Kaiwen Chang

Ratiometric Luminescent Detection of Bacterial Spores with Terbium Chelated Semiconducting Polymer Dots

We report a ratiometric fluorescent sensor based on semiconducting polymer dots chelated with terbium ions to detect bacterial spores in aqueous solution. Fluorescent polyfluorene (PFO) dots serve as a scaffold to coordinate with lanthanide ions that can be sensitized by calcium dipicolinate (CaDPA), an important biomarker of bacterial spores. The absorption band of PFO dots extends to deep UV region, allowing both the reference and the sensitizer can be excited with a single wavelength (~275 nm). The fluorescence of PFO remains constant as a reference, while the Tb(3+) ions exhibit enhanced luminescence upon binding with DPA. The sharp fluorescence peaks of β-phase PFO dots and the narrow-band emissions of Tb(3+) ions enable ratiometric and sensitive CaDPA detection with a linear response over nanomolar concentration and a detection limit of ~0.2 nM. The Pdots based sensor also show excellent selectivity to CaDPA over other aromatic ligands. Our results indicate that the Tb(3+) chelated Pdots sensor is promising for sensitive and rapid detection of bacterial spores.

Amplified Singlet Oxygen Generation in Semiconductor Polymer Dots for Photodynamic Cancer Therapy

This paper described the energy-transfer amplified singlet oxygen generation in semiconductor polymer dots (Pdots) for in vitro and in vivo photodynamic therapy. Hydrophobic photosensitizer tetraphenylporphyrin was facilely doped in the nanoparticles consisting of densely packed semiconductor polymers. Optical characterizations indicated that the fluorescence of Pdots was completely quenched by the photosensitizer, yielding an energy transfer efficiency of nearly 100% and singlet-oxygen generation quantum yield of ∼50%. We evaluated the cellular uptake, dark toxicity, and photodynamic therapy of the Pdot photosensizer in human gastric adenocarcinoma cells. The in vitro studies indicated that cancer cells were efficiently destroyed at very low dose of the Pdots such as 1 μg/mL by using the light dose of 90 J/cm(2), which is considerably less than that in clinical practice. The antitumor effect of the Pdots was further evaluated in vivo with human gastric adenocarcinoma xenografts in Balb/c nude mice, which show that the xenograft tumors were significantly inhibited and eradicated in some cases. Our results indicate the energy transfer amplified Pdot platforms have great therapeutic potential for treating malignant cancers.

Incorporation of Porphyrin to π-Conjugated Backbone for Polymer-Dot-Sensitized Photodynamic Therapy

The photosensitizers used in photodynamic therapy are mainly based on porphyrin derivatives. However, clinical applications encounter several limitations regarding photosensitizers such as their low absorption coefficients, poor water-solubility, and leaching from delivery carriers. Here, we describe covalent incorporation of porphyrin in conjugated polymer backbone for development of efficient polymer-dot photosensitizer. Spectroscopic characterizations revealed that the light-harvesting polymer dominantly transfer the excitation energy to the porphyrin unit, yielding efficient singlet oxygen generation for photodynamic therapy. The polymer dots (Pdots) also possess excellent stability that overcomes the photosensitizer leaching problem as encountered in other nanoparticle carriers. In vitro cytotoxicity and photodynamic efficacy of the Pdots were evaluated in MCF-7 cells by in vitro assay, indicating that the Pdots can efficiently damage cancer cells. In vivo photodynamic therapy by using the Pdots was further investigated with xenograft tumors in Balb/c nude mice, which show that the tumors were significantly inhibited or eradicated in certain cases. The high-yield singlet oxygen generation and excellent stability of porphyrin-incorporated Pdots are promising for photodynamic treatment of malignant tumors.

Covalent Patterning and Rapid Visualization of Latent Fingerprints with Photo-Cross-Linkable Semiconductor Polymer Dots

Fingerprint imaging and recognition represent the most important approach in personal identification. Here we designed and synthesized oxetane-functionalized semiconductor polymer dots (Ox-Pdots) for covalent patterning and rapid visualization of latent fingerprints. The high fluorescence brightness, large Stokes shift, and excellent surface properties of the Ox-Pdots lead to fingerprint imaging with high sensitivity and resolution. Fingerprint ridge structures with the first, second, and third levels of details were clearly developed within minutes. The method was facile and robust for visualization of fingerprints on various surfaces including glass, metal, and plastics. Moreover, the oxetane groups in the Ox-Pdots undergo cross-linking reactions induced by a short-time UV irradiation, yielding 3-D intermolecular polymer network. The resulting fingerprint patterns exhibit unparalleled stability against rigorous treatment, as compared to those by traditional Pdots. Our results demonstrate that the Ox-Pdots hold great promise for latent fingerprint imaging and fluorescence anticounterfeiting applications.

