Direct grafting of cellulose nanocrystals with poly(ionic liquids) via Gamma-ray irradiation and their utilization for adsorptive removal of CR.

In this work, a simple but effective method based on Gamma-ray initiated polymerization was reported for the first time through direct irradiation of CNCs and ionic liquid monomer to obtain poly (ionic liquids) functionalized CNCs (IL@CNCs). The adsorptive removal of Congo red (CR) from aqueous solution by IL@CNCs was also examined and the influence of contact time, pH values, initial concentrations and temperature on adsorption behavior was investigated in detail. Under the same adsorption conditions, the adsorption capacity was increased from 59.72 mg/g (CNCs) to 195.83 mg/g (IL@CNCs). The results of the adsorption isotherm and adsorption kinetics showed that the experimental data were more suitable to be described by the Freundlich isotherm adsorption model and the pseudo-second-order model. The adsorption process of CR on the surface of the adsorbent was endothermic and spontaneous. When the aqueous solution was acidic, it was more conducive to the adsorption of CR. At 100% breakthrough, the value of adsorption capacity is 199.95 mg/g and the value of partition coefficient is 9.64. Moreover, the adsorption capacity is expected to be further improved through adjustment of polymerization parameters and this method can also be used for preparation other poly (ionic liquids) modified composites.

Surface functionalization of MXene with chitosan through in-situ formation of polyimidazoles and its adsorption properties.

In this work, a novel imidazoles-MXene hybrid composite, namely polyimidazoles chain overlaying on the surface of MXene (Ti3C2@IMIZ), was prepared by a simple method. Through this strategy, imidazoles can be in situ growth on the surface of MXenes via a facile multicomponent reaction using chitosan as a renewable reactant. Based on the characterization results, we demonstrated that a thin layer imidazoles with an ordered chain structure was embedded on the surface of Ti3C2, which resulted in the formation of a novel imidazoles-MXene hybrid composite. The adsorption performance of Ti3C2@IMIZ for removal environmental pollutants was evaluated using heavy metal ions of Cr(Ⅵ) as adsorbate. Detailed adsorption characteristics of Ti3C2@IMIZ including operational factors, adsorption kinetics and isotherms models were investigated. XPS analysis showed that Cr(VI) was converted to Cr(III) with low toxicity during the adsorption process. The adsorption of Cr(VI) and reduction of Cr(VI) to Cr(III) contribute to elimination of Cr(VI) species. The adsorption behavior and process analysis show that the adsorption mechanism is mainly physical adsorption through electrostatic interaction. The excellent reproducibility suggests that Ti3C2@IMIZ may be a potential candidate for remove of Cr(Ⅵ) in actual sewage treatment.

Surface grafting of fluorescent polymers on halloysite nanotubes through metal-free light-induced controlled polymerization: Preparation, characterization and biological imaging.

Halloysite nanotubes (HNTs) are a kind of aluminosilicate clay with a unique hollow tubular structure that has been intensively explored for various applications especially in biomedical fields owing to their excellent biocompatibility, biodegrading potential and low cost. Surface modification of HNTs with functional polymers will greatly improve their properties and endow new functions for biomedical applications. In this work, a light-induced reversible addition-fragmentation chain transfer (RAFT) polymerization was introduced to successfully prepare HNTs based fluorescent HNTs/poly(PEGMA-Fl) composites in the presence of oxygen using diacrylate-fluorescein and poly (ethylene glycol) methyl ether methacrylate (PEGMA) as the monomers. Without other catalysts, heating, and deoxygenation procedure, the polymerization process can take place under mild conditions. Besides, owing to the introduction of fluorescein and PEGMA on the surface of HNTs, the resultant HNTs/poly(PEGMA-Fl) composites display high water dispersibility and stable fluorescence. The results from cell viability examination and confocal laser scanning microscopy also demonstrated that HNTs/poly(PEGMA-Fl) composites could be internalized by L929 cells with bright fluorescence and low cytotoxicity. Taken together, we developed a novel photo-initiated RAFT polymerization method for the fabrication of HNTs based fluorescent polymeric composites with great potential for biomedical applications. More importantly, many other multifunctional HNTs based polymer composites could also be fabricated through a similar strategy owing to good designability of RAFT polymerization.

The combination of Diels-Alder reaction and redox polymerization for preparation of functionalized CNTs for intracellular controlled drug delivery.

