CN112336644A - Folic acid-metal ion composition, preparation method thereof and application thereof in sun protection - Google Patents
Folic acid-metal ion composition, preparation method thereof and application thereof in sun protection Download PDFInfo
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Abstract
The invention provides a folic acid-metal ion composition, a folic acid-metal ion hydrogel, a sunscreen containing the hydrogel and application of the sunscreen in ultraviolet absorption. After the folic acid aqueous solution and the metal ion aqueous solution are mixed, folic acid and metal ions are crosslinked to form solution, gel or suspension containing the reticular hydrogel. The sunscreen effect of the folic acid-metal ion hydrogel is almost constant with folic acid, the safety is good, the reliability is high, the chemical property is stable, the sunscreen agent prepared from the folic acid-metal ion hydrogel is very fresh and cool, and the use experience is good. The folic acid-metal ion hydrogel has controllable property, and can meet different production requirements and consumer requirements.
Description
Technical Field
The invention relates to application of folic acid in sun protection, in particular to a folic acid-metal ion composition and application of folic acid-metal ion hydrogel in sun protection.
Background
The sunlight is composed of 5% ultraviolet (200-400nm), 43% visible light (400-700nm), and 52% near infrared (700-2500nm), wherein the ultraviolet can be divided into short-wave ultraviolet (200-275nm), medium-wave ultraviolet (275-320nm), and long-wave ultraviolet (320-400 nm). Short-wave Ultraviolet (UVC) is almost always filtered by the atmosphere; medium-wave Ultraviolet (UVB) rays penetrate the cornified cortex causing most skin damage; long-wave Ultraviolet (UVA) light penetrates the dermis, which produces melanin in the dermis, causing tanning and aging of the skin or sunburn.
The traditional sun protection principle is mainly divided into two categories:
1. physical sun protection: the main components are zinc oxide and titanium dioxide, which can stay on the surface of the skin and reflect and scatter ultraviolet rays, and the purpose of sunscreen is achieved by reducing the amount of ultraviolet rays reaching the skin. Titanium dioxide completely blocks UVB, but blocks only shorter wavelengths of UVA. Zinc oxide blocks almost all wavelengths of UVA and UVB and is safe, but is whitish and sticky when applied to the skin.
2. Chemical sun protection. The chemical light absorber forms an ultraviolet phagocytic barrier on the surface of the skin through other film-forming substances, absorbs and neutralizes ultraviolet rays, and prevents the ultraviolet rays from being injected into the skin to cause damage.
Currently, the development direction in the field of sun protection is mainly divided into three areas:
1. effectiveness: the Sun Protection Factor (SPF) is a measure of the ability of a sunscreen to protect against ultraviolet light in the sun, indicating how much sunscreen can be used. It is determined based on the lowest erythemal dose of the skin, i.e., the shortest sun exposure time for the skin to develop erythema. The value of the SPF sun protection factor means how many times the time the sunscreen can withstand uv light at the same uv intensity. After use of the sunscreen, the skin's minimum erythematous dose increases, with a sun protection factor SPF of: SPF ═ lowest (post-use)/lowest (pre-use) erythemal dose, the current development direction is naturally looking to develop sunscreen products of higher SPF ratings.
2. Safety: some chemical sunscreens, such as Avobenzone (Avobenzone, BMDM), Octyl Methoxycinnamate (OMC), etc., can damage cells and tissues by free radicals or molecular fragments generated after decomposition by sunlight. In addition, some sunscreen components can be absorbed by the skin, absorb ultraviolet rays in the skin, and can be removed by human metabolism after the skin is treated, but the sunscreen components also have safety and health concerns, and even cause skin dependence. Developers desire safer, stable chemical sunscreens.
The safety issues of chemical sunscreens are of particular importance in research and development. The FDA performed a test on tissue volunteers in 2019 (JAMA.2019; 321(21):2082-2091.doi:10.1001/jama.2019.5586) to test the components of sunscreens in plasma with a frequency of four consecutive days for four days per day. The results show that the concentration of four common commercial sunscreen chemical components, avobenzone, benzophenone-3 (BP-3), Octyl salicylate, Octyl methoxycinnamate, in plasma exceeds the maximum FDA-specified blood concentration.
3. Consumer acceptance: traditional sunscreens are creams or creams, etc., and in hot summer, a too greasy product can increase the stuffiness sensation of the user. Consumers are interested in new sunscreen formulations in the form of sprays, gels, etc.
Based on the background of safety development of the chemical sunscreen agents, the application of water-soluble vitamin B9 folic acid in ultraviolet absorbers is provided, and particularly the application of a folic acid metal ion composition and a folic acid-metal ion hydrogel in sunscreen is provided.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have found that: the problem of poor folic acid solubility can be obviously improved after folic acid and metal ions are prepared into the hydrogel, so that folic acid exists in the hydrogel in a molecular state, and the sunscreen effect of the hydrogel is almost constant with that of a single folic acid solution. The prepared folic acid-metal ion hydrogel can easily regulate and control the properties of the folic acid-metal ion hydrogel, and the hydrogel with different fluid properties can be obtained within a certain folic acid-metal ion ratio range. The hydrogel has the advantages of viscosity, spreadability and uniformity of gel, good safety, high reliability and stable chemical property, is very fresh after being prepared into a sun-screening agent, and has good use experience, thereby completing the invention.
The object of the present invention is to provide the following:
in a first aspect, the present invention provides the use of folic acid for the prevention or prophylaxis of UV absorption.
