Reverse Microemulsion Research Articles

Preparation of Silver Nanoparticles in a Water-in-Oil Microemulsion Stabilized by Ecosurf EH3 and Determination of Their Electrophoretic Mobility.

This work describes a study on the electrophoresis of silver nanoparticles in reverse microemulsions with varying water content. The microemulsion was stabilized using a nonionic ethoxylated surfactant, 2-ethylhexanol triethoxylate (Ecosurf EH3). This study represents the second example of electrophoresis research conducted in media with a low dielectric constant for etoxylated surfactants. The study also determined the boundaries of thermodynamic stability and the conditions required to obtain nanoparticles with a high yield. The hydrodynamic diameter and electrophoretic mobility of nanoparticles were measured using dynamic light scattering and laser Doppler electrophoresis. The study determined the boundary conditions for applying these methods to laser-absorbing samples. The electrophoretic mobility of nanoparticles was found to be dependent on the fraction of water in the range of 2-5%vol. (equivalent to a metal content of 10-25mM), as determined by electrophoresis in a free medium. The increase in volume fraction of water leads to agglomeration of micelles, which causes a decrease in the electrokinetic potential of nanoparticles, likely due to the blurring of the diffuse part of the electrical double layer.

Insights into Mechanisms of Reverse Water Gas Shift Activity Enhancement over Reverse Microemulsion‐Synthesized CuCeO2

AbstractCopper‐doped ceria (CuCeO2) catalysts with 0–26.5 Cu/(Cu+Ce) at% were synthesized via the reverse microemulsion method. X‐ray diffraction analysis of freshly synthesized and spent (post‐reaction) catalysts showed no separate phase of copper or copper oxide, indicating that Cu was incorporated into the CeO2 lattice, replacing Ce. Temperature programmed desorption experiments showed that the activation energy of CO2 desorption increased for higher Cu loadings, indicating stronger CO2 adsorption. This phenomenon was attributed to enhanced formation of oxygen vacancies due to Cu doping. X‐ray photoelectron spectroscopy further confirmed the enhanced generation of oxygen vacancies due to Cu incorporation. Catalytic performance evaluation with the H2/CO2 feed in the 300–600 °C range showed that all catalysts were 100 % selective to CO generation, with higher Cu loadings resulting in CO2 conversion close to equilibrium values at 500–600 °C. The activation energy of the reaction, determined through reaction tests, exhibited inverse relationship with the activation energy of CO2 desorption. The relationship between these two energy barriers is explored, providing valuable insights into the mechanism of RWGS activity enhancement.

Interfacial coupling of sandwich like Zn3V2O8/ZnO/NiCo2S4 nano-heterojunction for the enhanced photocatalytic degradation of rifampicin

The overuse of antibiotics and the release of these pharmaceuticals into the water system has emerged as a serious issue posing a life-threatening environment to aquatic species. In contrast to various contaminants, antibiotics are specifically engineered for durability and efficacy in the system of the human body (human health). Although this design ensures their performance, it also results in their extended longevity and resilience against degradation in natural contexts. These challenges can be addressed by an advanced oxidation process (AOP) utilizing ternary heterojunction nano catalysts (NCs). In this study, the NCs were synthesized through a combination of calcinated-assisted reverse microemulsion and hydrothermal methods. The synthesized NCs were characterized by using various analytical techniques. The enhanced charge separation and migration in Zn3V2O8/ZnO/NiCo2S4 (ZZN) NCs results in 97.3 % degradation of rifampicin (RIF) within 80 min. ZZN NCs exhibit superior catalytic performance under visible light irradiation compared to its pristine Zn3V2O8, ZnO, NiCo2S4, and binary ZnO/NiCo2S4. The enhanced photocatalytic performance can be primarily attributed to the synergetic effects among Zn3V2O8, ZnO, and NiCo2S4 facilitated by the cascade-driven charge transfer mechanism. The prominent reactive oxygen species that participated in photocatalytic degradation activity were found to be superoxide (O2•-) and hydroxide radicals (•OH) which were confirmed through ESR and quenching experiments. From the practical application perspective, ZZN NCs ternary heterostructure demonstrated excellent stability and durability after being recycled six times. This study serve as a vital reference for future investigation into the photocatalytic mechanism related to heterostructure NCs, highlighting their potential for eco-friendly methods to eliminate pollutants and paves a way for manufacturing innovation in near future.