Carbon nanotubes (CNTs) are a novel type of one-dimensional carbon nanomaterials that have been widely utilized for biomedical applications such as drug delivery, cancer photothermal treatment owing to their high surface area and unique interaction with cell membranes. However, their biomedical applications are still impeded by some drawbacks, including poor water dispersibility, lack of functional groups and toxicity. Therefore, surface modification of CNTs to overcome these issues should be importance and of great interest. In this work, we reported for the first time that CNTs could be surface modification through the combination of Diels-Alder (D-A) reaction and redox polymerization, this strategy shows the advantages of mild reaction conditions, water tolerance, low temperature and hydroxyl-surfaced initiator. In this modification procedure, the hydroxyl groups were introduced on the surface of CNTs through the D-A reaction that was adopted for grafting the copolymers, which were initiated by the Ce(IV)/HNO3 redox system using the hydrophilic and biocompatible poly(ethylene glycol) methyl ether methacrylate (PEGMA) and carboxyl-rich acrylic acid (AA) as monomers. The final CNTs-OH-PAA@PEGMA composites were characterized by a series of characterization techniques. The drug loading and release results suggested that anticancer agent cis­platinum (CDDP) could be loaded on CNTs-OH-PAA@PEGMA composites through coordination with carboxyl groups and drug release behavior could be controlled by pH. More importantly, the cell viability results clearly demonstrated that CNTs-OH-PAA@PEGMA composites displayed low toxicity and the drug could be transported in cells and still maintain their therapeutic effects.

Preparation and biological imaging of fluorescent hydroxyapatite nanoparticles with poly(2-ethyl-2-oxazoline) through surface-initiated cationic ring-opening polymerization.

Fluorescent hydroxyapatite (HAp) nanoparticles have received significant attention in biomedical fields due to their outstanding advantages, such as low immunogenicity, excellent biocompatibility and biodegradability. However, fluorescent HAp nanoparticles with well controlled size and morphology are coated with hydrophobic molecules and their biomedical applications are largely restricted by their poor dispersibility in physiological solutions. Therefore, surface modification of these hydrophobic fluorescent HAp nanoparticles to render them water dispersibility is of utmost importance for biomedical applications. In this work, we reported for the first time for preparation of water-dispersible hydrophilic fluorescent Eu3+-doped HAp nanoparticles (named as HAp-PEOTx) through the cationic ring-opening polymerization using hydrophilic and biocompatible 2-ethyl-2-oxazoline (EOTx) as the monomer. The characterization techniques, such as nuclear magnetic resonance (NMR) spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) have been used to characterize these samples. Results confirmed that we could successfully obtain the hydrophilic fluorescent HAp-PEOTx composites through the strategy described above. These fluorescent HAp-PEOTx composites display great water dispersibility, unique fluorescent properties and excellent biocompatibility, making them promising for in vitro bioimaging applications.

Click multiwalled carbon nanotubes: A novel method for preparation of carboxyl groups functionalized carbon quantum dots.

As potential alternatives to conventional semiconductor quantum dots, fluorescent carbon quantum dots (CQDs) have received increasing research attention in biomedical fields owing to their splendid advantages of low cytotoxicity, strong fluorescence and excellent water dispersion. However, the preparation procedures of CQDs with designable chemical properties and functions are complicated and low efficient. In this work, we developed a facile, economical and straightforward strategy to prepare CQDs by a one-step thiol-ene click reaction between multiwalled carbon nanotubes (CNTs) and thiomalic acid (TA). The successful synthesis of CQDs was confirmed by a series of characterization data. The results manifested that CQDs were well combined with TA through surface thiol-ene click chemistry. In addition, the optical property is also desirable, the maximum emission wavelength was located in 500 nm and CQDs still could emit strong blue fluorescent light after irradiation with UV irradiation for 3 h. Besides, the pH value makes no significant changes for fluorescence emission wavelength of CQDs and CQDs can emit strongest fluorescence in weak acid solution. Furthermore, CQDs could be internalized by cells and show great cell dyeing performance and low cytotoxicity. All these features imply that TA functionalized CQDs possess great potential for biological imaging. The one-step thiol-ene click strategy provided a novel tool to prepare functionalized CQDs with great potential for biomedical applications.

