Core-Shell Polymethyl-Methacrylate Research Articles

Preparation and Tracking of Oblate Core-Shell Polymethyl-Methacrylate Ellipsoids.

Although single-particle level studies on prolate ellipsoidal colloids are relatively abundant, similar studies on oblate ellipsoids are rare because suitable model systems are scarcely available. Here, we present the preparation of monodisperse hard core-shell oblate ellipsoids that can be imaged and tracked in 3D with confocal laser scanning microscopy. Using a thermomechanical squeezing method, we transform spherical core-shell polymethyl-methacrylate (PMMA) particles into oblate ellipsoids. We show how the shape polydispersity as well as the aspect ratio of the obtained oblate ellipsoids can be controlled. In addition, we discuss how the core-shell geometry limits the range of aspect ratios because of the different viscoelastic properties of the cross-linked PMMA core and linear PMMA shell. We further demonstrate imaging of the core-shell oblate dispersions on a single-particle level in real space and time and the tracking of position and orientation using our recently developed tracking algorithm for anisotropic core-shell colloids. Our results thus provide the tools for the future investigation of the behavior of oblate ellipsoids, especially in dense suspensions.

Core–shell poly-methyl methacrylate nanoparticles covalently functionalized with a non-symmetric porphyrin for anticancer photodynamic therapy

Photodynamic therapy (PDT) is an anticancer modality that exploits singlet oxygen and other reactive oxygen species, that are formed by selective irradiation of photosensitive molecules, to kill cancer cells. Most photosensitizers (PS) are hydrophobic and poorly soluble in water and several nanoplatforms have been established to achieve a more efficient delivery. Moreover, the covalent binding of the PS to nanoparticles could in principle reduce unwanted bleaching of the PS, while preserving its photodynamic activity. In this study we report the synthesis of a novel non-symmetrical diaryl-porphyrin suitably modified with a polymerizable pendant, that was used for the preparation of core-shell poly-methyl methacrylate nanoparticles covalently loaded with the diaryl-porphyrin (PMMA@PorVa). Particles, which were prepared with two different porphyrin loadings, are spherical in shape and with a narrow hydrodynamic diameter around 70 nm and a positive zeta potential. Their photo-toxicity was tested against the human colon carcinoma cell line HCT116 and the human ovarian adenocarcinoma cell line SKOV3. PMMA@PorVa were able to inhibit tumor cells proliferation similarly to the free porphyrin, thus confirming that the covalent attachment of the PS to PMMA nanoparticles allows to preserve PS photodynamic activity and in vitro efficacy. Flow cytometric analysis of apoptotic cells demonstrates that, especially in SKOV3 cells, the free diaryl-porphyrin is more effective in inducing apoptosis.

Core-shell microbioreactor microencapsulated denitrifying bacteria for nitrate-nitrogen treatment

Droplets of water-in-oil-in-water (w/o/w) emulsion were prepared using sodium alginate solution with denitrifying bacteria (Paracoccus denitrificans IFO13301) and dichloromethane (DCM) with polymethylmethacrylate (PMMA). By phase-separation and solvent-evaporation these droplets could be formed into core-shell PMMA microencapsulated denitrifying bacteria (PMMA-MC) possessing a large single core and a highly porous wall. The average thickness of the PMMA shell was 30 μm and the denitrifying bacteria were incorporated in the inner core at a high density. The PMMA-MC completely reduced 20 mg/L nitrate-nitrogen (NO3-N) and the intermediate product, nitrite-nitrogen (NO2-N), to N2 in the presence of H2 using a batchwise method. Thus, incorporated denitrifying bacteria can be used to treat water polluted with NO3-N. The PMMA-MC can be used repeatedly, and the third denitrification experiment directly denitrified (NO3-N → N2) without the intermediate step (NO3-N → NO2-N). In addition, the PMMA-MC with decreased activity could be reactivated by incubating in a culture medium.

Core–shell nanospheres for oligonucleotide delivery. V: Adsorption/release behavior of 'stealth' nanospheres

The adsorption/release behavior of oligodeoxynucleotides (ODNs) on new PEGylated core-shell polymethylmethacrylate nanospheres is described. The outer shell consists of alkyl chains containing quaternary ammonium groups and of poly(ethylene glycol) chains, both covalently bound to the inner core. Ion pair formation between negatively charged ODN phosphate groups and positively charged groups on the nanosphere surface is the main interaction mechanism. No cellular toxicity in HL60 cells is observed at nanosphere concentrations required for biologically active ODN delivery. These results indicate that these novel cationic polymeric nanoparticles are safe and represent promising vectors for oligonucleotide delivery.

Tailor-made core-shell nanospheres for antisense oligonucleotide delivery: IV.Adsorption/release behaviour

The adsorption/release behaviour of oligodeoxynucleotides (ODNs) on double functional core-shell polymethylmethacrylate nanospheres, with a narrow size distribution, is described. The outer shell consists of alkyl or glycolic chains containing permanently-charged quaternary ammonium groups. Ion pair formation between negatively-charged ODN phosphate groups and positively-charged groups, present on the nanosphere surface, is the main mechanism of interaction. The amount of adsorbed ODN depends on both the ODN concentration and the nanosphere surface charge density. An adsorption-induced swelling mechanism is proposed in which a modification of the charged diffuse layer around the nanospheres increases the ODN binding site accessibility with increasing ODN concentration. Adsorption on the nanosphere surface prevents serum degradation of the ODNs. ODN release is negligible in the presence of culture medium but occurs gradually in the presence of serum. No significant cytotoxicity of the free nanoparticles was found in PBMC and CEM cells after 24 h at ODN concentrations required for antisense activity.