In a second aspect, the present invention provides the use of a folate-metal ion composition comprising folic acid and one or more of zinc, silver, magnesium and calcium ions;
preferably, the folate-metal ion composition is a folate-metal ion hydrogel.
In a third aspect, the present invention provides a folate-metal ion hydrogel prepared by steps comprising:
(1) dissolving folic acid in water or aqueous buffer solution to prepare folic acid aqueous solution;
(2) dissolving metal salt in water or aqueous buffer solution to prepare metal ion aqueous solution;
(3) uniformly mixing the folic acid aqueous solution and the metal ion aqueous solution at room temperature, and standing to obtain folic acid-metal ion hydrogel;
the folic acid-metal ion hydrogel is in a solution, gel or suspension state.
Wherein the metal salt is hydrochloride, nitrate or sulfate;
the metal ion in the metal salt is one or more selected from zinc, silver, magnesium and calcium ion.
Preferably, in the step (1), when the folic acid is dissolved in water or an aqueous buffer solution, the pH value of the water or the aqueous buffer solution is adjusted to 7.0 to 9.5.
Further, in the steps (1) and (2), the aqueous buffer solution is selected from one or more of acetic acid-sodium acetate, boric acid-borax, N- (2-hydroxyethyl) piperazine-N' -2-ethanesulfonic acid, 3-morpholine propanesulfonic acid, 2- (N-morpholine) ethanesulfonic acid, trimethylol methylamine-hydrochloric acid, trimethylol methylamine-boric acid and trimethylol methylamine-acetic acid.
Preferably, in the step (3), after the folic acid aqueous solution and the metal ion aqueous solution are mixed,
the final concentration of folic acid is 0.5mM-200mM, preferably 5mM-100 mM;
the final concentration of metal ions is 0.1mM-500mM, preferably 5mM-400 mM.
Further, in the step (3), after the folic acid aqueous solution and the metal ion aqueous solution are mixed, the molar ratio of folic acid to metal ions is 1: 0.1-10, preferably 1: 1-5.
The folic acid-metal ion hydrogel can be prepared into various fluid forms such as solution, gel, suspension and the like by changing the ratio of folic acid to metal ions. When the metal ions are zinc ions, the folic acid-zinc ion hydrogel is prepared;
after mixing the folic acid aqueous solution and the zinc ion aqueous solution, with the increase of the folic acid concentration, the lower limit of the folic acid/zinc ion molar ratio of the folic acid-zinc ion hydrogel forming a gel state is gradually reduced, the upper limit is gradually increased, and the gel area is enlarged;
when the concentration of folic acid is not changed, the molar ratio of folic acid to zinc ions is gradually increased, and the folic acid-zinc ion hydrogel is changed into a gel state from a solution state and then into a suspension state.
In a fourth aspect, the present invention also provides a sunscreen comprising the folic acid-metal ion composition of the first aspect, wherein the sunscreen further comprises zinc oxide;
the mass fraction of the zinc oxide in the sun-screening agent is 0.1-10%, preferably 0.5-5%.
Preferably the sunscreen is an ointment, cream or gel.
In a fifth aspect, the present invention also provides the use of a folate-metal ion composition provided in the first aspect and a sunscreen provided in the second aspect to prevent or prevent ultraviolet absorption;
preferably as a sunscreen.
According to the folic acid-metal ion hydrogel and the application thereof in sunscreen, the folic acid-metal ion hydrogel has the following beneficial effects:
(1) after the folic acid is added into the metal ions to prepare the hydrogel, the sun-screening effect of the hydrogel is almost kept constant, the character of the folic acid-metal ion hydrogel can be easily regulated, and the hydrogel can be obtained within a certain folic acid-metal ion ratio range. The hydrogel has controllable properties, and can meet different production requirements and consumer requirements.
(2) The folic acid prepared into the folic acid-metal ion hydrogel has viscosity, spreadability and uniformity, and is very beneficial to the preparation and forming of the sunscreen agent.
(3) The appearance and the character of the folic acid-metal ion hydrogel are similar to those of aloe gel sold in the market, compared with the traditional greasy sunscreen cream, the consumer experience of the hydrogel is obviously improved, and the acceptance degree of the consumer can be improved.
(4) The folic acid-metal ion hydrogel can be compounded with other chemical ultraviolet absorbers and physical sunscreens to improve the sun-screening effect.
(5) The folic acid-metal ion hydrogel is good in safety, high in reliability, stable in chemical property, very fresh after being prepared into a sun-screening agent, and good in use experience.
Drawings
FIG. 1 shows a UV absorption spectrum of a chemical absorbent in Experimental example 1;
FIG. 2 shows UV absorption spectra of folate-zinc hydrogels of different folate-zinc ion ratios in Experimental example 2;
FIG. 3 is a graph showing a comparison of the sunscreen effect of various amounts of avobenzone, benzophenone-3, isooctyl salicylate, octyl methoxycinnamate in Experimental example 3 and the hydrogel prepared in example 1;
FIG. 4 is a graph showing a comparison of the sunscreen effect of different amounts of zinc oxide and zinc oxide formulated in Experimental example 4 with the hydrogel prepared in example 1;
FIG. 5 is a graph showing a comparison of the sunscreen effect of commercial sunscreen agent and zinc oxide formulated in Experimental example 5 with the hydrogel prepared in example 1;
FIG. 6 shows a schematic representation of the formation of a tetrad by hydrogen bonding of the pterin head group of folate during hydrogel formation;
FIG. 7 shows a schematic of a tetrad forming a reticulated hydrogel;
fig. 8 shows the phase diagram of folate-zinc ions, including solutions, gels and suspensions.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention, as illustrated in the accompanying drawings. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
In the description of the present invention, it should be noted that the terms "first", "second", "third" and "fourth" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
The present invention is described in detail below.
