Controllable photodynamic performance via an acidic microenvironment based on two-dimensional metal-organic frameworks for photodynamic therapy

Photodynamic therapy(PDT)is a widely-used technology for cancer therapy,but conventional photosensitizers still face some drawbacks,such as hydrophobicity,inadequate pharmacokinetics,low cell/tissue specificity,and uncontrollable photodynamic performance during the therapeutic process.Herein,we present a controllable photodynamic performance based on two-dimensional metal-organic frameworks(2D Zn-TCPP MOF)that displayed a week PDT effect under a neutral environment upon exposure to a 660 nm laser due to the degeneracy of Q bands of TCPP.However,the 2D Zn-TCPP MOF showed a significantly enhanced PDT effect in an acidic environment under irradiation with a 660 nm laser due to the released TCPP from decomposed MOF structure.From the in vitro outcomes,the 2D Zn-TCPP MOF showed controllable photodynamic performance from neutral to acidic environments.Due to the acidic tumor microenvironment,the 2D Zn-TCPP MOF presented the strongest antitumor effect in vivo under irradiation with a 660 nm laser.This work offers a promising strategy to develop a next-generation photosensitizer.     

Aptameric enzyme subunit for biosensing based on enzymatic activity measurement

The aptameric enzyme subunit (AES), which is a DNA aptamer composed of an enzyme-inhibiting aptamer and a target molecule-binding aptamer, has been developed for the biosensing of target molecules. We used a thrombin-inhibiting aptamer as the aptamer that inhibits enzymatic activity. The thrombin-inhibiting aptamer folds into the G-quartet structure, which plays an important role in its inhibitory activity. As a target molecule-binding aptamer, an adenosine-binding aptamer was inserted into the G-quartet structure of the thrombin-inhibiting aptamer to enable the change of the G-quartet structure upon the recognition of adenosine. In the present study, the change in the G-quartet structure led to a change in the thrombin inhibition activity, and adenosine was successfully detected by measuring the thrombin activity in a homogeneous solution without bound/free separation. We constructed two kinds of AESs; one of the structures is universal and can be used for designing any target molecule-binding aptamer. Since the enzyme activity is measured, AESs enable the simple and high-sensitivity detection of target molecules in a homogeneous assay.     

Microsurface plasmon resonance biosensing based on gold-nanoparticle film

We use a gold-nanoparticle coated film to achieve highly spatially resolved biosensing that is based on localized surface-plasmon resonance. Unlike the planar gold film employed for conventional surface-plasmon resonance sensing, the gold-nanoparticle film relies exclusively on shifting of the peak extinction wavelength for detection of biointeraction and does not depend critically on the angle of incidence. These characteristics permit integration of surface-plasmon resonance with large-numerical-aperture optics to achieve biosensing with high sensitivity and spatial resolution as high as 25 microm.     

Novel biosensing platform based on self-assembled supramolecular hydrogel

The supramolecular hydrogel self-assembled from α-cyclodextrin (α-CD) and an amphiphilic triblock copolymer was used for the first time as a biosensing platform by the in-situ incorporation of horseradish peroxidase and polyaniline (PANI) nanoparticles. It was found that the used triblock copolymer could disperse well PANI nanoparticles in aqueous system and then interact with α-CD in the presence of horseradish peroxidase for the formation of supramolecular hydrogel composite. The content of PANI nanoparticles was found to affect the gelation time and gel strength. The circular dichroism analyses showed that the entrapped horseradish peroxidase could retain its native conformation. By electrochemical experiments, the incorporated PANI nanoparticles were confirmed to improve the current response and enzymatic activity, and the fabricated biosensor was found to provide a fast amperometric response to hydrogen peroxide.     

Nanoparticles for two-photon photodynamic therapy in living cells

We describe here a nontoxic two-photon photodynamic nanoparticle platform and its cellular application. We demonstrate that the dye's potential toxicity can be circumvented by its permanent encapsulation into a biocompatible nanoparticle polymer matrix; this was examined by dye leaching experiments and confirmed by cell uptake experiments. Infrared two-photon nanoplatform phototoxicity was demonstrated for rat C6 glioma cells, while the controls showed no dark toxicity for these living cells.     

