Multifunctional chitosan-based lanthanide luminescent hydrogel with stretchability, adhesion, self-healing, color tunability and antibacterial ability.

Lanthanide luminescent hydrogels have broad application prospects in various fields. However, most of lanthanide hydrogels possess relatively simple functions, which is not conducive to practical applications. Therefore, it is becoming increasingly urgent to develop multifunctional hydrogels. Herein, a multifunctional chitosan-based lanthanide luminescent hydrogel with ultra-stretchability, multi-adhesion, excellent self-healing, emission color tunability, and good antibacterial ability was prepared by a simple one-step free radical polymerization. In this work, our designed lanthanide complexes [Ln(4-VDPA)3] contain three reaction sites, which can be copolymerized with N-[tris(hydroxymethyl) methyl] acrylamide (THMA), acrylamide (AM), and diacryloyl poly(ethylene glycol) (DPEG) to form the first chemical crosslinking network, while hydroxypropyltrimethyl ammonium chloride chitosan (HACC) interacts with the hydroxyl and amino groups derived from the chemical crosslinking network through hydrogen bonds to form the second physical crosslinking network. The structure of the double network as well as the dynamic hydrogen bond and lanthanide coordination endow the hydrogel with excellent stretchability, adhesion and self-healing properties. Moreover, the introduction of lanthanide complexes and chitosan makes the hydrogel exhibit outstanding luminescence and antibacterial performances. This research not only realizes the simple synthesis of multifunctional luminescent hydrogels, but also provides a new idea for the fabrication of biomass-based hydrogels as intelligent and sustainable materials.

Multicolor, injectable BSA-based lanthanide luminescent hydrogels with biodegradability.

Protein hydrogels have attracted increasing attention because of their excellent biodegradability and biocompatibility, but frequently suffer from the single structures and functions. As a combination of luminescent materials and biomaterials, multifunctional protein luminescent hydrogels can exhibit wider applications in various fields. Herein, we report a novel, multicolor tunable, injectable, and biodegradable protein-based lanthanide luminescent hydrogel. In this work, urea was utilized to denature BSA to expose disulfide bonds, and tris(2-carboxyethyl)phosphine (TCEP) was employed to break the disulfide bonds in BSA to generate free thiols. A part of free thiols in BSA rearranged into disulfide bonds to form a crosslinked network. In addition, lanthanide complexes (Ln(4-VDPA)3), containing multiple active reaction sites, could react with the remaining thiols in BSA to form the second crosslinked network. The whole process avoids the use of nonenvironmentally friendly photoinitiators and free radical initiators. The rheological properties and structure of hydrogels were investigated, and the luminescent performances of hydrogels were studied in detail. Finally, the injectability and biodegradability of hydrogels were verified. This work will provide a feasible strategy for the design and fabrication of multifunctional protein luminescent hydrogels, which may have further applications in biomedicine, optoelectronics, and information technology.

Color-tunable, self-healing albumin-based lanthanide luminescent hydrogels fabricated by reductant-triggered gelation.

Luminescent hydrogels show extensive applications in many fields because of their excellent optical properties. Although there are many matrixes used to prepare luminescent hydrogels, the synthesis of protein-based luminescent hydrogels is still urgently needed to explore due to their good biodegradability and biocompatibility. In this work, a color-tunable, self-healing protein-based luminescent hydrogel consisting of bovine serum albumin (BSA) and lanthanide complexes is prepared via reductant-triggered gelation. Firstly, a bifunctional organic ligand named 4-(phenylsulfonyl)-pyridine-2,6-dicarboxylic acid (4-PSDPA) is synthesized, which can react with thiol groups and effectively sensitize the luminescence of Eu3+ and Tb3+ ions. Then, the BSA is treated with a reducing agent tris(2-carboxyethyl)phosphine (TCEP) to produce thiol groups. And the newly formed thiol groups can re-match to form disulfide bonds between two BSA molecules or react with Ln(4-PSDPA)3 complexes, resulting in the formation of an albumin-based luminescent hydrogel. Furthermore, the self-healing, biodegradability and biocompatibility of albumin-based hydrogels have also been demonstrated. We expect that the newly developed multifunctional protein-based hydrogels will find potential applications in the fields of biomedical engineering and optical devices.

[Pollution Characteristics and Risk Assessment of Typical Organophosphate Esters in Beijing Municipal Wastewater Treatment Plant and the Receiving Water].

