Improvement of antifungal activity of 10-undecyn-1-ol by inclusion complexation with cyclodextrin derivatives

The inclusion complexation behavior between 10-undecyn-1-ol and cyclodextrin (CD) derivatives, namely, randomly methylated beta-CD (RM-beta-CD) and hydroxypropyl-beta-CD (HP-beta-CD), was studied in terms of solubility improvement, apparent stability constant, and the inclusion ratios of the resultant inclusion complexes. The aqueous solubility of 10-undecyn-1-ol was greatly improved through complexation with the CD derivatives. RM-beta-CD is comparatively more efficient in solubilizing 10-undecyn-1-ol with an apparent stability constant outstripping that of HP-beta-CD by about an order of magnitude. Comparative in vitro evaluations of the growth inhibition effects of inclusion complex solutions toward Rosellinia necatrix, a phytopathogenic fungus, were performed. In comparison with the positive control, appreciable improvements of the antifungal activity of 10-undecyn-1-ol through the addition of CD derivatives were observed visually. The improvement was evaluated in terms of area covered by the mycelia of Rosellinia necatrix and their growth rate. RM-beta-CD was proven to be more effective compared to HP-beta-CD with regard to the reduction of both fungal mycelium-covered area and growth rate constant, presumably owing to greater solubility enhancement by RM-beta-CD and thus the bioavailability of 10-undecyn-1-ol. Inclusion complexation of 10-undecyn-1-ol with CD derivatives suggests a potential means for production of an environmentally friendly 10-undecyn-1-ol-based fungicide to counteract R. necatrix.     

Environmental effects of inclusion complexation between methylated beta-cyclodextrin and diclofop-methyl

Diclofop-methyl (DM) is a broad-spectrum herbicide but often shows a reduced biological activity against the target grasses due to its poor water solubility and slow translocation within plant tissues. Randomly methylated beta-cyclodextrin (MCD) is an effective inclusion complexation agent and, as a potential formulation additive, may thus improve the behavior of DM. We evaluated the complexing role of MCD by measuring the solubility and soil sorption of DM as a function of MCD concentration, as well as the dissolution rates of DM-MCD complexes. The complex was also extensively characterized by UV, fluorescence, Fourier transform infrared, nuclear magnetic resonance, and differential scanning calorimetry techniques. The apparent solubility of DM linearly increased with MCD concentration, indicating the formation of a 1:1 complex. In contrast, diclofop was not complexed by MCD. The DM-MCD complex appeared to have formed within the hydrophobic cavity of MCD. With the measured stability constant of 4740 L mol(-)(1), the complex was apparently stable, which resulted in DM resistant to hydrolysis, and hence the ratio of DM to the sum of DM and diclofop increased toward unity with increasing MCD concentration. The DM-MCD complex also quickly dissolved to a maximum within 5 min, due presumably to the hydrophilicity of MCD. The sorption of DM by soil was significantly reduced in the presence of MCD. All the results suggest that MCD may effectively improve the availability of DM to pests and for bioremediation.     

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.     

Formation of natamycin:cyclodextrin inclusion complexes and their characterization

Natamycin is a broad spectrum antimycotic with very low water solubility, which is used to extend the shelf life of shredded cheese products. beta-Cyclodextrin (beta-CD), hydroxypropyl beta-cyclodextrin (HP beta-CD), and gamma-cyclodextrin (gamma-CD) were found to form inclusion complexes with natamycin in aqueous solution. The increase in solubility of natamycin with added beta-CD was observed to be linear (type A(L) phase solubility diagram). The 1:1 stability constant of natamycin:beta-CD complex was estimated from its phase solubility diagram to be 1010 M(-1). The phase solubility diagrams of both gamma-CD and HP beta-CD exhibited negative deviation from linearity (type A(N) diagram) and, therefore, did not allow the estimation of binding constants. The water solubility of natamycin was increased 16-fold, 73-fold, and 152-fold with beta-CD, gamma-CD, and HP beta-CD, respectively. The natamycin:CD inclusion complexes resulted in in vitro antifungal activity nearly equivalent to that of natamycin in its free state.     

