Formation and disappearance of aldehydes during simulated gastrointestinal digestion of fried clams.

The formation and disappearance of aldehydes during simulated gastrointestinal digestion (SD) of fried clams was investigated in order to shed light on the underlying mechanism. Results from the thiobarbituric acid reactive substance (TBARS) and fluorometric assays using a specific aldehyde probe indicated that the SD (with lipase) of fried clams initially reduced (at the gastric stage), but subsequently increased (mainly at the intestinal stage) the contents of total aldehydes. Meanwhile, eight specific aldehydes including propanal, acrolein, trans-2-pentenal, hexanal, trans,trans-2,4-octadienal, trans,trans-2,4-decadienal, 4-hydroxy-hexenal and 4-hydroxy-nonenal in the digested meal were determined by using a high-performance liquid chromatography-tandem electrospray ionization mass spectrometry (HPLC-ESI-MS/MS) method. Results indicated that the changes in the trend of the contents of the eight aforementioned aldehydes were similar to those of total aldehydes during SD (with lipase) of fried clams. However, a similar SD process without lipase time-dependently reduced the contents of total and individual aldehydes. Moreover, lipid classes and free fatty acids (FFAs) in the digested meal were determined to reveal the degree of hydrolysis of lipids during the SD process. Results indicated that the SD (with lipase) of fried clams significantly hydrolyzed triacylglycerols (TAG) and polar lipids (PL) and produced FFAs, but the SD process without lipase resulted in negligible lipid hydrolysis. Thus, our results demonstrated a positive correlation between lipid hydrolysis and aldehyde generation during the SD of fried clams. Alternatively, unsaturated FFAs instead of TAG and PL could have served as the main precursors for aldehyde generation due to their high oxidative susceptibility.

Effects of temperature and heating time on the formation of aldehydes during the frying process of clam assessed by an HPLC-MS/MS method.

This study aimed at investigating the formation and accumulation of 16 reactive aldehydes in clam (Ruditapes philippinarum) during oil frying in both the tissue and the oil using an HPLC-ESI-MS/MS methodology. After processing, the accumulation of acrolein, crotonaldehyde, pentanal, trans-2-hexenal, hexanal, trans, trans-2,4-heptadienal, heptanal, nonanal, trans, trans-2,4-decadienal and 4-hydroxy-2-nonenal was most noticeable in both fried clam and frying oil. Most of the aldehyde species showed a time- and temperature-dependent manner of formation and accumulation during frying due to continuous oxidative degradation under conditions employed. However, several species of aldehyde such as acrolein and trans-2-pentenal slightly decreased at higher temperatures and/or longer frying times, which may be due to the imbalance toward disappearance of aldehydes resulting from their evaporation under the extreme conditions. Presence of natural polyphenols in bamboo leaves significantly prevented the formation of aldehydes in both fried clam and frying oil due to their antioxidant activity (P < 0.05).

Stability of resveratrol esters with caprylic acid during simulated in vitro gastrointestinal digestion.

Lipophenols, esterified phenols with fatty acids, have attracted increasing attention because of their better protective effects in lipid-based food matrices from oxidation. However, little is known about their digestion. In this study, the digestive stability of resveratrol (RSV) esters with caprylic acid (RCAPs) in a model gastrointestinal digestion system was evaluated. The results demonstrated that RCAPs were relatively stable without hydrolysis in mouth and gastric phases. However, in the intestinal phase, pancreatic lipase rather than phospholipase A2 could hydrolyze monoester and diesters to free RSV. After 120 min of incubation at 37 °C, 53.68% of monoester and 11.36% of diesters were hydrolyzed. However, no hydrolysis of the triester was noticed. Obviously, the level of hydrolysis of RCAPs was negatively correlated with the degree of substitution. Therefore, it was speculated that RSV in fatty acid ester forms could partially be absorbed by intestinal lumen in the form of free RSV.

Evaluation of the stability of tyrosol esters during in vitro gastrointestinal digestion.

