A facile preparation of FePt-loaded few-layer MoS2 nanosheets nanocomposites (F-MoS2-FePt NCs) and their application for colorimetric detection of H2O2 in living cells.

BACKGROUND: Rapid and sensitive detection of H2O2 especially endogenous H2O2 is of great importance for series of industries including disease diagnosis and therapy. In this work, uniform FePt nanoparticles are successfully anchored onto Few-layer molybdenum disulfide nanosheets (F-MoS2 NSs). The powder X-ray diffraction, transmission electron microscopy, UV-Vis spectra and atomic force microscopy were employed to confirm the structure of the obtained nanocomposites (F-MoS2-FePt NCs). The prepared nanocomposites show efficient peroxidase-like catalytic activities verified by catalyzing the peroxidation substrate 4,4'-diamino-3,3',5,5'-tetramethylbiphenyl (TMB) with the existence of H2O2. RESULTS: The optimal conditions of the constructed colorimetric sensing platform is proved as 35 °C and pH 4.2. Under optimal catalytic conditions, the detection limit for H2O2 detection reaches 2.24 µM and the linear ranger is 8 µM to 300 µM. Furthermore, the proposed colorimetric sensing platform was successfully utilized to detect the intracellular H2O2 of cancer cells (MCF-7). CONCLUSIONS: These findings indicated that the F-MoS2-FePt-TMB-H2O2 system provides a potential sensing platform for hydrogen peroxide monitoring in living cells.

Cationic polymer-based plasmonic sensor array that discriminates proteins.

Breaking the restrictions of a lock-and-key sensing strategy which relies only on the most dominant interactions between the sensing element and target, here, we develop a colorimetric sensor array with three kinds of cationic polymers (polydiallyl dimethylammonium chloride (PDDA), chitosan (CTS), and cetyltrimethylammonium bromide (CTAB)) as nonspecific receptors. Diverse interactions between cationic polymers and proteins make gold nanoparticles (Au NPs) exhibit different aggregation behaviors, resulting in changes in color and absorbance of Au NPs. Based on the diverse colorimetric response patterns, seven proteins were successfully discriminated visually at the 20 nM level by linear discrimination analysis (LDA). Furthermore, the practicability of the sensor array was validated by the successful identification of proteins without any overlap in human serum samples.

An injectable hydrogel based on Bi2Se3 nanosheets and hyaluronic acid for chemo-photothermal synergistic therapy.

To resolve poor accumulation caused by systemic administration, injectable and responsive hydrogels are the prospective drug delivery systems for localized tumor treatment, owning to negligible invasiveness and accurate administration. Herein, an injectable hydrogel, based on dopamine (DA) crosslinked hyaluronic acid and Bi2Se3 nanosheets (NSs) loading with doxorubicin (DOX) coated with polydopamine (Bi2Se3-DOX@PDA), was developed for synergistic chem-photothermal cancer therapy. The ultrathin functional Bi2Se3-DOX@PDA NSs could be responsive to the weak acidic condition and photothermal effect under NIR laser irradiation, achieving controlled release of DOX. Moreover, nanocomposite hydrogel based on hyaluronic acid matrix could be precisely administrated through intratumoral injection since its injectability and self-healing capacity, remaining at injected sites for at least 12 days. Furthermore, the excellent therapeutics effect of Bi2Se3-DOX@PDA nanocomposite hydrogel was demonstrated on 4 T1 xenograft tumor with outstanding injectability and negligible systemic side-effect. In short, the construction of Bi2Se3-DOX@PDA nanocomposite hydrogel paves a prospective path for local treatment of cancers.

Molecularly imprinted colloidal array with multi-boronic acid sites for glycoprotein detection under neutral pH.

Glycoproteins play vital roles in living organisms and often serve as biomarkers for some disease. However, due to the low content of glycoprotein in biological fluids, selective detection of glycoproteins is still a challenging issue that needs to be addressed. In this study, molecularly imprinted colloidal array with multi-boronic acid sites for glycoprotein detection under physiological pH was proposed. Monodispersed glycoprotein imprinted particles (SiO2@PEI/MIPs) was first prepared based on surface imprinting strategy using horseradish peroxidase (HRP) as template, and polyethyleneimine (PEI) was used to increase the number of boronic acid groups. The binding experiment indicated that the SiO2@PEI/MIPs hold satisfactory adsorption capacity (1.41 µmol/g), rapid adsorption rate (40 min) and preferable selectivity toward HRP. Then the SiO2@PEI/MIPs was assembled into close-packed colloidal array to construct a label free optical sensor (denoted as GICA). Benefiting from the high ordered photonic crystal structure, binding of HRP onto the GICA could be directly readout from the changes in structure color and diffracted wavelength. The structure color of the GICA changed from bright blue to yellow with the diffraction wavelength red shifted 59 nm when the HRP concentration increased from 2.5 to 15 µmol/L. Importantly, the GICA was capable of detecting HRP from human serum samples. All those results indicated the potential of the GICA for naked-eye detection of glycoprotein.

