The effect of POSS nanoparticles on crosslinking of styrene-butadiene rubber nanocomposites.

The effect of octaisobutyl-polyhedral oligomeric silsesquioxane (OIB-POSS) as a nanosized reinforcement on the cure kinetics, crosslinking density, and mechanical properties of styrene-butadiene rubber (SBR) nanocomposites was examined in this study. For this purpose, SBR compounds with various OIB-POSS nanoparticle loadings at 1, 3, and 5 phr were prepared and their results were compared with a reference compound without OIB-POSS. When 1 phr of OIB-POSS was added to the rubber matrix, the elongation at break values and tensile strength of the corresponding nanocomposite increased by 24.1% and 29.2% compared to the reference sample, respectively. The presence of OIB-POSS nanoparticles and their random distribution in the SBR matrix was confirmed by transmission electron microscopy. The crosslinking density of nanocomposites was calculated by the Flory-Rehner method and a decrease was observed with the addition of OIB-POSS nanoparticles. In addition, thermal aging process as 70 °C for 70 h was applied to vulcanized samples. It was noted that the mechanical properties of SBR/OIB-POSS nanocomposites remarkably improved, whereas their crosslinking densities gradually decreased after thermal aging.

In situ preparation of hetero-polymers/clay nanocomposites by CUAAC click chemistry.

A series of polymer/clay nanocomposites containing mechanistically two different polymers, poly(ethylene glycol) (PEG) and poly(epsilon caprolactone) (PCL), were prepared by simultaneous copper(I)-catalyzed alkyne-azide cycloaddition click reactions. Both clickable polymers, PEG-Alkyne and PCL-Alkyne, were simultaneously clicked on to azide-functional montmorillonite (MMT-N3) nanoclay to get corresponding PEG-PCL/MMT nanocomposites. The chemical structures of the resulting nanocomposites were verified by following azide and silicone-oxygen bands using FT-IR and characteristic bands of PEG and PCL segments using 1H-NMR spectroscopy. The combined XRD and TEM analysis confirmed that all PEG-PCL/MMT nanocomposites had partially exfoliated/intercalated morphologies. In addition, the increase of MMT-N3 loading not only improved the onset and maximum degradation temperatures of the nanocomposites but also their char yields. Furthermore, the incorporation of MMT-N3 in the polymer matrix did not significantly influence the crystallization behavior of both PEG and PCL segments.

Facile UV-induced covalent modification and crosslinking of styrene-isoprene-styrene copolymer via Paterno-Büchi [2 + 2] photocycloaddition.

The chemical functionalization or modification of polymers to alter or improve the physical and mechanical properties constitutes an important field in macromolecular research. Fabrication of polymeric materials via structural tailoring of commercial or commodity polymers that are produced in vast quantities especially possess unique advantages in material applications. In the present study, we report on benign chemical modification of unsaturated styrene-isoprene-styrene (SIS) copolymer using available backbone alkene groups. Covalent attachment of aldehyde functional substrates onto reactive isoprene double bond residues was conveniently carried out using UV-induced Paterno-Büchi [2 + 2] cycloaddition. Model organic compounds with different structures were utilized in high efficiency chemical modification of parent polymer chains via oxetane ring formation. Functionalization studies were confirmed via 1H NMR, FT-IR and SEC analyses. The methodology was extended to covalent crosslinking of polymer chains to obtain organogels with tailorable crosslinking degrees and physical characteristics. Considering the outstanding elastic properties of unsaturated rubbers and their high commercial availability, abundant reactive double bonds in backbone chains of these polymers offer easy to implement structural modification via proposed Paterno-Büchi photocycloaddition.

The Utilization of Poly(2-ethyl-2-oxazoline)-b-Poly(ε-caprolactone) Ellipsoidal Particles for Intracellular BIKDDA Delivery to Prostate Cancer.

Prostate cancer is the most common cancer, which is about 15-20% among male cancers worldwide. As most common strategies such as radiotherapy, chemotherapy, or surgery alone can be unsuccessful in the treatment of prostate cancer, this study aims to develop a new approach to deliver newly generated proapoptotic gene, BIKDDA, to androgen independent prostate cancer cells, 22RV1, using new generation nanocarriers called ellipsoids. As far as it is known, this is the first study that assesses the ability of proapoptotic gene BIKDDA to induce apoptosis in prostate cancer cell. BIKDDA encapsulating PEtOx-b-PCL-based ellipsoids are fabricated by solvent-switch method, and their morphology, size, and BIKDDA content are characterized. Gene delivery efficiency of BIKDDA loaded PEtOx-b-PCL ellipsoids is demonstrated by analysis of BIK mRNA expression with real-time PCR. The apoptotic effect of PEtOx-b-PCL ellipsoids loaded with BIKDDA (EPs-BIKDDA) on 22RV1 is shown by Annexin V staining. The obtained results demonstrate that the treatment of 22RV1 cells with EPs-BIKDDA can significantly increase BIK mRNA levels by 4.5-fold leading to cell death. This study not only represents BIKDDA as a potential therapeutic strategy in prostate cancer but also the capacity of ellipsoids as promising in vivo gene delivery vehicles.

Exploiting ionisable nature of PEtOx-co-PEI to prepare pH sensitive, doxorubicin-loaded micelles.

