A dual-gas release type nanocomposite material, a preparation method and application thereof

Abstract

The application discloses a kind of dual-gas release type nanocomposites and its preparation method and application, the nanocomposite includes sodium nitroprusside and manganese pentacarbonyl bromide, through cyanogen in sodium nitroprusside molecule and manganese center coordination effect in manganese pentacarbonyl bromide, fully mixed in methanol solvent at room temperature, after ultrasonic dispersion, stirring, washing purification and vacuum drying, obtain NO / CO dual-gas release type nanocomposite.

Description

Technical Field

[0001] This invention relates to the field of nanobiomaterials, and more particularly to a dual-gas-release nanocomposite material, its preparation method, and its application. Background Technology

[0002] Nitric oxide (NO) and carbon monoxide (CO) are important endogenous gaseous signaling molecules that play crucial roles in physiological regulation and disease treatment. In recent years, NO and CO-based gas therapy strategies have been extensively studied, with the key being the construction of donor molecules or release systems capable of achieving controlled gas release under specific conditions.

[0003] Sodium nitroprusside is a typical NO donor, containing nitrosyl and cyano ligands in its structure, which can release NO under certain stimuli. However, the decomposition process of sodium nitroprusside under light or physiologically relevant conditions is relatively complex and may be accompanied by cyano-related side reactions, thus affecting its application safety and release controllability. Manganese pentacarbonyl bromide is a type of manganese carbonyl complex that can serve as a precursor for constructing CO-releasing molecules. The manganese carbonyl structure can release CO under light and other conditions, and therefore it has been used to construct light-responsive CO-releasing systems.

[0004] In existing technologies, NO and CO release systems mostly involve a single gas donor or achieve multi-component coexistence through physical mixing or carrier loading. In such systems, the lack of clear structural relationships between different gas donors can easily lead to asynchronous release behaviors, unstable release efficiencies, and insufficient synergistic effects. Furthermore, complex carrier systems may increase preparation difficulty and hinder the clarification of the relationship between structure and release performance.

[0005] Existing research on dual-gas-release precursors, while showcasing design concepts of "integrating two gas-release units within the same molecule," largely still relies on organic framework splicing, physical coupling, or proximity excitation modes. For example, there are already... S-dual donors typically employ organic templates to connect different gas-releasing groups, achieving dual gas release through reverse Diels-Alder reaction, hydrolysis, or ROS response; S-type dual prodrugs often involve introducing CO-releasing groups and [other components] onto the same organic skeleton. Releasing groups achieve synergistic release through chemical triggering. These systems are essentially "parallel splicing of two releasing modules," with no direct coordination relationship between the two gas donors. On the other hand, although classic CORMs (carbonmonoxide-releasing molecules) widely employ transition metal carbonyl coordination structures such as Mn, Ru, and Fe to construct CO precursors, their core remains a single CO coordination-releasing system, staying only at the level of metallic CO. Summary of the Invention

[0006] Based on this, one of the objectives of the present invention is to provide a dual-gas release nanocomposite material, which forms a NO / CO dual-gas release precursor through the coordination of the cyano group in the sodium nitroprusside molecule with the manganese center in the pentacarbonyl manganese bromide.

[0007] To achieve the above-mentioned objectives, the specific technical solution is as follows: A dual-gas-emission nanocomposite material comprises sodium nitroprusside and manganese pentacarbonyl bromide, wherein the molar ratio of sodium nitroprusside to manganese pentacarbonyl bromide is 1:2; the NO / CO dual-gas-emission nanocomposite material is formed through the coordination of the cyano group in the sodium nitroprusside molecule with the manganese center in the manganese pentacarbonyl bromide molecule.

[0008] In some embodiments, the nanocomposite material comprises sodium nitroprusside and manganese pentacarbonyl bromide in a molar ratio of 2:1; through the coordination of the cyano group in the sodium nitroprusside molecule with the manganese center in the manganese pentacarbonyl bromide, a NO / CO dual-gas release nanocomposite material is formed. The nanocomposite material is water-soluble, and its apparent saturation solubility in deionized water is 10-20 mg / mL.

[0009] The second objective of this invention is to provide a method for preparing the above-mentioned dual-gas release nanocomposite material.

