Cr(VI) anion-imprinted polymer synthesized on mesoporous silicon via synergistic action of bifunctional monomers for precise identification and separation of Cr(VI) from aqueous solution by fixed-bed adsorption.

The novel Cr(VI) anion-imprinted polymer (Cr(VI)-IIP) was prepared by a surface imprinting technique with bifunctional monomers pre-assembly system based on mesoporous silicon (SBA-15). The synthesized Cr(VI)-IIP was characterized by Fourier transmission infrared spectra (FT-IR), energy dispersive spectrometer (EDS), scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray powder diffractometer, N2 adsorption-desorption and thermogravimetric analysis (TGA), proving to be with a highly ordered mesoporous structure, as well as favorable thermal stability. The saturated adsorption amount was 96.32 mg/g, which was 2.7 times higher than that of non-imprinted polymer (NIP). Kinetic experiments showed that the adsorption equilibrium state was obtained within 70 min. In addition, in the selectivity experiments, Cr(VI)-IIP exhibited strong specific recognition ability for Cr(VI) and could realize the separation of Cr(VI) and Cr(III) from an aqueous solution. The dynamic adsorption experiments exhibited that the dynamic adsorption efficiency of Cr(VI)-IIP was as high as 71.57%. Meanwhile, the dynamic regeneration experiments showed that the adsorption amount of Cr(VI)-IIP did not decrease significantly after repeating for five times. All of the findings suggested that Cr(VI)-IIP could achieve precise identification as well as efficient separation of Cr(VI) from aqueous solution.

Ag NPs/PMMA nanocomposite as an efficient platform for fluorescence regulation of riboflavin.

The fluorescence detection platform has broad application in many fields. In this paper, we report a simple and efficient fluorescence detection platform based on the synergistic effects of Ag nanoparticles (Ag NPs) and polymethylmethacrylate (PMMA). Ag NPs were introduced to realize the plasmon enhancement fluorescence and a thin PMMA layer was used to adjust the distance between Ag NPs and riboflavin. The thin PMMA layer not only enhances the fluorescence by enhancing adhesion of substrate, but also optimizes the plasmon enhancement fluorescence effect by serving as the spacer. The fluorescence enhancement factor based on this platform shows a trend of increasing with the decrease of the concentration of riboflavin, and the detection of riboflavin is realized based on this feature, the lowest detectable concentration is as low as 0.27 µM. In addition to the detection based on plasmon enhancement fluorescence, the detection of riboflavin at low concentrations can also be realized by the shift and broadening of the fluorescence peak due to the Ag NPs. The combination of the two ways of plasmon enhancement fluorescence and shift of the fluorescence spectra is used for the detection of riboflavin. These results show that the platform has great potential applications in the field of detection and sensing.

Fluorescein isothiocyanate-doped conjugated polymer nanoparticles for two-photon ratiometric fluorescent imaging of intracellular pH fluctuations.

Herein, we report a two-photon ratiometric fluorescent pH nanosensor based on conjugated polymer poly(9,9-di-n-octylfluorenyl-2,7-diyl) (PFO) nanoparticles loaded with pH-sensitive fluorescein isothiocyanate (FITC) for intracellular pH monitoring. The obtained nanosensor (FITC-PFO NPs) possesses high sensitivity, excellent stability, good reversibility, favorable two-photon excitability and low cytotoxicity. The ratiometric fluorescence of FITC and PFO (F517/F417) in FITC-PFO NPs solution shows an efficient pH-sensitive response over the pH range from 3 to 10 (pKa = 6.43) under two-photon excitation. Additionally, the FITC-PFO NPs is successfully applied for ratiometric imaging of intracellular pH and its fluctuation in both one-photon and two-photon excitation modes. Overall, the two-photon pH nanosensor based on FITC-PFO NPs exhibits great potential in crucial physiological and biological processes related to intracellular pH fluctuations.

Fluorescence copolymer-based dual-signal monitoring tyrosinase activity and its inhibitor screening via blue-green emission transformation.

