Platinum Nanozymes Research Articles

Photothermal-promoted O2/[rad]OH generation of gold nanotetrapod @ platinum nano-islands for enhanced catalytic/photodynamic therapy

Ultrasmall platinum (Pt) nanozymes are used for catalytic therapy and oxygen (O2)-dependent photodynamic therapy (PDT) by harnessing the dual-enzyme activities of catalase (CAT) and peroxidase (POD). However, their applications as nanocatalysts are limited due to their low catalytic activity. Herein, we constructed a photothermal-promoted bimetallic nanoplatform (AuNTP@Pt-IR808) by depositing ultrasmall Pt nano-islands and modifying 1-(5-Carboxypentyl)-2-(2-(3-(2-(1-(5-carboxypentyl)-3,3-dimethylindolin-2-ylidene)ethylidene)-2-chlorocyclohex-1-en-1-yl)vinyl)-3,3-dimethyl-3H-indol-1-ium bromide (IR808) on gold nanotetrapod (AuNTP) with CAT/POD activities to enhance PDT/catalytic therapy. In the tumor microenvironment, the ultrasmall Pt can catalyze endogenous hydrogen peroxide (H2O2) to produce O2, relieving tumor hypoxia and enhancing the PDT performance. Moreover, AuNTP integration into the bimetallic nanoplatform showed good electron transfer properties and promoted the POD activity of ultrasmall Pt. Importantly, AuNTP@Pt-IR808 possessed higher photothermal conversion performance than single AuNTPs, which enhanced photothermal therapy (PTT). It also accelerated the CAT/POD dual-enzyme activities, and promoted the generation of singlet oxygen (1O2) and hydroxyl radical (OH). By enhancing the performances of PTT/PDT/catalytic therapy, the developed AuNTP@Pt-IR808 nanoplatform demonstrated good antitumor efficacy against breast cancer.

Chiral metal-organic frameworks incorporating nanozymes as neuroinflammation inhibitors for managing Parkinson’s disease

Nanomedicine-based anti-neuroinflammation strategy has become a promising dawn of Parkinson’s disease (PD) treatment. However, there are significant gaps in our understanding of the therapeutic mechanisms of antioxidant nanomedicines concerning the pathways traversing the blood-brain barrier (BBB) and subsequent inflammation mitigation. Here, we report nanozyme-integrated metal-organic frameworks with excellent antioxidant activity and chiral-dependent BBB transendocytosis as anti-neuroinflammatory agents for the treatment of PD. These chiral nanozymes are synthesized by embedding ultra-small platinum nanozymes (Ptzymes) into L-chiral and D-chiral imidazolate zeolite frameworks (Ptzyme@L-ZIF and Ptzyme@D-ZIF). Compared to Ptzyme@L-ZIF, Ptzyme@D-ZIF shows higher accumulation in the brains of male PD mouse models due to longer plasma residence time and more pathways to traverse BBB, including clathrin-mediated and caveolae-mediated endocytosis. These factors contribute to the superior therapeutic efficacy of Ptzyme@D-ZIF in reducing behavioral disorders and pathological changes. Bioinformatics and biochemical analyses suggest that Ptzyme@D-ZIF inhibits neuroinflammation-induced apoptosis and ferroptosis in damaged neurons. The research uncovers the biodistribution, metabolic variances, and therapeutic outcomes of nanozymes-integrated chiral ZIF platforms, providing possibilities for devising anti-PD drugs.

Endogenous H2O2 Self-Replenishment and Sustainable Cascades Enhance the Efficacy of Sonodynamic Therapy.

Sonodynamic therapy (SDT), with its high tissue penetration and noninvasive advantages, represents an emerging approach to eradicating solid tumors. However, the outcomes of SDT are typically hampered by the low oxygen content and immunosuppression in the tumor microenvironment (TME). Accordingly, we constructed a cascade nanoplatform to regulate the TME and improve the anti-tumor efficiency of SDT. In this study, we rationally design cascade nanoplatform by incorporating immunostimulant hyaluronic acid (HA) and sonosensitizer chlorin e6 (Ce6) on the polydopamine nanocarrier that is pre-doped with platinum nanozymes (designated Ce6/Pt@PDA-HA, PPCH). The cascade reactions of PPCH are evidenced by the results that HA exhibits reversing immunosuppressive that converts M2 macrophages into M1 macrophages in situ, while producing H2O2, and then platinum nanozymes further catalyze the H2O2 to produce O2, and O2 produces abundant singlet oxygen (1O2) under the action of Ce6 and low-intensity focused ultrasound (LIFU), resulting in a domino effect and further amplifying the efficacy of SDT. Due to its pH responsiveness and mitochondrial targeting, PPCH effectively accumulates in tumor cells. Under LIFU irradiation, PPCH effectively reverses immunosuppression, alleviates hypoxia in the TME, enhances reactive oxygen species (ROS) generation, and enhances SDT efficacy for eliminating tumor cells in vivo and in vitro. Meanwhile, an in vivo dual-modal imaging including fluorescence and photoacoustic imaging achieves precise tumor diagnosis. This cascade nanoplatform will provide a promising strategy for enhancing SDT eradication against tumors by modulating immunosuppression and relieving hypoxia.

