A porous carrier-based organic zinc sustained-release deodorant composition, and a preparation method and application thereof

Abstract

The application relates to the technical field of daily chemical products, and discloses a porous carrier-loaded organic zinc slow-release deodorizing composition and a preparation method and application thereof, wherein the organic zinc slow-release deodorizing composition comprises the following components in percentage by mass: organic zinc pre-loaded on a porous carrier, wherein the mass percentage of the organic zinc is 8-25%, and the mass percentage of the porous carrier is 3-25%; a physical embedding type synergist: 1-10%; an enzyme inhibition type synergist: 0.5-8%; and the balance is water. The composition provided by the application realizes a 12-hour or longer sustained deodorizing effect through a multiple synergistic mechanism of porous carrier slow release, physical embedding capture of odor molecules and enzyme inhibition reduction of odor precursor generation, and is suitable for human body, pets, oral cavity, household environment and textile deodorizing finishing fields.

Description

Technical Field

[0001] This invention relates to the field of daily chemical products technology, and in particular to an organic zinc slow-release deodorizing composition based on a porous carrier, its preparation method and application. Background Technology

[0002] The generation and presence of malodorous substances, whether originating from human metabolism, pet activity, or microbial decomposition in the home environment, seriously affect people's quality of life and social interactions. Chemically, malodors primarily originate from several classes of volatile small-molecule compounds with characteristic odors, including: sulfur-containing compounds (such as hydrogen sulfide H2S, methanethiol CH3SH), nitrogen-containing compounds (such as ammonia NH3, trimethylamine (CH3)3N, and indole), short-chain fatty acids (such as isovaleric acid and butyric acid), and unsaturated aldehydes (such as 2-nonenal). These odor molecules share the common structural feature of containing nitrogen (N), sulfur (S), and oxygen (O) atoms that can provide lone pairs of electrons, making them chemically Lewis bases.

[0003] The use of metal ions as Lewis acids to coordinate with odor molecules is an important chemical principle in the field of deodorization technology. Among them, zinc (Zn) 2+ Due to its good safety and coordination ability, zinc glycinate has become a research hotspot. In particular, zinc glycinate, as an organozinc chelate, has been shown to have deodorizing activity based on a dual mechanism: one is Zn... 2+ It directly undergoes irreversible coordination reactions with odor molecules such as H2S and NH3 to form precipitates or stable complexes (such as ZnS precipitate, Ksp≈2×10). -25 Zn(NH3)4 2+ Complex ion, β4≈10 9 Firstly, it quickly neutralizes odor; secondly, it effectively inhibits the secretion of arylsulfatase and β-glucuronidase by odor-producing bacteria on the skin surface, blocking the conversion of odorless steroid precursors into odorous volatile steroids, thus reducing body odor at its source.

[0004] However, despite the recognized deodorizing potential of organic zinc (especially zinc glycinate), existing technologies still face significant technical bottlenecks in practical applications. After searching and analyzing existing patents and literature, the core shortcomings are summarized as follows: 1. Lack of long-lasting sustained-release capability: Most zinc-based deodorizing products on the market, including those with published patents (such as CN117503971A and CN102973966B), use organic zinc in a freely dissolved form. When sprayed onto the skin or fabric surface, the active ingredient Zn2+ is quickly washed away by sweat or rapidly consumed by the limited odor molecules in the environment, resulting in an extremely short effective deodorizing time, typically only 2 to 6 hours, which cannot meet users' needs for all-day protection.

[0005] 2. Lack of Application of Carrier Technology: While porous materials (such as mesoporous silica, metal-organic frameworks (MOFs), and chitosan microspheres) have been widely used in drug delivery to achieve sustained release of active ingredients, no patents disclose the use of such porous carriers to load pre-chelated organozinc for sustained release in the field of organozinc deodorants. The closest technical solution (such as CN117883622A) contains both glycine and zinc salt, but they are added separately and do not form a stable chelate structure beforehand. This non-chelated system cannot leverage the synergistic enzyme inhibition effect and ligand exchange-based sustained-release kinetics unique to chelates; its effect is equivalent to simple physical mixing.

[0006] 3. Lack of Intelligent Release Based on Environmental Response: Deodorizing needs are closely related to factors such as human perspiration and environmental humidity. Ideally, deodorants should release more active ingredients when there is heavy sweating and strong odor, while remaining stable when dry and odorless. Current technologies lack the ability to automatically adjust the release rate based on environmental humidity or pH, leading to problems such as ineffectiveness upon sweating or waste of effective ingredients.

[0007] 4. Single synergistic mechanism: Most patents rely on only a single deodorization pathway, such as simply relying on zinc salt neutralization or plant extracts to mask odors. They fail to organically integrate multiple mechanisms such as chemical coordination neutralization, physical encapsulation adsorption, enzyme activity inhibition, and environmental response release into the same formulation system, thus limiting deodorization efficiency and broad spectrum.

[0008] In summary, developing an organic zinc composition that can provide long-lasting sustained release, has environmental responsiveness, and integrates multiple mechanisms for synergistic deodorization is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0009] In view of the shortcomings of the prior art, the purpose of this invention is to provide an organic zinc slow-release deodorizing composition based on a porous carrier, its preparation method and application, in order to solve the technical problems of short effective deodorization time and lack of slow-release ability of existing organic zinc deodorizing compositions.

[0010] The technical solution of the present invention is as follows: An organozinc slow-release deodorizing composition based on a porous carrier, wherein the organozinc slow-release deodorizing composition comprises, by weight percentage: Organic zinc preloaded on a porous support, wherein the mass percentage of organic zinc is 8%-25% and the mass percentage of the porous support is 3%-25%; Physically encapsulated synergist: 1%-10%; Enzyme inhibitory synergists: 0.5%-8%; The remainder is water.

[0011] The organic zinc slow-release deodorizing composition based on porous carrier loading, wherein the organic zinc is in the form of a pre-formed chelate, and the organic zinc is selected from one or more of zinc glycinate, zinc peptide, zinc gluconate and zinc glucosamine.