Limited dissolution of transition metals in the nanocrystalline cerium (IV) oxide

Nanocrystalline cerium (IV) oxides doped with transition metals have gained significant interest recently, mostly in the field of catalysis. Herein, we present the comprehensive studies on ceria doped with 10 mol.% of transition metals (Mn, Fe, Co, Ni or Cu) synthesized by the reverse microemulsion method. The aim of this work is to study the properties of those materials with the use of different complementary methods like XRD, SEM, TPR, and XPS and to determine the possibility of fabrication of single-phase materials with that doping level. Studies presented here prove that despite showing single-phase XRD patterns with high nanocrystallinity, in all obtained materials, the dopants are not fully incorporated in the ceria lattice. Spectroscopy studies show that additional transition metal oxides are present on the surface of all materials. Herein, we also present the analyses of L3,2-edges of transition metals in ceria, as well as high energy Ce K-edge to prove that 10 mol.% of any of those transition metals cannot be incorporated in the ceria host without the formation of additional phases. Using techniques presented here, it was found that the highest share of Mn can be dissolved in the lattice, while Cu is mostly present as a surficial Cu2O. Studies presented are an important contribution to the discussion about the solubility limits in nanocrystalline ceria and its properties which may be utilized for e.g various catalysts or as electrolytes.

Laser diagnostics of micellar nanoreactors in ZnSO4/water/AOT/heptane reverse microemulsion system

In the article, for the first time, a method has been developed for remote monitoring of the composition of the reaction medium of micellar nanoreactors and for determining the parameters of nanoparticles during their synthesis using Raman spectroscopy. The sensitivity of spectral characteristics to changes in the size of nanoreactors and the concentration of the nanoparticle precursor in reverse ZnSO4/water/AOT/heptane microemulsions has been experimentally established. It has been shown that the intensity of the band of symmetrical S-O stretching vibrations in the Raman spectrum of the ZnSO4/water/AOT/heptane microemulsion can be used to determine the concentration of ZnSO4 in the micelle cores with the accuracy of 2.4 %. The calibration dependence of the center of mass position of the symmetrical O–H stretching vibrations band of the specified microemulsion on the micelles diameter ensures the determination of the sizes of micellar nanoreactors with an accuracy of 11 %.

Enhanced In Vitro Efficacy of Verbascoside in Suppressing Hepatic Stellate Cell Activation via ROS Scavenging with Reverse Microemulsion.

Numerous approaches targeting hepatic stellate cells (HSCs) have emerged as pivotal therapeutic strategies to mitigate liver fibrosis and are currently undergoing clinical trials. The investigation of herbal drugs or isolated natural active compounds is particularly valuable, due to their multifaceted functions and low risk of side effects. Recent studies have hinted at the potential efficacy of verbascoside (VB) in ameliorating renal and lung fibrosis, yet its impact on hepatic fibrosis remains to be elucidated. This study aims to evaluate the potential effects of VB on liver fibrosis by assessing its ability to inhibit HSC activation. VB demonstrated significant efficacy in suppressing the expression of fibrogenic genes in activated LX-2 cells. Additionally, VB inhibited the migration and proliferation of these activated HSCs by scavenging reactive oxygen species (ROS) and downregulating the AMPK pathway. Furthermore, a biosafe reverse microemulsion loaded with VB (VB-ME) was developed to improve VB's instability and low bioavailability. The optimal formulation of VB-ME was meticulously characterized, revealing substantial enhancements in cellular uptake, ROS-scavenging capacity, and the suppression of HSC activation.

Water-in-oil microemulsions with greener oil solvents as sustainable nanoreactors of biopolymer nanoparticles

Microemulsions have been widely used in multidisciplinary fields, yet reverse water-in-oil microemulsions are traditionally dispersed in petroleum-based oil solvents. For greener approaches, it should be also feasible to use less toxic, bio-based hydrocarbon solvents as continuous oil phase. Herein, reverse microemulsions in different alkanes, middle-chain alkanols, middle-chain esters or combinations of nonpolar solvent with alkanol are compared, using Aerosol-OT as common surfactant. As model of bio-based solvents, ethyl caprylate, isoamyl acetate and isoamyl alcohol are proposed as a more sustainable approach of oil solvents. Various characterization techniques were used to compare the properties and stability of reverse microemulsions for the different oil phase compositions, ranging from ternary phase diagrams to conductometry and turbidity titrations, micro-Differential Scanning Calorimetry and cryo-Scanning Electron Microscopy. As sustainable application, these microemulsions in bio-based solvents were proved suitable as template phase for the synthesis of cross-linked chitosan nanoparticles. The sizes of the resulting biopolymer nanoparticles were characterized by Dynamic Light Scattering and Atomic Force Microscopy, so that the effect of different crosslinkers and different the oil phase compositions was also compared. Thus, the use bio-based alkyl esters can provide similar microemulsion properties as the conventional alkanes, especially when using a combination of nonpolar solvents with alkanols.

