Quasi-Chromophores Segregated by Single-Chain Nanoparticles of Fluorinated Zwitterionic Random Copolymers Showing Remarkably Enhanced Fluorescence Emission Capable of Fluorescent Cell Imaging.

Organic and polymer fluorescent nanomaterials are a frontier research focus. Here in this work, a series of fluorinated zwitterionic random copolymers end-attached with a quasi-chromophoric group of pyrene or tetraphenylethylene (TPE) are well synthesized via atom transfer radical polymerization with activators regenerated by electron transfer (ARGET ATRP). Those random copolymers with total degree of polymerization 100 or 200 are able to produce fluorescent single-chain nanoparticles (SCNPs) through intra-chain self-folding assembly with quite uniform diameters in the range of 10-20 nm as characterized by dynamic light scattering and transmission electron microscopy. By virtue of the segregation or confinement effect, both SCNPs functionalized with pyrene or TPE group are capable of emitting fluorescence, with pyrene tethered SCNPs exhibiting stronger fluorescence emission reaching the highest quantum yield ≈20%. Moreover, such kind of fluorescent SCNPs manifest low cytotoxicity and good cell imaging performance for Hela cells. The creation of fluorescent SCNPs through covalently attached one quasi-chromophore to the end of one fluorinated zwitterionic random copolymer provides an alternative strategy for preparing polymeric luminescence nanomaterials, promisingly serving as a new type of fluorescent nanoprobes for biological imaging applications.

A Comparison of Interpolyelectrolyte Complexes (IPECs) Made from Anionic Block Copolymer Micelles and PDADMAC or q-Chitosan as Polycation.

Block copolymers synthesized via Atom Transfer Radical Polymerization from alkyl acrylate and t-butyl acrylate and the subsequent hydrolysis of the t-butyl acrylate to acrylic acid were systematically varied with respect to their hydrophobic part by the variation in the alkyl chain length and the degree of polymerisation in this block. Depending on the architecture of the hydrophobic part, they had a more or less pronounced tendency to form copolymer micelles in an aqueous solution. They were employed for the preparation of IPECs by mixing the copolymer aggregates with the polycations polydiallyldimethylammonium chloride (PDADMAC) or q-chit. The IPEC structure as a function of the composition was investigated by Static Light and Small Angle Neutron Scattering. For weakly-associated block copolymers (short alkyl chain), complexation with polycation led to the formation of globular complexes, while already existing micelles (long alkyl chain) grew further in mass. In general, aggregates became larger upon the addition of further polycation, but this growth was much more pronounced for PDADMAC compared to q-chit, thereby leading to the formation of clusters of aggregates. Accordingly, the structure of such IPECs with a hydrophobic block depended largely on the type of complexing polyelectrolyte, which allowed for controlling the structural organisation via the molecular architecture of the two oppositely charged polyelectrolytes.

Progress in the Free and Controlled Radical Homo- and Co-Polymerization of Itaconic Acid Derivatives: Toward Functional Polymers with Controlled Molar Mass Distribution and Architecture.

Polymeric derivatives of itaconic acid are becoming increasingly more interesting for research and industry because itaconic acid is accessible from renewable resources. In spite of the structural similarity of poly(itaconic acid derivatives) to poly(methacrylates), they are much less reactive, homopolymerize only sluggishly by free radical polymerization (FRP), and are often obtained with low molar masses and conversions. This has so far limited their use. The reasons for the low reactivity of itaconic acid derivatives (including itaconimides, diitaconates, and diitaconamides) are combined steric and electronic effects, as demonstrated by the body of literature on the FRP homopolymerization kinetics of these monomers which is summarized herein. These problems can be solved to a large extent by using controlled radical polymerization (CRP) techniques, notably atom transfer radical polymerization (ATRP) and reversible addition and fragmentation chain transfer radical polymerization (RAFT). By optimizing the reaction conditions for the ATRP and RAFT of itaconic acid derivatives, in particular the reaction temperature, linear relations between molar mass and conversion are obtained in many cases, and homopolymers with high molar masses and reasonably narrow polydispersity indices become accessible. This review presents the state-of-the-art FRP and CRP of itaconic acid derivatives, and highlights functional polymers obtained by these methods.

