pH-Responsive NIR-Absorbing Fluorescent Polydopamine with Hyaluronic Acid for Dual Targeting and Synergistic Effects of Photothermal and Chemotherapy

In cancer therapy, optimizing tumor-specific delivery, tumor distribution, and cellular uptake of a drug is important for ensuring minimal toxicity and maximum therapeutic efficacy. This study characterized the therapeutic efficacy of a stimulus responsive and dual targeting nanocarrier for a bioimaging-guided photothermal and chemotherapeutic platform. Hyaluronic acid (HA) conjugated with triphenylphosphonium (TPP) and boronic acid (BA) diol-linked β-cyclodextrin (β-CD) forms an inclusion complex with paclitaxel (PTX), creating a shell-like composite on a core of carbonized fluorescent polydopamine nanoparticles (FNPs-pDA) applicable for photothermal therapy as well as bioimaging. The successful diol cross-linking between core@shells generates nanocarriers [FNPs-pDA@HA-TPP-CD-PTX] that can be used as an extracellular HA- and intracellular TPP-mediated dual targeting system. The carbonized FNPs-pDA was cross-linked with the boronic acid groups of HA-TPP-CD-PTX to promote the formation of boronate esters for pH-mediated photothermal activity, which have shown time dependent complete PTX release along with a photothermal mediated response. The in vitro dual bioimaging and photothermal-chemotherapeutic activities were compared between cancer and normal cells. Lysosomal escape and live/dead cells staining confocal images highlight the promise of this system, which might open up a new approach, a simple and versatile method for site-specific synergetic drug delivery

Iron Oxide@PEDOT-Based Recyclable Photothermal Nanoparticles with Poly(vinylpyrrolidone) Sulfobetaines for Rapid and Effective Antibacterial Activity

Growing microbial resistance that renders antibiotic treatment vulnerable has emerged, attracting a great deal of interest in the need to develop alternative antimicrobial treatments. To contribute to this effort, we report magnetic iron oxide (Fe₃O₄) nanoparticles (NPs) coated with catechol-conjugated poly­(vinylpyrrolidone) sulfobetaines (C-PVPS). This negatively charged Fe₃O₄@C-PVPS is subsequently encapsulated by poly­(3,4-ethylenedioxythiophene) (PEDOT) following a layer-by-layer (LBL) self-assembly method. The obtained Fe₃O₄@C-PVPS:PEDOT nanoparticles appear to be novel NIR-irradiated photothermal agents that can achieve effective bacterial killing and are reusable after isolation of the used particles using external magnetic fields. The recyclable Fe₃O₄@C-PVPS:PEDOT NPs exhibit a high efficiency in converting photothermal heat for rapid antibacterial effects against <i>Staphylococcus aureus</i> and <i>Escherichia coli</i>. In this study, antibacterial tests for repeated uses maintained almost 100% antibacterial efficiency during three cycles and provided rapid and effective killing of 99% Gram-positive and -negative bacteria within 5 min of near-infrared (NIR) light exposure. The core–shell nanoparticles (Fe₃O₄@C-PVPS:PEDOT) exhibit the required stability, and their paramagnetic nature means that they rapidly convert photothermal heat sufficient for use as NIR-irradiated antibacterial photothermal sterilizing agents

Bi₂S₃ Nanorods Deposited on Reduced Graphene Oxide for Potassium-Ion Batteries

Hierarchical nanocomposites with surface active bonding features serve as an efficient electrode material for high-performance Li-/Na-/K-ion batteries. Tuning the physiochemical properties of these hierarchical nanocomposites has a great impact on the extremely improved electrochemical performance, and it is attributed to the synergistic effect of heterogeneous components. Herein, we report a hydrothermally synthesized bismuth sulfide (Bi2S3) nanorod bonding on the surface of the reduced graphene oxide (rGO) matrix and investigate it as an anode material for potassium-ion batteries. This hierarchical nanocomposite anode exhibits a high initial reversible capacity (586 mA h g–1 at 100 mA g–1), long-term cycling stability (410 mA h g–1 after 1000 cycles, 70% capacity retention), and an outstanding rate capability (140 mA h g–1 at 3 A g–1). This excellent electrochemical performance of the Bi2S3/rGO nanocomposite is attributed to the presence of active sites in rGO nanosheets that not only enhances the electrical conductivity of Bi2S3 nanorods but also prevents the shuttle effect of polysulfide through the formation of the in-built C–S bond, which is confirmed by X-ray photoelectron spectroscopy. Through the ex-situ X-ray diffraction patterns analysis at different voltage regions, a phase transformation mechanism has been proposed for K-ion storage in Bi2S3 nanorods. An ex-situ high-resolution transmission electron microscopy analysis reveals the structural and morphological stability of Bi2S3 nanorods. Further, the kinetic studies confirmed that the surface dominated pseudocapacitive K-ion storage also plays a major role in improving the electrochemical performance of the Bi2S3 nanorods/rGO nanocomposite. The K-ion full cell is successfully assembled, which exhibits stable cycling performance after 100 cycles at 1 C rate

