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Deciphering the Non‐Equivalence of Serine and Threonine O‐Glycosylation Points: Implications for Molecular Recognition of the Tn Antigen by an anti‐MUC1 Antibody 下载免费PDF全文
Dr. Nuria Martínez‐Sáez Jorge Castro‐López Jessika Valero‐González Dr. David Madariaga Ismael Compañón Dr. Víctor J. Somovilla Míriam Salvadó Dr. Juan L. Asensio Dr. Jesús Jiménez‐Barbero Dr. Alberto Avenoza Dr. Jesús H. Busto Dr. Gonçalo J. L. Bernardes Dr. Jesús M. Peregrina Dr. Ramón Hurtado‐Guerrero Dr. Francisco Corzana 《Angewandte Chemie (International ed. in English)》2015,54(34):9830-9834
The structural features of MUC1‐like glycopeptides bearing the Tn antigen (α‐O‐GalNAc‐Ser/Thr) in complex with an anti MUC‐1 antibody are reported at atomic resolution. For the α‐O‐GalNAc‐Ser derivative, the glycosidic linkage adopts a high‐energy conformation, barely populated in the free state. This unusual structure (also observed in an α‐S‐GalNAc‐Cys mimic) is stabilized by hydrogen bonds between the peptidic fragment and the sugar. The selection of a particular peptide structure by the antibody is thus propagated to the carbohydrate through carbohydrate/peptide contacts, which force a change in the orientation of the sugar moiety. This seems to be unfeasible in the α‐O‐GalNAc‐Thr glycopeptide owing to the more limited flexibility of the side chain imposed by the methyl group. Our data demonstrate the non‐equivalence of Ser and Thr O‐glycosylation points in molecular recognition processes. These features provide insight into the occurrence in nature of the APDTRP epitope for anti‐MUC1 antibodies. 相似文献
87.
Castro K Pérez-Alonso M Rodríguez-Laso MD Etxebarria N Madariaga JM 《Analytical and bioanalytical chemistry》2007,387(3):847-860
Non-destructive and non-invasive micro-Raman fibre optic and micro-XRF analyses were performed to study a wallpaper from the
beginning of the 19th century. The complementarity of these two non-destructive techniques is shown in this work. The analysed
artwork is considered one of the most beautiful wallpapers ever manufactured according to the catalogues and books; it is
known as Chasse de Compiègne, manufactured by Jacquemart, Paris, in 1812. During the analysis, an unexpected pigment was detected by both analytical techniques:
lead-tin yellow type II. This pigment was used until ca. 1750, when other yellow pigments replaced it, thus it is very difficult
to find it in paintings afterwards. Together with this pigment, red lead, Prussian blue, brochantite, yellow iron oxide, calcium
carbonate, vermilion, carbon black of animal origin (bone black), lead white, and raw and burnt sienna were also determined
by combining the analytical information provided by both techniques. A possible degradation of brochantite to antlerite is
also discussed. 相似文献
88.
Sanz J Raposo JC Larreta J Martinez-Arkarazo I de Diego A Madariaga JM 《Journal of separation science》2004,27(14):1202-1210
Inorganic mercury and methylmercury are determined in natural waters by injecting the filtered samples onto a low cost commercial flow injection system in which an anion exchange microcolumn is inserted after the injection loop (FIA-IE). If hydrochloric acid is used as the carrier solution, the HgCl4(2-) species (inorganic mercury) will be retained by the anion exchanger while the CH3HgCI species (methylmercury) will flow through the resin with negligible retention. Four anion exchangers and seven elution agents were checked, in a batch mode, to search for the best conditions for optimal separation and elution of both species. Dowex M-41 and L-cysteine were finally selected. Mercury detection was performed by cold vapour-electrothermal atomic adsorption spectrometry (HG-ETAAS). Both systems were coupled to perform the continuous on-line separation/detection of both inorganic mercury and methylmercury species. Separation and detection conditions were optimized by two chemometric approaches: full factorial design and central composite design. A limit of detection of 0.4 microg L(-1) was obtained for both mercury species (RSD < 3.0% for 20 microg L(-1) inorganic and methylmercury solutions). The method was applied to mercury speciation in natural waters of the Nerbioi-lbaizabal estuary (Bilbao, North of Spain) and recoveries of more than 95% were obtained. 相似文献
89.
J.A. Carrero N. GoienagaS. Fdez-Ortiz de Vallejuelo G. AranaJ.M. Madariaga 《Spectrochimica Acta Part B: Atomic Spectroscopy》2010
The aim of this work was to demonstrate that an archaeological ceramic piece has remained buried underground in the same stratum for centuries without being removed. For this purpose, a chemometric model based on Principal Component Analysis, Soft Independent Modelling of Class Analogy and Linear Discriminant Analysis classification techniques was created with the concentration of some selected elements of both soil of the stratum and soil adhered to the ceramic piece. Some ceramic pieces from four different stratigraphic units, coming from a roman archaeological site in Alava (North of Spain), and its respective stratum soils were collected. The soil adhered to the ceramic pieces was removed and treated in the same way as the soil from its respective stratum. The digestion was carried out following the US Environmental Pollution Agency EPA 3051A method. A total of 54 elements were determined in the extracts by a rapid screening inductively coupled plasma mass spectrometry method. After rejecting the major elements and those which could have changed from the original composition of the soils (migration or retention from/to the buried objects), the following elements (25) were finally taken into account to construct the model: Li, V, Co, As, Y, Nb, Sn, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Au, Th and U. A total of 33 subsamples were treated from 10 soils belonging to 4 different stratigraphic units. The final model groups and discriminate them in four groups, according to the stratigraphic unit, having both the stratum and soils adhered to the pieces falling down in the same group. 相似文献
90.
Castro K Sarmiento A Maguregui M Martínez-Arkarazo I Etxebarria N Angulo M Barrutia MU González-Cembellín JM Madariaga JM 《Analytical and bioanalytical chemistry》2008,392(4):755-763
A complete study of several English polychromed alabaster sculptures is presented. The support, pigment, and binders were
characterised by combining μEDXRF, μRaman, and FTIR spectroscopies. Among the pigments, minium, vermilion, lead white, carbon
black, red iron oxide, and a degraded green copper pigment were determined, together with gold leaf. The presence of the rare
mineral moolooite (copper oxalate) was also found as a degradation product in the green areas, where weddellite (calcium oxalate
dihydrate) was also determined. These facts, together with degradation of the green copper pigment, suggest microbiological
degradation of the original materials. Remains of glue and a varnish were also determined by FTIR spectroscopy and principal-components
analysis (PCA) of the spectra. Finally, PCA analysis was carried out to confirm whether the pieces came from the same quarry. 相似文献