Silica-Based Platform Decorated with Conjugated Polymer Dots and Prussian Blue for Improved Photodynamic Cancer Therapy.

To advance cancer treatment, we have developed a novel composite material consisting of conjugated polymer dots (CPDs) and Prussian blue (PB) particles, which were immobilized on, and encapsulated within, silica particles, respectively. The CPDs functioned as both a photosensitizer and a photodynamic agent, and the PB acted as a photothermal agent. The silica platform provided a biocompatible matrix that brought the two components into close proximity. Under laser irradiation, the fluorescence from the CPDs in the composite material enabled cell imaging and was subsequently converted to thermal energy by PB. This efficient energy transfer was accomplished because of the spectral overlap between the emission of donor CPDs and the absorbance of acceptor PB. The increase in local temperature in the cells resulted in a significant increase in the amount of reactive oxygen species (ROS) generated by CPDs, in which their independent use did not produce sufficient ROS for cancer cell treatment. To assess the impact of the enhanced ROS generation by the composite material, we conducted experiments using cancer cells under 532 nm laser irradiation. The results showed that with the increase in local temperature, the generated ROS increased by 30% compared with the control, which did not contain PB. When the silica-based composite material was positioned at the periphery of the tumor for 120 h, it led to a much slower tumor growth than other materials tested. By using a CPD-based photodynamic therapy platform, a new simplified approach to designing and preparing cancer treatments could be achieved, which included photothermal PB-assisted enhanced ROS generation using a single laser. This advancement opens up an exciting new opportunity for effective cancer treatment.

Fabrication of a porous polyacrylonitrile nanofiber adsorbent for removing radioactive 60Co.

A Co2+ adsorbent was prepared using electrospun porous polyacrylonitrile (PAN) nanofibers, featuring easy recovery for reuse compared with a nanoparticle-based adsorbent. As an efficient ligand for Co2+, ethylenediaminetetraacetic acid (EDTA) was introduced on the surface of porous PAN nanofibers with the aid of a branched polyethyleneimine (PEI) linker to obtain an adsorbent with carboxylic acid groups. On the adsorbent surface, the carboxylic acid and amine groups from EDTA could adsorb Co2+ via ion exchange and chelation, and amine groups from PEI that remained after EDTA functionalization played a role in coordinating Co2+. The amine and carboxylic acid groups were simultaneously involved in the adsorption on the surface, making it possible to remove Co2+ over a wide pH range. An investigation of the adsorption isotherms and kinetics of the nanofibrous adsorbent indicated that monolayer chemisorption was achieved with a maximum Co2+ adsorption capacity of 8.32 mg/g. In addition, radioactive 60Co was efficiently removed by the adsorbent with a removal extent of more than 98%. Considering the easy separation from Co2+ solution and regeneration of the nanofibrous adsorbent and its availability in a wide pH range, the adsorbent has great advantages in practical applications.

Cesium ion adsorption and desorption on electrospun mesoporous silica nanofibers immobilized with Prussian blue.

To fabricate an efficient Cs ion adsorbent and prevent unexpected loss of Prussian blue (PB) colloidal particles during use, PB was immobilized on the surface of electrospun mesoporous silica nanofibers (MSFs) via a newly developed method of double exposure to Fe (III) ions. To introduce PB on MSFs, the MSFs were functionalized with ethylenediamine moiety to bind to Fe (III) ions, which would firmly anchor PB. MSFs were pretreated with Fe (III) ions and exposed to K4 [Fe(II) (CN)6] to form PB. We found that this process did not provide a sufficient PB amount on the MSFs. To increase the PB amount, after initial PB formation, the MSFs were treated with Fe (III) ions again so that the unreacted K4 [Fe(II) (CN)6] remaining on the MSFs could become PB. An investigation of the adsorption isotherms and kinetics of the nanofibrous adsorbent indicated that monolayer chemisorption had occurred. The maximum Cs ion adsorption capacity using the method of double exposure to Fe (III) ions was determined to be 14.66 mg/g, which was higher by a factor of 2.24 than the case that was not prepared by this method. Cs ions were selectively adsorbed over other cations and could be removed in both acidic and basic conditions, presumably because of the robust MSFs.

Fluorescence Modulation of Conjugated Polymer Nanoparticles Embedded in Poly(N-Isopropylacrylamide) Hydrogel.

A series of conjugated polymers (CPs) emitting red, green, and blue (RGB) fluorescence were synthesized via the Suzuki coupling polymerization. Polymer dots (Pdots) were fabricated by the reprecipitation method from corresponding CPs, in which the Pdot surface was functionalized to have an allyl moiety. The CP backbones were based on the phenylene group, causing the Pdots to show identical ultraviolet-visible absorption at 350 nm, indicating that the same excitation wavelength could be used. The Pdots were covalently embedded in poly(N-isopropylacrylamide) (PNIPAM) hydrogel for further use as a thermoresponsive moiety in the polymer hydrogel. The polymer hydrogel with RGB emission colors could provide thermally reversible fluorescence changes. The size of the hydrogel varied with temperature change because of the PNIPAM's shrinking and swelling. The swollen and contracted conformations of the Pdot-embedded PNIPAM enabled on-and-off fluorescence, respectively. Fluorescence modulation with 20 to 80% of the hydrogel was possible via thermoreversibility. The fluorescent hydrogel could be a new fluorescence-tuning hybrid material that changes with temperature.

Visible-Light-Driven Asymmetric TiO2-Based Photocatalytic Micromotor Hybridized with a Conjugated Polyelectrolyte and Glucose Oxidase.