[0010] The specific technical solution is as follows: A method for preparing the above-mentioned dual-gas release nanocomposite material includes the following steps: weighing sodium nitroprusside and manganese pentacarbonyl bromide according to the ratio, mixing them thoroughly in methanol solvent at room temperature, and obtaining the NO / CO dual-gas release nanocomposite material after ultrasonic dispersion, stirring, washing and purification and vacuum drying.

[0011] In some embodiments, the ultrasonic dispersion time is 20 minutes.

[0012] In some embodiments, the stirring speed is 800 rpm and the stirring time is 12 h.

[0013] In some embodiments, the washing and purification includes: washing with deionized water when the molar ratio of sodium nitroprusside to manganese pentacarbonyl bromide is 1:2; and washing with dichloromethane when the molar ratio of sodium nitroprusside to manganese pentacarbonyl bromide is 2:1.

[0014] The third objective of this invention is to provide an application of the above-mentioned dual-gas release nanocomposite material.

[0015] The specific technical solution is as follows: In some embodiments, it is used as a gas release agent for the release of carbon monoxide and / or nitric oxide in vitro or in vivo.

[0016] The beneficial effects of this invention are: First: The core structure of sodium nitroprusside is an octahedral complex ion. Compared with existing dual-gas release precursors, this application utilizes octahedral complex ions. The bridging coordination ability of the CN ligand itself enables it to directly form a molecular-level coordination coupling with the manganese center in manganese pentacarbonyl bromide, thereby directly connecting the NO donor and the CO donor into a dual-gas release precursor with a unified structure. Therefore, this application does not simply "install" the two gas release units in the same carrier or organic framework, but utilizes the ligand (CN) of one gas donor to directly participate in the construction of the metal center of the other gas donor, so that the two gas release centers form a structural coupling relationship at the molecular level. This design not only changes the way the two gas donors exist, but also provides a new structural basis for the synergistic release of dual gases.

[0017] Second: This application does not rely on complex support materials (such as nanocarriers, metal-organic frameworks, polymer supports, etc.) to achieve dual-gas coexistence. The core advantage of this application lies in achieving molecular-level structural coupling of NO donor and CO donor through CN bridging coordination, breaking away from the traditional support co-loading mode, forming a dual-gas release precursor with a clear composition, simple preparation and controllable release behavior. The preparation process is simple and convenient for batch preparation and further application.

[0018] Third: This invention integrates two different gas donors through chemical coordination, which enhances the structural correlation between the components in the system. By adjusting the ratio of the two donors, it is beneficial to control the release rate, release sequence and total release of NO / CO, improve the controllability and stability of the dual-gas release behavior, and reduce the problems of component dispersion and unstable release in traditional physical mixing systems. Attached Figure Description

[0019] Figure 1 (A) shows the mass change of the two synthetic ratio samples by thermogravimetric analysis; (B) shows the content of key Fe and Mn metal elements in the two synthetic ratio samples by inductively coupled plasma atomic emission spectrometry; (C) shows the key chemical bonds in the two synthetic ratio samples by Fourier transform infrared spectroscopy.

[0020] Figure 2 XPS data for samples with two different synthesis ratios.

[0021] Figure 3 (A) is the E-space data of the 1:2 ratio sample; (B) is the R-space data of the 1:2 ratio sample; (C) is the wavelet transform data of the 1:2 ratio sample.

[0022] Figure 4(A) is the E-space data of the 2:1 ratio sample; (B) is the R-space data of the 2:1 ratio sample; (C) is the wavelet transform data of the 2:1 ratio sample.

[0023] Figure 5 (A) shows the carbon monoxide (CO) release data for the two synthesis ratios of the samples; (B) shows the nitric oxide (NO) release data for the two synthesis ratios of the samples; (C) is a subplot of (B). Standard curve.

[0024] Figure 6 The apparent saturation solubility curves for samples with a 2:1 ratio. Detailed Implementation

[0025] The technical solutions in the embodiments of the present invention will now be clearly and completely described in conjunction with the accompanying drawings.

