SERS Tracking Oxidative Stress on a Metalloporphyrin Framework by Vitamin C.

Accurate control of charge transfer is crucial to investigate the catalytic reaction mechanism of the biological oxidation process that biomedicine participates in. Herein, we have established an assembly model of metalloporphyrin framework (MPF) nanosheets as the active centers of biological enzymes. The introduction of Vitamin C (VC) into the MPF system can precisely modulate its content of charges. The surface-enhanced Raman scattering activity and peroxidase-like catalytic performance are enhanced simultaneously for the first time by manipulating the optimal molar ratio of an MPF to VC and the reaction sequence with target model molecules. We have confirmed that the formation of the intermediate of Fe(2+)-OOH species is specifically enhanced after VC modulation, which indicates that VC can regulate the oxidative stress of the active center of biological enzymes. This discovery not only accurately resolves the mechanism of VC-selective anticancer therapy but also has important significance for the precise treatment of VC synergistic targeting medicines.

Chelating adsorption-engaged synthesis of ultrafine iridium nanoparticles anchored on N-doped carbon nanofibers toward highly efficient hydrogen evolution in both alkaline and acidic media.

Developing highly efficient and stable precious metal electrocatalysts toward hydrogen evolution reaction (HER) is crucial for energy application, while it is still challenging to achieve highly dispersed ultrafine metal nanoparticles on some promising supports to synergistically promote their electrocatalytic performance. Herein, we propose a feasible chelating adsorption-engaged strategy by introducing de-doped polyaniline with abundant amino groups to immobilize ultrafine iridium (Ir) nanoparticles on their derived N-doped carbon nanofibers (Ir-NCNFs). Experimental results demonstrate that the synthesized Ir-NCNFs can effectively promote the charge transfer and expose more electrochemical active sites, which eventually accelerate the reaction kinetics. Thus, the synthesized Ir-NCNFs catalyst exhibits admirable HER activities in both alkaline and acidic conditions with overpotentials of only 23 and 8 mV, which are even superior or close to the benchmark Pt/C catalyst. Furthermore, the synthesized Ir-NCNFs catalyst also exhibits a long-term durability. This study affords a reliable means to construct high-performance supported ultrafine metal nanocatalysts for electrocatalytic applications to alleviate the growing demand for energy conversion.

Ag Aerogel-Supported Single-Atom Hg Nanozyme Enables Efficient SERS Monitoring of Enhanced Oxidase-Like Catalysis.

In this work, three-dimensional (3D) Ag aerogel-supported Hg single-atom catalysts (SACs) were explored as an efficient surface-enhanced Raman scattering (SERS) substrate to monitor the enhanced oxidase-like reaction. The influence of the concentrations of Hg2+ to prepare 3D Hg/Ag aerogel networks on their SERS properties to monitor the oxidase-like reaction has been investigated, and a specific enhancement with an optimized addition of Hg2+ has been achieved. The formation of Ag-supported Hg SACs with the optimized Hg2+ addition was identified from a high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) image and X-ray photoelectron spectroscopy (XPS) measurement at an atomic level. This is the first discovery of Hg SACs for enzyme-like reaction applications inferred by SERS techniques. And density functional theory (DFT) was used to further reveal the oxidase-like catalytic mechanism of Hg/Ag SACs. This study provides a mild synthetic strategy to fabricate Ag aerogel-supported Hg single atoms to display promising prospects in various catalytic fields.

Advances on delta 5-unsaturated-polymethylene-interrupted fatty acids: Resources, biosynthesis, and benefits.

Though the knowledge on delta 5-unsaturated-polymethylene-interrupted fatty acids (Δ5-UPIFAs) is being updated, the issue of their integration still exists within the field. Thus, this review systematically summarizes the sources, biosynthesis and metabolism, analytical methods, preparation, and health-promoting roles of Δ5-UPIFAs. In plants, the content of Δ5-UPIFAs is higher, which is an ideal source. In animals, although the content of Δ5-UPIFAs is not high, there are many species, which is the possible source of some special Δ5-UPIFAs. At present, although the extraction of Δ5-UPIFAs is mainly from plants, the fermentation by organisms, especially for genetically modified microorganisms engineering maybe be a substitue of pepration of Δ5-UPIFAs. Δ5-UPIFAs have been proved to possess multi-beneficial effects, such as lipid lowering, anti-inflammation and so on, so it has a certain potential application value. However, related knowledge of the underlying molecular mechanisms regarding Δ5-UPIFAs limited, and how Δ5-UPIFAs work is not clear. Further clinical and human studies about Δ5-UPIFAs are also needed. Studies on tapping new resources, developing structured lipide rich in Δ5-UPIFA and enhancing delivery were quite deficient. This review emphasizes the further directions on Δ5-UPIFAs with scientific suggestions to pay more attention to the applications of Δ5-UPIFAs in food, pharmaceutical and cosmetic industries.