Stability of natamycin and its cyclodextrin inclusion complexes in aqueous solution

Aqueous solutions of natamycin and its beta-cyclodextrin (beta-CD), hydroxypropyl beta-cyclodextrin, and gamma-cyclodextrin (gamma-CD) inclusion complexes were completely degraded after 24 h of exposure to 1000 lx fluorescent lighting at 4 degrees C. After 14 days of storage in darkness at 4 degrees C, 92.2% of natamycin remained in active form. The natamycin:beta-CD complex and natamycin:gamma-CD complex were significantly more stable (p < 0.05) than natamycin in its free state in aqueous solutions stored in darkness at 4 degrees C. Clear poly(ethylene terephthalate) packaging with a UV light absorber allowed 85.0% of natamycin to remain after 14 days of storage under 1000 lx fluorescent lighting at 4 degrees C. Natamycin:cyclodextrin complexes can be dissociated for analysis in methanol/water/acetic acid, 60:40:5, v/v/v. Natamycin and its complexes in dissociated form were quantified by reverse phase HPLC with detection by photodiode array at 304 nm.     

Evolution of toxicity upon hydrolysis of fenoxaprop-p-ethyl

Hydrolysis of fenoxaprop-p-ethyl (FE), a widely used herbicide, was studied in aqueous buffer solutions at pH ranging from 4.0 to 10.0. The degradation kinetics, strongly dependent on pH values, followed first-order kinetics. FE was relatively stable in neutral media, whereas it degraded rapidly with decreasing or increasing pH. In acidic conditions (pH = 4, 5), the benzoxazolyl-oxy-phenyl ether linkage of FE was cleaved to form ethyl 2-(4-hydroxyphenoxy)propanoate (EHPP) and 6-chloro-2,3-dihydrobenzoxazol-2-one (CDHB). While in basic conditions (pH = 8, 9, 10), herbicidal activity fenoxaprop-p (FA) was formed via breakdown of the ester bond of the herbicide. Both the two pathways were concurrent in neutral conditions (pH = 6, 7). Toxicity studies on Daphnia magna showed that FE was most toxic to D. magna with 48 h EC(50) of 14.3 micromol/L, followed by FA (43.8 micromol/L), CDHB (49.8 micromol/L), and EHPP (333.1 micromol/L). Mode of toxic action analysis indicated that EHPP exhibited toxicity via polar narcosis, whereas CDHB belonged to reactive acing compound. The mixture toxicity of CDHB and EHPP was nonadditive and can be predicted by a response addition model. Therefore, the evaluation of overall FE toxicity to D. magna in the aquatic systems needs to consider the degradation of FE.     

More toxic and photoresistant products from photodegradation of fenoxaprop-p-ethyl

The photodegradation pathway of the commonly used herbicide fenoxaprop-p-ethyl (FE) was elucidated, and the effects of the photodegradation on its toxicity evolution were investigated. Under solar irradiation, FE could undergo photodegradation, and acetone enhanced the photolysis rates significantly. The same photoproducts formed under the irradiation of lambda > 200 nm and lambda > 290 nm through rearrangement, loss of ethanol after rearrangement, de-esterification, dechlorination, photohydrolysis, and the breakdown of the ether linkages. One of the main transformation products, 4-[(6-chloro-2-benzoxazolyl)oxy] phenol (CBOP), was resistant to photodegradation under the irradiation of lambda > 290 nm, and its photolysis rate was seven times slower than the parent under the irradiation of lambda > 200 nm. Among the metabolites, CBOP (48 h EC50 of 1.49-1.64 mg/L) and hydroquinone (48 h EC50 of 0.25-0.28 mg/L) were more toxic to Daphnia magna than the parent FE (48 h EC50 of 4.2-6.9 mg/L). Thus, more toxic and photoresistant products were generated from photolysis of the herbicide. Ecotoxicological effects of phototransformed products from pesticides should be emphasized for the ecological risk assessment of these anthropogenic pollutants.     