Light Controllable Surface Coating for Effective Photothermal Killing of Bacteria

Although the electronic properties of conducting films have been widely explored in optoelectronic fields, the optical absorption abilities of surface-coated films for photothermal conversion have been relatively less explored in the production of antibacterial coatings. Here, we present catechol-conjugated poly­(vinylpyrrolidone) sulfobetaine (PVPS) and polyaniline (PANI) tightly linked by ionic interaction (PVPS:PANI) as a novel photothermal antibacterial agent for surface coating, which can absorb broadband near-infrared (NIR) light. Taking advantage of the NIR light absorption, this coating film can release eminent photothermal heat for the rapid killing of surface bacteria. The NIR light triggers a sharp rise in photothermal heat, providing the rapid and effective killing of 99.9% of the Gram-positive and -negative bacteria tested within 3 min of NIR light exposure when used at the concentration of 1 mg/mL. Although considerable progress has been made in the design of antibacterial coatings, the user control of NIR-irradiated rapid photothermal destruction of surface bacteria holds increasing attention beyond the traditional boundaries of typical antibacterial surfaces

Determination of Cancer Cell-Based pH-Sensitive Fluorescent Carbon Nanoparticles of Cross-Linked Polydopamine by Fluorescence Sensing of Alkaline Phosphatase Activity on Coated Surfaces and Aqueous Solution

The tumor-specific sensitive fluorescence sensing of cellular alkaline phosphatase (ALP) activity on the basis of host–guest specific and pH sensitivity was conducted on coated surfaces and aqueous states. Cross-linked fluorescent nanoparticles (C-FNP) consisting of β-cyclodextrin (β-CD)/boronic acid (BA) and fluorescent hyaluronic acid [FNP­(HA)] were conjugated to fluorescent polydopamine [FNP­(pDA)]. To determine the quenching effect of this system, hydrolysis of 4-nitrophenyl phosphate (NPP) to 4-nitrophenol (NP) was performed in the cavity of β-CD in the presence of ALP activated photoinduced electron transfer (PET) between NP and C-FNP. At an ALP level of 30–1000 U/L, NP caused off-emission of C-FNP because of their specific host–guest recognition. Fluorescence can be recovered under pH shock due to cleavage of the diol bond between β-CD and BA, resulting in release of NP from the fluorescent system. Sensitivity of the assays was assessed by confocal imaging not only in aqueous states, but also for the first time on coated surfaces in MDAMB-231 and MDCK cells. This novel system demonstrated high sensitivity to ALP through generation of good electron donor/acceptor pair during the PET process. Therefore, this fluorescence sensor system can be used to enhance ALP monitoring and cancer diagnosis on both coated surfaces and in aqueous states in clinical settings

In Vitro and In Vivo Tumor Targeted Photothermal Cancer Therapy Using Functionalized Graphene Nanoparticles

Despite the tremendous progress that photothermal therapy (PTT) has recently achieved, it still has a long way to go to gain the effective targeted photothermal ablation of tumor cells. Driven by this need, we describe a new class of targeted photothermal therapeutic agents for cancer cells with pH responsive bioimaging using near-infrared dye (NIR) IR825, conjugated poly­(ethylene glycol)-<i>g</i>-poly­(dimethylaminoethyl methacrylate) (PEG-<i>g</i>-PDMA, PgP), and hyaluronic acid (HA) anchored reduced graphene oxide (rGO) hybrid nanoparticles. The obtained rGO nanoparticles (PgP/HA-rGO) showed pH-dependent fluorescence emission and excellent near-infrared (NIR) irradiation of cancer cells targeted in vitro to provide cytotoxicity. Using intravenously administered PTT agents, the time-dependent in vivo tumor target accumulation was exactly defined, presenting eminent photothermal conversion at 4 and 8 h post-injection, which was demonstrated from the ex vivo biodistribution of tumors. These tumor environment responsive hybrid nanoparticles generated photothermal heat, which caused dominant suppression of tumor growth. The histopathological studies obtained by H&E staining demonstrated complete healing from malignant tumor. In an area of limited successes in cancer therapy, our translation will pave the road to design stimulus environment responsive targeted PTT agents for the safe eradication of devastating cancer

