The chemistry of 5-oxodihydroisoxazoles .19. The synthesis and photolysis of N-thioacylisoxazol-5(2H)-ones

5-Oxodihydroisoxazoles react with thiocarbonyl chlorides to afford N-thioacylisoxazol-5(2H)-ones which lose carbon dioxide under photochemical conditions and undergo intramolecular cyclisation of the iminocarbene to afford thiazoles, However, in some cases loss of carbon dioxide is accompanied by loss of sulfur, giving 1,3-oxazin-6-ones.

The chemistry of novolac resins .3. C-13 and N-15 nmr studies of curing with hexamethylenetetramine

The reactions between novolac resins and hexamethylenetetramine (HMTA) which occur on curing have been studied by C-13 and N-15 high-resolution n.m.r. in both solution and the solid state. Strong evidence for the existence of many curing intermediates is obtained. New curing intermediates are reported along with experimental data to support previously postulated intermediates. The initial curing reactions between novolac and HMTA produce various substituted benzoxazines and benzylamines. Thermal decomposition/oxidation and further reactions of these initial intermediates generate methylene linkages between phenolic rings for chain extension and cross-linking. Among the three kinds of methylene linkages, the para-para methylene linkages are formed at relatively lower temperatures. Various imine, amide and imide side-products also concurrently appear during the process. The initial amount of HMTA plays a critical role in the curing reactivity and chemical structures of the cured resins. The lower the amount of HMTA, the lower the temperature at which curing occurs, and the lower the amount of the nitrogen-containing side-products in the finally cured resins. The ortho-linked intermediates are relatively stable, and can remain in the cured resins up to higher temperatures. The study provides an extensive description of the curing reactions of novolac resins. (C) 1997 Elsevier Science Ltd.

Phenolics and Antioxidant Properties of Fruit Pulp and Cell Wall Fractions of Postharvest Banana (Musa acuminata Juss.) Cultivars

Banana fruits are important foods, but there have been very few studies evaluating the phenolics associated with their cell walls. In the present study, (+) catechin, gallocatechin, and (-) epicatechin, as well as condensed tannins, were detected in the soluble extract of the fruit pulp; neither soluble anthocyanidins nor anthocyanins were present. In the soluble cell wall fraction, two hydroxycinnamic acid derivatives were predominant, whereas in the insoluble cell wall fraction, the anthocyanidin delphinidin, which is reported in banana cell walls for the first time, was predominant. Cell wall fractions showed remarkable antioxidant capacity, especially after acid and enzymatic hydrolysis, which was correlated with the total phenolic content released after the hydrolysis of the water-insoluble polymer, but not for the posthydrolysis water-soluble polymer. The acid hydrolysis released various monosaccharides, whereas enzymatic hydrolysis released one peak of oligosaccharides. These results indicate that banana cell walls could be a suitable source of natural antioxidants and that they could be bioaccessible in the human gut.

Synthesis of Fructooligosaccharides in Banana `Prata` and Its Relation to Invertase Activity and Sucrose Accumulation

Levels of sucrose and total fructool igosaccha rides (FOS) were quantified in different phases of banana `Prata` ripening during storage at ambient (similar to 19 degrees C) and low (similar to 10 degrees C) temperature. Total FOS levels were detected in the first days after harvest, whereas 1-kestose remained undetectable until the sucrose levels reached approximately 200 mg/g (dry weight) in both groups. Sucrose levels increased slowly but constantly at low temperature, but they elevated rapidly when the temperature was raised to 19 degrees C. Total FOS and sucrose levels were higher in bananas stored at low temperature than in the control group. In both samples, total FOS levels were higher than those of 1-kestose. The carbohydrate profiles obtained by HPLC and TLC suggest the presence of neokestose, 6-kestose, and bifurcose. The enzymes putatively involved in banana fructosyltransferase activity were also evaluated. Results obtained indicate that the banana enzyme responsible for the synthesis of FOS by transfructosylation is an invertase rather than a sucrose-sucrosyl transferase-like enzyme.