[0012] The organic zinc slow-release deodorizing composition based on a porous carrier is wherein the porous carrier is selected from one or more of mesoporous silica nanoparticles, chitosan microspheres, γ-cyclodextrin metal-organic frameworks, and zeolites.

[0013] The organic zinc slow-release deodorizing composition based on porous carrier loading, wherein the physically encapsulated synergist is selected from one or both of β-cyclodextrin and cucurbituril [7].

[0014] The organic zinc sustained-release deodorizing composition based on porous carrier loading, wherein the enzyme-inhibiting synergist is selected from one or more of triethyl citrate, octanoyl glycine and epigallocatechin gallate.

[0015] The organic zinc slow-release deodorizing composition based on a porous carrier further comprises 1%-8% by mass of an acid-base neutralizing buffer, wherein the acid-base neutralizing buffer is composed of sodium bicarbonate and trisodium citrate.

[0016] The organic zinc slow-release deodorizing composition based on a porous carrier further comprises 0.5%-5% by weight of a dispersant solubilizer, wherein the dispersant solubilizer is one or more selected from PEG-40 hydrogenated castor oil, alkyl glycosides and glycerol.

[0017] The organic zinc slow-release deodorizing composition based on a porous carrier further comprises 0.5%-2% by weight of probiotic lysate, wherein the probiotic lysate is an inactivated lysate of Bacillus subtilis and / or Lactobacillus.

[0018] A method for preparing an organozinc slow-release deodorizing composition based on a porous carrier as described in this invention, comprising the steps of: Organic zinc was loaded onto the porous support to obtain a drug-loaded powder; Physically encapsulated synergists and enzyme-inhibiting synergists were mixed with water to obtain a liquid mixture. The drug-loaded powder is mixed and dispersed with the liquid mixture to obtain the organic zinc sustained-release deodorizing composition.

[0019] An application of the organozinc slow-release deodorizing composition based on a porous carrier as described in this invention, wherein the organozinc slow-release deodorizing composition is used to prepare deodorizing products for human body, pets, oral cavity, home environment, fabric washing and deodorizing agents, or textile deodorizing finishing agents.

[0020] Beneficial effects: In the organic zinc slow-release deodorizing composition provided by this invention, the porous carrier anchors organic zinc in the pores or surface through physical adsorption, hydrogen bonding, or electrostatic interaction, so that zinc ions no longer exist in a free dissolved state, thereby significantly slowing down their release rate; the physical encapsulation type synergist (such as β-cyclodextrin) can capture odor molecules in situ after application, enrich them in the cavity, increase the local odor concentration, and accelerate the coordination reaction with the released zinc ions; the enzyme-inhibiting type synergist (such as triethyl citrate and octanoyl glycine) can inhibit the activity of odor-producing enzymes, reducing the generation of odor precursors from the source; the three mechanisms are independent and complementary: the porous carrier provides long-lasting slow release, physical encapsulation improves instantaneous deodorization efficiency, and enzyme inhibition reduces the amount of odor generated, which together extend the effective deodorization time from the existing 2-6 hours to more than 12-48 hours, and significantly improves the removal rate of various odors such as hydrogen sulfide, ammonia, and isovaleric acid, and can still maintain less attenuation in high humidity or sweating environments. Attached Figure Description

[0021] Figure 1 The present invention provides a flowchart of a method for preparing an organic zinc slow-release deodorizing composition based on a porous carrier.

[0022] Figure 2 This is a schematic diagram of the slow-release prediction curve of organic zinc loaded on a porous carrier in Test Example 1 of the present invention.

[0023] Figure 3 This is a comparison of the deodorizing durability of different compositions in Test Example 2 of the present invention. Detailed Implementation

[0024] This invention provides an organic zinc slow-release deodorizing composition based on a porous carrier, its preparation method, and its application. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention.

[0025] This invention provides an organozinc slow-release deodorizing composition based on a porous carrier, wherein the organozinc slow-release deodorizing composition comprises, by mass percentage: organozinc preloaded on a porous carrier, wherein the mass percentage of organozinc is 8%-25% and the mass percentage of the porous carrier is 3%-25%; a physically embedded synergist: 1%-10%; an enzyme inhibitor synergist: 0.5%-8%; an acid-base neutralizing buffer: 1%-8%; and the balance being water.

[0026] In this embodiment, the explanations of several key technical terms are as follows: Organic zinc: refers to chelates formed by organic ligands (such as amino acids, small peptides, and sugar acid derivatives) coordinating with zinc ions (Zn2+) through functional groups such as carboxyl and amino groups, rather than simple physical mixtures of ligands and zinc salts. The molar ratio of the organic ligand to Zn2+ is 1:1 to 2:1. Porous carrier: refers to materials with nano- to micro-scale pore structures that can load and immobilize active substances through physical or chemical actions. Its function is to control the release kinetics of active ingredients. Physical encapsulation synergist: refers to compounds that have specific cavity structures (such as hydrophobic cavities) and can capture odor molecules in situ through host-guest encapsulation after application. Its function is not to pre-form inclusion complexes, but to dynamically enrich odors during use. Enzyme inhibitor synergist: refers to compounds that can inhibit or reduce the activity of enzymes (such as arylsulfatase and lipase) related to the generation of odor substances.

[0027] The organic zinc slow-release deodorizing composition provided in this embodiment is mainly applied to various scenarios such as human deodorization, pet care, oral cleaning, home environment purification, and textile deodorization finishing. This composition solves the problems of rapid zinc ion release and short effective deodorization time (only 2-6 hours) of traditional organic zinc deodorants by pre-loading organic zinc into a porous carrier and combining physical encapsulation with enzyme inhibition synergistic mechanisms. Specifically, the porous carrier anchors organic zinc molecules through physical adsorption, hydrogen bonding, or electrostatic interactions, transforming them from a free dissolved state to a loaded slow-release state, significantly slowing down the release rate of zinc ions. Physically encapsulated synergists (such as β-cyclodextrin) dynamically capture odor molecules in situ after application, increasing their local concentration near the zinc active site and accelerating the coordination reaction. Enzyme-inhibiting synergists (such as triethyl citrate) inhibit the activity of key odor-producing enzymes on the skin or environmental surface, reducing odor generation at its source. These three mechanisms are independent of each other and complement each other, working together to achieve a long-lasting and highly efficient deodorization effect of 12-48 hours or more, and showing excellent removal capabilities for various odor molecules such as hydrogen sulfide, ammonia, and isovaleric acid.

