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1.
In order to clarify the prooxidative role of carotenoids on the oxidation of unsaturated lipids this study examined the effects of β‐carotene and its oxidative breakdown product, retinal, on primary oxidation products of linoleic acid methyl ester. Formation as well as isomer distribution of methyl linoleate hydroperoxides were followed by highperformance liquid chromatography. Oxidation of methyl linoleate without or with added β‐carotene (5, 20, 200 μg/g) or retinal (7, 18, 180, 360 μg/g) was carried out in the dark under air at 40 °C. Both β‐carotene and retinal promoted the formation of hydroperoxides and thus acted as prooxidants in a concentration‐dependent way. Moreover, carotenoids also had an effect on the isomeric distribution of primary oxidation products as high contents of retinal increased the portion (%) of trans,trans‐hydroperoxides. Being thermodynamically more stable isomers than cis,trans‐isomers of hydroperoxides they are known to accumulate during later phases of oxidation or during hydroperoxide decomposition. The results showed that β‐carotene and retinal were not effective hydrogen donors. These findings raise the question that carotenoids and their oxidative breakdown products enhance the decomposition of lipid hydroperoxides and this effect partially explains the prooxidative effect of carotenoids.  相似文献   

2.
BACKGROUND: Supercritical antisolvent (SAS) micronisation of synthetic trans ‐β‐carotene was studied using tetrahydrofuran (THF) as solvent and supercritical carbon dioxide (CO2) as antisolvent, with the objective of increasing its bioavailability and facilitating its dispersion in oil and emulsion formulations as a result of its smaller particle size. The micronised powder was analysed by scanning electron microscopy and high‐performance liquid chromatography. Micronisation experiments were performed in order to evaluate the effects of temperature (308.15–333.15 K), pressure (6.5–13 MPa) and concentration of the liquid solution (6–9 g L?1). The effect of the supercritical CO2/THF flow ratio in the range between 4 and 44 (on a mass basis) was also analysed. Determinations of equilibrium concentrations of β‐carotene in the CO2/THF mixture were also performed. RESULTS: The particle size obtained ranged from 1 to 500 µm, with mean particle diameters around 100 µm. Three types of morphology were found in the precipitated powder: crystalline with superficial pores and leaf‐like appearance; crystalline with regular shapes and blade‐like edges; and crystalline without superficial pores and leaf‐like apearance. The Peng–Robinson equation of state was used to calculate the density of the CO2/THF binary mixture, and the solubility of β‐carotene in this mixture was correlated with its density. CONCLUSION: The use of the SAS technique to micronise β‐carotene proved to be efficient, and the absence of degradation in the micronised powder allows the industrial application of this technique. Copyright © 2008 Society of Chemical Industry  相似文献   

3.
The effect of pretreatment of molasses, nitrogen sources, natural oils, fatty acids, antioxidant, precursors, and mixtures of the above substances on β‐carotene production by Blakeslea trispora in shake flask culture was investigated. Also, a central composite design was employed to determine the maximum β‐carotene concentration at optimum values for the process variables (linoleic acid, kerosene, antioxidant). The highest concentration of the carotenoid pigment was obtained in molasses solution treated with invertase. Corn steep liquor and yeast extract at concentrations of 5.0% and 0.5% (w/v), respectively, increased slightly the concentration of β‐carotene, while the natural oils, fatty acids, and precursors (except kerosene) did not improve the production of pigment when they were added separately to the medium. On the other hand, the mixture of linoleic acid, kerosene and antioxidant increased significantly the concentration of β‐carotene. The fit of the model was found to be good. Linoleic acid, kerosene and antioxidant had a strong linear effect on β‐carotene concentration. The concentration of β‐carotene was significantly affected by linoleic acid–antioxidant and kerosene–antioxidant interactions as well as by the negative quadratic effects of these variables. The interaction between linoleic acid–kerosene had no significant linear effect. Maximum β‐carotene concentration (790.0 mg dm?3) was obtained in culture grown in molasses solution supplemented with linoleic acid (30.74 g dm?3), kerosene (27.79 g dm?3) and antioxidant (10.22 g dm?3). © 2002 Society of Chemical Industry  相似文献   