Lipophenols such as tea polyphenol palmitate derivatives (palmitoyl esters of tea polyphenols) have been classified as non-toxic food additives due to their better protective effects on lipidic food matrices from oxidation, but their digestion and absorption have remained unexplored. In this study, the digestive stability of tyrosol acyl esters (TYr-Es) with fatty acids of different chain lengths and different degrees of unsaturation such as C12:0, C14:0, C16:0, C18:0, C18:1, C18:2, and C22:6 was evaluated using an in vitro simulated gastrointestinal tract model containing various digestive enzymes (pancreatin, pancreatic lipase and phospholipase A2). HPLC-UV measurements demonstrated that only pancreatin and pancreatic lipase, but not phospholipase A2, could hydrolyze TYr-Es to free TYr. The degree of TYr-E hydrolysis negatively correlated with the chain length but positively correlated with the degree of unsaturation of their lipid moiety. In addition, the fact that TYr in fatty acid ester forms could be absorbed by the intestinal lumen, at least partially in the form of free TYr, may explain a sustained release behavior of TYr-Es to TYr during the time-course following the digestion process.

Characterization of lipids in three species of sea urchin.

Sea urchin gonad has been regarded as a "healthy" food. Although previous studies have suggested that sea urchin gonad might serve as a potential rich source of long chain omega-3 polyunsaturated fatty acids (n-3 LC-PUFA) enriched phospholipid (PL), the molecular species profile of its PL has rarely been reported. In this study, about 200 molecular species of glycerophospholipid (GP), including glycerophosphocholine, glycerophosphoethanolamine, glycerophosphoserine, glycerophosphoinositol, lysoglycerophosphocholine and lysoglycerophosphoethanolamine, in gonads from three species of sea urchin (Glyptocidaris crenularis, Strongylocentrotus intermedius and Strongylocentrotus nudus) were characterized using tandem mass spectrometry. Most of the predominant GP molecular species contained PUFA, especially eicosapentaenoic acid (EPA). Meanwhile, the sea urchin lipids contained a high proportion of PL (39.45-50.30% of total lipids) and PUFA (34.47-46.56% of total FA). Among PL, phosphatidylcholine (67.88-72.58mol%) was dominant. Considering the high level of PUFA enriched GP, sea urchin gonads provide great potential as health-promoting food for human consumption.

Lipid profiles in different parts of two species of scallops (Chlamys farreri and Patinopecten yessoensis).

Different classes of lipids and phospholipids (PL) as well as fatty acid (FA) compositions, and glycerophospholipid (GP) molecular species in edible parts (adductor muscles) and by-products (gonads and mantles) of scallops Patinopecten yessoensis and Chlamys farreri were characterized. The lipids contained high levels of polyunsaturated FA (PUFA) (20.44-58.81% of total FAs) and PL (54.99-78.26% of total lipids). Among PL, phosphatidylcholine (41.39-51.86 mol%) was dominant. More than 230 GP species belonging to glycerophosphocholine, glycerophosphoethanolamine, glycerophosphoserine, glycerophosphoinositol, lysoglycerophosphocholine, lysoglycerophosphoethanolamine and lysoglycerophosphoinositol were characterized. Individual GP molecular species in different body parts of scallops were also partially quantified. Most of the dominant GP species contained PUFA, especially eicosapentaenoic acid (EPA, 20:5n-3) and docosahexaenoic acid (DHA, 22:6n-3). Considering the high level of PUFA enriched GP, edible parts and by-products (gonads and mantles) of scallops Patinopecten yessoensis and Chlamys farreri provide great potential as health-promoting food for human consumption.

Effect of high hydrostatic pressure and retrogradation treatments on structural and physicochemical properties of waxy wheat starch.

In this study, the effects of high hydrostatic pressure and retrogradation (HHPR) treatments on in vitro digestibility, structural and physicochemical properties of waxy wheat starch were investigated. The waxy wheat starch slurries (10%, w/v) were treated with high hydrostatic pressures of 300, 400, 500, 600MPa at 20°C for 30min, respectively, and then retrograded at 4°C for 4d. The results indicated that the content of slowly digestible starch (SDS) in HHPR-treated starch samples increased with increasing pressure level, and it reached the maximum (31.12%) at 600MPa. HHPR treatment decreased the gelatinization temperatures, the gelatinization enthalpy, the relative crystallinity and the peak viscosity of the starch samples. Moreover, HHPR treatment destroyed the surface and interior structures of starch granules. These results suggest that the in vitro digestibility, physicochemical, and structural properties of waxy wheat starch are effectively modified by HHPR.