Antifouling, antibacterial and non-cytotoxic transparent cellulose membrane with grafted zwitterion and quaternary ammonium copolymers.

Copolymer brushes with different ratios of sulfobetaine methacrylate (SBMA) and [2-(Acryloyloxy)ethyl]trimethylammonium chloride (DAC) were grafted from transparent cellulose membrane (CM) via surface-initiated atom transfer radical polymerization (SI-ATRP) method for improving its antifouling and antibacterial performance. Surface concentrated copolymer grafting on the cellulose membranes can be obtained without significantly sacrificing the transparency and mechanical properties. The zwitterionic PSBMA chains of the copolymers can lead to an extremely hydrophilic surface with significantly reduced non-specific protein adsorption and bacterial attachment, therefore, leading to satisfying antifouling and antibacterial property. While the PDAC chains of the copolymers improved antibacterial performance against both Gram-positive and Gram-negative bacteria due to the presence of quaternary ammonium groups, the PDAC modified CM (CM-1) possessed best antibacterial performance, reaching to 95.1 % against S. aureus and 90.5 % against E. coli, respectively. More importantly, the biocompatibility of all grafted CM was retained, leading to over 100 % cell viability.

Grafting Poly(Methyl Methacrylate) (PMMA) from Cork via Atom Transfer Radical Polymerization (ATRP) towards Higher Quality of Three-Dimensional (3D) Printed PMMA/Cork-g-PMMA Materials.

Cork is a unique material and its by-products are attracting an ever-growing interest for preparing new materials in an attempt to extend the outstanding properties of cork toward innovative and high value applications. Yet, the miscibility of cork particles with thermoplastic matrices is not easy due to its low density and surface properties. Here, cork is functionalized with poly(methyl methacrylate) (PMMA) via atom transfer radical polymerization (ATRP) to yield cork grafted with PMMA chains particles (cork-g-PMMA). Both the ATRP macroinitiator and the cork-g-PMMA obtained are fully characterized by Fourier-transform infrared spectroscopy (FT-IR), 13C cross-polarized magic-angle spinning solid-state nuclear magnetic resonance (13C CP/MAS solid state NMR), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), X-ray diffraction (XRD) and thermogravimetric analyses (TGA). The functionalized cork particles are then blended with commercial PMMA to afford cork-g-PMMA/PMMA. To compare, cork also is mixed with PMMA and the ensuing cork/PMMA sample and its morphology, thermal, and mechanical properties are compared with those of cork-g-PMMA/PMMA and commercial PMMA. The cork surface modification via ATRP of the methyl methacrylate (MMA) yields better dispersion in the matrix. Consequently, a blend with enhanced mechanical performance, higher thermal stability, and a higher melt flow index (MFI) is obtained when compared to the blend prepared using unmodified particles. The similarity of the MFI of cork-g-PMMA/PMMA to that of PMMA suggests good printability. Indeed, a three-dimensional (3D) printed specimen is obtained confirming that grafting using ATRP is a promising route for the preparation of high quality 3D printed products.

Enhancing antifouling property of PVA membrane by grafting zwitterionic polymer via SI-ATRP method.

