• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    Most formulations in the cosmetic, pharmaceutical and agrochemical sector contain chemical compounds, such as adjuvants, that help stabilize these emulsions and favor the permeability of the active substances through cell membranes. Many of these adjuvants are chemically synthesized compounds that can cause problems of biocompatibility, irritability and allergies, unlike natural extracts, such as lecithin and/or phospholipids extracted from plant sources, since these are naturally present in tissues such as skin. This patent includes the procedure and use of an aqueous residual stream from the fractionation of corn by wet route, as a source of lecithin and phospholipids for application in the cosmetic, pharmaceutical, food and agrochemical fields, due to the emulsifying and regenerating properties of phospholipids and/or lecithin. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2739050A1
    申请号:ES201800169
    申请日:2018-07-25
    公开日:2020-01-28
    发明作者:Menduina Ana Belén Moldes；Freire José Manuel Cruz；Lopez Lorena Rodriguez；Fontan Mirian Rincon
    申请人:Universidade de Vigo；
    IPC主号:
    专利说明:

    [0001]
    [0002] Use of corn wash liquors as a source of phospholipids and lecithin.
    [0003]
    [0004] Technical sector
    [0005]
    [0006] The present invention belongs to the sector of natural substances with emulsifying and regenerative capacity of cells, including phospholipids and / or lecithin.
    [0007]
    [0008] The main object of the invention is to obtain a natural extract based on lecithin and / or phospholipids, from an aqueous residual stream, from the process of fractionation of corn by wet route, with potential uses in the pharmaceutical, cosmetic industry , food and agrochemicals, as adjuvants in their formulations, in order to improve their emulsifying and regenerative properties as well as to improve the permeability of the active compounds through cell membranes.
    [0009]
    [0010] Background of the invention
    [0011]
    [0012] Lecithin is an oily extract formed by phospholipids (PL) of a different nature, including phosphatidylcholine, phosphatidylethanolamine, phosphatidityl inositol, phosphatidic acid and phosphatidylserine. Generally these phospholipids are part of the membranes of animal and plant cells. Usually lecithin is obtained from eggs or cereals such as soybeans, there is ample information and evidence in this regard (Wagner and Richling, 2010; John et al., 2015; Ishii, 2016; Simedru et al., 2016; Akashi et al., 2017). However, there is no evidence of the extraction of lecithin and phospholipids from corn wash liquors. The only information that relates lecithin and phospholipids to corn, establishes the presence of lecithin and phospholipids with the germ or oil fraction thereof (Kwiatkowski and Cheryan, 2005; Bilbie, James; Blaszczyk, 2009; Liu et al., 2018 ).
    [0013]
    [0014] Liu et al., 2018 have described a process for the production of phospholipids and lecithin from corn germ, after a wet maceration stage. Corn germ accounts for about 11-12% of the grain weight and contains 45-50% oil. Liu et al., 2018 have discovered that corn germ is also rich in lecithin and that it can be obtained after grinding the corn germ to a particle size of 0.30-0.45 mm, followed by a supercritical extraction process with CO2 using a pressure of 30 MPa, a temperature of 50 ° C and a flow of 25 L / h, to remove the oil. This step supposes a reduction of oil in the corn germ of 95% and a loss of phospholipids of 6% with respect to the total.
    [0015]
    [0016] Subsequently, the oil-free corn germ is subjected to 95% ethanol extraction using microwaves and ultrasound, obtaining a supernatant and a solid fraction. The latter is dissolved in diethyl ether, resulting in the precipitation of solids that are removed by filtration with whatman paper. Then, the phospholipids are precipitated with cold acetone and subsequently washed carefully with it. Finally, the precipitate is dried with N2 at room temperature, obtaining 2.92% lecithin from the oil-free corn germ. The lecithin obtained by these authors has an N content of 1.77% and a phosphorus content of 3.47%.