Facile fabrication of glycosylated and PEGylated carbon nanotubes through the combination of mussel inspired chemistry and surface-initiated ATRP.

Surface modification of carbon nanotubes (CNTs) through controlled living polymerization has demonstrated to be a useful route for preparation of CNTs based polymer composites. However, surface oxidation of CNTs is often required to generate functional groups, which can be further utilized for immobilization of polymerization initiator and grafting polymers. The surface oxidation procedure is rather complex, high energy cost, low efficient and will destroy the structure of CNTs. Therefore, the development of simple and efficient strategies for preparation of CNTs based composites should be of great research interest and raised much attention recently. In this work, a novel mussel inspired strategy that combination of ATRP and ring-opening reaction has been developed for simultaneous preparation of glycosylated and PEGylated CNTs for the first time. CNTs were first coated with polydopamine (PDA) through self-polymerization of dopamine under alkaline aqueous solution. Then polymerization initiator was immobilized on CNT-PDA through simple esterification and amidation reaction to obtain CNT-PDA-Br. The PEGylated CNTs were synthesized through ATRP using CNT-PDA-Br as initiator and polyethylene glycol monoester acrylate and itaconic anhydride (IA) as the monomers. Finally, glucosamine was conjugated with IA via ring-opening reaction. The successful preparation of glycosylated and PEGylated CNTs (CNT-PDA-Poly(PEGMA-co-IA)-Glu) was confirmed by a number of characterization techniques in details. The obtained CNTs based composites showed improved aqueous dispersibility and desirable cytocompatibility, implying their biomedical application potential. As compared with the conventional covalent strategies, the mussel inspired method described in this work will not destroy the structure for introduction functional groups on the surface of CNTs, that can occur under rather mild experimental conditions, including room temperature, short reaction time and aqueous solution. On the other hand, the mussel inspired chemistry can also be used for surface modification of almost any materials regardless of their size, morphology and compositions. Therefore, we believe that the mussel inspired strategy should be a general method for fabrication of various polymer composites for different applications.

Facile preparation of fluorescent nanodiamond based polymer nanoparticles via ring-opening polymerization and their biological imaging.

Fluorescent nanodiamond (ND) has been regarded as one of the most promising fluorescent nanoprobes owing to their chemical inert, biocompatibility, optical properties, and rich surface chemistry. The fluorescent ND has been mainly fabricated through high-energy ion beam irradiation of type Ib diamonds and subsequent thermal annealing. The generation of nitrogen-vacancy centers is the reason for the fluorescence. However, the physical method is relatively complicated and it need to expensive equipment as well as high cost. On the other hand, the resultant fluorescent ND particles are lack of functional groups and difficult to be dispersed in aqueous solution. Therefore, the development of facile methods to direct preparation of fluorescent ND and surface modification with functional polymers is of great research interest for expanding the biomedical applications of fluorescent ND. In this report, a facile strategy was reported for the first time to prepare hydrophilic polymers functionalized fluorescent ND (named as ND-PhE-PETOx) composites through the ring-opening polymerization and simultaneous simple nucleophilic substitution reaction using the non-fluorescent detonation ND as the raw material. The obtained fluorescent ND composites were characterized by various characterization techniques in details. The as-obtained ND-PhE-PETOx composites exhibit high water dispersibility, low toxicity and strong fluorescence intensity. Cell uptake results indicating that the fluorescent ND based composites can be effectively internalized by cells. Taken together, we have developed a novel and simple method for the preparation of fluorescent ND based composites, which show excellent physicochemical properties and great potential for biomedical applications.

Surface modification of fluorescent Tb3+-doped layered double hydroxides with hyperbranched polymers through host-guest interaction.