SERS Resolving of the Significance of Acetate on the Enhanced Catalytic Activity of Nanozymes.

Understanding the structure-activity correlation and reaction mechanism of the catalytic process in an acetic acid-sodium acetate (HAc-NaAc) buffer environment is crucial for the design of efficient nanozymes. Here, we first reported a lattice restructuration of Au-LaNiO3-δ nanofibers (NFs) after acidification with the HAc-NaAc buffer to show a significantly enhanced oxidase-like property. Surface-enhanced Raman spectroscopy (SERS) and density functional theory (DFT) calculation confirm the direct evidence for the formation of specific enhanced intermediate O-O species after acidification, indicating that the insertion of the carboxyl group in the A-Au/LaNiO3-δ NFs plays crucial roles in both producing vacancies in HAc-NaAc solution from its dissociation during the catalytic process and the protection of the vacancies, which can be directly interacted with oxygen in the environment to produce O-O species, realizing the enhanced oxidation of substrate molecules. The insertion of the carboxyl group increased the oxidase-like catalytic activity by 2.38 times and the SERS activity by 5.27 times. This strategy offers a way to construct an efficient nanozyme-linked immunosorbent assay system for the diagnosis of cancer through the highly sensitive SERS identification of exosomes.

Investigation of Sulfur Doping in Mn-Co Oxide Nanotubes on Surface-Enhanced Raman Scattering Properties.

Doping engineering is an efficient strategy to manipulate the optoelectronic properties of metal oxides for sensing, catalysis, and energy applications. Herein, we have demonstrated the fabrication of sulfur (S)-doped Mn-Co oxides to regulate their band and surface electronic structures, which is beneficial to enhancing the charge transfer (CT) between the metal oxides and their adsorbed molecules. As expected, significantly enhanced SERS signals are achieved on S-doped Mn-Co oxide nanotubes, and the minimum detection concentration can reach as low as 10-8 M. Furthermore, the change in the electronic structure caused by S-doping provides different microelectric fields to influence the orientation of the interaction between the probe molecules and the substrate. Additionally, the evaluation of the oxidase-like catalytic activity of the substrate proved that, with an increase in the ratio of Co2+/Co3+ content, the number of electrons on the substrate increases, which promotes the CT process and further increases the degree of CT. The nonmetallic doping route in semiconducting metal oxides can provide effective and stable SERS activity; moreover, it provides a new strategy for exploring the relationship between CT in catalysis and SERS performance of semiconductors.

A nanozyme-based enhanced system for total removal of organic mercury and SERS sensing.

Total removal of organic mercury in industrial wastewater is a crucially important task facing environmental pollution in the current world. Herein, we demonstrate the fabrication of Au-NiFe layered double hydroxide (LDH)/rGO nanocomposite as not only an efficient nanozyme with oxidase-like activity but also an efficient surface-enhanced Raman spectroscopy (SERS) substrate to determine organic mercury, with the minimum detection concentration as low as 1 × 10-8 M. According to the binding energy of X-Ray photoelectron spectrometer (XPS) and the free radicals of electron paramagnetic resonance (EPR) spectra, the mechanism of catalytic enhanced degradation is the production of Au-amalgam on Au surface, accelerating the electron transfer and the generation of O2•- radicals from oxygen molecules and •CH3 radicals from the methyl group in MeHg to participate the oxidase-like reaction. Furthermore, the Au-NiFe LDH/rGO nanocomposite is able to degrade and remove 99.9% of organic mercury in two hours without the secondary pollution by Hg2+. In addition, the material can be used for the multiple degradation-regeneration cycles in actual applications, which is significant in terms of the environmental and economic point of view. This work may open a new horizon for both highly sensitive detection and thorough degradation of organic mercury in environmental science and technology.

Accurate Monitoring Platform for the Surface Catalysis of Nanozyme Validated by Surface-Enhanced Raman-Kinetics Model.

Surface-enhanced Raman scattering (SERS) is a supersensitive technique for monitoring catalytic reactions. However, building a SERS-kinetics model to investigate catalytic efficiency on the surface or interface of the catalyst remains a great challenge. In the present study, we successfully obtained an excellent semiconducting SERS substrate, reduced MnCo2O4 (R-MnCo2O4) nanotubes, whose favorable SERS sensitivity is mainly related to the promoted interfacial charge transfer caused by the introduction of oxygen vacancies as well as the electromagnetic enhancement effect. Furthermore, the R-MnCo2O4 nanotubes showed a favorable oxidase-like activity toward oxidation with the aid of molecular oxygen. It was also showed the oxidase-like catalytic process could be monitored using the SERS technique. A new SERS-kinetics model to monitor the catalytic efficiency of the oxidase-like reaction was developed, and the results demonstrate that the Vm values measured by the SERS-kinetics method are close to that obtained by the UV-vis approach, while the Km values measured by the SERS-kinetics method are much lower, demonstrating the better affinity between the enzyme and the substrate from SERS results and further confirming the high sensitivity of the SERS-kinetics approach and the actual enzyme-like reaction on the surface of nanozymes, which provides guidance in understanding the kinetics process and catalytic mechanism of natural enzymatic and other artificial enzymatic reactions. This work demonstrated the improved SERS sensitivity of defective semiconductors for the application of enzyme mimicking, providing a new frontier to construct highly sensitive biosensors.

