐I bond and could be investigated by X‐ray diffraction. Attempted ligand exchange reactions of the chlorido derivative with the pseudohalide anions cyanide, azide, cyanate and thiocyanate yielded the desired [(oedtc)MnIVX] complex only as the isothiocyanate derivative while for the other species the reduction to manganese(III) was observed. 相似文献
177.
Bunick CG Nelson MR Mangahas S Hunter MJ Sheehan JH Mizoue LS Bunick GJ Chazin WJ 《Journal of the American Chemical Society》2004,126(19):5990-5998
The extent of conformational change that calcium binding induces in EF-hand proteins is a key biochemical property specifying Ca(2+) sensor versus signal modulator function. To understand how differences in amino acid sequence lead to differences in the response to Ca(2+) binding, comparative analyses of sequence and structures, combined with model building, were used to develop hypotheses about which amino acid residues control Ca(2+)-induced conformational changes. These results were used to generate a first design of calbindomodulin (CBM-1), a calbindin D(9k) re-engineered with 15 mutations to respond to Ca(2+) binding with a conformational change similar to that of calmodulin. The gene for CBM-1 was synthesized, and the protein was expressed and purified. Remarkably, this protein did not exhibit any non-native-like molten globule properties despite the large number of mutations and the nonconservative nature of some of them. Ca(2+)-induced changes in CD intensity and in the binding of the hydrophobic probe, ANS, implied that CBM-1 does undergo Ca(2+) sensorlike conformational changes. The X-ray crystal structure of Ca(2+)-CBM-1 determined at 1.44 A resolution reveals the anticipated increase in hydrophobic surface area relative to the wild-type protein. A nascent calmodulin-like hydrophobic docking surface was also found, though it is occluded by the inter-EF-hand loop. The results from this first calbindomodulin design are discussed in terms of progress toward understanding the relationships between amino acid sequence, protein structure, and protein function for EF-hand CaBPs, as well as the additional mutations for the next CBM design. 相似文献
178.
Excess enthalpies of tetrachloromethane + 2-propanone at 303.15 K and 318.15 K, and + 2-propanone-d6 at 303.15 K, have been measured. 相似文献
179.
Potter CV Dean JL Kybett AP Kidd R James M Canning M 《Organic & biomolecular chemistry》2004,2(24):3535-3540
In January 2003, the Royal Society of Chemistry launched Organic & Biomolecular Chemistry (OBC)--a journal promising to provide high quality research from all aspects of synthetic, physical and biomolecular organic chemistry. The journal was set to build upon the foundations laid down by its predecessor publications (J. Chem. Soc., Perkin Trans. 1 and J. Chem. Soc., Perkin Trans. 2) as well as complement the subject coverage already published in prestigious general chemistry journals such as Chemical Communications and Chemical Society Reviews. Nearly two years on, just how is the programme developing and what can the community expect to see from the Royal Society of Chemistry (RSC)? 相似文献
180.
Stephen Caddick Duncan B JuddAlexandra K.de K Lewis Melanie T ReichMeredith R.V Williams 《Tetrahedron》2003,59(29):5417-5423
The scope of nickel boride mediated reduction of nitriles has been extended further to allow the preparation of Boc protected amines via a mild catalytic process. It is noteworthy that the toxicity of this procedure is greatly reduced due to its catalytic nature in nickel(II) chloride used in combination with excess sodium borohydride. The protocol is marked by its resilience towards air and moisture and hence an easy and general practical protocol. 相似文献