Evidence of starch inclusion complexation with lactones

Starch, in particular the linear amylose, is able to form inclusion complexes with a wide spectrum of ligand molecules, among them flavor compounds. The complexing ability of a homologous series of gamma- and delta-lactones with potato starch was followed by amperometric iodine titration, differential scanning calorimetry, and wide-angle X-ray diffraction measurements. Lactones with a linear chain of a size > or = C(5) form inclusion complexes with starch, whereas lactones with a short linear chain, such as gamma-heptalactone, show poor complexing ability. The thermal stability of starch-lactone complexes increases with increasing chain length of the lactone. In general, lactones induce the formation of V(h) helices. Only delta-decalactone complexes with starch were not definitely identified as V(h) amylose helices. Complexation of starch dispersions with lactones induce turbidity and gelation or phase separation, both phenomena being the result of microphase separation.     

Behavior of flavor compounds in model food systems: a thermodynamic study

Physicochemical parameters, such as hydrophobicity, water solubility, and volatility, of four flavor compounds (ethyl acetate, ethyl butyrate, ethyl hexanoate, and 2-pentanone) were determined. The amount of flavor compounds released from different model matrices (mineral water, purified triolein, an oil-in-water emulsion, a carbohydrate matrix, and a complex matrix containing lipids and carbohydrates) into the gaseous phase was determined at thermodynamic equilibrium, at 37 degrees C, by static headspace gas chromatography. The degree of interaction between the flavor compounds and the matrix components was shown by measuring the percentage retention using the water matrix as the reference. The partition of flavor compounds was principally dependent on their hydrophobicity. Physicochemical interactions that occurred in the different media led to different degrees of flavor retention. An impact of fat on flavor retention was demonstrated when a water matrix and an oil-in-water matrix or carbohydrate and complex matrices were compared. A carbohydrate impact on flavor compound retention was also detected, which was evident even in the presence of lipids.     

Sorption of volatile flavor compounds by microcellular cereal starch

Wheat starch based microcellular foam (MCF) forms of (dry) starch possess a significant percentage of micropores in the range of 5-14 A. The present study confirmed earlier preliminary studies that MCF starch (in a 0.25-1.0 mm diameter bead form) is effective in sorbing and lowering the headspace partial pressure of many volatile compounds in a manner similar (although less efficient) to that exhibited by other microcavity sorbants such as charcoal. It was found that the proportion of polar compounds sorbed was much greater than the proportion of nonpolar compounds. A major portion of the sorbed volatile compound was readily displaced from the MCF microcellular starch by the addition of water. These properties make this form of edible starch a potential useful carrier of flavor compounds for dried foods.     

Transcriptome profiling of heat-resistant strain Bacillus licheniformis CGMCC3962 producing Maotai flavor

Although Maotai flavor liquor is exclusive due to its soy sauce flavor, knowledge of its key compound and production mechanism is still scarce until now. To gain insight into the production mechanism of soy sauce flavor, a soy sauce flavor producing strain with high efficiency and heat-resistant capability was obtained, and the metabolic mechanism of the strain was investigated with the technique of microarray profiling. Because high temperature was a key factor for soy sauce flavor production, the global gene expression of this heat-resistant strain fermented at 55 °C was analyzed. Except for the responsive increase of heat shock proteins, which maintained cell survival during heat stress, biosynthesis of cysteine was also up-regulated. In addition, some metabolites were significantly increased when cysteine was added to the fermentation medium, such as 2,3-butanediol, 3-hydroxy-2-butanone, and tetramethylpyrazine, which were important flavor compounds in soy sauce flavor liquor and might be related with soy sauce flavor. The results indicated that cysteine might play an important role in the formation of soy sauce flavor compound, and it might act as an indirect precursor or stimulator of soy sauce flavor formation. This was the first use of the microarray profiling tool to investigate the fermentative strains for Chinese traditional liquor, which would allow a deeper insight into the mechanism of the formation of soy sauce flavor compound.     

