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1.
The effects of 0, 1.0 × 10”−5, 2.5 × 10−5, and 5.0 × 10−5 M β-apo-8'-carotenal, β-carotene, and canthaxanthin on the photooxidation of soybean oil in methylene chloride containing 3.3 × 10−9 M chlorophyll b were studied by measuring peroxide values and conjugated diene content. β-Apo-8'-carotenal, β-carotene, and canthaxanthin contain 10,11, and 13 conjugated double bonds, respectively. The peroxide values and conjugated diene contents of oils containing the carotenoids were significantly lower (P<0.05) than those of control oil containing no carotenoid. As the number of conjugated double bonds of the carotenoids increased, the peroxide values of soybean oils decreased significantly (P<0.05). The quenching mechanisms and kinetics of the carotenoids in the photosensitized oxidation of soybean oil were studied by measuring peroxide values. The steady-state kinetics study showed that carotenoids quenched singlet oxygen to reduce chlorophyll-sensitized photooxidation of soybean oil. The singlet-oxygen quenching rate constants ofβ- apo-8'-carotenal, β-carotene, and canthaxanthin were 3.06 × 109, 4.60 × 109, and 1.12 × 1010 M−1sec−1, respectively.  相似文献   

2.
The stability of raw peanut oil to autoxidation at 40 C increased with ambient relative humidity, reaching a maximum stability at 90.5% RH (KM × 10−3 2.54, 1.83, 0.50 meq O2/kg/hr at RH of 2, 47.5, 90.5%, respectively). Degumming with water or with phosphoric acid accelerated autoxidation at all test humidities. The trend in the rate of autoxidation was opposite that of the raw oil, increasing with relative humidity. It reached its maximum at 90.5% RH (KM × 10−3 of 3.93, 3.16, 6.65 meq O2/kg/hr at RH of 2, 47.5, 90.5% respectively for phosphoric acid degummed oil). Adding back the water washed gums removed during degumming to the water degummed peanut oil substantially restored the stability of the oil to autoxidation. These studies indicate that water washed gums retain most of their native state antioxidant activity. Hence, the gums removed during processing of oils could be added back to the oil after final processing to impart increased stability to the oil in some applications. The antioxidant efficacy of water washed gums was as good as that of synthetic antioxidants. These have an advantage over synthetic antioxidants in that they are natural components of most oils and fats.  相似文献   

3.
It is difficult to remove β-carotene from oils with alumina-column chromatography, because β-carotene is even less-polar than triacylglycerols (TAGs) are. The objective of this study was to obtain butter oil TAGs free from β-carotene and antioxidants via sequential treatments with activated carbon (AC) adsorption and alumina column chromatography. The AC used was prepared from waste apricots. The effects of AC dosages, temperatures and time courses on β-carotene adsorption were studied. The Langmuir and Freundlich isotherms were used to describe the adsorption of β-carotene onto AC, and it was found to be more consistent with the Freundlich isotherm with a higher R 2 value (0.9784). Adsorption kinetics of β-carotene was analyzed by pseudo-first order and pseudo-second order models. The pseudo-second order model was found to explain the kinetics of β-carotene adsorption more effectively (R 2 = 0.9882). The highest β-carotene reduction was achieved (from 31.9 to 1.84 mg/kg) at an AC dosage of 10 wt%, temperature of 50 °C, and adsorption time of 240 min. A considerable amount of α-tocopherol was also adsorbed during the AC treatment. Remaining portions of α-tocopherol were completely removed with alumina adsorption chromatography. The method described may be used for purification of vegetable oil TAGs, which will be used as model compounds in model oxidation studies.  相似文献   

4.
The adsorption of β-carotene from solution in benzene on acid-activated Canakkale montmorillonite of Turkey has been investigated. The adsorption isotherm had two steps. The first step was of the Langmuir type, and the isosteric heat of adsorption corresponding to this step was equal to −193.514 kJ/mol. The decrease in the total number of acid sites of the clay surface was determined to be 0.45×10−4 mol/g clay by nonaqueous titration with diethylamine. The phenomenon seems to be mainly a chemisorption stemming from the interaction of β-carotene with acid sites. Also, the activated clay acts as an oxidation catalyst on the β-carotene left in the solution.  相似文献   

