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91.
Matthews CJ Elsegood MR Bernardinelli G Clegg W Williams AF 《Dalton transactions (Cambridge, England : 2003)》2004,(3):492-497
The crystal structures of three complexes of dicarboxy-2,2'-bipyridyl ligands, 5,5'-dicarboxy-2,2'-bipyridyl (1) and 4,4'-dicarboxy-2,2'-bipyridyl (2) are reported. [Rh(1H)3] shows two interpenetrating, homochiral rhombohedral networks linked by short carboxylate-carboxylic acid hydrogen bonds, in which each complex acts as a node for six hydrogen bonds. [Ru(1H2)(1H)2] forms only four such hydrogen bonds, leading to the formation of heterochiral chains held together by stacking between bipyridyls. [Co(2H)3] can in principle form six hydrogen bonds, but in practice forms only four in a layer structure where stacking interactions are important. This is attributed to differences in molecular shape. 相似文献
92.
Jeffrey P. Whitten Donald P. Matthews James R. Mccarthy Robert J. Barbuch 《Journal of heterocyclic chemistry》1988,25(6):1845-1847
Imidazoles substituted in the 2-position with methyl, 1e , phenyl, 1a , 2-imidazole, 1b-d , or t-butyldiphenylsilyl, If, react with soft electrophiles 2 to give modest yields of 4(5)-C-alkylated-imidazoles 3 and N-alkylated products 5. These two products are readily separated by flash chromatography. 相似文献
93.
G. Keglevich H. R. Hudson R. W. Matthews I. Petneházy O. O. Shode L. Toke 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4)
Abstract α-Hydroxyphosphonates are formed, in addition to vinyl phosphates and dehalogenated ketones, in the reactions of trimethyl phosphite (in methanol) or triethyl phosphite (in ethanol) with variously substituted α-chloro, α-bromo, and α,α,-dichloro-acetophenones. Tri-isopropyl phosphite in propan-2-ol gives only the vinyl phosphate. Ketophosphonates are not detectable amongst the reaction products under the conditions used. Trends in product composition can be correlated with the leaving ability of halogen, substituent effects, structure of the phosphite, and reaction temperature. Reactant ratios may also influence the product composition. The reactions of trimethyl phosphite in methanol with 4-nitro-α-chloroacetophenone, or α,α-dichloroacetophenones yield the dehalogenated α-hydrogxyphosphonates in addition. In the case of the 4-nitro derivative, this product cannot be accounted for by reaction of the phosphite with dehalogenated ketone (4-nitroacetophenone). Dehalogenation of the first-formed α-hydroxyphosphonate was, however, shown to occur under reaction conditions and appears to require the removal of positive chlorine, followed by protonation. Reactions of the α,α-dichloroacetophenones were similar to those of the α-chloroacetophenones, giving the corresponding chlorovinyl phosphate, α,α-dichloro-α-hydroxyphosphonate, and monodehalogenated ketone(i.e. α-chloroacetophenone); the latter was not however detected as it reacted further with excess phosphite to give the expected products as described above. Possible mechanisms for the various reactions are discussed. The 1H and 13C nmr spectra of the α-hydroxy-phosphonates show magnetic non-equivalence of the two alkoxy groups, attributed to restricted rotation about the P-C bond as a result of intramolecular hydrogen-bonding. 相似文献
94.
95.
96.