Effect of cultivar and storage time on the volatile flavor components of baked potato

Tubers of five cultivars of potato were stored at 4 degrees C for 2, 3, and 8 months and baked in a conventional oven. The flavor compounds from the baked potato flesh were isolated by headspace adsorption onto Tenax and analyzed by gas chromatography-mass spectrometry. On a quantitative basis, compounds derived from lipid and Maillard reaction/sugar degradation dominated the flavor isolates, with sulfur compounds, methoxypyrazines, and terpenes making smaller contributions. Levels of 37 of the >150 detected compounds were monitored in each cultivar with time of storage. Many significant differences were found in levels of individual compounds, compound classes, and total monitored compounds for the individual effects of cultivar and storage time and for their two-way interaction. Differences may be explained by variations in levels of flavor precursors and activities of enzymes mediating flavor compound formation among cultivars and storage times. In addition, differences in agronomic conditions may partly account for variations among cultivars. Overall, of the compounds monitored, those most likely having the greatest flavor impact were 2-isopropyl-3-methyoxypyrazine, 2-isobutyl-3-methoxypyrazine, dimethyl trisulfide, decanal, and 3-methylbutanal, with methylpropanal, 2-methylbutanal, methional, and nonanal also being probable important contributors to flavor.     

Complexation of several benzimidazole-type fungicides with alpha- and beta-cyclodextrins

The potential increase in water solubility of three benzimidazole-type fungicides (thiabendazole, carbendazim, and fuberidazole) due to complexation with alpha- and beta-cyclodextrins was investigated. Fluorescence emission spectra of the fungicides in the presence of different concentrations of the cyclodextrins were measured. Analysis of these spectra by the method of principal components global analysis (PCGA) yielded precise values for the association constants and the emission spectra of the fungicide-cyclodextrin inclusion complexes. Phase-solubility diagrams confirmed the formation of inclusion complexes between each of the fungicides and beta-cyclodextrin and showed significant increases of their solubilities due to complexation.     

Effects of Heat-Moisture Treatment and Lipids on Gelatinization and Retrogradation of Maize and Potato Starches

Effects of heat-moisture treatment (HMT) and lipids on the structure and gelatinization of maize and potato starches were studied, and the retrogradation process of 20% HMT starch gels was also investigated. Maize starch was physically modified by HMT or by defatting. Potato starch was physically modified by HMT or by adding monoglycerides. The X-ray pattern of the HMT maize starch was assigned to a combination of A and V patterns, which indicated that HMT formed crystallized amylose complexes and recrystallized amylose in maize starch granules. However, the X-ray pattern of defatted maize starch did not change for HMT, so the lipids originally existing in starch granules were important to the formation of new crystallites during this treatment. Differential scanning calorimetry (DSC) results suggested that weaker structures in amylopectin crystallites were more susceptible to degradation after HMT, while crystallized amylose complexes developed thermal stability after treatment. The amylose contents increased with increasing degree of HMT, which suggested that the newly created amylose arose from exterior linear chains of amylopectin degraded by the treatment. Investigation of retrogradation process showed that HMT significantly promoted retrogradation of starch gels, especially the initiation of recrystallization.     

Characterization of inclusion complexation between fenoxaprop-p-ethyl and cyclodextrin

Cyclodextrins (CDs) derived from natural starches are capable of forming inclusion complexes with a variety of organic compounds. This work evaluated the complexation role of CDs toward fenoxaprop-p-ethyl (FE) in an attempt to assess their potential as new formulation additives for more efficient FE delivery and better environmental approaches. beta-CD and its two derivatives, randomly methylated beta-CD (RAMEB) and 2-hydroxypropyl beta-CD (HP-beta-CD), were tested. The solubility of FE was enhanced in the presence of the CDs due to the formation of inclusion complexes, with RAMEB being >6 times more effective than the other two. The complexation was confirmed by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD), where the FE melting peaks in DSC, the FTIR bands, and the XRD peaks were generally weakened. Within the tested time up to 60 min, the dissolution of the FE-CD complexes resulted in higher FE concentrations than did that of FE by itself. The dissolution of the FE-RAMEB complex was much faster than other complexes and FE alone. These results indicate that RAMEB was a better inclusion complexation agent for FE in terms of both solubility enhancement and dissolution rate. RAMEB may thus be used to improve FE delivery and to mobilize FE in soil for bioremediation.     