5.
The autoxidation of linoleic acid dispersed in an aqueous media and the antioxidant effect of hydroxytyrosol, oleuropein, caffeic acid and tyrosol were studied. Linoleic acid autoxidation rate was estimated by the increase of conjugated diene level and by the decrease of linoleic acid content in the samples. The phenolic compounds exhibited an antioxidant activity which increased in the order: tyrosol < caffeic acid < oleuropein < hydroxytyrosol. The analysis of the hydroperoxide isomers pointed out that hydroxytyrosol, oleuropein and caffeic acid at a concentration of 10−4M inhibited the formation oftrans- trans isomers in the increasing order: caffeic acid < oleuropein < hydroxytyrosol. This inhibition could be related to the ability of phenolic compounds to scavenge peroxyl radical. Tyrosol did not inhibit the formation oftranstrans isomers. Phenolic compounds were degraded as a consequence of their antioxidant activity and their degradation rate was positively correlated to their antioxidant efficacy. These phenolic compounds, at a concentration of 6 × 10−3M, also scavenged hydroxyl radical, with an efficiency which increased in the order: tyrosol < hydroxytyrosol < oleuropein < caffeic acid. Polar substituents at the para position, such as in caffeic acid and oleuropein, were correlated with higher hydroxyl radical quenching ability.  相似文献   

6.
The relation between oxidative stability and composition in 58 virgin olive oils from different cultivars and Argentinian regions was studied over four harvest years. The oxidative stability of the oils was assessed using the OSI index (110 °C, 20 L/h air flow). A multiple linear regression model is proposed using OSI values as the dependent variable (multiple R = 0.933, p = 1 × 10−15), with positive contributions of the independent variables: fatty acid composition [oleic acid/(linoleic acid + linolenic acid), 55.3%, p = 1 × 10−15], total polyphenols (24.1%, p = 1.8 × 10−9), carotenes (4.8%, p = 6.1 × 10−5), β-tocopherol (1.9%, 6.0 × 10−3) and other compounds (13.9%). Highly significant correlation was observed between oxidative stability indexes estimated by the compositional model and those experimentally determined by Rancimat method (b = 0.981, R = 0.924). Chlorophylls and Δ-5-avenasterol contributions to the model were non-significant when variables related with fatty acids and polyphenols were included. The results suggest that the fatty acid composition and the polyphenol content are the main factors that affect the oxidative stability of olive oils. The proposed model allows the estimation of the oxidative stability in olive oils independently of the cultivar. The model was obtained also taking into account samples that lie out of the international legal limits in some compositional values due to natural variations.  相似文献   

7.
An expeditious colorimetric methodology for the determination of the deoxycholic acid (DCA) and of the ursodeoxycholic acid (UDCA) in pharmaceutical formulations is reported. The method is based on their competitive complexation reaction with a color indicator to form β-cyclodextrin-inclusion complexes. Several pH color indicators were tested, but phenolphthalein (PHP) showed the best interaction with the β-cyclodextrin (β-CD) with an inclusion yield higher than 95%. The best concentrations of β-cyclodextrin to form inclusion complexes were 1.24 × 10−3 and 6.2 × 10−4 M at pH 9.5 and 10.5. Statistical analysis of the results showed that the pH had a significant effect on the DCA determination and that high β-CD-PHP inclusion complex concentrations had a significant negative effect on the UDCA determination (p < 0.05). The limit of detection and limit of quantification were 3.94 × 10−5 and 1.31 × 10−4 M for DCA (range: 6.1 × 10−6–3.13 × 10−3 M), 4.08 × 10−5  and 1.36 × 10−4 M for UDCA (range: 6.05 × 10−6–3.88 × 10−4 M). This simple and cheap method showed high stability and feasible instrumentation.  相似文献   