One-step paper-based SlipChip for the sensitive detection of C-reactive protein with porous platinum nanozyme-assisted signal amplification

The development of efficient and sensitive point-of-care testing is crucial for preparedness in the post-pandemic era. Although paper-based lateral flow assays have attracted attention and have various advantages for rapid, on-site diagnosis, they have low sensitivity. To overcome the limitations of the existing assays, in this study, we aimed to develop a new, one-step, nanozyme-amplified SlipChip for the sensitive detection of C-reactive protein (CRP). The SlipChip was constructed by combining wax-printed paper with different channel designs. The three-dimensional (3D) fluidic configuration of the SlipChip allowed for the sequential delivery of reagents, enabling mixing and signal amplification with a one-step sliding operation. As a signal-amplifying reagent, peroxidase-mimicking porous platinum nanozyme (pPtNZ) was synthesized using a simple wet chemical method. The pPtNZ conjugated on the test line catalyzes the oxidation of diaminobenzidine (DAB) in the presence of hydrogen peroxide, increasing the color intensity. The immunoassay results of the SlipChip were easily interpreted within 20 min, and the color intensity was visually enhanced by DAB precipitation over time, resulting in up to 6-fold signal amplification. The proposed pPtNZ-SlipChip exhibited high analytical performances for the one-step detection of serum and salivary CRP from 0.1 to 1000 ng/mL, with a limit of detection of 0.03 ng/mL. These results revealed the potential and applicability of the pPtNZ-SlipChip, with the advantages of simplicity, sensitivity, low cost, and portability for on-site detection and point-of-care testing.

Confining Prepared Ultra-Small Nanozymes Loading Ato for Lung Cancer Catalytic Therapy/Immunotherapy.

Nanozymes with inherent enzyme-mimic catalytic properties combat malignant tumor progression via catalytic therapy, while the therapeutic efficacy still needs to be improved. In this work, we innovatively synthesized ultra-small platinum nanozymes (nPt) in confined domain of wormlike pore channel in gold nanobipyramidal-mesoporous silica dioxide nanocomposites, producing nanozyme carriers AP-mSi with photo-enhanced peroxidase ability. Afterwards, based on the prepared AP-mSi, the lung cancer nanozymes probe (AP-HAI) was ingeniously produced by removing SiO2 template, modifying HSA, and loading ATO as well as IR780. Under NIR light irradiation, inner AuP and IR780 collaborated for photothermal process, thus facilitating the peroxidase-like catalytic process of H2 O2 . Additionally, loaded atovaquone molecules (ATO), a cell respiration inhibitor, could impair tumor respiration metabolism and cause oxygen retention, hence enhancing IR780's PDT effectiveness. In a result, IR780's PDT property and nPt nanozymes' photo-enhanced peroxidase-like ability endowed probes a high ROS productivity, eliciting anti-tumor immune responses to destroy tumor tissue. Systematic studies revealed that the obvious ROS generation was obtained by the strategy of using nPt nanozymes and reducing oxygen consumption by ATO, which in turn enabled lung cancer synergetic catalytic therapy/ICD-based immunotherapy. The results of this work would provide theoretical justification for the practical use of photo-enhanced nanozyme probes. This article is protected by copyright. All rights reserved.