The preparation of fluorescent inorganic-organic polymer composites for biomedical applications has become one of the most interest research focuses recently. In this work, we reported a novel method for the preparation of Tb3+-doped luminescent layered double hydroxides (LDHs) based composites by taken advantage of a one-pot supramolecular chemistry. The adamantane can be immobilized on the surface of Tb3+-doped LDHs to obtain LDH-Ad, which could be further utilized for modified by the ß-cyclodextrin (ß-CD) containing hyperbranched polyglycerols (ß-CD-HPG) through the host-guest interaction. Based on the characterization results, we demonstrated that the hyperbranched polyglycerol could be facilely introduced on these fluorescent Tb3+-doped LDHs through the method described in this work. The obtained Tb3+-doped LDHs based polymer composites (LDHs-ß-CD-HPG) display improved water dispersibility and still maintain their fluorescence. The results based on various biological assays suggest that LDHs-ß-CD-HPG polymer composites are of low cytotoxicity and their cell uptake behavior can be effectively traced using confocal laser imaging. All of the above results demonstrated that the fluorescent Tb3+-doped LDHs based polymer composites could be effectively surface modified with hydrophilic hyperbranched polymers through a one-pot facile host-guest interaction and the resultant fluorescent composites are of excellent physicochemical properties and display great potential for biomedical applications. This novel surface modification method should also be important for fabrication of other multifunctional composites and therefore great advanced the development of biomedical applications of fluorescent LDHs based polymer composites and related materials.

Facile preparation of luminescent cellulose nanocrystals with aggregation-induced emission feature through Ce(IV) redox polymerization.

Cellulose nanocrystals (CNCs) are a novel type of natural nanomaterials that have attracted tremendous research interest for various applications especially in the biomedical fields owing to their natural origin, biodegradable potential, remarkable biocompatibility and massive reactive hydroxyl groups. In this work, a novel strategy has been developed for fabrication of luminescent CNCs with aggregation-induced emission (AIE) feature for the first time through a facile one-step Ce(IV) redox polymerization for direct surface grafting of AIE dye (PhE) and hydrophilic monomer Poly(ethylene glycol) monomethyl ether acrylate (PEGMA) on CNCs. Various characterization techniques would demonstrate the successful preparation of resultant CNC-PhE-PEGMA with uniform nanoscale size, remarkable fluorescent properties and extremely low cytotoxicity. Furthermore, compared with conventional modification strategy of CNCs, Ce(IV) redox polymerization only need moderate temperature and can operate in aqueous solution utilizing surface hydroxyl groups of CNCs as polymerization activity sites. More importantly, CNC-PhE-PEGMA show desirable fluorescent properties and can be used for cell dyeing, indicating their potential for biomedical applications.

Functionalization of carbon nanotubes with chitosan based on MALI multicomponent reaction for Cu2+ removal.

In this work, we reported a novel "one-pot" strategy for preparation of chitosan-coated carbon nanotubes (CNTs) composites via a combination of Diels-Alder (DA) reaction and mercaptoacetic acid locking imine (MALI) reaction for the first time. To evaluate the adsorption characteristics, the as-prepared samples were applied to remove copper ions (Cu2+) from aqueous solution. The effects of contact time, solution pH, temperature and initial Cu2+ concentration on the adsorption of Cu2+ onto the as-prepared samples were investigated. The chitosan modified CNTs composites showed high affinity and fast kinetics for the adsorption of Cu2+ ions, and adsorption capacity of the composites was found to be 2 times that of pristine CNTs. Adsorption kinetics and thermodynamic indicated a spontaneous and endothermic nature of the adsorption of Cu2+ on the surface of chitosan-coated CNTs composites, kinetically obeyed the pseudo-second-order model. Equilibrium data could be best described by the Langmuir isotherm model, with a maximum monolayer adsorption capacity of 115.84 mg/g. In view of the extensive applicability of DA chemistry and MALI reaction, different carbon nanomaterials based composites with various functional groups could be fabricated and applicable to different fields such as environmental catalysis and biomedicine.

Facile fabrication of cross-linked fluorescent organic nanoparticles with aggregation-induced emission characteristic via the thiol-ene click reaction and their potential for biological imaging.