Effect of flavor compound chemical structure and environmental relative humidity on the binding of volatile flavor compounds to dehydrated soy protein isolates

Influence of flavor compound chemical structure, including functional group and stereochemistry, and environmental relative humidity (RH) on the binding of volatile flavor compounds to dehydrated soy protein isolates (SPIs) was evaluated by inverse gas chromatography. Binding of selected volatile flavor compounds differed slightly between SPIs of different origins. Results showed that the flavor compound chemical structure greatly determined its binding potential to SPIs. Binding of nonpolar flavor compounds (hydrocarbon) to soy proteins was attributed mainly to nonspecific van der Waals dispersion forces and was not affected by adsorbed water. The more polar flavor compounds (ester, ketone, aldehyde, and alcohol) exhibited both specific (hydrogen bonding, dipole forces) and nonspecific interactions, and their binding with soy proteins was greatly impaired by adsorbed water in the extremely low humidity region (approaching 0% RH). Further water uptake in the 30 to 50% RH region did not significantly affect the binding of polar compounds, although sorption of alcohol compounds (when present at high levels) further increased.     

The effect of solvent interactions on alpha-, beta-, and gamma-cyclodextrin/flavor molecular inclusion complexes

Three commonly used flavor industry solvents (propylene glycol, triacetin, and triethyl citrate) were tested for their capacity to interfere with the ability of alpha-, beta-, and gamma-cyclodextrin to form molecular inclusion complexes with flavors. Six flavor compounds (ethyl butyrate, ethyl heptanoate, l-menthol, methyl anthranilate, neral, and geranial) were measured by headspace gas chromatography above 2:1 water/ethanol containing appropriate additions of cyclodextrin and flavor solvent. The smallest and most polar solvent molecule represented by propylene glycol had the least effect on cyclodextrin/flavorant complex formation. In contrast, triacetin, intermediate in size among the three flavor diluents studied, had the greatest effect, even though, based on at least some computed molecular parameters, it appears to be more polar than triethyl citrate. The explanation for this apparent anomaly may lie in differences in the extent to which triacetin and triethyl citrate are able to interact with cyclodextrins by means of partial interaction with the hydrophobic cavities of the latter.     

Effect of Complexation Temperature on Thermal Properties and Enzymatic Hydrolysis of Starch–Oleic Acid Complexes

The effect of complexation temperature (30, 60, and 90°C) on the gelatinization properties, glass transition, enzymatic hydrolysis, and crystalline structure of high‐amylose corn starch–oleic acid (HACS‐OA) complexes created by a dimethyl sulfoxide (DMSO)‐based complexation method and of normal corn starch–oleic acid (NCS‐OA) complexes created by an alkaline‐based complexation method were investigated by using differential scanning calorimetry, thermogravimetric analysis, and X‐ray diffractometry. The results indicated that the highest complex indices were found in the complexes created at 30 and 60°C with the DMSO‐based complexation method and alkaline‐based complexation method, respectively. The X‐ray diffraction patterns of both HACS‐OA complexes and NCS‐OA complexes created at different complexation temperatures were the V‐type pattern. For the complexes created by the two methods, both the melting temperature and the glass transition temperature increased obviously with increasing complexation temperature. Complexation temperature also influenced the enzymatic hydrolysis rate of starch‐OA complexes.     

Complexation of several fungicides with beta-cyclodextrin: determination of the association constants and isolation of the solid complexes

The formation of inclusion complexes with beta-cyclodextrin was studied for several popular fungicides of different types: prochloraz, 2-phenylphenol, thiophanate methyl, 8-hydroxyquinoline, and benalaxyl. Phase solubility diagrams showed that in all cases complexation takes place, leading to an important increase of water solubility in prochloraz and benalaxyl. Equilibrium association constants could be determined from the phase solubility data and from NMR titrations in the case of 2-phenylphenol. Because of the low solubility of the complex formed between 8-hydroxyquinoline and beta-cyclodextrin, the corresponding association constant could not be determined. The solid complexes of fungicide-cyclodextrin were prepared and isolated by different methods. The isolation of real complexes and not physical mixtures was confirmed in the cases of prochloraz, 2-phenylphenol, and benalaxyl by differential scanning calorimetry.     

气流粉碎对玉米淀粉结构及理化性质的影响

为研究气流粉碎对玉米淀粉结构及理化性质的影响,该文以普通玉米淀粉为原料,通过流化床气流粉碎处理,采用扫描电子显微镜、偏光显微镜、粒度分析仪、X-射线衍射仪、红外光谱仪、差示扫描量热仪、快速黏度分析仪等分析手段研究经微细化处理前后玉米淀粉颗粒形貌、晶体结构、热力学特性、糊化特性、溶解度和膨胀度、冻融稳定性、持水能力等结构及性质的变化。结果表明,微细化处理后,淀粉颗粒形变的不规则,粒径明显减小,中位径(D50)由14.37μm减小到5.25μm,偏光十字减少,相对结晶度由33.43%降低至15.46%,淀粉颗粒结晶结构被破坏,由多晶态向无定形态转变,粉碎过程淀粉无新的基团产生;热焓值、糊化温度均降低,热糊稳定性好;溶解度、膨胀度均升高,持水能力增加,冻融稳定性好,产生较好的热糊稳定性和冷糊力学稳定性,该研究为玉米淀粉的深度加工与应用提供了理论依据及技术支撑。     