Ultrasonic sonication assisted in sol–gel stӧber and reverse microemulsion method for fabrication of silica nanoparticles and the potential application in agriculture

Ultrasonic sonication assisted in sol–gel stӧber and reverse microemulsion method for fabrication of silica nanoparticles and the potential application in agriculture

Direct and specific detection of methyl-paraoxon using a highly sensitive fluorescence strategy combined with phosphatase-like nanozyme and molecularly imprinted polymer

Methyl paraoxon (MP) is a highly toxic, efficient and broad-spectrum organophosphorus pesticide, which poses significant risks to ecological environment and human health. Many detection methods for MP are based on the enzyme catalytic or inhibition effect. But natural biological enzymes are relatively expensive and easy to be inactivated with a short service life. As a unique tool of nanotechnology with enzyme-like characteristics, nanozyme has attracted increasing concern. However, a large proportion of nanozymes lack the intrinsic specificity, becoming a main barrier of constraining their use in biochemical analysis. Here, we use a one-pot reverse microemulsion polymerization combine the gold nanoclusters (AuNCs) with molecularly imprinted polymers (MIPs), polydopamine (PDA) and hollow CeO2 nanospheres to synthesize the bright red-orange fluorescence probe (CeO2@PDA@AuNCs-MIPs) with high phosphatase-like activity for selective detection of MP. The hollow structure possesses a specific surface area and porous matrix, which not only increases the exposure of active sites but also enhances the efficiency of mass and electron transport. Consequently, this structure significantly enhances the catalytic activity by reducing transport distances. The introduced MIPs provide the specific recognition sites for MP. And Ce (III) can excite aggregation induced emission of AuNCs and enhance the fluorescent signal. The absolute fluorescence quantum yield (FLQY) of CeO2@PDA@AuNCs-MIPs (1.41 %) was 12.8-fold higher than that of the GSH-AuNCs (0.11 %). With the presence of MP, Ce (IV)/Ce (III) species serve as the active sites to polarize and hydrolyze phosphate bonds to generate p-nitrophenol (p-NP), which can quench the fluorescent signal through the inner-filter effect. The as-prepared CeO2@PDA@AuNCs-MIPs nanozyme-based fluorescence method for MP detection displayed superior analytical performances with wide linearities range of 0.45–125 nM and the detection limit of 0.15 nM. Furthermore, the designed method offers satisfactory practical application ability. The developed method is simple and effective for the in-field detection.

Study of self-organization and structural phase transitions in water /AOT / isopropyl myristate biocompatible system

This work reports preparation and characterization of biocompatible sodium bis(2-ethylhexyl) sulfosuccinate (AOT) / water/ isopropyl myristate (IPM) systems. We studied their ability to form various self-organized structures such as microemulsions and liquid crystal templates for producing nanoparticles such as drug delivery vehicles, which play an important role in delivery of various substances. We determined concentration and temperature conditions that allow for forming various structures in this system and characterized the structural phase transition from the microemulsion to liquid crystalline phase, which is important for delivery of bioactive compounds. The parameters of the liquid crystalline phase of the water/AOT/isopropyl myristate system were calculated for the first time in this work. The sizes of microemulsion droplets were determined. To describe molecular motions in the studied microemulsion, self-diffusion coefficients of each component were measured. The values of relative diffusion coefficients demonstrated that reverse microemulsions were observed at AOT concentrations up to 60 % wt. Further increase in surfactant concentration slows down their molecular mobility and results in formation of aggregates with a bimodal size distribution and a subsequent formation of the hexagonal liquid crystalline phase. Geometry of the mesophase and its structure were investigated by X-ray diffraction. The respective phase diagram was plotted and analyzed using the data of polarized light microscopy, dynamic light scattering, and NMR self-diffusion. In this diagram, the areas corresponding to the microemulsion, the liquid crystal phase, and the structural phase transition were identified.The study of the structural phase transition from the microemulsion to liquid crystal will offer a predictive power for characterizing incorporation of drugs and controlling their delivery to target cells. A deeper understanding of the structural changes is necessary to clearly determine the conditions of drug delivery.

