Modification of Silica Nanoparticles with Miktoarm Polymer Brushes via ATRP

Silica nanoparticles were successfully modified with miktoarm brushes via atom transfer radical polymerization (ATRP) using three different approaches. In the first approach: “graft onto and from”, a poly(tert-butyl acrylate) (PtBA) macroinitiator was grafted onto the surface of a monomer-modified silica nanoparticle. Then, polystyrene (PSt) brush was grafted from the surface-tethered reactive chain end. In the second approach: “two-step reverse ATRP”, the PtBA and poly(n-butyl acrylate) (PBA) brushes were consecutively grafted from initiator-modified silica particles via ATRP. The polymerization was initiated from the silica surface via a two-step controlled thermal decomposition of surface-tethered diazo initiator moieties. In the third method: “diblock first”, a diblock copolymer of poly(tert-butyl acrylate) and poly(glycidyl methacrylate) (PtBA-b-PGMA) was grafted onto amine-modified silica particles. The diblock copolymer was covalently attached to the silica surface via interaction between surface-tethered amine groups and the short reactive block containing glycidyl groups. Next, the polystyrene brushes were grafted from surface-tethered reactive chain end. The materials prepared by three different approaches were characterized using gel permeation chromatography (GPC) and thermogravimetric analysis (TGA). The PtBA brushes were hydrolyzed under acidic conditions to form poly(acrylic acid) (PAA) brushes. The resulting materials were imaged using atomic force microscopy (AFM) and transmission electron microscopy (TEM).     

Synthesis and self-assembly behavior of POSS tethered amphiphilic polymer based on poly(caprolactone) (PCL) grafted with poly(acrylic acid) (PAA) via ROP,ATRP, and CuAAC reaction

This investigation reports the preparation and self-assembly behavior of polyhedral oligomeric silsesquioxane (POSS) containing poly(caprolactone)-graft-poly(acrylic acid) (POSS-PCL-graft-PAA) polymer. This article focuses on the self-assembly behavior of POSS tethered amphiphilic graft copolymer. In this investigation, POSS tethered alkyne functionalized polycaprolactone (PCL) was prepared by strategic ring opening polymerization (ROP) of ε-caprolactone and α-propargyl-ε-caprolactone using hydroxyl-terminated POSS as an initiator. Azide-terminated poly(tert-butyl acrylate) (P ^t BA) was grafted onto functional PCL via Cu-catalyzed azide-alkyne “click” (CuAAC) reaction. Finally, hydrolysis of the tert-butyl ester group into acid furnished the POSS tethered PCL-graft-PAA polymer. This amphiphilic graft copolymer was characterized by GPC, NMR, and FT-IR analyses and the morphology of the graft copolymer analyzed by HRTEM and FESEM analyses. On changing the graft copolymer concentration (low to high) in water, the morphology of the final graft copolymer changed from micelles to worm-like and core-shell. The structural motif of POSS plays an important role in this morphological transformation. The pH sensitivity was studied using DLS analysis as well as via release profile of rhodamine B as a model compound.     

Polyelectrolytes based on poly(<Emphasis Type="Italic">p</Emphasis>-acryloyloxybenzaldehyde) with arsonic acid groups useful in the colloidal synthesis of silver nanoparticles

Several methods have been developed for synthesis of Ag nanoparticles. However, Ag nanoparticles are unstable materials, and they tend to agglomerate losing their properties. Polymers are commonly employed for the stabilization of Ag nanoparticles in colloidal solutions. Polymers with ionic groups such polyelectrolytes can stabilize metallic nanoparticles through electrostatic and steric effects. In this work we employed poly(p-acryloyloxybenzaldehyde) and their derivates containing arsonic acid groups in ortho and para positions as reducing and stabilizing agents in the synthesis of Ag nanoparticles. Polyelectrolytes containing arsonic acid groups in ortho position were better reducing agents than the poly(p-acryloyloxybenzaldehyde) and the polyelectrolyte with arsonic acid group in para position, leading to the reduction of Ag⁺ ions in short reaction time. The polyelectrolyte with arsonic acid groups in para position was the best stabilizing agent leading to obtaining Ag nanoparticles with the smallest average size.     