Poly(zwitterions) polymer brushes were fabricated by surface-initiated atom transfer radical polymerization (SI-ATRP) on PVA substrate. The results of XPS and FTIR proved the successful graft of CBMA and SBMA to PVA. The surface of the PVA films would be rougher after the functionalization. Its hydrophilicity increased dramatically and the water contact angle decreased from 45.2° to 7.2°. The visible light transmittance was above 88%. Mechanical properties decreased slightly after grafting, the tensile strength and tensile strain at break were in 1.23-1.85 MPa and 361.7-471.1%, respectively. The anti-protein adsorption performance of the modified PVA film was significantly enhanced and the lowest adsorption amount was up to 2.25 µg/cm2. The cytotoxicity grade of modified PVA film was 0-1, which indicated the modified film possessed no cytotoxicity. Additionally, the surface of zwitterion-grafted PVA film had strongly resistance to cell adhesion. All the results confirmed that the zwitterions modified PVA was a promising anti-fouling material for the further biomedical use.

Mannosylated brush copolymers based on poly(ethylene glycol) and poly(ε-caprolactone) as multivalent lectin-binding nanomaterials.

A class of linear and four-arm mannosylated brush copolymers based on poly(ethylene glycol) and poly(ε-caprolactone) is presented here. The synthesis through ring-opening and atom transfer radical polymerizations provided high control over molecular weight and functionality. A post-polymerization azide-alkyne cycloaddition allowed for the formation of glycopolymers with different mannose valencies (1, 2, 4, and 8). In aqueous media, these macromolecules formed nanoparticles that were able to bind lectins, as investigated by concanavalin A binding assay. The results indicate that carbohydrate-lectin interactions can be tuned by the macromolecular architecture and functionality, hence the importance of these macromolecular properties in the design of targeted anti-pathogenic nanomaterials.

Polar Organic Solvent-Tolerant Perovskite Nanocrystals Permanently Ligated with Polymer Hairs via Star-like Molecular Bottlebrush Trilobe Nanoreactors.

The key to exploiting perovskite nanocrystals (NCs) for long-term practical use in optoelectronic materials and devices lies in the ability to access stable NCs. Herein, we report the crafting of hairy perovskite NCs with a set of markedly improved stabilities by capitalizing on rationally designed star-like molecular bottlebrush trilobes as nanoreactors. An intriguing star-like molecular bottlebrush trilobe, poly(2-hydroxyethyl methacrylate)-graft-(poly(acrylic acid)-block-partially cross-linked polystyrene (denoted PHEMA-g-(PAA-b-cPS)) is synthesized. Subsequently, it is employed as a polymeric nanoreactor to direct the growth of green-emitting all-inorganic perovskite CsPbBr3 NCs intimately and stably tethered by partially cross-linked PS "hairs" (i.e., cPS-capped CsPbBr3 NCs). The resulting CsPbBr3 NCs exhibit an array of impressive stabilities against UV irradiation, moisture, heat, and water, due to permanently ligated hydrophobic cPS "hairs" on the surface of CsPbBr3 NCs as a result of the original covalent bonding between PAA and cPS blocks. More importantly, cPS-capped CsPbBr3 NCs manifest outstanding stability in various polar organic solvents. Such greatly improved stability can be attributed to the reduced surface defects enabled by the favorable interaction (i.e., coordination interaction and hydrogen bonding) between CsPbBr3 NCs and polar solvents, which dominates over their dissolution by polar solvents. Such exceptional stabilities impart the use of cPS-capped CsPbBr3 NCs as a selective probe for tracing the presence of Cl-/I- in polar organic solvents. The amphiphilic nonlinear block copolymer nanoreactor strategy can afford easy access to stable perovskite NCs of interest with controlled compositions and surface chemistry. They may find applications in solar cells, LEDs, photodetectors, lasers, bioimaging, biosensors, etc.

Surface Carbon Shell-Functionalized ZrO2 as Nanofiller in Polymer Gel Electrolyte-Based Dye-Sensitized Solar Cells.