[0028] In this embodiment, to balance formulation cost and active ingredient content while ensuring excellent sustained-release effect and achieve better cost-effectiveness, the organic zinc pre-loaded on the porous carrier contains 8%-25% organic zinc and 3%-25% porous carrier by mass percentage. This content range is an optimized range verified by extensive experiments. Organic zinc content below 8% may result in insufficient deodorization ability, making it difficult to handle high concentrations of odor; above 25%, although the instantaneous deodorization ability is enhanced, it may increase the risk of skin irritation and increase costs. Porous carrier content below 3% results in limited sustained-release effect and difficulty in significantly prolonging the duration of action; above 25%, although the sustained-release effect is stronger, it may affect the fluidity of the formulation or the spray atomization effect, and make the formulation tend to be thicker. As an example, a long-lasting deodorizing spray was designed with an organic zinc (calculated as zinc glycinate) content of 15% and a total porous carrier (MSN and γ-CD-MOF combination) content of 10%. Human trials showed that the median effective deodorization time of this formulation reached 24 hours, and the subjects' skin tolerance was good.

[0029] In some embodiments, to further enhance the deodorization spectrum and biocompatibility of the composition, the organic zinc is selected from one or more of zinc glycinate, zinc peptides (zinc peptides are typically composed of 3-5 amino acids with a molecular weight of approximately 300-600 Da), zinc gluconate, and zinc glucosamine, but is not limited thereto. In this embodiment, the organic zinc is in a pre-formed chelate form, i.e., a stable structure formed by the organic ligand and zinc ions through coordination bonds, rather than formed by the in-situ mixing of the organic ligand and zinc salt in the composition. 2+ The molar ratio is 1:1 to 2:1. These organozinc compounds are all linked through stable five- or six-membered chelate rings, resulting in more stable release and lower skin irritation compared to inorganic zinc salts. Furthermore, some ligands (such as glycinate) can participate in conjugate base buffering and potentially inhibit odor-producing enzyme processes. As a typical example, when the organozinc is zinc glycinate, its chemical formula is Zn(Gly)2, and the ligands are related to Zn... 2+ The molar ratio is 2:1. For a specific application scenario, when the composition is designed for sensitive skin, zinc peptides or zinc glucosamine can be selected, as they generally have better skin penetration and anti-inflammatory adjuvant activity. Through the above design, this embodiment effectively expands the range of deodorizing active ingredients while ensuring the mildness and diversity of the composition's mechanism of action.

[0030] In some embodiments, to provide an ideal sustained-release platform and adsorption sites for organozinc, the porous support is selected from one or more of mesoporous silica nanoparticles, chitosan microspheres, γ-cyclodextrin metal-organic frameworks, and zeolites, but is not limited thereto. Different porous supports can achieve differentiated sustained-release effects due to their different pore structures, surface properties, and response mechanisms. For example, mesoporous silica nanoparticles (MSN) have regular and relatively large pore sizes (typically 2-10 nm) and high specific surface areas (≥500 m²). 2 / g), with a large loading capacity and rapid initial release; chitosan microspheres contain amino groups, and their swelling behavior is pH-regulated, enabling responsive accelerated release in acidic sweat environments; γ-cyclodextrin metal-organic frameworks (γ-CD-MOFs), due to their organic-inorganic hybrid framework characteristics, are sensitive to humidity, and their release rate increases in high-humidity environments. By loading organic zinc onto the pores or surface of these carriers, it is possible to prevent zinc ions from dissolving too quickly, prolonging the action time, and also to utilize the pores of the carrier itself to adsorb some odor molecules. For a specific application example, when preparing a general-purpose deodorizing spray, MSN can be selected as the main carrier. At 25°C, zinc glycine is loaded onto the carrier through aqueous impregnation, achieving a loading rate of 15%-35% (w / w). The resulting drug-loaded powder showed an initial rapid release of 0-2 hours followed by a slow release in simulation experiments. Through the above design, this embodiment allows for flexible selection and combination of porous carriers according to the target application scenario to control the release curve.

[0031] In some specific implementations, to integrate the release kinetic advantages of different types of carriers and achieve a three-stage (rapid start-up, sustained release, and environmental response) release curve that better meets actual deodorization needs, the porous carrier is composed of mesoporous silica nanoparticles and γ-cyclodextrin metal-organic frameworks, with a mass ratio of mesoporous silica nanoparticles to γ-cyclodextrin metal-organic frameworks of 1:0.5 to 1:2. In this embodiment, the mesoporous silica nanoparticles (MSN) have a larger pore size, allowing the loaded organic zinc to diffuse easily, and are mainly responsible for rapid release within 0-2 hours after application to cope with immediate odor impact; the γ-cyclodextrin metal-organic framework (γ-CD-MOF) has unique humidity responsiveness, and its release rate is regulated by ambient humidity, providing sustained release for 2-48 hours under normal conditions, while automatically accelerating release under high humidity or sweating conditions to compensate for possible loss. As an example, MSN and γ-CD-MOF are compounded at a mass ratio of 1:1, and zinc glycinate is loaded onto each and then mixed. In vitro release experiments showed that the dual-carrier combination released approximately 30% of zinc ions in the initial stage (2 hours), and a cumulative release of approximately 60% after 12 hours. Under simulated high humidity (80% RH) conditions, its release rate within 4-8 hours was approximately 2-3 times higher than under normal humidity conditions. Through the above design, this embodiment can effectively achieve intelligent control of release behavior, enabling the deodorization effect to be both rapid and long-lasting, and to adaptively respond to high-demand scenarios.