In the case of the existing chemical absorbents,
the content of avobenzone is as follows,
benzophenone-3 (BP-3)
The content of the salicylic acid is octyl ester,
octyl Methoxycinnamate (OMC),
can absorb ultraviolet rays in the ultraviolet ray region, and the research shows that folic acid can also absorb ultraviolet rays in the ultraviolet ray region.
In the UV-B region, folic acid has an absorption coefficient comparable to that of OMC and BP-3; folic acid also has some absorbance in the UV-a region. Therefore, folic acid can be used as an ultraviolet light absorber in the UV-A, UV-B double region.
Based on this, the present invention provides the use of folic acid in UV absorbers, preferably in UV-a and UV-B region UV absorbers, more preferably in sun protection.
Folic acid is water-soluble vitamin B9, which is widely applied to pregnant women as a medicament or additive for preventing fetal neural tube malformation and has very high safety.
Folic acid has good biocompatibility, and its photoproduct has no biotoxicity. After the folic acid is applied to the surface of the skin to be absorbed, no biotoxicity is generated, the absorbed folic acid can also participate in the normal folic acid cyclic metabolism in the human body, and even has the function of supplementing folic acid to a certain degree.
Compared with the chemical sun-screening agent in the prior art, the ultraviolet absorbent using folic acid as the chemical absorption active component has higher safety and smaller influence on skin health.
In order to further improve the ultraviolet-proof effect of folic acid, ZnO and/or TiO can be added2And the physical sun-proof inorganic components are compounded, so that the sun-proof effect is further improved.
In view of the poor solubility of folic acid in both water-soluble and oil-soluble solvents, and the tendency of conventional creams or creams to impart a greasy feel to the skin, the present invention also provides a relatively refreshing folic acid composition, particularly a folic acid-metal ion composition, for use in the prevention or prevention of ultraviolet absorption, particularly for use in sun protection.
The folate-metal ion composition comprises folic acid and one or more of zinc, silver, magnesium, and calcium ions;
preferably, the folate-metal ion composition is a folate-metal ion hydrogel. In the invention, the folic acid-metal ion hydrogel is a complex of folic acid molecules and metal ions, which are fully cross-linked and coordinated to form hydrogel molecules with a net structure. The folic acid-metal ion hydrogel has a fluid state such as solution, gel or suspension according to the dispersibility of the hydrogel molecules with a reticular structure in water.
The preparation method of the folic acid-metal ion hydrogel comprises the following steps:
(1) preparing a folic acid aqueous solution;
(2) preparing a metal ion aqueous solution;
(3) and uniformly mixing the folic acid aqueous solution and the metal ion aqueous solution at room temperature, and standing to obtain the folic acid-metal ion hydrogel.
Among them, in the step (1), it is preferable to prepare a folic acid aqueous solution by dissolving folic acid in an aqueous solution. The aqueous solution comprises water or an aqueous buffer solution.
Since water may contain undesirable cations and anions, it is not intended that folic acid and the set metal ion form a complex in the present invention. Preferably, the water used in the present invention is purified water containing no ions, and more preferably ultrapure water.
When the aqueous folic acid solution is prepared using pure water, an alkaline reagent is dropped so that the pH of the aqueous folic acid solution is alkaline, preferably 7.0 to 9.5.
The alkaline reagent is selected from one or more of ammonia water, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide and cesium hydroxide; preferably one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide and cesium hydroxide; more preferably sodium hydroxide or potassium hydroxide.
When the hydroxide is used for reaction with carboxyl in folic acid, the types and the contents of inorganic anions in the aqueous solution of folic acid are not increased, and the interference of coordination of folic acid and metal ions is reduced as much as possible.
In addition, it has been found that sodium, potassium, lithium, rubidium, and/or cesium metal ions can be added to aqueous folic acid solutions by adjusting the pH of the solutions using one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, and cesium hydroxide. Sodium, potassium, lithium, rubidium and/or cesium metal ions may play a stabilizing role to a certain extent on the tetranection formed by folic acid and metal ions during the formation of the hydrogel.
The aqueous buffer solution is selected from one or more of Acetic acid-sodium acetate, Boric acid-borax, HEPES (N- (2-hydroxyethyl) piperazine-N' -2-ethanesulfonic acid), MOPS (3-morpholinopropanesulfonic acid), MES (2- (N-morpholino) ethanesulfonic acid), trimethylolmethylamine-hydrochloric acid (Tris-HCl), trimethylolmethylamine-Boric acid (Tris-Boric acid), and trimethylolmethylamine-Acetic acid (Tris-Acetic acid).
When the aqueous folic acid solution is prepared by using an aqueous buffer solution, the aqueous buffer solution is preferably selected from one or more of trimethylol methylamine-hydrochloric acid, trimethylol methylamine-boric acid, and trimethylol methylamine-acetic acid.
In order to improve the solubility of folic acid in an aqueous buffer solution, the pH value of the aqueous buffer solution is 7.0-9.5.
In the aqueous folic acid solution prepared in the step (1), the concentration of folic acid is 0.5mM-200mM, preferably 5mM-100 mM.