Supported copper nanoarchitecture for selective ethylbenzene oxidation (EBO) reaction

Copper-based (Cu-NP) uniformly dispersed on various inorganic supports (alumina, silica, titania, and zirconia) were prepared by the reverse microemulsion technique. These nanoparticles were used for the selective oxidation of ethylbenzene (EB) to produce acetophenone (AP) as the main product in the presence of Tert‑butyl hydroperoxide(TBHP) as an oxidant. This study focused on creating Cu-nanoparticles evenly dispersed on alumina using varying Cu-loadings (5 %, 10 %, and 15% wt.) and Brij-35 as the surfactant. The resulting catalytic material was characterized using various physicochemical techniques like XRD, FESEM, HRTEM, XPS and physisorption techniques. Various parametric studies were conducted, such as the effects of temperature, catalyst support, catalyst loading, and TBHP loading to optimize the EB conversions and AP selectivity. Among the various catalyst loadings, 15 % CuO/Al2O3 (15 % of the copper content) nanocomposites showed exceptional performance, with the highest EB conversion rate (99.7 %) and AP selectivity (98.5 %) compared to other nanocomposites. The catalyst's stability and recyclability over four cycles were attributed to the strong copper oxide-alumina interaction. These findings suggest that this nanocomposite material is a promising candidate for catalytic applications, offering high selectivity and consistent EB conversion rates.

C. Halicacabum derived “turn-on-off” non-invasive molecularly imprinted polymer for selective profiling of 2-(3,4-dihydroxy phenyl) ethylamine in human fluid samples

A rationally designed “Turn on-off” molecularly imprinted fluorescent probe SCDs-MPs serves as a robust platform for the specific identification of aberrant dopamine (DA) levels. In this study, carbon dots (SCDs) were synthesized usingCardiospermum Halicacabum leaf extract as a carbon source via a step hydrothermal process. The synergistic integration of the synthesized fluorophore SCDs (QY–27.6 %) with molecularly imprinted elements via reverse micro-emulsion technique forms novel C. Halicacabum derived SCDs-MPs nanocomposite. The synthesized SCDs-MPs possess various inimitable properties such as hydrophilicity (WCA of 12.9°) suitability for detection in aqueous media, the narrow bandgap of 3.45 eV attributed to the electron-donating nature, and photostability. Fluorescence lifetime, from 6.38 ns to 6.17 ns after adding dopamine to SCDs-MPs, and zeta potential studies (–32.9 mV to –23.9 mV) validate the static fluorescence quenching mechanism in SCDs-MPs. Under various modifications and experimental conditions, SCDs-MPs consistently achieved a low dopamine detection limit of 6.4 pM within the range of 0–50 µM. Excellent recovery experiments in human fluid samples (98–102 %) confirm the fluorescent probe’s empirical reliability. The MTT assay confirms the superior biocompatibility of SCDs-MPs, with cell viability remaining at ± 24.03 % at a concentration of 200 µg/ml suggesting the safe usage for invitro administration. This opens new possibilities for utilizing C. Halicacabum derived SCDs-MPs material in biomedical contexts.

Brightly Luminescent and Color‐Tunable CsPbBr3 Nanocrystals with Enhanced Stability and Room Temperature Cubic Structure through Codoping with MnCl2

Lead halide perovskites have attracted much attention from the scientific community in recent years due to their attractive properties and their proven potential in many applications. Nevertheless, their stability and lead toxicity have remained a problem. Herein, the potential of manganese as a divalent dopant to offer better stability and replace a fraction of the toxic lead ions is investigated. Moreover, the reverse microemulsion method is used to obtain tunability in emission and bandgap by doping cesium lead bromide. Furthermore, cubic cesium lead bromide particles are managed to obtain at room temperature as a result of doping.