[0032] In some specific embodiments, to endow the composition with the ability to automatically enhance release in acidic environments (such as sweat environments) and improve its deodorizing efficacy in scenarios prone to sweating, such as sports and high temperatures, the porous carrier includes chitosan microspheres with a particle size of 5 μm to 50 μm. The chitosan molecular chain is rich in amino groups, with a pKa of approximately 6.3. In a near-neutral pH environment (6.0-7.0), the amino groups are deprotonated, causing the microspheres to shrink, resulting in smaller pores and slower release; however, in the acidic environment of sweat (pH 4.5-5.5), a large number of amino groups are protonated (-NH3). + The increased repulsive forces between molecular chains cause the microspheres to swell, opening pores and significantly accelerating the release rate of the loaded organic zinc. The particle size is controlled within the range of 5-50 μm, ensuring sufficient specific surface area for efficient loading while facilitating dispersion in liquid formulations and subsequent skin application. For example, chitosan microspheres with a particle size of approximately 20 μm were prepared using an emulsification crosslinking method and loaded with zinc glycine. In vitro release experiments showed that in a pH 5.0 buffer solution, the zinc ion release from these drug-loaded microspheres in the first 4 hours was 3-5 times that in a pH 7.0 buffer solution. Through this design, this embodiment effectively achieves intelligent sensing and response of the composition to the usage environment, providing the strongest deodorizing guarantee during periods of peak sweating.

[0033] In some embodiments, in order to capture and enrich hydrophobic or specific odor molecules in situ through host-guest inclusion, thereby accelerating their subsequent coordination reaction with zinc ions and improving instantaneous deodorization efficiency, the physical encapsulation synergist is selected from one or both of β-cyclodextrin and cucurbituril [7], but is not limited thereto. In this embodiment, β-cyclodextrin has a hydrophobic cavity (approximately 0.60-0.65 nm in diameter), the size of which matches common hydrophobic odor molecules such as isovaleric acid and short-chain thiols, and can form inclusion complexes; the molecular ring of cucurbituril [7] is composed of 7 glycoure structural units in a closed ring, and its cavity has a very high binding constant for nitrogen-containing odor molecules such as trimethylamine and indole. They are not added in the form of pre-encapsulation, but after the composition is applied, they dynamically capture odor molecules in the surrounding environment in a free state at the site of action, fix them locally, and increase the probability of odor molecules meeting and reacting with slowly released zinc ions. As an example, when 2% β-cyclodextrin was added to the deodorizing composition, in a closed headspace test, the composition containing β-cyclodextrin showed an approximately 8-10 percentage point increase in the 30-minute removal rate of isovaleric acid compared to the control composition without β-cyclodextrin but with the same zinc content. Through the above design, this embodiment achieves immediate locking and pre-concentration of free odor molecules, significantly improving the deodorizing efficiency of the composition in a short time, especially effective against hydrophobic odors.

[0034] In some embodiments, to inhibit or reduce the generation of odor precursors at the source and reduce dependence on zinc ion-consuming coordination, thereby achieving more fundamental and longer-lasting deodorization, the enzyme-inhibiting synergist is selected from one or more of triethyl citrate, octanoylglycine, and epigallocatechin gallate, but is not limited thereto. In this embodiment, these compounds function through different mechanisms: triethyl citrate (TEC) inhibits the lipase activity of bacteria on the skin surface, reducing the generation of fatty acid odor precursors; octanoylglycine itself has antibacterial activity and can exchange ligands with zinc ions to form mixed ligand complexes, further regulating the release rate; epigallocatechin gallate (EGCG) inhibits the activity of odor-producing enzymes (such as arylsulfatase) by forming multi-point hydrogen bonds with its polyphenolic hydroxyl groups. As an example, 3% triethyl citrate and 1% octanoylglycine are added simultaneously to the underarm deodorant formula. In vitro enzyme activity inhibition experiments showed that the combination inhibited arylsulfatase by more than 70%; human trials showed that after using the formula, the generation rate of odor substances in the underarms of subjects was significantly reduced, and the effective deodorization time was prolonged. Through the above design, this embodiment effectively intervened in the odor generation pathway, forming a three-dimensional deodorization network that combines blocking and unblocking with the direct neutralization effect of zinc ions, further optimizing the overall solution.

[0035] In some embodiments, to more effectively neutralize acidic odors (such as isovaleric acid and butyric acid) and maintain the pH of the formulation within a suitable range, thereby improving skin comfort and deodorizing efficiency, the organic zinc sustained-release deodorizing composition further includes 1%-8% by weight of an acid-base neutralizing buffer. Acidic odors are highly volatile and have a pronounced odor in their molecular state; after neutralization, they are converted to an ionic state, which not only weakens the odor but also makes them easier to precipitate or coordinate with zinc ions. The addition of the buffer can stabilize the pH of the system, preventing drastic local pH changes from affecting the active form and release behavior of zinc ions.

[0036] In this embodiment, to achieve the dual purpose of rapid neutralization and long-term buffering, and to precisely control the pH value of the final product, the acid-base neutralizing buffer consists of 1%-3% sodium bicarbonate and 0.5%-2% trisodium citrate by mass. Sodium bicarbonate, as a neutralizing agent, reacts rapidly with acidic odors, immediately reducing their volatility; trisodium citrate, as a buffer salt, forms a buffer pair with the reaction products or existing acid / base components in the system, stably maintaining the pH within the preset range of 5.5-7.0. The synergistic effect of both ensures the efficiency of the neutralization reaction while avoiding drastic pH fluctuations caused by the one-time addition of strong bases and acids. For example, 1.5g of sodium bicarbonate and 1.0g of trisodium citrate are added to 100g of the composition. Testing showed that this formulation can raise the pH of simulated sweat (initial pH 4.0) to approximately 6.0 within 30 seconds, and stabilize the pH within the range of 6.0 ± 0.3 for the following 3 hours. Through the above technical solution, this application effectively achieves immediate suppression of acidic odor and sustained stable regulation of the local microenvironment, further optimizing the overall solution.