Over the past several years, the biomedical applications of fluorescent organic nanoparticles (FONs) with aggregation-induced emission (AIE) feature have been extensively explored because the AIE-active FONs could effectively overcome the aggregation caused quenching (ACQ) effect of FONs based on conventional organic dyes. The development of novel methods for synthesis of AIE-active FONs plays a centre role for their biomedical applications. In this work, we reported a facile one-step thiol-ene click reaction for fabrication of AIE-active FONs through conjugation of acrylated PEG and AIE-active tetraphenylethylene (TPE) with two ene bonds using pentaerythritol tetra(3-mercaptopropionate) as the linkage. The successful synthesis of TPE containing AIE-active copolymers was evidenced by various characterization techniques. The particle size and fluorescence properties of the resultant TPE-S-PEG copolymers were evaluated by transmission electronic microscopy and fluorescence spectroscopy. Moreover, the cell viability and cell uptake behavior was also examined to evaluate their potential for biological imaging. We demonstrated that the cross-linked TPE-S-PEG show small size, high water dispersibility, low cytotoxicity and strong fluorescence for tracing. All of these advantages endow the TPE-S-PEG FONs great potential for biological imaging applications. Furthermore, this novel click reaction can take place under mild experimental conditions with high efficiency. It could be also further expanded for preparation of multifunctional AIE-active materials due to the universality of the thiol-ene click reaction and good precursor applicapability. Taken together, we have developed a novel and effective thiol-ene click reaction to fabricate the cross-linked AIE-active FONs, which display excellent physicochemical and biological properties and are promising for biomedical applications.

Mussel-inspired preparation of layered double hydroxides based polymer composites for removal of copper ions.

A novel ternary composite consisting of Mg/Al layered double hydroxides (LDH), polydopamine (PDA) and poly(methyl vinyl ether-alt-maleic anhydride) (PMVE-MA) was fabricated by a facile combination of mussel-inspired chemistry and a ring-opening reaction. Dopamine can serve as a "minimalist mimic" of mussel adhesive protein to form a layer of polydopamine (PDA) on the LDH surface under rather mild conditions (including air atmosphere, aqueous solution, and catalyst free). Subsequently, the PMVE-MA brushes were immobilized onto the PDA modified LDH via a ring-opening reaction. The morphology and chemical compositions of the as-prepared samples were characterized by SEM, TEM, FT-IR, TGA, and XPS. To evaluate the adsorption performance of the PMVE-MA modified LDH (LDH@PDA@PMVE-MA) composites, the obtained samples were used as adsorbents for the removal of copper ions (Cu2+) from an aqueous solution. The results demonstrated that the LDH@PDA@PMVE-MA composites showed a significant improvement in the adsorption efficiency towards Cu2+, and the adsorption capacity of the LDH@PDA@PMVE-MA composites was found to be 2 times higher than that of pristine LDH. Adsorption kinetics showed that the experimental data were fitted well by the pseudo-second-order kinetic model. Equilibrium data could be best described by the Langmuir isotherm model, with the maximum monolayer adsorption capacity of 193.78 mg/g. Thermodynamic studies indicated that the adsorption of Cu2+ onto the LDH@PDA@PMVE-MA composites is an endothermic and spontaneous process. Importantly, it can be easily regenerated by low-cost reagents, and exhibited high removal efficiencies after four cycles of adsorption-desorption. These results suggest that the LDH@PDA@PMVE-MA nanocomposites are good candidate for Cu2+ removal from aqueous solutions.

A facile surface modification strategy for fabrication of fluorescent silica nanoparticles with the aggregation-induced emission dye through surface-initiated cationic ring opening polymerization.

Fluorescent silica nanoparticles (FSNPs) have attracted great interest for potential applications in biological and biomedical fields because they possess higher fluorescence quantum yield and better fluorescence stability as comparison with small organic fluorescent molecules. The encapsulation of covalent linkage with fluorescent organic dyes or fluorescent metal complexes has demonstrated to be the commonly adopted strategies for fabrication of FSNPs previously. However, it is still challengeable to obtain FSNPs based polymer composites with intensive fluorescence and good water dispersibility through a one-pot surface modification strategy. In this paper, we developed a facile method to fabricate novel FSNPs based polymer composites (PhE@MSNs-PEtOx) through introducing the aggregation-induced emission (AIE) dye (PhE-OH) and poly(2-ethyl-2-oxazoline) (PEtOx) onto mesoporous silica nanoparticles (MSNs) based on cationic ring opening polymerization (CROP). The resulting PhE@MSNs-PEtOx composites possess strong fluorescence emission, excellent hydrophilicity and biocompatibility. These features make the final FSNPs based polymer composites great potential for biomedical applications. Taken together, we have developed for the first time that FSNPs based polymer composites can be facilely prepared through the one-pot introduction of AIE dyes and hydrophilic PEtOx on MSNs. Moreover, the novel FSNPs based composites could also be utilized for other biomedical applications considered their properties.

Fabrication and biological imaging of hydrazine hydrate cross-linked AIE-active fluorescent polymeric nanoparticles.