8.
Honglian Shi  Etsuo Niki 《Lipids》1998,33(4):365-370
Owing to increasing evidence showing the importance of lipid peroxidation in oxidative stress in vivo, the role and evaluation of antioxidants have received much attention. Ginkgo biloba extract (GBE), well-known as an efficient drug against diseases induced by free radicals, has been suggested to exert its effect by antioxidant action. A method was established to determine the activity of GBE as a hydrogen donor by stoichiometric and kinetic studies, and GBE was compared with several other antioxidants such as α-tocopherol, propyl gallate, and two kinds of flavonoids which are found in GBE, quercetin, and kaempferol. It was found that there were 6.62×1019 active hydrogens in 1g of GBE. Stoichiometric studies showed that one molecule of α-tocopherol reacted with one molecule of galvinoxyl radical. For quercetin, kaempferol and propyl gallate, the experimental stoichiometric numbers were 4.0, 1.9, and 3.1, respectively. The rates of reaction of antioxidants with galvinoxyl in ethanol were determined spectrophotometrically, using a stopped-flow technique. The second-order rate constant, k 2, obtained at 25°C was 0.13 (g/l)−1s−1 for GBE and 5.9×103, 2.1×103, 1.2×104, and 2.4×103 M−1s−1 for quercetin, kaempferol, propyl gallate, and α-tocopherol, respectively. The second-order rate constant, k 2′, on the molar basis of active hydroxyl groups in the tested substances obtained at 25°C decreased in the order of propyl gallate > α-tocopherol> quercetin>GBF∼kaempferol. This is the first study on GBE as an antioxidant which reports both stoichiometric and kinetic results.  相似文献   

9.
This study chemically characterizes and evaluates the bactericidal and antioxidant activities of essential oils from Myristica fragrans and Salvia microphylla. The essential oils were obtained by steam distillation and were subsequently subjected to analysis by GC–MS and GC. The agar diffusion test was employed to evaluate the bactericidal activity, while the 1,1-diphenyl-2-picrylhydrazyl (DPPH) and β-carotene/linoleic acid tests were used to determine the antioxidant activity. Terpin-4-ol (14.95%), sabinene (13.07%) and γ-terpinene (11.22%) were found to be the major constituents in the essential oil of M. fragrans by gas chromatography, whereas (E)-caryophyllene (15.35%), α-eudesmol (14.06%), β-eudesmol (8.74%) and γ-eudesmol (7.64%) were encountered in the essential oil of S. microphylla. Both essential oils showed bactericidal activity, with the essential oil of S. microphylla being more efficient. The antioxidant activity of the essential oils from M. fragrans and S. microphylla were demonstrated by the β-carotene/linoleic acid test, with IC50 976 and IC50 770 μg/mL, respectively.  相似文献   

10.
The physicochemical characteristics and minor component contents of blended oils packed in pouches in relation to starting oils used for blending were studied over a period of 6 mon at two storage temperatures and humidity conditions: 27°C/65% RH and 40°C/30–40% RH. Color, PV, FFA value, β-carotene content, tocopherol content, and oryzanol content of the oils were monitored at regular intervals. The color, PV (0.6–20.7 meq O2/kg, FFA value (0.08–2.1%), tocopherol content (360–1700 ppm%), oryzanol content (460–2,000 mg%), and sesame oil antioxidants (400–2,000 mg%) were not changed in either the starting oils or their blends. Oils and oil blends containing a higher initial PV (18.9–20.7 meq O2/kg) showed a slight reduction in value at 40°C, whereas oils having lesser PV of 5–10 showed a slight increase during the storage period. Among the minor components studied, only β-carotene showed a reduction, 8.9–60.2% at 27°C and 48–71% at 40°C, for the different oil blends studied. The observed results indicated that the packed oil blends studied were stable under the conditions of the study, and the minor components, other than β-carotene, remained unaltered in the package even at the end of 6 mon of storage.  相似文献   

11.
The kinetics of photoperoxidation of [1−14C]arachidonic acid (20∶4n−6) at 1.32 mM was studied either with the unsaturated fatty acid alone or in the presence of 10μM of antioxidants and/or inhibitors of eicosanoid metabolism. The photosensitizer used wasmeso-tetraphenylporphine. The time-course of the reactions was followed by ultraviolet spectral analysis, thiobarbituric acid reactivity and high-performance liquid chromatographic analysis of aliquots sampled every 15 min during the 4 h of irradiation. The kinetics of photoperoxidation of 20∶4n−6 can be divided into three main successive steps: (i) monohydroperoxidation, characterized by the appearance of conjugated diene patterns and monohydroperoxidized 20∶4n−6; (ii) secondary oxidation characterized by polyoxygenated products such as dihydroperoxidized 20∶4n−6 possessing conjugated triene patterns; and (iii) the disappearance of conjugated patterns and the oxidative cleavage of the products of the two first steps into aldehydic molecules reacting with thiobarbituric acid. During the first 90 min of irradiation, the mechanism of monohydroperoxidation (step one) is purely or predominantly type II photoperoxidation involving only singlet oxygen. This step was inhibited by β-carotene and by BW755C (3-amino-1-[3-trifluoromethylphenyl]2-pyrazoline). In contrast, the reactions involved in the second and third steps were predominantly type I photoperoxidation involving radical mechanisms. These latter steps were inhibited by β-carotene, BW755C, vitamin E and probucol. Indomethacin and 5,8,11,14-eicosatetraynoic acid did not alter 20∶4n−6 photoperoxidation. Thisin vitro model of lipid photoperoxidation allows the screening of antioxidants in accordance with their singlet oxygen quenching and/or free radical scavenging properties.  相似文献   