植物精油与环糊精包合物的制备及对柑橘绿霉病的抑制作用

植物精油及其活性组分能降低柑橘采后病害且不影响果实品质,是一种潜在的生物杀菌剂,但存在易挥发和不稳定等问题,限制了其实际应用。将植物精油与环糊精包合能有效克服上述缺陷,提高植物精油的应用效果。为了提升植物精油组分反式-2-己烯醛对柑橘绿霉病菌的控制效果,该研究拟采用饱和水溶液法制备反式-2-己烯醛与α-环糊精（α-CD）、β-环糊精（β-CD）、γ-环糊精（γ-CD）和羟丙基-β-环糊精（HP-β-CD）包合物,并考察包合物对指状青霉的离体和活体控制效果,在此基础上解析效果较优包合物的结构特点和包合模式。结果显示,通过饱和水溶液法成功制备了反式-2-己烯醛与α-CD、β-CD、γ-CD和HP-β-CD的4种包合物（α-CDTH、β-CDTH、γ-CDTH和HP-β-CDTH）。外观形态结果显示,α-CDTH、β-CDTH和γ-CDTH粉末细腻绵密,HP-β-CDTH粉末粗糙,颗粒分明。4种环糊精包合物均能有效抑制P.digitatum菌丝体的生长且具有浓度依赖性,β-CDTH和γ-CDTH抑制P.digitatum菌丝体生长的最小杀菌浓度（Minimum Fugicide Concen...     

Characterization of cyclodextrin glycosyltransferase of the same gene expressed from Bacillus macerans, Bacillus subtilis, and Escherichia coli

The plasmid pHG contains a cyclodextrin glycosyltransferase (CGTase) gene (cgt) derived from Bacillus macerans. Two transformants, Bacillus subtilis (pHG) and Escherichia coli (pHG), were found to produce CGTases with the same primary structure as the enzyme from B. macerans. However, the beta-cyclodextrin coupling activity of the CGTase from E. coli (pHG) was 14-fold higher than that of the enzymes from the other strains. By contrast, no differences in alpha-cyclodextrin coupling activities were observed among these CGTases. CGTase from E. coli (pHG) was found to be less thermostable than the other CGTases. When the CGTase produced by B. subtilis was treated with increasing urea concentrations (10-1000 mM) to promote increasing degrees of protein unfolding, a bell-shaped beta-cyclodextrin coupling activity profile was obtained. Subtle differences in the conformation of the CGTase produced by E. coli are therefore proposed to be responsible for the markedly increased beta-cyclodextrin coupling activity of this enzyme.     

Influence of complexation between amylose and a flavored model sponge cake on the degree of aroma compound release

Flavoring is used in the food industry to reinforce the aroma profile of baked cereal goods. During the processing of such products, interactions between starch and aroma compounds can occur, and this may have an impact on aroma release and perception. In the present study, 20 aroma compounds were tested to establish whether they formed complexes with amylose. The structure of the complexes was determined by wide-angle X-ray scattering (WAXS). A cocomplexation study proved that several complexing compounds could be present in the same crystalline aggregate. WAXS and differential scanning calorimetry (DSC) experiments were performed in a flavored model sponge cake at different steps of processing and showed that aroma compounds might form complexes with amylose in a sponge cake as they can do in simple system containing only amylose. Some of the aroma compounds trapped in the sponge cake were quantified, and their release behavior was followed by headspace analysis. The V-type structure could partly explain aroma retention in the product and the rate of aroma release.     

Characterization of interactions between chitosan and an anionic surfactant

Chitosan is a cationic biopolymer that has many potential applications in the food industry because of its unique nutritional and physiochemical properties. Many of these properties depend on its ability to interact with anionic surface-active molecules, such as phospholipids, surfactants, and bile acids. The purpose of this study was to characterize the interaction between chitosan and a model anionic surfactant (sodium dodecyl sulfate, SDS) using isothermal titration calorimetry (ITC), surfactant-selective electrode (SSE), and turbidity measurements. ITC and SSE indicated that SDS bound strongly to chitosan via a highly exothermic interaction. The turbidity measurements indicated that chitosan formed insoluble complexes with SDS that strongly scattered light. The chitosan bound approximately 4 mM of SDS per 0.1 wt % chitosan before becoming saturated with surfactant. The SDS-chitosan interaction was weakened appreciably by the presence of 100 mM NaCl, which suggested that it was electrostatic in origin. This study provides information about the origin and characteristics of molecular interactions between chitosan and anionic surface-active lipids that may be useful for the rational design of chitosan-based food ingredients with specific nutritional and functional characteristics, e.g., cholesterol lowering or fat replacement.     