Amphiphilic copolymers play a paramount role in the fabrication of fluorescent polymeric nanoparticles (FPNs) through the self-assembly procedure. In this work, novel hydrazine hydrate cross-linked amphiphilic poly(PEG­co­FHMA) copolymers were constructed via reversible addition-fragmentation chain transfer (RAFT) polymerization, containing an aggregation-induced emission (AIE) active hydrophobic moiety and a hydrophilic poly(ethylene glycol) (PEG) group. Different characterization techniques have been employed to confirm their successful synthesis. Due to their amphiphilic property, the resulting poly(PEG­co­FHMA) copolymers can self-assemble into FPNs in aqueous solution and form poly(PEG­co­FHMA) FPNs with size ranging from 100 to 200 nm. The investigation of photophysical properties demonstrated poly(PEG­co­FHMA) FPNs possess strong fluorescence, large Stokes shift, excellent AIE characteristic, low critical micelle concentration and remarkable photostability. Biological assay results suggested that these cross-linked AIE-active FPNs are of low toxicity and excellent cell dyeing performances. All of these features make them promising candidates for biomedical applications. As compared with typical AIE-active FPNs based on the synthetic AIE-active compounds, the novel cross-linked AIE-active FPNs based on the Schiff base is rather simple, good designable and universal. More importantly, this strategy could also be adopted for preparation of a large number of AIE-active FPNs because of the well designability of copolymers and salicylaldehyde derivatives. Thus this work will provide a novel route for preparation of multifunctional AIE-active FPNs in a rather facile manner.

One-pot ultrafast preparation of silica quantum dots and their utilization for fabrication of luminescent mesoporous silica nanoparticles.

Silica quantum dots (SiQDs) and their luminescent composites have displayed great potential for biomedical applications owing to their chemical inert and low cost. In this work, we report a facile, cost-effective and ultrafast strategy to prepare a stable luminescent SiQDs using N-[3-(trimethoxysilyl)propyl]ethylenediamine (EDAS) and salicylaldehyde as precursors for the first time. These luminescent SiQDs were further utilized for fabrication of luminescent mesoporous silica nanoparticles (MSNs) through direct encapsulation of SiQDs by MSNs. The novel synthetic and modified SiQDs uses commercial raw materials and the entire reaction can be completed within 30 s. The successful preparation of SiQDs and SiQDs@MSNs were characterized by various characterization equipments. The cell viability as well as cell uptake behavior of SiQDs@MSNs were also examined to evaluate their potential for biomedical applications. We demonstrated that these SiQDs@MSNs are low toxicity and of great potential for biological imaging. Based on the above results, we believe that these SiQDs@MSNs should be novel and promising candidates for biomedical applications owing to their intense fluorescence, biocompatibility and high specific surface areas.

A novel strategy for fabrication of fluorescent hydroxyapatite based polymer composites through the combination of surface ligand exchange and self-catalyzed ATRP.

A novel and facile strategy that combination of surface ligand exchange and photo-initiated atom transfer radical polymerization (ATRP) has been developed for the preparation of fluorescent hydroxyapatite (HAp) based polymer composites, which were utilized for biological imaging applications. In particular, the photo-initiated ATRP not only inherited advantages of traditional ATRP but also overcome its deficiencies such as high energy consumption, transition metal contamination and long reaction time. In this method, a hydrophilic and biocompatible PEGMA was introduced to enhance the hydrophilic and biocompatibility of HAp nanocomposites. Simultaneously, the HAp-poly(PEGMA-co-AcFl) composites are endowed with bright green fluorescence by grafting with AcFl on the surface via copolymerization. The physicochemical properties of HAp-poly(PEGMA-co-AcFl) composites were characterized by a series of methods in detail. Results confirmed that HAp-poly(PEGMA-co-AcFl) composites possess controlled size and morphology, high water dispersibility and strong fluorescence. The cell viability and cell uptake behavior demonstrated that HAp-poly(PEGMA-co-AcFl) composites present low toxicity and can be potentially used for biological imaging. Taken together, we have developed a facile and efficient method for the fabrication of fluorescent HAp composites with desirable physicochemical and biological properties.

Surface PEGylation and biological imaging of fluorescent Tb3+-doped layered double hydroxides through the photoinduced RAFT polymerization.