Tyrosinase (TYR) is a crucial enzyme in melanin metabolism and catecholamine production, its abnormal overexpression is closely associated with many human diseases involving melanoma cancer, vitiligo, Parkinson's disease and so on. Herein, a dual-signal fluorescence sensing system for monitoring TYR activity is constructed depending on the transformation of blue-green fluorescence emission of copolymer. The developed sensing system is based on TYR catalyzing the hydroxylation of mono-phenol to o-diphenol and the conversion of fluorescence copolymer (FCP) blue emission (430 nm) and green emission (535 nm) in the presence of PEI. In the system, both blue and green emission exhibit a high selectivity and sensitivity (S/B up to 300 and 30 for blue and green emission, respectively) toward TYR in the range from 0.5 to 2.5 U/mL with the detection limit of 0.002 U/mL and 0.06 U/mL, respectively. Additionally, this assay is used to detect TYR in human serum with excellent recovery even at 30% human serum concentrations. Furthermore, it still has been successfully applied to TYR inhibitor screening by taking kojic acid as a model. We believe that our developed sensor has great potential application in TYR-associated disease diagnosis and treatment and drug discovery.

Chlorin e6-1,3-diphenylisobenzofuran polymer hybrid nanoparticles for singlet oxygen-detection photodynamic abaltion.

A dual-functional nanosysterm is developed by means of Chlorin e6 (Ce6) as photosensitizer and 1,3-Diphenylisobenzofuran (DPBF) as fluorescent singlet oxygen (1O2) probe. Under 660 nm laser irradiation, Ce6 exhibites efficient 1O2 generation, and subsequently the production of 1O2 is assessed by the ratiometric fluorescence of PFO and DPBF under one-photon and two-photon excitation mode. The nanoparticles with excellent biocompatibility can be internalized into Hela cells and applied for tumor treatment. For intracellular PDT, the nanoparticles perform a high phototoxicity, while the PDT proccess can be evaluated in time by monitoring fluorescence signals of DPBF. This theranostic nanosysterm provides a facile strategy to fabricate 1O2-detection PDT, which can realize accurate and efficient photodynamic therapy based on singlet oxygen detection.

Blue and green emission-transformed fluorescent copolymer: Specific detection of levodopa of anti-Parkinson drug in human serum.

Levodopa, commonly used anti-Parkinson drugs in the clinic, is the most significant prodrug of dopamine that plays important roles in the treatment of Parkinson's disease. Therefore, monitoring content of levodopa of anti-parkinson drugs in human serum is extremely necessary. Herein, a simple, fast and low-cost method for levodopa detection is proposed depending on the in situ formation of blue and green emission fluorescent copolymer (FCP). The proposed method is based on the conversion of fluorescence emission peak of FCP from blue (430 nm) to green emission (535 nm) in 2 h. In this sensing system, both blue and green emission exhibit a high selectivity and sensitivity for levodopa determination in the range from 0 to 50 µM with a detection limit of 0.2 µM and 0.36 µM, respectively. Among them green emission FCP shows excellent recovery even at human serum concentrations up to 30%. Additionally, the proposed method was successfully applied to assess the content of levodopa in three anti-Parkinson drugs (carbidopa and levodopa CR tablets, levodopa and benserazide hydrochloride tablets, and levodopa tablets). More importantly, the levodopa determination of three anti-Parkinson drugs in human serum also exhibit an excellent recovery. Therefore, our strategy provides a promising method for mechanism study and treatment of Parkinson's disease.

Mitochondria-targeted polydopamine nanoprobes for visualizing endogenous sulfur dioxide derivatives in a rat epilepsy model.

Epilepsy is the fourth most common neurological disorder, and aberrantly elevated sulfur dioxide derivatives (SO32-/HSO3-) are thought to underlie the hippocampal neuronal apoptosis in epilepsy. We have designed and synthesized a mitochondria-targeted polydopamine nanoprobe for visualizing endogenous SO32-/HSO3- by the nucleophilic addition reaction. The nanoprobe was used for imaging SO2 derivatives both in the mitochondria of cultured cells and zebrafish, and successfully applied in the hippocampus of a rat model of epilepsy. The PDAD nanoprobe could be of great value for the elucidation of mechanisms of abnormal SO32-/HSO3- involved in diseases such as epilepsy.

Polydopamine Dots-Based Fluorescent Nanoswitch Assay for Reversible Recognition of Glutamic Acid and Al3+ in Human Serum and Living Cell.