4.
The kinetics of trans‐β‐carotene and trans‐lutein degradation were individually investigated in palm olein and Vegetaline®, at four temperatures ranging from 120 to 180 °C. HPLC‐DAD analysis was carried out to monitor trans and cis carotenoid variations over the heating time at each temperature. In both oils, initial trans‐β‐carotene and trans‐lutein degradation rates increased with temperature. Trans‐lutein was found to degrade at a slower rate than trans‐β‐carotene, suggesting a higher thermal resistance. The isomers identified were 13‐cis‐ and 9‐cis‐β‐carotene, and 13‐cis‐, 9‐cis‐, 13'‐cis‐, and 9'‐cis‐lutein. In spite of the higher number of lutein cis isomers, their total amount was lower than that of β‐carotene cis isomers. Trans and cis carotenoids were involved in degradation reactions at rates that increased with temperature. All degradation rates were generally found to be lower in Vegetaline® than in palm olein. These results were explained by the initial composition of the two oils and especially their peroxide and vitamin E contents.  相似文献   

5.
A new enantioselective α‐alkylation of α‐tert‐butoxycarbonyllactams for the construction of β‐quaternary chiral pyrrolidine and piperidine core systems is reported. α‐Alkylations of N‐methyl‐α‐tert‐butoxycarbonylbutyrolactam and N‐diphenylmethyl‐α‐tert‐butoxycarbonylvalerolactam under phase‐transfer catalytic conditions (solid potassium hydroxide, toluene, −40 °C) in the presence of (S,S)‐3,4,5‐trifluorophenyl‐3,3′,5,5′‐tetrahydro‐2,6‐bis(3,4,5‐trifluorophenyl)‐4,4′‐spirobi[4H‐dinaphth[2,1‐c:1′,2′‐e]azepinium] bromide [(S,S)‐NAS Br] (5 mol%) afforded the corresponding α‐alkyl‐α‐tert‐butoxycarbonyllactams in very high chemical (up to 99%) and optical yields (up to 98% ee). Our new catalytic systems provide attractive synthetic methods for pyrrolidine‐ and piperidine‐based alkaloids and chiral intermediates with β‐quaternary carbon centers.  相似文献   

6.
Butter fat solid fraction/rapeseed oil mixtures were interesterified in the presence of Candida cylindracea lipase as catalyst. The changes in the triglyceride composition were followed through quantitative determination of triglycerides with different acyl carbon number and level of unsaturation by high resolution gas chromatography. The inter-esterification decreased the proportions of trisaturated triglycerides and increased those of monoene triglycerides in the acyl carbon number range 44-52. The triglyceride compositions of reaction products were similar to the triglyceride composition calculated according to random distribution. The melting and crystallisation properties of the reaction products were determined by DSC method. The melting curves of reaction products showed narrower melting ranges than untreated mixtures, and lower proportions of fat melting at high temperature range.  相似文献   

7.
Monoclinic (α) and hexagonal (β) polypropylene (α‐ and β‐PP) were stained in the vapor of a ruthenium tetroxide solution prepared in situ. The effect of staining on the fusion behavior was investigated using a DSC. A staining duration between 10 and 24 h was found suitable for obtaining a good electron contrast between the crystalline and amorphous regions for TEM examination without causing severe damage to the crystals. The spherulites of the water‐quenched α‐PP were found to be composed of very fine cross‐hatched lamellae whose long period was about 10 nm. In comparison, the β‐PP spherulites crystallized isothermally at 130°C had a category 2 morphology and the lamellae have a long period of 20 nm. The morphology of the spherulite boundary varied depending on the contact angle between the lamellae of the neighboring spherulites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1529–1538, 1999  相似文献   