We prepare dye-sensitized solar cells (DSSCs) fabricated with a poly (ethylene glycol) based polymer gel electrolytes (PGEs) incorporating surface carbon shell-functionalized ZrO2 nanoparticles (ZrO2-C) as nanofillers (NFs). ZrO2 are polymerized via atom transfer radical polymerization (ATRP) using poly (ethylene glycol) methyl ether methacrylate (POEM) as a scaffold to prepare the ZrO2-C through carbonization. The power conversion efficiency of DSSC with 12 wt% ZrO2-C/PGEs is 5.6%, exceeding that with PGEs (4.4%). The enhanced efficiency is attributed to Lewis acid-base interactions of ZrO2-C and poly (ethylene glycol), catalytic effect of the carbon shells of ZrO2-C, which results in reduced crystallinity, enhanced ion conductivity of electrolytes, decreased counterelectrode/electrolyte interfacial resistance, and improved charge transfer rate. These results demonstrate that ZrO2-C introduction to PGEs effectively improves the performance of DSSCs.

Fabrication of topologically anisotropic microparticles and their surface modification with pH responsive polymer brush.

This paper describes the fabrication of topologically anisotropic cup shaped polylactide (PLA)/poly[methyl methacrylate­co­2­(2­bromopropionyloxy) ethyl methacrylate] (poly(MMA-co-BEMA)) (75/25) composite particles of ~6 µm size using electrojetting technique. An attempt was made to understand the mechanism of cup shape formation from the miscible blend by electrojetting. Both the solution parameters and the processing conditions affected the particles' shape which can be varied from cup shaped to discoid type. Surface initiated atom transfer radical polymerization (ATRP) of stimuli responsive DMAEMA (2­dimethylamino ethyl methacrylate) was subsequently carried out for 1 h onto the surface of cup shaped particles to observe pH responsiveness of the modified anisotropic particles. Interestingly, morphology of the cup shaped particles was changed to elongated cup which did show significant swelling under acidic pH (swelling ratio:~1.6) and enhanced dye adsorption at specific pH as observed by optical microscope and confocal laser scanning microscope implying that DMAEMA polymerization happened onto the surface of the composite microparticles. The Raman microscopy and FTIR spectra obtained from the particles after polymerization further confirmed the immobilization of pH responsive poly(DMAEMA) brushes onto the cup shaped particles which may potentially function as triggered/targeted drug delivery vehicles. Moreover, the brush modified cup shaped particles were found to be two times more efficient in adsorbing dye compared to disc shaped one indicating a clear advantage of using cup shaped particles over other shapes for immobilizing/adsorbing charged species e.g. sensitive biomolecules.

ICAR ATRP Polymerization-Induced Self-Assembly Using a Mixture of Macroinitiator/Stabilizer with Different Molecular Weights.

The poly[oligo(ethylene oxide) methyl ether methacrylate]s, POEOMA24 and POEOMA78 with average degree of polymerization (DP) of 24 and 78, respectively, are separately achieved by initiators for continuous activator regeneration (ICAR) atom transfer radical polymerization (ATRP) of OEOMA300 monomer. The mixtures of [POEOMA24 ]0 /[POEOMA78 ]0 = 1/1, 2/1, or 4/1 are employed as macroinitiator/stabilizer to practice the ICAR ATRP polymerization-induced self-assembly (PISA) of benzyl methacrylate (BnMA) at 65 °C. When the obtained dispersions are sequentially cooled to room temperature, diluted into ethanol, and observed by transmission electron microscopy (TEM) measurement, the cases of [POEOMA24 ]0 /[POEOMA78 ]0 = 1/1 or 2/1 and target DPPB n MA = 100 or 200 lead to nanoparticles with irregular sizes, while the cases of [POEOMA24 ]0 /[POEOMA78 ]0 = 4/1 and target DPPB n MA = 300 give the regular ones. When the obtained dispersions at a high temperature (65 °C) are directly diluted into room temperature ethanol and observed by TEM, nanoparticles with light contrast but clear contour can be observed. The results show that the higher content of POEOMA78 tends to improve the solubility of diblock copolymer and thus leads to insufficient stabilization of the nanoparticles. The morphological difference from the room-temperature and 65 °C dispersions help elucidate the intrinsic character of the PISA system.