几种胡敏酸还原容量的表征与比较

还原容量(RC)是衡量胡敏酸(HA)还原特性的重要指标。采用饱和H2振荡法和土壤溶液法对HA分别进行化学和微生物预处理,分别以硝酸铁(Fe(NO3)3)、柠檬酸铁(FeCit)作电子受体,测定了三种HA(上海巨枫SH,天津光复TJ,缙云山JY)的本底还原容量(NRC),化学还原容量(CRC),微生物还原容量(MRC)。对不同电子受体条件下、不同初始状态和不同种类的胡敏酸的RC进行比较。结果表明：三种HA中,以缙云山土壤提取的胡敏酸RC值最高,还原容量最大,分别为20.21?0.26mmolc mol-1C (NRC)、26.02?1.12mmolc mol-1C (CRC)和29.29?1.56mmolc mol-1C (MRC)。两种电子受体中,采用Fe(NO3)3得到的RC明显高于在FeCit条件下。另外,溶液态HA的RC明显高于固态。由此证明胡敏酸还原容量是一个相对量;其容量大小不仅和自身结构、性质有关,也受到HA初始形态和不同电子受体的影响。对比三个还原容量指标发现CRC和MRC显著大于NRC,而CRC和MRC之间无明确大小关系,因此用CRC来表征HA被微生物还原后的还原容量(MRC)还需作进一步验证。     

Properties of and heavy metal complexation by aqueous humic extracts

Aqueous extracts of terrestrial and underwater soils were prepared by Soxhlet extractions at temperatures between 100 and 37°C (under reduced pressure). From the law of mass action, stability constants were derived for the complexation of Cd, Cu, and Pb by these extracts. The activity of the heavy metals was determined polarographically, whereas the concentration of acid functional groups was used for ligand activity. Visible spectra, electrical conductivity, organic matter contents, and complexation constants depended on extraction temperature as well as on soil properties. In most cases, complex stability increased with increasing pH of the polarographic medium, but sometimes maximum stability was found around pH 7.     

魔芋葡甘聚糖-硼复合物结构表征研究

通过11B-NMR、1H-NMR、IR、RS、DSC、X-RD对魔芋葡甘露聚糖-硼复合物结构进行了初步的阐述.硼砂与魔芋葡甘露聚糖发生配位反应,主要的反应位点在糖的C6位羟基及甘露糖基的C2、C3位羟基上,形成了B K2和KB K两种类型配合物.红外及Raman光谱图上1380 cm-1的B-O特征振动、2640 cm-1的B-H的伸缩振动也表征了配位化合物的生成.热特性和结晶性分析也证实了配合物的形成.     

Enhancement of plant essential oils' aqueous solubility and stability using alpha and beta cyclodextrin

Sodium benzoate has been shown to produce benzene in combination with ascorbic acid. This has led to research for safe alternatives from plant essential oils and parabens that have shown some antimicrobial activity, but many of these compounds exhibit poor solubility in aqueous solutions. Cyclodextrins can increase the solubility of many compounds. This work aimed to investigate the solubility of 23 plant essential oils and 4 parabens in water and an apple juice medium. Four of these compounds were chosen for their low aqueous solubility to determine if complexing the compound with α- and β-cyclodextrin would increase solubility. Three of the complexes were dissolved in an acidified aqueous solution and then studied in glass and polyethylene terephthalate (PET) to determine if storage material would affect the stability. Solubility of the 27 compounds in distilled water ranged from 1.6 mg/L to 2460.6 mg/L and the solubility of 18 of the compounds decreased from 2.5 to 84.7% in apple juice medium (pH = 3.4, 12-13 °Brix). Complexation with cyclodextrin dramatically increased the solubility of the compounds, up to 10-fold. Packaging material had no effect on concentration of compounds present over 7 days. Cyclodextrins were able to increase solubility of these compounds to more suitable concentrations, and may lead to viable natural alternatives to sodium benzoate.     

