Polymerization-induced emission and selective detection to Fe3+/ Fe2+ of triazine-containing polyureas.

In this study, four polyureas with triazine moiety (PUAs) were successfully synthesized through the polymerization of triazine-containing diamine and diisocyanate. The intramolecular aggregation of triazine rings and urea groups along the macromolecular backbone gives PUAs a significant polymerization-induced emission (PIE). Among the four PUAs, PUA-LP shows a significant fluorescent emission at 450 nm, compared to non/weak fluorescent 2,4-diamino-6-phenyl-1,3,5-triazine and L-Lysine diisocyanate ethyl ester monomers. Additionally, the external factors such as solution concentration, excitation wavelength, and precipitants also play a crucial role in the fluorescence of PUAs. As expected, PUA-LP can selectively recognize and detect Fe3+/Fe2+ ions even in the presence of 12 other metal ions and 10 anions. The limit of detection of PUA-LP to Fe3+/Fe2+ is as low as 1.02 µM (0.06 mg/L) and 0.86 µM (0.05 mg/L), respectively, and far below 0.3 mg/L of the allowable national standard for drinking water by WHO. Furthermore, the quenching mechanism of Fe3+/Fe2+ to PUA-LP is attributed to static quenching caused by the coordination of Fe3+/Fe2+ ions with a coordination ratio of 2:1. Based on PIE, the fluorescent PUA-LP was made into an observable and portable testing paper for detecting Fe3+/Fe2+ ions. Finally, we measured the recovery rate of the actual tap water samples and compared the performance of PIE-active PUA-LP with the other reported fluorescent probes to Fe3+/Fe2+ ions.

Simultaneous Regulation of the Mechanical/Osteogenic Capacity of Brushite Calcium Phosphate Cement by Incorporating with Poly(ethylene glycol) Dicarboxylic Acid.

Brushite calcium phosphate cement (brushite CPC) is a prospective bone repair material due to its ideal resorption rates in vivo. However, the undesirable mechanical property and bioactivity limited its availability in clinic application. To address this issue, incorporating polymeric additives has emerged as a viable solution. In this study, poly(ethylene glycol) dicarboxylic acid, PEG(COOH), was synthesized and employed as the polymeric additive. The setting behavior, anti-washout ability, mechanical property, degradation rate, and osteogenic capacity of brushite CPC were regulated by incorporating PEG(COOH). The incorporation of PEG(COOH) with carboxylic acid groups demonstrated a positive effect on both mechanical properties and osteogenic activity in bone repair. This study offers valuable insights and suggests a promising strategy for the development of materials in bone tissue engineering.

Morpholine-modified polyacrylamides with Polymerization-Induced emission and its specific detection to Cu2+ ions.

In this work, three morpholine-modified polyacrylamide derivatives (MMPAm) were successfully prepared by free radical polymerization of monomers with morpholine moiety. The intramolecular aggregation of morpholine rings on macromolecular backbone gives MMPAm a significant polymerization-induced emission (PIE). Particularly, poly(N-morpholine acrylamide) (PNMPA) has the characteristics of strong fluorescence at 450 nm, and its fluorescence quantum yield reaches 2.87 %. The introduction of morpholine moiety, the length of CH2 spacer between morpholine ring and the backbone and the molecular weight play the important roles in PIE properties of PNMPA. Interestingly, PNMPA can recognize and detect Cu2+ specifically even in the presence of 12 other metal ions by thorough fluorescence quenching, and the detection limit of PNMPA is 17.3 µM. Furthermore, the dynamic quenching of PNMPA by Cu2+ ions and the complexation ratio of 1:2 according to JOB's working diagram were confirmed by fluorescence titration. Under the assistance of EDTA, a reversible detection system for Cu2+ is achieved, and a portable test paper from PNMPA for the detection of Cu2+ was also made. In conclusion, PNMPA is endowed with a significant PIE effect by the intramolecular aggregation of morpholine rings along the backbone in the polymerization of non-fluorescent monomer, and is expected to be a promising material for specific detection to Cu2+ ions.

Supramolecular polymers with dual energy storage mechanism for high-performance supercapacitors.