Preparation of Graft Poly(Arylene Ether Sulfone)s-Based Copolymer with Enhanced Phase-Separated Morphology as Proton Exchange Membranes via Atom Transfer Radical Polymerization.

Novel proton exchange membranes (PEMs) based on graft copoly(arylene ether sulfone)s with enhanced phase-separated morphology were prepared using atom transfer radical polymerization (ATRP). A series of PEMs with different graft lengths and sulfonation degrees were prepared. The phase-separated morphologies were confirmed by transmission electron microscopy. Among the membranes prepared and evaluated, PAESPS18S2 exhibited considerably high proton conductivity (0.151 S/cm, 85 °C), benefitting from the graft polymer architecture and phase-separated morphology. The membranes also possessed excellent thermal and chemical stabilities. Highly conductive and stable copoly(arylene ether sulfone)-based membranes would be promising candidates as polymer electrolytes for fuel cell applications.

Reversible Two-Enzyme Coimmobilization on pH-Responsive Imprinted Monolith for Glucose Detection.

A new enzymatic glucose biosensor based on reversible co-immobilization of horseradish peroxidase (HRP) and glucose oxidase (GOx) on a pH-responsive imprinted monolith is prepared. The poly(4-vinylphenylboronic acid)-grafted imprinted polymer using HRP as a template is formed via surface initiated atom transfer radical polymerization within the pores of brominated poly(glycidyl methacrylate-co-ethylene dimethacrylate) macroporous monolith contained in a 100 µm I.D. capillary column. The two enzymes conjugate is formed via the strong affinity interaction between biotin-labeled GOx and streptavidin-labeled HRP. The modulation of the external pH value enables reusability of the biosensor simply using stripping of the inactive enzymes at a low pH value and subsequent immobilization of fresh enzymes at a high pH value. Under the optimized conditions, the enzymatic biosensor features excellent performance in detection of glucose with a linear range of its concentration from 0.11 to 38.85 mmol/L and a limit of detection of 0.03 mmol/L. A relative standard deviation of 3.7% is calculated from determination of twenty glucose samples. This novel enzymatic sensing system is successfully applied for determination of glucose in human serum, and confirms an enhancement both in selectivity and specificity compared to the more traditionally clinical methods.

In Situ Crosslinking of Nanoparticles in Polymerization-Induced Self-Assembly via ARGET ATRP of Glycidyl Methacrylate.

Polymerization-induced self-assembly (PISA) and in situ crosslinking of the formed nanoparticles are successfully realized by activators regenerated by electron-transfer atom transfer radical polymerization (ARGET ATRP) of glycidyl methacrylate (GMA) or a mixture of GMA/benzyl methacrylate (BnMA) monomers in ethanol. Poly(oligo(ethylene oxide) methyl ether methacrylate) was employed as macroinitiator/stabilizer, and a cupric bromide/tris(pyridin-2-ylmethyl)amine complex as catalyst. Tin (2-ethylhexanoate) was used as reducing agent for ARGET ATRP, and simultaneously acted as a catalyst for ring-opening polymerization of oxirane ring in GMA. The kinetics shows that the double bond in GMA was completely polymerized in 4.0 h, while only a 33% conversion of oxirane ring in GMA was reached at 117.0 h. Such a large difference would guarantee a smooth PISA and a subsequent in situ crosslinking of formed nanoparticles. The transmission electron microscopy and dynamic light scattering show spherical nanoparticles formed. With a feed molar ratio [BnMA]0 /[GMA]0 = 150/50, 100/100, and 50/150, the nanoparticles formed in ethanol can dissociate or swell in toluene. When pure GMA was used, the solid nanoparticles were observed in toluene or ethanol. The ARGET ATRP provides an efficient strategy to stabilize the nanoparticles formed in the PISA of GMA-containing system.