Craig Aalseth Erica Andreotti Dirk Arnold Joan-Albert Sanchez Cabeza Detlev Degering Andrea Giuliani Raquel Gonzales de Orduña Rodolfo Gurriaran Mikael Hult Martin Keillor Matthias Laubenstein Gilbert le Petit Romul Mircea Margineanu Murray Matthews Harry Miley Iolanda Osvath Monica Pellicciari Wolfango Plastino Hardy Simgen Marc Weber Robert Werzi 《Journal of Radioanalytical and Nuclear Chemistry》2009,282(3):731-735
Aerosol samples collected on filter media were analyzed using HPGe detectors employing varying background-reduction techniques in order to experimentally evaluate the opportunity to apply ultra-low background measurement methods to samples collected, for instance, by the Comprehensive Test Ban Treaty International Monitoring System (IMS). In this way, realistic estimates of the impact of low-background methodology on the sensitivity obtained in systems such as the IMS were assessed. The current detectability requirement of stations in the IMS is 30 μBq/m3 of air for 140Ba, which would imply ~106 fissions per daily sample. Importantly, this is for a fresh aerosol filter. One week of decay reduces the intrinsic background from radon daughters in the sample allowing much higher sensitivity measurement of relevant isotopes, including 131I. An experiment was conducted in which decayed filter samples were measured at a variety of underground locations using Ultra-Low Background (ULB) gamma spectroscopy technology. The impacts of the decay and ULB are discussed. 相似文献
97.
98.
In this paper we investigate some notions of completion of partial metric spaces, including the bicompletion, the Smyth completion, and a new “spherical completion”. Given an auxiliary relation, we show that it arises from a totally bounded partial metric space, and the spherical completion of such a space is its round ideal completion. We also give an example of a totally bounded partial metric space whose bicompletion and Smyth completion are not continuous posets. Finally, we present an example of a totally bounded partial metric giving rise to the Scott and lower topologies of a continuous poset, but whose spherical completion is not a continuous poset. 相似文献
99.
Qiu JX Petersson EJ Matthews EE Schepartz A 《Journal of the American Chemical Society》2006,128(35):11338-11339
Folded polymers in nature are assembled from simple monomers and adopt complex folded structures through networks of stabilizing noncovalent interactions. These interactions define secondary and tertiary structure and in most cases specify a unique three-dimensional architecture. Individual secondary or tertiary structures can also associate with one another to form multi-subunit quaternary structures. Nonnatural folded polymers have potential for similar structural versatility. Here we describe a pair of beta3-peptides whose sequences were designed to promote a 14-helix structure in water, favor hetero-oligomer formation, and disfavor nonspecific aggregation. These beta3-peptides assemble noncovalently into a well-defined hetero-oligomer characterized by a defined stoichiometry, a highly stabilized secondary structure, and a cooperative melting transition (TM > 55 degrees C). This work demonstrates that beta3-peptides can assemble into defined, cooperatively folded quaternary structures and constitutes an important step toward designing protein-like assemblies from nonnatural polymers. 相似文献
100.
N-acetyl-l-cysteine (NAC) is a well-known antioxidant that is capable of facilitating glutathione (GSH) biosynthesis and replenishing intracellular GSH under oxidatively challenging circumstances. N-acetyl-cysteine-amide (NACA), the amide form of NAC, is a newly designed and synthesized thiol-containing compound which is believed to be more lipophilic and permeable through cell membranes than NAC. The metabolic and antioxidant effects of these compounds in vitro and in vivo are under investigation. However, an analytical method that can separate and quantify both compounds simultaneously is not yet available, to the best of our knowledge. Because of their structural similarities, the two compounds are difficult to separate using earlier HPLC methods which were designed for NAC quantification. Therefore, the goal of this work was to develop an HPLC method with fluorescence detection for simultaneous quantification of NAC and NACA in biological blood and tissue samples. A gradient HPLC program with fluorescence detection (lambda(ex) = 330 nm, lambda(em) = 376 nm) using N-(1-pyrenyl)maleimide (NPM) as the derivatizing agent was developed. The calibration curves were linear over a concentration range of 25-5000 nm (r(2) > 0.997). The coefficients of variation for within-run precision and between-run precision ranged from 0.67 to 5.23% and for accuracy ranged from 0.98 to 10.54%; the percentage relative recovery ranged from 94.5 to 102.8%. This new method provides satisfactory separation of NAC and NACA, along with other biological thiols, in 20 min with a 5 nm limit of detection (LOD) per 5 microL injection volume. 相似文献