Further, in step (2), the same aqueous solution as in step (1) is used to prepare an aqueous metal ion solution.
The metal ion is selected from the group consisting of chemically stable metal ions in the monovalent or divalent state, preferably the metal ion is selected from the group consisting of sodium, potassium, lithium, rubidium, cesium, zinc (Zn)2+) Copper (Cu)2+) Nickel (Ni)2+) Cobalt (Co)2+) Manganese (Mn)2+) Chromium (Cr)3+) Molybdenum (Mo)2+) Silver (Ag)+) Cadmium (Cd)2+) Magnesium (Mg)2+) Calcium (Ca)2+) Lead (Pb)2+) And barium.
Further, the metal ions include one or more of zinc, silver, magnesium, and calcium ions.
In the preparation, it is preferable to use an inorganic salt containing the metal ion, for example, a hydrochloride, a nitrate, a sulfate, or the like, and it is preferable to use a nitrate or a sulfate, because most nitrates and sulfates have relatively good solubility and thus it is easier to prepare an aqueous solution of the metal ion.
In the aqueous solution of metal ions prepared in step (2), the concentration of the metal ions is 0.1mM-500mM, preferably 5mM-400 mM.
Further, in the step (3), the folic acid aqueous solution and the metal ion aqueous solution are uniformly mixed, and the mixing method is not particularly limited as long as uniform mixing is possible, and for example, vortexing, stirring, ultrasound, or the like may be used.
After mixing, the final concentration of folic acid in the mixed system is 0.5mM-200mM, preferably 5mM-100mM, more preferably 5mM-50 mM.
After mixing, the final concentration of the metal ion in the mixed system is 0.1mM-500mM, preferably 5mM-400mM, more preferably 10mM-200 mM.
Research shows that the viscosity of the prepared solution or the mechanical strength (modulus) of the hydrogel can be obviously improved by increasing the concentration of folic acid; when the concentration of folic acid is too low, a hydrogel cannot be obtained.
In the step (3), after the folic acid aqueous solution and the metal ion aqueous solution are mixed, the molar concentration ratio of folic acid to metal ions is 1: 0.1-10.
In order to further optimize the mechanical strength of the hydrogel and make the hydrogel have good mechanical strength and suitable for skin application, the molar ratio of folic acid to metal ions in the mixed system after mixing is preferably 1: 0.4-10, preferably 1: 1-5.
After the folic acid aqueous solution and the metal ion aqueous solution are mixed, the dosage proportion of folic acid and metal ions in the mixed system can influence the fluid property of the folic acid-metal ion hydrogel. In the present invention, the folic acid-metal ion hydrogel has a fluid state such as a solution, a gel, or a suspension.
Specifically, in a preferred embodiment, the phase diagram of the folate-zinc ion hydrogel is shown in figure 8: with the increase of the concentration of folic acid, the lower limit of the folic acid/zinc ion molar ratio of the folic acid-zinc ion hydrogel forming a gel state is gradually reduced, the upper limit is gradually increased, and the gel area is enlarged; correspondingly, with the reduction of the folic acid concentration, the lower limit of the folic acid/zinc ion molar ratio of the folic acid-zinc ion hydrogel forming a gel state is gradually increased, the upper limit is gradually decreased, and the gel area is reduced. As can be seen from fig. 8, when the molar ratio of folic acid/zinc ion is gradually increased under the condition of the unchanged folic acid concentration, the folic acid-zinc ion hydrogel changes from the solution state to the gel state and then to the suspension state.
Preferably, when the concentration of folic acid is 15mM, the folic acid aqueous solution and the zinc ion aqueous solution are mixed, and when the molar ratio of folic acid to zinc ion is 1:0-0.9, the obtained hydrogel is in a solution state; when the molar concentration ratio of folic acid to zinc ions is 1:0.9-1.9, the obtained hydrogel is in a gel state; when the molar concentration ratio of folic acid and zinc ions is 1:2.0-10, preferably 1:2.0-2.2, the obtained hydrogel is in the form of suspension,
preferably, when the selected metal ions are zinc ions and the concentration of folic acid is 10mM, the molar concentration ratio of folic acid to zinc ions is 1:0-1.0, and the obtained hydrogel is in a solution state; when the molar concentration ratio of folic acid to zinc ions is 1:1.0-1.9, the obtained hydrogel is in a gel state; when the molar concentration ratio of folic acid to zinc ions is 1:2.0-10, preferably 1:2.0-2.2, the hydrogel obtained is in the form of a suspension.
Preferably, when the selected metal ions are zinc ions and the concentration of folic acid is 2mM, the molar concentration ratio of folic acid to zinc ions is 1:0-1.5, and the obtained hydrogel is in a solution state; when the molar concentration ratio of folic acid to zinc ions is 1:1.5-1.7, the obtained hydrogel is in a gel state; when the molar concentration ratio of folic acid to zinc ions is 1:1.9-10, preferably 1:2.0-2.2, the hydrogel obtained is in the form of a suspension.
Further research finds that the pH value of the mixed system may influence the forming and the property of the hydrogel, and the mechanical strength of the hydrogel prepared by the mixed system is obviously weakened when the mixed system is too alkaline; when the alkalinity is too low or even acidic, precipitation occurs in the mixed system and hydrogel formation is not possible.
Alternatively, the pH of the mixed system solution is adjusted to be neutral or alkaline, preferably 7.0 to 9.5.