Synthesis of PAA-g-PNIPAM well-defined graft polymer by sequential RAFT and SET-LRP and its application in preparing size-controlled super-paramagnetic Fe3O4 nanoparticles as a stabilizer

A series of well-defined double hydrophilic graft copolymers, poly(acrylic acid)-g-poly(N-isopropylacrylamide) (PAA-g-PNIPAM), was employed as a novel water-soluble coating for constructing superparamagnetic iron oxide nanoparticles. The copolymer was synthesized via a three-step procedure: firstly, a well-defined hydrophobic PtBA-based backbone, poly(tert-butyl 2-((2-chloropropanoyloxy)-methyl)acrylate)-co-poly(tert-butyl acrylate), (PtBCPMA₁₉-co-PtBA₁₈), was prepared through RAFT copolymerization of a new trifunctional acrylic monomer, tert-butyl 2-((2-chloropropanoyloxy)methyl)acrylate and tert-butyl acrylate; secondly, taking this backbone as a macroinitiator to initiate SET-LRP of N-isopropylacrylamide resulted in well-defined (poly(tert-butyl 2-((2-chloropropanoyloxy)methyl)-acrylate)-co-poly(tert-butyl acrylate))-g-poly(N-isopropylacrylamide) ((PtBCPMA-co-PtBA)-g-PNIPAM) amphiphilic graft copolymers with relatively narrow polydispersities (M_w/M_n ≤ 1.31); thirdly, handling (PtBCPMA-co-PtBA)-g-PNIPAM in acidic conditions afforded PAA-g-PNIPAM graft copolymers. The resulting PAA-g-PNIPAM copolymers were directly utilized as a polymeric stabilizer in the preparation of superparamagnetic Fe₃O₄ nanoparticles. The particle size can be readily tuned in the range of 12.1–23.2 nm by varying the amount of PAA-g-PNIPAM copolymer or the length of PNIPAM side chain. Besides, the structure and properties of prepared Fe₃O₄/polymer nanocomposites were characterized by XRD, FT-IR, TGA, TEM, and magnetic measurement in detail.     

Synthesis of amphiphilic triblock copolymers and application for morphology control of calcium carbonate crystals

A series of amphiphilic triblock copolymers poly(ethylene glycol)-block-poly(acrylic acid)-block-poly(n-butyl acrylate) (PEG-b-PAA-b-PnBA) differing only in the relative block lengths were synthesized by the acid-catalyzed elimination of the tert-butyl groups from poly(ethylene glycol)-block-poly(tert-butyl acrylate)-block-poly(n-butyl acrylate) (PEG-b-PtBA-b-PnBA), which was synthesized by atom-transfer radical polymerization (ATRP). The degree of polymerization, molecular weight and percentage of hydrolysis of the product PEG-b-PAA-b-PnBA were studied by gel permeation chromatography (GPC), NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF-MS). Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were used to study the aggregation states of copolymers in water solution. The radii of the copolymer micelles shrink as Ca²⁺ is introduced into the solutions. The crystallization behaviors of calcium carbonate controlled by copolymer 1 (PEG₁₁₂-b-PAA₈₆-b-PnBA₆₀) and copolymer 2 (PEG₁₁₂-b-PAA₄₀-b-PnBA₇₂) differing mainly in the length of PAA block were systematically studied. It was found that the crystallization products are composed of calcite and vaterite, and the ratio of vaterite to calcite increases with increasing the concentration of copolymer 1. For copolymer 2, however, only calcite is obtained at all the concentration range investigated in this work.     

