| 1. |
- Matxain, Jon M., et al.
(författare)
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Evidence of High dot OH Radical Quenching Efficiency by Vitamin B-6
- 2009
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Ingår i: Journal of Physical Chemistry B. - Washington, D. C. : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 113:29, s. 9629-9632
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Tidskriftsartikel (refereegranskat)abstract
- Molecules acting as antioxidants capable of scavenging reactive oxygen species (ROS) are of the utmost importance in the living cell. The antioxidative properties of pyridoxine (vitamin B6) have recently been discovered. Previous theoretical calculations have shown a high reactivity of pyridoxine toward hydroxyl radicals, where the latter preferably abstract H from either carbon of the two methanol substituents (C8 or C9). In this study, we have explored the reactivity of pyridoxine toward further hydroxyl radicals, considering as the first step the H abstraction from either C8 or C9, also including addition reactions and cyclization. Many of the reactions display similar ΔG, and hence, the quenching of hydroxyl radicals by pyridoxine may undergo different pathways leading to a mix of products. In addition, we observe that pyridoxine, under high hydroxyl radical concentrations, may scavenge up to eight radicals, supporting its observed high antioxidant activity.
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| 2. |
- Matxain, Jon M., et al.
(författare)
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Theoretical study of the antioxidant properties of pyridoxine
- 2006
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Ingår i: Journal of Physical Chemistry A. - Washington, DC : American Chemical Society. - 1089-5639 .- 1520-5215. ; 110:48, s. 13068-13072
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Tidskriftsartikel (refereegranskat)abstract
- Molecules acting as antioxidants capable of scavenging reactive oxygen species (ROS) are of utmost importance in the living cell. The antioxidative properties of pyridoxine (vitamin B6) have recently been discovered. In this study, we have analyzed the reactivity of pyridoxine toward the ROS .OH, .OOH, and .O2- at the density functional theory level (functionals B3LYP and MPW1B95). Two reaction types have been studied as follows: addition to the aromatic ring atoms and hydrogen/proton abstraction. Our results show that .OH is the most reactive species, while .OOH displays low reactivity and .O2- does not react at all with pyridoxine. The most exergonic reactions are those where .H is removed from the CH2OH groups or the ring-bound OH group and range from -33 to -39 kcal/mol. The most exergonic addition reactions occur by attacking the carbon atoms bonded to nitrogen but with an energy gain of only 6 kcal/mol.
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| 3. |
- Matxain, Jon M, et al.
(författare)
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Theoretical study of the reaction of vitamin B6 with 1O2
- 2007
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Ingår i: Chemistry - A European Journal. - Weinheim : Wiley-VCH Verlag. - 0947-6539 .- 1521-3765. ; 13:16, s. 4636-42
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Tidskriftsartikel (refereegranskat)abstract
- Singlet oxygen is known to cause oxidative stress in cells, leading to severe damage (e.g., lipid peroxidation, membrane degradation, mutagenic alterations to DNA, protein misfunctionality). Recently, pyridoxine has been discovered to be capable of quenching singlet oxygen, however, the mechanism of this reaction remains essentially unknown. In this work, we have investigated four sets of reactions: 1) 1,3-addition to a double bond connected to a hydrogen-carrying group,resulting in the formation of allylic hydroperoxides; 2) [p2+p2] 1,2-cycloaddition to an isolated double bond, resulting in the formation of 1,2-peroxides; 3) 1,4-cycloaddition to a system containing at least two conjugated double bonds, resulting in the formation of the so-called 1,4-peroxides;4) 1,4-addition to phenols and naphthols with the formation of hydroperoxide ketones. Thermodynamically, reaction 4 and the 6(9), 3(8), and 5(8) cases of reaction 1 are the most exergonic ones, with energies ranging from 16 to 18 kcalmol 1. Furthermore, reaction 4 shows the lowest barrier through the reaction path, and is predicted to be the preferred mechanismfor the pyridoxine + singlet-oxygen reaction, which is in agreement with previous experimental results.
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| 4. |
- Ristilä, Mikael, et al.
