Microkinetic modeling of the autoxidative curing of an alkyd and oil-based paint model system

Oakley, Lindsay H.; Casadio, Francesca; Shull, Kenneth R.; Broadbelt, Linda J.

doi:10.1007/s00339-015-9363-1

Cited by 22 publications

(22 citation statements)

References 63 publications

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“…Glutamine was detected in all modern samples but not in historic samples, and its deamination products glutamate and 5-oxoproline were detected in higher concentration in all 17 samples, although at much higher concentration in modern than historic samples. Oxidation, which is widely documented in the degradation of oil paintings (Oakley et al 2015 ) and food spoilage (Velasco and Dobarganes 2002 ) also occurs in dental calculus. For example, the ratio of cholesterol and its oxidation product 7-ketocholesterol was reversed between modern and historic calculus, and kynurenin, an oxidation product of tryptophan that is known to accumulate in archaeological bone over time (Cappellini et al 2012 ), was detected in historic calculus while tryptophan was absent.…”

Section: Resultsmentioning

confidence: 99%

The dental calculus metabolome in modern and historic samples

et al. 2017

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IntroductionDental calculus is a mineralized microbial dental plaque biofilm that forms throughout life by precipitation of salivary calcium salts. Successive cycles of dental plaque growth and calcification make it an unusually well-preserved, long-term record of host-microbial interaction in the archaeological record. Recent studies have confirmed the survival of authentic ancient DNA and proteins within historic and prehistoric dental calculus, making it a promising substrate for investigating oral microbiome evolution via direct measurement and comparison of modern and ancient specimens.ObjectiveWe present the first comprehensive characterization of the human dental calculus metabolome using a multi-platform approach.MethodsUltra performance liquid chromatography-tandem mass spectrometry (UPLC–MS/MS) quantified 285 metabolites in modern and historic (200 years old) dental calculus, including metabolites of drug and dietary origin. A subset of historic samples was additionally analyzed by high-resolution gas chromatography–MS (GC–MS) and UPLC–MS/MS for further characterization of metabolites and lipids. Metabolite profiles of modern and historic calculus were compared to identify patterns of persistence and loss.ResultsDipeptides, free amino acids, free nucleotides, and carbohydrates substantially decrease in abundance and ubiquity in archaeological samples, with some exceptions. Lipids generally persist, and saturated and mono-unsaturated medium and long chain fatty acids appear to be well-preserved, while metabolic derivatives related to oxidation and chemical degradation are found at higher levels in archaeological dental calculus than fresh samples.ConclusionsThe results of this study indicate that certain metabolite classes have higher potential for recovery over long time scales and may serve as appropriate targets for oral microbiome evolutionary studies.Electronic supplementary materialThe online version of this article (doi:10.1007/s11306-017-1270-3) contains supplementary material, which is available to authorized users.

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Section: Resultsmentioning

confidence: 99%

The dental calculus metabolome in modern and historic samples

et al. 2017

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“…Drying oils in paintings are composed of triglyceride molecules with unsaturated fatty acid chains that polymerize when exposed to oxygen, forming a rigid crosslinked network once "cured" [2][3][4]. Metal soaps in these networks form by reaction between long alkyl chain, saturated carboxylic acids (fatty acids), naturally present in the binding media, and Zn or Pb oxides or carbonates (white pigments).…”

Section: Introductionmentioning

confidence: 99%

The influence of commercial primed canvases in the manifestation of metal soaps protrusions in Georgia O’Keeffe’s oil paintings

2020

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During a routine condition survey in 2007 at the Georgia O’Keeffe Museum in Santa Fe, micro-protrusions were found scattered across the surfaces of the artist’s oil paintings produced between 1920 and 1950. In many of her works, including Pedernal (1941) and A Man from the Desert (1941), lead soaps were found aggregated at the painting surface, forcing the surrounding paint to deform into pin-sized protrusions. The structure and composition of the protrusions was analyzed to determine why they formed. Microsamples were removed from four of O’Keeffe’s paintings and investigated using a combination of SEM–EDX, GC–MS, and FT-IR. The combined GC–MS and FT-IR results indicate that the protrusions contain primarily lead carboxylates. The results obtained for a series of ground samples removed from four different paintings were then compared with samples collected from a commercially pre-primed canvas roll found in the artist’s house in Ghost Ranch, NM. We identified two different types of canvases: i) a commercially pre-primed canvas and ii) artist primed canvas. This commercially pre-primed canvas roll has a similar morphology to the ground layers in her paintings that contain protrusions additionally these grounds were found to contain an excess of free fatty acids and metal carboxylates (lead soaps) based on a comparison to canvases the artist primed herself. Based on the analytical results from the four paintings and the commercial pre-primed canvas, we concluded that the artist’s use of this particular commercially pre-primed canvas between 1920 and 1950 play an important role in the observed micro-protrusions.

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“…Autoxidation processes with formation of hydroperoxides and their subsequent free-radical transformations with generation of carbon- and oxygen-centered radicals are key reactions in the drying process of oil-based and alkyd paints containing double bonds [ 57 – 61 ].…”

Section: Introductionmentioning

confidence: 99%

Rearrangements of organic peroxides and related processes

Yaremenko¹,

Vil²,

Demchuk³

et al. 2016

Beilstein J. Org. Chem.

193

136

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SummaryThis review is the first to collate and summarize main data on named and unnamed rearrangement reactions of peroxides. It should be noted, that in the chemistry of peroxides two types of processes are considered under the term rearrangements. These are conventional rearrangements occurring with the retention of the molecular weight and transformations of one of the peroxide moieties after O–O-bond cleavage. Detailed information about the Baeyer−Villiger, Criegee, Hock, Kornblum−DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given. Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related processes of important natural and synthetic peroxides are discussed separately.

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Microkinetic modeling of the autoxidative curing of an alkyd and oil-based paint model system

Cited by 22 publications

References 63 publications

The dental calculus metabolome in modern and historic samples

The dental calculus metabolome in modern and historic samples

The influence of commercial primed canvases in the manifestation of metal soaps protrusions in Georgia O’Keeffe’s oil paintings

Rearrangements of organic peroxides and related processes

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