And standing the mixed system to ensure that the metal ions and the folic acid are fully crosslinked and coordinated to form hydrogel molecules.
It was found that the formation of metal ion hydrogel based on folic acid (folate-metal ion gel) is a multi-step process: first, the pterin head group of folic acid forms quadruplets through hydrogen bonding, as shown in fig. 6, and the quadruplets are further pi-pi stacked to form fibers, as shown in fig. 7; finally, the metal ions and the carboxylic acid of folic acid coordinate to crosslink the fibers, and the fibers intertwine with each other to form hydrogel molecules with a net structure, as shown in fig. 7.
Forming a solution of hydrogel when hydrogel molecules of a network structure formed by metal ions and folic acid molecules are uniformly dispersed in water; when the hydrogel molecules with the network structure have good dispersibility and can wrap water in the hydrogel molecules to cause the hydrogel molecules to lose fluidity, a gel state is formed; when the hydrogel molecules of the network structure cannot be dispersed in water, a suspension of the folic acid-metal ion hydrogel is formed.
The mixed system is preferably allowed to stand at room temperature, which means 10 to 35 ℃, preferably 15 to 30 ℃, more preferably 20 to 30 ℃, for example 25 ℃.
In the step (3), the time for forming the hydrogel by standing is related to the type of the selected metal ions; preferably, the hydrogel is allowed to stand for 1 to 2 days, so that the crosslinking molecules in the hydrogel can be more stable.
In the preparation method provided by the invention, the metal ions are prepared into the aqueous solution in advance, so that the non-uniformity of gelling of the metal ion solid and the folic acid aqueous solution can be avoided, and more uniform and reliable folic acid-metal ion hydrogel can be prepared.
The folic acid prepared into the folic acid-metal ion hydrogel still has the similar ultraviolet absorption property as the folic acid, has the application in ultraviolet absorbers in the UV-A and UV-B regions, can prevent or prevent ultraviolet absorption, more preferably has the application in sunscreen, and can be used in sunscreen.
The folic acid prepared into the folic acid-metal ion hydrogel has the viscosity, spreadability and uniformity of gel, and is very beneficial to the preparation and forming of the sun-screening agent. The folic acid-metal ion hydrogel is similar to commercially available aloe gel, and compared with the traditional greasy sunscreen cream, the folic acid-metal ion hydrogel has the advantages that the consumer experience of the hydrogel is obviously improved, and the consumer acceptance degree can be improved.
After folic acid is added with metal ions to prepare the folic acid-metal ion hydrogel, the sunscreen effect is almost kept constant, and the folic acid-metal ions with different proportions can obtain hydrogels with different viscosities and even different flowing states (or fluid states), thereby bringing diversity for production and providing various choices for consumers.
In a more preferred embodiment, the folic acid-metal ion hydrogel can be compounded with zinc oxide to form a sunscreen, the zinc oxide has a physical sunscreen effect, the folic acid-metal ion hydrogel has a chemical sunscreen effect, namely an ultraviolet absorbent effect, and the sunscreen effect is remarkably improved through the compounding of the folic acid-metal ion hydrogel and the zinc oxide.
The mass fraction of the zinc oxide in the sun-screening agent is 0.1-10%, preferably 0.5-5%.
More preferably, the mass fraction of the zinc oxide in the folic acid-metal ion hydrogel and zinc oxide compound mixture is 0.1% -10%, and preferably 0.5% -5%.
When the folic acid-metal ion hydrogel and the zinc oxide are compounded, the folic acid-metal ion hydrogel and the zinc oxide are uniformly mixed in a set dosage.
Preferably, the folic acid-metal ion hydrogel and zinc oxide are formulated, optionally with the addition of other ingredients of different function, such as skin nutrients, solvents, thickeners, complexing agents and/or sunscreen substances.
The skin nutrient comprises one or more of glycerol, vitamin E, one or more of animal and plant extracts, allantoin and decyl glucoside;
the solvent comprises one or more of water, propylene glycol, ethanol, glyceryl stearate, sodium cocoyl sarcosinate, potassium cetyl phosphate, cetyl alcohol, caprylyl glycol, undecane, isohexadecane, isododecane, phenethyl alcohol benzoate, dioctyl carbonate, dioctyl ether, propylene carbonate, acrylamide/ammonium acrylate copolymer and polysorbate-20;
the complexing agent comprises disodium EDTA;
the thickener comprises one or more of aluminum starch octenyl succinate, xanthan gum, alumina, glycerol tri (ethyl hexanoate), triethoxy octyl silane, sodium chloride, talcum powder, aluminum hydroxide, disteardimonium hectorite, silica and isostearic acid;
the sunscreen substance comprises one or more of zinc oxide, ethylhexyl methoxycinnamate, octocrylene, polysiloxane-15, titanium dioxide, diethylamino hydroxybenzoyl hexyl benzoate, bis-ethylhexyloxyphenol methoxyphenyl triazine, avobenzone, benzophenone-3, octyl salicylate and octyl methoxycinnamate.
Optionally, preservatives, such as sorbic acid or potassium sorbate, may also be added.
When the folic acid-metal ion hydrogel is prepared into a sun-screening agent, the folic acid-metal ion hydrogel is preferably prepared into a common ointment, cream or gel, and the dosage of the folic acid-metal ion hydrogel is 0.1-10mg/cm when the folic acid-metal ion hydrogel is applied to the skin2Has better ultraviolet-proof function.