Polyisobutylene-based miktoarm star polymers via a combination of carbocationic and atom transfer radical polymerizations

Poly(isobutylene-b-styrene) (PIB-PS) copolymers and polyisobutylene (PIB) homopolymers were synthesized via quasiliving carbocationic polymerization from the initiator 3,3,5-trimethyl-5-chlorohexyl acetate, which contains a protected hydroxyl group. The PIB block was created at −70 °C in a methylcyclohexane/methyl chloride (60:40) cosolvent system, using TiCl₄ as co-initiator, followed optionally by sequential addition of styrene. Using a strong base, the acetate head group of the resulting block copolymer was cleaved to yield a hydroxyl group, which was subsequently esterified with the branching agent 2,2-bis((2-bromo-2-methyl)propionatomethyl)propionyl chloride (BPPC) to create dual initiating sites for atom transfer radical polymerization (ATRP). ATRP of tert-butyl acrylate was carried out using a Cu(I)Br/1,1,4,7,7-pentamethyldiethylenetriamine (PMDETA) catalyst system. In some cases, the ester side chains of the poly(tert-butyl acrylate) (PtBA) blocks were cleaved to create poly(acrylic acid) (PAA) blocks. The final miktoarm star polymers had compositions that were very close to theoretical.     

Synthesis and characterization of polyimides from 4,4′-(3-(<Emphasis Type="Italic">tert</Emphasis>-butyl)-4-aminophenoxy)diphenyl ether

A novel diamine 4,4′-(3-(tert-butyl)-4-aminophenoxy)diphenyl ether (4) was synthesized from 2-tert-butylaniline and 4,4′-oxydiphenol through iodination, acetyl protection, coupling reaction and deacetylation protection. Then some polyimides (PIs) were obtained by one-pot polycondensation of diamne 4 with several commercial aromatic dianhydrides respectively. They all exhibit enhanced solubility in organic solvents (such as NMP, DMF, THF and CHCl₃ etc.) at room temperature. Their number-average molecular weights are in the range of (2.1–3.7)?×?10⁴ g/mol with PDI from 2.25 to 2.74 by GPC. They can form transparent, tough and flexible films by solution-casting. The light transparency of them is higher than 90% in the visible light range from 400 nm to 760 nm and the cut-off wavelengths of UV–vis absorption are below 370 nm. They also display the outstanding thermal stability with the 5% weight loss temperature from 525 °C to 529 °C in nitrogen atmosphere. The glass transition temperatures (T _g s) are higher than 264 °C by DSC. XRD results demonstrate that these PIs are amorphous polymers with the lower water absorption (<0.66%). In summary, the incorporation of tert-butyl groups and multiple phenoxy units into the rigid PI backbones can endow them excellent solubility and transparency with relatively high T _g s.     

Synthesis of novel polymer brushes of poly(acrylonitrile-<Emphasis Type="Italic">g</Emphasis>-<Emphasis Type="Italic">N,N</Emphasis>ʹ-dimethylaminoethyl methacrylate) by nitrile modification

Functional polymer brushes of poly(acrylonitrile-g-N,N?-dimethylaminoethyl methacrylate) were efficiently synthesized by a novel approach of combining Cu(0)-mediated controlled/“living” radical polymerization and nitrile click chemistry. The poly(acrylonitrile-g-N,N?-dimethylaminoethyl methacrylate) as a promising material exhibited excellent hydrophile–lipohile balance in the process of self-assembly and could autonomously develop the orderly structure micelle in N,N?-dimethylformamide/water mixture solvent for the potential application of a new drug delivery carrier. In the process of self-assembly, polyacrylonitrile acted as a backbone of the functional polymer brushes due to its hydrophobic feature and poly(N,N?-dimethylaminoethyl methacrylate) as the branch of functional polymer brushes due to its hydrophilic characteristic, which both were prepared by Cu(0)-mediated controlled/“living” radical polymerization with ethyl-bromoisobutyrate as initiator. Poly(N,N?-dimethylaminoethyl methacrylate) containing azide end group was synthesized by substitution reaction of poly(N,N?-dimethylaminoethyl methacrylate) containing bromine end groups with sodium azide in N,N?-dimethylformamide. The click reaction between the nitrile of polyacrylonitrile and the azide group of poly(N,N?-dimethylaminoethyl methacrylate) was carried out under ammonium chloride as catalyst in N,N?-dimethylformamide. The polymer was further confirmed by GPC, FTIR, ¹H NMR and TGA. Meanwhile, the micelles with different morphologies were observed by TEM, and the particle diameter distribution of self-assembled micelle from the PAN-g-PDMAEMA brushes was determined by DLS.     