[0026] The raw materials used in the embodiments of this invention are as follows: Sodium nitroprusside, manganese pentacarbonyl bromide, methanol, deionized water, and dichloromethane are all commercially available products. Example 1

[0027] This embodiment describes a dual-gas-release nanocomposite material prepared from the following components in a molar ratio of 1:2:sodium nitroprusside to manganese pentacarbonyl bromide.

[0028] The preparation method of this dual-gas release nanocomposite material is as follows: 25 mg of sodium nitroprusside, 50 mg of manganese pentacarbonyl bromide, and 20 mL of methanol were weighed. The sodium nitroprusside and manganese pentacarbonyl bromide were thoroughly mixed in the methanol solvent, ultrasonically dispersed for 20 min, and stirred at 800 rpm for 12 hours to obtain a mixed solution. To further remove soluble impurities that did not participate in coordination or reaction, the obtained mixed solution was purified by solvent washing. 50 mg of the mixed solution was weighed and placed in a 2 mL centrifuge tube, and 1.5 mL of deionized water was added. After thorough dispersion, the mixture was centrifuged at 12000 rpm for 5 min. The supernatant was removed, and the water-insoluble precipitate was retained to obtain nanomaterials with a molar ratio of 1:2 after deionized water washing and purification. The nanomaterials were then placed in a vacuum drying oven and dried for 12 hours to obtain NO / CO dual-gas release nanocomposite materials.

[0029] Furthermore, parameters such as ultrasonic dispersion time, stirring rate, and stirring time can be adjusted according to actual conditions. Example 2

[0030] This embodiment describes a dual-gas-release nanocomposite material prepared from the following components in a molar ratio of 2:1:sodium nitroprusside to manganese pentacarbonyl bromide.

[0031] The preparation method of this dual-gas release nanocomposite material is as follows: 50 mg of sodium nitroprusside, 25 mg of manganese pentacarbonyl bromide, and 20 mL of methanol were weighed. The sodium nitroprusside and manganese pentacarbonyl bromide were thoroughly mixed in methanol and ultrasonically dispersed for 20 min. The mixture was stirred at 800 rpm for 12 hours to obtain a mixed solution. To further remove soluble impurities that did not participate in coordination or reaction, the mixed solution was purified by solvent washing. 50 mg of the nanomaterial was weighed and placed in a 2 mL centrifuge tube. 1.5 mL of dichloromethane was added and the mixture was thoroughly dispersed. The mixture was centrifuged at 12000 rpm for 5 min. The supernatant was removed, and the precipitate that was insoluble in dichloromethane was retained to obtain nanomaterials with a molar ratio of 2:1 after washing and purification with dichloromethane. The nanomaterials were then placed in a vacuum drying oven and dried for 12 hours to obtain a water-soluble NO / CO dual-gas release nanocomposite material.

[0032] Furthermore, parameters such as ultrasonic dispersion time, stirring rate, and stirring time can be adjusted according to actual conditions.

[0033] Further reference Figure 6 Water solubility experiment: The apparent saturated solubility of the material was determined by ultraviolet-visible spectrophotometry. Specifically, an excess of the nanocomposite material (approximately 40 mg) was added to 2 mL of deionized water, and after shaking at 25°C for 12 h to reach equilibrium, it was centrifuged at 12000 rpm for 10 min. The supernatant was appropriately diluted, and the absorbance was measured at a specific wavelength. The solubility was calculated based on a pre-established standard curve. The results showed that the apparent saturated solubility of the 2:1 ratio sample was 15.89 mg / mL (i.e., 31.78 mg of the 40 mg sample was soluble), confirming its good water solubility. The 1:2 ratio sample was almost insoluble under the same conditions (solubility <0.5 mg / mL).

[0034] The 2:1 ratio nanocomposite material prepared in this application exhibits good water solubility (apparent saturation solubility of 10-20 mg / mL), facilitating its application in physiological environments; the 1:2 ratio nanocomposite material exhibits better hydrophobicity, making it suitable for scenarios requiring sustained release or local drug delivery. Both ratios can be purified to obtain high-purity products through a simple washing and purification process.

[0035] An application of a NO / CO dual-gas-releasing nanocomposite material, which is used as a gas release agent for the release of carbon monoxide and / or nitric oxide in vitro or in vivo.

