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121.
In this paper a commercial electronic tongue (αAstree, Alpha M.O.S.) was applied for botanical classification and physicochemical characterization of honey samples. The electronic tongue was comprised of seven potentiometric sensors coupled with an Ag/AgCl reference electrode. Botanical classification was performed by PCA, CCA and ANN modeling on 12 samples of acacia, chestnut and honeydew honey. The physicochemical characterization of honey was obtained by ANN modeling and the parameters included were electrical conductivity, acidity, water content, invert sugar and total sugar. The initial reference values for the physicochemical parameters observed were determined by traditional methods. Botanical classification of honey samples obtained by ANN was 100% accurate while the highest correlation between observed and predicted values was obtained for electrical conductivity (0.999), followed by acidity (0.997), water content (0.994), invert sugar content (0.988) and total sugar content (0.979).All developed ANN models for rapid honey characterization and botanical classification performed excellently showing the potential of the electronic tongue as a tool in rapid honey analysis and characterization. The advantage of using such a technique is a simple sample preparation procedure, there are no chemicals involved and there are no additional costs except the initial measurements required for ANN model development. 相似文献
122.
Schade D Kotthaus J Klein N Kotthaus J Clement B 《Organic & biomolecular chemistry》2011,9(14):5249-5259
N(ω)-Hydroxy-L-arginine (NOHA)--the physiological nitric oxide precursor--is the intermediate of NO synthase (NOS) catalysis. Besides the important fact of releasing NO mainly at the NOS-side of action, NOHA also represents a potent inhibitor of arginases, making it an ideal therapeutic tool to treat cardiovascular diseases that are associated with endothelial dysfunction. Here, we describe an approach to impart NOHA drug-like properties, particularly by wrapping up the chemically and metabolically instable N-hydroxyguanidine moiety with different prodrug groups. We present synthetic routes that deliver several more or less highly substituted NOHA derivatives in excellent yields. Versatile prodrug strategies were realized, including novel concepts of bioactivation. Prodrug candidates were primarily investigated regarding their hydrolytic and oxidative stabilities. Within the scope of this work, we essentially present the first prodrug approaches for an interesting pharmacophoric moiety, i.e., N-hydroxyguanidine. 相似文献
123.
Petar T. Todorov Nikola D. Pavlov Boris L. Shivachev Rosica N. Petrova Jean Martinez Emilia D. Naydenova Monique Calmes 《Heteroatom Chemistry》2012,23(2):123-130
Novel racemic and optically active constrained N‐phosphonoalkyl bicyclic β‐amino acids have been synthesized via the Kabachnik–Fields reaction of the (RS) or (R)‐1‐aminobicyclo[2.2.2]octane‐2‐carboxylic acids with paraformaldehyde and benzaldehyde, and the dimethyl‐H‐phosphonate. The structure of obtained compounds was characterized by NMR (1H, 13C, and 31P), LC/MS, and X‐ray diffraction analyses. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:123–130, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20759 相似文献
124.
Veljković J Uzelac L Molčanov K Mlinarić-Majerski K Kralj M Wan P Basarić N 《The Journal of organic chemistry》2012,77(10):4596-4610
Five new (2-adamantyl)naphthol derivatives (5-9, quinone methide precursors, QMP) were synthesized and their photochemical reactivity was investigated by preparative photolyses, fluorescence spectroscopy, and laser flash photolysis (LFP). Excitation of QMP 5 to S(1) leads to efficient excited state intramolecular proton transfer (ESIPT) coupled with dehydration, giving quinone methide QM5 which was characterized by LFP (in CH(3)CN-H(2)O, λ(max) = 370 nm, τ = 0.19 ms). On irradiation of QMP 5 in CH(3)OH-H(2)O (4:1), the quantum yield of methanolysis is Φ = 0.70. Excitation of naphthols QMP 6-8 to S(1) in CH(3)CN leads to photoionization and formation of naphthoxyl radicals. In a protic solvent, QMP 6-8 undergo solvent-assisted PT giving QM6 or zwitterion QM8 that react with nucleophiles delivering adducts, but with a significantly lower quantum efficiency. QMP 9 in a protic solvent undergoes two competitive processes, photosolvolysis via QM9 and solvent-assisted PT to carbon atom of the naphthalene giving zwitterion. QM9 has been characterized by LFP (in CH(3)CN-H(2)O, λ(max) > 600 nm, τ = 0.9 ms). In addition to photogenerated QMs, two stable naphthalene QMs, QM10 and QM11 were synthesized thermally and characterized by X-ray crystallography. QM10 and QM11 do not react with H(2)O but undergo acid-catalyzed fragmentation or rearrangement. Antiproliferative activity of 5-9 was investigated on three human cancer cell lines. Exposure of MCF-7 cells treated with 5 to 300 nm irradiation leads to an enhanced antiproliferative effect, in accordance with the activity being due to the formation of QM5. 相似文献
125.