12.
Kazuo Mukai  Yuji Okauchi 《Lipids》1989,24(11):936-939
A kinetic study of the reaction between a tocopheroxyl radical and unsaturated fatty acid esters has been undertaken. The rates of allylic hydrogen abstraction from various unsaturated fatty acid esters (ethyl oleate2, ethyl linoleate3, ethyl linolenate4, and ethyl arachidonate5) by the tocopheroxyl radical (5,7-diisopropyltocopheroxyl6) in benzene have been determined spectrophotometrically. The second-order rate constants, k3, obtained are 1.04×10−5 M−1s−1 for2, 1.82×10−2 M−1s−1 for3, 3.84×10−2 M−1s−1 for4, and 4.83×10−2 M−1s−1 for5 at 25.0°C. Thus, the rate constants, kabstr/H, given on an available hydrogen basis are k3/4=2.60×10−6 M−1s−1 for2, k3/2=9.10×10−3 M−1s−1 for3, k3/4=9.60×10−3 M−1s−1 for4, and k3/6=8.05×10−3 M−1s−1 for5. The kabstr/H values obtained for the polyunsaturated fatty acid esters3,4, and5 containing H-atoms activated by two π-electron systems are similar to each other, and are about three orders of magnitude higher than that for the ethyl oleate2 containing H-atoms activated by a single π-system. From these results, it is suggested that the prooxidant effect of α-tocopherol in edible oils and fats may be induced by the above hydrogen abstraction reaction.  相似文献   

13.
The odor detection thresholds of carvacrol (5-isopropyl-2-methyl-phenol), thymol (2-isopropyl-5-methyl-phenol) and p-cymene 2,3-diol (2,3-dihydroxy-4-isopropyl-1-methyl-benzene) in sunflower oil, determined by the three-alternative, forced-choice procedure, were 30.97, 124 and 794.33 mg kg−1, respectively. Sunflower oil containing 13, 70, or 335 mg kg−1 of carvacrol, thymol or p-cymene 2,3-diol, respectively, was judged to be similar (P < 0.01) in taste and odor to its antioxidant-free counterpart. The rate constant of sunflower oil oxidation, measured from the increase in peroxide value during storage at 25 °C, was 9.2 × 10−9 mol kg−1 s−1 while the rate constants were 9.3 × 10−9, 9.8 × 10−9, and 4.3 × 10−9 mol kg−1 s−1 in the presence of 13 mg kg−1 carvacrol, 70 mg kg−1 thymol, and 335 mg kg−1 p-cymene 2,3-diol, respectively. At a level of 335 mg kg−1, p-cymene 2,3-diol did not impart flavor taints and effected a 46.7% reduction in the rate of oxidation of sunflower oil. These findings indicate that the diphenolic p-cymene 2,3-diol could potentially replace synthetic antioxidants and is a valuable addition to the antioxidants used by the food industry in its quest to meet consumer demands for synthetic-additives-free and ‘natural’ foods.  相似文献   