Biomimetic redox-responsive prodrug micelles with diselenide linkage for platinum nanozymes augmented sonodynamic/chemo combined therapy of colon cancer

Due to the complexity of tumorigenesis, it is hard to completely cure tumors with a single tumor therapy. Combined sonodynamic therapy and chemotherapy (sono-chemotherapy) based on the stimulus-responsive nano-delivery system is a prospective antitumor strategy that has demonstrated synergistic treatment effects and higher treatment effects than any monotherapy. The multiple diselenide linkages-contained DSeDP-alt-PEG conjugated with Ce6/PTX to yield prodrugs DC and DP micelles, and platinum nanozymes that possessed multiple enzyme activities were loaded in DC to form stable micelles (DC@Pt). The nanomicelles were modified with the homologous tumor cell membrane (DPC@Pt@M) to generate a REDOX-responsive bionic nanoplatform to realize the sono-chemotherapy combined treatment for colon cancer. As a redox-responsive nanoplatform, DPC@Pt@M exhibited excellent water solubility and bioavailability, and good targeting ability both in vitro and in vivo to realize the controlled release of Ce6 and PTX at the tumor site. Pt nanozymes acted as a cascade catalyst (SOD-CAT, SOD-POD) to alleviate hypoxia and improve SDT. Under ultrasonic irradiation, the novel micelle DPC@Pt@M increased ROS production and induced apoptosis efficiently in vitro and in vivo to improve sono-chemotherapeutic efficiency for colon cancer. Therefore, sonodynamic/chemo therapies demonstrated a clear synergistic effect, and this research is expected to provide a paradigm of combination therapy strategies for colon cancer.

Construction of platinum nanozyme by using carboxymethylcellulose with improved laccase-like activity for phenolic compounds detection

Natural laccases are multicopper oxidases widely applied in enzymatic biotransformation. However, using natural laccases in real-world settings is expensive and usually hampered by their stability. Most reported laccase-like nanozymes are limited to copper-containing, while other materials have yet to receive sufficient attention. Herein, platinum (Pt) nanoparticles (NPs) have been constructed as a laccase-like nanozyme using sodium carboxymethylcellulose (CMC-PtNPs). The as-prepared CMC-PtNPs have small particle size (3.79 ± 0.03 nm), good dispersion, and clear interaction mode between polysaccharides and nanozyme. CMC-PtNPs were found to own applicable laccase-like activity by producing O2•− as oxidants to oxidize laccase-related substrates. According to the steady-state dynamic assay, the apparent Km value of CMC-PtNPs was calculated as 0.218 mM. Compared with natural laccase or laccase-like materials, the laccase-like CMC-PtNPs have the advantage of higher substrate affinity and catalytic effect. More significantly, CMC-PtNPs were found to be highly stable at wide-ranged pH and temperature. On a practical level, the adequacy of the developed CMC-PtNPs was also confirmed by the efficient detection of the laccase-related phenolic compounds (e.g., 2,4-dichlorophenol, dopamine, noradrenaline, and adrenaline). A highly linear relationship (R2 = 0.996) was obtained by plotting the absorbance at 510 nm and 2,4-DCP concentration in a range of 6.25–225 μM with a low limit of detection (LOD) of 900 nM. Also, the colorimetric sensor exhibited outstanding sensing performance toward other phenolic compounds. Looking forward, this work provides a new design of laccase-like Pt nanozyme and demonstrates its utilization potentiality in nanozyme research, environmental remediation, and other fields.

Catalytic Bioswitch of Platinum Nanozymes: Mechanistic Insights of Reactive Oxygen Species Scavenging in the Neurovascular Unit.

Oxidative stress is known to be the cause of several neurovascular diseases, including neurodegenerative disorders, since the increase of reactive oxygen species (ROS) levels can lead to cellular damage, blood-brain barrier leaking, and inflammatory pathways. Herein, we demonstrate the therapeutic potential of 5 nm platinum nanoparticles (PtNPs) to effectively scavenge ROS in different cellular models of the neurovascular unit. We investigated the mechanism underlying the PtNP biological activities, analyzing the influence of the evolving biological environment during particle trafficking and disclosing a key role of the protein corona, which elicited an effective switch-off of the PtNP catalytic properties, promoting their selective in situ activity. Upon cellular internalization, the lysosomal environment switches on and boosts the enzyme-like activity of the PtNPs, acting as an intracellular "catalytic microreactor" exerting strong antioxidant functionalities. Significant ROS scavenging was observed in the neurovascular cellular models, with an interesting protective mechanism of the Pt-nanozymes along lysosomal-mitochondrial axes.

Role of Platinum Nanozymes in the Oxidative Stress Response of Salmonella Typhimurium.