Changes in Cell Wall Composition Associated to the Softening of Ripening Papaya: Evidence of Extensive Solubilization of Large Molecular Mass Galactouronides

Papaya (Carica papaya) is a climacteric fruit that undergoes dramatic pulp softening. Fruits sampled at three different conditions (natural ripening or after exposition to ethylene or 1-methylcyclopropene) were used for the isolation of cell wall polymers to find changes in their degradation pattern. Polymers were separated according to their solubility in water, CDTA, and 4 M alkali, and their monosaccharide compositions were determined. Water-soluble polymers were further characterized, and their increased yields in control and ethylene-treated fruit, in contrast to those that were treated with 1-MCP, indicated a strong association between fruit softening and changes in the cell wall water-soluble polysaccharide fraction. The results indicate that the extensive softening in the pulp of ripening papayas is a consequence of solubilization of large molecular mass galacturonans from the pectin fraction of the cell wall. This process seems to be dependent on the levels of ethylene, and it is likely that the releasing of galacturonan chains results from an endo acting polygalacturonase.

Plantain and Banana Starches: Granule Structural Characteristics Explain the Differences in Their Starch Degradation Patterns

Different banana cultivars were used to investigate the influences of starch granule structure and hydrolases on degradation. The highest degrees of starch degradation were observed in dessert bananas during ripening. Scanning electron microscopy images revealed smooth granule surface in the green stage in all cultivars, except for Mysore. The small and round granules were preferentially degraded in all of the cultivars. Terra demonstrated a higher degree of crystallinity and a short amylopectin chain length distribution, resulting in high starch content in the ripe stage. Amylose content and the crystallinity index were more strongly correlated than the distribution of amylopectin branch chain lengths in banana starches. alpha- and beta-amylase activities were found in both forms, soluble in the pulp and associated with the starch granule. Starch-phosphorylase was not found in Mysore. On the basis of the profile of alpha-amylase in vitro digestion and the structural characteristics, it could be concluded that the starch of plantains has an arrangement of granules more resistant to enzymes than the starch of dessert bananas.

Benzylglucosinolate, Benzylisothiocyanate, and Myrosinase Activity in Papaya Fruit during Development and Ripening

Papaya is a climacteric fruit that has high amounts of benzylglucosinolates (BG) and benzylisothiocyanates (BITC), but information regarding levels of BG or BITC during fruit development and ripening is limited. Because BG and BITC are compounds of importance from both a nutritional and a crop yield standpoint, the aim of this work was to access data on the distribution and changes of BG and BITC levels during fruit development and ripening. BG and BITC levels were quantified in peel, pulp, and seeds of papaya fruit. Volatile BITC was also verified in the internal cavity of the fruit during ripening. The influence of the ethylene in BG and BITC levels and mirosinase activity was tested by exposing mature green fruits to ethylene and 1-methylcyclopropene (1-MCP). The highest BG levels were detected in seeds, followed by the peel and pulp being decreased in all tissues during fruit development. Similarly, the levels of BITC were much higher in the seeds than the peel and pulp. The levels of BG for control and ethylene-treated fruit were very similar, increasing in the pulp and peel during late ripening but not changing significantly in seeds. On the other hand, fruit exposed to 1-MCP showed a decrease in BG amount in the pulp and accumulation in seed. The treatments did not result in clear differences regarding the amount of BITC in the pulp and peel of the fruit. According to the results, ethylene does not have a clear effect on BITC accumulation in ripening papaya fruit. The fact that BG levels in the pulp did not decrease during ripening, regardless of the treatment employed, and that papaya is consumed mainly as fresh fruit, speaks in favor of this fruit as a good dietary source for glucosinolate and isothiocyanates.

Ripening-associated changes in the amounts of starch and non-starch polysaccharides and their contributions to fruit softening in three banana cultivars

BACKGROUND: Fruit softening is generally attributed to cell wall degradation in the majority of fruits. However, unripe bananas contain a large amount of starch, and different banana cultivars vary in the amount of starch remaining in ripe fruits. Since studies on changes in pulp firmness carried outwith bananas are usually inconclusive, the cell wall carbohydrates and the levels of starch and soluble cell wall monosaccharides from the pulps of three banana cultivars were analysed at different ripening stages. RESULTS: Softening of Nanicao and Mysore bananas seemed to be more closely related to starch levels than to cell wall changes. For the plantain Terra, cell wall polysaccharide solubilisation and starch degradation appeared to be the main contributors. CONCLUSION: Banana softening is a consequence of starch degradation and the accumulation of soluble sugars in a cultivar-dependent manner. However, contributions from cell wall-related changes cannot be disregarded. (C) 2011 Society of Chemical Industry