Surface imprinted core-shell nanorod for selective extraction of glycoprotein.

In this paper, combining phenylboronic affinity, surface imprinting, and magnetic Fe3O4, a novel surface imprinted core-shell nanorod (Fe3O4@SiO2/MIPs) was developed for glycoprotein extraction. The Fe3O4@SiO2/MIPs was prepared in water solution using dopamine as functional monomer. The Fe3O4@SiO2/MIPs showed high binding capacity (175.2 mg/g) and fast mass transfer rate (40 min) toward the template protein (ovalbumin, OVA). In addition, the successful extraction of OVA from egg white confirmed the outstanding selectivity of the obtained material. All these results demonstrated that the Fe3O4@SiO2/MIPs had broad application prospects in glycoprotein recognition, biomedical research and clinical diagnosis.

Biomass activated carbon-derived imprinted polymer with multi-boronic acid sites for selective capture of glycoprotein.

Glycoproteins play crucial roles in many biological events such as protein folding, information transmission, nerve conduction, and molecular recognition. Some glycoproteins serve as disease biomarkers in clinical settings. However, selective detection of glycoprotein often faces great challenges, owing to its low abundance in complex biological samples. In this case, develop a highly sensitive and selective approach for glycoprotein detection is urgently needed. Molecularly imprinted polymers (MIPs) have proved to be an ideal absorbent material in detection and separation science. Herein, a novel biomass activated carbon-derived imprinted polymer (BAC@PEI/PBA/MIPs) was fabricated for selective recognition of glycoprotein. The as-prepared BAC@PEI/PBA/MIPs was synthesized using waste tea derived carbon as matrix, albumin chicken egg (OVA) as template, and dopamine as functional monomer. Branched polyethyleneimine (PEI) was covalently bonded on the BAC surface to increase the number of boronic acid moieties. Benefiting from the self-polymerization of dopamine and multi-boronic acid sites, a great number of recognition sites were presented under mild conditions. The static adsorption experiment showed that the BAC@PEI/PBA/MIPs exhibited a high binding capacity of 196.2 mg/g, rapid adsorption dynamics of 40 min, excellent selectivity and satisfactory reusability for OVA. Furthermore, the practicability of BAC@PEI/PBA/MIPs was verified by isolation of OVA from egg white. The good binding performance and facile preparation process make BAC@PEI/PBA/MIPs attractive for glycoprotein recognition, indicating its potential applications in biomedical research and clinical diagnostics.

Charge-reversal nanomedicine based on black phosphorus for the development of A Novel photothermal therapy of oral cancer.

Driven by the lifestyle habits of modern people, such as excessive smoking, drinking, and chewing betel nut and other cancer-causing foods, the incidence of oral cancer has increased sharply and has a trend of becoming younger. Given the current mainstream treatment means of surgical resection will cause serious damage to many oral organs, so that patients lose the ability to chew, speak, and so on, it is urgent to develop new oral cancer treatment methods. Based on the strong killing effect of photothermal therapy on exposed superficial tumors, we developed a pH-responsive charge reversal nanomedicine system for oral cancer which is a kind of classic superficial tumor. With excellent photothermal properties of polydopamine (PDA) modified black phosphorus nanosheets (BP NSs) as basal material, then used polyacrylamide hydrochloride-dimethylmaleic acid (PAH-DMMA) charge reversal system for further surface modification, which can be negatively charged at blood circulation, and become a positive surface charge in the tumor site weakly acidic conditions due to the breaking of dimethylmaleic amide. Therefore, the uptake of oral cancer cells was enhanced and the therapeutic effect was improved. It can be proved that this nanomedicine has excellent photothermal properties and tumor enrichment ability, as well as a good killing effect on oral cancer cells through in vitro cytotoxicity test and in vivo photothermal test, which may become a very promising new model of oral cancer treatment.

A novel multifunctional FePt/BP nanoplatform for synergistic photothermal/photodynamic/chemodynamic cancer therapies and photothermally-enhanced immunotherapy.

