Construction of ionic liquid functionalized MXene with extremely high adsorption capacity towards iodine via the combination of mussel-inspired chemistry and Michael addition reaction.

In this work, a highly efficient adsorbent based on ionic liquid functionalized MXene has been fabricated through the combination of mussel-inspired chemistry and Michael addition reaction. The surface of MXene was first coated with polydopamine (PDA) through self-polymerization of dopamine and the amino groups were introduced on the surface of MXene simultaneously. After that, the ene bond-containing ionic liquid was further immobilized on the surface of MXene-PDA to obtain MXene-PDA-IL. As a concept, the adsorptive removal of iodine using MXene-PDA-IL was conducted and the effects of various factors on the adsorption behavior were examined. The experimental data were analyzed by intermittent adsorption experiments, the adsorption kinetics, adsorption isotherm, adsorption thermodynamics, and cyclic adsorption experiments. We found that the adsorption procedure could reach equilibrium within 10 min after mixing adsorbent and iodine. The maximum adsorption capacity of MXene-PDA-IL towards iodine was as high as 695.4 mg g-1, which is greater than most of reported adsorbents. Considered the advantages of mussel-inspired chemistry for surface functionalization and the adsorption capacity of ionic liquids, the method could be used for construct a number of composites with potential for adsorption applications.

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.

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.

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.

AIE-active self-assemblies from a catalyst-free thiol-yne click reaction and their utilization for biological imaging.

Aggregation-induced emission (AIE) should be the most interest fluorescent phenomenon over the past few decades. The luminescence polymeric nanoparticles (LPNs) with AIE characteristic have attracted great research attention for biological imaging and many other biomedical applications owing to their good biocompatibility and negative toxicity. However, the preparation of LPNs with desirable optical properties using traditional organic dyes still remains a great challenge for the aggregation-caused quenching (ACQ) effect and aggregation of hydrophobic dyes in the core of LPNs. In this work, we reported a novel and simple method for fabrication of biodegradable AIE-active LPNs via the combination of condensation and click reactions. For preparation of these AIE-active LPNs, the thiol groups-containing hydrophilic copolymers (PEG-MA) were first synthesized through the condensation reaction between polyethylene glycol and mercaptosuccinic acid. The PEG-MA copolymers were further reacted with AIE dye PhE-OE through a catalyst-free thiol-yne click reaction. These obtained PEG-MA-PhE LPNs were fully characterized by a number of characterization techniques. All the results confirmed that PEG-MA-PhE LPNs possess excellent compatibility, intense red luminescence, great photostability and high water dispersibility. These features make PEG-MA-PhE LPNs promising candidates for various biomedical applications.

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.

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.

One-step synthesis of europium complexes containing polyamino acids through ring-opening polymerization and their potential for biological imaging applications.

Lanthanide-doped nanoprobes have received significant attentions for utilization in biological sensing and imaging due to their unique optical properties. However, only few works were focused on fabrication of europium complexes based fluorescence polymeric nanoparticles (FPNs) with excellent biocompatibility and biodegradability. In this study, we fabricated the FPNs (named as Eu(TTA)3Phen-GluEG FPNs) with encapsulated europium complexes which show low cytotoxicity, high sensitivity and deep penetration. Free amine group present on europium complexes initiated the ring-opening polymerization (ROP) of side-chain modified glutamic acid NCAs, offering a simple and effective method to prepare europium core FPNs with a uniform size distribution. Europium (III) chelates were furnished with a functional polyamino acid shell to fabricate biocompatible and biodegradable FPNs. Biological evaluation results demonstrate that such fabricated FPNs process excellent biocompatibility and dyeing performance. Therefore, we can expect that the fabrication approach will attract much research interest and effort on the preparation of biodegradable probes for various biological applications.

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.

Fabrication and characterization of hyperbranched polyglycerol modified carbon nanotubes through the host-guest interactions.