Microstructure study of poly(isobutyl acrylate) and poly(<Emphasis Type="Italic">sec</Emphasis>-butyl acrylate) by incremental analysis of <Superscript>13</Superscript>C NMR spectra

Microstructure of poly(isobutyl acrylate) (PiBuA) and poly(sec-butyl acrylate) (PsBuA), prepared by free radical and anionic polymerization, was investigated by ¹³C NMR spectroscopy. The carbonyl signal in the 100 MHz ¹³C NMR spectra of both homopolymers provided sufficient resolution to perform detailed analysis of distribution of configurational sequences at the pentad/heptad level. Application of Bernoulli and first order Markov statistics to determine probabilities of configurational sequences and incremental calculation to estimate chemical shifts of the individual sequences allowed for positive simulation of carbonyl signals.     

Polymer Protected and Gel Immobilized Gold and Silver Nanoparticles in Catalysis

This mini-review is focused on preparation of polymer protected gold (AuNPs) and silver (AgNPs) nanoparticles that are immobilized on the surface of inorganic supporters and within hydrogel and/or cryogel matrices. A series of water soluble polymers such as poly(N-vinylpyrrolidone), poly(acrylic acid), branched polyethyleneimine, and amphoteric cryogel based on the copolymer of N,N-dimethylaminoethylmethacrylate and methacrylic acid poly(DMAEM-MAA) were used for reduction and stabilization of metal nanoparticles. The catalytic properties of polymer protected AuNPs and AgNPs were evaluated with respect to hydrogen peroxide decomposition, hydrogenation of 4-nitrophenol and oxidation of cyclohexane.     

Amphiphilic cylindrical brushes with poly(acrylic acid) core and poly(n-butyl acrylate) shell and narrow length distribution

Core-shell cylindrical polymer brushes with poly(t-butyl acrylate)-b-poly(n-butyl acrylate) (PtBA-b-PnBA) diblock copolymer side chains were synthesized via ‘grafting from’ technique using atom transfer radical polymerization (ATRP). The formation of well-defined brushes was confirmed by GPC and ¹H NMR. Multi-angle light scattering (MALS) measurements on brushes with 240 arms show that the radius of gyration scales with the degree of polymerization of the side chains with an exponent of 0.57±0.05. The hydrolysis of the PtBA block of the side chains resulted amphiphilic cylindrical core-shell nanoparticles. In order to obtain a narrow length distribution of the brushes, the backbone, poly(2-hydroxyethyl methacrylate), was synthesized by anionic polymerization in addition to ATRP. The characteristic core-shell cylindrical structure of the brush was directly visualized on mica by scanning force microscopy (SFM). Brushes with 1500 block copolymer side chains and a length distribution of l_w/l_n=1.04 at a total length l_n=179 nm were obtained. By choosing the proper solvent in the dip-coating process on mica, the core and the shell can be visualized independently by SFM.     