A new multi-modal therapy agent, FePt/BP-PEI-FA nanoplatform, with FePt nanoparticles (FePt NPs) loaded onto ultrathin black phosphorus nanosheets (BPNs), has been constructed to enhance synergistic photothermal therapy (PTT), photodynamic therapy (PDT), and chemodynamic therapy (CDT) that target primary tumors. In this work, BPNs exhibit excellent photothermal and photodynamic behaviors under different wavelength laser irradiation. After polyethylenimine (PEI) modification, FePt NPs with sizes of 3-4 nm are uniformly attached onto the surface of modified BPNs via electrostatic adsorption. FePt NPs, as a ferroptosis agent, can transform endogenous H2O2 into reactive oxygen species (ROS) through the Fenton reaction, ultimately inducing cell death. Based on magnetic resonance imaging (MR) and thermal imaging, the as-prepared FePt/BP-PEI-FA NCs can inhibit tumor growth by achieving synergistic therapies. More significantly, combined with cytotoxic T lymphocyte-associated protein 4 (CTLA-4) checkpoint blockade, FePt/BP-PEI-FA NC-induced PTT can control both primary and untreated distant tumors' growth. Therefore, FePt/BP-PEI-FA NCs is a potential multifunctional nanoagent for effective anti-tumor applications.

Protein recognition by polydopamine-based molecularly imprinted hollow spheres.

A facile method to prepare hollow molecularly imprinted polymers (HMIPs) for specific recognition of horseradish peroxidase (HRP) from biological samples was proposed in this paper. The HMIPs was prepared using silica nanoparticles as the sacrificial matrix and dopamine as functional monomer. The thickness of polydopamine shells can be easily modulated by tuning the mass ratio of silica matrix and dopamine. The polymerization conditions and recognition behaviors of the HMIPs were investigated systematically. The results suggested that the hollow structure endowed the HMIPs with fast adsorption kinetics of 25 min, high binding capacity of 172.1 mg/g, and reusability of no less than four adsorption-regeneration cycles without apparent deterioration. Meanwhile, excellent binding specificity towards HRP was presented in the selectivity studies. Moreover, enriching of HRP from human serum sample by the obtained HMIPs was conducted. The HMIPs displayed satisfactory binding specificity to HRP, in spite of the complex composition of the human serum.

A close-packed imprinted colloidal array for naked-eye detection of glycoproteins under physiological pH.

According to the combination of colloidal crystals and molecular imprinting techniques, a novel close-packed imprinted colloidal array (CPICA) for naked-eye horseradish peroxidase (HRP) detection at physiological pH was proposed. The CPICA was fabricated by self-assemble of monodispersed HRP imprinted particles. The HRP imprinted particles were prepared based on surface imprinting technique and immobilized template strategy using 2,4-difluoro-3-formylphenylboronic acid (DFFPBA) as functional monomer which allowed the material binding of HRP at physiological pH (denoted as SiO2@DFFPBA/MIPs). The adsorption capacity of the SiO2@DFFPBA/MIPs for HRP was 1.16 µmol/g, and reached saturated adsorption within 25 min. The limit of detection (LOD) of the CPICA was 3.0 × 10-13 mol/mL. In addition, the adsorption of HRP on the CPICA could be directly transferred into visible color changes and readable optical signals through the reflection peak shifts. The structure color of the CPICA changed from brilliant blue to dark red with an maximum red shift of 87 nm when the HRP concentration increased from 2.5 to 20.0 µmol/L. Moreover, the CPICA could be used to detect HRP from human serum sample, which demonstrated the promising application prospects in colorimetric sensors.

Fluorescent sensor array for discrimination of biothiols based on poly(thymine/cytosine)-templated copper nanoparticles.

In medicine, the detection and identification of biothiols have received increasing attention due to their crucial roles in life activities. Hence, we present a facile, rapid, and effective method for identification of five kinds of biothiols including glutathione (GSH), l-cysteine (Cys), dithiothreitol (DTT), 2-mercaptoethanol (MCE), and 3-mercaptopropionic acid (MPA). The proposed sensor array is fabricated based on single-stranded poly (thymine/cytosine)-templated fluorescent copper nanoparticles (CuNPs), which are controlled through thymine-Hg2+-thymine (T-Hg2+-T) and cytosine-Ag+-cytosine (CAg+C) coordination. The results show that single-stranded poly T and poly C are used as a highly efficient template, and ascorbic acid acts as a reductant to form CuNPs. Owing to the different thiol binding affinity between Hg2+ (pKd = 3.90) and Ag+ (pKd = 5.50), the sensor array produces a unique pattern of fluorescence variations when it interacts with the five biothiols. Linear discriminant analysis (LDA) is applied to analyze the fluorescence pattern and generated a clustering map for a clear identification of the five biothiols. By employing this "turn-on" sensor array, five thiols were successfully discirminated at the 50 nM level in buffer solution and serum samples.

