Cosmetic composition containing surface-modified gold nanorods for use with beauty device

Abstract

The present invention relates to surface-modified gold nanorods and a cosmetic composition containing same. The surface-modified gold nanorods are characterized in that the gold nanorods are modified with citrate. By including the surface-modified gold nanorods, the cosmetic composition can achieve reduced cytotoxicity and improved dispersion stability. In addition, the cosmetic composition containing the surface-modified gold nanorods can improve the movement speed of negatively charged proteins by means of the surface-modified gold nanorods, thereby maximizing a photothermal effect and a lightning rod effect when used together with a handheld multifunctional beauty device.

Description

Cosmetic composition for beauty devices containing surface-modified gold nanorods

[0001] The present invention relates to a cosmetic composition for use in beauty devices containing surface-modified gold nanorods. The cosmetic composition is characterized by being usable as a cosmetic composition for use in handheld composite beauty devices capable of having photothermal effects and electric field amplification effects in near-infrared LEDs and galvanic currents.

[0002] Recently, handheld multi-functional beauty devices utilizing microcurrents have emerged as a major trend. The primary benefit of these devices is the galvanic effect. The galvanic effect utilizes the property of galvanic current—where like poles repel each other—to ionize cosmetics, allowing them to penetrate deep into the skin. The principle involves leveraging the characteristics of galvanic current, where the positive electrode repels positively charged substances and the negative electrode repels negatively charged substances. This allows negatively charged functional active ingredients to move toward the positive electrode via an electric field, enabling absorption into the dermis layer. Consequently, the active ingredients penetrate deep into the skin tissue, enhancing the effectiveness of skin care. Typical benefits of these handheld devices include sebum removal, exfoliation, pore tightening, skin soothing, improvement of pigmentation, skin regeneration, and increased elasticity.

[0003] However, the reality is that the galvanic current is very weak, at about 200 μA or less, so the delivery rate of active ingredients is not actually high. Therefore, when this handheld combination beauty device is used with ionizing or water-soluble cosmetic compositions specifically designed for beauty devices that can induce microcurrents, such as mask packs, cosmetics, and patches, it can have an excellent absorption effect.

[0004] Meanwhile, nanoparticles such as gold nanoparticles (GNPs) are characterized by their small size, high surface area-to-volume ratio, and the ability to modify their surface. In particular, due to the characteristics of the peritumoral region, small nanoparticles possess the advantage of being able to accumulate in the tumor site and facilitate cellular uptake. This is achieved through the EPR effect, where nanoparticles, due to their nano-size, cannot penetrate normal tissues but instead infiltrate and remain within tumor tissue.

[0005] Among these nanoparticles, gold nanorods (GNRs) are characterized by their ease of surface deformation and, compared to spherical gold nanoparticles, differing lengths in the longitudinal and transverse directions, which results in different vibration paths for electron clouds. Depending on the aspect ratio of gold nanorods, they possess a photothermal effect in which they absorb light in the near-infrared region (approximately 700–1,200 nm) capable of penetrating the skin, causing collisions between free electrons and gold atoms to generate heat. This photothermal effect is widely utilized in targeted cancer therapy. However, cetyltrimethylammonium bromide (CTAB), a cationic surfactant currently used in the synthesis process of these gold nanorods, binds to the surface of GNRs through electrostatic attraction and plays a key role in controlling the aspect ratio of the gold nanorods. While controlling the aspect ratio allows for the adjustment of the optical properties of gold nanorods, it presents a problem regarding cytotoxicity. Consequently, various methods are being applied to remove or replace CTAB; however, in reality, it is difficult to completely eliminate CTAB surfactants, and appropriate guidelines are required.

[0006] Meanwhile, the inventors possess technology for a cosmetic composition for blocking near-infrared rays containing gold nanorods in Korean Registered Patent No. 10-1776140. Accordingly, while researching methods to overcome the cytotoxicity problem caused by CTAB associated with gold nanorods and methods to improve the dispersion stability of gold nanorods in cosmetic compositions, they confirmed the effect of reducing cytotoxicity by replacing the CTAB on the surface of gold nanorods with citrate after synthesis. Furthermore, they completed the present invention by confirming that the composition can be utilized as a cosmetic composition for handheld complex beauty devices that exhibits excellent photothermal and electric field amplification effects when a near-infrared LED and galvanic current are applied.

[0007]

[0008] The objective of the present invention is to provide a cosmetic composition for beauty devices containing surface-modified gold nanorods.

[0009] Specifically, the surface-modified gold nanorods (C-GNR) are gold nanorods (GNRs) whose surface is surface-modified with citrate, and the present invention aims to provide a cosmetic composition for beauty devices containing the surface-modified gold nanorods that has the effects of reducing cytotoxicity and improving dispersion stability.

[0010] In addition, the cosmetic composition for beauty devices containing the surface-modified gold nanorods aims to provide a cosmetic composition for handheld complex beauty devices that can increase the absorption rate of active ingredients into the dermis layer of the skin by more effectively imparting photothermal effects and electric field amplification effects (hereinafter referred to as lightning rod effects) by containing the surface-modified gold nanorods.

[0011]

[0012] The present invention relates to a cosmetic composition for beauty devices containing surface-modified gold nanorods. The surface-modified gold nanorods are characterized by having effects of reducing cytotoxicity and improving dispersion stability. The invention relates to a cosmetic composition for beauty devices containing the surface-modified gold nanorods that can more effectively impart photothermal and electric field amplification effects.