The folic acid-metal ion hydrogel provided by the invention is simple to prepare, has controllable and adjustable process, has a good ultraviolet absorption effect, can be used in combination with other chemical absorbents and physical sunscreens, and improves the ultraviolet and sunscreen effects. The folic acid-metal ion hydrogel is good in safety, high in reliability, stable in chemical property, very fresh after being prepared into a sun-screening agent, and good in use experience.
Examples
Example 1
Adding folic acid into ultrapure water, adding potassium hydroxide to adjust the pH of the solution to about 9 so as to dissolve folic acid, thereby obtaining folic acid aqueous solution.
And adding zinc nitrate into ultrapure water for dissolving to obtain a metal ion aqueous solution.
Respectively taking and mixing a metal ion aqueous solution and a folic acid aqueous solution to ensure that the final mass fraction of folic acid in the mixed solution is 0.72 wt%; the final mass fraction of zinc ions was 0.90 wt%. Stirring in vortex, standing, getting turbid solution, clarifying and transparentizing after 10 min to obtain folic acid-zinc ion (F-Zn)2+) The mass concentration ratio of substances is 1-1.8 (folic acid: zinc ion ═ 1: 1.8, the same below).
Example 2
The preparation method is the same as that of example 1, except that:
the final mass fraction of folic acid in the mixed solution was 0.72 wt%; the final mass fraction of zinc ions was 0.28 wt%. Stirring and mixing evenly by vortex, and standing for 10 minutes to obtain folic acid-zinc ion (F-Zn)2+) Folic acid-zinc water with substance concentration ratio of 1-0.4Gel, in this case in solution.
Example 3
The preparation method is the same as that of example 1, except that:
the final mass fraction of folic acid in the mixed solution was 0.72 wt%; the final mass fraction of zinc ions was 0.46 wt%. Stirring and mixing evenly by vortex, and standing for 10 minutes to obtain folic acid-zinc ion (F-Zn)2+) The folic acid-zinc hydrogel with the ratio of the amount to the concentration of the substance of 1 to 0.8 is in a solution state.
Example 4
The preparation method is the same as that of example 1, except that:
the final mass fraction of folic acid in the mixed solution was 0.72 wt%; the final mass fraction of zinc ions was 0.63 wt%. Stirring and mixing evenly by vortex, and standing for 10 minutes to obtain folic acid-zinc ion (F-Zn)2+) The folic acid-zinc hydrogel has a substance concentration ratio of 1-1.2, and is in a gel state.
Example 5
The preparation method is the same as that of example 1, except that:
the final mass fraction of folic acid in the mixed solution was 0.72 wt%; the final mass fraction of zinc ions was 0.81 wt%. Stirring and mixing evenly by vortex, and standing for 10 minutes to obtain folic acid-zinc ion (F-Zn)2+) The folic acid-zinc hydrogel having a concentration ratio of the substance of 1 to 1.6 is in a gel state, and the gel is excellent in rheology.
Example 6
Preparing trihydroxymethyl methylamine-boric acid buffer solution, and controlling pH at about 9.5. 10.74mg of folic acid was dissolved in 0.225mL of a buffered trimethylolmethylamine-boric acid solution to obtain an aqueous folic acid solution.
And dissolving 19.38mg of silver nitrate in 1.275mL of trimethylol methylamine-boric acid buffer solution to obtain a metal ion aqueous solution.
Respectively taking and mixing the metal ion aqueous solution and the folic acid aqueous solution, wherein the mass fraction of folic acid in the final mixed solution is 0.72 wt%; the mass fraction of silver ions was 0.89 wt%. And (3) stirring uniformly by vortex, standing, wherein the mixed solution is turbid initially, and is clarified and transparent gradually after 30 minutes to obtain the mixture with the quantity concentration ratio of folic acid to silver ion substances of 1: 5 of folic acid-silver hydrogel.
Example 7
The preparation method is the same as example 6, except that:
the final mass fraction of folic acid in the mixed solution was 0.72 wt%; the final mass fraction of calcium ions was 0.37 wt%. Stirring and mixing uniformly by vortex, standing for 1 hour to obtain the mixture with the quantity concentration ratio of folic acid to calcium ion substances of 1:1.5 Folic acid-calcium hydrogel.
Example 8
The preparation method is the same as example 6, except that:
the final mass fraction of folic acid in the mixed solution was 0.72 wt%; the final mass fraction of magnesium ions was 0.33 wt%. Stirring and mixing uniformly in a vortex mode, standing for 1 hour to obtain folic acid and magnesium ion substances with the mass concentration ratio of 1:1.5 Folic acid-magnesium hydrogel.
Examples of the experiments
Experimental example 1 UV absorption behavior of different chemical absorbers (sunscreen components)
0.01 percent of avobenzone, benzophenone-3, octyl salicylate and octyl methoxycinnamate solution by mass percent are respectively prepared by using ethyl acetate. An aqueous solution having a folic acid molarity of 15mM was prepared in accordance with the procedure of example 1.
The solution was uv scanned in the range of 250-450nm and the absorbance values were then normalized to 1% and 1cm (according to lambert beer's law) for concentration and optical path, and as shown in figure 1, it was found that:
in the UV-B (280-320nm) region, the ultraviolet absorption capacity of folic acid is equivalent to that of benzophenone-3, is higher than that of octyl salicylate and avobenzone, and is comparable to that of octyl methoxycinnamate;
in the UV-AII (320-340nm) region, the ultraviolet absorption capacity of folic acid is higher than that of octyl salicylate, and is comparable to that of benzophenone-3 and octyl methoxycinnamate;
in the UV-AI (340-.