Investigation of dextran-coated magnetic nanoparticles encapsulated by medication and modified with folate for targeted drug delivery: Invitro and docking studies

In this study, we synthesized dextran (DEX)-coated iron oxide (Fe3O4) and encapsulated it by the anticancer drug cisplatin (CP). This nano-composite functionalized with folic acid (FA) molecules for targeted delivery. These nanoparticles (NPs) were then used as nanocarriers for the targeted administration of CP for treating thyroid tumor cancer. The Fe3O4 NPs were synthesized using a chemical technique. The development of the Fe3O4@DEX-CP-FA nanosystem was achieved using a reverse microemulsion technique. The morphological features of the NPs were characterized using several methods, including dynamic light scattering, atomic force microscopy, vibrating sample magnetometry, high-resolution transmission electron microscopy, and field emission scanning electron microscopy. The docking study has verified that nanoparticles have anti-proliferative effects in thyroid cancer by attaching strongly to molecular targets. The MTT test evaluated the effects of a curative Fe3O4@DEX-CP-FA effect on cancerous and non-cancerous cell lines. The results obtained from the formulation of Fe3O4@DEX-CP-FA revealed the presence of spherical particles with an average size of 107.3 nm, a zeta potential of −28.7 mV, and a polydispersity value of 0.055 mV. Depending on the dose, the nanosystem exhibited cytotoxic effects on thyroid tumor (TT) and normal human thyroid (NHT) cell lines. The study findings indicate that Fe3O4@DEX-CP-FA demonstrated sustained antitumor efficacy while not revealing a harmful impact on normal cells.

Electrodeposition of iron from 1-ethyl-3-methylimidazolium trifluoromethanesulfonate and reverse microemulsions of Triton X-100.

Electrodeposition of iron (Fe) was investigated in three different media, namely a hydrophilic ionic liquid (IL), 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, conventional reverse microemulsion (RME)/reverse micellar solution, and IL-based RME of a non-ionic surfactant, Triton X-100, with a view to electrodepositing iron with desired morphology. Electrochemical behaviour of Fe2+ was studied using cyclic voltammetric technique with a copper electrode as the working electrode. Electrochemical reduction of Fe2+ in all the studied media was found to be an electrochemically irreversible, diffusion-controlled process. Successful potentiostatic electrodeposition of metallic iron was performed in all the studied media on copper substrate using bulk electrolysis method. The obtained iron electrodeposits were characterized using a scanning electron microscope and an X-ray diffractometer. The controlled diffusion of Fe2+ towards electrode surface in all the media resulted in the formation of nanoparticles of iron, but compact layers of granular nanoparticles could be achieved from both the conventional and IL-based RME systems. The IL-based microemulsions synergistically combined the advantageous features of both the IL and RME and showed promise for tuning the size, shape, and morphology of the electrodeposited iron.

Leaching of non-ferrous metals using a microemulsion in the system sodium dodecyl sulfate–butanol–caproic acid–kerosene–water

The possibility of using reverse microemulsion based on sodium dodecyl sulfate containing an extractant caproic acid for the selective recovery of non-ferrous metals and their separation from iron in the process of microemulsion leaching has been demonstrated. Using a model system with a mixture of oxides, the following recovery factors of metals are achieved in 5 h of leaching (%): Cu, 47.6; Mn, 12.8; Ni, 9.4; Co, 9.1; Fe, 4.3. When leaching from a sample of oxidized cobalt–copper concentrate, the recovery of metals is as follows (%): Cu, 60.0; Co, 51.3; Mn, 16.5; Fe, 10.0; Ni, 9.3.

Machine learning-assisted wide-gamut fluorescence visual test paper for propazine determination in fish and seawater samples

Molecularly imprinted polymer (MIP-QDs) with fluorescence quenching ability toward propazine was synthesized for propazine detection. b(Blue)-MIP-QDs were prepared using ZnCdS/ZnS QDs via reverse micro-emulsion, whereas r(red)-MIP-QDs were synthesized using CdSe/ZnS QDs. By utilizing graphene quantum dots (GQDs) as a stable fluorescence intensity reference, the wide-gamut fluorescence test paper was constructed on the basis of mixing b-MIP-QDs, r-MIP-QDs, and GQDs under the optimal ratio. When analyzing spiked propazine in fish and seawater samples using a test paper, satisfactory recoveries of 104.0 %–114.6 % and 92.0 %–96.4 % were obtained, with corresponding limits of detection of 5.0 μg/kg and 1.0 μg/L, respectively. The RGB extractor was utilized to extract the actual fluorescence color and construct a dataset consisting of R, G, and B values, as well as concentration data from 400 samples. The SVR model of Python 3.9.7 was used to obtain and analyze the concentration and feature data. After optimization, the constructed model achieved a correlation coefficient of 0.98 and an RMSE of only 1.81, indicating high prediction accuracy and excellent generalization ability that meet quenching prediction requirements. As an intelligent and rapid detection method, this model holds significant practical significance.