[0013] One aspect of the present invention for achieving the above objective relates to a surface-modified gold nanorod (Citrate-Gold Nano Rod; C-GNR) characterized in that the surface of the gold nanorod (GNR) is surface-modified with citrate.

[0014] In the above embodiment, the survival rate of mouse muscle fibroblasts (BLO-11 (Mouse muscle fibroblast cell)) at a concentration of 100 ppm or less of the surface-modified gold nanorods may be 80% or more.

[0015] In the above embodiment, when a DC 30 V electric field is applied to an acrylamide gel containing the surface-modified gold nanorods at a concentration of 100 ppm or less, the electrophoretic migration distance of SDS-albumin may be 2.15 cm or more.

[0016] In one embodiment above, the surface-modified gold nanorod may be manufactured by including the following steps: (A) forming a gold seed; (B) growing the gold seed to produce a gold nanorod; and (C) replacing the cetyltrimethylammonium bromide on the surface of the gold nanorod with a citrate to produce a surface-modified gold nanorod.

[0017] In one embodiment of the above, the cosmetic composition for beauty devices may have a photothermal effect and an electric field amplification effect in near-infrared LEDs and galvanic currents.

[0018]

[0019] The present invention relates to a cosmetic composition containing surface-modified gold nanorods, wherein the surface-modified gold nanorods are modified with citrate.

[0020] Specifically, the surface-modified gold nanorods are characterized by having effects of reduced cytotoxicity and dispersion stability, and the present invention relates to a cosmetic composition for beauty devices containing the surface-modified gold nanorods that can more effectively impart photothermal and electric field amplification effects.

[0021] In addition, the cosmetic composition containing the surface-modified gold nanorods can maximize photothermal effects and electric field amplification effects in near-infrared LEDs and galvanic currents when used with a handheld complex beauty device.

[0022]

[0023] Figure 1 shows the UV-Vis analysis results of gold nanorods and surface-modified gold nanorods.

[0024] Figure 2 shows the zeta-potential charge of gold nanorods and surface-modified gold nanorods according to the dispersion solvent.

[0025] Figure 3 is a photograph showing the stability of gold nanorods and surface-modified gold nanorods according to the dispersion solvent.

[0026] Figure 4 shows the results of a cytotoxicity test of surface-modified gold nanorods.

[0027] Figure 5 shows the results of acrylamide gel electrophoresis containing surface-modified gold nanorods.

[0028] Figure 6 is a schematic diagram illustrating the photothermal and galvanic amplification effects of a cosmetic composition containing surface-modified gold nanorods.

[0029] Figure 7 shows the results of a clinical trial of a surface-modified gold nanorod-containing galvanic ampoule for eye wrinkles.

[0030] Figure 8 shows the clinical trial results of a surface-modified gold nanorod-containing galvanic ampoule for nasolabial folds.

[0031] Figure 9 shows the results of a clinical trial on pigmentation of a surface-modified gold nanorod-containing galvanic ampoule.

[0032] Figure 10 shows the results of a clinical trial on skin density of a surface-modified gold nanorod-containing galvanic ampoule.

[0033] Figure 11 shows the results of a clinical trial on skin thickness of a surface-modified gold nanorod-containing galvanic ampoule.

[0034] Figure 12 shows the clinical trial results of the pore area of ​​a surface-modified gold nanorod-containing galvanic ampoule.

[0035] Figure 13 shows the results of a clinical trial on skin exfoliation using a surface-modified gold nanorod-containing galvanic ampoule.

[0036] Figure 14 shows the results of a clinical trial on microcirculation of a surface-modified gold nanorod-containing galvanic ampoule.

[0037] Figure 15 shows the results of a clinical trial on the moisture content of the upper layer of the stratum corneum of a surface-modified gold nanorod-containing galvanic ampoule.

[0038] Figure 16 shows the results of a clinical trial on the moisture content of the subcutaneous layer of a surface-modified gold nanorod-containing galvanic ampoule.

[0039] Figure 17 shows the results of a clinical trial on the water density of a surface-modified gold nanorod-containing galvanic ampoule.

[0040]

[0041] A cosmetic composition for beauty devices containing surface-modified gold nanorods according to the present invention will be described in detail below. The drawings presented below are provided as examples to ensure that the concept of the present invention is sufficiently conveyed to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the concept of the present invention. Unless otherwise defined, technical and scientific terms used herewith have the meaning commonly understood by those skilled in the art to which this invention pertains, and descriptions of known functions and configurations that could unnecessarily obscure the essence of the present invention are omitted in the following description and attached drawings.

[0042] The present invention provides a cosmetic composition for use in beauty devices containing surface-modified gold nanorods, wherein the surface-modified gold nanorods (C-GNR) are characterized in that the surface of the gold nanorods (GNR) is surface-modified with citrate.

[0043] The surface-modified gold nanorods mentioned above are,

[0044] (Step A) Step of forming gold seeds;

[0045] (Step B) A step of manufacturing gold nanorods by growing the gold seeds; and

[0046] (Step C) A step of preparing surface-modified gold nanorods by replacing cetyltrimethylammonium bromide (CTAB) on the surface of the gold nanorods with citrate;

[0047] It can be manufactured including.