8.
To evaluate molecular recognition function of β‐cyclodextrin to xylene isomers, β‐CD polymer of branching chain extension (β‐CD‐EGDE) was synthesized by crosslinking β‐CD with ethylene glycol diglycidyl ether (EGDE). The pervaporation blend membranes of β‐CD‐EGDE/PVA were prepared by casting an aqueous solution of PVA and β‐CD polymer mixture, and the membranes were used for separation of p‐/m‐ and p‐/o‐xylene mixtures. It was observed that the pristine PVA membrane almost had no selectivity for xylene isomer mixtures. The PVA membrane incorporating β‐CD polymer had molecular recognition function, which selectively facilitated the transport of the xylene isomers. To ascertain pervaporation behavior, the sorption and desorption processes of the membrane in xylenes were investigated. The sorption result showed that the complex formation constant between β‐CDs and xylenes played a key role in swelling behavior. There was a significant difference between diffusion coefficients D and D0, calculated from the sorption and desorption measurements, respectively, indicating that the diffusivity selectivity in desorption stage may have remarkable effect on the total selectivity during pervaporation process. © 2012 American Institute of Chemical Engineers AIChE J, 59: 604–612, 2013  相似文献   

9.
A new diimide–diacid monomer, N,N′‐bis(4‐carboxyphenyl)‐4,4′‐oxydiphthalimide (I), was prepared by azeotropic condensation of 4,4′‐oxydiphthalic anhydride (ODPA) and p‐aminobenzoic acid (p‐ABA) at a 1:2 molar ratio in a polar solvent mixed with toluene. A series of poly(amide–imide)s (PAI, IIIa–m) was synthesized from the diimide–diacid I (or I′, diacid chloride of I) and various aromatic diamines by direct polycondensation (or low temperature polycondensation) using triphenyl phosphite and pyridine as condensing agents. It was found that only IIIk–m having a meta‐structure at two terminals of the diamine could afford good quality, creasable films by solution‐casting; other PAIs III using diamine with para‐linkage at terminals were insoluble and crystalline; though IIIg–i contained the soluble group of the diamine moieties, their solvent‐cast films were brittle. In order to improve their to solubility and film quality, copoly(amide–imide)s (Co‐PAIs) based on I and mixtures of p‐ABA and aromatic diamines were synthesized. When on equimolar of p‐ABA (m = 1) was mixed, most of Co‐PAIs IV had improved solubility and high inherent viscosities in the range 0.9–1.5 dl g?1; however, their films were still brittle. With m = 3, series V was obtained, and all members exhibited high toughness. The solubility, film‐forming ability, crystallinity, and thermal properties of the resultant poly(amide–imide)s were investigated. © 2002 Society of Chemical Industry  相似文献   

10.
The phase behavior of binary mixtures of γ‐oryzanol and β‐sitosterol and ternary mixtures of γ‐oryzanol and β‐sitosterol in sunflower oil was studied. Binary mixtures of γ‐oryzanol and β‐sitosterol show double‐eutectic behavior. Complex phase behavior with two intermediate mixed solid phases was derived from differential scanning calorimetry (DSC) and small‐angle X‐ray scattering (SAXS) data, in which a compound that consists of γ‐oryzanol and β‐sitosterol molecules at a specific ratio can be formed. SAXS shows that the organization of γ‐oryzanol and β‐sitosterol in the mixed phases is different from the structure of tubules in ternary systems. Ternary mixtures including sunflower oil do not show a sudden structural transition from the compound to a tubule, but a gradual transition occurs as γ‐oryzanol and β‐sitosterol are diluted in edible oil. The same behavior is observed when melting binary mixtures of γ‐oryzanol and β‐sitosterol at higher temperatures. This indicates the feasibility of having an organogelling agent in dynamic exchange between solid and liquid phase, which is an essential feature of triglyceride networks.  相似文献   

