Synthesis and characterization of poly(styrene-co-fluorescein O-methacrylate)/poly(N-isopropylacrylamide)-Fe3O4 core/shell composite particles

We demonstrate the synthesis and characteristics of multifunctional poly(styrene-co-fluorescein O-methacrylate)/poly(N-isopropylacrylamide)-Fe₃O₄ [P(St/FMA)/PNIPAAm-Fe₃O₄] core/shell composite particles, in which the core consists of fluorescent materials and the shell consists of magnetic and thermo-responsive components. First, core/shell particles consisting of a fluorescent P(St/FMA) core and thermo-responsive PNIPAAm-rich shell were prepared by two-stage shot-growth emulsion polymerization. Next, Fe₃O₄ nanoparticles were immobilized via electrostatic interactions and then covalently linked to the shell via surface coordinated Aphen by a coupling reaction in order to obtain magnetic properties. The morphology of P(St/FMA)/PNIPAAm-Fe₃O₄ composite particles, confirmed by transmission electron microscopy (TEM), reveals that Fe₃O₄ nanoparticles are located in the PNIPAAm shell. The thermo-sensitivity of composite particles to hydrodynamic diameter was confirmed by using dynamic light scattering (DLS). Photoluminescence (PL) spectra indicate that the fluorescence emission intensity of core/shell particles is highly sensitive to the pH of an aqueous medium. The core/shell composite particles exhibited a combination of fluorescent, magnetic, pH and thermo-responsive behavior.     

Redispersible dried hydroxyapatite particles with grafted pH-sensitivity polymer brushes of poly(styrene-co-4-vinylpyridine)

Reversible aggregation-redispersion transition of colloidal particles is of considerable importance in colloidal science and various industrial fields. In the present study, stimuli-responsive hybrid hydroxyapatite (HA) particles were prepared with redispersible ability in aqueous solutions even after separation from the “as synthesized” state and subsequent dry heat treatment. We firstly modified HA particles with sodium oleate as chelating agent, then introduced bromoalkyl functional groups through an addition reaction of unsaturated oleate molecule with bromine, and finally grafted polymer brushes of polystyrene-co-4-vinylpyridine onto HA. It was the pH-sensitive polymer shell that had rendered HA particles the redispersible ability, which was attributed to the protonation of the pyridine blocks in acidic solutions. The reversible dispersion-aggregation transition of HA could be controlled by alternating the pH value of aqueous solution. Protonated pyridine blocks had provided enough electrostatic and steric repulsions for colloidal HA to avoid effective collision.     

Dendron-polymer hybrid mediated anticancer drug delivery for suppression of mammary cancer

Dendron-polymer-based nanoscale and stimuli-responsive drug delivery systems have shown great promise in tumor-targeting accumulation without significant toxicity.Here we report a dendronized polymer-doxorubicin(DOX)hybrid(DPDH)with an improved in vivo drug delivery efficiency for cancer therapy compared with a linear polymer-DOX conjugate(LPDC).The in vitro drug release profile of DOX indicates that DPDH displays pH-responsive drug release due to cleavage of hydrazone bonds since a greater amount of DOX is released at pH 5.2 at a faster rate than at pH 7.4.DPDH efficiently enters 4 T1 cells and releases DOX to induce cytotoxicity and apoptosis.Owing to the dendronzied structure,DPDH has a significantly longer blood circulation time than LPDC.DPDH substantially enhances the therapeutic efficacy to suppress tumor growth in a 4 T1 mammary cancer model than LPDC as well as free drug,evidenced from tumor growth inhibition,TUNEL assessment and histological analysis.Biosafety of DPDH is also confirmed from hemolysis,body weight shifts during treatment and pathological analysis.This study demonstrates the use of dendronized polymer-DOX hybrids for specific drug molecules is a promising approach for drug delivery.     

Self-healable,Eu~(3+)-based polymeric gels containing terpyridyl groups with tunable luminescence based on ion recognition

Novel luminescent materials that change their emission colors in responding to external stimuli have attracted increasing attentions in the past decades.Herein,we report the preparation of a novel kind of Eu~(3+)-based polymeric organogel with three networks.With dynamic coordination interactions,the organogel shows fast self-healing and adjustable fluorescent emission properties in the presence of different metal ions via coordination interaction competition effect.Dynamic coordination interaction also endows the gel with multiple stimuli-responsive properties such as water,base and acid.The multistimuli responsive fluorochromic organogel demonstrates a new way of preparing optical materials and bio-relevant sensors.     

Programmed morphing of liquid crystal networks

A promising candidate for the development of stimuli-responsive morphing materials are based on liquid crystal polymer networks. These anisotropic materials will contract along the alignment director and expand perpendicular to it when subjected to an anisotropy-reducing stimulus, such as heat. As the liquid crystals can be aligned prior to polymerization using various alignment techniques, it is possible to create networks with programmed, complex director profiles in three dimensions. This review shows the various designs that can be implemented and the complex morphing behavior that can be achieved in liquid crystal polymer networks.     