[0048] The present invention will be described in detail below.

[0049] In the step of manufacturing surface-modified gold nanorods,

[0050] Specifically, in step (A), a solution containing a gold seed can be prepared by adding an aqueous sodium borohydride solution to a solution in which an aqueous solution of hexadecylcetyltrimethylammonium bromide (CTAB) and an aqueous solution of gold chloride (HAuCl4·3H2O) are mixed.

[0051] At this time, in the above (step A), the volume and concentration of each solution are not significantly limited, but preferably, an aqueous solution of hexadecyl cetyltrimethylammonium bromide (CTAB) has a concentration of 0.01 to 5 mM, an aqueous solution of hydrogen tetrachloroaurate (III) trihydrate has a concentration of 0.05 to 5 mM, and an aqueous solution of sodium borohydride has a concentration of 1 to 50 mM, and the mixing ratio of each solution is preferably a volume ratio of 1 : 0.1 to 5 : 0.05 to 0.5.

[0052] In addition, in the above (step A), it is preferable to age the solution containing the gold seed for at least 90 minutes after preparation, and although the time is not significantly limited, it is preferable to age it for 90 minutes to 6 hours before use.

[0053] Specifically, the above (Step B) may be a step of mixing and stirring a solution containing gold seeds and a growth solution, then centrifuging to remove the upper layer of the solution, and then dispersing the remaining solution in distilled water to obtain a solution containing gold nanorods.

[0054] The above growth solution can be prepared by adding an aqueous silver nitrate solution, which is a synthesis catalyst for gold nanorods, and an aqueous ascorbic acid solution, which is a reducing agent, to a mixed aqueous solution of gold chloride, hexadecyl cetyltrimethylammonium bromide, and benzyldimethylhexadecylammonium chloride under stirring.

[0055] In the above (step B), the solution containing the gold seed and the growth solution for the gold nanorod can be mixed in a volume ratio of 1:500 to 2,000.

[0056] In the above (Step B), although the volume and concentration of each solution or sample for preparing the growth solution are not significantly limited, preferably 300 to 3,000 ml of 0.5 to 5 mM gold chloride (HAuCl4·3H2O) is added to 300 to 3,000 ml of an aqueous solution (40 to 300 mM hexadecylcetyltrimethylammonium bromide (CTAB) and 30 to 70 mM benzyldimethylhexadecylammonium chloride (BDAC)) mixed with hexadecylcetyltrimethylammonium bromide (CTAB), 20 to 70 ml of an aqueous solution of 1 to 10 mM silver nitrate, which is a synthesis catalyst for gold nanorods, and 10 to 20 ml of a reducing agent, an aqueous solution of 50 to 100 mM ascorbic acid, is added under stirring. Can be manufactured.

[0057] In the above (step B), a washing step of centrifuging the solution containing gold nanorods again, removing the supernatant, and dispersing the remaining solution in distilled water may be added 1 to 3 times, through which hexadecylcetyltrimethylammonium bromide is removed to obtain a more purified solution containing gold nanorods.

[0058] Through this step, preferably, gold nanorods (GNRs) with a concentration of 90 to 130 ppm Au (µg Au / ml) and a yield of 70 to 80% can be obtained.

[0059] The above (C) step is a step of preparing surface-modified gold nanorods (C-GNR) by substituting cetyltrimethylammonium bromide (CTAB) on the surface of the gold nanorods with citrate. Specifically, the step may be to obtain gold nanorods (C-GNR) surface-modified with citrate by adding 0.1 to 0.5 wt% of poly(sodium 4-styrenesulfonate) (Mw= 70 KDa) to 400 to 500 ppm of the gold nanorod solution prepared in the above (B) and stirring for at least 6 hours, then centrifuging to remove the supernatant, and then dispersing the remaining solution in a sodium citrate dihydrate solution for at least 12 hours, centrifuging, and then dispersing it again in distilled water.

[0060] More specifically, when using 100 ml of the gold nanorod solution of 500 ppm of step (C) surface-modified with the citrate, the sodium citrate dihydrate can be reacted at 500 ml of 1 to 5 mM, and within this range of mixing amounts, the substitution of CTAB with citrate occurs efficiently, enabling more stable surface modification.

[0061] Surface-modified gold nanorods (C-GNRs) prepared in this way can achieve a viability of over 80% in mouse muscle fibroblasts (BLO-11) at a concentration of 100 ppm or less. This can solve the problem of cytotoxicity associated with conventional GNRs, which are not surface-modified with citrate and thus have CTAB present on their surface.

[0062] Although the surface of the above GNR carries a (+) charge due to CTAB, the surface of C-GNR modified by citrate changes to a (-) charge, allowing it to maintain a stable state for several months not only when dispersed in distilled water but also when dispersed in phosphate-buffered saline (PBS) with a high salt concentration. Therefore, compared to GNR, C-GNR has improved dispersion stability within cosmetic compositions, enabling the cosmetic effect to be uniformly displayed over a long period.

[0063] The present invention is characterized by the fact that when a DC 30 V electric field is applied to an acrylamide gel containing the surface-modified gold nanorods at a concentration of 100 ppm or less, the electrophoretic migration distance of SDS-albumin is 2.15 cm or more. Specifically, when the above C-GNR solution is mixed with acrylamide to prepare an acrylamide gel containing C-GNR, the migration speed of negatively charged SDS-albumin increases as the concentration of C-GNR increases at a concentration of 100 ppm or less of C-GNR in the acrylamide gel, and the electrophoretic migration distance may be 2.15 cm or more.