[0036] Figure 1 Thermogravimetric analysis (TGA) in section (A) shows that pure sodium nitroprusside (SNP) and pure manganese pentacarbonyl bromide are... The weight loss characteristics during the heating process are significantly different, especially for the nanocomposite materials of this application. and The TGA curves of both groups of samples differed from those of pure sodium nitroprusside (SNP) or pure manganese pentacarbonyl bromide. This indicates that the thermal decomposition behavior of pure sodium nitroprusside and pure manganese pentacarbonyl bromide changed after entering the composite system, rather than being a simple superposition of the thermal weight loss processes of individual components.

[0037] The curve shows a significant continuous weight loss in the low to medium temperature range. While the initial weight loss temperature is lower than that of pure sodium nitroprusside, the overall decomposition process is not concentrated and rapidly completed in the low-temperature region like that of pure manganese pentacarbonyl bromide. This suggests that the combination of sodium nitroprusside and manganese pentacarbonyl bromide retains both the characteristics of easily thermally induced dissociation of the manganese carbonyl component and the high-temperature decomposition of sodium nitroprusside, exhibiting a staged release / decomposition process. This indicates... The gas donor in the sample is more likely to be gradually activated during the heating process, which may correspond to a faster release response and a higher cumulative release.

[0038] In comparison, The TGA curve of the sample showed a smoother, continuous weight loss trend. Compared to... Compared to the samples, The sample exhibited slightly higher residual mass in some mid-to-high temperature regions and a slower overall weight loss process, indicating that the thermal decomposition pathway of the material was further altered with the increased proportion of pentacarbonyl manganese bromide. The CO-related components may have been subject to stronger coordination environment constraints or structural embedding, thus delaying their thermally induced dissociation process. Therefore, Although the sample contained more It is a source component, but its release behavior tends to be slow and continuous rather than rapid.

[0039] This shows that the two samples with different ratios exhibit different thermal response weight loss modes during heating, reflecting that the release behavior of their gas donors is proportionally dependent. Specifically, The sample exhibited more pronounced weight loss in the low and medium temperature range, suggesting a stronger release response, a relatively faster release rate, and potentially a higher cumulative release amount; while The smoother weight loss of the sample indicates that its release process is subject to stronger structural constraints, resulting in a relatively slower release rate and potentially better persistence. Therefore, the two different formulation ratios alter the actual loading ratio of NO / CO donors in the composite material and their thermal decomposition / dissociation pathways, thereby causing differences in gas release rate, release persistence, and cumulative release amount, ultimately achieving controllable gas release behavior, release rate, and release amount.

[0040] Figure 1 (B) Based on the ICP results, it can be seen that... The sample contained 143,531 mg / kg of Fe, accounting for approximately 14%, and 77,957 mg / kg of Mn, accounting for approximately 7%. Since Fe and Na primarily originate from SNPs, this result indicates... The sample showed a high content of SNP-derived components and a richer abundance of NO donor units; it also contained a certain amount of Mn components, indicating that CO donors were successfully introduced. Furthermore... The Fe content in the sample decreased to 77,620 mg / kg, accounting for approximately 7.7%, while the Mn content increased to 95,845 mg / kg, accounting for approximately 9.5%. This change is consistent with the designed ratio. In the sample The source component is higher, while the source component of SNP is lower.

[0041] Figure 1 (C) For Composite materials whose spectra simultaneously retain SNPs and The main characteristic signals are as follows: CN-related absorption is still observed in the approximately 2140–2160 cm⁻¹ region, and superposition of NO and CO-related absorption signals is visible in the approximately 1930–2050 cm⁻¹ region. Compared with pure sodium nitroprusside and pure manganese pentacarbonyl bromide, the peak shapes of these peaks in the composite sample have changed, and some peak positions have shifted slightly, indicating that the Fe–CN / Fe–NO structure in the SNP is different from that in pure sodium nitroprusside and pure manganese pentacarbonyl bromide. The Mn–CO structure in the composite system does not exist completely independently, but may be influenced by the surrounding coordination environment or intermolecular interactions. Because The sample has a high proportion of SNPs, so its CN and NO related peaks are relatively more obvious, indicating that NO donor units account for a high proportion in the composite material.