Platinum nanoparticles (PtNPs) are being intensively explored as efficient nanozymes due to their biocompatibility coupled with excellent catalytic activities, which make them potential candidates as antimicrobial agents. Their antibacterial efficacy and the precise mechanism of action are, however, still unclear. In this framework, we investigated the oxidative stress response of Salmonella enterica serovar Typhimurium cells when exposed to 5 nm citrate coated PtNPs. Notably, by performing a systematic investigation that combines the use of a knock-out mutant strain 12023 HpxF- with impaired response to ROS (ΔkatE ΔkatG ΔkatN ΔahpCF ΔtsaA) and its respective wild-type strain, growth experiments in both aerobic and anaerobic conditions, and untargeted metabolomic profiling, we were able to disclose the involved antibacterial mechanisms. Interestingly, PtNPs exerted their biocidal effect mainly through their oxidase-like properties, though with limited antibacterial activity on the wild-type strain at high particle concentrations and significantly stronger action on the mutant strain, especially in aerobic conditions. The untargeted metabolomic analyses of oxidative stress markers revealed that 12023 HpxF- was not able to cope with PtNPs-based oxidative stress as efficiently as the parental strain. The observed oxidase-induced effects comprise bacterial membrane damage as well as lipid, glutathione and DNA oxidation. On the other hand, in the presence of exogenous bactericidal agents such as hydrogen peroxide, PtNPs display a protective ROS scavenging action, due to their efficient peroxidase mimicking activity. This mechanistic study can contribute to clarifying the mechanisms of PtNPs and their potential applications as antimicrobial agents.

Nanohybrid Double Network Hydrogels Based on a Platinum Nanozyme Composite for Antimicrobial and Diabetic Wound Healing.

Along with hypoxia, severe bacterial infection, and abnormal pH, continuous inflammatory response hinders diabetic wounds from healing. It leads to the accumulation of large amounts of reactive oxygen species (ROS) and therefore prevents the transition of diabetic wounds from the inflammatory phase to the proliferative phase. In this work, a nanohybrid double network hydrogel with injectable, self-healing, and tissue adhesion properties based on a platinum nanozyme composite (PFOB@PLGA@Pt) was constructed to manage diabetic wound healing. PFOB@PLGA@Pt exhibited oxygen supply capacity and enzyme catalytic performance accompanied by pH self-regulation in the entire phases of wound healing. In the first stage, the oxygen carried by perfluorooctyl bromide (PFOB) can ameliorate the hypoxia and boost the glucose oxidase-like catalyzed reaction of Pt NPs, leading to a lowered pH environment with gluconic acid. As a result, the NADH oxidase-like, peroxidase-like, and oxidase-like multiple enzyme activities were activated successively, leading to synergistic antibacterial effects through the production of ROS. After the bacterial infection had cleared, the catalase-like and superoxide dismutase-like activities of Pt NPs reshaped the redox microenvironment by scavenging the excess ROS, which transitioned the wound from the inflammatory phase to the proliferative phase. The microenvironmentally adaptive hydrogel treatment can cover all phases of wound healing, showing the significant promoting effect in the repair of diabetic infected wounds.

A cascade nanoreactor for enhancing sonodynamic therapy on colorectal cancer via synergistic ROS augment and autophagy blockage

The ultrasound-triggered sonodynamic therapy (SDT) with high tissue penetration, high spatiotemporal selectivity, and non-invasive advantages represents an emerging approach to eradicating deep-seated solid tumors. However, the outcomes of SDT are typically hampered by the inefficient generation of reactive oxygen species (ROS) and the activation of protective autophagy. Here, to improve the antitumor efficiency of SDT on colorectal cancer, we rationally design a cascade nanoreactor by incorporating sonosensitizer Ce6 and autophagy inhibitor chloroquine into the homologous tumor cell membrane-modified hollow polydopamine nanocarrier that is pre-doped with platinum nanozymes (designated as CCP@HP@M). The cascade reactions of CCP@HP@M are evidenced by the results that HP exhibits superoxide dismutase-mimicking activity that converts O2·− to O2 and H2O2, and platinum nanozymes further catalyze the excess H2O2 to produce toxic ·OH and O2. CCP@HP@M effectively accumulates in the tumor cells, resulting in a remarkably enhanced SDT efficiency for eliminating the tumor cells in vitro and in vivo. Under ultrasound irradiation, CCP@HP@M effectively alleviates the hypoxic condition, enhances ROS generation, and inhibits the protective autophagy pathway, which results in stimulating apoptosis and ferroptosis in vitro and in vivo. The RNA-seq analyses also confirmed apoptosis and ferroptosis pathways involved in the CCP@HP@M treatment. This cascade nanoreactor will provide a promising strategy for augmenting SDT eradication against tumors by modulation of ROS and autophagy.