Electrochemical biosensing based on polypyrrole/titania nanotube hybrid

The glucose oxidase (GOD) modified polypyrrole/titania nanotube enzyme electrode is fabricated for electrochemical biosensing application. The titania nanotube array is grown directly on a titanium substrate through an anodic oxidation process. A thin film of polypyrrole is coated onto titania nanotube array to form polypyrrole/titania nanotube hybrid through a normal pulse voltammetry process. GOD-polypyrrole/titania nanotube enzyme electrode is prepared by the covalent immobilization of GOD onto polypyrrole/titania nanotube hybrid via the cross-linker of glutaraldehyde. The morphology and microstructure of nanotube electrodes are characterized by field emission scanning electron microscopy and Fourier transform infrared analysis. The biosensing properties of this nanotube enzyme electrode have been investigated by means of cyclic voltammetry and chronoamperometry. The hydrophilic polypyrrole/titania nanotube hybrid provides highly accessible nanochannels for GOD encapsulation, presenting good enzymatic affinity. As-formed GOD-polypyrrole/titania nanotube enzyme electrode well conducts bioelectrocatalytic oxidation of glucose, exhibiting a good biosensing performance with a high sensitivity, low detection limit and wide linear detection range.     

Photonic devices based on preferential etching

We introduce a design concept of optical waveguides characterized by a practical and reproducible process based on preferential etching of crystalline silicon substrates. Low-loss waveguides, spot-size converters, and power dividers have been obtained with polymers. We have also aligned liquid crystals in the waveguides and demonstrated guided propagation. Therefore this technology is a suitable platform for soft-matter photonics and heterogeneous integration.     

Amperometric biosensing systems based on motility and gravitaxis of flagellate algae for aquatic risk assessment

Electrochemical biosensing systems for toxic substances were developed on the basis of motility and negative gravitaxis of the unicellular flagellate Chlamydomonas reinhardtii. Changes in the flagellar movement of the flagellates in response to three toxic chemicals, toluene, copper(II) sulfate, and nickel(II) chloride, were monitored as changes in the redox currents for a coexisiting redox marker. The gravitaxis-based flagellate biosensing system was more sensitive to toluene than the motility-based system. A thin-layer flagellate biosensor was also developed. In comparison with the conventional algal biosensors monitoring the photosynthetic activity, the gravitaxis-based thin-layer sensor was more sensitive by more than 1 order of magnitude.     

Self-powered photoelectrochemical biosensing platform based on Au NPs@ZnO nanorods array

Photoanodes, which are used in photoelectrochemical (PEC) water splitting, have been shown to be applicable in the construction of a PEC biosensing platform. This was realized by replacing water oxidization with oxidation of an appropriate test molecule. Here, we have demonstrated the feasibility of adopting photoanodes consisting of zinc oxide nanorods arrays decorated with plasmonic gold nanoparticles (Au NPs@ZnO NRs) for the self-powered PEC bioanalysis of glutathione (GSH) in phosphate-buffered saline (PBS) at an applied bias potential of 0 V vs. Ag/AgCl. This heterostructure exhibited enhanced PEC properties because of the introduction of the Au/ZnO interface. Under visible light illumination, hot electrons from surface-plasmon resonance (SPR) at the Au NP surface were injected into the adjacent ZnO and subsequently driven to the photocathode. Under ultraviolet (UV) light illumination, the photogenerated electrons in ZnO tended to transfer to the fluorine-doped tin oxide due to the step-wise energy band structure and the upward energy band bending at the ZnO/ electrolyte interface. These results indicate that plasmonic metal/semiconductor heterostructure photoanodes have great potential for self-powered PEC bioanalysis applications and extended field of other photovoltaic beacons.

Open image in new window

     

New design of textile light diffusers for photodynamic therapy

A homogeneous and reproducible fluence delivery rate during clinical photodynamic therapy (PDT) plays a determinant role in preventing under- or overtreatment. PDT applied in dermatology has been carried out with a wide variety of light sources delivering a broad range of more or less adapted light doses. Due to the complexities of the human anatomy, these light sources do not in fact deliver a uniform light distribution to the skin. Therefore, the development of flexible light sources would considerably improve the homogeneity of light delivery. The integration of plastic optical fiber (POF) into textile structures could offer an interesting alternative.In this article, a textile light diffuser (TLD) has been developed using POF and Polyester yarns. Predetermined POF macrobending leads to side emission of light when the critical angle is exceeded. Therefore, a specific pattern based on different satin weaves has been developed in order to improve light emission homogeneity and to correct the decrease of side emitted radiation intensity along POF. The prototyped fabrics (approximately 100 cm²: 5 × 20 cm) were woven using a hand loom, then both ends of the POF were coupled to a laser diode (5 W, 635 nm).The fluence rate (mW/cm²) and the homogeneity of light delivery by the TLD were evaluated. Temperature evolution, as a function of time, was controlled with an infrared thermographic camera. When using a power source of 5 W, the fluence rate of the TLD was 18 ± 2.5 mw/cm². Due to the high efficiency of the TLD, the optical losses were very low. The TLD temperature elevation was 0.6 °C after 10 min of illumination. Our TLD meets the basic requirements for PDT: homogeneous light distribution and flexibility. It also proves that large (500 cm²) textile light diffusers adapted to skin, but also to peritoneal or pleural cavity, PDTs can be easily produced by textile manufacturing processes.     

