RESUMEN
In this work, the effect of water uptake on the structural reorganization and elastic properties of three types of biopolymer films was studied. The water-biopolymer interaction for hydroxypropyl cellulose (HPC), gelatin, and cassava starch films prepared from aqueous solutions was studied and compared using Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction, dynamic vapor sorption (DVS), and dynamic mechanical thermal analysis with humidity generator and controller (DMTA) techniques. The FTIR spectral variations due to the water sorption were generalized into two-dimensional (2D) correlation graphs for each biopolymer, and the effect of water on the molecular conformation was compared. The water sorption isotherms were fitted with Guggenheim-Anderson-De Boer (GAB) and D'Arcy and Watt models. The water content in the mono- and multilayers predicted by both models for each biopolymer was discussed and compared. The correlation of the fitted data obtained from the sorption isotherms to the DMTA data allowed us to conclude that the elastic properties of the HPC films depended on the total water content in contrast to the elastic properties of the gelatin and cassava starch films, which decrease only with the appearance of multilayer water.
Asunto(s)
Biopolímeros/química , Celulosa/análogos & derivados , Gelatina/ultraestructura , Almidón/ultraestructura , Agua/química , Rastreo Diferencial de Calorimetría , Celulosa/química , Celulosa/ultraestructura , Elasticidad , Gelatina/química , Manihot/química , Espectroscopía Infrarroja por Transformada de Fourier , Almidón/química , Difracción de Rayos XRESUMEN
About 10% of plant genomes are devoted to cell wall biogenesis. Our goal is to establish methodologies that identify and classify cell wall phenotypes of mutants on a genome-wide scale. Toward this goal, we have used a model system, the elongating maize (Zea mays) coleoptile system, in which cell wall changes are well characterized, to develop a paradigm for classification of a comprehensive range of cell wall architectures altered during development, by environmental perturbation, or by mutation. Dynamic changes in cell walls of etiolated maize coleoptiles, sampled at one-half-d intervals of growth, were analyzed by chemical and enzymatic assays and Fourier transform infrared spectroscopy. The primary walls of grasses are composed of cellulose microfibrils, glucuronoarabinoxylans, and mixed-linkage (1 --> 3),(1 --> 4)-beta-D-glucans, together with smaller amounts of glucomannans, xyloglucans, pectins, and a network of polyphenolic substances. During coleoptile development, changes in cell wall composition included a transient appearance of the (1 --> 3),(1 --> 4)-beta-D-glucans, a gradual loss of arabinose from glucuronoarabinoxylans, and an increase in the relative proportion of cellulose. Infrared spectra reflected these dynamic changes in composition. Although infrared spectra of walls from embryonic, elongating, and senescent coleoptiles were broadly discriminated from each other by exploratory principal components analysis, neural network algorithms (both genetic and Kohonen) could correctly classify infrared spectra from cell walls harvested from individuals differing at one-half-d interval of growth. We tested the predictive capabilities of the model with a maize inbred line, Wisconsin 22, and found it to be accurate in classifying cell walls representing developmental stage. The ability of artificial neural networks to classify infrared spectra from cell walls provides a means to identify many possible classes of cell wall phenotypes. This classification can be broadened to phenotypes resulting from mutations in genes encoding proteins for which a function is yet to be described.
Asunto(s)
Pared Celular/genética , Redes Neurales de la Computación , Zea mays/genética , Algoritmos , Aumento de la Célula , Pared Celular/clasificación , Pared Celular/ultraestructura , Cotiledón/genética , Cotiledón/crecimiento & desarrollo , Cotiledón/ultraestructura , Análisis de Fourier , Genoma de Planta , Hibridación Genética , Modelos Lineales , Mutación , Fenotipo , Espectrofotometría Infrarroja , Zea mays/crecimiento & desarrollo , Zea mays/ultraestructuraRESUMEN
Fourier transform infrared (FT-IR) spectroscopy was used to monitor changes in the secondary structure of wheat prolamins, the main components of gluten, during mechanical deformation in a series of cycles of extension and relaxation. A sample derived from protein bodies isolated from developing grain showed a buildup of persistent beta-sheet structure. In gluten, the ratio of beta-sheet to random and beta-turn structures changed on extension. After the applied force was released, the sample recovered some of its original shape and structure, but the material became stiffer in consecutive extension cycles. The relationship between gluten structure and mechanical properties is discussed in terms of a model in which conversion of beta-turn to beta-sheet structure is a response to extension and a means by which elastic energy is stored in the system.