    [0017]
    [0018] Kwiatkowski and Cheryan, 2005 have proposed the use of membranes for the concentration of a solution of corn oil dissolved in ethanol, obtaining a retentate or solid fraction composed of solids, concentrated corn oil, proteins and lecithin.
    [0019]
    [0020] Bilbie, James; Blaszczyk, 2009 have patented the extraction of lecithin from an oily fraction from corn processing.
    [0021] On the other hand, in previous studies, it has been shown that from corn washing liquors, from wet corn processing, an extract with surfactant capacity can be obtained using different organic solvents. It has detected the presence of lipopeptides, (Vecino et al., 2014, 2015; Rodríguez-López et al., 2016), although there is no evidence until the moment of the possibility that this extract contains lecithin or phospholipids.
    [0022]
    [0023] There is no evidence until the moment of obtaining phospholipids and / or lecithin from corn washing liquors, obtained after the process of maceration thereof. Figure 1 shows the stages of the process of fractionation of corn by wet way to obtain different products, the aqueous stream being a by-product without much added value.
    [0024]
    [0025] Explanation of the invention.
    [0026]
    [0027] The use of corn wash liquors, also called "corn steep liquid", is proposed as a source of lecithin and phospholipids for use in the food and cosmetic industry as an emulsifier, humectant or excipient that favors the permeability of active substances.
    [0028] Detailed Explanation of the Invention
    [0029]
    [0030] Several aqueous streams of corn wash liquors were analyzed, including those provided by FeedStimulants and SantaCruz Biotechnology, obtaining an extract with a yield, based on the precipitate obtained, consisting of lecithin and phospholipids of 2 g / Kg and 1 g / kg, respectively.
    [0031]
    [0032] Flay to take into account that lecithin and / or phospholipids are very poorly soluble in water (Kass, Gus; Skokie, 1981) and that, probably, the presence of it in corn wash liquors is favored by existing surfactants in this same current, with solubilizing capacity and whose existence we have demonstrated previously (Vecino et al., 2014, Vecino et al., 2015; Rodríguez-López et al., 2016).
    [0033]
    [0034] Due to its low water solubility, lecithin and / or phospholipids are easily extracted from aqueous streams using organic solvents such as chloroform or ethyl acetate, which are removed from the extract under study by distillation. Note that, during this extraction process with organic solvents, fatty acids and high molecular weight biosurfactants coinciding with the latter with lipopeptides are also extracted. Therefore, a subsequent step of precipitation and washing with acetone is necessary, so that an extract based on phospholipids and / or lecithin is obtained, separated from the other components (fatty acids and biosurfactants of high molecular weight), which is they also obtain in the first stage of extraction with organic solvents.
    [0035]
    [0036] Figure 2 shows, by way of example, the mass spectrum of the extract obtained after the first stage carried out to obtain phospholipids and lecithin from corn washing liquors, consisting of an extraction with ethyl acetate or chloroform, observing in the obtained extracts a mass at 758 Da in both cases, which correspond to lecithin and / or phospholipids.
    [0037]
    [0038] In addition, Figure 3 shows the complete mass spectrum of the precipitate and the supernatant, obtained after the second stage carried out to obtain lecithin and phospholipids from corn wash liquors, consisting of the precipitation of lecithin and phospholipids with acetone.
    [0039] According to the mass spectrum of the precipitate (Figure 3a), it can be seen that it is mainly composed of a mass compound of 758 Da, coinciding with the majority mass that is repeated in phospholipid patterns.
    [0040] On the other hand, in the supernatant (Figure 3b) a disappearance of the corresponding signal with the phospholipids and / or lecithin, of molecular weight of 758 Da, is observed, with other compounds concentrated in this supernatant among which the hydroxynamic acid has been identified, of molecular mass 441 Da, with a relative abundance of 80.6%, corresponding to an antioxidant compound, which has been identified in previous work in different fractions of corn (LeClere, Schmelz and Chourey, 2007; Rodríguez-López et al., 2016) .