Janus gold nanoparticle with bicompartment polymer brushes templated by polymer single crystals

Janus particles have attracted increasing attention from the communities of materials science, chemistry, physics and biology. While large size Janus particles are readily achieved, synthesizing Janus nanoparticles (JNP) with diameters smaller than ∼20 nm remains a challenging task. In this article, we report a systematic study on growing polymer brushes on polymer-single-crystal-immobilized 6 and 15 nm diameter gold nanoparticles (AuNPs) using atom transfer radical polymerization. JNPs with bicompartment polymer brushes, such as poly(ethylene oxide) (PEO)/poly(methyl methacrylate), PEO/poly(tert-butyl acrylate), and PEO/poly(acrylic acid), were synthesized. The grafting densities can be carefully controlled. The Janus feature of these particles was confirmed using both platinum nanoparticle decoration and UV/Vis spectroscopy analysis. The surface plasmon resonance absorbance of Janus particles exhibited a blue shift compared with that of symmetric AuNPs with either homopolymer or mixed polymer brushes. This work demonstrated that using polymer single crystal as the templates, small size (<20 nm diameter) JNPs having bicompartment polymer brushes can be readily obtained. The ability to tune grafting density and molecular weight of polymer brushes can lead to controlled particle amphiphilicity.     

Development of pH-sensitive and antibacterial gelatin/citric acid/Ag nanocomposite hydrogels with potential for biomedical applications

This work aimed to prepare pH-sensitive and antibacterial drug releasing systems through a completely green route. To achieve this, the gelatin natural biopolymer was crosslinked with citric acid in the presence of Ag nanoparticles (NPs). Interestingly, Ag NPs formation and gelatin crosslinking were simultaneously occurred during annealing of samples without need for any toxic chemicals, which were confirmed by FTIR, UV-vis spectra, SEM and TEM observations. In addition, potential of the citric acid crosslinked-gelatin/Ag nanocomposite hydrogels was successfully explored for drug delivery applications using cefixime as a model drug. It was found that these hydrogels have pH-dependent swelling and drug release behavior with higher drug release at pH 7.4 compared to pH 1.2. Also, an antibacterial effect against the E. coli and S. aureus microorganisms was achieved by incorporation of Ag NPs into hydrogels. These hydrogels can be considered as stimuli responsive materials for oral drug delivery and wound dressing applications.     

Pectin-graft-poly(2-acrylamido-2-methyl-1-propane sulfonic acid) silver nanocomposite hydrogel beads: evaluation as matrix material for sustained release formulations of ketoprofen and antibacterial assay

Pectin-graft-poly(2-acrylamido-2-methyl-1-propane sulfonic acid) (Pec-g-PAMPS) gel was made in the form of beads by subjecting the solution containing pectin (Pec), 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS) and ammonium peroxodisulphate to microwave irradiation followed by ionic crosslinking in CaCl₂ solution. Gel beads containing silver nanoparticles were also prepared by the same method but with the addition of silver nitrate and trisodium citrate solution prior to microwave irradiation. The synthesized Pec-g-PAMPS and its silver nanocomposite (Pec-g-PAMPS-Ag) gel beads were characterized using FTIR, TGA, XRD, SEM, EDS and TEM techniques. The effect of incorporation of Ag NPs on the biological activity of Pec-g-PAMPS was studied by zone inhibition method considering two bacterial strains namely E. coli and B. subtilis. The nanocomposite gel exhibited higher antibacterial activity compared to the parent gel, which was comparable with the standard drug, Streptomycin. The in vitro drug release profiles of the parent gel and its composite were analyzed using Ketoprofen (KF) to study the effect of incorporation of Ag NPs on the drug release behavior of the Pec-g-PAMPS. The presence of silver nanoparticles enhanced both swelling of the gel beads and the extent of drug release significantly.     