A laser unit for photodynamic therapy and robot-assisted microsurgery in dentistry

Results are presented of photochemical experiments with an IR-laser unit for microsurgery and photodynamic therapy in dentistry. The efficiency of direct generation of singlet oxygen in model organic media in the continuous-wave and pulsed nanosecond modes is examined. The unit can serve both as an independent instrument and as a part of a complex for robot-assisted surgery and dentistry.     

Photonic crystals based on natural oceanic biominerals

The photonic-crystal properties of natural biomineral crystals—siliceous basal spicules of glass sea sponges—have been studied for the first time. It is shown that the periodic arrangement of concentric cylindrical layers composed of nanodimensional silica particles leads to the formation of forbidden photonic bands.     

Modeling of photosensitizer fluorescence emission and photobleaching for photodynamic therapy dosimetry

Photon diffusion theory was used to model photobleaching and tissue necrosis resulting from broad-beam therapeutic light irradiation of tissue containing a photosensitizer. The photosensitizer fluorescence signal at the tissue surface was simulated with both broad-beam and pencil-beam excitation. The relationship between the decreasing fluorescence signal and the increasing depth of tissue photodynamic damage during treatment was examined. By analyzing spatially resolved fluorescence measured at the tissue surface in terms of an equivalent virtual point or planar source of fluorescence within the tissue, predictions of necrosis depth that are insensitive to a range of initial treatment parameters were shown to be possible. Preliminary measurements in tissue-simulating phantoms supported the main theoretical findings. The potential value and feasibility of this technique for photodynamic therapy dosimetry are discussed.     

A new multifunctional phosphor based on yttrium oxysulfide

Novel one-component multifunctional phosphors with the general formula Y_1.975?x Yb_0.025Er _x O₂S:Ti_0.12Mg_0.04 have been prepared via sulfiding of rare-earth, titanium, and magnesium oxides in melts of different sulfur-containing compounds of alkali metals and mineralizers under an SO₂ atmosphere. The phosphors combine a long afterglow with anti-Stokes luminescence and offer unique optical emission properties: yellow luminescence under cw UV excitation with a broadband afterglow around λ_max = 626 nm, predominantly narrow-band green anti-Stokes luminescence with λ_max = 546 nm under 0.96-μm IR excitation, and red anti-Stokes luminescence with λ_max = 670 nm under 1.55-μm IR excitation. Owing to this combination of luminescent properties, the phosphors have considerable potential for practical application.     

Positively charged calcium phosphate/polymer nanoparticles for photodynamic therapy

The charge of nanoparticles influences their ability to pass through the cellular membrane, and a positive charge should be beneficial. The negative charge of calcium phosphate nanoparticles with an inner shell of carboxymethyl cellulose (CMC) was reversed by adding an outer shell of poly(ethyleneimine) (PEI) into which the photoactive dye 5,10,15,20-tetrakis(3-hydroxyphenyl)-porphyrin (mTHPP) was loaded. The aqueous dispersion of the nanoparticles was used for photodynamic therapy with HT29 cells (human colon adenocarcinoma cells), HIG-82 cells (rabbit synoviocytes), and J774A.1 cells (murine macrophages). A high photodynamic activity (killing) together with a very low dark toxicity was observed for HIG-82 and for J774.1 cells at 2 μM dye concentration. The killing efficiency was equivalent to the pure photoactive dye that, however, needs to be administered in alcoholic solution.     

Spectral matching technology for light-emitting diode-based jaundice photodynamic therapy device

The objective of this paper is to obtain the spectrum of light-emitting diode (LED)-based jaundice photodynamic therapy device (JPTD), the bilirubin absorption spectrum in vivo was regarded as target spectrum. According to the spectral constructing theory, a simple genetic algorithm as the spectral matching algorithm was first proposed in this study. The optimal combination ratios of LEDs were obtained, and the required LEDs number was then calculated. Meanwhile, the algorithm was compared with the existing spectral matching algorithms. The results show that this algorithm runs faster with higher efficiency, the switching time consumed is 2.06?s, and the fitting spectrum is very similar to the target spectrum with 98.15% matching degree. Thus, blue LED-based JPTD can replace traditional blue fluorescent tube, the spectral matching technology that has been put forward can be applied to the light source spectral matching for jaundice photodynamic therapy and other medical phototherapy.