Preparation and characterization of inclusion complex of iprodione and beta-cyclodextrin to improve fungicidal activity

The effect of beta-cyclodextrin (beta-CD) on the improvement of the fungicidal activity of iprodione has been investigated. The inclusion complexation of beta-CD with iprodione has been prepared and characterized by integrating some analytical techniques (such as electrospray ionization-mass spectrometry, differential scanning calorimetry, thermogravimetry, x-ray diffraction, and scanning electron microscopy) and molecular simulation methods. The beta-CD/iprodione inclusion complex has exhibited different spectroscopic features and properties from iprodione. The stoichiometric ratio and stability constant describing the extent of formation of inclusion complexes have been determined by phase solubility studies. The calculated apparent stability constant of the iprodione/beta-CD complex was 407.5 M-1. The obtained inclusion complexes were found to significantly improve the water solubility of iprodione, and there is a 4.7-fold increase in the presence of 13 mM beta-CD as compared with the solubility of iprodione in deionized water in the absence of beta-CD. The bioassay demonstrated that the complex displayed over two-fold increase of the fungicidal activity. In addition, the possible structure of the beta-CD/iprodione complex was proposed according to the results of the molecular dynamic simulation. The present study provided useful information for a more rational application of iprodione, diminishing the use of organic solvents and increasing its efficacy.     

Effect of Partial Gelatinization and Lipid Addition on α‐Amylolysis of Barley Starch Granules

The effect of partial gelatinization with and without lipid addition on the granular structure and on α‐amylolysis of large barley starch granules was studied. The extent of hydrolysis was monitored by measuring the amount of soluble carbohydrates and the amount of total and free amylose and lipids in the insoluble residue. Similarly to the α‐amylolysis of native large barley starch granules, lipid‐complexed amylose (LAM) appeared to be more resistant than free amylose and amylopectin. Partial gelatinization changed the hydrolysis pattern of large barley starch granules; the pinholes typical of α‐amylase‐treated large barley starch granules could not be seen. Lipid addition during partial gelatinization decreased the formation of soluble carbohydrates during α‐amylolysis. Also free amylose remained in the granule residues and mostly amylopectin hydrolyzed into soluble carbohydrates. These findings indicate that lysophospholipid (LPL) complexation with amylose occurred either during pretreatment or after hydrolysis, and free amylose was now part of otherwise complexed molecules instead of being separate molecules. Partial gelatinization caused the granules to swell somewhat less during heating 2% starch‐water suspensions up to 90°C, and lipid addition prevented the swelling completely. α‐Amylolysis changed the microstructure of heated suspensions. No typical twisting of the granules was seen, although the extent of swelling appeared to be similar to the reference starch. The granules with added LPL were partly fragmented after hydrolysis.     

Dynamic flavor release from sucrose solutions

The initial dynamic flavor release from sucrose solutions was modeled. Modeling was based on the theoretical hydration behavior of sucrose, theoretical physicochemical data of flavor volatiles, and process parameters of a headspace apparatus used for model validation. The rate-limiting factor determining the initial flavor release was the hydration of sucrose, which in turn depends on the molarity of sucrose in the solution and, therefore, on the actual amount of nonbound water. Improved solubility of the more hydrophilic compounds due to their orientation toward the hydration shells of the sugar molecules was considered. The viscosity of nonassociated water forming the microregion for mass transfer of volatiles was considered instead of the bulk solution viscosity. Experimental validation of the model by real-time measurements of dynamic flavor release using foodlike flavor concentrations confirmed the above theory. Increasing sucrose concentrations resulted predominantly in increased flavor release, and bulk solution viscosity showed no effect.     