[0037] In some embodiments, to ensure the uniform dispersion and stability of the components in the composition (especially the hydrophobic synergist and the solid drug-carrying powder) and to avoid precipitation or stratification, the organozinc sustained-release deodorizing composition further includes 0.5%-5% of a dispersant by weight. The dispersant by weight is one or more of PEG-40 hydrogenated castor oil, alkyl glycosides, and glycerol, but is not limited to these. Good dispersibility not only affects the appearance stability of the product but also directly impacts the uniformity of the distribution of the active ingredient and the accuracy of the dosage during use. Dispersants (such as PEG-40 hydrogenated castor oil, alkyl glycosides, etc.) promote the wetting and dispersion of solid particles in the aqueous phase by reducing interfacial tension, and can also solubilize some oil-soluble enzyme inhibitors (such as triethyl citrate) or plant essential oils. As an example, when preparing a deodorizing emulsion containing triethyl citrate and MSN drug-loaded powder, adding 1% PEG-40 hydrogenated castor oil and homogenizing at 3000 rpm under high shear for 5 minutes yields a uniform and stable micro-milky white liquid. After standing for 24 hours, no visible precipitation or oil phase separation is observed. Through the above design, this embodiment effectively achieves the long-term physical stability of the composition system, ensuring consistent performance in every use.

[0038] In some embodiments, to introduce competitive inhibition and beneficial metabolites of probiotics and enhance the ecological regulation of odor-producing bacteria, the organic zinc slow-release deodorizing composition further includes 0.5%-2% of probiotic lysate by weight. The probiotic lysate is an inactivated lysate of Bacillus subtilis and / or Lactobacillus, but is not limited to this. In this embodiment, the probiotic lysate contains inactivated bacterial cells and their cell wall fragments, metabolic enzymes, etc. These substances can competitively occupy ecological niches on the skin or environmental surface, inhibiting the colonization of harmful odor-producing bacteria. Simultaneously, some components may directly inhibit odor-producing enzyme activity or act as a slow-release carrier of zinc ions. Using inactivated lysate instead of live bacteria avoids concerns regarding the storage stability, safety, and regulatory aspects of live bacteria. For example, 1.5% of Bacillus subtilis lysate was added to a pet environment deodorizing spray. Tests showed that after spraying this formula, the ammonia generation rate in pet urine stain areas was reduced by approximately 25% compared to a control formula without lysate. Through the above design, this embodiment effectively introduces a bioregulatory dimension, adding an additional, sustainable deodorization pathway to the composition and further optimizing the overall solution.

[0039] In some embodiments, a method for preparing an organozinc slow-release deodorizing composition supported on a porous carrier is also provided, such as... Figure 1 As shown, it includes the following steps: S10. Load the organic zinc onto the porous support to obtain the drug-loaded powder; S20. Mix the physically encapsulated synergist and the enzyme-inhibiting synergist with water to obtain a liquid mixture; S30. The drug-loaded powder is mixed and dispersed with the liquid mixture to obtain the organic zinc sustained-release deodorizing composition.

[0040] In this embodiment, step S10 is the core of the method to achieve sustained-release function. The loading process varies depending on the selected carrier. For example, when the porous carrier includes mesoporous silica nanoparticles, step S10 may specifically be as follows: disperse the mesoporous silica nanoparticles in water at 3-5 times their mass, sonicate (e.g., 200W power, 10 minutes) to form a uniform suspension, add an aqueous solution of organozinc (e.g., concentration 10%-30%), and stir at 200-400 rpm for 1-3 hours at 10°C to 40°C (preferably 25°C) to allow the organozinc molecules to fully diffuse and adsorb into the carrier pores; then perform solid-liquid separation by filtration or centrifugation, and vacuum dry the obtained solid at 30°C to 50°C (preferably 40°C) for 2-6 hours to obtain mesoporous silica drug-loaded powder with a loading rate of 15%-35%.

[0041] When the porous carrier includes a γ-cyclodextrin metal-organic framework, step S10 can specifically be as follows: The γ-cyclodextrin metal-organic framework is dispersed in anhydrous ethanol (solid-liquid ratio approximately 1:10-1:20 w / v), ultrasonically dispersed for 10 minutes, and then solid organozinc powder is added. The mixture is stirred at 150-300 rpm for 2-5 hours at 10°C to 40°C, utilizing the weakly polar environment of ethanol to promote the diffusion and surface coordination of organozinc within the MOF channels. Subsequently, the mixture is separated by centrifugation at 2000-4000 rpm for 10-15 minutes, and the solid fraction is vacuum-dried at 35°C to 45°C for 10-14 hours to obtain the γ-cyclodextrin metal-organic framework drug-loaded powder. When using multiple carriers, each carrier can be loaded with the drug separately, and then the resulting drug-loaded powders can be physically mixed uniformly.

[0042] Step S20 involves preparing the main phase. Most of the water in the formulation can be heated to 35°C to 45°C. Then, under stirring (e.g., 300-600 rpm), physical encapsulation synergists (e.g., β-cyclodextrin), enzyme inhibitor synergists (e.g., triethyl citrate, octanoyl glycine), and other optional water-soluble components (e.g., acid-base neutralizing buffers, dispersing solubilizers, probiotic lysates, etc.) are added sequentially. The mixture is stirred until completely dissolved or uniformly dispersed. The solution is then cooled to room temperature for later use.

[0043] Step S30 involves fusing the solid-phase active core with the liquid-phase matrix. Under low-speed stirring (e.g., 500-1000 rpm), the mixed drug-loaded powder obtained in step S10 is slowly added to the liquid-phase mixture prepared in step S20. After the addition is complete, the stirring intensity is increased. Specifically, mixing and dispersion can be performed under high-shear homogenization at a speed of 1000 rpm to 5000 rpm for 1 to 10 minutes (preferably 3-5 minutes) to ensure sufficient dispersion of the drug-loaded powder and the absence of visible agglomerates. After homogenization, preservatives, fragrances, and other post-additional components can be added and stirred evenly. If necessary, the mixture can be filtered through a 0.45 μm microporous membrane to obtain the final composition.

