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91.
Nicolis S Zucchelli M Monzani E Casella L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(28):8661-8673
The generation of reactive quinone species (DAQ) from oxidation of dopamine (DA) is involved in neurodegenerative pathologies like Parkinson's disease (A. Borta, G. U. H?glinger, J. Neurochem. 2007, 100, 587-595). The oxidation of DA to DAQ can occur either in a single two-electron process or in two consecutive one-electron steps, through semiquinone radicals, giving rise to different patterns of reactions. The former type of reaction can be promoted by tyrosinase, the latter by peroxidases in the presence of H(2)O(2), which can be formed under oxidative stress conditions. Both enzymes were employed for the characterization of the thiol-catechol adducts formed by reaction of DA and cysteine or glutathione, and for the identification of specific amino acid residues modified by DAQs in two representative target proteins, human and horse heart myoglobin. Our results indicate that the cysteinyl-DA adducts are formed from the same quinone intermediate independently of the mechanism of DA oxidation, and that the hallmark of a radical mechanism is the formation of the cystine dimer. The reactivity of quinone species also controls the DA-promoted derivatization of histidine residues in proteins. However, for the modification of the cysteine residue in human myoglobin, a radical intramolecular mechanism has been proposed, in which the protein acts both as the catalyst and target of the reaction. Most importantly, the modification of myoglobins through DAQ linkages, and in particular by DA oligomers, has dramatic effects on their stability, as it induces protein unfolding and incorporation into insoluble melanic precipitates. 相似文献
92.
Aromí G Bouwman E Burzurí E Carbonera C Krzystek J Luis F Schlegel C van Slageren J Tanase S Teat SJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(35):11158-11166
A highly asymmetric Ni(II) cluster [Ni(4)(OH)(OMe)(3)(Hphpz)(4)(MeOH)(3)](MeOH) (1) (H(2)phpz=3-methyl-5-(2-hydroxyphenyl)pyrazole) has been prepared and its structure determined by means of single-crystal X-ray diffraction by using synchrotron radiation. Variable-temperature bulk-magnetization measurements show that the complex exhibits intramolecular-ferromagnetic interactions leading to a spin ground state S=4 with close-lying excited states. Magnetization and high-frequency EPR measurements suggest the presence of sizable Ising-type magnetic anisotropy, with zero-field splitting parameters D=-0.263 cm(-1) and E=0.04 cm(-1) for the spin ground state, and an isotropic g value of 2.25. The presence of both axial and transverse anisotropy was confirmed through low-temperature specific heat determinations down to 300 mK, but no slow relaxation of the magnetization was observed by AC measurements down to 1.8 K. Interestingly, AC susceptibility measurements down to temperatures as low as 23 mK showed no indication of slow relaxation of the magnetization in 1. Thus, despite the presence of an anisotropy barrier (U approximately 4.21 cm(-1) for the purely axial limit), the magnetization relaxation remains extremely fast down to the lowest temperatures. The estimated quantum tunneling rate, Gamma>0.667 MHz, makes this complex a prime candidate for observation of coherent tunneling of the magnetization. 相似文献
93.
Mosca M Boniglia C Carratù B Giammarioli S Nera V Sanzini E 《Analytica chimica acta》2008,617(1-2):192-195
Some dietary supplements, so-called 'starch-blockers', used to control overweight, are based on the protein concentrate of the kidney bean, known to contain high levels of the alpha-amylase inhibitor phaseolamin, which may hinder the digestion of complex carbohydrates, thereby promoting or supporting weight loss. Currently, methods to determine the levels of alpha-amylase inhibitor are based on the measurement of alpha-amylase activity using colorimetric methods that cannot be applied to dietary supplements because they are complex mixtures of different ingredients that may interfere with the measurement. The aim of this study was to develop an alternative method to determine the level of phaseolamin in dietary supplements, using high-performance anion-exchange chromatography coupled with pulsed amperometric detection (HPAEC-PAD) to measure the amount of maltose resulting from the action of the enzyme porcine alpha-amylase on soluble starch in the presence and absence of the inhibitor. The assay described proved sensitive and accurate for use with both dietary supplements and raw materials. 相似文献
94.
Stefania Capone Iris Kieltsch Oliver Flögel Gerald Lelais Antonio Togni Dieter Seebach 《Helvetica chimica acta》2008,91(11):2035-2056
The new electrophilic trifluoromethylating 1‐(trifluoromethyl)‐benziodoxole reagents A and B (Scheme 1) have been used to selectively attach CF3 groups to the S‐atom of cysteine side chains of α‐ and β‐peptides (up to 13‐residues‐long; products 7 – 14 ). Other functional groups in the substrates (amino, amido, carbamate, carboxylate, hydroxy, phenyl) are not attacked by these soft reagents. Depending on the conditions, the indole ring of a Trp residue may also be trifluoromethylated (in the 2‐position). The products are purified by chromatography, and identified by 1H‐, 13C‐, and 19F‐NMR spectroscopy, by CD spectroscopy, and by high‐resolution mass spectrometry. The CF3 groups, thus introduced, may be replaced by H (Na/NH3), an overall Cys/Ala conversion. The importance of trifluoromethylations in medicinal chemistry and possible applications of the method (spin‐labelling, imaging, PET) are discussed. 相似文献
95.