Bimetallic Metal–Organic Framework for Mitigating Aseptic Osteolysis

The disability rate of joint diseases can be reduced by the use of artificial joints, but joint loosening at a late state limits the lifespan and surgical efficacy of the joints. Wear particles can be recognized by macrophages and induce cells to produce reactive oxygen species (ROS) and inflammatory factors, causing persistent inflammation and decreased osteogenic activity, which ultimately leads to loosening of joint prostheses. Here, the platinum (Pt) nanozymes with excellent ROS scavenging and anti-inflammatory capabilities were encapsulated in zinc imidazolium zeolite framework-8 (ZIF-8), and then the osteogenic active element lanthanum (La) was introduced through ion exchange to finally construct a bimetallic metal-organic framework (Pt@ZIF-8@La). In vitro and in vivo experiments demonstrated that this multifunctional nanoplatform possessed the functions of efficient scavenging of ROS, immune regulation, and promotion of osteogenic differentiation. Meanwhile, the mechanism is explored that Pt@ZIF-8@La can also promote osteogenic mineralization by upregulating the ratio of the osteoprotegerin (OPG)/receptor activator of the NF-κB ligand (RANKL), which can achieve a synergistic therapeutic effect of immunomodulation and osteogenesis, thereby realizing the purpose of relieving aseptic osteolysis.

Anti-inflammatory potential of platinum nanozymes: mechanisms and perspectives.

Inflammation is a complex process of the body in response to pathogen infections or dysregulated metabolism, involving the recruitment and activation of immune system components. Repeated dangerous stimuli or uncontrolled immune effector mechanisms can result in tissue injury. Reactive Oxygen Species (ROS) play key roles in physiological cell signaling as well as in the destruction of internalized pathogens. However, aberrant ROS production and release have deleterious effects on the surrounding environment, making ROS regulation a priority to reduce inflammation. Most of the current anti-inflammatory therapies rely on drugs that impair the release of pro-inflammatory mediators. Nevertheless, increasing the enzymatic activity to reduce ROS levels could be an alternative or complementary therapeutic approach to decrease inflammation. Nanozymes are nanomaterials with high catalytic activity that mimic natural enzymes, allowing biochemical reactions to take place. Such functional particles typically show different and regenerable oxidation states or catalytically reactive surfaces offering long-term activity and stability. In this scenario, platinum-based nanozymes (PtNZs) exhibit broad and efficient catalytic functionalities and can reduce inflammation mainly through ROS scavenging, e.g. by catalase and superoxide dismutase reactions. Dose-dependent biocompatibility and immune compatibility of PtNZs have been shown in different cells and tissues, both in vitro and in vivo. Size/shape/surface engineering of the nanozymes could also potentiate their efficacy to act at different sites and/or steps of the inflammation process, such as cytokine removal or specific targeting of activated leukocytes. In the present review, we analyze key inflammation triggering processes and the effects of platinum nanozymes under exemplificative inflammatory conditions. We further discuss potential platinum nanozyme design and improvements to modulate and expand their anti-inflammatory action.

Mesoporous platinum nanozyme-based competitive immunoassay for sensitive detection of 25-hydroxyvitamin D

• Mesoporous platinum nanozymes (MPNs) were fabricated by a surfactant-based self-assembly method. • MPNs showed the higher peroxidase-mimic activity than horseradish peroxidase. • MPNs were applied to colorimetric vitamin D detection using a competitive immunoassay. • MPNs-based immunoassay exhibited good linearity for vitamin D detection with a LOD of 1.0 ng/mL. In this study, mesoporous platinum nanozymes (MPNs) were fabricated by a surfactant-based self-assembly method and then used to develop a novel competitive immunoassay for sensitive detection of 25-hydroxyvitamin D 3 (25(OH)VD 3 ). The MPNs showed enhanced peroxidase-like activity that catalyzes the reaction between hydrogen peroxide (H 2 O 2 ) and 3,3′,5,5′-tetramethylbenzidine (TMB). The excellent peroxidase-like MPNs were employed to develop a competitive immunoassay for the sensitive colorimetric detection of 25(OH)VD 3 . The immunoassay detected 25(OH)VD 3 in the range of 1.6 to 100 ng/mL, with a detection limit of 1.0 ng/mL. The recovery values of 25(OH)VD 3 from the spiked human serum samples were between 104% and 95%. These results indicate the applicability of MPNs as alternatives for natural enzymes and the feasibility for sensitive 25(OH)VD 3 detection.