The electronic charge redistribution and the infrared intensities of the two types of intramolecular hydrogen bonds, O-H···O and O-H···π, of o-hydroxy- and o-ethynylphenol, respectively, together with a set of related intermolecular hydrogen bond complexes are described in terms of atomic charges and charge fluxes derived from atomic polar tensors calculated at the B3LYP/cc-pVTZ level of theory. The polarizable continuum model shows that both the atomic charges and charge fluxes are strongly dependent on solvent. It is shown that their values for the OH bond in an intramolecular hydrogen bond are not much different from those for the "free" OH bond, but the changes are toward the values found for an intermolecular hydrogen bond. The intermolecular hydrogen bond is characterized not only by the decreased atomic charge but also by the enlarged charge flux term of the same sign producing thus an enormous increase in IR intensity. The overall behavior of the charges and fluxes of the hydrogen atom in OH and ≡CH bonds agree well with the observed spectroscopic characteristics of inter- and intramolecular hydrogen bonding. The main reason for the differences between the two types of the hydrogen bond lies in the molecular structure because favorable linear proton donor-acceptor arrangement is not possible to achieve within a small molecule. The calculated intensities (in vacuo and in polarizable continuum) are only in qualitative agreement with the measured data. 相似文献
126.
Howson SE Chmel NP Clarkson GJ Deeth RJ Simpson DH Scott P 《Dalton transactions (Cambridge, England : 2003)》2012,41(15):4477-4483
Optically pure phenylethaniminopyridine (S(C)-L) tris-chelates of Fe(II) and other first row transition metal systems have previously been shown to give exclusively the fac structures in the solid state. Here it is shown by powder X-ray diffraction that the complex [CuL(3)][ClO(4)](2) crystallises exclusively as the mer isomer, although--for a given absolute configuration of the ligand--of the same helicity (Δ/Λ) as that displayed by the other metal complexes. The similar ligand R(C)-L(F), which contains a peripheral (19)F spin label, gave [CuL(F)(3)][ClO(4)](2) which also adopts exclusively the mer structure in the crystal, but is shown by NMR spectroscopy to have a fac:mer ratio of 1:6 in solution at low temperature. Molecular mechanics calculations for a number of isomers and conformers are consistent with the presence of such a mixture of isomers in solution for both complexes. The origin of the difference in behaviour between Fe(II) and Cu(II) is the presence of a Jahn-Teller distortion (and the generally longer M-N bonds) in the Cu(II) complexes. This disturbs intra-ligand π-stacking, leading to the poor fac/mer stereoselectivity while leaving enantioselectivity Δ/Λ apparently unaffected. 相似文献
127.
128.
129.
Synchronization of the minimal models of bursting neurons coupled by delayed chemical or electrical synapses
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The minimal two-dimensional model of bursting neuronal dynamics is used to study the influence of time-delay on the properties of synchronization of bursting neurons. Generic properties of bursting and dependence of the stability of synchronization on the time-lag and the strength of coupling are described, and compared with the two common types of synaptical coupling, i.e., time-delayed chemical and electrical synapses. 相似文献
130.
In this paper, we investigate the problem of classifying feature vectors with mutually independent but non-identically distributed elements that take values from a finite alphabet set. First, we show the importance of this problem. Next, we propose a classifier and derive an analytical upper bound on its error probability. We show that the error probability moves to zero as the length of the feature vectors grows, even when there is only one training feature vector per label available. Thereby, we show that for this important problem at least one asymptotically optimal classifier exists. Finally, we provide numerical examples where we show that the performance of the proposed classifier outperforms conventional classification algorithms when the number of training data is small and the length of the feature vectors is sufficiently high. 相似文献