Self-assembled natural rubber/silica nanocomposites : its preparation and characterization

A novel natural rubber/silica (NR/SiO2) nanocomposite is developed by combining self-assembly and latex-compounding techniques. The results show that the SiO2 nanoparticles are homogenously distributed throughout NR matrix as nano-clusters with an average size ranged from 60 to 150 nm when the SiO2 loading is less than 6.5 wt%. At low SiO2 contents (less-than-or-equals, slant4.0 wt%), the NR latex (NRL) and SiO2 particles are assembled as a core-shell structure by employing poly (diallyldimethylammonium chloride) (PDDA) as an inter-medium, and only primary aggregations of SiO2 are observed. When more SiO2 is loaded, secondary aggregations of SiO2 nanoparticles are gradually generated, and the size of SiO2 cluster dramatically increases. The thermal/thermooxidative resistance and mechanical properties of NR/SiO2 nanocomposites are compared to the NR host. The nanocomposites, particularly when the SiO2 nanoparticles are uniformly dispersed, possess significantly enhanced thermal resistance and mechanical properties, which are strongly depended on the morphology of nanocomposites. The NR/SiO2 has great potential to manufacture medical protective products with high performances.

Fabrication of high specificity hollow mesoporous silica nanoparticles assisted by Eudragit for targeted drug delivery.

Hollow mesoporous silica nanoparticles (HMSNs) are one of the most promising carriers for effective drug delivery due to their large surface area, high volume for drug loading and excellent biocompatibility. However, the non-ionic surfactant templated HMSNs often have a broad size distribution and a defective mesoporous structure because of the difficulties involved in controlling the formation and organization of micelles for the growth of silica framework. In this paper, a novel "Eudragit assisted" strategy has been developed to fabricate HMSNs by utilising the Eudragit nanoparticles as cores and to assist in the self-assembly of micelle organisation. Highly dispersed mesoporous silica spheres with intact hollow interiors and through pores on the shell were fabricated. The HMSNs have a high surface area (670m(2)/g), small diameter (120nm) and uniform pore size (2.5nm) that facilitated the effective encapsulation of 5-fluorouracil within HMSNs, achieving a high loading capacity of 194.5mg(5-FU)/g(HMSNs). The HMSNs were non-cytotoxic to colorectal cancer cells SW480 and can be bioconjugated with Epidermal Growth Factor (EGF) for efficient and specific cell internalization. The high specificity and excellent targeting performance of EGF grafted HMSNs have demonstrated that they can become potential intracellular drug delivery vehicles for colorectal cancers via EGF-EGFR interaction.

Self-assembled multimicellar vesicles via complexation of a rigid conjugated polymer with an amphiphilic block copolymer

A viable method of encapsulating block copolymer micelles inside vesicles using a conjugated polymer is reported in this study. Self-assembly and complexation between an amphiphilic block copolymer poly(methyl methacrylate)-b-poly(acrylic acid) (PMMA-b-PAA) and a rod-like conjugated polymer polyaniline (PANI) in aqueous solution were studied using transmission electron microscopy, atomic force microscopy and dynamic light scattering. The complexation and morphology transformation were driven by electrostatic interaction between PANI and the PAA block of the block copolymer. Addition of PANI to PMMA-b-PAA induced the morphology transformation from micelles to irregular vesicles through vesicles, thick-walled vesicles (TWVs) and multimicellar vesicles (MMVs). Among the observed morphologies, MMVs were observed for the first time. Morphology transformation was studied as a function of aniline/acrylic acid molar ratio ([ANI]/[AA]). Micelles were observed for the pure block copolymer, while vesicles and TWVs were observed at [ANI]/[AA] = 0.1 and 0.3, respectively. MMVs were observed at [ANI]/[AA] = 0.5 and irregular vesicles were observed for molar ratios at 0.7 and above. Clearly, a conjugated polymer like polyaniline can induce a morphology transformation even at its lower concentrations and produce complex morphologies.

Non-isothermal crystallisation kinetics of self-assembled polyvinylalcohol/silica nano-composite

A novel polyvinylalcohol/silica (PVA/SiO₂) nano-composite is prepared with the self-assembly monolayer (SAM) technique. The SiO₂ nano-particles are homogenously distributed throughout the PVA matrixes as nano-clusters with an average diameter ranged from 15 to 240 nm depending on the SiO₂ contents. Using differential scanning calorimetry (DSC), the non-isothermal crystallisation behaviour and kinetics of the PVA/SiO₂ nano-composites are investigated and compared to those of the pure PVA. There are strong dependences of the degree of crystallinity (X_c), peak crystallisation temperature (T_p), half time of crystallisation (t_1/2), and Ozawa exponent (m) on the SiO₂ content and cooling rate. The crystallisation activation energy (E) calculated with the Kissinger model is markedly lower when a small amount of SiO₂ is added, then gradually increases and finally becomes higher than that of the pure PVA when there is more than 10% SiO₂ in the composite.

