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51.
Raatikainen K Huuskonen J Rissanen K 《Dalton transactions (Cambridge, England : 2003)》2011,40(21):5706-5710
New tripodal transition metal ion receptors, tris(5-ethoxycarbonyl-2,2'-bipyridine) and tris(5-carboxylate-2,2'-bipyridine) substituted 27-membered trimeric piperazine cyclophanes 5 and 7 as well as tetra(5-ethoxycarbonyl-2,2'-bipyridine) substituted 36-membered tetrameric piperazine cyclophane 6, have been prepared and their transition metal ion complexing properties studied in solution by UV-vis spectroscopy and in the solid state by single-crystal X-ray diffraction. The crystal structures of [H(3)5(3+)·Fe(2+)]·4(ClO(4)(-))·CF(3)COO(-) (V), [H(3)7(2+)·Fe(2+)]·2(SO(4)(2-)) (VII) and the reference complex [tris(5,5'-bis(ethoxycarbonyl)-2,2'-bipyridine)Fe(II) perchlorate] (I) showed that the robust piperazine cyclophane is an optimal platform in preorganizing the 2,2'-bipy moieties to form a very fixed octahedral coordination site. In an acidic water solution, the highly preorganized structure of 5 gives a [5·Fe(2+)] complex, the stability of which is comparable with the classical tris(2,2'-bipy) Fe(2+)-complex but it is a significant 3.7 logK units more stable than the non-preorganized tetrameric analog [6·Fe(2+)]. Detailed studies with other similar divalent octahedral transition metal cations showed that the restricted octahedral coordination in complexes of 5 results in an unusual selectivity. The selectivity order [Zn(2+)相似文献
52.
53.
Hiltunen Y Kaartinen J Pulkkinen J Häkkinen AM Lundbom N Kauppinen RA 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2002,154(1):1-5
Long echo time (TE=270 ms) in vivo proton NMR spectra resembling human brain metabolite patterns were simulated for lineshape fitting (LF) and quantitative artificial neural network (ANN) analyses. A set of experimental in vivo 1H NMR spectra were first analyzed by the LF method to match the signal-to-noise ratios and linewidths of simulated spectra to those in the experimental data. The performance of constructed ANNs was compared for the peak area determinations of choline-containing compounds (Cho), total creatine (Cr), and N-acetyl aspartate (NAA) signals using both manually phase-corrected and magnitude spectra as inputs. The peak area data from ANN and LF analyses for simulated spectra yielded high correlation coefficients demonstrating that the peak areas quantified with ANN gave similar results as LF analysis. Thus, a fully automated ANN method based on magnitude spectra has demonstrated potential for quantification of in vivo metabolites from long echo time spectroscopic imaging. 相似文献
54.
Nieminen Juhani 《manuscripta mathematica》1972,7(1):13-21
Let L be a distributive lattice characterized by a ternary operation (, ,), where (a,b,c)=(ab)(bc)(ac)=(ab)(ac)(bc), a,b,cL. The note considers convex sublattices of L, called generalized ideals of L generated by the operation (, ,). Some remarks have been stated about the graph of a distributive lattice. 相似文献
55.
Juhani Nieminen 《Proceedings Mathematical Sciences》1985,94(1):47-49
Semimodularity and the Jordan-Hölder chain condition are characterized in a finite latticeL by means of special closed sets ofL. 相似文献
56.
Structural information of natural organic matter (NOM) at the molecular level is very essential in understanding their nature and reactivity. Nuclear magnetic resonance (NMR) is an excellent tool for estimating the gross chemical composition of the very complex humic matter (HM). A well-known fact is that the solid state 13C NMR spectral analysis is very parameter-sensitive especially in the study of the heterogenous HM (e.g. baseline corrections, different pulse techniques and spinning rates of the rotor vs. different disruptive sidebands in the spectra). This being the case, it has been emphasized the importance of qualitative and quantitative analyses for generating as real spectra as possible by means of different pulse and polarization techniques, sampling spinning rates as well as certain correction factors. In the present study a practical accuracy for quantitative determination of NOM type material by solid state 13C NMR spectroscopy was assessed using a known HM sample. Different magnetic-field strengths, sampling spinning rates, single and ramped amplitude cross polarization techniques and TOSS pulse sequence were applied for obtaining a more reliable insight into the disruptive effect of the chemical shift anisotropy (CSA), especially the most disturbing first order spinning side bands (SSB). The results demonstrated that the SSB problem is not so significant as sometimes stated, at least in the context of HM samples and in the light of the overall reproducibility and uncertainty connected with the sample itself. 相似文献
57.
Peter N. Taylor Andrew P. Wylie Juhani Huuskonen Harry L. Anderson 《Angewandte Chemie (International ed. in English)》1998,37(7):986-989
Despite their larger separation , the porphyrin groups in 1 are more strongly conjugated than in analogous compounds in which butadiyne is the bridging unit. This stronger electronic coupling in 1 results in a bathochromic shift in its absorption and emission spectra. 相似文献
58.
Boyle has given a condition for defining a homomorphism in terms of minimal paths for undirected graphs. The purpose of such homomorphisms is to provide a simpler graph which will reflect the structure of the more complex graph, and thereby enable the researcher to make observations which may have been shrouded by a preponderance of nodes and edges. This paper develops Boyle's ideas and introduces further homomorphisms for directed as well as undirected graphs. The relationships between the various homomorphisms are also examined. 相似文献
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60.
Kaufmann L Dzyuba EV Malberg F Löw NL Groschke M Brusilowskij B Huuskonen J Rissanen K Kirchner B Schalley CA 《Organic & biomolecular chemistry》2012,10(30):5954-5964
The binding behaviour of differently substituted diamide axle molecules to Hunter/V?gtle tetralactam macrocycles was studied with a combination of NMR titration, isothermal titration calorimetry (ITC) experiments and calculations employing density functional theory (DFT), along with dispersion-corrected exchange-correlation functionals. Guests with alkyl or alkenyl chains attached to the diamide carbonyl groups have a significantly higher binding affinity to the macrocycle than guests with benzoyl amides and their substituted analogues. While the binding of the benzoyl and alkenyl substituted axles is enthalpically driven, the alkyl-substituted guest binds mainly because of a positive binding entropy. The electronic effects of para-substituents at the benzoyl moieties have an influence on the binding affinities. Electron donating substituents increase, while electron-withdrawing substituents decrease the binding energies. The binding affinities obtained from both NMR titration and ITC experiments correlate well with each other. The substituent effects observed in the experimental data are reflected in adiabatic interaction energies calculated with density functional methods. The calculated structures also agree well with pseudorotaxane crystal structures. 相似文献