Experimental example 2 ultraviolet absorption behavior of hydrogels with different folic acid-zinc ion ratios
The folic acid solution of experimental example 1 was identical to the folic acid-zinc hydrogel prepared in examples 2 to 5. The folic acid-zinc hydrogel has good fluidity, and can be measured by dripping into a cuvette by using a rubber-tipped dropper.
The solution was uv scanned in the range of 250-450nm and then the absorbance values were normalized to 1% and 1cm (according to lambert beer's law) for concentration and optical path, and the results are shown in fig. 2 and can be found:
after folic acid is prepared into hydrogel, the ultraviolet absorption behavior of folic acid is basically the same as that of folic acid aqueous solution, and only folic acid-zinc ion (F-Zn) is available2+) 1-1.2 and 1-1.6 slightly differ from the aqueous folic acid solution at 250-280nm, but do not affect the UV absorption behavior in the UV-B, UV-AII and UV-AI regions. The ultraviolet absorption behavior of the folic acid formed hydrogel is not obviously changed, and the folic acid still has the ultraviolet absorption capacity.
Experimental example 3 comparison of sunscreen Effect of different sunscreen Components
Using a test paper sensitive to ultraviolet light (the test paper is purchased from Beijing Boda Green high-tech Co., Ltd., model number of sunlight purple), coating a sunscreen component on the surface of the test paper, and irradiating with sunlight at noon in summer (the sunlight intensity is 0.1W/cm)2) For 30 minutes.
Before sunlight irradiation, the test paper is white; after sunlight irradiation, the test paper without the sunscreen component is changed into purple, and whether the part coated with the sunscreen component is changed into purple can reflect the sunscreen performance of the sunscreen component, namely, the closer to the original white color, the better the sunscreen performance is.
The experimental conditions are as follows: dissolving avobenzone, BP-3, isooctyl salicylate and OMC in ethyl acetate, respectively, coating on the surface of test paper, and waiting for ethyl acetate to be coatedAnd volatilizing to obtain the test paper coated with the sunscreen component. Folic acid-Zn prepared in example 12+The hydrogel was coated directly on the surface of the test paper. The test is carried out according to the weight of the sunscreen components on test paper of 0.02mg,0.1mg,0.2mg,1mg and 2 mg.
As a result, as shown in fig. 3, it can be found that:
(1) folic acid-Zn in 0.02mg and 0.1mg of sunscreen component2+The hydrogel can play a role in sunscreen, and the sunscreen effect of the hydrogel is comparable to that of avobenzone and is obviously higher than that of other sunscreen components.
(2) Folic acid-Zn at 0.2mg,1mg and 2mg of sunscreen component2+The sun-screening effect of the hydrogel is similar to that of avobenzone and BP-3, and is obviously higher than that of other sun-screening components.
(3) Whether the amount of sunscreen used is 0.02mg,0.1mg,0.2mg,1mg or 2mg, folic acid-Zn2+The sun-screening effect of the hydrogel is obviously better than that of isooctyl salicylate and OMC.
2+Experimental example 4 comparison of Folic acid-Zn hydrogel and sunscreen effect of compounding the same with Zinc oxide
The ultraviolet light sensitive test paper, the illumination condition and the illumination time are the same as those in experimental example 3.
Folic acid-Zn prepared in example 1 was used2+Hydrogel, adding ZnO powder with mass fraction of 0.5%, 1%, 2%, 5%, respectively, and mixing to obtain folic acid-Zn2+hydrogel/ZnO compound sunscreen agent.
ZnO aqueous suspensions having mass fractions of 0.5%, 1%, 2% and 5% were prepared as controls.
The experimental conditions are as follows: 100mg of ZnO aqueous suspension and folic acid-Zn are respectively taken2+The hydrogel/ZnO compound sunscreen agent is coated on the upper end surface of the test paper, and the coating area is basically 1cm multiplied by 1 cm.
As shown in fig. 4, it can be found that: 0.5 percent, 1 percent and 2 percent of ZnO can not play a complete sun-screening role after being coated, and the coated area still has purple;
and folic acid-Zn with different zinc oxide mass fractions2+The hydrogel/ZnO compound sun-screening agent can play a role in completely screening sunThe effect is equivalent to the sunscreen effect of a 5% ZnO water suspension, and even better.
2+Experimental example 5 comparison of sunscreen Effect of Folic acid-Zn hydrogel/Zinc oxide combination with commercial sunscreen agent
The ultraviolet light sensitive test paper, the illumination condition and the illumination time are the same as those in experimental example 3.
Test groups: folic acid-Zn prepared in example 12+Adding ZnO powder with mass fraction of 5% into hydrogel, and mixing to obtain folic acid-Zn2+Hydrogel/5% -ZnO compound sunscreen agent.
Control group: commercial sunscreens used were THE "vibrant Sun-clearing Sun-transparent sunscreen" (Vita Sun Block Aqua Sun position), SPF50+, PA + + +.
The experimental conditions are as follows:
collecting commercial sunscreen agent 50mg according to 2.5mg/cm2The coating weight is uniformly coated on the surface of the test paper; taking folic acid-Zn2+Hydrogel/5% -ZnO compound sunscreen agent 20mg according to 1mg/cm2The coating amount is uniformly coated on the surface of the test paper. The coating was applied as a circle with a radius of about 2.5 cm.