[0064] From this, it can be seen that when an electric field is applied to a cosmetic composition containing C-GNR, the electrostatic repulsion of the negatively charged active ingredient around C-GNR increases significantly, allowing it to be absorbed more effectively into the dermis layer.

[0065] The above cosmetic composition may have photothermal effects and electric field amplification effects in near-infrared LEDs and galvanic currents. When a dedicated handheld composite beauty device is applied to the cosmetic composition containing the surface-modified gold nanorods, a photothermal effect may be induced when the power LED of the beauty device in the 780 to 1,400 nm near-infrared region is irradiated. In addition, when the galvanic mode of the beauty device is applied, the cosmetic composition can be used to increase the absorption rate of active ingredients into the dermis layer due to the electric field amplification effect of the C-GNRs in the cosmetic composition.

[0066]

[0067] Hereinafter, a cosmetic composition for beauty devices containing surface-modified gold nanorods according to the present invention will be described in more detail through examples. However, the following examples are merely for reference to explain the present invention in detail, and the present invention is not limited thereto and can be implemented in various forms.

[0068] Furthermore, unless otherwise defined, all technical and scientific terms have the same meaning as generally understood by one of the art to which the present invention pertains. The terms used in the description herein are merely for the purpose of effectively describing specific embodiments and are not intended to limit the present invention.

[0069]

[0070] <Preparation Example 1. Preparation of Surface-Modified Gold Nanorods (C-GNR) Dispersed in Distilled Water>

[0071] 1. Synthesis of Gold Seed

[0072] To synthesize gold nanorods, gold seeds were first synthesized. Gold seeds were prepared by mixing 5 ml of a 0.02 M aqueous solution of hexadecylcetyltrimethylammonium bromide (CTAB) and 5 ml of a 0.5 mM aqueous solution of gold(III) chloride trihydrate (HAuCl4·3H2O), adding 0.6 ml of a 0.01 M aqueous solution of NaBH4 cooled to approximately 4°C, and vortexing for 3 minutes to produce a solution containing gold seeds with a size of 2–3 nm. The synthesized seed solution was aged at room temperature for at least 2 hours and 30 minutes before use to facilitate the growth of gold nanorods.

[0073]

[0074] 2. Preparation of growth solution

[0075] A gold nanorod growth solution was prepared to produce gold nanorods from gold seeds. First, 1,000 ml of a 1 mM aqueous solution of HAuCl4·3H2O was mixed with 1,000 ml of an aqueous solution of hexadecylcetyltrimethylammonium bromide (CTAB) and BDAC (Benzyldimethylhexadecylammonium chloride) (CTAB 150 mM, BDAC 50 mM, with BDAC / CTAB ratio being approximately 1 / 3). Then, an aqueous solution of AgNO3 4 mM (50 ml), a catalyst for gold nanorod synthesis, was added, and an aqueous solution of Ascorbic acid 7.9 mM (14 ml), a reducing agent, was added under stirring. At this time, the color of the solution changes from deep yellow to colorless as Au(III) is reduced to Au(I).

[0076]

[0077] 3. Gold Nanorod Growth and Washing

[0078] When 2.4 ml of the aged Gold seed solution prepared in 1. above was added to a gold nanorod growth solution (2,064 ml) under stirring, the color of the solution changed from colorless to wine color within about 3 hours. The solution was then reacted for an additional 24 hours to obtain a solution containing gold nanorods (aspect ratio of about 4, length: about 88 nm, width: about 22 nm). Next, to remove excess CTAB present in this solution, the solution was centrifuged at 11,000 rpm for 25 minutes, the supernatant was removed, and the remaining solution was dispersed in 200 ml of distilled water. This washing process was repeated twice to prepare the final gold nanorod solution. The concentration of the final gold nanorod solution was measured using Atomic Absorption Spectroscopy (AAS) analysis to produce a gold nanorod solution with a concentration of about 90 to 130 ppm.

[0079]

[0080] 4. Synthesis of Surface-Modified Gold Nanorods (C-GNR)

[0081] 0.25 wt% of Poly(sodium 4-styrenesulfonate) (MW = 70 kDa) was added to 100 mL of the above 500 ppm GNR and reacted under stirring for more than 12 hours. After centrifugation at 9,000 rpm for 20 minutes, the supernatant was removed as much as possible, and the remaining solution was dispersed in 500 mL of 2 mM sodium citrate dihydrate solution and reacted under stirring for more than 12 hours. After centrifugation at 9,000 rpm for 20 minutes, the solution was dispersed in 35 mL of distilled water to prepare citrate-surface-modified gold nanorods (C-GNR).

[0082]

[0083] <Preparation Example 2. Preparation of Surface-Modified Gold Nanorods (C-GNRs) Dispersed in Phosphate Buffered Saline (PBS) Solution>

[0084] In Preparation Example 1 above, gold nanorods surface-modified with citrate (CGNR) were prepared by dispersing them in 35 ml of phosphate buffered saline (PBS) solution instead of 35 ml of distilled water as in 4. above.