RGD peptide modified platinum nanozyme Co-loaded glutathione-responsive prodrug nanoparticles for enhanced chemo-photodynamic bladder cancer therapy

Bladder cancer is one of the most common malignant tumors in the urinary system worldwide. The poor permeability and uncontrollable release of drug and hypoxia of tumor tissues were the main reasons leading to poor therapeutic effect of chemo-photodynamic therapy for bladder cancer. To solve the above problems, a tumor-targeting peptide Arg-Gly-Asp (RGD) modified platinum nanozyme (PtNP) co-loaded glutathione (GSH)-responsive prodrug nanoparticles (PTX–SS–HPPH/Pt@RGD-NP) was constructed. Firstly, a GSH-responsive prodrug (PTX–SS–HPPH) was prepared by introducing a disulfide bond between paclitaxel (PTX) and photosensitizer 2-(1-hexyloxyethyl)-2-devinyl pyropheophorbide-a (HPPH), which could realize the GSH-responsive release of the drug at the tumor sites. Also, the distearoylphosphoethanolamine-poly (ethylene glycol)-RGD peptide (DSPE-PEG-RGD) modified the prodrug to enhance the targeting and permeability ability to bladder cancer cells. Besides, to alleviate the hypoxia of tumor tissues, PtNP was introduced to produce oxygen (O2) and improve photodynamic therapy efficiency. The results showed that the PTX–SS–HPPH/Pt@RGD-NP could achieve GSH-responsive drug release in tumor microenvironment, enhance the drug accumulation time and permeability at tumor sites in T24 subcutaneous tumor model and T24 orthotopic bladder tumor model, and alleviate hypoxia in tumor tissues, thus realizing enhanced chemo-photodynamic therapy for bladder cancer, and providing new strategies and methods for clinical treatment of bladder cancer.

Progress and perspectives of platinum nanozyme in cancer therapy.

Malignant tumors, one of the worst-case scenarios within human health problems, are now posing an increasing threat to the well-being of the global population. At present, the treatment of malignant tumors mainly includes surgery, radiotherapy, chemotherapy, immunotherapy, etc. Radiotherapy and chemotherapy are often applied to inoperable tumors, and some other tumors after surgery as important adjuvant therapies. Nonetheless, both radiotherapy and chemotherapy have a series of side effects, such as radiation-induced lung injury, and chemotherapy-induced bone marrow suppression. In addition, the positioning accuracy of radiotherapy and chemotherapy is not assured and satisfactory, and the possibility of tumor cells not being sensitive to radiation and chemotherapy drugs is also problematic. Nanozymes are nanomaterials that display natural enzyme activities, and their applications to tumor therapy have made great progress recently. The most studied one, platinum nanozyme, has been shown to possess a significant correlation with radiotherapy sensitization of tumors as well as photodynamic therapy. However, there are still several issues that limited the usage of platinum-based nanozymes in vivo. In this review, we briefly summarize the representative studies regarding platinum nanozymes, and especially emphasize on the current challenges and the directions of future development for platinum nanozymes therapy.

Zwitterionic Sulfhydryl Sulfobetaine Stabilized Platinum Nanoparticles for Enhanced Dopamine Detection and Antitumor Ability.

Herein, three kinds of molecules were used to modify the surface of platinum nanoparticles (Pt NPs) to tune their surface charge. Zwitterionic thiol-functionalized sulfobetaine (SH-SB) stabilized Pt NPs (SH-SB/Pt NPs) had the highest oxidase activity and peroxidase activity in the prepared platinum nanozymes due to the generation of reactive oxygen species. In addition, a colorimetric dopamine detection method was established based on the peroxidase activity of SH-SB/Pt NPs. This method had a wide range (0-120 μM), a low detection limit (0.244 μM), and high specificity. More importantly, SH-SB/Pt NPs displayed little hemolysis and good stability in the presence of proteins. SH-SB/Pt NPs demonstrated high cytotoxicity in vitro and good antitumor ability in vivo, which was attributed to the photothermal conversion ability of SH-SB/Pt NPs and the generation of reactive oxygen species in the acidic environment. The surface modification of nanozymes using zwitterionic molecules opens a new method to improve the catalytic activity and antitumor ability of nanozymes.