Conjugated polymer dots for ultra-stable full-color fluorescence patterning.

Stable full-color fluorescence patterning are achieved by multicolor polymer-dot inks. The fluorescent patterns show extraordinary stability upon various treatments, offering a superior combination of bright fluorescence, excellent photostability, chemical resistance, and eco-friendship.

Enhanced Phototherapy by Nanoparticle-Enzyme via Generation and Photolysis of Hydrogen Peroxide

Light has been widely used for cancer therapeutics such as photodynamic therapy (PDT) and photothermal therapy. This paper describes a strategy called enzyme-enhanced phototherapy (EEPT) for cancer treatment. We constructed a nanoparticle platform by covalent conjugation of glucose oxidase (GOx) to small polymer dots, which could be persistently immobilized into a tumor. While the malignant tumors have high glucose uptake, the GOx efficiently catalyzes the glucose oxidation with simultaneous generation of H2O2. Under light irradiation, the in situ generated H2O2 was photolyzed to produce hydroxyl radical, the most reactive oxygen species, for killing cancer cells. In vitro assays indicated that the cancer cells were destroyed by using a nanoparticle concentration at 0.2 μg/mL and a light dose of ∼120 J/cm2, indicating the significantly enhanced efficiency of the EEPT method when compared to typical PDT that requires a photosensitizer of >10 μg/mL for effective cell killing under the same light dose. Furthermore, remarkable inhibition of tumor growth was observed in xenograft-bearing mice, indicating the promise of the EEPT approach for cancer therapeutics.

Photo-Cross-Linkable Polymer Dots with Stable Sensitizer Loading and Amplified Singlet Oxygen Generation for Photodynamic Therapy

Photodynamic therapy (PDT) is a promising treatment modality for clinical cancer therapy. However, the therapeutic effect of PDT is strongly dependent on the property of photosensitizer. Here, we developed photo-cross-linkable semiconductor polymer dots doped with photosensitizer Chlorin e6 (Ce6) to construct a nanoparticle platform for photodynamic therapy. Photoreactive oxetane groups were attached to the side chains of the semiconductor polymer. After photo-cross-linking reaction, the Ce6-doped Pdots formed an interpenetrated structure to prevent Ce6 leaching out from the Pdot matrix. Spectroscopic characterizations revealed an efficient energy transfer from the polymer to Ce6 molecules, resulting in amplified generation of singlet oxygen. We evaluated the cellular uptake, cytotoxicity, and photodynamic effect of the Pdots in gastric adenocarcinoma cells. In vitro photodynamic experiments indicated that the Ce6-doped Pdots (∼10 μg/mL) effectively killed the cancer cells under low dose of light irradiation (∼60 J/cm2). Furthermore, in vivo photodynamic experiments were carried out in tumor-bearing nude mice, which indicated that the Pdot photosensitizer apparently suppressed the growth of solid tumors. Our results demonstrate that the photo-cross-linkable Pdots doped with photosensitizer are promising for photodynamic cancer treatment.

Silica-encapsulated semiconductor polymer dots as stable phosphors for white light-emitting diodes

Semiconductor polymer dots (Pdots) were encapsulated into a SiO2 matrix to form fluorescent nanocomposites using a modified Stober method. Significantly, the photostability and thermal stability of the nanocomposites were greatly improved as compared to those of pure Pdots. The luminescent nanocomposites combined with blue LEDs result in white-light emitting devices with a high color-rendering index.

Engineering a protein-based nanoplatform as an antibacterial agent for light activated dual-modal photothermal and photodynamic therapy of infection in both the NIR I and II windows

The rapid rise of drug- and multi-drug resistant pathogenic bacteria constitutes an increasing risk to global public health. Thus, it is essential to develop new agents and/or strategies to overcome the antibiotic resistance crisis. Herein, ultra-small protein-based nanoparticles (NPs) with absorption covering both the near-infrared (NIR) I and II windows were constructed as novel antibacterial agents, which introduced a killing strategy utilizing the synergistic photothermal and photodynamic effects. The agent engineered by the conjugation of Ce6 molecules to ultra-small hydrophilic protein-modified copper sulfide NPs can transfer light energy into thermal energy for photothermal therapy and produce reactive oxygen species for photodynamic therapy. Under the irradiation of both NIR I and II lasers, the agent demonstrated a potent bacteria killing activity on both Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) in vitro bacteria with high efficacy and safety. Furthermore, the as-prepared NPs also displayed an efficient in vivo bactericidal activity in a mouse model as monitored by measuring the photoacoustic signals of the blood vessels around the infection site. Consequently, leveraging the synergistic photothermal and photodynamic effects, the as-designed ultra-small NIR NPs may eliminate the emergence of drug resistance due to the mechanical destruction of the bacteria cell, thus representing a promising approach to control the antibiotic resistance crisis.