Furfural-cysteine model reaction in food grade nonionic oil/water microemulsions for selective flavor formation

The thermal reaction between cysteine and furfural was investigated at 65 degrees C in five-component food grade oil/water (O/W) microemulsions of R-(+)-limonene/ethanol, EtOH/water/propylene glycol, PG/Tween 60 as apart of a systematic study on the generation of aroma compounds by utilizing structured W/O and O/W fluids. The furfural-cysteine reaction led to the formation of unique aroma compounds such as 2-furfurylthiol (FFT), 2-(2-furanyl)thiazolidine (main reaction product), 2-(2-furanyl)thiazoline, and N-(2-mercaptovinyl)-2-(2-furanyl)thiazolidine. These products were determined and characterized by GC-MS. Enhancement in flavor formation is termed "microemulsion catalysis". The chemical reaction occurs preferably at the interfacial film, and therefore a pseudophase model was assumed to explain the enhanced flavor formation. The product internal composition is dictated by process conditions such as temperature, time, pH, and mainly the nature of the interface. Increasing water/PG ratio leads to a dramatic increase in the initial reaction rate (V(0)). V(0) increased linearly as a function of the aqueous phase content, which could be due to the increase in the interfacial concentration of furfural. Microemulsions offer a new reaction medium to produce selective aroma compounds and to optimize their formation.     

桃果实风味物质的研究进展

该文综述了桃果实风味物质的组成、主要组成成分的风味阈值、部分风味物质的气味特征、与风味物质合成有关的酶和前体、低温贮藏条件下桃果实风味物质的变化特点及其与呼吸、乙烯关系的研究进展;并对桃果实风味物质与果实品质相关性进行了分析,对影响桃果实风味物质形成的各种因素及桃果实风味物质的研究方法进行了简要评述。目前已从桃果实中分离到近百种芳香成分,但并非所有芳香成分都能决定果实的特征风味,而只有较少的成分甚至某一种化合物决定特征风味。低温贮藏桃果实易发生冷害,冷害桃果实的重要表现之一是原有的桃风味变淡或丧失,甚至产生异味。不同品种果实所含风味物质不尽相同,桃果实风味物质的形成是一个动态的变化过程,采前和采后处理均可不同程度的对果实风味物质产生影响。     

METAL-COMPLEX FORMATION BY LICHEN COMPOUNDS

The formation of soluble complexes, frequently coloured, when solid lichen compounds were shaken with water suspensions of biotite, granite, and basalt indicated that chemical weathering had occurred. The formation of colourless complexes and the adsorption of the dissolved lichen compound or complex by the silicate phase complicate the interpretation of the spectrophotometric analysis data. Lichen compounds invariably released greater amounts of Ca than of Mg, Fe, and Al from the silicates and, for each lichen compound, the release of Ca was usually greater from biotite than from granite or basalt. Release of cations from the silicate materials resulted largely from metal-complex formation rather than from reactions directly involving hydrogen ions. Citric, salicylic, and phydroxy-benzoic acids and EDTA, used as control organic acids, usually released considerably greater amounts of cations from the silicates than did the lichen compounds, consistent with the higher water solubility of the control organic acids. Similar amounts of Fe, Al, Ca, and Mg were released from the silicates by solutions of the lichen compounds and by solid lichen compounds. Lichen compounds are sufficiently soluble in water to form soluble metal complexes and to effect chemical weathering of minerals and rocks.     

Enzyme Susceptibility of High‐Amylose Starch Precipitated from Sodium Hydroxide Dispersions

Type III resistant starch (RS) is understood to be due to the ordered structure formation in the process of retrogradation. Most treatments of granular high‐amylose maize starch (HAMS) do not completely eliminate the original ordered structure. We hypothesized that residual ordered structure would constrain subsequent physical reassociation of chains and the formation of RS. The objective was to generate differences in enzyme susceptibility using two means of precipitation of fully dispersed starch and to relate differences in enzyme susceptibility to the structure of the precipitates. Dispersions in sodium hydroxide were precipitated either with ethanol or ammonium sulfate. RS and the timecourse of digestion were determined. Crystallinity and helicity were estimated using wide‐angle X‐ray diffraction and solid‐state ¹³C CP/MAS NMR, respectively. Precipitation of whole starch with ethanol led to lower RS values (≈24%) than precipitation with ammonium sulfate (≈39%) and also to higher reaction rate constants for an early component of digestion. Ethanol precipitation of a branched starch fraction gave essentially no RS, whereas ammonium sulfate precipitation of the same branched material had >20% RS. Ethanol precipitates contained single helices, in most but not all cases, contributing to V‐type crystallinity. Ammonium sulfate precipitates had double helices contributing to B‐type crystallinity.