Simple Microwave-Assisted Synthesis of Amphiphilic Carbon Quantum Dots from A₃/B₂ Polyamidation Monomer Set

Highly fluorescent and amphiphilic carbon quantum dots (CQDs) were prepared by microwave-assisted pyrolysis of citric acid and 4,7,10-trioxa-1,13-tridecanediamine (TTDDA), which functioned as an A₃ and B₂ polyamidation type monomer set. Gram quantities of fluorescent CQDs were easily obtained within 5 min of microwave heating using a household microwave oven. Because of the dual role of TTDDA, both as a constituting monomer and as a surface passivation agent, TTDDA-based CQDs showed a high fluorescence quantum yield of 29% and amphiphilic solubility in various polar and nonpolar solvents. These properties enable the wide application of TTDDA-based CQDs as nontoxic bioimaging agents, nanofillers for polymer composites, and down-converting layers for enhancing the efficiency of Si solar cells

Visible-Light-Driven Photocatalysts of Perfluorinated Silica-Based Fluorescent Carbon Dot/TiO₂ for Tunable Hydrophilic–Hydrophobic Surfaces

In this study, a new hydrophilic–hydrophobic transition surface was designed via visible-light-induced photocatalytic perfluorinated silica-based fluorescent carbon nanoparticles (FNPs)/TiO₂. Perfluorinated silica–polydopamine hybrid FNPs (<i>f</i>-FNPs) were easily fabricated by carbonization in an emulsion system consisting of tetraethyl orthosilicate and dopamine, followed by the deposition of TiO₂ on <i>f</i>-FNPs, which demonstrated the reversal from hydrophobic to hydrophilic nature during successful photocatalysis. The synergistic effect of silica–carbon and the deposited TiO₂ NPs led to the decomposition of methylene blue under UV and visible light irradiation, demonstrating that FNPs/TiO₂ sustains photocatalytic activity. The profound contact angle with the catalytic kinetics curve and precise morphology and extension of cells detach antifouling exceptionally unrestricted the synergistic effect of silica–carbon on TiO₂ NPs on a coated paper substrate. Given the interest in the manipulation of hydrophobicity and hydrophilicity, this study can serve as a guideline for the fabrication of photocatalytic surfaces where water spreads completely

Tunable Exciton Dissociation and Luminescence Quantum Yield at a Wide Band Gap Nanocrystal/Quasi-Ordered Regioregular Polythiophene interface

A comprehensive understanding of the effect of polymer chain aggregation-induced molecular ordering and the resulting formation of lower excited energy structures in a conjugated polymer on exciton dissociation and recombination at the interface with a wide-bandgap semiconductor is provided through correlation between structural arrangement of the polymer chains and the consequent electrical and optoelectronic properties. A vertical diode-type photovoltaic test probe is combined with a field effect current modulating device and various spectroscopic techniques to isolate the interfacial properties from the bulk properties. Enhanced energy migration in the quasi-ordered (poly­(3-hexylthiophene)) (P3HT) film, processed through vibration-induced aggregation of polymer chains in solution state, is attributed to the presence of the aggregation-induced interchain species in which excitons are allowed to migrate through low barrier energy sites, enabling efficient iso-energetic charge transfer followed by the downhill energy transfer. We discovered that formation of nonemissive excitons that reduces the photoluminescence quantum yield in the P3HT film deactivates exciton dissociation at the donor (P3HT) close to the acceptor (ZnO) as well as in the P3HT far away from the ZnO. In other words, exciton deactivation in its film state arising from the quasi-ordered structural arrangement of polymer chains in solution is retained at the donor/acceptor interface as well as in the bulk P3HT. Effect of change in the highest occupied molecular orbital level and the resulting energy band bending at the P3HT/ZnO interface on exciton dissociation is also discussed in relation to the presence of vibration-induced aggregates in the P3HT film

Highly Efficient Visible Blue-Emitting Black Phosphorus Quantum Dot: Mussel-Inspired Surface Functionalization for Bioapplications

The preparation of blue-emitting black phosphorus quantum dots (BPQDs) is based on the liquid-phase exfoliation of bulk BP. We report the synthesis of soluble BPQDs showing a strong visible blue-light emission. Highly fluorescent (photoluminescence quantum yield of ≈5% with the maximum emission (λ_max) at ≈437 nm) and dispersible BPQDs in various organic solvents are first prepared by simple ultrasonication of BP crystals in chloroform in the ambient atmosphere. Furthermore, simple mussel-inspired surface functionalization of BPQDs with catechol-grafted poly­(ethylene glycol) in basic buffer afforded water-soluble blue-emitting BPQDs showing long-term fluorescence stability, very low cytotoxicity, and excellent fluorescence live cell imaging capability