[0085]

[0086] <Comparative Example 1. Preparation of Gold Nanorods (GNRs) Dispersed in Distilled Water>

[0087] Gold nanorods were prepared using the same process as in Preparation Example 1, except that the process of 4. was not performed in Preparation Example 1.

[0088]

[0089] <Comparative Example 2. Preparation of Gold Nanorods (GNRs) Dispersed in Phosphate-Buffered Saline (PBS) Solution>

[0090] In Preparation Example 1 above, gold nanorods were prepared using the same process as Preparation Example 1, except that the 200 ml of distilled water in 3. above was replaced with 200 ml of phosphate-buffered saline (PBS) solution and the process of 4. above was not performed.

[0091]

[0092] <C-GNR의 표면개질 상태 확인>

[0093] The UV-Vis analysis results of the above Preparation Example 1 and Comparative Example 1 are shown in Figure 1.

[0094] The Zeta-Potential of Manufacturing Examples 1 to 2 and Comparative Examples 1 to 2 above was confirmed and is shown in FIG. 2.

[0095] The dispersion stability of the above Preparation Example 2 and Comparative Example 2 is shown in FIG. 3.

[0096] Referring to Figure 1, it was confirmed that the maximum absorption wavelength of the GNR of Comparative Example 1 appeared as a peak of 780±10 nm, and the C-GNR surface-modified with citrate of Preparation Example 1 showed a Blue Shift with a maximum absorption wavelength of 760±10 nm.

[0097] As confirmed in Figures 2 and 3, Comparative Examples 1 and 2, which were not surface-modified with citrate, had a Zeta-Potential of (+) charge when dispersed in distilled water or a phosphate-buffered physiological salt solution, whereas Preparation Examples 1 and 2, which were surface-modified with citrate, had a (-) charge and maintained dispersion stability for several months not only when dispersed in distilled water but also when dispersed in a phosphate-buffered physiological salt solution.

[0098]

[0099] Cytotoxicity Test

[0100] Cytotoxicity was confirmed by performing the MTT (3-(4,5)-dimethylthiazo(-z-yl)-3,5-diphenyltetrazoliumromide) assay on normal cells (mouse fibroblasts, BLO-11, mouse muscle fiberblast cell).

[0101] Example 1-1: BLO-11 (Mouse muscle fiberblast cell) cells were aliquoted into 48-well culture plates at a rate of 6×104 cells / well and cultured for 24 hours in DMEM culture medium supplemented with 10% FBS and 1% Penicillin.

[0102] After removing the previous culture medium, the C-GNR of Preparation Example 1, which was prepared in advance, was prepared at a concentration of 0 ppm, and the prepared culture medium was injected into the cells and cultured for 6 hours.

[0103] After removing the previous culture and adding the same DMEM culture medium, 0.5 mg / ml MTT (3-(4,5)-dimethylthiazo(-z-yl)-3,5-diphenyltetrazoliumromide) solution was added at 50 µl / well and incubated in an incubator for 3 hours and 30 minutes.

[0104] Afterward, all the culture medium was removed, 500 µl of DMSO (Dimethyl Sulfoxide) was injected, and pipetting was performed to ensure the cells were well dispersed in the DMSO.

[0105] The absorbance of a 48-well culture plate was measured at 540 nm using an MTT Assay reader.

[0106] Example 1-2: The absorbance was measured as in Example 1, except that the C-GNR of Preparation Example 1 was set to a concentration of 30 ppm.

[0107] Examples 1-3: The absorbance was measured as in Example 1-1, except that the C-GNR of Preparation Example 1 was set to a concentration of 50 ppm.

[0108] Examples 1-4: The absorbance was measured as in Example 1-1, except that the C-GNR of Preparation Example 1 was set to a concentration of 70 ppm.

[0109] Examples 1-5: The absorbance was measured as in Example 1-1, except that the C-GNR of Preparation Example 1 was set to a concentration of 100 ppm.

[0110] Examples 1-6: The absorbance was measured as in Example 1-1, except that the C-GNR of Preparation Example 1 was set to a concentration of 150 ppm.

[0111] As a result of testing the cytotoxicity of C-GNR on normal cells (BLO-11, mouse fibroblast cell line) using C-GNR, referring to Figure 4, it was confirmed that normal cells showed a cell viability of over 100% at a concentration of C-GNR from 0 to 50 ppm, and also a cell viability of over 80% in the range of 70 to 100 ppm.

[0112]

[0113] Protein migration speed test

[0114] Example 2-1: An acrylamide gel containing C-GNR was prepared by adding 0 ppm of C-GNR from Preparation Example 1 to acrylamide, and the rate at which negatively charged SDS-albumin protein moved from the negative electrode to the positive electrode in a DC 30V electric field was measured.

[0115] Example 2-2: In addition to adding 20 ppm of C-GNR from Preparation Example 1 to acrylamide, the protein migration rate was measured as in Example 2-1.

[0116] Example 2-3: In addition to adding 50 ppm of C-GNR from Preparation Example 1 to acrylamide, the protein migration rate was measured as in Example 2-1.

[0117] Example 2-4: In addition to adding 100 ppm of C-GNR from Preparation Example 1 to acrylamide, the protein migration rate was measured as in Example 2-1.