14.
Antioxidant activity of Magnolol, honokiol, and related phenolic compounds   总被引:14,自引:0,他引:14  
The antioxidant activity of 10 Japanese and Chinese crude drugs (Kampo drugs) was determined in vitro. Extract of Magnolia cortex, which had the highest antioxidant activity, contained phenolic compounds magnolol and honokiol. However, inhibitory effects of these compounds on lipid oxidation were weaker than that of α-tocopherol as measured by thiobarbituric acid assay. The structure-activity relationship of phenolic compounds showed that antioxidant activities were in the order 4-allyl-2,6-dimethoxyphenol ≥ p,p′-biphenol > eugenol > 2-allyl-6-methylphenol > honokiol > magnolol > caffeic acid > p-ethylphenol > guaiacol. As expected, these results showed that an electron donor and/or bulky groups at the ortho- or para-position of the phenol were required for inhibition of lipid oxidation. Electron spin resonance spin trapping experiments showed that phenol compounds with an allyl substituent on their aromatic rings directly scavenged superoxide (O 2 ), and that only eugenol trapped hydroxyl radicals. These findings suggest that phenolic compounds that contain allyl groups may be effective antioxidants because of the scavenging ability of O 2 or hydroxyl radical, whereas other phenols, without an allyl moiety such as α-tocopherol, may play a role in the termination of free radical chain reactions.  相似文献   

15.
The water-soluble polypyrrole, poly[4-(3-pyrrolyl)butanesulfonic acid] (P3PyBSH), in which the β-position of pyrrole ring is substituted with n-butanesulfonic acid group, is synthesized by oxidation polymerization of 3PyBSNa followed with an ion-exchange of Na+ with H+. It can be cast into free-standing film from its aqueous solution and has a conductivity of 4.0×10−4 S/cm, higher than that of its sodium salt (5.5× 10−6 S/cm) by about 2 orders. The increase in conductivity is attributed to the self-doping by the protons originally on the side chains as supported by the absence of the anion FeCl4 (which generates during the polymerization) and the presence of polaron and bipolaron characteristics in its UV-Vis and IR spectra.  相似文献   

16.
Palm oil contains high concentrations of carotenoids and tocopherols that can be recovered by first converting them to methyl esters and then applying membrane technology to separate the carotenoids from the methyl esters. Several solvent-stable nanofiltration membranes were investigated for this application. Flux with a model red palm methyl ester solution ranged from 0.5 to 10 Lm−2h−1, and rejection of β-carotene was 60–80% at a transmembrane pressure of 2.76 MPa and 40°C. A multistage membrane process was designed for continuous production of palm carotene concentrate and decolorized methyl esters. With a feed rate of 10 tons per hour of red palm methyl esters containing 0.5 gL−1 β-carotene, the process could produce 3611 L·h−1 of carotene concentrate containing 1.19 gL−1 carotene and 7500 Lh−1 of decolorized methyl esters containing less than 0.1 gL−1 β-carotene. The economics of this process is promising.  相似文献   

17.
Laboratory treatment of soybean oil were carried out at the following conditions: atmospheric pressure in the presence of air or nitrogen at different temperatures ranging from 160 to 250°C for 12 to 72 h. These conditions were used to study geometric isomerization of cis,cis-linoleic and cis,cis,cis-linolenic acid in the presence or in the absence of oxidative degradation reactions. Based on these experiments, a model of consecutive, parallel reactions was developed to describe the reaction steps occurring in the soybean oil during heating at constant temperature. For both cis,cis-linoleic and cis,cis,cis-linolenic acid, the reaction of formation isomers followed a first-order reaction, and the rate constant of isomerization varied according to the Arrhenius law. The isomerization rate constant for linoleic acid was 9.57×10−3±0.50 h−1 in the presence of oxygen and 7.39×10−3±0.39 h−1 in its absence, and the isomerization rate constant for linolenic acid was 1.18×10−1±0.10 h−1 in the presence of oxygen and 0.87×10−1±0.07 h−1 in its absence (all obtained at 250°C).  相似文献   