    [0041] In addition, Figure 4 shows the similarity of the masses found, between 700-800 Da, of the precipitate under study, obtained from corn wash liquors, with different patterns of lecithin and phospholipids. In this same Figure 4, the spectrum of the supernatant is also included, observing that after the precipitation process the presence of phospholipids and / or lecithin is hardly appreciated, in the same, there is no signal in the studied mass range.
    [0042] In addition, the signal corresponding to the molecular mass of 758 Da, obtained from the corn wash liquors, in their respective molecular ions (Figure 5a), has been compared with the decomposition of the molecular masses of the lecithin standard samples (Figure 5b) and phosphatidylethanolamine (Figure 5c). It has been observed that the molecular ions obtained from the precursor masses are very similar.
    [0043] On the other hand, Tables 1 and 2 show the relative abundance of the masses according to the mass spectra obtained for the precipitate and supernatant from the corn wash liquors, collected in Figure 3. As can be seen in Figure 3a, the peak of greater intensity relative to the precipitate, corresponds to the mass of lecithin and / or phospholipids, so that the relative abundance of all other peaks was calculated based on this mass in the precipitate sample (Table 1) . In the case of the supernatant (Table 2, Figure 3b), the relative abundance was determined based on the maximum intensity signal, this being the mass of 933 Da.
    [0044] Table 1. Relative abundance of the signals obtained by ESI-MS for the precipitate obtained from the corn wash liquors formed mainly by lecithin and / or phospholipids.
    [0045] A. Precipitate
    [0046] m / z Relative abundance (%)
    [0047] 302.30677 10.2
    [0048] 395.22287 12.1
    [0049] 516.01794 14.9
    [0050] 614.04531 46.4
    [0051] 758.57853 100.0
    [0052] Table 2. Relative abundance of the signals obtained by ESI-MS for the supernatant resulting from the extraction of phospholipids and / or lecithin.
    [0053] B. Supernatant
    [0054] m / z Relative abundance (% (
    [0055] 211.14502 10.7
    [0056] 309.28078 74.8
    [0057] 441.20591 80.6
    [0058] 617.52081 92.6
    [0059] 758.56957 0
    [0060] 933.79001 100
    [0061] On the other hand, Table 3 shows the molecular ions obtained from the decomposition of the compound of greater relative and more representative abundance both for the precipitate, obtained from the corn wash liquors, as for all the lecithin and phospholipid patterns used. It should be noted that the lecithin used as a standard was extracted from soybeans, therefore considering a set of phospholipids of varied nature. This can cause small variations in molecular ions when similar samples of phospholipids from other sources such as corn are compared.
    [0062] Table 3. Molecular ions obtained from the decomposition of the majority and / or characteristic signal for the precipitate obtained from the corn wash liquors, and the lecithin and phospholipid patterns.
    [0063] Compound m / z Decomposition Precipitate of corn wash liquors 758 575; 184
    [0064] Lecithin 782 599; 184 Lecithin 758 184 Phosphatidylcholine 760 184 Phosphatidylserine 685 601; 440; 194 Phosphatidylethanolamine 758 577; 182 Based on the decomposition of the majority masses of the precipitate from the corn wash liquors, it is corroborated that there is evidence that the precipitate obtained from the corn wash liquors has mostly phospholipids coinciding with the lecithin, and similar to phosphatidylethanolamine and phosphatidylcholine.
    [0065] Brief description of the drawings
    [0066] To complement the description that is being made and in order to help a better understanding of the characteristics of the invention, a set of drawings is attached as an integral part of said description, where illustrative and non-limiting nature has been represented. next:
    [0067] Figure 1. Scheme of the main products and by-products obtained from wet corn processing.
    [0068] Figure 2. ESI-MS spectrum of extracts with biosurfactant capacity obtained from corn wash liquors with acetate (A) and chloroform (B).