Multi-functional forward osmosis draw solutes for seawater desalination

Forward osmosis (FO), as one of the emerging desalination technologies, has the potential to produce freshwater from a variety of water sources by utilizing the osmotic pressure gradient across a semi-permeable membrane. Drawsolution, as an essential component of any FO process, can extract watermolecules fromseawater orwastewater. An ideal draw solution should meet three essential requirements, namely high osmotic pressure, low reverse flux, and facile regeneration mechanism. The selection of proper draw solutes is especially critical for an energy-efficient FO process since the energy consumption mostly arises from the separation or regeneration of the draw solution. Recently, we developed a few multi-functional FO draw solutes, mainly aiming to enhance the FO water flux and to explore facile re-concentration methods. This review summarizes these draw solutes, including Na⁺-functionalized carbon quantum dots, thermoresponsive copolymers, hydrophilic magnetic nanoparticles, and thermoresponsive magnetic nanoparticles.     

Preparation of polymer latex particles carrying salt-responsive fluorescent graft chains

We prepared the novel fluorescent polymer latex particles which can change their fluorescence intensity in response to the increasing NaCl concentration in water. Core polymer latex particles were synthesized by emulsifier-free emulsion polymerization of styrene and 2-(2-chloroisobutyroyloxy)ethyl methacrylate. Hydrophilic polymer chains containing epoxy groups were grafted from the core particles by surface-initiated atom transfer radical copolymerization of methoxy polyethyleneglycol methacrylate (MEO_xMA, x = 4 or 9) and glycidyl methacrylate in aqueous media. After azidation of epoxy groups in graft chains, a water-soluble fluorescent dansyl derivative was successfully coupled with the graft chains by copper-catalyzed azide-alkyne cycloaddition in aqueous media. The wavelength of maximum fluorescence intensity of polymer particles carrying graft chains with longer PEG side chains (x = 9) was slightly blue-shifted (7 nm) and the fluorescence intensity increased (1.35 times) with an increase in NaCl concentration as opposed to polymer particles with shorter PEG chains (x = 4).     

Photografted poly(acrylic acid) thin layers with ultra-high swelling ratios and high swelling and pH response rates

Polymeric thin films with a stimuli-responsive surface layer have many potential applications. Surface photografting is a simple and versatile method for introducing grafted chains onto polymeric substrates. However, photografted layers usually have very low swelling ratios, swelling and stimuli-response rates. This work demonstrates that photografting of acrylic acid onto polyethylene films carried out with films on the top or at the bottom of a solution leads to huge differences in the grafting reactions and the final properties of the grafted layers. The photografting reaction on the top surface of a solution is much faster, and the grafted poly(acrylic acid) layers have ultra-high equilibrium swelling ratios (>100) and very high swelling and pH response rates (in seconds).     

Guest release and solution behavior of a hydrogen-bonding physical micelle during chemoresponsive shell disruption

The guest release and solution behavior during shell disruption of a polymeric nanocapsule are described. Hyperbranched polyethylenimine (PEI, M_n = 10?000) is chemically functionalized with multiple DAD hydrogen-bonding motifs (D and A: hydrogen-bonding donor and acceptor), leading to PEI₂₃₂-(DAD)_x (3) (x = 93 (3a), x = 46 (3b), x = 23 (3c), x = 12 (3d)). Meanwhile, polyethylene oxide (M_n = 2 200) is end-capped with thymine moieties (PEO-ADA) (4). Mixing of the hydrogen-bonding complementary 3 and 4 (DAD/ADA = 1) leads to a physical micelle (3·4) in apolar media, and the resulting micelle can completely and irreversibly transfer the ionic and water-soluble Congo red (CR) into chloroform phase by encapsulation. Experiment proves that the micelle can exist as a pseudo-unimolecular micelle (p-UIM, meaning one PEI in one micelle) or as aggregate, depending on the shell density. As a result, 3b·4 generally exists as a p-UIM while 3d·4 can exist as p-UIM only in a very narrow range of concentrations. The critical aggregation concentration (CAC) is also dependent on the core structure of the micelle, thus when the residual amines in the core of 3b are transformed into amide, the resulting 5b·4 shows a very low CAC. Small chemicals bearing DAD hydrogen-bonding motif can compete to bind with the PEO-ADA shell and destruct the p-UIM, leading to aggregation and precipitation of the p-UIM along with the CRs. Experiment proves that the CR has strong acid-base interaction with the PEI core of the p-UIM, but when the basicity of the PEI core is reduced by amidation, partial CRs can be released into the water phase.     

Self-association of double-hydrophilic copolymers of acrylic acid and poly(ethylene oxide) macromonomer

Poly(ethylene oxide) (PEO) end-capped by a methacrylate unsaturation was copolymerized with acrylic acid by RAFT with dibenzyltrithiocarbonate as a chain transfer agent. Tapered triblock copolymers consisting of a poly(acrylic acid) (PAA) inner block and comb-like outer blocks of PEO macromomers were formed as result of the comonomers reactivity ratios. Composition of these copolymers and length of the PEO branches were varied. Dynamic light scattering (DLS) was used to characterize the aggregates formed in water and to investigate their response to stimuli, such as pH, temperature and ionic strength. In parallel, the morphology of the aggregates was directly observed by transmission electron microscopy (TEM). Well-defined aggregates were formed in the 5<pH<8 range, with a morphology strongly depending on the copolymer composition. At pH<5, the copolymers were poorly soluble and no well-defined structure was observed, whereas free chains were formed at pH>8 as consequence of the complete ionization of the PAA block.