Enzyme-Catalyzed Synthesis of Monoacylglycerols Citrate: Kinetics and Thermodynamics

The kinetics and thermodynamics of the esterification of citric acid (CA) and monoglycerides (MGs) for citrate esters of monoacylglycerols catalyzed by Novozym 435 in tert-butyl alcohol system was studied in this work. The relationship between initial reaction rate and temperature was established, based on the Arrhenius law. A linear relationship was established between the initial reaction rate and enzyme load up to 3 g/L, which demonstrated that the influence of external mass transfer limitations on the reaction could be eliminated. The reaction kinetics agreed with the Ping-Pong Bi–Bi mechanism with CA inhibition characterized by V _max, K _B, K _A, and K _iA , values of 0.7092 mmol/(min g), 0.0553, 0.0136 and 0.1948 mol/L, respectively. The model was used to simulate the reaction process. The values calculated from the kinetic mode agreed well with the experimental rate data under the different MG and CA concentrations.     

Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles coated by new functionalized tetraaza-2,3 dialdehyde micro-crystalline cellulose: synthesis,characterization, and catalytic application for degradation of Acid Yellow 17

In this study, we developed an original approach for preparing cellulose-coated magnetite nanoparticles (NPs). Two novel Schiff bases (PDA-g-DAC) and [Bz-(PDA-g-DAC)] were synthesized via condensation reactions of periodate oxidized micro-crystalline cellulose (DAC) with o-phenylene diamine (PDA) to obtain its azomethine derivative with 85% yield. Subsequently, the functionalization of (PDA-g-DAC) with benzil (Bz) yields the tetraaza macrocycle [Bz-(PDA-g-DAC)]. The physicochemical characterization of the condensation products was performed using ¹³CNMR, FTIR, ATG, DSC, and X-ray diffraction techniques. Magnetic nanomaterial-based Schiff base cellulose was successfully prepared using in situ chemical co-precipitation of coordinated ferric and ferrous ions in cellulose Schiff base matrix under optimized conditions, and then, its magnetic properties were characterized. The results demonstrated that the Fe₃O₄ NPs coated with [Bz-(PDA-g-DAC)] were homogeneously coated in the matrix under ultrasonic irradiation with the saturation magnetization of 69.50 emu g^?1. In addition, XRD line broadening analysis showed that the average particle size of the NPs was 37.3 nm. Furthermore, FTIR spectra demonstrated that [Bz-(PDA-g-DAC)] concavity was anchored to magnetite Fe₃O₄ NPs through azomethine groups. Vibrating sample magnetometry (VSM) of [Bz-(PDA-g-DAC)@Fe₃O₄] magnetic nanocomposite samples showed the typical behavior of ferromagnetism. This study provided a green and facile method to inhibit magnetic nanoparticle aggregation. Activity results revealed that the prepared [Bz-(PDA-g-DAC)@Fe₃O₄] catalyst shows the maximum activity for degradation of Acid Yellow 17 (AY17) compared to other prepared catalysts. After degradation reaction, the [Bz-(PDA-g-DAC)@Fe₃O₄] catalyst was recovered from the reaction mixture via an external magnet and used for further five consecutive cycles with excellent catalytic activity, successively, which was comparable to the fresh catalyst. The catalyst degradation efficiency and its easy separation exhibited that [Bz-(PDA-g-DAC)@Fe₃O₄] catalyst is a promising material for the removal of AY17 from aqueous solutions in green chemistry perspectives.     

Mechanistic studies of methyl methacrylate polymerization in the presence of cobalt complex with sterically-hindered redox-active ligand

The influence of bis[4,6-di-tert-butyl-N-(2,6-dimethylphenyl)-o-iminobenzosemiquinono]cobalt (II) on radical polymerization of methyl methacrylate initiated by AIBN at 70–90 °C was studied. The introduction of cobalt complex bearing redox ligands into reaction media allows to provide polymerization of methyl methacrylate without self-acceleration with linear increase of molecular weight with conversion giving polymers with relatively low molecular weight distribution. The results of IR and NMR spectrometry and MALDI mass spectroscopy measurements show that the possibility of β-hydrogen transfer between complex and propagating radical during polymerization is minimal. The electron donating additives as tert.-butyl amine and pyridine have no activating effect on polymerization. The results of our experiments provided at different concentrations of initiator show that polymerization proceeds via degenerative chain transfer mechanism.     