[0042] for The composite material exhibits more pronounced absorption in the 1900–2100 cm⁻¹ range, indicating that... The contribution of CO ligands from the source is more significant. Compared with the 2:1 sample, the CO-related peaks in the 1:2 sample are relatively stronger, while the CN / NO peaks from the SNP source are still observable, indicating that both precursors successfully entered the composite system. The CO absorption region in this sample also shows peak broadening and slight shift, suggesting that the Mn–CO ligands are subject to varying degrees of coordination constraint or microenvironment influence in the nanocomposite structure. In summary, the nanomaterial successfully achieved the SNP-related peaks from the source. The hybrid encapsulation, with different ratios, allows for controllable thermal stability, gas release behavior, and molecular structure, providing a foundation for the controllable synergistic release of CO / NO.

[0043] Figure 2As can be seen, XPS analysis of the nanocomposite material further confirms the presence and chemical state of each component. The Fe 2p photoelectron spectrum, after peak decomposition, reveals... and The two chemical states indicate that iron exists in different oxidation states in sodium nitroprusside; the Mn 2p high-resolution spectrum shows... and Two characteristic peaks confirm the successful introduction of manganese components into the material system from pentacarbonylmanganese bromide. Simultaneously, the slight shift in the Mn 2p peak position in the mixed sample suggests a change in the local electronic environment at the Mn center. Peak decomposition in the O 1s region reveals different oxygen environments, including M–O, C–O / C=O, and O=C–O, reflecting the presence of metal oxidation states and carbonyl-related structures on the material surface. The N 1s region decomposes into different nitrogen environments, including Pyridinic-N, Pyrrolic-N, Graphitic-N, and Oxidized-N, indicating the presence of CN / NO-related nitrogen structures and their potential involvement in coordination or electronic interactions. Compared to the two pure precursor materials (sodium nitroprusside and pentacarbonylmanganese bromide), the slight shifts in the Fe, Mn, O, and N-related peak positions and changes in peak area in the mixed sample indicate that sodium nitroprusside and pentacarbonylmanganese bromide form a new local chemical environment, suggesting possible coordination interactions or electron transfer between the two. In summary, the XPS results validated the successful composite of sodium nitroprusside and manganese pentacarbonyl bromide, and showed that different ratios can regulate the elemental chemical state and local structure of the material, providing a structural basis for subsequent CO / NO synergistic release.

[0044] Figure 3 It can be seen from this that: SNP and XAFS characterization results of the composite sample at a 1:2 ratio revealed the electronic structure and local coordination environment of Fe and Mn in the sample.

[0045] E-space XANES spectroscopy revealed distinct absorption edges at both the Fe and Mn K-edges, confirming the coexistence of Fe and Mn elements. Furthermore, the location of the absorption edges and the near-edge structure of the sample were similar to those of Fe foil, FeO, and... FePc and Mn foil, MnO, The differences between the standard compounds indicate that the valence state and electronic environment of Fe and Mn changed after recombination.

[0046] The R-space EXAFS Fourier transform spectrum shows that there are obvious first coordination shell signals around Fe and Mn in the sample. The peak positions and intensities are different from those of individual metal foils and oxide standards, indicating that the sample has a local coordination structure that is different from that of traditional metals or metal oxides.

[0047] Wavelet transform (WT) results further revealed that the scattering signal distributions of Fe and Mn in the sample differed from those of the corresponding standards, indicating changes in the type and spatial structure of coordinating atoms around the metal center. Overall, the XAFS data showed that the SNPs and... The successful recombination formed a new Fe / Mn local chemical environment, which provides a structural basis for the subsequent co-release of CO / NO.

[0048] Figure 4 It can be seen from this that: SNP and XAFS characterization results of composite samples at a 2:1 ratio.