Characterization of glycerophospholipid molecular species in six species of edible clams by high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry.

The molecular species of glycerophosphocholine (GPCho), glycerophosphoethanolamine (GPEtn), glycerophosphoserine (GPSer), lysoglycerophosphocholine (LGPCho) and lysoglycerophosphoethanolamine (LGPEtn) from six species of edible clams were characterized by using high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry. At least 435, 453, 468, 443, 427 and 444 glycerophospholipid (GP) molecular species were characterized, respectively, from Cyclina sinensis, Mactra chinensis Philippi, Mactra veneriformis Reeve, Meretrix meretrix, Ruditapes philippinarum and Saxidomus purpurata. Most of the predominant GP molecular species in clam contained polyunsaturated fatty acids (PUFA), mainly eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), indicating that clam is a potential resource of GP enriched PUFA. According to the amount of the major molecular species containing EPA and DHA, Cyclina sinensis was the best fit species for GPCho, Mactra veneriformis Reeve was the best fit species for GPEtn, Mactra chinensis Philippi was the best fit species for GPSer and LGPEtn, and Saxidomus purpurata was the best fit species for LGPCho.

Identification of glycerophospholipid molecular species of mussel (Mytilus edulis) lipids by high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry.

This study was carried out to identify the glycerophosphocholine (GPCho), glycerophosphoethanolamine (GPEtn) and glycerophosphoserine (GPSer) compositions in lipids extracted from mussels using Folch, Bligh-Dyer and methyl-tert-butyl ether (MTBE) methods by high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS). The molecular species of GPCho, GPEtn and GPSer were characterized according to the MS and MS/MS information. A semi-quantitative method using internal standard was established to compare the difference in glycerophospholipids (GP) between samples recovered with different methods. At least 212, 230 and 206 GP species were identified, respectively, from lipids recovered by Folch, Bligh-Dyer and MTBE methods. Most of the abundant GP species in mussels contained EPA and DHA. Some GP species with low content were not present in lipids recovered by the Folch and MTBE methods when compared with that recovered by the Bligh-Dyer method. However, for most GP species in lipids recovered by different methods, no quantitative differences existed.

Insight into Metalized Interfaces in Nano Devices by Surface Analytical Techniques.

Connections between metals and heterogeneous solid state materials form buried interfaces. These ubiquitous structures play an essential role in determining the performances of many nano- and microdevices. However, the information about the chemistry, structure, and properties of these real interfaces is intrinsically difficult to extract by traditional techniques. Therefore, approaches to efficiently discovering metalized interfaces are in high demand. Here, we demonstrate the transformation of nanoscale metal/oxide interface problems into surface problems through a novel metal-hydrogenation detaching method. We applied this technique to study the thickness dependence in Pb(Zr,Ti)O3 (PZT) ferroelectric thin films, a long-standing interface problem in a model metal/insulator device, and this allowed comprehensive surface analytical techniques to be adapted. A nonstoichiometric interfacial layer of 4.1 nm thick with low mass density, low permittivity, and weak ferroelectricity was quantified at the Pt/PZT interface and attributed to the preferential diffusions among the compositional elements. Targeted interface engineering by Pb rebalance led to a substantial recovery of ferroelectric properties. Our results therefore pave the way to a better understanding of metallized interface in ferroelectric and dielectric nanodevices. We hope that more useful information about metalized interfaces of other solid materials could, analogously, be accessed by surface analytical techniques.

Effects of continuous and intermittent retrogradation treatments on in vitro digestibility and structural properties of waxy wheat starch.