Enhanced toughness for polyamide 6 with a core-shell structured polyacrylic modifier

Polyamide 6 (PA 6) is an important thermoplastic with excellent strength, stiffness, and good chemical resistance. The notch sensitivity and low notch impact toughness of PA 6, however, limit its application. A core-shell structured polyacrylic modifier, poly(n-butyl acrylate)/poly(methyl methacrylate-co-methacrylic acid) modifier (PBM-co-MAA), was used to toughen PA 6. To study the effect of PBM-co-MAA particles on the toughness of PA 6, various contents of poly(BA) in PBM-co-MAA latexes of 300 nm were synthesized by seed emulsion polymerization. The results showed that polymerization had an instantaneous conversion higher than 95 wt% and an overall conversion higher than 97 wt%. The PBM-co-MAA particles had a clear core–shell structure confirmed by transmission electron microscope (TEM). The mechanical properties of PA 6/PBM-co-MAA blends showed that the notch impact strength of PA 6/PBM-co-MAA blends with 85 wt% poly(BA) and 0.5 wt% MAA in PBM-co-MAA was nearly six times greater than that of pure PA 6, being consistent with the scanning electron microscope (SEM) observations on the fractured surfaces. The notch impact strengths of PA 6/PBM-co-MAA blends were also better than that of PA 6/PBM blend, which did not contain MAA functional group in the modifier. Dynamic mechanical analysis (DMA) results showed improved compatibility between PA 6 matrix and core-shell toughening modifier, which should contain a functional group in the shell layer and a suitable core rubbery content to toughen PA 6 effectively.     

A magnetic polypeptide nanocomposite with pH and near-infrared dual responsiveness for cancer therapy

A magnetic polypeptide nanocomposite with pH and near-infrared (NIR) dual responsiveness was developed as a drug carrier for cancer therapy, which was prepared through the self-assembly of Fe₃O₄ superparamagnetic nanoparticles, poly(aspartic acid) derivative (mPEG-g-PDAEAIM) and doxorubicin (DOX) in water. Fe₃O₄ nanoparticles were prepared to provide the superparamagnetic core of nanocomposites for tumor targeting via chemical co-precipitation. The protonable imidazole groups of mPEG-g-PDAEAIM with a pKa of ~7 were accountable for the pH-responsiveness of nanocomposites. The photothermal effect of nanocomposites under the irradiation of NIR laser was induced via the interactions between dopamine groups of mPEG-g-PDAEAIM and Fe₃O₄ superparamagnetic nanoparticles to trigger the drug release. NMR, FT-IR, TEM, hysteresis loop analysis and MRI were utilized to characterize the materials. The DOX loaded nanocomposites exhibited pH-responsive and NIR dependent on/off switchable release profiles. The nanocomposites without drug loading (Fe₃O₄@mPEG-g-PDAEAIM) showed excellent biocompatibility while DOX loaded nanocomposites caused MCF-7 cells’ apoptosis due to the photothermal/chemotherapy combination effects. Overall, the pH and near-infrared dual responsive magnetic nanocomposite had a great potential for cancer therapy.     

Synthesis of cyclophane carrying poly(acrylic acid) chains and its complexation behavior

Poly(tert-butyl acrylate)-coupled cyclophane was obtained by coupling 1,6,20,25-tetraaza[6.1.6.1]paracyclophane with carboxyl-terminated poly(tert-butyl acrylate). The poly(tert-butyl acrylate) was quantitatively hydrolyzed to poly(acrylic acid). The cyclophane carrying poly(acrylic acid) was soluble in alkaline water and formed an inclusion complex with trimethyl-2-naphthylmethylammonium bromide as a guest. Received: 2 July 1997/Revised: 22 August 1997/Accepted: 29 August 1997