Preparation and Characterization of Uniform and Controlled Silica Encapsulating on Lithium Yttrium Fluoride-Based Upconversion Nanoparticles.

In this work, we present an advancement in the encapsulation of lithium yttrium fluoride-based (YLiF4:Yb,Er) upconversion nanocrystals (UCNPs) with silica (SiO2) shells through a reverse microemulsion technique, achieving UCNPs@SiO2 core/shell structures. Key parameters of this approach were optimized to eliminate the occurrence of core-free silica particles and ensure a controlled silica shell thickness growth on the UCNPs. The optimal conditions for this method were using 6 mg of UCNPs, 1.5 mL of Igepal CO-520, 0.25 mL of ammonia, and 50 μL of tetraethyl orthosilicate (TEOS), resulting in a uniform silica shell around UCNPs with a thickness of 8 nm. The optical characteristics of the silica-encased UCNPs were examined, confirming the retention of their intrinsic upconversion luminescence (UC). Furthermore, we developed a reliable strategy to avoid the coencapsulation of multiple UCNPs within a single silica shell. This approach led to a tenfold increase in the UC luminescence of the annealed particles compared to their nonannealed counterparts, under identical silica shell thickness and excitation conditions. This significant improvement addresses a critical challenge and amplifies the applicability of the resulting UCNPs@SiO2 core/shell structures in various fields.

Pyrene doped silica nanoparticles: Synthesis, oxygen sensing, and singlet oxygen generation

Dye-doped silica nanoparticles have garnered attention from researchers owing to their beneficial properties, such as signal amplification, surface modification, and biocompatibility. In this study, pyrene-doped silica nanoparticles (PSNPs) were prepared using the reverse microemulsion approach. Pyrenebutyric acid conjugated with aminopropyltriethoxysilane was synthesized to obtain durable PSNPs with low dye leaching via the covalent encapsulation of pyrene inside a silica matrix. The PSNPs were spherical, with a diameter of 72 nm. The PSNPs exhibited excimer fluorescence upon photoexcitation. To demonstrate the applicability of the synthesized PSNPs in biological applications, including photodynamic therapy (PDT) and oxygen sensing, the influence of oxygen on the fluorescence spectrum was investigated. The excimer fluorescence intensity was quenched by oxygen, along with a decrease in fluorescence lifetime. Ratiometric fluorescence sensing and fluorescence lifetime sensing of oxygen concentration were demonstrated. The biomolecular quenching rate constant was evaluated using the Stern–Volmer plot of the fluorescence lifetime. Moreover, utilizing a chemical trap of singlet oxygen molecules, it was demonstrated that singlet oxygen was generated by the photosensitization of PSNP. The PSNPs synthesized in this study are potentially capable of oxygen sensing, PDT, and bioimaging for various biological applications.

Glutathione-Responsive and Hydrogen Sulfide Self-Generating Nanocages Based on Self-Weaving Technology To Optimize Cancer Immunotherapy.

As an ideal drug carrier, it should possess high drug loading and encapsulation efficiency and precise drug targeting release. Herein, we utilized a template-guided self-weaving technology of phase-separated silk fibroin (SF) in reverse microemulsion (RME) to fabricate a kind of hyaluronic acid (HA) coated SF nanocage (HA-gNCs) for drug delivery of cancer immunotherapy. Due to the hollow structure, HA-gNCs were capable of simultaneous encapsulation of the anti-inflammatory drug betamethasone phosphate (BetP) and the immune checkpoint blockade (ICB) agent PD-L1 antibody (αPD-L1) efficiently. Another point worth noting was that the thiocarbonate cross-linkers used to strengthen the SF shell of HA-gNCs could be quickly broken by overexpressed glutathione (GSH) to reach responsive drug release inside tumor tissues accompanied by hydrogen sulfide (H2S) production in one step. The synergistic effect of released BetP and generated H2S guaranteed chronological modulation of the immunosuppressive tumor microenvironment (ITME) to amplify the therapeutic effect of αPD-L1 for the growth, metastasis, and recurrence of tumors. This study highlighted the exceptional prospect of HA-gNCs as a self-assistance platform for cancer drug delivery.