Microenvironment-regulated dual-hydrophilic coatings for glaucoma valve surface engineering.

Glaucoma valves (GVs) play an essential role in treating glaucoma. However, fibrosis after implantation has limited their long-term success in clinical applications. In this study, we aimed to develop a comprehensive surface-engineering strategy to improve the biocompatibility of GVs by constructing a microenvironment-regulated and dual-hydrophilic antifouling coating on a GV material (silicone rubber, SR). The coating was based on a superhydrophilic polydopamine (SPD) coating with good short-range superhydrophilicity and antifouling abilities. In addition, SPD coatings contain many phenolic hydroxyl groups that can effectively resist oxidative stress and the inflammatory microenvironment. Furthermore, based on its in situ photocatalytic free-radical polymerization properties, the SPD coating polymerized poly 2-methylacryloxyethylphosphocholine, providing an additional long-range hydrophilic and antifouling effect. The in vitro test results showed that the microenvironment-regulated and dual-hydrophilic coatings had anti-protein contamination, anti-oxidation, anti-inflammation, and anti-fiber proliferation capabilities. The in vivo test results indicated that this coating substantially reduced the fiber encapsulation formation of the SR material by inhibiting inflammation and fibrosis. This design strategy for dual hydrophilic coatings with microenvironmental regulation can provide a valuable reference for the surface engineering design of novel medical implantable devices. STATEMENT OF SIGNIFICANCE: Superhydrophilic polydopamine (SPD) coatings were prepared on silicone rubber (SR) by a two-electron oxidation method. Introduction of pMPC to SPD surface using photocatalytic radical polymerization to obtain a dual-hydrophilic coating. The dual-hydrophilic coating effectively modulates the oxidative and inflammatory microenvironment. This coating significantly reduced protein contamination and adhesion of inflammatory cells and fibroblasts in vitro. The coating-modified SR inhibits inflammatory and fibrosis responses in vivo, promising to serve the glaucoma valves.

Two-electron oxidized polyphenol chemistry-inspired superhydrophilic drug-carrying coatings for the construction of multifunctional nasolacrimal duct stents.

Nasolacrimal duct obstruction due to infection, inflammation, or excessive fibroblast proliferation may result in persistent tearing, intraocular inflammation, or even blindness. In this study, surface engineering techniques are applied to nasolacrimal duct stents for the first time. Based on the functioning of marine mussels, "one-pot" and "stepwise" methods were employed to construct a novel multifunctional superhydrophilic PDA/RAP coating using dopamine and rapamycin. Micron-sized rapamycin crystals combined with nano-sized polydopamine particles form a micro-nano topographical structure. Therefore, acting synergistically with in situ-generated hydrophilic groups (amino, carboxyl, and phenolic hydroxyl), they impart excellent and long-lasting superhydrophilicity to the nasolacrimal duct stent. The PDA/RAP coating effectively maintained the stability of the initial microenvironment during stent implantation by inhibiting the onset of acute inflammation and infection during the early stages of implantation. Meanwhile, the rapamycin crystals, supported by the superhydrophilic platform, exhibited a sustained-release capability that helped them to better exert their anti-inflammatory, antibacterial, and anti-fibroblast proliferative properties, ensuring conducive conditions for the rapid repair of nasolacrimal duct epithelial cells, verified by a series of experiments. In conclusion, the PDA/RAP hydrophilic coating has anti-inflammatory, antifibrotic, antibacterial, and antithrombotic properties, offering a new strategy to address restenosis following clinical nasolacrimal duct stent implantation.

A high-protein retained PES hemodialysis membrane with tannic acid as a multifunctional modifier.

A high protein retention polyethersulfone (PES) membrane was prepared by nonsolvent-induced phase separation and surface coating, which exhibited enhanced hemocompatibility and antioxidant stress performance. The cross-linked network was constructed by tannic acid (TA) and alpha-lipoic acid (α-LA) on the surface of the membrane, which controlled the pores to a reasonable size. The enrichment of heparin-like groups on the membrane surface, implemented by "hydrophobic interaction" and "click reaction", confers anticoagulant properties; the presence of a large number of phenolic hydroxyl groups from TA and the introduction of α-LA allows the modified membranes to intervene in oxidative stress. The hemocompatibility characterizations included plasma recalcification time (PRT), activated partial thromboplastin time (APTT), prothrombin time (PT), thrombin time (TT) and hemolysis rate (HR). Additionally, the DPPH ABTS radical scavenging capacity was tested to evaluate the antioxidant performance. The results show that the modified membrane presents an outstanding protein retention rate (99.3%) along with permeability. In addition, the PRT is prolonged to 341.7 s, and the DPPH• scavenging ability reaches 0.74 µmol•cm-2. The membranes can be easily prepared and present excellent comprehensive performance. This work provides a simple and facile strategy for the fabrication of hemodialysis membranes with controllable pore sizes.

Electrophoretic Desalting To Improve Performance in Electrospray Ionization Mass Spectrometry.

Mass spectrometers are sensitive tools used to identify and quantify both small and large analytes using the mass-to-charge ratios ( m/ z) of ions generated by electrospray ionization (ESI) or other methods. Ionization typically generates protonated or deprotonated forms of the analytes or adducts with adventitious metal ions derived from the spray solvent. The formation of a variety of ionized forms of the analyte as well as the presence of cluster ions complicates the data and can have deleterious effects on the performance of the mass spectrometer, especially under high salt or buffer conditions. To address this, a method involving a dual-electrode nano-electrospray source has been implemented to rapidly and temporarily desalt the spray solution of interfering cationic and anionic species using electrophoretic transport from the spray tip. Peptides, proteins, and pharmaceutical drugs all showed improved results after the desalting process as measured by the quality of the mass spectra and the limits of detection achieved. Importantly ordinary phosphate buffers could be used to record protein mass spectra by nano-ESI.

Electro-kinetic assisted electrospray ionization for enhanced complex sample analysis.

In this work, an electro-kinetic assisted electrospray ionization (EK-ESI) source is proposed and characterized. In EK-ESI, an additional auxiliary electric field is introduced in the liquid flow of a nano-ESI. While traveling forward in the electrospray flow, charged analytes also experience a reverse electric field, which pushes them backwards. As a result, analytes could be separated preliminarily based on their electrophoretic mobility during the electrospray process. Experiments show that EK-ESI can reduce charge competition effects in the ESI source and increase biomolecule detection sensitivities. It was also found that EK-ESI effectively ionizes proteins in a relatively mild solvent condition, which does not require the addition of acids or salt buffers into the solvent. As a proof-of-concept study, a very rough separation effect was observed in this study, further experiments and theoretical study will be carried out to enhance its performances.