Ultra-sensitive SERS detection, rapid selective adsorption and degradation of cationic dyes on multifunctional magnetic metal-organic framework-based composite.

In-situ and real-time ultra-sensitive monitoring for the degradation process of environmental pollutants is always an important issue of concern to many people. Herein, a multifunctional magnetic metal-organic framework (MOF)-based composite has been successfully constructed and applied in monitoring the disposal of cationic dyes. Owing to its particular MOFs shell and internal gold particles, the composite can be used as an efficient SERS substrate to ultra-sensitively detect the cationic dyes. Furthermore, the prepared MOF-based composite is also a peroxidase-like nanozyme, which can catalytically degrade the adsorbed cationic dyes. Additionally, the magnetic core in the MOF-based composite offers a good magnetic separation capacity, which makes a facile and rapid separation of the catalyst from the reacted solution for recyclability. This work has provided a new way to monitor the catalytic degradation process by SERS technique in the co-existence of catalyst and dye molecules in the reaction system, which can effectively eliminate the absorption of the catalyst compared with the UV-vis technique, showing promising applications in in-situ and real-time pollution disposal monitoring.

Thalidomide induce response in patients with corticosteroid-resistant or relapsed ITP by upregulating Neuropilin-1 expression.

BACKGROUND: Immune thrombocytopenia (ITP) is an immune-mediated acquired autoimmune hemorrhagic disease. About one-third of patients are unresponsive to first-line therapies. Thalidomide (THD) as an immunomodulatory agent is now used to treat several autoimmune disorders. Therefore, we assessed the safety and efficacy of THD in corticosteroid-resistant or relapsed ITP patients, and preliminarily explore its mechanism. METHODS: 50 newly-diagnosed ITP patients and 47 healthy volunteers were enrolled in this study. Additionally, 17 corticosteroid-resistant or relapsed ITP patients were recruited, with 7 cases in the rhTPO + THD group and 10 cases in the THD monotherapy group. Overall response rate at 6, 12, and 24 months were assessed. Levels of Neuropilin-1(NRP-1), regulatory T cells (Tregs) and regulatory B cells (Bregs) were detected. RESULTS: Expression of NRP-1, Tregs and Bregs were reduced in newly-diagnosed ITP patients. In vitro, THD treatment upregulated expression of NRP-1and Tregs only in ITP patients. As for corticosteroid-resistant or relapsed ITP patients, overall response rate at 6, 12, and 24 months was 85.7%, 57.1% and 100% in the rhTPO + THD group and 60%, 75% and 83.3% in the THD group, respectively. Additionally, rhTPO plus THD or THD therapy significantly increased the levels of NRP-1, Tregs and Bregs in responders. CONCLUSIONS: Our study shows for the first time that NRP-1 is involved in the pathogenesis of ITP, THD could induce response in ITP patients by upregulating NRP-1 expression and restoring the proportion of Tregs and Bregs. THD might be served as a novel therapeutic agent in corticosteroid-resistant or relapsed ITP patients.

Controllable Synthesis of SERS-Active Magnetic Metal-Organic Framework-Based Nanocatalysts and Their Application in Photoinduced Enhanced Catalytic Oxidation.

Fabrication of multifunctional nanocatalysts with surface-enhanced Raman scattering (SERS) activity is of vital importance for monitoring catalytic courses in situ and studying the reaction mechanisms. Herein, SERS-active magnetic metal-organic framework (MOF)-based nanocatalysts were successfully prepared via a three-step method, including a solvothermal reaction, an Au seed-induced growth process, and a low-temperature cycling self-assembly technique. The as-synthesized magnetic MOF-based nanocatalysts not only exhibit outstanding peroxidase-like activity, but can also be applied as a SERS substrate. Owing to these features, they can be used for monitoring in situ catalytic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2 via a SERS technique, and the concentration of H2O2 was determined. Owing to the intrinsic character of the Fe-based MOF material (MIL-100(Fe)), a novel photoinduced enhanced catalytic oxidation effect was demonstrated, in which the catalytic oxidation of TMB and o-phenylenediamine was accelerated. This study provides a versatile approach for the fabrication of functional MOF-based nanocomposites as a promising SERS substrate with a unique photoinduced enhanced peroxidase-like activity for potential applications in ultrasensitive monitoring, biomedical treatment, and environmental evaluation.