Facile strategy to prepare a metalloporphyrin-based hydrophilic porous organic polymer with enhanced peroxidase-like activity and high stability for colorimetric detection of H2O2 and glucose.

Nanozymes, nanomaterial-based artificial enzymes, have attracted researchers' enormous interest due to their unique properties compared with natural enzymes. To mimic the catalytic function of natural enzymes, designing high-efficient, novel nanozymes is crucial yet challenging task. In this article, we described the synthesis and functions of a metalloporphyrin-based porous organic polymer, namely FePPOPs-SO3H. FePPOPs-SO3H was synthesized effortlessly via an extensive aromatic electrophilic substitution and the following sulfonation reactions. This strategy was cost-efficient without the participation of precious metal catalysts. The resultant FePPOPs-SO3H is intriguing since the framework itself is constructed by covalently linked porphyrin units, which could serve as a built-in catalyst and strengthen the stability of polymer. With sulfonic acid side groups, FePPOPs-SO3H is well water-dispersive. Owing to these unique characteristics, FePPOPs-SO3H exhibited excellent peroxidase-like activity toward a classical peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) to produce a blue product only within 20 s. The peroxidase-mimicking performance of FePPOPs-SO3H outperforms the ferric porphyrin monomer and normal Fe3O4 nanoparticles. Based on the excellent catalytic activity of FePPOPs-SO3H, two visual colorimetric sensors for ultrafast detecting H2O2 and glucose, respectively, were constructed with a wide linear range of 50-1800 µM (for H2O2) and 200-1500 µM (for glucose), as well as a relative lower limit of detection (LOD) [26.70 µM (for H2O2) and 16.38 µM (for glucose)]. Our strategy highlights opportunities for the design of new metalloporphyrin-based porous organic polymers with built-in catalytic skeletons and inherently excellent peroxidase-mimicking performance.

FePt@MnO-Based Nanotheranostic Platform with Acidity-Triggered Dual-Ions Release for Enhanced MR Imaging-Guided Ferroptosis Chemodynamic Therapy.

Reactive oxygen species (ROS)-based anticancer therapy methods were heavily dependent on specific tumor microenvironments such as acidity and excess hydrogen peroxide (H2O2). In this work, an acidity-sensitive nanotheranostic agent (FePt@MnO)@DSPE-PEG5000-FA (FMDF NPs)  was successfully constructed for MR imaging guided ferroptosis chemodynamic therapy (FCDT) of cancer. The FMDF NPs could specifically target folic acid (FA) receptor-positive tumor cells (HeLa etc.) and induce ferroptosis efficiently by rapidly releasing active Fe2+ to catalyze intracellular H2O2 into ROS based on Fenton reaction. On the other hand, the Mn2+ could also be released due to acidity  and further coordinate with GSH to enhance the longitudinal-transverse relaxivity (T1/T2-weighted MR imaging), which could obviously strengthen the contrast distinction between solid tumors and the surrounding tissue to accurately real-time monitor the tumor location. Furthermore, the in vivo anticancer study revealed that the growth of solid tumor models could be suppressed remarkably after treating with FMDF NPs and no obvious damage to other major organs. Therefore, the FMDF NPs were competent simultaneously as an enhanced imaging diagnosis contrast agent and efficient therapy agent for promoting more precise and effective treatment in the bionanomedicine field.

A highly sensitive label-free electrochemical immunosensor based on an aligned GaN nanowires array/polydopamine heterointerface modified with Au nanoparticles.

