Acetylation of cellulose - Another pathway of natural cellulose aging during library storage of books and papers.

Gaseous acetic acid is formed under conditions of storage of historic paper objects. Its presence not only promotes hydrolytic cleavage of cellulose, but also causes acetylation of the cellulosic material to very small degree. The acetylation reaction proceeds under ambient conditions and without catalyst. Different analytical methods were used to prove the presence of organic acetates on cellulosic paper matrices. DESI-MS in combination with 2H-isotopic labeling showed the presence of sugar fragments with different acetylation patterns. A method based on Zemplen saponification was applied and worked also in the presence of a large excess of acetic acid and/or inorganic acetates. The acetylation effect was quantified for model papers and original, naturally aged paper samples. While cellulose acetylation was clearly proven to be another general pathway of paper aging, further studies of this acetylation phenomenon are needed with regard to conservational aspects and suitable paper storage conditions.

Cellulose Degradation by Calcium Thiocyanate.

The dissolution process of cellulose aerogels is an important part of their production. However, if the cellulose is severely degraded during the dissolution process, the quality may be low. To evaluate the degradation of cellulose during the dissolution process using calcium thiocyanate, the hydrolysis and oxidation of cellulose were evaluated by the change in absolute molecular weight and by the changes in the content of carboxyl and carbonyl groups introduced into the cellulose hydroxyl group, respectively. A noteworthy hydrolysis phenomenon was found in the cellulose dissolution process. The rate of hydrolysis increased as the number of hydrates in calcium thiocyanate decreased and as the reaction temperature increased. In the case of the reaction with calcium thiocyanate containing six hydrates, the time to reach a 50% loss of the degree of polymerization of cellulose reduced from 196 to 47 min as the reaction temperature was increased from 100 to 120 °C; however, the effect on oxidation was not significant. The Brunauer-Emmett-Teller (BET) surface area reduced as the degree of cellulose polymerization decreased. Therefore, it is necessary to consider how the cellulose degradation occurring during the cellulosic dissolution process can affect the quality of the final cellulose aerogels.

Degradation of cellulose at the wet-dry interface. II. Study of oxidation reactions and effect of antioxidants.

To better understand the degradation of cellulose upon the formation of a tideline at the wet-dry interface when paper is suspended in water, the production of chemical species involved in oxidation reactions was studied. The quantitation of hydroperoxides and hydroxyl radicals was carried out in reverse phase chromatography using triphenylphosphine and terephthalic acid, respectively, as chemical probes. Both reactive oxygen species were found in the tideline immediately after its formation, in the range of micromoles and nanomoles per gram of paper, respectively. The results indicate that hydroxyl radicals form for the most part in paper before the tideline experiment, whereas hydroperoxides appear to be produced primarily during tideline formation. Iron sulfate impregnation of the paper raised the production of hydroperoxides. After hygrothermal aging in sealed vials the hydroxyl radical content in paper increased significantly. When aged together in the same vial, tideline samples strongly influenced the degradation of samples from other areas of the paper (multi-sample aging). Different types of antioxidants were added to the paper before the tideline experiment to investigate their effect on the oxidation reactions taking place. In samples treated with iron sulfate or artificially aged, the addition of Irgafos 168 (tris(2,4-ditert-butylphenyl) phosphate) and Tinuvin 292 (bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate) reduced the concentration of hydroperoxides and hydroxyl radicals, respectively. Tinuvin 292 was also found to considerably lower the rate of cellulose chain scission reactions during hygrothermal aging of the paper.

Deterioration of ancient Korean paper (Hanji), treated with beeswax: a mechanistic study.

In the early 15th century, beeswax coating was applied to some of the cellulosic documents in a futile attempt to better conserve the paper. However, this treatment caused much more severe degradation compared to untreated Hanji. In the current study, the degradation pathway of this beeswax-treated Hanji has been clarified for the first time. The degradation of cellulose was investigated by labeling of oxidized groups combined with gel permeation chromatography, providing profiles of carbonyl and carboxyl groups relative to the molar mass distribution. The beeswax caused purely hydrolytic damage, leading to a decrease in molar mass to about one fifth of the original value. Oxidative degradation, by contrast, did not occur to any significant extent. Hydrolysis was not caused by acids but by microorganism feeding on the beeswax and excreting cellulolytic enzymes, which cause similar cellulose damage patterns. The hydrolytic enzymes were identified by typical metabolites present in the Hanji.