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The cross-infection effect of 105 polymer samples was studied, using cellulose as a reference test material. In total 14 polymer types were studied, comprising “modern materials” commonly found in historic and artistic collections including: cellulose acetate (CA), cellulose nitrate (CN), poly(vinyl chloride) (PVC), polyurethane (PUR) and a selection of specialised packaging materials used in art and heritage conservation. Polymer samples were placed in glass vials containing a piece of the cellulose reference and vials were sealed before being heated to 80 C for 14 days. The cross-infection effect on the reference cellulose was measured using viscometry to calculate the degree of polymerisation relative to that of a control reference and a classification system of the cross-infection or preservation effect is proposed. Solid phase micro-extraction (SPME)-GC/MS was used to detect and identify the emitted volatile organic compounds (VOCs) from a select number of polymer samples. CN was identified as the polymer with the most severe cross-infection effect while others e.g. polycarbonate (PC) had no effect or even a beneficial effect. Acetic acid was found to be the most characteristic emission detected from the most severely cross-infecting materials

A new analytical method was developed to non-destructively determine pH and degree of polymerisation (DP) of cellulose in fibres in 19 th -20 th century painting canvases, and to identify the fibre type: cotton, linen, hemp, ramie or jute. The method is based on NIR spectroscopy and multivariate data analysis, while for calibration and validation a reference collection of 199 historical canvas samples was used. The reference collection was analysed destructively using microscopy and chemical analytical methods.Partial least squares regression was used to build quantitative methods to determine pH and DP, and linear discriminant analysis was used to determine the fibre type. To interpret the obtained chemical information, an expert assessment panel developed a categorisation system to discriminate between canvases that may not be fit to withstand excessive mechanical stress, e.g. transportation. The limiting DP for this category was found to be 600. With the new method and categorisation system, canvases of 12 Dalí paintings from the Fundació Gala-Salvador Dalí (Figueres, Spain) were non-destructively analysed for pH, DP and fibre type, and their fitness determined, which informs conservation recommendations. The study demonstrates that collection-wide canvas condition surveys can be performed efficiently and non-destructively, which could significantly improve collection management.

Historic parchment is an extremely complex material, not only due to the various methods of production used and various past environmental histories of objects, but also due to its inhomogeneous structure. Many traditional methods of characterisation are empirical, but useful since they have gained recognition by the end-users. In this paper, we investigated the shrinkage temperature of collagen and the influence of lipids contained in parchment on the measurements. While the content of lipids does not seem to significantly affect shrinkage temperature measurements themselves, it strongly affects the decrease of shrinkage temperature of collagen during degradation, and thus its thermomechanical properties. This confirms the high importance of lipid peroxidation during degradation of parchment.While shrinkage temperature determination is a micro-destructive method, we also demonstrated that it is possible to determine this property using near infrared (NIR) spectroscopy based on partial least squares calibration. The root-mean square error of validation (RMSEV), obtained on a set of variously delipidised and degraded samples, was 7 o C, so the method could be used for condition assessment or classification of historic objects. Using a set of 185 historic objects dating from 1200-1800, we also developed a method for non-destructive dating of parchment based on NIR spectroscopy using partial least squares calibration (RMSEV = 72 years), and successfully determined the correct age of a historic charter from the collection of Nationaal Archief, The Netherlands.

Carboxyl functional groups of poly(L-glutamic acid) (PGlu) were modified with a D-(+)-glucosamine (GlcN) by amidation using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM) as a coupling reagent. The coupling reaction was performed in aqueous medium without protection of hydroxyl functional groups of D-(+)-glucosamine. Poly(L-glutamic acid) and GlcN functionalized polyglutamates (P(Glu-GlcN)) were thoroughly characterized by 1D and 2D NMR spectroscopy and SEC-MALS to gain detailed information on their structure, composition and molar mass characteristics. The results reveal successful functionalization with GlcN through the amide bond and also to a minor extent through ester bond formation in position 1 of GlcN. In addition, a ratio between the α-and β-form of glucosamine substituent coupled to polyglutamate repeating units as well as the content of residual dimethoxy triazinyl active ester moiety in the samples were evaluated.

Parchment has been in use for thousands of years and has been used as the writing or drawing support for many important historic works. A variety of analytical techniques is currently used for routine assessment of the degree of denaturation of historic parchment; however, because parchment has a heterogeneous nature, analytical methods with high spatial resolution are desirable. In this work, the use of small-angle X-ray scattering (SAXS) and synchrotron-IR (SR-IR) was examined in conjunction with multivariate data analysis to study degradation of an extended set of historic parchment samples, and particularly to investigate the effect of lipids and the presence of iron gall ink on the degradation processes. In the data analysis, shrinkage temperature, lipid content, sample age, presence of ink and accelerated degradation were included. The analysis of loading factors in partial least-squares regression and principal component analyses based on SAXS, SR-IR and other analytical and descriptive data reveals the effect of lipid removal on diffraction patterns, and lipids are found to cause the degradation process in parchment to accelerate. The effect of iron gall ink is also evident, although the mechanism of ageing is different to that of natural ageing in the absence of ink. In addition, a historic parchment score from ca. 1750 is examined, demonstrating the significant effect of iron gall ink, and lipids and inorganic soiling on its increased degradation.

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BackgroundAt first glance, there appears to be a high degree of similarity between the metabolism of yeast (the Crabtree effect) and human cancer cells (the Warburg effect). At the root of both effects is accelerated metabolic flow through glycolysis which leads to overflows of ethanol and lactic acid, respectively. It has been proposed that enhanced glycolytic flow in cancer cells is triggered by the altered kinetic characteristics of the key glycolytic regulatory enzyme 6-phosphofructo-1-kinase (Pfk). Through a posttranslational modification, highly active shorter Pfk-M fragments, which are resistant to feedback inhibition, are formed after the proteolytic cleavage of the C-terminus of the native human Pfk-M. Alternatively, enhanced glycolysis is triggered by optimal growth conditions in the yeast Saccharomyces cerevisiae. ResultsTo assess the deregulation of glycolysis in yeast cells, the sfPFKM gene encoding highly active human shorter Pfk-M fragments was introduced into pfk-null S. cerevisiae. No growth of the transformants with the sfPFKM gene was observed on glucose and fructose. Glucose even induced rapid deactivation of Pfk1 activities in such transformants. However, Pfk1 activities of the sfPFKM transformants were detected in maltose medium, but the growth in maltose was possible only after the addition of 10 mM of ethanol to the medium. Ethanol seemed to alleviate the severely unbalanced NADH/NADPH ratio in the sfPFKM cells. However, the transformants carrying modified Pfk-M enzymes grew faster than the transformants with the human native human Pfk-M enzyme in a narrow ecological niche with a low maltose concentration medium that was further improved by additional modifications. Interestingly, periodic extracellular accumulation of phenylacetaldehyde was detected during the growth of the strain with modified Pfk-M but not with the strain encoding the human native enzyme.ConclusionsHighly active cancer-specific shorter Pfk-M fragments appear to trigger several controlling mechanisms in the primary metabolism of yeast S. cerevisiae cells. These results suggest more complex metabolic regulation is present in S. cerevisiae as free living unicellular eukaryotic organisms in comparison to metazoan human cells. However, increased productivity under broader growth conditions may be achieved if more gene engineering is performed to reduce or omit several controlling mechanisms.Electronic supplementary materialThe online version of this article (doi:10.1186/s12896-017-0362-5) contains supplementary material, which is available to authorized users.