Synthesis of Cross-Linked 2-Aminoethyl Methacrylate in P22 Viral Capsid via Atom-Transfer Radical Polymerization.

Virus-like particles (VLPs) resemble viruses, but are devoid their genetic material, rendering them as noninfectious, hollow protein shells. VLPs are ideal templates to synthesize nanoparticles because they have homogeneous size and their empty cavity can provide a confined environment for selectively directed synthesis. Atom-transfer radical polymerization (ATRP) is well suited for directed synthesis of polymers inside VLPs. In addition to being rapid, monomer-promiscuous, and resulting in products with relatively low polydispersity, the simplicity of the ATRP initiator allows it to be readily modified for amending to biomolecules. This chapter describes the polymerization of 2-aminoethyl methacrylate (AEMA) via ATRP in a viral capsid derived from the bacteriophage P22.

Poly(Ionic Liquid): A New Phase in a Thermoregulated Phase Separated Catalysis and Catalyst Recycling System of Transition Metal-Mediated ATRP.

Poly(ionic liquid)s (PILs) have become the frontier domains in separation science because of the special properties of ionic liquids as well as their corresponding polymers. Considering their function in separation, we designed and synthesized a thermoregulated PIL. That is, this kind of PIL could separate with an organic phase which dissolves the monomers at ambient temperature. When heated to the reaction temperature, they become a homogeneous phase, and they separate again when the temperature falls to the ambient temperature after polymerization. Based on this, a thermoregulated phase separated catalysis (TPSC) system for Cu-based atom transfer radical polymerization (ATRP) was constructed. The copper catalyst (CuBr2) used here is easily separated and recycled in situ just by changing the temperature in this system. Moreover, even when the catalyst had been recycled five times, the controllability over resultant polymers is still satisfying. Finally, only 1~2 ppm metal catalyst was left in the polymer solution phase, which indicates the really high recycling efficiency.

Synthesis of Highly Biocompatible and Temperature-Responsive Physical Gels for Cryopreservation and 3D Cell Culture.

There is considerable interest in the cryopreservation in 3D cell culture, as structurally preserving intact cells and tissues is critical in utilizing these systems to promote cell differentiation and tissue organization. Temperature-responsive physical gels and zwitterionic polymers are useful materials as 3D scaffolds for cell culture which may also provide cryoprotection to the composite cells. Nevertheless, there has been a lack of relevant data for polymer systems that have both of these properties. In this study, highly biocompatible triblock copolymers were examined for their effectiveness both as gelators and as cryo-protectants. The triblock copolymers were synthesized with 2-methacryloyloxyethyl phosphorylcholine (MPC) and di(ethylene glycol) methyl ether methacrylate (DEGMA) via atom transfer radical polymerization (PDEGMA113-b-PMPC243-b-PDEGMA113). ABA triblock copolymers composed of hydrophilic "B" block and temperature responsive "A" block could form physical gels above their lower critical solution temperatures (LCST). PDEGMA113-b-PMPC243-b-PDEGMA113 triblock copolymer exhibited the LCST derived from DEGMA and assembled in micellar structures forming physical gels above the LCST. The mechanical properties of the physical gels were evaluated by rheological tests, and the low toxicity of PDEGMA113-b-PMPC243-b-PDEGMA113 was confirmed by MTT assay. Interestingly, the triblock copolymer showed ice recrystallization inhibition (IRI) activity which was determined to be suitable for the cryopreservation of several cell lines. In vitro studies were conducted to demonstrate the cryo-protectant properties and the formation of two and three-dimensional (2D/3D) cell culture scaffolds with high biocompatibility. This stimuli-responsive gelator polymers can therefore be useful for cryopreservation of different cells models, and a promising material for 3D cell culture.

A novel approach for UV-patterning with binary polymer brushes.