11.
Glycine‐ɛ‐caprolactone‐based and α‐alanine‐ɛ‐caprolactone‐based polyesteramides with a strong tendency to form alternating sequences (degree of randomness = 1.64 and 1.31) were synthesized by melt polycondensation of intermediate hydroxy‐ and ethyl ester‐terminated amides. These intermediates were synthesized by the reaction of equimolar amounts of ɛ‐caprolactone and glycine or L‐α‐alanine ethyl esters in mild conditions. The structure and microstructure of these polyesteramides are discussed on the basis of an in‐depth nuclear magnetic resonance study. Both polyesteramides are semi‐crystalline, but the glycine‐based one presents the highest melting enthalpy. This polyesteramide also exhibits higher Young's modulus and stress at break than its α‐ and β‐alanine counterparts. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44220.  相似文献   

12.
In order to increase the isotactic content of β‐nucleated polypropylene (β‐iPP) and decrease the cost of its production, the investigation and development of novel highly efficient β‐nucleators are important issues. Nano‐CaCO3 was used as a support to prepare a supported β‐nucleator, nano‐CaCO3‐supported calcium pimelate. Fourier transform infrared spectral analysis shows that an in situ chemical reaction takes place between nano‐CaCO3 and pimelic acid. Differential scanning calorimetry results indicate that the crystallization and melting temperatures of β‐phase in supported β‐nucleator‐nucleated iPP are higher than those of calcium pimelate‐nucleated iPP. The β‐nucleating ability of the supported β‐nucleator is little influenced by the cooling rate and crystallization temperature over a wide range. The decreased content of pimelic acid in the supported β‐nucleator slightly decreases the crystallization temperature of iPP but it has no influence on the content of β‐phase in nucleated iPP. A novel supported β‐nucleator has been successfully synthesized via pimelic acid supported on the surface of CaCO3. The crystallization temperature of iPP and melting temperature of β‐phase in iPP nucleated using the supported β‐nucleator are higher than those of iPP nucleated using calcium pimelate. The concept of a supported nucleator will provide a new way to increase the efficiency of polymer additives and to decrease the amounts of them that need to be used by using nanoparticles as supports. Copyright © 2010 Society of Chemical Industry  相似文献   

13.
RP HPLC method coupled to ESI‐MS was used for the analysis and characterization of the oxidation of model triacylglycerols (TAGs) in presence of β‐carotene. β‐Carotene was added to the TAGs and oxidized in the Rancimat at 110°C. The samples were separated isocratically using a mixture of isopropanol with methanol and a Phenomenex C18 column. β‐Carotene degradation was measured using high performance TLC. We found that β‐carotene plays an important role during the thermal degradation of high oleic acid model TAGs. Half of the β‐carotene was degraded before 3 h of thermal treatment. β‐Carotene significantly increases the peroxide value of the TAGs after the third hour, suggesting a pro‐oxidant action. However, different TAGs show different activity toward thermal treatment and β‐carotene. The LLL was found to be less stable, OLL and OLO were stable till 10 and 12 h respectively, while POO, OOO, and OSO were the stable TAGs till 14 h. In TAGs, replacing linoleic acid by oleic acid, the stability of the corresponding TAG was found to increase by 2 h. A new class of oxidized TAGs was reported for the first time, together with previously reported species. The proposed mechanism of formation and identification of the newly identified species have been explained. Among the oxidized species of TAGs, mono‐hydroperoxides, bis‐hydroperoxides, epoxy‐epidioxides, and epoxides were the major compounds identified.  相似文献   