[0118] Referring to Fig. 5, the speed at which negatively charged SDS-albumin protein migrated from the cathode to the anode in an electrophoretic gel (acrylamide gel) containing the C-GNR solution of Preparation Example 1 at a concentration of 0 to 100 ppm was observed. As a result, the electrophoretic migration distance of SDS-albumin was found to be 2.15 cm or more at a concentration of surface-modified gold nanorods of 100 ppm or less, and it can be confirmed that the migration speed of SDS-albumin increases as the concentration of C-GNR present on the gel increases.

[0119] The results of Figure 5 suggest that when a cosmetic device is applied to a cosmetic composition containing the C-GNR, the electric field at both ends of the C-GNR can be amplified due to the excellent conductivity of the C-GNR, which acts as a lightning rod under an electric field, and as a result, the electrostatic repulsion of the negatively charged active ingredients around the C-GNR is greatly increased, thereby improving the absorption rate of the active ingredients into the dermis layer, making it useful for application as a cosmetic composition.

[0120] Based on these results, a galvanic ampoule, i.e., a cosmetic composition, was prepared as follows using the above C-GNR.

[0121]

[0122] <C-GNR 함유 갈바닉 앰플 제조>

[0123] An ampoule mixture was prepared by mixing 100 parts by weight of purified water with 5 to 15 parts by weight of glycerin, 3 to 15 parts by weight of methylpropanediol, 3 to 10 parts by weight of butylene glycol, 2 to 7 parts by weight of niacinamide, 0.1 to 2 parts by weight of sodium hyaluronate, and 0.1 to 1.5 parts by weight of a preservative.

[0124] A cosmetic composition containing gold nanorods surface-modified with citrate was prepared by mixing the C-GNR of Preparation Example 1 into the mixture at a concentration of 50 ppm to produce a C-GNR galvanic ampoule (hereinafter referred to as 'ampoule').

[0125]

[0126] <Clinical Trial 1: No Ampoule Application (None (Control))>

[0127] A clinical trial was conducted for 4 weeks on 10 clinical subjects, with half of the face not having the above-mentioned ampoule applied and the other half having the above-mentioned ampoule applied.

[0128]

[0129] <Clinical Trial 2: Ampoule Application (C-GNR ampoule (AP))>

[0130] A clinical trial was conducted for 4 weeks on 22 clinical subjects by applying the above ampoule to half of their faces.

[0131]

[0132] <Clinical Trial 3: Ampoule Application and Device Use (C-GNR AP+Booster)>

[0133] Clinical trials were conducted on the 22 clinical subjects mentioned above for 4 weeks using a handheld combination beauty device (galvanic lightning device) after applying the ampoule to the remaining half of the face.

[0134] The device was used by pumping the ampoule once into the head portion for each of the three modes with near-infrared wavelengths of the galvanic lightning device (Galvanic Booster Mode (10–1,000 μA), Photothermal Mode (High Frequency), and Lifting Mode (Low Frequency). (A total of 3 ampoule pumps)

[0135]

[0136] <Clinical Trial Progress and Results>

[0137] 1. Oral wrinkles: For a 6 x 6 cm square area covering the entire periorbital wrinkles of the clinician, the degree of periorbital wrinkles was measured and analyzed using Antera 3D (Miravex, Ireland) before the test, 2 weeks after the test, and 4 weeks after the test, and the improvement rate was calculated as shown in Equation 1 below.

[0138] [Equation 1]

[0139]

[0140] Referring to Figure 7, when the ampoule was applied, the wrinkle index around the eyes decreased to 97% or less after 2 weeks and to 95% or less after 4 weeks, and when the ampoule was applied and the device was used, it decreased to 93% or less after 2 weeks and to 90% or less after 4 weeks.

[0141] In addition, when the ampoule was applied, the improvement rate of wrinkles around the eyes improved by more than 3.21% after 2 weeks and more than 5.35% after 4 weeks, and in particular, when the ampoule was applied and the device was used, it was confirmed that it improved significantly by more than 6.65% after 2 weeks and more than 10.35% after 4 weeks.

[0142] 2. Nasolabial folds: For a 6 x 6 cm square area covering the entire nasolabial fold of the clinician, the nasolabial fold index was measured and analyzed using Antera 3D before the test, 2 weeks after the test, and 4 weeks after the test, and the improvement rate was calculated as shown in Equation 1 above.

[0143] Referring to Figure 8, when the ampoule was applied, the nasolabial fold index decreased to 96% or less after 2 weeks and to 93% or less after 4 weeks, and when the ampoule was applied and the device was used, it decreased to 92% or less after 2 weeks and to 87% or less after 4 weeks.

[0144] In addition, when the ampoule was applied, the improvement rate of nasolabial folds improved by more than 3.4% after 2 weeks and more than 6.63% after 4 weeks, and in particular, when the ampoule was applied and the device was used, it was confirmed that it improved significantly by more than 7.53% after 2 weeks and more than 12.58% after 4 weeks.

[0145] 3. Pigmentation: For a 6 x 6 cm square area containing the clinician's facial pigmented lesions, the pigmented area (Affected Area, Melanin, mm) was measured using Antera 3D before, 2 weeks after, and 4 weeks after the test. 2 ) was measured and analyzed, and the improvement rate was calculated as shown in Equation 1 above.

[0146] Referring to Figure 9, when the ampoule was applied, the pigmentation area decreased to 92% or less after 2 weeks and 83% or less after 4 weeks, and when the ampoule was applied and the device was used, it decreased to 85% or less after 2 weeks and 73% or less after 4 weeks.