We fabricated a TiO2-based micromotor that was asymmetrically decorated with a water-soluble conjugated polymer (WSP) on one hemisphere and glucose oxidase (GOx) on the opposite hemisphere. The WSP, which had photocatalytic activity for H2O2 decomposition, enabled motion of the micromotor under visible light. The GOx on the other hemisphere of the micromotor decomposed glucose to produce H2O2 and enabled motion of the micromotor without light irradiation. In addition, WSP and GOx were attached to TiO2 by chemical bonds, providing stability during use. As a result, the micromotor could move by self-generating H2O2 for its own fuel by consuming glucose even without photoirradiation. The micromotor could move faster than without visible light irradiation through the synergistic decomposition of glucose and H2O2 under visible light by the diffusiophoretic mechanism with a speed of 7.49 µm/s.

Unusual fluorescence of o-phenylazonaphthol derivatives with aggregation-induced emission and their use in two-photon cell imaging.

o-Phenylazonaphthol (o-PAN) derivatives including 6-bromo-1-((4-bromophenyl)diazenyl)naphthalen-2-ol (AN-Br-OH) and 1-phenylazo-2-naphthol (AN-OH, known as Sudan I (Color Index 12055)) were synthesized to investigate their fluorogenic behaviors, in which their aggregated-induced emission (AIE) is reported. The o-PANs showed a two-photon absorption. The protection of hydroxyl groups in o-PANs was used for fluorescence imaging of esterase-expressed HepG2 cells, which is potentially suitable for sensing and two-photon cell imaging applications.

A Single-Benzene-Based Fluorophore: Optical Waveguiding in the Crystal Form.

A single-benzene-based, blue-emissive diethyl 2,5-dihydroxyterephthalate (DDT) was prepared by Fischer esterification of 2,5-dihydroxyterephthalic acid (DHT) and ethanol. The strong fluorescence in both the solution and the solid state from such a simple framework stemmed from the push-pull structure of the electron-donating hydroxy groups and the accepting carbonyl groups, as well as structural planarity from intramolecular hydrogen bonds. The strong intermolecular hydrogen bonds enabled DDT to crystallize easily. The color CCD imaging technique showed efficient 1D optical waveguiding with a large optical loss coefficient of 0.15 dB/µm. DDT has potential application in optical sensors, photonic devices, and optoelectronic communication, because of its highly ordered structure and light-emitting ability.

Conjugated polymer dots-on-electrospun fibers as a fluorescent nanofibrous sensor for nerve gas stimulant.

A novel chemical warfare agent sensor based on conjugated polymer dots (CPdots) immobilized on the surface of poly(vinyl alcohol) (PVA)-silica nanofibers was prepared with a dots-on-fibers (DoF) hybrid nanostructure via simple electrospinning and subsequent immobilization processes. We synthesized a polyquinoxaline (PQ)-based CP as a highly emissive sensing probe and employed PVA-silica as a host polymer for the elctrospun fibers. It was demonstrated that the CPdots and amine-functionalized electrospun PVA-silica nanofibers interacted via an electrostatic interaction, which was stable under prolonged mechanical force. Because the CPdots were located on the surface of the nanofibers, the highly emissive properties of the CPdots could be maintained and even enhanced, leading to a sensitive turn-off detection protocol for chemical warfare agents. The prepared fluorescent DoF hybrid was quenched in the presence of a chemical warfare agent simulant, due to the electron transfer between the quinoxaline group in the polymer and the organophosphorous simulant. The detection time was almost instantaneous, and a very low limit of detection was observed (∼1.25 × 10(-6) M) with selectivity over other organophosphorous compounds. The DoF hybrid nanomaterial can be developed as a rapid, practical, portable, and stable chemical warfare agent-detecting system and, moreover, can find further applications in other sensing systems simply by changing the probe dots immobilized on the surface of nanofibers.

Conjugated poly(fluorene-quinoxaline) for fluorescence imaging and chemical detection of nerve agents with its paper-based strip.

Conjugated polymer of poly(fluorene-co-quinoxaline) was synthesized via Suzuki coupling polymerization. The emission color of the polymer can be tuned depending on the concentration of the polymer in solution. A low-energy bandgap is observed both in the concentrated solution and in the solid state, caused by aggregation of the polymer chains, resulting in long wavelength emission from the quinoxaline moiety, while short wavelength emission can be seen in diluted, well-dissolved solution. The presence of quinoxaline units enables us to demonstrate fluorescence switching and imaging. Paper-based strips containing the polymer are prepared via simple immersion of filter paper in the polymer solution for practical use in the detection of nerve agents. The emission of the paper-based strip is quenched upon exposure to diethyl chlorophosphate (DCP), a nerve agent simulant, and the initial emission intensity can be almost restored by treatment with aqueous sodium hydroxide solution, making a possible reversible paper-based sensor.

Simple technique for spatially separated nanofibers/nanobeads by multinozzle electrospinning toward white-light emission.

Electrospun, emission color-tunable nanofibrous sheets were fabricated by multinozzle electrospinning equipped with a secondary electrode for the preparation of white-emissive sheets under a single excitation source, manipulating energy transfer between dyes. By control of the concentration of commercially available red, green, and blue dyes in the matrix polymer [poly(methyl methacrylate)], emission color tuning can be easily accomplished because each dye is located in spatially separated fibers to maintain enough distance to prevent or suppress energy transfer, allowing white-light emission. The application of dye separation for the white-light emission upon excitation with a blue light-emitting-diode lamp is demonstrated, indicative of its potential application for the easy and facile tuning of fluorescence color toward flexible illumination.