Tb3+-doped layered double hydroxides (LDHs) exhibit excellent optical characteristics, uniform size and uniform morphologies when synthesized through a hydrothermal method. However, due to their lack of functional groups and poor dispersibility, applications of these fluorescent Tb3+-doped LDHs have been largely impeded especially in the biomedical fields. In this work, a novel strategy was developed for the surface modification of these fluorescent Tb3+-doped LDHs using photoinduced surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization with hydrophilic poly(ethylene glycol) methacrylate (PEGMA) as the monomer. The final products were obtained via the metal free surface-initiated RAFT polymerization with light irradiation. Successful preparation of these fluorescent LDHs polymer composites (LDH-PEG) was confirmed by a number of analytical technologies, such as transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis. In addition, laser scanning confocal microscope was employed to examine the cell uptake behavior of the LDH-PEG composites and evaluate their potential for biomedical applications. We demonstrated that the hydrophilic monomer PEGMA could be facilely grafted on the surface of Tb3+-doped LDHs through metal free photoinduced surface-initiated RAFT polymerization. The resultant LDH-PEG composites displayed high water dispersibility, strong fluorescence, low cytotoxicity and a desirable cell uptake performance. These features of the LDH-PEG composites indicated their great potential for biomedical applications. More importantly, photoinduced RAFT polymerization has the advantages of a conventional controlled living radical polymerization, which could overcome drawbacks such as toxicity, the fluorescence quenching effects of metal catalysts and the complex synthesis of chain transfer agents. Therefore, this method could be an alternative tool for the surface modification of materials and fabrication of multifunctional fluorescent nanomaterials based polymer composites.

A one-step ultrasonic irradiation assisted strategy for the preparation of polymer-functionalized carbon quantum dots and their biological imaging.

Fluorescent carbon nanoparticles (FCNs) have gradually become the most promising alternative candidates to other traditional fluorescent nanomaterials for biological applications on account of their excellent fluorescence property and remarkable biocompatibility. Although many methods have reported on the preparation of FCNs, to date, no studies have reported the preparation of polymers of functionalized FCNs. A high-efficiency method was developed in this work to synthesize high-quality poly(ethylene oxide) (PEG)-functionalized FCNs from cigarette ash and thiol group-containing PEG via a facile one-pot ultrasonic irradiation treatment. A series of characterization techniques demonstrated the uniform nanoscale size, good fluorescence stability, high water dispersibility and remarkable biocompatibility of the generated FCNs. Furthermore, cell imaging was easily achieved at high resolution using the synthetic FCNs as probes, which validates their potential for bioimaging applications. In summary, an efficient one-pot strategy is reported for the first time on the preparation of PEG-functionalized FCNs with the assistance of ultrasonic irradiation. This method should be of great research interest for the fabrication of other polymer-functionalized FCNs with designable properties and functions.

Facile fabrication of luminescent hyaluronic acid with aggregation-induced emission through formation of dynamic bonds and their theranostic applications.

Aggregation-induced emission (AIE) is an abnormal phenomenon, which has been extensively explored for various applications. Taken advantage of the unique AIE feature, a number of luminescent nanoprobes with strong fluorescence intensity could thus be fabricated through different strategies; however, the fabrication of AIE-active carbohydrate polymers is still challenge owing to the poor solubility of carbohydrate polymers in most of organic solvents. In this work, a rather facile strategy has been developed for fabricating AIE-active sodium hyaluronate (Sh) through the formation of dynamic phenyl borate between the phenylboronic acid groups of AIE dye (An-B(OH)2)) and Sh in a "one-pot" route. This reaction could occur under low temperature, air atmosphere and in the present water. The physicochemical properties, biocompatibility, biological imaging and drug delivery performance of the final An-Sh fluorescent organic nanoparticles (FNPs) were confirmed by different characterization techniques. Results suggested that An-Sh FNPs possess high water dispersibility, strong fluorescence, and good biocompatibility. These excellent properties make An-Sh FNPs great potential for biological imaging and controlled drug delivery applications. In conclusion, we have developed a facile one-pot strategy for the preparation of AIE-active FNPs through the formation of dynamic bonds in rather mild experimental conditions. The outstanding properties and performance of An-Sh FNPs make them promising candidates for biological imaging and controlled drug delivery applications.