In this paper, we prepared the supramolecular polymers (MWCNT-APP-s) with a dual energy storage mechanism as the electrode materials by the coordination of four transition metal ions with the small molecule chelator (APP) and functionalized carbon nanotubes, respectively. Among four MWCNT-APP-s, MWCNT-APP-Fe has the characteristics of moderate micropore/mesopore, significant hydrophobicity, redox property and functional groups. Interestingly, the redox reaction of Fe3+/Fe2+ and -CN-/-CN- transformation give MWCNT-APP-Fe an energy storage basis of pseudocapacitance, while MWCNTs and the micro/mesopore structure in MWCNT-APP-Fe provide a double-layer energy storage platform. As expected, on base of the dual energy storage mechanism, the symmetric supercapacitor assembled with MWCNT-APP-Fe has a higher specific capacity (Cs, 421 F g-1 at 1 mV s-1) as well as a long-lasting stability of 94.8% capacity retention with 99% Coulombic efficiency after 10,000 cycles at 20 mV s-1. More notably, the relevant aqueous Zn2+ hybrid supercapacitor provides a high capacity (Cm) of 191 mAh g-1 at 0.5 A g-1 and a long duration of over 2000 cycles at 50 A g-1, with a capacity retention of 92.4%. In summary, MWCNT-APP-Fe with a dual energy storage mechanism enables a potential application as an electrode material for high-performance supercapacitor.

Polymerization-induced emission (PIE) of multifunctional polyamides synthesized by Ugi polymerization and targeted imaging of lysosomes.

In this paper, a series of polyamide derivatives (PAMs) containing morpholine groups were prepared by Ugi polymerization from dialdehyde, diacid, N-(2-aminoethyl)-morpholine and isonitrile compounds as novel multi-responsive fluorescent sensors. As non-conjugated light-emitting polymers, PAMs were endowed with unique polymerization-induced emission (PIE) performance at 450 nm by through-space conjugation (TSC) between heteroatoms and heterocycles. It was also found that PAMs exhibited reversible responses to the external temperature and pH values and became responsive fluorescent switches. In addition, PAMs can specifically recognize Fe3+ with a limit of detection (LOD) of 54 nM and the introduction of EDTA reversibly restores the fluorescence of the quenched PAMs-Fe3+ system. By virtue of thermosensitivity, PAMs are easily separated from the above system by changing the temperature above or below the lower critical solution temperature (LCST). It is worth noting that PIE-active PAMs with good biocompatibility can selectively accumulate in lysosomes due to the presence of morpholine groups, and its Pearson colocalization coefficient is as higher as 0.91. Furthermore, a PIE-active PAM was successfully used to track exogenous Fe3+ in lysosomes. In conclusion, these multi-functional PIE-active PAMs have higher potential applications in biomedical or environmental fields.

Light emitting CMC-CHO based self-healing hydrogel with injectability for in vivo wound repairing applications.

Self-healing hydrogels with biodegradability have great potential biomedical application in drug loading and delivery, wound dressing and tissue engineering. In this research, biodegradable hydrogels were designed from oxidized CMC (CMC-CHO) and PEO23 dinaphthoate hydrazide (PEO23 DNH) with naphthalene structure for potential bio-imaging purpose. Results showed that the gelation time of this self-healing hydrogels was very fit for in situ injectable applications for drug loading and controlled release. The hydrogels also showed excellent biocompatibility because all the components and the acylhydrazone bond are biocompatible. Moreover, the in vitro and in vivo drug release study revealed the CMC-CHO based hydrogels could reduce the acute toxicity of the drugs with a controlled and sustained release manner. The hydrogel also showed hemostatic activity by sealing effect and mEGF loaded hydrogel accelerated the wound repairing efficacy. All above result proved the CMC-CHO/PEO23 DNH hydrogel with luminescent property have great application property in bioscience and biotechnology.

Tunable Three-Dimensional Nanostructured Conductive Polymer Hydrogels for Energy-Storage Applications.

Three-dimensional (3D) nanostructured conducting polymer hydrogels represent a group of high-performance electrochemical energy-storage materials. Here, we demonstrate a molecular self-assembly approach toward controlled synthesis of nanostructured polypyrrole (PPy) conducting hydrogels, which was "cross-linked" by a conjugated dopant molecule trypan blue (TB) to form a 3D network with controlled morphology. The protonated TB by ion bonding aligns the free sulfonic acid groups into a certain spatial structure. The sulfonic acid group and the PPy chain are arranged by a self-sorting mechanism to form a PPy nanofiber structure by electrostatic interaction and hydrogen bonding. It is found that PPy hydrogels doped with varying dopant concentrations and changing dopant molecules exhibited controllable morphology and tunable electrochemical properties. In addition, the conjugated TB dopants promoted interchain charge transport, resulting in higher electrical conductivity (3.3 S/cm) and pseudocapacitance for the TB-doped PPy, compared with PPy synthesized without TB. When used as supercapacitor electrodes, the TB-doped PPy hydrogel reaches maximal specific capacitance of 649 F/g at the current density 1 A/g. The result shows that PPy nanostructured hydrogels can be tuned for potential applications in next-generation energy-storage materials.