(författare)
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pH-dependent electronic and spectroscopic properties of pyridoxine (vitamin B6)
- 2006
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Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 110:33, s. 16774-16780
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Tidskriftsartikel (refereegranskat)abstract
- The key electronic and spectroscopic properties of vitamin B6 (pyridoxine) and some of its main charged and protonated/deprotonated species are explored using hybrid density functional theory (DFT) methods including polarized solvation models. It is found that the dominant species at low pH is the N1-protonated form and, at high pH, the O3¢-deprotonated compound. Computed and experimental UV-spectra for these species (experimental spectra recorded at pH 1.7 and 11.1, respectively) show a very close resemblance. At pH 4.3, the protonated species dominates, but with onset of the zwitterionic oxo form which is also the dominant species at neutral pH. The computational studies furthermore show that neither a polarized continuum model of the polar aqueous solvent or explicit hydrogen bonding through additional water molecules are sufficient to describe accurately the spectrum at physiological pH. Instead, Na+ and Cl- counterions were required to give a blue-shift of approximately 0.15 eV.
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| 5. |
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| 6. |
- Ristilä, Mikael, et al.
(författare)
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The role of the pyridoxine (vitamin B6) biosynthesis enzyme PDX1 in ultraviolet-B radiation responses in plants
- 2011
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Ingår i: Plant physiology and biochemistry (Paris). - Amsterdam : Elsevier. - 0981-9428 .- 1873-2690. ; 49:3, s. 284-292
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Tidskriftsartikel (refereegranskat)abstract
- Ultraviolet-B radiation regulates plant growth and morphology at low and ambient fluence rates but can severely impact on plants at higher doses. Some plant UV-B responses are related to the formation of reactive oxygen species (ROS) and pyridoxine (vitamin B6) has been reported to be a quencher of ROS. UV-B irradiation of Arabidopsis Col-0 plants resulted in increased levels of PDX1 protein, compared with UV-A-exposed plants. This was shown by immunoblot analysis using specific polyclonal antibodies raised against the recombinant PDX1.3 protein and confirmed by mass spectrometry analysis of immunoprecipitated PDX1. The protein was located mainly in the cytosol but also to a small extent in the membrane fraction of plant leaves. Immunohistochemical analysis performed in pea revealed that PDX1 is present in UV-B-exposed leaf mesophyll and palisade parenchyma but not in epidermal cells. Pyridoxine production increased in Col-0 plants exposed to 3 days of UV-B, whereas in an Arabidopsis pdx1.3 mutant UV-B did not induce pyridoxine biosynthesis. In gene expression studies performed after UV-B exposure, the pdx1.3 mutant showed elevated transcript levels for the LHCB1*3 gene (encoding a chlorophyll a/b-binding protein of the photosystem II light-harvesting antenna complex) and the pathogenesis-related protein 5 (PR-5) gene, compared with wild type.
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| 7. |
- Ristilä, Mikael
(författare)
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Vitamin B6 as a potential antioxidant : a study emanating from UV-B-stressed plants
- 2006
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Increased influx of solar UV-B radiation (280-320 nm), due to a decreasing stratospheric ozone layer, impacts severely on plants. Some of the UV-B effects on plants are related to stress induced by produced reactive oxygen species (ROS). Pyridoxine (vitamin B6) has been reported to be a potential quencher of ROS.Previous studies have shown that the PDX1.3 gene (encoding a key enzyme in vitamin B6 biosynthesis) is up-regulated by UV-B. We showed that this up-regulation also occurs at the protein level in UV-B exposed Col-0 wild-type plants. Studies performed using pdx1 knock-out mutants of Arabidopsis thaliana showed elevated transcripts levels for LHCB1*3 and PR-5 compared with the Col-0 wild-type. The pdx1 knock-out mutants showed an increased sensitivity towards H2O2-stress, but no increased sensitivity towards low dose UV-B-stress.To study the postulated role of pyridoxine as quencher of ROS in more detail, both theoretical and experimental studies were performed. Theoretical and experimental UV absorption spectra obtained at different protonation/deprotonation states of pyridoxine showed a very close resemblance at low and high pH. However, for the computational studies at physiological pH addition of counterions were required to accurately describe the experimental spectra.When theoretically studying the reactivity of pyridoxine towards three different ROS, .OH, .OOH and .O2-, the hydroxyl radical (.OH) was shown to be the most reactive species, while the superoxide radical (.O2-) showed no reactivity towards pyridoxine.In order to study the role of G-proteins in UV-B signal transduction pathways, UV-B irradiated G-protein mutants of Arabidopsis thaliana were studied. The regulation of the PDX1.3 gene was not affected in the G-protein mutants, regardless of the developmental stage of the plant. However, the expression of CHS was affected in the Ga subunit mutants.
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