The effects of continuous retrogradation (CR) and intermittent retrogradation (IR) treatments under 4 °C and 25 °C or temperature-cycled condition of 4/25 °C on the digestibility and structural properties of waxy wheat starch were investigated. The results indicated that IR treatment under temperature cycles of 4/25 °C (IR-4/25) was more beneficial to the formation of slowly digestible starch (SDS, 42.24%). Moreover, the gelatinisation enthalpy of IR-4/25-treated starch sample was lower than that of CR-4/25-treated sample. Variation in infrared absorbance ratio of 1047 cm(-1)/1022 cm(-1) of IR-treated starch samples was consistent with relative crystallinity. Through retrogradation treatment under 4/25 °C or 4 °C, starch samples exhibited X-ray diffraction pattern of B-type, while CR-25 and IR-25-treated samples showed a mixed A+B type pattern. Besides, the swelling power of CR-4/25-treated starch sample was higher than that of IR-4/25-treated sample. The pasting temperatures of IR-treated starch samples were higher than those of the CR-treated samples.

Effect of repeated retrogradation on structural characteristics and in vitro digestibility of waxy potato starch.

The effects of repeated retrogradation (RR) treatment on the structural characteristics and in vitro digestibility of waxy potato starch were investigated. The cycling times of RR ranging from 1 to 5 were designated as RR-1, RR-2, RR-3, RR-4, and RR-5, respectively. A maximum SDS content (40.41%) was obtained by RR-2 treatment with the time interval of 48h. RR-2-treated starch product exhibited a narrower melting temperature range, a higher onset temperature and a lower melting enthalpy compared with RR-1 treatment. Compared with native starch, X-ray diffraction patterns of treated starches were altered from B-type to C-type. The variation in relative crystallinity of RR-treated starch products was consistent with that in melting enthalpy. Moreover, compared with RR-1-treated starch, a large number of cavities were observed on the surface of RR-2-treated starch product with a time interval of 48h, whereas more smooth regions were found on the surface of RR-5-treated starch product. This study suggested that structural changes of waxy potato starch treated with different cycling times of RR significantly affected the digestibility.

Effect of single-, dual-, and triple-retrogradation treatments on in vitro digestibility and structural characteristics of waxy wheat starch.

The effects of single-retrogradation (SR), dual-retrogradation (DR) and triple-retrogradation (TR) treatments on in vitro digestibility and structural characteristics of waxy wheat starch were investigated. The yield of slowly digestible starch in a DR-treated starch with retrogradation time interval of 48 h reached a maximum of 44.41%. The gelatinization temperature range and gelatinization enthalpy of DR-treated starch samples were the lowest. Moreover, compared with native starch, X-ray diffraction patterns of treated starches were altered from A-type to B-type and relative crystallinity was significantly decreased, which was responsible for the interaction between amylose-amylose and/or amylose-amylopectin chains that may generate more imperfect structures. Scanning electron micrographs revealed that compared with SR-treated and TR-treated starches, the surface of DR-treated starch with a retrogradation time interval of 48 h exhibited a net-like structure with numerous cavities. These results suggest that structural changes of waxy wheat starch by cycled retrogradation treatment significantly affect digestibility, and DR treatment can be used for preparing SDS product.

Effect of temperature-cycled retrogradation on in vitro digestibility and structural characteristics of waxy potato starch.

The effects of temperature-cycled retrogradation treatment on the structural characteristics and in vitro digestibility of waxy potato starch were investigated in this study. The results showed that the maximum yield of slowly digestible starch (SDS) in waxy potato starch reached 38.63% by retrogradation treatment under temperature cycles of 4/25°C for 3 days with an interval of 24h. The starch products prepared under the temperature cycles of 4/25°C exhibited a narrower melting temperature range (Tc-To), a higher melting enthalpy (ΔH) and a higher IR absorbance ratio (1047cm(-1)/1022cm(-1)) than that prepared at a constant temperature of 25°C. Compared to native starch, X-ray diffraction pattern of treated starch was altered from B-type to C-type. Furthermore, the relative crystallinity of the starch products prepared under temperature-cycled retrogradation was the highest. This study suggests that more imperfect crystallites are formed in the crystalline matrix under temperature-cycled retrogradation, resulting in a high yield of SDS.