Mango starch degradation. I. A microscopic view of the granule during ripening

The starch content of unripe mango Keitt is around 7% (FW), and it is converted to soluble sugars during the ripening of the detached fruit. Despite the importance of starch-to-soluble sugar metabolism for mango quality, little literature is found on this subject and none concerning the physical aspects of starch degradation. This manuscript presents some changes in the physical aspects of the starch granule during ripening, as analyzed by light microscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM). According to the analysis, unripe Keitt-mango-starch being spherical in shape and measuring around 15,mu m, has A-type X-ray diffraction pattern with a degree of crystallinity around 21% with slight changes after 8 days of ripening. AFM images of the surface of the granules showed ultra microstructures, which are in agreement with a blocklet-based organization of the granules. The AFM-contrast image of growing layers covering the granule showed fibril-like structures, having 20 nm in diameter, transversally connecting the layer to the granule. The appearance of the partially degraded granules and the pattern of degradation were similar to those observed as a result of amylase activity, suggesting a hydrolytic pathway for the degradation of starch from mango cultivar Keitt. These results provide clues to a better understanding of starch degradation in fruits.

Mango starch degradation. II. The binding of alpha-amylase and beta-amylase to the starch granule

During mango ripening, soluble sugars that account for mango sweetening are accumulated through carbon supplied by both photosynthesis and starch degradation. The cultivar Keitt has a characteristic dependence on sugar accumulation during starch degradation, which takes place during ripening, only a few days after detachment from the tree. Most knowledge about starch degradation is based on seeds and leaves currently used as models. However, information about the mango fruit is scarce. This work presents the evaluation of alpha- and beta-amylases in the starch granule surface during fruit development and ripening. Extractable proteins were assayed for amylase activity and detected by immunofluorescence microscopy and correlated to gene expression. The results suggest that both amylases are involved in starch degradation during mango ripening, probably under the dependence of another signal triggered by the detachment from the mother-plant.

Identification of fructooligosaccharides in different banana cultivars

Banana has been currently indicated as a good source of fructooligosaccharides (FOS), which are considered to be functional components of foods. However, significant differences in their amounts in bananas have been observed in the literature. This work aims to identify and quantify FOS during ripening in different banana cultivars belonging to the most common genomic groups cultivated in Brazil. Considering that these differences can be due to cultivar, stage of ripening, and the methodologies used for FOS analyses, sugar contents were analyzed by high performance anion exchange chromatography-pulsed amperometric detection (HPAEC-PAD) and gas chromatography-mass spectrometry (GC-MS). An initial screening of eight cultivars (Ouro, Nanicao, Prata, Maca, Mysore, Pacovan, Terra, and Figo) in a full-ripe stage showed that 1-kestose, the first member of the FOS series (amounts between 297 and 1600 mu g/g of DM), was accumulated in all of them. Nystose, the second member, was detected only in Prata cultivar. Five of the cultivars were analyzed during ripening, and a strong correlation could be established with a specific sucrose level (similar to 200 mg/g of DM), which seems to trigger the synthesis of 1-kestose (the low amounts of FOS, below the functional recommended dose, indicates that banana cannot be considered a good source of FOS).

Debaryomyces hansenii UFV-1 Intracellular alpha-Galactosidase Characterization and Comparative Studies with the Extracellular Enzyme

Debaryomyces hansenii cells cultivated on galactose produced extracellular and intracellular alpha-galactosidases, which showed 54.5 and 54.8 kDa molecular mass (MALDI-TOF), 60 and 61 kDa (SDS-PAGE) and 5.15 and 4.15 pI values, respectively. The extracellular and intracellular deglycosylated forms presented 36 and 40 kDa molecular mass, with 40 and 34% carbohydrate content, respectively. The N-terminal sequences of the alpha-galactosidases were identical. Intracellular alpha-galactosidase showed smaller thermostability when compared to the extracellular enzyme. D. hansenii UFV-1 extracellular alpha-galactosidase presented higher k(cat) than the intracellular enzyme (7.16 vs 3.29 s(-1), respectively) for the p-nitrophenyl-alpha-D-galactopyranoside substrate. The K(m) for hydrolysis of pNP alpha Gal, melibiose, stachyose, and raffinose were 0.32, 2.12, 10.8, and 32.8 mM, respectively. The intracellular enzyme was acompetitively inhibited by galactose (K(i) = 0.70 mM), and it was inactivated by Cu(II) and Ag(I). Enzyme incubation with soy milk for 6 h at 55 degrees C reduced stachyose and raffinose amounts by 100 and 73%, respectively.