[0044] The above-described preparation process of this invention ensures the effective fixation and high loading rate of organic zinc on the porous carrier through precise control of the loading step, which is the basis for achieving long-term sustained release; while the subsequent high-shear homogenization ensures the uniform and stable dispersion of solid loaded particles in the liquid medium, giving the product good application performance and dosage consistency.

[0045] In some embodiments, an application of the organozinc slow-release deodorizing composition based on a porous carrier as described in this invention is also provided, wherein the organozinc slow-release deodorizing composition is used to prepare deodorizing products for human body, pets, oral cavity, home environment, fabric washing and deodorizing agents, or textile deodorizing finishing agents, but is not limited thereto.

[0046] The present invention will be further explained and illustrated below through specific embodiments: Example 1: Spray-type deodorant for underarms (optimal formula) This embodiment provides a spray-type deodorant for human use based on MSN+γ-CD-MOF dual carriers. The formulation is detailed in Table 1.

[0047] Table 1: Formulation of Example 1 (total 100g)

[0048] Its preparation methods include: Step 10 (Pre-preparation of tea tree oil inclusion complex): Mix β-CD and tea tree oil at a mass ratio of 10:1, add a small amount of deionized water (solid-liquid ratio of about 1:3 w / v), grind at room temperature for 2 hours (Kneading method), vacuum dry at 50°C for 24 hours, pulverize and pass through an 80-mesh sieve, and set aside.

[0049] Step 20 (Carrier Loading—Phase-Separated Drug Loading): (2a) MSN aqueous phase loading: MSN was dispersed in 15g of deionized water and sonicated for 10min to form a suspension; 20.0g of organic zinc (for example, zinc glycinate) aqueous solution was added and stirred at 25℃ for 2h; vacuum filtered and dried at 40℃ for 4h to obtain MSN drug-loaded powder.

[0050] (2b) γ-CD-MOF non-aqueous phase loading: γ-CD-MOF was dispersed in 30 mL of anhydrous ethanol and sonicated for 10 min; 1.0 g of organic zinc (zinc glycinate as an example) solid powder was added and stirred at room temperature for 3 h; centrifuged at 3000 rpm for 10 min and vacuum dried at 40 °C for 12 h to obtain γ-CD-MOF drug-loaded powder.

[0051] (2c) Physically mix the drug-loaded powders obtained in steps (2a) and (2b) until homogeneous.

[0052] Step 30 (Primary Phase Preparation): Heat the remaining deionized water to 40°C, then add β-CD, sodium bicarbonate, trisodium citrate, and octyl glycine in sequence, stirring to dissolve. After cooling to room temperature, add TEC, glycerin, and PEG-40 hydrogenated castor oil.

[0053] Step 40 (Combined Filling): Add the mixed drug-loaded powder from step 2c to the main phase of step 30, homogenize at 3000 rpm for 5 min under high shear; finally add tea tree oil inclusion complex and phenoxyethanol, stir for 15 min, filter through a 0.45 μm microporous membrane, fill into a container, and obtain a spray-type deodorant for human use.

[0054] The performance of the spray-type deodorant prepared in Example 1 was tested, and the test results are shown in Table 2. The performance test methods are briefly described below: H2S / NH3 / CH3SH removal rate: Headspace GC method (or detection tube method) was used in a sealed container. The initial gas concentration was 50 ppm, the temperature was 25℃, the RH was 60%, and the residual concentration was measured after 30 min of contact. The removal rate was calculated. n=3, and the reported values ​​are the mean ± standard deviation.

[0055] Arylsulfatase inhibition rate: Using human recombinant arylsulfatase (e.g., Sigma A9420) and 4-methylumbelliferyl sulfate (4-MUS) as a substrate (final concentration 0.5 mM), the initial reaction rate was measured after pre-incubation at pH 5.5 and 37°C for 15 min. The inhibition rate was calculated as the ratio of the rates before and after inhibitor addition. The inhibitor concentration corresponds to the steady-state epidermal concentration after skin penetration conversion of the formulation's usage concentration. n=3, SD<5%.

[0056] Effective deodorization duration: Human trial (IRB approved), n=20, underarm spray, subjective scoring method (0-10 points VAS) combined with instrument detection (electronic nose TGS sensor), effective if the score is ≥5 points or the H2S removal rate is ≥60%.

[0057] Table 2 Performance Test Results

[0058] Example 2: High-content organic zinc slow-release spray-type deodorant This embodiment provides a spray-type deodorant for the human body, which differs from Example 1 in that it has an increased content of organic zinc. The formula is shown in Table 3, and the preparation method is the same as that of Example 1.

[0059] Table 3 Formulation of Example 2

[0060] Performance tests on the spray-type deodorant of Example 2 revealed that with the increased content of organic zinc (taking zinc glycinate as an example), the H2S removal rate at 30 min was expected to be ≥97%, and the effective deodorization time was expected to be ≥24 h. However, attention should be paid to the assessment of skin irritation at high concentrations.

[0061] Example 3: Pet Environment Deodorizing Spray This embodiment provides a pet environment deodorizing spray. This embodiment demonstrates a formulation using chitosan microspheres and zeolite as carriers, applied to pet bedding and space deodorization. The formulation is shown in Table 4. The preparation method is similar to that of Example 1: chitosan microspheres and zeolite are mixed with zinc glycine solution for adsorption, and then mixed and homogenized with the remaining components.

[0062] Table 4 Formulation of Example 3

[0063] The performance of the pet environment deodorizing spray in Example 3 was tested. The pet skin irritation was tested using the modified Draize method. The results showed that the NH3 removal rate was 91%, the H2S removal rate was 96%, and the effective duration was ≥18h. The modified Draize method test showed that it did not irritate the pet skin.