Asunto(s)
Glútenes/química , Proteínas/química , Espectroscopía Infrarroja por Transformada de Fourier/métodos , Estructura Secundaria de Proteína , Factores de TiempoRESUMEN
Fourier-transform infrared (FT-IR) microspectroscopy was used to investigate both the chemical composition of, and the effects of an applied strain on, the structure of the Chara corallina cell wall. The inner layers of the cell wall are known to have a transverse cellulose orientation with a gradient through the thickness to longitudinal orientation in the older layers. In both the native state and following the removal of various biopolymers by a sequential extraction infrared dichroism was used to examine the orientation of different biopolymers in cell-wall samples subjected to longitudinal strain. In the Chara system, cellulose microfibrils were found to be aligned predominantly transverse to the long axis of the cell and became orientated increasingly transversely as longitudinal strain increased. Simultaneously, the pectic polysaccharide matrix underwent molecular orientation parallel to the direction of strain. Following extraction in CDTA, microfibrils were orientated transversely to the strain direction, and again the degree of transverse orientation increased with increasing strain. However, the pectic polysaccharides of the matrix were not detected in the dichroic difference spectra. After a full sequential extraction, the cellulose microfibrils, now with greatly reduced crystallinity, were detected in a longitudinal direction and they became orientated increasingly parallel to the direction of strain as it increased.
Asunto(s)
Pared Celular/química , Chara/química , Chara/citología , Ácido Edético/análogos & derivados , Carbonatos/química , Carbonatos/farmacología , Extractos Celulares/química , Tamaño de la Célula , Pared Celular/efectos de los fármacos , Cristalografía por Rayos X , Ácido Edético/farmacología , Hidróxidos/química , Hidróxidos/farmacología , Compuestos de Potasio/química , Compuestos de Potasio/farmacología , Espectroscopía Infrarroja por Transformada de Fourier , Estrés MecánicoRESUMEN
Specific strain-induced orientation and interactions in three Acetobacter cellulose composites: cellulose (C), cellulose/pectin (CP) and cellulose/xyloglucan (CXG) were characterized by FT-IR and dynamic 2D FT-IR spectroscopies. On the molecular level, the reorientation of the cellulose fibrils occurred in the direction of the applied mechanical strain. The cellulose-network reorientation depends on the composition of the matrix, including the water content, which lubricates the motion of macromolecules in the network. At the submolecular level, dynamic 2D FT-IR data suggested that there was no interaction between cellulose and pectin in CP and that they responded independently to a small amplitude strain, while in CXG, cellulose and xyloglucan were uniformly strained along the sample length.
Asunto(s)
Acetobacter/química , Celulosa/química , Glucanos , Espectroscopía Infrarroja por Transformada de Fourier/métodos , Xilanos , Pectinas/química , Polisacáridos/químicaRESUMEN
Mid-infrared spectroscopy was used to discriminate between pure beef and beef containing 20% w/w of a range of potential adulterants (heart, tripe, kidney, and liver). Spectra were acquired from raw samples and from samples cooked using two different cooking regimes. Chemometric methods (principal component analysis, partial least squares regression, and linear discriminant analysis) applied to the spectra showed that discrimination between the pure and adulterated sample types was possible, irrespective of cooking regime. The cross-validated classification success rate obtained was approximately 97%. Discrimination between all five sample types (pure beef and beef containing one of each of the four adulterants) at each level of cook was also possible, but became more difficult as the cooking level increased.