Viciano-Chumillas M Tanase S Mutikainen I Turpeinen U de Jongh LJ Reedijk J 《Inorganic chemistry》2008,47(13):5919-5929
The synthesis, crystal structure, and magnetic properties of three new manganese(III) clusters are reported, [Mn 3(mu 3-O)(phpzH) 3(MeOH) 3(OAc)] (1), [Mn 3(mu 3-O)(phpzMe) 3(MeOH) 3(OAc)].1.5MeOH (2), and [Mn 3(mu 3-O)(phpzH) 3(MeOH) 4(N 3)].MeOH (3) (H 2phpzH = 3(5)-(2-hydroxyphenyl)-pyrazole and H 2phpzMe = 3(5)-(2-hydroxyphenyl)-5(3)-methylpyrazole). Complexes 1- 3 consist of a triangle of manganese(III) ions with an oxido-center bridge and three ligands, phpzR (2-) (R = H, Me) that form a plane with the metal ions. All the complexes contain the same core with the general formula [Mn 3(mu 3-O)(phpzR) 3] (+). Methanol molecules and additional bridging ligands, that is, acetate (complexes 1 and 2) and azide (complex 3), are at the terminal positions. Temperature dependent magnetic susceptibility studies indicate the presence of predominant antiferromagnetic intramolecular interactions between manganese(III) ions in 1 and 3, while both antiferromagnetic and ferromagnetic intramolecular interactions are operative in 2. 相似文献
96.
Dr. Ali Munaim Yousif Stefania Colarusso Elisabetta Bianchi 《European journal of organic chemistry》2023,26(12):e202300099
Peptide drug discovery often benefits from the large structural diversity permitted by unnatural amino acids (UAAs). Indeed, numerous approved peptide drugs include UAAs in their sequences. Therefore, innovative chemical approaches either to synthesize UAAs or to allow late-stage functionalization of peptides are emerging themes in peptide drug discovery. Thanks to the recent advances in deaminative strategies using alkylpyridiniums salts, often referred to as Katritzky salts, a variety of radical alkylation methods have been developed. In recent years the use of Katritzky salts have become popular in peptide chemistry due to their ease of preparation from a primary amine, which is a predominant functional group in amino acids. This review highlights the progress that has been made by using Katritzky salts in the synthesis of UAAs, late-stage peptide functionalization, and peptide macrocyclization. 相似文献
97.
Corrigendum: Muropeptides in Pseudomonas aeruginosa and their Role as Elicitors of β‐Lactam‐Antibiotic Resistance 下载免费PDF全文
98.
Isothiourea‐Catalysed Acylative Kinetic Resolution of Aryl–Alkenyl (sp2 vs. sp2) Substituted Secondary Alcohols 下载免费PDF全文
Stefania F. Musolino Dr. O. Stephen Ojo Prof. Nicholas J. Westwood Dr. James E. Taylor Prof. Andrew D. Smith 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(52):18916-18922
The non‐enzymatic acylative kinetic resolution of challenging aryl–alkenyl (sp2 vs. sp2) substituted secondary alcohols is described, with effective enantiodiscrimination achieved using the isothiourea organocatalyst HyperBTM (1 mol %) and isobutyric anhydride. The kinetic resolution of a wide range of aryl–alkenyl substituted alcohols has been evaluated, with either electron‐rich or naphthyl aryl substituents in combination with an unsubstituted vinyl substituent providing the highest selectivity (S=2–1980). The use of this protocol for the gram‐scale (2.5 g) kinetic resolution of a model aryl–vinyl (sp2 vs. sp2) substituted secondary alcohol is demonstrated, giving access to >1 g of each of the product enantiomers both in 99:1 e.r. 相似文献
99.
Francesca Scazzocchio Stefania Garzoli Cinzia Conti Claudia Leone Clio Renaioli Federico Pepi 《Natural product research》2016,30(17):1909-1918
Because of the emergence of multi-drug resistance bacteria and fungi, alternatives to conventional antimicrobial therapy are needed. This study aims to evaluate in vitro the antimicrobial activity of: Mirtus communis, Coriandrum sativum, Pelargonium capitatum, Cuminum cyminum, Ocimum basilicum, Citrus aurantium amara, Cymbopogon. winterianus, Cymbopogon martini, Salvia sclarea, Melaleuca alternifolia and Mentha suaveolens essential oils on bacteria and fungi, in relation to their chemical composition. The potential interaction of M. alternifolia (TTO), C. sativum (CDO) and M. suaveolens (EOMS) essential oils when used in combination with gentamicin and fluconazole has been evaluated. The results obtained showed a synergic effect on some bacteria and fungi, with FICI values ≤5. The cytotoxicity of TTO, CDO and EOMS was investigated towards HeLa cells. Only EOMS did not result cytotoxic at the active concentrations on micro-organisms. Further studies are necessary to obtain optimal ratios and dosing regimens for higher therapeutic efficacy and to decrease toxicological profiles. 相似文献
100.