We developed a facile and feasible fluorescent nanoswitch assay for reversible recognition of glutamate (Glu) and Al3+ in human serum and living cell. The proposed nanoswitch assay is based on our recently developed method for controlled synthesis of fluorescent polydopamine dots (PDADs) at room temperature with dopamine as the sole precursor. The fluorescence of nanoswitch assay could be quickly and efficiently quenched by Glu (turn-Off), and the addition of Al3+ could recover the fluorescence of the PDADs-Glu system (turn-On). Meanwhile, the reversible recognition of Glu and Al3+ in this nanoswitch system was stable after three cycles. Additionally, the system displayed excellent performance for Glu and Al3+ determination with a low detection limit of 0.12 and 0.2 µM, respectively. Moreover, PDADs are successfully applied to determine Glu and monitor Al3+ in human serum. Noteworthy, the nanoswitch assay is transported into HepG2 cells and realized "Off" detection of Glu and "On" sensing Al3+ in the living cells. Therefore, this PDADs-based nanoswitch assay provides a strategy to develop reversible recognition biosensors for intracellular and external molecular analysis.

Preparation and in vitro and in vivo characterization of cyclosporin A-loaded, PEGylated chitosan-modified, lipid-based nanoparticles.

BACKGROUND AND METHODS: A new cyclosporin A-loaded, PEGylated chitosan-modified lipid-based nanoparticle was developed to improve upon the formulation of cyclosporin A. PEGylated chitosan, synthesized in three steps using mild reaction conditions, was used to modify the nanoparticles. Cyclosporin A-loaded, PEGylated chitosan-modified nanoparticles were prepared using an emulsification/solvent evaporation method. The drug content and encapsulation efficiency of the cyclosporin A-loaded, PEGylated chitosan-modified nanoparticles were measured by high-performance liquid chromatography. The average size of the nanoparticles was determined by transmission electron microscopy and dynamic light scattering. The pharmacokinetic behavior of the nanoparticles was investigated in rabbits after intravenous injection. Cyclosporin A concentrations in a whole blood sample were analyzed by high-performance liquid chromatography using tamoxifen as the internal standard. The pharmacokinetic parameters were calculated using the 3p87 software program. RESULTS: Fourier transform infrared spectroscopy and nuclear magnetic resonance confirmed the structure of PEGylated chitosan. The drug content and encapsulation efficiency of the cyclosporin A-loaded, PEGylated chitosan-modified nanoparticles were 37.04% and 69.22%, respectively. The average size of the nanoparticles was 89.4 nm. The nanoparticles released 30% cyclosporin A-loaded in 48 hours in vitro, with no initial burst release. The mode of release in vitro was prone to bulk erosion. The in vivo results showed the biological half-life of the elimination phase (t(1/2ß)) of the nanoparticles was 21 times longer than that of the cyclosporin A solution, and the area under the curve for the nanoparticles was 25.8 times greater than that of the cyclosporin A solution. CONCLUSION: Modification of PEGylated chitosan prolonged the retention time of the nanoparticles in the circulatory system and improved the bioavailability of cyclosporin A.

A novel fluorescent probe for copper ions based on polymer-modified CdSe/CdS core/shell quantum dots.

Quantum dots (QDs) have become one of the most attractive fields of current research because of their unique optical properties. Novel copper-sensitive fluorescent fluoroionophores based on CdSe/CdS core/shell QDs modified with a polymer of MAO-mPEG were synthesized and characterized in the present work. A pH of 6.47 was optimally selected for measurements. By modifying QDs with MAO-mPEG, significant aqueous fluorescence quenching was observed upon binding with copper ions involving both reduced and oxidized environments, indicating great sensitivity and specificity for copper-ion sensing. No significant interfering effects from other metal ions, such as Ag(+), Al(3+), Ba(2+), Ca(2+), Cd(2+), Co(2+), Cr(3+), Fe(2+), Fe(3+), Hg(2+), K(+), Mg(2+), Mn(2+), Na(+), Ni(2+), Pb(2+), Sn(2+), and Zn(2+), were observed. The linear response range for Cu(2+) was found to be 0.01-0.50 µM, and the limit of detection was evaluated to be 16 nM. The proposed method demonstrated improved sensitivity and selectivity characteristics for Cu(II) determinations based on CdSe/CdS core/shell QDs modified with MAO-mPEG by using a typical liquid-phase quenching assay, showing its potential application to multiplex sensing of different analytes through distinct ligand conjugation and functionalization of individual fluorophores.