[0064] Example 4: Oral deodorizing mouthwash This embodiment provides an oral deodorizing mouthwash. This embodiment demonstrates a low-concentration, palatable mouthwash formula that utilizes MSN to achieve long-lasting antibacterial and deodorizing effects. The formula is shown in Table 5. The preparation method is similar to that of Example 1: MSN is loaded with zinc glycine and then simply mixed and dissolved with other water-soluble ingredients.

[0065] Table 5 Formulation of Example 4

[0066] The performance of the oral deodorizing mouthwash in Example 4 was tested. Oral H2S was measured using a portable oral gas detector (Halimeter) with 15 subjects (n=15). After rinsing for 30 seconds, the mouth spit out the mouthwash, and oral VSC values ​​were measured at 0, 30 min, 3 h, and 6 h. The percentage reduction in H2S was calculated. The results showed that oral H2S was reduced by ≥80% after 30 min, ≥55% after 3 h, and ≥35% after 6 h, with a taste acceptance score of ≥4.0 / 5.0.

[0067] Example 5 (Spray-type deodorant for the human body, using MSN carrier only) This embodiment provides a spray-type deodorant for the human body based on MSN single carrier. The only difference between its formulation and that of Example 1 is that the amount of MSN is increased to 5.0g, and γ-CD-MOF is not added; only 33g of 30% zinc glycinate aqueous solution is used, without adding 1g of zinc glycinate solid powder, and deionized water is used to make up the difference; the preparation method is different from that of Example 1 in that steps 2b and 2c are not included, and the rest are the same as in Example 1.

[0068] The performance of the spray-type deodorant prepared in Example 5 was tested. The results showed that its H2S removal rate was 92.5% after 30 minutes and 51.3% after 12 hours. This indicates that the single MSN carrier provides a certain sustained-release effect, but the release kinetics are insufficient in the mid-to-late stages, and its long-lasting effect is significantly weaker than the dual-carrier combination in Example 1.

[0069] Example 6 (Spray-type deodorant for human use, using only γ-CD-MOF carrier) This embodiment provides a spray-type deodorant for human use based on MSN single carrier. The only difference between its formulation and that of Example 1 is that the amount of γ-CD-MOF is increased to 5.0g and MSN is not added; only 10g of zinc glycinate solid powder is used, without adding 30% zinc glycinate aqueous solution, and deionized water is used to make up the difference; the preparation method is different from that of Example 1 in that steps 2a and 2c are not included, and the rest are the same as in Example 1.

[0070] The performance of the spray-type deodorant prepared in Example 6 was tested. The results showed that its H2S removal rate was 87.1% at 30 min (slow initial release) and 58.7% at 12 h. This indicates that the single γ-CD-MOF performs better than the single MSN in the middle and later stages, but its initial effect is insufficient. Moreover, with the same total carrier amount, the effect at 12 h is still lower than that of the dual carrier combination in Example 1.

[0071] Comparative Example 1 (without porous carrier) An organic zinc slow-release deodorizing composition is provided, the formulation of which differs from that of Example 1 in that MSN and γ-CD-MOF are not added; instead, an equal amount of 30g of 30% zinc glycinate solution is directly added to the formulation, and deionized water is used to bring the total to 100g. This comparative example simulates the most common free-dissolved organic zinc deodorizers in the prior art.

[0072] Performance tests were conducted on the organic zinc slow-release deodorizing composition of Comparative Example 1. The results showed that its H2S removal rate was 89.2% at 30 min (slightly low, due to the lack of enrichment effect from physical encapsulation), but the H2S removal rate dropped sharply to 21.3% after 12 h. This indicates that without carrier protection, organic zinc is rapidly consumed or deactivated, resulting in extremely poor long-term effectiveness.

[0073] Comparative Example 2 (without enzyme inhibitor) An organic zinc slow-release deodorizing composition is provided, the formulation of which differs from that of Example 1 in that: triethyl citrate and octyl glycine are not added, and the amount is made up to 100g with deionized water.

[0074] Performance tests were conducted on the organic zinc slow-release deodorizing composition of Comparative Example 2. The results showed that its H2S removal rate was 90.8% at 30 min and 42.5% at 12 h. The mid-term effect showed significant attenuation, which proves that enzyme inhibitors (Class B synergists) are indispensable for maintaining long-term effectiveness and achieving source control.

[0075] Comparative Example 3 (Reproduction of Scheme CN117883622A – Pre-chelated State) A deodorizing composition is provided, reproduced according to Example 1 of CN117883622A: 1.5g glycine, 2.0g basic zinc carbonate, 5.0g kaolin, and 91.5g deionized water are stirred at room temperature for 30 minutes. In this formulation, glycine and zinc salt react in situ in the system, but due to reaction kinetics, only a partial chelate is formed, with the remainder existing as free glycine and unreacted zinc salt.

[0076] Performance tests were conducted on the deodorizing composition of Comparative Example 3. The results showed that its H2S removal rate was 78.6% after 30 minutes and 15.2% after 12 hours. The effect was far worse than that of all embodiments of the present invention. This proves that in the non-chelated system, the reaction between glycine and zinc salt is incomplete and unstable, and cannot provide an effective chelating effect and long-term protection.

[0077] Comparative Example 4 (glycine + zinc salt + carrier of this invention, non-prechelated) An odor-degrading composition is provided, which uses the same carrier combination (MSN 3.0g + γ-CD-MOF 2.0g) and drug loading process as in Example 1, but replaces the organozinc prechelate with glycine and basic zinc carbonate in equal molar amounts of zinc and adds them separately to the drug loading system.

[0078] Performance tests were conducted on the deodorizing composition of Comparative Example 4. The results showed that its H2S removal rate was 84.3% after 30 minutes and 28.7% after 12 hours. This is a significant difference compared to Example 1 (≥65% after 12 hours). This clearly demonstrates that even with the same high-quality carrier system, the long-lasting deodorizing effect is greatly reduced without the use of pre-chelated organic zinc.