Carbon nanotubes (CNTs) are novel carbon composites that have received extensive research attention for biomedical applications thanks to their excellent cell membrane penetration capability and large specific surface areas. Nevertheless, the poor dispersibility in aqueous solution still perplexes the biomedical applications of CNTs. Although, there are many researched about that modify hydrophilic polymers to the surface of CNTs, facile and efficient strategies are still highly desirable to be developed. In this produce, an efficient and facile strategy for surface modification of CNTs with excellent water dispersibility was developed via supramolecular chemistry. On the one hand, we synthesize the ß-CD-HPG via anionic polymerization. On the other hand, adamantane chloride was first reacted with the hydroxyl group of radiant CNTs through esterification to obtain CNT-Ad. Finally, it only need mild reaction conditions and fast reaction time (30 min) that ß-CD-HPG form an exact 1:1 inclusion complex with CNT-Ad via host-guest interaction. The successful preparation of CNT-ß-CD-HPG composites could be confirmed via a series of characterization techniques. Then, we further verify that CNT-ß-CD-HPG composites possess the remarkable water dispersibility and enormous potential for controlled drug delivery systems. Therefore the facile strategy for the preparation of CNT-ß-CD-HPG composites with excellent water dispersibility via supramolecular chemistry would possess rosy prospects in biomedical applications.

Preparation of water dispersible and biocompatible nanodiamond-poly(amino acid) composites through the ring-opening polymerization.

Nanodiamond (ND) is one of the most fascinating carbon materials that have been extensively investigated for biomedical applications owing to its small size, high specific surface areas, chemical inert and desirable biocompatibility. It has been reported that surface modification of ND with polymers could not only improve the dispersibility of final ND based composites but also endow them novel functions to fulfill the requirement for biomedical applications. Although some strategies have been developed previously, surface modification of ND with poly(amino acid)s has not been reported previously. In this work, poly(amino acid)s functionalized ND composites were fabricated through a ring-opening polymerization of α-amino acid N-carboxyanhydrides (NCAs), which was synthesized by conjugation of hydrophilic ethylene glycol with glutamic acid. The successful preparation of ND-GluEG composites was confirmed by a series of characterization techniques. The results suggest that the water dispersibility of final ND-GluEG composites is obviously improved. Moreover, ND-GluEG composites show low toxicity and are of great potential for biomedical applications.

Surface grafting of rare-earth ions doped hydroxyapatite nanorods (HAp:Ln(Eu/Tb)) with hydrophilic copolymers based on ligand exchange reaction: Biological imaging and cancer treatment.

Rare-earth ions doped hydroxyapatite nanoparticles (HAp:Ln NPs) have demonstrated to be very promising candidates for biological imaging applications owing to their small size and chemical compositions similar to bone. However, these HAp:Ln NPs with controllable size and morphology should be prepared under hydrothermal treatment with hydrophobic molecules as the protective layers. The hydrophobic nature of these luminescent HAp:Ln NPs largely impeded their applications in biomedical fields. In this study, a novel and effective strategy has been developed for the surface modification of HAp:Ln nanorods through the combination of surface ligand exchange reaction and reversible-addition fragmentation chain transfer (RAFT) polymerization using 2-methacryloyloxyethyl phosphorylcholine (MPC) and itaconic acid (IA) as the monomers. Herein, a small molecule adenosine 5'-monophosphate disodium salt (AMP) that contains a phosphate group and two hydroxyl groups was used to displace the hydrophobic oleic acid on pristine HAp NPs through surface ligand exchange reaction owing to its stronger interaction with HAp NPs. On the other hand, the MPC and IA were introduced on HAp NPs through RAFT polymerization after the chain transfer agent was immobilized on the HAp NPs through the esterification reaction. The poly(IA-MPC) could not only endow the high water dispersibility but also be used for loading anticancer agent cisplatin (CDDP) through coordination interaction. To evaluate their potential biomedical applications, the cell uptake behavior, drug loading capacity and release behavior as well as cell viability of HAp:Ln-AMP-poly(IA-MPC) polymeric composites were examined. We demonstrated that the method developed in this work is very effective for introduction of functional polymers onto HAp:Ln nanorods. The HAp:Ln-AMP-poly(IA-MPC) composites are promising for cell imaging and controlled delivery of CDDP.