[0049] E-space XANES spectroscopy revealed distinct absorption edges at both the Fe K-edge and Mn K-edge in the 2:1 sample, indicating the successful presence of both Fe and Mn elements in the composite system. This is consistent with Fe foil, FeO, and... Compared with standard samples such as FePc, the 2:1 sample showed changes in the position of the Fe K-edge absorption edge and the shape of the white line peak, indicating a change in the electronic structure of the Fe center in the SNP. Figure 3 Compared to the 1:2 ratio sample, the 2:1 sample exhibits certain differences in the near-edge structure of Fe K-edge, indicating that the local electronic environment around Fe is further modulated with increasing SNP ratio. In the Mn K-edge region, the absorption edge position and near-edge peak shape of the 2:1 sample also differ from those of Mn foil, MnO, and [other samples / materials]. Standard sample, explanation The Mn center forms a chemical environment different from that of metallic manganese or manganese oxides after recombination. Compared with the 1:2 sample, the peak shape and absorption edge characteristics of Mn K-edge in the 2:1 sample changed, suggesting that the coordination environment around Mn was affected by the increased SNP content.

[0050] Further R-space EXAFS Fourier transform spectroscopy revealed that the 2:1 sample exhibited distinct first coordination shell signals around both Fe and Mn, with peak positions and intensities differing from the corresponding standard samples, indicating a reconstruction of the local coordination structure around Fe / Mn after recombination. Compared to the 1:2 sample, the 2:1 sample showed differences in both R-space peak intensities and shapes for Fe and Mn, suggesting differences in coordination distance, coordination intensity, or scattering environment around the metal centers under the two ratios.

[0051] Wavelet transform (WT) results also show that the Fe and Mn scattering signal distributions of the 2:1 sample are not completely consistent with those of the 1:2 sample, further proving that SNPs and The ratio change can regulate the local structure of Fe / Mn centers.

[0052] In summary, both the 2:1 and 1:2 composite samples successfully formed Fe / Mn-containing composite systems, but significant differences were observed in their XANES absorption edges, R-space peak intensities, and WT signal distributions, indicating that SNP and Variations in the stoichiometric ratio can modulate the electronic structure and local coordination environment of materials. This ratio-dependent structural difference may be an important reason affecting the subsequent CO / NO co-release behavior.

[0053] The table below shows the EXAFS fitted coordination numbers for samples with different Fe / Mn ratios. 2:1 5.78±0.33 1.68±0.16 11.71±0.83 5.71±0.22 4.33±0.27 1:2 6.33±0.43 1.17±0.31 4.39±0.51 5.88±0.56 5.02±0.84 Table 1 The higher gas release rate in the 2:1 sample is determined by its local metal coordination environment and the number of activatable sites. Synchrotron radiation fitting results show that the Fe–N–Fe coordination number in the 2:1 sample is 11.71 ± 0.83, significantly higher than the 4.39 ± 0.51 in the 1:2 sample. This indicates that the Fe centers in the 2:1 system form a richer Fe–N–Fe linkage structure through N bridging. This highly bridged Fe coordination network provides more metal sites that can participate in electron transfer and coordination activation, and is more likely to induce dynamic rearrangement or breakage of metal-ligand bonds under light / thermal stimulation, thereby promoting gas donor release. Therefore, the 2:1 sample may not only have a faster release rate, but its cumulative release amount may also be higher.

[0054] Meanwhile, the Fe–Fe coordination number in the 2:1 sample was 1.68 ± 0.16, higher than that in the 1:2 sample (1.17 ± 0.31), suggesting stronger Fe-related metal-neighbor interactions in the 2:1 system, which may enhance electronic coupling and photothermal response efficiency between metal centers. For gas donors, this enhanced metal-center coupling may lower the activation energy during release, allowing more coordinated or loaded gas molecules to be released under stimulation conditions. In other words, the higher release rate in the 2:1 sample is not necessarily due to "more loading," but may also be because its coordination environment makes it easier for the loaded or coordinated gas donors to be activated and released.

[0055] This application enables the controllable adjustment of the NO / CO release rate and total release amount by adjusting the molar ratio of sodium nitroprusside to manganese pentacarbonyl bromide (1:2 or 2:1). Specifically, the 2:1 ratio sample exhibits a richer Fe-N-Fe bridging structure (coordination number 11.71±0.83), demonstrating a faster release response and higher cumulative release amount; the 1:2 ratio sample exhibits more saturated metal-nitrogen coordination (Fe-N coordination number 6.33±0.43), showing a slower and more sustained gas release behavior.