A mixed self-assembled monolayer (SAM) of an initiator (3-(2-bromo-2-isobutyryloxy)propyl triethoxysilane) for atom transfer radical polymerization (ATRP) and an agent (6-(triethoxysilyl)hexyl 2-(((methylthio)carbonothioyl)thio)-2-phenylacetate) for reversible addition-fragmentation chain transfer (RAFT) polymerization was constructed on the surface of a silicon wafer or glass plate by a silane coupling reaction. When a UV light at 254nm was irradiated at the mixed SAM through a photomask, the surface density of the bromine atom at the end of BPE in the irradiated region was drastically reduced by UV-driven scission of the BrC bond, as observed by X-ray photoelectron spectroscopy. Consequently, the surface-initiated (SI)-ATRP of 2-ethylhexyl methacrylate (EHMA) was used to easily construct the poly(EHMA) (PEHMA) brush domain. Subsequently, SI-RAFT polymerization of a zwitterionic vinyl monomer, carboxymethyl betaine (CMB), was performed. Using the sequential polymerization, the PCMB and PEHMA brush domains on the solid substrate could be very easily patterned. Patterning proteins and cells with the binary polymer brush is expected because the PCMB brush indicated strong suppression of protein adsorption and cell adhesion, and the PEHMA brush had non-polar properties. This technique is very simple and useful for regulating the shape and size of bio-fouling and anti-biofouling domains on solid surfaces.

Sustainable thermoplastic elastomers derived from cellulose, fatty acid and furfural via ATRP and click chemistry.

Cellulose-based thermoplastic elastomers (TPEs) have attracted considerable attention because of their rigid backbone, good mechanical properties, renewable nature and abundance. In the present study, sustainable TPEs based on ethyl cellulose (EC), fatty acid and furfural were generated by the combination of ATRP and "click chemistry". To fabricate sustainable TPEs with higher toughness, a range of polymers, including mono random-copolymer poly(tetrahydrofurfuryl methacrylate-co-lauryl methacrylate) (P(THFMA-co-LMA), dual polymer side chains PTHFMA and PLMA, and mono-block copolymer PTHFMA-b-PLMA, were designed as side chains to fabricate EC brush copolymers with random, dual or block side chain architectures using the "grafting from" and "grafting onto" methods. The multi-armed structures, chemical compositions and phase separation of these EC brush copolymers were confirmed by FT-IR, 1H NMR, GPC, DSC, TEM and SEM. Overall, three types of EC brush copolymers all exhibited the desired mechanical properties of TPEs. In addition, the EC brush copolymers with dual/block side chain architectures showed higher tensile strength than that of the random polymers with similar compositions.

Codelivery for Paclitaxel and Bcl-2 Conversion Gene by PHB-PDMAEMA Amphiphilic Cationic Copolymer for Effective Drug Resistant Cancer Therapy.

Antiapoptotic Bcl-2 protein's upregulated expression is a key reason for drug resistance leading to failure of chemotherapy. In this report, a series of biocompatible amphiphilic cationic poly[(R)-3-hydroxybutyrate] (PHB)-b-poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) copolymer, comprising hydrophobic PHB block and cationic PDMAEMA block, is designed to codeliver hydrophobic chemotherapeutic paclitaxel and Bcl-2 converting gene Nur77/ΔDBD with enhanced stability, due to the micelle formation by hydrophobic PHB segment. This copolymer shows less toxicity but similar gene transfection efficiency to polyethyenimine (25k). More importantly, this codelivery approach by PHB-PDMAEMA leads to increased drug resistant HepG2/Bcl-2 cancer cell death, by increased expression of Nur77 proteins in the Bcl-2 present intracellular mitochondria. This work signifies for the first time that cationic amphiphilic PHB-b-PDMAEMA copolymers can be utilized for the drug and gene codelivery to drug resistant cancer cells with high expression of antiapoptosis Bcl-2 protein and the positive results are encouraging for the further design of codelivery platforms for combating drug resistant cancer cells.