[0079] Comparing the results of Comparative Examples 3 and 4 with those of Example 1, it is evident that even with the introduction of the advanced dual-carrier system of this invention (Comparative Example 4), the 12-hour effect (28.7%) is still significantly lower than that of Example 1 (67.5%) without the use of pre-chelated organic zinc. This indicates a strong positive synergistic effect between pre-chelation and the porous carrier, rather than a simple additive effect. The pre-chelated form is Zn. 2+ It provides a slow-release switch (ligand exchange mechanism), while the porous carrier provides a physical barrier and an environmental response trigger for this switch, and the combination of the two produces a synergistic effect.

[0080] Test Example 1 To verify the long-lasting sustained-release effect of the dual-carrier combination, samples of free organic zinc (without carrier), MSN carrier only (Example 5), and MSN+γ-CD-MOF dual-carrier combination (Example 1) were placed in dialysis bags and immersed in phosphate buffer (pH 5.5, simulating sweat). The samples were then kept at 37°C with constant shaking, and Zn was measured at different time points. 2+ Concentration, plotted cumulative release rate-time curve, results as follows Figure 2 As shown, from Figure 2 It can be seen that the free organic zinc curve shows extremely rapid release, almost complete release within 2 hours, followed by rapid deactivation; the MSN curve shows explosive release from 0-2 hours, entering the Fick diffusion plateau from 2-12 hours, but release essentially stops after 12 hours; the MSN+γ-CD-MOF curve exhibits a typical three-stage pattern: Stage I (0-2 hours) explosive release (MSN-dominated), rapidly neutralizing existing odors; Stage II (2-12 hours) Fick diffusion slow release (dual carrier synergy); Stage III (12-48 hours) humidity-responsive degradation of γ-CD-MOF continuously releasing Zn. 2+ The curve demonstrates that the dual-carrier combination achieves the best long-lasting sustained release (release continues after 48 hours).

[0081] Test Example 2 Samples from Examples 1, 5, 6, Comparative Examples 1, 2, and 3 were prepared using the same Zn... 2+ The concentration was sprayed onto a standard fabric and placed in a sealed container. 50 ppm H2S gas was continuously introduced. The H2S concentration in the outlet gas was measured at different time points (0, 2, 4, 6, 8, 10, 12 h), the removal rate was calculated, and a removal rate-time decay curve was plotted. The 80% effective threshold line and the 12-hour time point are marked on the graph. The results are as follows: Figure 3 As shown. From Figure 3 As can be seen, the curve of Example 1 showed the gentlest decline, with the removal rate remaining at 67.5% after 12 hours, far above the 80% threshold (meaning continued effectiveness); the curves of Comparative Example 1 (without carrier) and Comparative Example 3 (existing technology) dropped below the 80% threshold within 4-6 hours, and were close to 20% after 12 hours; the curves of Comparative Examples 5 and 6 (single carrier) were in the middle, at about 50-60% after 12 hours; the curve of Comparative Example 2 (without enzyme inhibitor) declined rapidly after 6-8 hours, and was only 44% after 12 hours.

[0082] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A slow-release deodorizing composition of organic zinc supported on a porous carrier, characterized in that, The organic zinc slow-release deodorizing composition comprises, by weight percentage: Organic zinc preloaded on a porous support, wherein the mass percentage of organic zinc is 8%-25% and the mass percentage of the porous support is 3%-25%; Physically encapsulated synergist: 1%-10%; Enzyme inhibitory synergists: 0.5%-8%; The remainder is water.

2. The organozinc slow-release deodorizing composition based on a porous carrier according to claim 1, characterized in that, The organic zinc is in the form of a pre-formed chelate, and the organic zinc is selected from one or more of zinc glycinate, zinc peptide, zinc gluconate, and zinc glucosamine.

3. The organozinc slow-release deodorizing composition based on a porous carrier according to claim 1, characterized in that, The porous carrier is selected from one or more of mesoporous silica nanoparticles, chitosan microspheres, γ-cyclodextrin metal-organic frameworks, and zeolites.

4. The organozinc slow-release deodorizing composition based on a porous carrier according to claim 1, characterized in that, The physical encapsulation synergist is selected from one or both of β-cyclodextrin and cucurbituril[7].

5. The organozinc slow-release deodorizing composition based on a porous carrier according to claim 1, characterized in that, The enzyme-inhibiting synergist is selected from one or more of triethyl citrate, octanoyl glycine, and epigallocatechin gallate.

6. The organozinc slow-release deodorizing composition based on a porous carrier according to claim 1, characterized in that, The organic zinc slow-release deodorizing composition also contains 1%-8% by weight of an acid-base neutralizing buffer, which is composed of sodium bicarbonate and trisodium citrate.

7. The organozinc slow-release deodorizing composition based on a porous carrier according to claim 1, characterized in that, The organic zinc slow-release deodorizing composition further comprises 0.5%-5% by weight of a dispersant solubilizer, wherein the dispersant solubilizer is one or more selected from PEG-40 hydrogenated castor oil, alkyl glycosides and glycerol.

8. The organozinc slow-release deodorizing composition based on a porous carrier according to claim 1, characterized in that, The organic zinc slow-release deodorizing composition further comprises 0.5%-2% by weight of probiotic lysate, wherein the probiotic lysate is an inactivated lysate of Bacillus subtilis and / or Lactobacillus.

9. A method for preparing an organozinc slow-release deodorizing composition based on a porous carrier as described in any one of claims 1-8, characterized in that, Including the following steps: Organic zinc was loaded onto the porous support to obtain a drug-loaded powder; Physically encapsulated synergists and enzyme-inhibiting synergists were mixed with water to obtain a liquid mixture. The drug-loaded powder is mixed and dispersed with the liquid mixture to obtain the organic zinc sustained-release deodorizing composition.

10. The application of an organozinc slow-release deodorizing composition based on a porous carrier as described in any one of claims 1-8, characterized in that, The organic zinc slow-release deodorizing composition is used to prepare deodorizing products for the human body, pets, mouth, home environment, fabric washing and deodorizing agents, or textile deodorizing finishing agents.

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