A nuclease-mimetic platinum nanozyme induces concurrent DNA platination and oxidative cleavage to overcome cancer drug resistance

Platinum (Pt) resistance in cancer almost inevitably occurs during clinical Pt-based chemotherapy. The spontaneous nucleotide-excision repair of cancer cells is a representative process that leads to Pt resistance, which involves the local DNA bending to facilitate the recruitment of nucleotide-excision repair proteins and subsequent elimination of Pt-DNA adducts. By exploiting the structural vulnerability of this process, we herein report a nuclease-mimetic Pt nanozyme that can target cancer cell nuclei and induce concurrent DNA platination and oxidative cleavage to overcome Pt drug resistance. We show that the Pt nanozyme, unlike cisplatin and conventional Pt nanoparticles, specifically induces the nanozyme-catalyzed cleavage of the formed Pt-DNA adducts by generating in situ reactive oxygen species, which impairs the damage recognition factors-induced DNA bending prerequisite for nucleotide-excision repair. The recruitment of downstream effectors of nucleotide-excision repair to DNA lesion sites, including xeroderma pigmentosum groups A and F, is disrupted by the Pt nanozyme in cisplatin-resistant cancer cells, allowing excessive accumulation of the Pt-DNA adducts for highly efficient cancer therapy. Our study highlights the potential benefits of applying enzymatic activities to the use of the Pt nanomedicines, providing a paradigm shift in DNA damaging chemotherapy.

Ultrasmall Pt Nanozymes Immobilized on Spherical Polyelectrolyte Brushes with Robust Peroxidase-like Activity for Highly Sensitive Detection of Cysteine.

Distinct platinum (Pt) nanozymes as peroxidase mimics have received extensive interest owing to their outstanding catalytic activity, high environmental tolerance, lower consumption, and great potential in replacing natural enzymes. However, easy agglomeration of Pt nanoparticles (Pt NPs) resulting from the high surface free energy significantly decrease their peroxidase-like activity. Herein, spherical polyelectrolyte brush (SPB)-stabilized ultrasmall Pt NPs (SPB@Pt NPs) were prepared by a novel synthetic strategy where the SPB not only performed as a nanoreactor for the synthesis of ultrasmall Pt NPs but also greatly stabilized Pt NPs against aggregation. The well-defined SPB@Pt NP nanozymes exhibited outstanding peroxidase-like activity for the catalytic oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxidized TMB and were then used to establish a colorimetric sensor for rapid detection of cysteine, giving a limit of detection of 0.11 μM. Moreover, the colorimetric detection system was demonstrated with outstanding performance in sensitive and selective detection of cysteine in the presence of several interference molecules. From these results, SPB@Pt NPs have been regarded as promising peroxidase mimics for a large number of applications such as in biosensing, biomedicine, the food industry, and environmental chemistry.

Fiber-based photothermal, UV-resistant, and self-cleaning coatings fabricated by silicon grafted copolymers of chitosan derivatives and gallic acid

Superhydrophobic and hydrophobic properties are generally created by adopting low surface free energy materials. Therefore, most studies have focused on creating surface hydrophobicity by using hydrophobic or fluorinated materials. However, few studies are reported on realizing surface hydrophobicity by directly introducing hydrophilic molecules, which is also a challenge. Herein, with platinum nanozyme as the catalyst, the novel hydrophobic coatings have been rapidly gained via anchoring the polymer of hydrophilic gallic acid and chitosan or chitosan quaternary ammonium salt onto cotton fabric surface. Notably, the novel hydrophobic coatings exhibit significant advances compared with conventional hydrophobic ones created by utilizing fluorinated or hydrophobic materials, which breaks the limitation of employing low surface energy materials for gaining surface hydrophobicity. Subsequently, the sodium methyl silicate was grafted on the polymer's coatings to strengthen surface hydrophobicity and the abrasion resistance of hydrophobicity. Interestingly, the heating could induce the hydrophilicity of cotton fabric to recover to hydrophobicity. Moreover, the hydrophobic coatings also possess good photothermal conversion, UV resistance, and anti-oxidation activity for self-cleaning application and oil water separation. Briefly, the present work may open a new direction for preparing novel hydrophobic coatings by combining gallic acid and chitosan-based macromolecular carbohydrates.