AIMS: This study was conducted to evaluate block copolymers containing two different poly(ethyleneimine) (PEI) amounts, as new pH-sensitive micellar delivery systems for doxorubicin. METHODS: Micelles were prepared with block copolymers consisting of poly(2-ethyl-2-oxazoline)-co-poly(ethyleneimine) (PEtOx-co-PEI) and poly(ε-caprolactone) (PCL) as hydrophilic and hydrophobic blocks, respectively. Doxorubicin loading, micelle size, pH-dependent drug release, and in vitro cytotoxicity on MCF-7 cells were investigated. RESULTS: The average size of drug-loaded micelles was under 100 nm and drug loading was between 10.7% and 48.3% (w/w). pH-sensitive drug release was more pronounced (84.7% and 68.9% (w/w) of drug was released at pH 5.0 and pH 7.4, respectively) for the micelles of the copolymer with the lowest PEI amount. The cell viability of doxorubicin-loaded micelles which were prepared by the copolymer with the lowest PEI amount was 28-33% at 72 h. CONCLUSIONS: PEtOx-co-PEI-b-PCL micelles of this copolymer were found to be stable and effective pH-sensitive nano-sized carriers for doxorubicin delivery.

Synthesis of self-curable polysulfone containing pendant benzoxazine units via CuAAC click chemistry.

Synthesis, characterization, and properties of new thermally curable polysulfone containing benzoxazine moieties in the side chain were investigated. First, chloromethylation and subsequent azidation processes were performed to form polysulfone containing pendant clickable azide groups. Independently, antagonist 3,4-dihydro-3-(prop-2-ynyl)-2H-benzoxazine was prepared by using paraformaldehyde, phenol and propargylamine. The following copper(I) catalyzed azide-alkyne cycloaddition click reaction was applied to obtain self-curable polysulfone with pendant benzoxazine units. The polymer and intermediates at various stages were characterized by 1H-NMR, 13C-NMR and FT-IR spectroscopies. The thermal properties and curing behavior of final polymer were investigated by differential scanning calorimetry and thermal gravimetric analysis. Compared to the neat polysulfone, the obtained polymers exhibited thermally more stable polymers.

Polymer Nanocomposites via Click Chemistry Reactions.

The emerging areas of polymer nanocomposites, as some are already in use in industrial applications and daily commodities, have the potential of offering new technologies with all manner of prominent capabilities. The incorporation of nanomaterials into polymeric matrix provides significant improvements, such as higher mechanical, thermal or electrical properties. In these materials, interface/interphase of components play a crucial role bringing additional features on the resulting nanocomposites. Among the various preparation strategies of such materials, an appealing strategy relies on the use of click chemistry concept as a multi-purpose toolbox for both fabrication and modulation of the material characteristics. This review aims to deliver new insights to the researchers of the field by noticing effective click chemistry-based methodologies on the preparation of polymer nanocomposites and their key applications such as optic, biomedical, coatings and sensor.

Benzodioxinone Photochemistry in Macromolecular Science: Progress, Challenges, and Opportunities.

This paper reviews the photoinduced reactions of benzodioxinones and how they function in polymer synthesis and UV curing applications. The mechanistic characteristics of the ketene and benzophenone production from the photolysis of benzodioxinone indicate that, under certain conditions, each intermediate may undergo further reactions expedient for the formation of various polymeric structures. While ketenes are efficient contributors to step-growth polymerization when subjected to reaction with the compounds possessing hydroxyl or amine groups, the released benzophenone can be utilized as a photoinitiator in both the free radical and cationic polymerizations. It has been shown that the photolysis of heterobifunctional monomers equipped with benzodioxinone and aliphatic hydroxyl groups leads to the formation of oligoesters with a narrow molecular weight distribution. We also validated the photochemical ability of benzodioxinone to induce the synthesis of block and graft copolymers, hybrid and branched polymers, and cross-linked monofunctional vinyl monomers or hydroxyl group-containing linear polymers.

Orthogonal Synthesis of Block Copolymer via Photoinduced CuAAC and Ketene Chemistries.

A novel route for the synthesis of poly(ethylene glycol)-b-polystyrene copolymer, starting from commercially available poly(ethylene glycol) methyl ether and azido terminated polystyrene prepared by atom transfer radical polymerization and subsequent nucleophilic substitution, is applied with simplicity and high efficiency. The combination of photoinduced copper (I)-catalyzed alkyne-azide cycloaddition (CuAAC) and ketene chemistry reactions proceeds either simultaneously or sequentially in a one-pot procedure under near-visible light irradiation. In both cases, excellent block copolymer formations are achieved, with an average molecular weight of around 7000 g mo1(-1) and a polydispersity index of 1.20.

Light-induced click reactions.

Spatial and temporal control over chemical and biological processes, both in terms of "tuning" products and providing site-specific control, is one of the most exciting and rapidly developing areas of modern science. For synthetic chemists, the challenge is to discover and develop selective and efficient reactions capable of generating useful molecules in a variety of matrices. In recent studies, light has been recognized as a valuable method for determining where, when, and to what extent a process is started or stopped. Accordingly, this Minireview will present the fundamental aspects of light-induced click reactions, highlight the applications of these reactions to diverse fields of study, and discuss the potential for this methodology to be applied to the study of biomolecular systems.

Photoinduced controlled radical polymerization.

Well-controlled radical polymerization of methyl methacrylate can be achieved by in situ photochemical generation of copper (I) complex from air-stable copper (II) species without using any reducing agent at room temperature. The living character of this polymerization was confirmed by both the linear tendency of molecular weight evolution with conversion and a chain extension experiment.