14.
The highly enantioselective organo‐co‐catalytic aza‐Morita–Baylis–Hillman (MBH)‐type reaction between N‐carbamate‐protected imines and α,β‐unsaturated aldehydes has been developed. The organic co‐catalytic system of proline and 1,4‐diazabicyclo[2.2.2]octane (DABCO) enables the asymmetric synthesis of the corresponding N‐Boc‐ and N‐Cbz‐protected β‐amino‐α‐alkylidene‐aldehydes in good to high yields and up to 99% ee. In the case of aza‐MBH‐type addition of enals to phenylprop‐2‐ene‐1‐imines, the co‐catalytic reaction exhibits excellent 1,2‐selectivity. The organo‐co‐catalytic aza‐MBH‐type reaction can also be performed by the direct highly enantioselective addition of α,β‐unsaturated aldehydes to bench‐stable N‐carbamate‐protected α‐amidosulfones to give the corresponding β‐amino‐α‐alkylidene‐aldehydes with up to 99% ee. The organo‐co‐catalytic aza‐MBH‐type reaction is also an expeditious entry to nearly enantiomerically pure β‐amino‐α‐alkylidene‐amino acids and β‐amino‐α‐alkylidene‐lactams (99% ee). The mechanism and stereochemistry of the chiral amine and DABCO co‐catalyzed aza‐MBH‐type reaction are also discussed.  相似文献   

15.
A novel highly active β‐nucleating agent, β‐cyclodextrin complex with lanthanum (β‐CD‐MAH‐La), was introduced to isotactic polypropylene (iPP). Its influence on isothermal crystallization and melting behavior of iPP was investigated by differential scanning calorimeter (DSC), wide‐angle X‐ray diffraction (WAXD), and polarized light microscopy (PLM). WAXD results demonstrated that β‐CD‐MAH‐La was an effective β‐nucleating agent, with β‐crystal content of iPP being strongly influenced by the content of β‐CD‐MAH‐La and the isothermal crystallization temperature. The isothermal crystallization kinetics of pure iPP and iPP/β‐CD‐MAH‐La was described appropriately by Avrami equation, and results revealed that β‐CD‐MAH‐La promoted heterogeneous nucleation and accelerated the crystallization of iPP. In addition, the equilibrium melting temperature (T) of samples was determined using linear and nonlinear Hoffman‐Weeks procedure. Finally, the Lauritzen‐Hoffman secondary nucleation theory was applied to calculate the nucleation parameter (Kg) and the fold surface energy (σe), the value of which verify that the addition of β‐CD‐MAH‐La reduced the creation of new surface for β‐crystal and then led to faster crystallization rate. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

16.
A highly novel nano‐CaCO3 supported β‐nucleating agent was employed to prepare β‐nucleated isotactic polypropylene (iPP) blend with polyamide (PA) 66, β‐nucleated iPP/PA66 blend, as well as its compatibilized version with maleic anhydride grafted PP (PP‐g‐MA), maleic anhydride grafted polyethylene‐octene (POE‐g‐MA), and polyethylene‐vinyl acetate (EVA‐g‐MA), respectively. Nonisothermal crystallization behavior and melting characteristics of β‐nucleated iPP and its blends were investigated by differential scanning calorimeter and wide angle X‐ray diffraction. Experimental results indicated that the crystallization temperature (T) of PP shifts to high temperature in the non‐nucleated PP/PA66 blends because of the α‐nucleating effect of PA66. T of PP and the β‐crystal content (Kβ) in β‐nucleated iPP/PA66 blends not only depended on the PA66 content, but also on the compatibilizer type. Addition of PP‐g‐MA and POE‐g‐MA into β‐nucleated iPP/PA66 blends increased the β‐crystal content; however, EVA‐g‐MA is not benefit for the formation of β‐crystal in the compatibilized β‐nucleated iPP/PA66 blend. It can be relative to the different interfacial interactions between PP and compatibilizers. The nonisothermal crystallization kinetics of PP in the blends was evaluated by Mo's method. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

17.
Carbonate on polymer is a valuable solid supported reagent (SSR) to promote, under eco‐friendly conditions, the preparation of 2H‐1,4‐benzoxazin‐2‐one derivatives starting from β‐nitroacrylates and aminophenols via a domino process.  相似文献   