Organophosphate esters (OPEs) are ubiquitous in the environment and pose a potential threat to ecosystems and human health. A method for the determination of eight OPEs by ultra-performance liquid chromatography-tandem mass spectrometer (UPLC-MS/MS) was established. The recovery rates of eight target compounds with different solid-phase extraction columns, different eluents, and different eluent volumes were compared. The results showed that using ENVI-18 column enrichment, OPEs were eluted with 8 mL acetonitrile containing 25% (volume fraction) dichloromethane, and the labeled recovery rate of the target compound was 92.5%-102.2%. The recoveries of different matrix samples were 88.5%-116.1% and relative standard deviation was 1.7%-9.9%. The concentration range of 8 different detectable organophosphate esters in the effluent of sewage treatment plant is 85.9-235.4 ng·L-1 during the six-day sampling process, permissive river downstream of the six-day ΣOPEs average total concentration was 130.3 ng·L-1, higher than the 119.4 ng·L-1 upstream water concentration, but lower than the sewage treatment plant effluent concentration of total 162.5ng·L-1. The study shows that the sewage treatment plant cannot completely remove OPEs; for triethyl phosphate (TEP) and 3 (2-ethyl hexyl) phosphate ester (TEHP) there exists a negative removal phenomenon, whereas for other OPEs the removal rate was between 14.1% and 84.9%, and the total ΣOPEs removal rate by the sewage plant was 50.0%. The TPhP in the effluent of the sewage treatment plant has medium environmental risk (RQ>0.1), and other organophosphates have low environmental risk (RQ<0.1); however, the long-term mixing effects of organophosphate esters on the ecosystem of the receiving river should not be ignored.

Two 8-hydroxyquinoline-based fluorescent chemosensors for ultra-fast and sensitive detection of water content in strong polar organic solvents with large Stokes shifts.

It is of great significance to detect the moisture in organic solvents before used in water-sensitive reactions. Herein, two Schiff base quinoline derivatives, 8-hydroxyquinoline-2-carboxaldehyde thiosemicarbazone (HQCT) and 8-hydroxyquinoline-2-carboxaldehyde (pyridine-2-carbonyl)-hydrazine (HQPH), were designed and synthesized by a simple one-step reaction, and used as fluorescent chemosensors for ultra-fast and sensitive detection of water content in strong polar organic solvents. Based on excited-state intramolecular proton transfer (ESIPT) process, HQCT and HQPH exhibited strong fluorescence emissions with large Stokes shifts in dimethyl sulfoxide (DMSO) and N, N-dimethylformamide (DMF) solvents compared to other various organic solvents, and their fluorescence quenching and fluorescent color changes were obviously observed with increasing water content. The experimental results revealed that the hydroxyl groups substituted at the 8-position of HQCT and HQPH played a key role in the fluorescence emission processes. Dynamic light scattering (DLS) and 1H NMR titration indicated that the sensing mechanism for the detection of water was based on inhibition of the ESIPT by H2O via forming hydrogen bonds. In the range of 0.0-1.8 wt%, the fluorescence intensity of chemosensors changed as a linear function of water content. The detection limits of water in DMSO by HQCT and HQPH were as low as 0.0220 wt% and 0.0274 wt%, respectively. Moreover, HQCT and HQPH are successfully applied for the detection of moisture content in real commercial organic solvents.

Site-specific tagging proteins via a rigid, stable and short thiolether tether for paramagnetic spectroscopic analysis.

Increasing the stability of protein bioconjugates and improving the resolution of protein complexes is important for spectroscopic analysis in structural biology. The reaction of phenylsulfonated pyridine derivatives and protein thiols generates a stable, rigid and short thiolether tether, which is valuable in high-resolution spectroscopic measurements.

Bioconjugation of proteins with a paramagnetic NMR and fluorescent tag.

Site-specific labeling of proteins with lanthanide ions offers great opportunities for investigating the structure, function, and dynamics of proteins by virtue of the unique properties of lanthanides. Lanthanide-tagged proteins can be studied by NMR, X-ray, fluorescence, and EPR spectroscopy. However, the rigidity of a lanthanide tag in labeling of proteins plays a key role in the determination of protein structures and interactions. Pseudocontact shift (PCS) and paramagnetic relaxation enhancement (PRE) are valuable long-range structure restraints in structural-biology NMR spectroscopy. Generation of these paramagnetic restraints generally relies on site-specific tagging of the target proteins with paramagnetic species. To avoid nonspecific interaction between the target protein and paramagnetic tag and achieve reliable paramagnetic effects, the rigidity, stability, and size of lanthanide tag is highly important in paramagnetic labeling of proteins. Here 4'-mercapto-2,2':6',2''-terpyridine-6,6''-dicarboxylic acid (4MTDA) is introduced as a a rigid paramagnetic and fluorescent tag which can be site-specifically attached to a protein by formation of a disulfide bond. 4MTDA can be readily immobilized by coordination of the protein side chain to the lanthanide ion. Large PCSs and RDCs were observed for 4MTDA-tagged proteins in complexes with paramagnetic lanthanide ions. At an excitation wavelength of 340 nm, the complex formed by protein-4MTDA and Tb(3+) produces high fluorescence with the main emission at 545 nm. These interesting features of 4MTDA make it a very promising tag that can be exploited in NMR, fluorescence, and EPR spectroscopic studies on protein structure, interaction, and dynamics.