18.
The chemical characteristics, phenolic content and antioxidant activity of olive oils flavored with garlic, lemon, oregano, hot pepper, and rosemary were evaluated during 9 months of storage. At the end of the storage period, the unflavored and the garlic-flavored oils maintained their chemical parameters within the limits fixed for extra-virgin olive oils. After 9 months of storage, a noticeable decrease in phenolic content was observed in all the oils. The highest (35.0 ± 3.9 mg/kg oil) and the lowest (6.3 ± 0.4 mg/kg) phenolic contents were detected in the unflavored and garlic-flavored oils, respectively. Compounds such as 3,4-DHPEA-EDA (3,4-dihydroxyphenylethyl 4-formyl-3-formylmethyl-4-hexenoate, the dialdehydic form of decarboxymethyl elenolic acid linked to hydroxytyrosol) and p-HPEA-EDA (dialdehydic form of the decarboxymethyl elenolic acid linked to tyrosol) were the most abundant in both unflavored and lemon-flavored oils up till 6 months of storage. At the end of the storage period, increases in 3,4-DHPEA (hydroxytyrosol) and p-HPEA (tyrosol) were measured in almost all the oils. During storage, the antioxidant activity coefficients of the phenolic extracts, calculated according to the β-carotene bleaching assay, significantly decreased and, after 9 months, were in a decreasing order: rosemary (51.3 ± 4.2), hot pepper, lemon, oregano, unflavored, and garlic (8.5 ± 0.7).  相似文献   

19.
To test if linolenic acid (18∶3n−3) from vegetable oils would affect bleeding times and platelet counts in new-borns, piglets were used as a model fed milk replacer diets containing 25% (by wt) vegetable oils or oil mixtures for 28 d and compared to sow-reared piglets. The oils tested included soybean, canola, olive, high oleic sunflower (HOAS), a canola/coconut mixture and a mixture of oils mimicking canola in fatty acid composition. All piglets fed the milk replacer diets showed normal growth. Bleeding times increased after birth from 4–6 min to 7–10 min by week 4 (P<0.001), and were higher in pigs fed diets containing 18∶3n−3, as well as in sowreared piglets receiving n−3 polyunsaturated fatty acids (PUFA) in the milk, as compared to diets low in 18∶3n−3. Platelet numbers increased within the first week in newborn piglets from 300 to 550×109/L, and remained high thereafter. Milk replacer diets, containing vegetable oils, generally showed a transient delay in the rise of platelet numbers, which was partially associated with an increased platelet volume. The oils showed differences in the length of delay, but by the third week of age, all platelet counts were >500×109/L. The delay in rise in platelet counts appeared to be related to the fatty acid composition of the oil, as the effect was reproduced by a mixture of oils with a certain fatty acid profile, and disappeared upon the addition of saturated fatty acids to the vegetable oil. There were no alterations in the coagulation factors due to the dietary oils. Blood plasma, platelets and red blood cell membranes showed increased levels of 18∶3n−3 and long-chain n−3 PUFA in response to dietary 18∶3n−3. The level of saturated fatty acids in blood lipids was generally lower in canola and HOAS oil-fed piglets as compared to piglets fed soybean oil or reared with the sow. The results suggest that consumption of milk replacer diets containing vegetable oils rich in 18∶3n−3 does not represent a bleeding risk, and that the transient lower platelet count can be counterbalanced by the addition of saturated fatty acids to the vegetable oils.  相似文献   

20.
Ayyildiz HF  Kara H  Sherazi ST 《Lipids》2011,46(12):1181-1190
A non-aqueous flow injection method for determining free fatty acid (FFA) content in corn and sunflower oil samples was developed. A single-line manifold system was built by modification of an HPLC for flow injection analysis (FIA). Without pre-treatment, oil samples were injected into a n-propanol solution containing KOH and phenolphthalein (PHP). The main parameters, such as flow rate of carrier phase, length, geometry, inner diameters of the coils and reagent concentration were all optimized. The proposed FIA method was validated for precision, accuracy, linear region, limit of detection (LOD) and limit of quantification (LOQ). The intra- and inter-day measurements of the precision of the method were found to be within the limits of acceptance criteria (RSD < 1%), and were rugged when the method was performed by a different analyst. The linear concentration range was calculated as 0.09–1.50 and 0.07–1.40 FFA% for corn and sunflower oils, correspondingly. The LOD and LOQ were found to be 7.53 × 10−4–2.28 × 10−3 oleic acid % and 7.11 × 10−4–2.23 × 10−3 oleic acid % for corn and sunflower oils, respectively. The results were compared with those obtained by the AOCS (Ca-5a-40) method using statistical t and F tests, and a significant difference was not observed between the methods at a 95% confidence level. The proposed method is suitable for quality control of routine applications due to its simplicity, high sample throughput, and economy of solvents and sample, offering considerable promise as a low cost analytical system that needs minimum human intervention over long periods of time.  相似文献   

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