As shown in fig. 5, it can be found that: a more pronounced purple region appeared in the coated areas of commercial sunscreen, as can be seen with 1mg/cm2Folic acid-Zn of2+Compared with a commercial sunscreen agent, the hydrogel/5% -ZnO compound sunscreen agent has the advantages that the sunscreen effect is equivalent to or even better.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. Use of folic acid for preventing or preventing UV absorption.
2. Use of a folate-metal ion composition for preventing or preventing uv absorption, wherein the folate-metal ion composition comprises folic acid and one or more of zinc, silver, magnesium and calcium ions;
preferably, the folate-metal ion composition is a folate-metal ion hydrogel.
3. A folate-metal ion hydrogel, wherein the hydrogel is prepared by the steps comprising:
(1) dissolving folic acid in water or aqueous buffer solution to prepare folic acid aqueous solution;
(2) dissolving metal salt in water or aqueous buffer solution to prepare metal ion aqueous solution;
(3) uniformly mixing the folic acid aqueous solution and the metal ion aqueous solution at room temperature, and standing to obtain folic acid-metal ion hydrogel;
the folic acid-metal ion hydrogel is in a solution, gel or suspension state.
4. The folate-metal ion hydrogel of claim 3, wherein said metal salt is a hydrochloride, nitrate or sulfate;
the metal ion in the metal salt is one or more selected from zinc, silver, magnesium and calcium ion.
5. The folic acid-metal ion hydrogel according to claim 3 or 4, wherein in the step (1), when folic acid is dissolved in water or an aqueous buffer solution, the pH of the water or the aqueous buffer solution is adjusted to 7.0 to 9.5.
6. The folate-metal ion hydrogel of claim 3, wherein in steps (1) and (2), the aqueous buffer solution is selected from one or more of acetic acid-sodium acetate, boric acid-borax, N- (2-hydroxyethyl) piperazine-N' -2-ethanesulfonic acid, 3-morpholinopropanesulfonic acid, 2- (N-morpholino) ethanesulfonic acid, trimethylolmethylamine-hydrochloric acid, trimethylolmethylamine-boric acid, and trimethylolmethylamine-acetic acid.
7. The folic acid-metal ion hydrogel according to claim 3, wherein in the step (3), the final concentration of folic acid after the aqueous folic acid solution and the aqueous metal ion solution are mixed is 0.5mM-200mM, preferably 5mM-100 mM;
the final concentration of metal ions is 0.1mM-500mM, preferably 5mM-400 mM;
more preferably, in the step (3), after mixing the folic acid aqueous solution and the metal ion aqueous solution, the molar concentration ratio of folic acid to metal ions is 1: 0.1-10, preferably 1: 1-5.
8. The folate-metal ion hydrogel of claim 3, wherein when the metal ions are zinc ions, a folate-zinc ion hydrogel is produced;
after mixing the folic acid aqueous solution and the zinc ion aqueous solution, with the increase of the folic acid concentration, the lower limit of the folic acid/zinc ion molar ratio of the folic acid-zinc ion hydrogel forming a gel state is gradually reduced, the upper limit is gradually increased, and the gel area is enlarged;
when the concentration of folic acid is not changed, the molar ratio of folic acid to zinc ions is gradually increased, and the folic acid-zinc ion hydrogel is changed into a gel state from a solution state and then into a suspension state.
9. A sunscreen comprising the folate-metal ion hydrogel of any one of claims 1-8, wherein the sunscreen further comprises zinc oxide;
the mass fraction of the zinc oxide in the sun-screening agent is 0.1-10%, preferably 0.5-5%;
the sunscreen agent is an ointment, a cream or a gel.
10. Use of the folate-metal ion hydrogel of any one of claims 3 to 8 and the sunscreen of claim 9 for preventing or preventing UV absorption;
preferably as a sunscreen.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113926398A (en) * | 2021-09-01 | 2022-01-14 | 李婷 | Metal organic gel, and preparation method and application thereof |
| CN115317513A (en) * | 2022-08-01 | 2022-11-11 | 宁波博雅格致健康科技有限公司 | Sterilization repair gel and preparation method and application thereof |
| CN115414274A (en) * | 2022-09-29 | 2022-12-02 | 宁波博雅格致健康科技有限公司 | Application of She Suanyin ionic material in preparation of scalp care composition, scalp care composition and preparation method |
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| CN1525848A (en) * | 2001-07-10 | 2004-09-01 | 高斯米特公开有限公司 | Folic acid containing personal care product and use thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113926398A (en) * | 2021-09-01 | 2022-01-14 | 李婷 | Metal organic gel, and preparation method and application thereof |
| CN115317513A (en) * | 2022-08-01 | 2022-11-11 | 宁波博雅格致健康科技有限公司 | Sterilization repair gel and preparation method and application thereof |
| CN115317513B (en) * | 2022-08-01 | 2024-10-01 | 宁波博雅格致健康科技有限公司 | Sterilization repair gel and preparation method and application thereof |
| CN115414274A (en) * | 2022-09-29 | 2022-12-02 | 宁波博雅格致健康科技有限公司 | Application of She Suanyin ionic material in preparation of scalp care composition, scalp care composition and preparation method |
| CN115414274B (en) * | 2022-09-29 | 2024-09-10 | 宁波博雅格致健康科技有限公司 | Application of silver folate ion material in preparation of scalp care composition, scalp care composition and preparation method |
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