Aligned GaN nanowire arrays show great potential not only in optoelectronic devices, but also in sensitive biosensor applications, owing to their excellent chemical stability and biocompatibility, as well as high electron mobility and surface-to-volume ratio. However, to construct electrochemical immunosensors, proper surface modification of GaN nanowires, which can enable efficient charge transfer and provide large densities of immobilization sites for antibodies to anchor, is still challenging. Herein we demonstrate a highly sensitive label-free electrochemical immunosensing platform based on the integration of polydopamine (PDA) on a GaN nanowire surface. The PDA polymer was self-assembled on GaN nanowire surfaces via organic polymerization. The interface dipole layer generated at the GaN nanowire array/PDA polymer heterointerface enabled efficient charge transfer. The aligned GaN nanowire array/PDA hybrids were further modified with gold nanoparticles for subsequent covalent binding of antibodies. The fabricated immunosensor yielded a wide linear range between 0.01 and 100 ng ml-1 and a detection limit as low as 0.003 ng ml-1 for the detection of alpha-fetoprotein (AFP). The immunosensor showed good selectivity, reproducibility, and stability and was utilized in human serum samples for AFP detection. This work demonstrates the superiority of taking advantage of a nanowire array configuration and a semiconductor/polymer heterointerface in an immunosensing platform for sensitivity enhancement.

Facile one-pot synthesis of a porphyrin-based hydrophilic porous organic polymer and application as recyclable absorbent for selective separation of methylene blue.

With the development of dye production and printing industry, dyes wastewater has increased dramatically. The resulting environmental pollution problem is increasing seriously. In the present work, a porphyrin-based porous organic polymer (PPOPs-OH) was synthesized by using pyrrole and 2,6-dihydroxynaphthalene-1,5-dicarbaldehyde (DHNDA) as basic building block in situ. This method was cost- and time-efficient, without the participation of metal catalysts. Further reaction of PPOPs-OH with chlorosulfonic acid, a new sulfonic acid functional material (PPOPs-SO3H) was obtained with the increasing electronegativity and hydrophilicity. PPOPs-SO3H exhibit good adsorption capacity for methylene blue (MB) from water (980.4 mg g-1) and excellent selectivity for MB in the present of rhodamine B (RhB) and methyl orange (MO). Mechanism investigation revealed that electrostatic in comparison with π-π interaction is the prominent force in the absorption process. Recycling experiments found the absorption properties of PPOPs-SO3H did not reduce significantly after several cycles. As a consequence, our findings highlight an appealing opportunities for covalent organic polymers with their potential application as high-efficiency and robust adsorbents for pollutants removal and environmental protection.

The catalytic activity of Ag2S-montmorillonites as peroxidase mimetic toward colorimetric detection of H2O2.

Nanocomposites based on silver sulfide (Ag2S) and Ca-montmorillonite (Ca(2+)-MMT) were synthesized by a simple hydrothermal method. The nanocomposites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier transform infrared spectra (FTIR). The as-prepared Ag2S-MMT nanocomposites were firstly demonstrated to possess intrinsic peroxidase-like activity and could rapidly catalytically oxidize the substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2 to produce a blue product which can be seen by the naked eye in only one minute. The experimental results revealed that the Ag2S-MMT nanocomposites exhibit higher thermal durance. Based on the TMB-H2O2 catalyzed color reaction, the Ag2S-MMT nanocomposites were exploited as a new type of biosensor for detection and estimation of H2O2 through a simple, cheap and selective colorimetric method.

Glucose-sensitive colorimetric sensor based on peroxidase mimics activity of porphyrin-Fe3O4 nanocomposites.

5,10,15,20-Tetrakis(4-carboxyphenyl)-porphyrin-functionalized Fe3O4 nanocomposites (H2TCPP-Fe3O4) were successfully prepared by a simple two-step method. These nanocomposites exhibited ultra-high peroxidase-like activity compared with pure Fe3O4 nanoparticles. Colorless peroxidase substrate 3,3,5,5-tetramethylbenzidine (TMB) was changed by H2O2 to its blue oxidized state. Kinetic studies indicated that the H2TCPP-Fe3O4 nanocomposites exhibited enhanced affinity toward H2O2 with a higher catalytic activity than Fe3O4 nanoparticles alone. Results of a fluorescent probe suggested that the catalase-mimic activity of the H2TCPP-Fe3O4 nanocomposites effectively catalyzed the decomposition of H2O2 into hydroxyl radicals. A simple, sensitive, and selective visual and colorimetric method with TMB as the substrate was designed to detect glucose when combined with glucose oxidase. This colorimetric method can be used for colorimetric detection of H2O2 with a minimum detection limit of 1.07×10(-6) M and a dynamic range of 5×10(-6) mol·L(-1) to 8×10(-5) mol·L(-1). This method can also be used to detect glucose at a minimum detection limit of 2.21×10(-6) M and a dynamic range of 25×10(-6) mol·L(-1) to 5×10(-6) mol·L(-1). Furthermore, the robustness of the nanocomposites makes them suitable for a wide range of applications in biomedicine and environmental chemistry fields.