Improving bioavailability and stability of genistein by complexation with high-amylose corn starch

Genistein, like other phytochemicals, has beneficial health effects, but its bioavailability is limited. This research studied the effect of complexation of genistein with starch on genistein bioavailability. Genistein release from these complexes was tested in vitro under simulated intestinal conditions and in vivo in rats fed high-amylose corn starch (HACS)-genistein complexes (experimental group) as compared to those fed a physical mixture of HACS and genistein (controls). In vitro results showed that genistein release is sustained and fits the normal transit time of food in the intestine. The genistein concentration in the plasma was twice as high in the experimental group versus controls; the genistein concentration in the urine was also higher in the experimental group but lower in the feces. These results indicate that starch-genistein complexes increase genistein bioavailability and suggest that starch can affect the bioavailability of additional food components.     

Modulation of cyclizing activity and thermostability of cyclodextrin glucanotransferase and its application as an antistaling enzyme

Cyclodextrin glucanotransferase from Bacillus stearothermophilus ET1 (CGTase ET1) is a potential antistaling enzyme with cyclodextrin (CD)-forming activity. To reduce cyclization activity of CGTase ET1, phenylalanine residues at 191 and 255 were replaced with a glycine (F191G-CGTase ET1) and an isoleucine (F255I-CGTase ET1), respectively. Temperature optima of both mutant enzymes were lower than that of the wild-type. Cyclization activities of both mutants decreased dramatically, but F255I-CGTase ET1 showed a 2-fold higher hydrolytic activity than the wild-type enzyme. CD content of bread loaf treated with F191G-CGTase ET1 was 28.6% of that treated with wild-type, whereas no CD was detected in the loaf treated with F255I-CGTase ET1. Loaves treated with CGTase ET1 or either of the two mutants contained more of the larger maltooligosaccharides such as maltopentaose and maltohexaose than the control and the commercial antistaling enzyme-treated loaves. Retrogradation rates decreased significantly in the loaves treated with either mutant, which indicates the applicability of CGTase ET1 in the bread industry by modulating the cyclizing and hydrolyzing activities of the enzyme.     

Characterization of reaction products formed in a model reaction between pentanal and lysine-containing oligopeptides

Aldehydes formed as a result of lipid oxidation form fluorophores after binding to proteins. The structure of the fluorophores formed by reaction between saturated aldehydes and lysine has not yet been identified. The reaction products formed in the reaction between pentanal and oligopeptides were studied by fluorescence spectroscopy and mass spectrometry. The emission spectra showed an increase in fluorescence intensity with incubation time, and the rates were linear with the concentration of pentanal. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analyses of the reaction products suggested a molar relation for peptide:pentanal of 1:4. Further tandem mass spectrometry analysis of one of the modified peptides (Pro-Thr-His-Ile-Lys-Trp-Gly-Asp) strongly suggested binding of one pentanal molecule to the amino terminal proline and three pentanal molecules bound to the lysine residue. The latter species is suggested to be the actual fluorophore, through the formation of conjugated double bonds, and a possible reaction pathway through a combination of aldol condensation of pentanal and Schiff base formation with the lysine is suggested.     

异硫氰酸烯丙酯及其包合物在冷却牛肉片保藏中的应用

该文研究了异硫氰酸烯丙酯及其包合物对冷却牛肉片中大肠杆菌和腐败细菌的抑制作用。结果表明,添加异硫氰酸烯丙酯或其环糊精包合物(4 μL/g),可以有效抑制冷却牛肉片中大肠杆菌和腐败细菌,明显延长保鲜期。环糊精包合物在牛肉中可缓释异硫氰酸烯丙酯,强化杀菌的效果,同时增加肉品的持水性。但异硫氰酸烯丙酯包合物的加入会对冷却牛肉片的色泽产生较大影响,可能更适合于添加到对牛肉原有色泽要求不严格的加工类产品中。     

Cycloamylose (cyclodextrin) glucanotransferase degrades intact granules of potato raw starch

Cycloamylose (cyclodextrin) glucanotransferase (EC 2.4.1.19, CGTase) originated from Bacillus macerans degraded intact granules of potato raw starch and converted them into cyclodextrins (CDs). The degradation required sufficient stirring of starch-CGTase suspension. The morphology of the degraded starch granules was unique; that is, the inner part of the granules was observed by scanning electron microscope to be more susceptible to CGTase than the outer part. Effects of pH, temperature, starch concentration, and enzyme amount on CD production were studied.