[0147] In addition, when the ampoule was applied, the improvement rate of pigmentation was improved by more than 7.66% after 2 weeks and more than 18.85% after 4 weeks, and in particular, when the ampoule was applied and the device was used, it was confirmed that it was significantly improved by more than 14.98% after 2 weeks and more than 27.86% after 4 weeks.

[0148] 4. Skin density: Skin density was measured using an ultrasound device (Ultrascan UC-22) at a point 1 cm horizontally lateral to the outer corner of the patient's eye (lateral canthus) before the test, 2 weeks after the test, and 4 weeks after the test, and the improvement rate was calculated as shown in Equation 1 above.

[0149] Referring to Figure 10, when the ampoule was applied, the skin density increased to over 110% after 2 weeks and over 119% after 4 weeks, and when the ampoule was applied and the device was used, it increased to over 117% after 2 weeks and over 125% after 4 weeks.

[0150] In addition, when the ampoule was applied, the improvement rate of skin density increased by more than 9.95% after 2 weeks and more than 19.41% after 4 weeks, and in particular, when the ampoule was applied and the device was used, it was confirmed that it improved significantly by more than 18.88% after 2 weeks and more than 27.45% after 4 weeks.

[0151] 5. Skin thickness: Skin thickness was measured using Ultrascan UC-22 at a point 1 cm horizontally lateral to the lateral canthus of the clinician, before the test, 2 weeks after the test, and 4 weeks after the test, and the improvement rate was calculated as shown in Equation 1 above.

[0152] Referring to Figure 11, when the ampoule was applied, the skin thickness increased by more than 106% after 2 weeks and more than 113% after 4 weeks, and when the ampoule was applied and the device was used, it increased by more than 112% after 2 weeks and more than 115% after 4 weeks.

[0153] In addition, when the ampoule was applied, the improvement rate of skin thickness increased by more than 6.24% after 2 weeks and more than 13.66% after 4 weeks, and in particular, when the ampoule was applied and the device was used, it was confirmed that it improved significantly by more than 12.76% after 2 weeks and more than 15.65% after 4 weeks.

[0154] 6. Pore Area: For a 6 x 6 cm area including the intersection of the horizontal line at the clinician's alar and the ipsilateral mid-pupillary line, the pore area (Affected Area, Melanin, mm) was measured using Antera 3D before, 2 weeks after, and 4 weeks after the test. 2 ) was measured and analyzed, and the improvement rate was calculated as shown in Equation 1 above.

[0155] Referring to Figure 12, when the ampoule was applied, the pore area decreased to 81% or less after 2 weeks and to 79% or less after 4 weeks, and when the ampoule was applied and the device was used, it decreased to 77% or less after 2 weeks and to 70% or less after 4 weeks.

[0156] In addition, when the ampoule was applied, the improvement rate of pore area increased by more than 15.56% after 2 weeks and more than 22.42% after 4 weeks, and in particular, when the ampoule was applied and the device was used, it was confirmed that it improved significantly by more than 22.224% after 2 weeks and more than 32.24% after 4 weeks.

[0157] 7. Skin keratin: Keratin was collected using a Corneofix D100 (Courage+Khazaka electronic GmbH, Germany) at the intersection point of the horizontal line at the clinician's alar and the ipsilateral mid-pupillary line before the test, 2 weeks after the test, and 4 weeks after the test. The desquamation index was analyzed using a Visioscan VC98 (Courage+Khazaka electronic GmbH, Germany), and the desquamation improvement rate was calculated as shown in Equation 1 above.

[0158] Referring to Figure 13, when the ampoule was applied, the skin exfoliation index decreased to 76% or less after 2 weeks and to 75% or less after 4 weeks, and when the ampoule was applied and the device was used, it decreased to 61% or less after 2 weeks and to 60% or less after 4 weeks.

[0159] In addition, when the ampoule was applied, the skin exfoliation improvement rate improved by more than 24.08% after 2 weeks and more than 24.92% after 4 weeks, and in particular, when the ampoule was applied and the device was used, it was confirmed that it improved significantly by more than 38.85% after 2 weeks and more than 39.04% after 4 weeks.

[0160] 8. Microcirculation: Skin microcirculation was measured on the facial area of ​​the clinician using OMEGAZONE-2STD (OMEGAWAVE, INC., Japan) before the test, 2 weeks after the test, and 4 weeks after the test, and the improvement rate was calculated as shown in Equation 1 above.

[0161] Referring to Figure 14, when the ampoule was applied, the microcirculation increased to over 120% after 2 weeks and over 127% after 4 weeks, and when the ampoule was applied and the device was used, it increased to over 126% after 2 weeks and over 135% after 4 weeks.

[0162] In addition, when the ampoule was applied, the improvement rate of microcirculation was increased by more than 23.97% after 2 weeks and more than 30.57% after 4 weeks, and in particular, when the ampoule was applied and the device was used, it was confirmed that it was significantly improved by more than 31.24% after 2 weeks and more than 39.21% after 4 weeks.

[0163] 9. Moisture content of the upper layer of the keratin: The moisture content of the upper layer of the keratin was measured using a Corneometer® CM 825 (Courage+Khazaka electronic GmbH, Germany) at the intersection point of the horizontal line at the clinician's alar and the ipsilateral mid-pupillary line, before the test, 2 weeks after the test, and 4 weeks after the test, and the improvement rate was calculated as shown in Equation 1 above.