Facile Synthesis and Properties of Multifunctionalized Polyesters by Passerini Reaction as Thermosensitive, Biocompatible, and Triggerable Drug Release Carriers.

We developed a facile synthesis for a series of multifunctionalized polyesters by Passerini three-component polymerization (Passerini-3CP) in a "one-pot" method at room temperature using serial dicarboxylic acids, dialdehyde, and tert-butyl isocyanide as monomers. First, the effects of monomer feed ratio, monomer concentration, and different dicarboxylic acids involved in the polymerization were systematically investigated. The in situ FTIR and GPC measurements have suggested a step-growth mechanism for Passerini-3CP. Second, five succinic acid end-capped polyethylene glycols (S-PEGs) with different molecular weights of 400, 800, 1000, 2000, and 4000 g/mol were prepared and selected as dicarboxylic acids for the subsequent Passerini-3CP to fabricate the thermosensitive and biocompatible polyesters. Among the five resulting polyesters, four polyesters from S-PEG-400, S-PEG-800, S-PEG-1000, and S-PEG-2000 show reversible response to the external temperature, and the lower critical solution temperature (LCST) in water is in the range of 28.5-84.2 °C. Through the copolymerization of S-PEG-400 and S-PEG-800, the LCSTs for functional polyesters can be conveniently controlled to be 38.7, 42.3, and 58.0 °C, respectively. After 24-72 h of incubation in polyester solution, the viability rate of HeLa cells reached up to 80-107%, showing its excellent biocompatibility. The cleavable polyesters were also prepared by integrating S-S bonds onto their backbones in Passerini-3CP of 3,3'-dithiodipropionic acid as one comonomer for the biomedical applications. With the aid of the hydrophobicity of doxorubicin (DOX) and thermosensitivity of polyesters, the doxorubicin-loaded carriers with the size of 200-400 nm and core-shell structure were easily obtained by dialysis below LCST and subsequent heating to LCST. The effective release of DOX from the carriers can be triggered by the characteristic reaction of l-glutathione (GSH) with S-S bonds in the functionalized polyester backbones.

Supramolecular template-directed synthesis of perfect phenelenediimino-bridged ladderlike polyphenylsiloxanes.

A template synthesis of the soluble, high molecular weight (Mw), and perfect p-phenylenediimino (p-PDA)-bridged ladderlike polyphenylsiloxane (PLPS) is reported. First, N,N'-bis(phenyldichlorosilyl)-p-PDA monomers were self-assembled into a perfect ladder superstructure (LS) by concerted interaction of aromatic pi-pi stacking and hydrogen bonding. Then the LS underwent a novel stoichiometric hydrolysis/dehydrochlorination-condensation reaction instead of the usual hydrolysis/dehydration-condensation reaction, leading to the PLPS. The perfect ladder structures of both the PLPS and, in particular, the unstable supramolecular LS were confirmed as follows. 1) There are two Bragg peaks in solid and/or solution X-ray diffraction (XRD) spectra representing the ladder width (w) and ladder thickness (t); these peaks were consistent with those calculated by molecular simulation. 2) Both the PLPS and LS have extremely sharp absorption peaks with small half-peak widths (Delta(1/2) < 0.3 ppm) in 29Si NMR spectra, suggesting the presence of the perfect ladder structure for PLPS and LS. 3) Moreover, no noticeable absorption peaks for the Si-OH and NH2 groups were observed in FT-IR and 29Si NMR spectra, indicating that the Si-N bond of the [triple bond]Si-NH-C6H4-NH-Si[triple bond] ladder rung of PLPS and LS is not cleaved. 4) Both PLPS and LS show similar emission peaks (in fluorescence spectroscopy) attributed to the excimer formed by face-to face pi-pi stacking of phenyl groups along the ladder chain rather than a branched direction. 5) Differential scanning calorimetry (DSC) measurements indicate a high glass temperature (Tg = 176.4 degrees C) for PLPS. As circumstantial evidence, this result further indicates very high stiffness of PLPSs ladder backbone as compared with flexible single-chain polyphenylmethylsiloxane with a low Tg = -69.4 degrees C.