[0056] Conversely, in the 1:2 sample, the coordination numbers for Fe–N were 6.33 ± 0.43, Mn–N were 5.88 ± 0.56, and Mn–Mn were 5.02 ± 0.84, all slightly higher than the corresponding values ​​in the 2:1 sample. This suggests that the metal-nitrogen coordination is more saturated in the 1:2 system, and the Mn-related structure is more stable. Higher metal-ligand coordination saturation may enhance overall structural stability, causing some gas donors to be more firmly bound within the coordination network, resulting in a slower release process and a lower cumulative release amount within the same stimulation time. Therefore, the 1:2 sample is more inclined towards "stable retention / slow release," while the 2:1 sample is more inclined towards "high-response release / higher cumulative release."

[0057] Figure 5 The results show the gas release behavior of materials with different proportions.

[0058] (A) shows two samples with different proportions. Both can continuously release CO over time, but their release kinetics differ significantly.

[0059] (B) The NO release signal gradually increases over time, indicating that the material can achieve continuous NO release, and the release amount increases with time. The proportions vary.

[0060] (C) is The standard curve shows good linearity and can be used for quantitative calculation of NO release. Overall, this result indicates... The composite material can achieve continuous release of CO and NO, and the release behavior has a clear ratio dependence.

[0061] The potential biomedical therapeutic advantages of this application: Both NO and CO are important endogenous gaseous signaling molecules, and have been shown to have potential in vasodilation, anti-inflammation, anti-proliferation, and as therapeutic signaling molecules. In the dual-gas release system constructed in this invention, the rational ratio and synergistic release mode of NO and CO are expected to exert a better therapeutic effect in related diseases (such as tumor microenvironment regulation, inflammatory response intervention, tissue repair, etc.), demonstrating the advantages of multimodal gas therapy.

[0062] The described embodiments are merely some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

Claims

1. A dual-gas release nanocomposite material, characterized in that: The nanocomposite material comprises sodium nitroprusside and manganese pentacarbonyl bromide, wherein the molar ratio of sodium nitroprusside to manganese pentacarbonyl bromide is 1:2; through the coordination of the cyano group in the sodium nitroprusside molecule with the manganese center in the manganese pentacarbonyl bromide, a NO / CO dual-gas release nanocomposite material is formed.

2. The dual-gas release nanocomposite material according to claim 1, characterized in that: The nanocomposite material comprises sodium nitroprusside and manganese pentacarbonyl bromide, wherein the molar ratio of sodium nitroprusside to manganese pentacarbonyl bromide is 2:1; through the coordination of the cyano group in the sodium nitroprusside molecule with the manganese center in the manganese pentacarbonyl bromide, a NO / CO dual-gas release nanocomposite material is formed. The nanocomposite material is water-soluble, and its apparent saturation solubility in deionized water is 10-20 mg / mL.

3. A method for preparing a dual-gas release nanocomposite material as described in any one of claims 1-2, characterized in that: Includes the following steps: Sodium nitroprusside and manganese pentacarbonyl bromide were weighed according to the specified ratio, and thoroughly mixed in methanol solvent at room temperature. After ultrasonic dispersion, stirring, washing and purification and vacuum drying, NO / CO dual-gas release nanocomposite material was obtained.

4. The method for preparing a dual-gas release nanocomposite material according to claim 3, characterized in that: The ultrasonic dispersion time is 20 min.

5. The method for preparing a dual-gas release nanocomposite material according to claim 3, characterized in that: The stirring speed is 800 rpm and the stirring time is 12 hours.

6. The preparation method according to claim 3, characterized in that: The washing and purification process includes: washing with deionized water when the molar ratio of sodium nitroprusside to manganese pentacarbonyl bromide is 1:2; and washing with dichloromethane when the molar ratio of sodium nitroprusside to manganese pentacarbonyl bromide is 2:

1.

7. An application of the dual-gas-release nanocomposite material as described in any one of claims 1-2, characterized in that: It can be used as a gas release agent for the release of carbon monoxide and / or nitric oxide in vitro or in vivo.

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