    [0069] Figure 3. ESI-MS spectra of the precipitate under study with the presence of phospholipids and / or lecithin (A), as well as the supernatant (B) obtained from the corn wash liquors. Figure 4. ESI-MS spectra of the precipitate and the supernatant obtained from the corn wash liquors and the phospholipid and lecithin standards used during the tests. Figure 5. ESI-MS-MS spectra of fragmentation of the 758 Da signals for the precipitate (A), lecithin (B) and phosphatidylethanolamine (C).
    [0070] Figure 6. General diagram of obtaining lecithin and / or phospholipids from corn wash liquors.
    [0071] Preferred Embodiment of the Invention
    [0072] Extracts were made to corn washing liquors from various sources to corroborate their use as a source of phospholipids and lecithin, including, for example, liquors supplied by Santa Cruz Biotechnology Inc. (Santa Cruz, USA) u ) or those supplied by FeedStimulants (Utrecht, The Netherlands).
    [0073] The extract object of this invention was obtained, from corn wash liquors, by extraction with organic solvents, including chloroform, ethyl acetate, among others. After this extraction, the solvent was removed by distillation and the extract obtained was subjected to a precipitation with acetone, using for example a 20: 1 ratio (acetone: extract), at -80 ° C for 24 h and then, the solid obtained was filtered under vacuum and analyzed. In Figure 6 one of the protocols followed for obtaining phospholipids and / or lecithin can be observed.
    [0074] In Table 4, some of the conditions used with ethyl acetate and chloroform that lead to good extraction yields are shown by way of example.
    [0075] Table 4. Conditions for obtaining the extract from corn wash liquors.
    [0076] Solvent ratio: residue
    [0077] Solvent Time (min) Temperature (° C)
    [0078] (v / v)
    [0079] Chloroform 2: 1 60 56
    [0080] Ethyl acetate 3: 1 45 25
    [0081]
    [0082] After extraction, phospholipid analysis was carried out using the High Resolution Electro Spray (ESI-HR) ionization technique. In addition to corroborating the presence of phospholipids and lecithin in the sample obtained from corn wash liquors, the following phospholipid and lecithin patterns were used: Soy lecithin (Scharlau Microbiology, Spain), L-alpha-phosphatidylcholine from yolk of egg> 99% and egg yolk L-alphaphosphatidylethanolamine> 97% (Sigma-Aldrich, USA), phosphatidyl-L-serine (Carbosynth, United Kingdom.
    权利要求:
    Claims (6)
    [1]
    1. The use of corn wash liquors as a source of phospholipids and lecithin.
    [2]
    2. The process of extracting phospholipids and / or lecithin from corn washing liquors by extraction with organic solvents such as chloroform or ethyl acetate, followed by a precipitation process with solvents such as acetone.
    [3]
    3. The use or application of lecithin and / or phospholipids present in corn wash liquors, according to claim 1, as an emulsifying agent, in the food and cosmetic industry.
    [4]
    4. The use of lecithin and / or phospholipids present in corn wash liquors, according to claim 1, as a cell regeneration agent in the cosmetic industry.
    [5]
    5. The use of lecithin and / or phospholipids present in corn wash liquors, according to claim 1, for the treatment of hair in order to improve its electrostatic properties and hydration.
    [6]
    6. The use of lecithin and / or phospholipids present in corn wash liquors, according to claim 1, to improve the permeability of active ingredients through cell membranes, including cosmetic, pharmaceutical and agrochemical formulations.
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    同族专利:
    公开号 | 公开日
    ES2739050B2|2020-12-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US8232418B1|2008-08-01|2012-07-31|Corn Products International, Inc.|Method for the preparation of lecithin|
    ES2435324A1|2012-06-18|2013-12-18|Universidade De Vigo|Method for separating the surfactants present in the washing liquors of corn, and uses|
    ES2527366A1|2013-07-22|2015-01-22|Universidade De Vigo|Detergent composition comprising a biosurfactant of plant origin |
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