TY - JOUR A1 - Haebel, Sophie A1 - Hejazi, Mahdi A1 - Frohberg, Claus A1 - Heydenreich, Matthias A1 - Ritte, Gerhard T1 - Mass spectrometric quantification of the relative amounts of C6 and C3 position phosphorylated glucosyl residues in starch N2 - The quantification of phosphate bound to the C6 and C3 positions of glucose residues in starch has received increasing interest since the importance of starch phosphorylation for plant metabolism was discovered. The method described here is based on the observation that the isobaric compounds glucose-6-phosphate (Glc6P) and glucose-3- phosphate (Glc3P) exhibit significantly different fragmentation patterns in negative ion electrospray tandem mass spectrometry (MS/MS). A simple experiment involving collision-induced dissociation (CID) MS2 spectra of the sample and the two reference substances Glc3P and Glc6P permitted the quantification of the relative amounts of the two compounds in monosaccharide mixtures generated by acid hydrolysis of starch. The method was tested on well-characterized potato tuber starch. The results are consistent with those obtained by NMR analysis. In contrast to NMR, however, the presented method is fast and can be performed on less than 1 mg of starch. Starch samples of other origins exhibiting a variety of phosphorylation degrees were analyzed to assess the sensitivity and robustness of the method. Y1 - 2008 UR - http://www.sciencedirect.com/science/journal/00032697 SN - 0003-2697 ER - TY - JOUR A1 - Tsukamoto, Junko A1 - Haebel, Sophie A1 - Valenca, Gustavo P. A1 - Peter, Martin G. A1 - FRanco, Telma T. T1 - Enzymatic direct synthesis of acrylic acid esters of mono- and disaccharides N2 - Background: There is an increased need to replace materials derived from fossil sources by renewables. Sugar- cane derived carbohydrates are very abundant in Brazil and are the cheapest sugars available in the market, with more than 400 million tons of sugarcane processed in the year 2007. The objective of this work was to study the prepn. of sugar acrylates from free sugars and free acrylic acid, thus avoiding the previous prepn. of protected sugar derivs., such as glycosides, or activated acrylates, such as vinyl acrylate. Results: Lipase catalyzed esterification of three mono- and two disaccharides with acrylic acid, in the presence or absence of mol. sieves was investigated. The reactions were monitored by high-performance liq. chromatog. (HPLC) and the products were analyzed by matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry. The main products are mono- and diacrylates, while higher esters are formed as minor products. The highest conversion to sugar acrylates was obsd. for the D-glucose and D- fructose, followed by D-xylose and D-maltose. Mol. sieves had no pronounced effect on the conversion. Conclusions: A feasible method is described to produce and to characterize sugar acrylates, including those contg. more than two acrylate groups. The process for prodn. of these higher esters could potentially be optimized further to produce mols. for crosslinking in acrylate polymn. and other applications. The direct enzymic esterification of free carbohydrates with acrylic acid is unprecedented. [on SciFinder (R)]. Y1 - 2008 UR - http://www3.interscience.wiley.com/journal/117946200/grouphome/home.html SN - 0268-2575 ER -