[0164] Referring to Figure 15, when the ampoule was applied, the moisture content of the upper layer of the stratum corneum increased to over 113% after 2 weeks and over 119% after 4 weeks, and when the ampoule was applied and the device was used, it increased to over 114% after 2 weeks and over 124% after 4 weeks.

[0165] In addition, when the ampoule was applied, the improvement rate of moisture content in the upper layer of the stratum corneum increased by more than 13.47% after 2 weeks and more than 20.69% after 4 weeks. In particular, when the ampoule was applied and the device was used, it was confirmed that it improved significantly by more than 14.65% after 2 weeks and more than 26.2% after 4 weeks.

[0166] 10. Moisture content of the subcutaneous layer: The moisture content of the subcutaneous layer was measured using a MoistureMeter EpiD® (Delfin Technologies Ltd, Finland) at the intersection point of the horizontal line at the clinician's alar and the ipsilateral mid-pupillary line, before the test, 2 weeks after the test, and 4 weeks after the test, and the improvement rate was calculated as shown in Equation 1 above.

[0167] Referring to Figure 16, when the ampoule was applied, the moisture content of the lower layer of the stratum corneum increased to over 107% after 2 weeks and over 109% after 4 weeks, and when the ampoule was applied and the device was used, it increased to over 109% after 2 weeks and over 111% after 4 weeks.

[0168] In addition, when the ampoule was applied, the improvement rate of moisture content in the lower layer of the stratum corneum increased by more than 7.02% after 2 weeks and more than 9.84% after 4 weeks. In particular, when the ampoule was applied and the device was used, it was confirmed that it improved significantly by more than 9.88% after 2 weeks and more than 11.67% after 4 weeks.

[0169] 11. Moisture density: Skin moisture density is measured and analyzed using Moisture MAP MM100 (Courage+Khazaka electronic GmbH, Germany) at the halfway point of the imaginary line connecting the corner of the patient's mouth (lip commissure) and the ipsilateral tragus, before the test, 2 weeks after the test, and 4 weeks after the test, and the improvement rate is calculated as shown in Equation 1 above.

[0170] Referring to Figure 17, when the ampoule was applied, the water density increased to over 115% after 2 weeks and over 129% after 4 weeks, and when the ampoule was applied and the device was used, it increased to over 121% after 2 weeks and over 143% after 4 weeks.

[0171] In addition, when the ampoule was applied, the improvement rate of moisture density was increased by more than 18.13% after 2 weeks and more than 34.94% after 4 weeks, and in particular, when the ampoule was applied and the device was used, it was confirmed that it was significantly improved by more than 25.84% after 2 weeks and more than 51.24% after 4 weeks.

[0172] As such, the cosmetic composition containing gold nanorods surface-modified with citrate according to the present invention has the effect of reducing wrinkles around the eyes, nasolabial folds, pigmentation, pore area, and skin keratinization when used alone, and improving skin density, skin thickness, microcirculation, moisture content and moisture density of the upper and lower layers of the keratinization. In particular, it can be seen that the above effects are further enhanced when used in combination with a handheld complex beauty device.

[0173]

[0174] Accordingly, it was confirmed that the cosmetic composition containing gold nanorods surface-modified with citrate according to the present invention contains 100 ppm or less of the gold nanorods surface-modified with citrate, and can have a photothermal effect and an electric field amplification effect under near-infrared LED and galvanic current.

[0175] Although the present invention has been described above through specific details and limited embodiments, this is provided merely to aid in a more comprehensive understanding of the invention, and the invention is not limited to the above embodiments. Those skilled in the art can make various modifications and variations from this description.

[0176] Accordingly, the scope of the present invention is not limited to the described embodiments, and all things equivalent to or having equivalent variations to the claims set forth below, as well as the claims set forth below, shall be considered to fall within the scope of the concept of the present invention.

Claims

1. A cosmetic composition for beauty devices containing surface-modified gold nanorods, The above surface-modified gold nanorods (C-GNR) are a cosmetic composition for use in beauty devices, characterized in that the surface of the gold nanorods (GNR) is surface-modified with citrate.

2. In Paragraph 1, A cosmetic composition for use in beauty devices, characterized by the above-mentioned surface-modified gold nanorods having a survival rate of 80% or more of mouse muscle fibroblasts (BLO-11 (Mouse muscle fibroblast cell)) at a concentration of 100 ppm or less.

3. In Paragraph 1, A cosmetic composition for use in beauty devices, characterized in that when a DC 30 V electric field is applied to an acrylamide gel containing the above-mentioned surface-modified gold nanorods at a concentration of 100 ppm or less, the electrophoretic migration distance of SDS-albumin is 2.15 cm or more.

4. In Paragraph 1, The above surface-modified gold nanorods (Step A) Step of forming gold seeds; (Step B) A step of manufacturing gold nanorods by growing the gold seeds; and (Step C) A step of preparing surface-modified gold nanorods by replacing cetyltrimethylammonium bromide on the surface of the gold nanorods with citrate; A cosmetic composition for beauty devices characterized by being manufactured including 5. In Paragraph 1, The above cosmetic composition for beauty devices is characterized by being capable of having a photothermal effect and an electric field amplification effect under near-infrared LED and galvanic current.

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