18.
Structure and properties of commercially available fully oriented thermoplastic and thermotropic polyester fibers have been investigated using optical birefringence, infrared spectroscopy, wide‐angle X‐ray diffraction and tensile testing methods. The effect of the replacement of p‐phenylene ring in poly(ethylene terephthalate) (PET) with stiffer and bulkier naphthalene ring in Poly(ethylene 2,6‐naphthalate) (PEN) structure to result in an enhanced birefringence and tensile modulus values is shown. There exists a similar case with the replacement of linear flexible ethylene units in PET and PEN fibers with fully aromatic rigid rings in thermotropic polyesters. Infrared spectroscopy is used in the determination of crystallinity values through the estimation of trans conformer contents in the crystalline phase. The analysis of results obtained from infrared spectroscopy data of highly oriented PET and PEN fibers suggests that trans conformers in the crystalline phase are more highly oriented than gauche conformers in the amorphous phase. Analysis of X‐ray diffraction traces and infrared spectra shows the presence of polymorphic structure consisting of α‐ and β‐phase structures in the fully oriented PEN fiber. The results suggest that the trans conformers in the β‐phase is more highly oriented than the α‐phase. X‐ray analysis of Vectran® MK fiber suggests a lateral organization arising from high temperature modification of poly(p‐oxybenzoate) structure, whereas the structure of Vectran® HS fiber contains regions adopting lateral chain packing similar to the room temperature modification of poly(p‐oxybenzoate). Both fibers are shown by X‐ray diffraction and infrared analyses to consist of predominantly oriented noncrystalline (63–64%) structure together with smaller proportion of oriented crystalline (22–24%) and unoriented noncrystalline (12–15%) structures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 142–160, 2006  相似文献   

19.
This work was initiated to prepare an oil‐in‐water (O/W) emulsion containing β‐carotene by microfluidization. The β‐carotene was dissolved in triolein and microfluidized with an aqueous phase containing sodium caseinate (SC) as the emulsifier. Microfluization at 140 MPa resulted in O/W emulsions with a mean droplet diameter of ca. 120 nm, which was further confirmed by transmission electron microscopy analysis. The influences of SC concentration and microfluidization parameters on the droplet size of the emulsions were studied. The results showed that the mean droplet diameter decreased significantly (p <0.05) from 310 to 93 nm with the increase in SC concentration from 0.1 to 2 wt‐%. However, a further increase in SC concentration did not much change the droplet diameter, although the polydispersity of the emulsions was slightly improved. The droplet diameter of the emulsions was found to decrease from 200 to 120 nm with increasing microfluidization pressure, with narrower droplet size distribution. The storage study showed that the emulsions were physically stable for about 2 weeks at 4 °C in the dark. The results provide a better understanding of the performance of SC in stabilizing the O/W emulsions.  相似文献   

20.
Blends of poly(3‐hydroxy butyrate‐co‐3‐hydroxy valerate) (PHBV) and poly(ethylene oxide) (PEO) were prepared by casting from chloroform solutions. Crystallization kinetics and melting behavior of blends have been studied by differential scanning calorimetry and optical polarizing microscopy. Experimental results reveal that the constituents are miscible in the amorphous state. They form separated crystal structures in the solid state. Crystallization behavior of the blends was studied under isothermal and nonisothermal conditions. Owing to the large difference in melting temperatures, the constituents crystallize consecutively in blends; however, the process is affected by the respective second component. PHBV crystallizes from the amorphous mixture of the constituents, at temperatures where the PEO remains in the molten state. PEO, on the other hand, is surrounded during its crystallization process by crystalline PHBV regions. The degree of crystallinity in the blends stays constant for PHBV and decreases slightly for PEO, with ascending PHBV content. The rate of crystallization of PHBV decreases in blends as compared to the neat polymer. The opposite behavior is observed for PEO. Nonisothermal crystallization is discussed in terms of a quasi‐isothermal approach. Qualitatively, the results show the same tendencies as under isothermal conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2776–2783, 2006  相似文献   

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