Self-assembled complexes of poly(4-vinylphenol) and poly(ε-caprolactone)-block-poly(2-vinylpyridine) via competitive hydrogen bonding

Nanostructured complexes were prepared from poly(ε-caprolactone)-block-poly(2-vinylpyridine) (PCL-b-P2VP) and poly(4-vinylphenol) (PVPh) in tetrahydrofuran (THF). The phase behavior, specific interactions, and morphology were investigated using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, optical microscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). In this A-b-B/C type block copolymer/homopolymer system, both blocks of the PCL-b-P2VP block copolymer have favorable intermolecular interaction toward PVPh via hydrogen bonding, but the interaction between P2VP block and PVPh is significantly stronger than that between PCL block and PVPh. It was found that the disparity in competitive intermolecular interactions, specifically PVPh and P2VP block interact strongly whereas PVPh and PCL block interact weakly, leads to the formation of a variety of nanostructures depending on PVPh concentration. Spherical micelles of 30−40 nm in diameter were obtained in the complex with 10 wt % PVPh, followed by wormlike micelles with size in the order of 40−50 nm in the complexes with 30−60 wt % PVPh. At low PVPh concentrations, PCL interacts weakly with PVPh, whereas in the complexes containing more than 20 wt % PVPh, the PCL block began to interact considerably with PVPh, leading to the formation of composition-dependent nanostructures. The complex becomes homogeneous with PVPh content beyond 60 wt %, since a sufficient amount of PVPh is available to form hydrogen bonds with both PCL and P2VP. Finally, a model was proposed to explain the self-assembly and microphase morphology of these complexes based on the experimental results obtained. The competitive hydrogen-bonding interactions cause the self-assembly and formation of different microphase morphologies.

Thermal degradation kinetics and morphology of natural rubber/silica nanocomposites

A novel natural rubber/silica (NR/SiO₂) nanocomposite with a SiO₂ loading of 4 wt% is developed by incorporating latex compounding with self-assembly techniques. The SiO₂ nanoparticles are homogenouslydistributed throughout the NR matrix as spherical nano-clusters with an average size of 75 nm. In comparison with the host NR, the thermal resistance of the nanocomposite is significantly improved. The degradation temperatures (T), reaction activation energy(E), and reaction order (n) of the nanocomposite are markedly higher than those of the pure NR, due to significant retardant effect of the SiO₂ nanoparticles.

Development of a novel micro-spray-assembly process for multilayer ultra-thin film formation

A novel micro-spray-assembly process and an automatic device to fabricate multilayer ultra-thin film are introduced. Employing self-assembly monolayer (SAM) technique, ultra-thin film can be assembled by utilizing the micro-spray-assembly device. The thickness and roughness of each monolayer can be controlled by varying various materials attributes, i.e., deposition time, ionic strength, pH value, molecular concentration and by selecting different manufacturing parameters of the automatic device such as spraying rate, size of micro-drop, N₂ flow rate, temperature of N₂ flow.

Self-assembled natural rubber/multi-walled carbon nanotube composites using latex compounding techniques

Functionalization of multi-walled carbon nanotubes (MWCNTs) plays an important role in eliminating nanotube aggregation for reinforcing polymeric materials. We prepared a new class of natural rubber (NR)/MWCNT composites by using latex compounding and self-assembly technique. The MWCNTs were functionalized with mixed acids (H2SO₄/HNO₃ = 3:1, volume ratio) and then assembled with poly (diallyldimethylammonium chloride) and latex particles. The Fourier transform infrared spectroscopy, transmission electron microscopy, and scanning electron microscopy were used to investigate the assembling mechanism between latex particles and MWCNTs. It is found that MWCNTs are homogenously dispersed in the natural rubber (NR) latex as individual nanotubes since strong self-aggregation of MWCNTs has been greatly depressed with their surface functionalization. The well-dispersed MWCNTs produce a remarkable increase in the tensile strength of NR even when the amount of MWCNTs is only 1 wt.%. Dynamic mechanical analysis shows that the glass transition temperature of composites is higher and the inner-thermogenesis and thermal stability of NR/MWCNT composites are better, when compared to those of the pure NR. The marked improvement in these properties is largely due to the strong interfacial adhesion between the NR phase and MWCNTs. Functionalization of MWCNTs represents a potentially powerful technology for significant reinforcement of natural rubber materials.

Self-assembled diblock copolymer complexes via competitive hydrogen bonding

This thesis investigates self-assembly and microphase separation induced by competitive hydrogen bonding in A-b-BC diblock copolymer/homopolymer systems. A series of ordered and disordered morphologies including lamellae, hexagonal cylinders, wormlike microdomains and hierarchical structures were observed. The morphological transitions are correlated with hydrogen bonding interactions in terms of the association constants.

Characterisation of gold electrodes modified with self-assembled monolayers of l-cysteine for the adsorptive stripping analysis of copper

Electrochemical sensors for copper ions in environmental samples were prepared by modifying gold electrodes with l-cysteine by self-assembly. The adsorption of l-cysteine on gold electrodes was studied by electrochemical reductive desorption in 0.5 M KOH, and the interaction of l-cysteine with copper ions was investigated by cyclic voltammetry, chronoamperometry and X-ray photoelectron spectroscopy. At low concentrations the ratio of l-cysteine to bound Cu(II) is 2:1. At higher concentrations (0.1 M) copper reacts with adsorbed cysteine forming copper sulfide on the electrode surface. On a modified l-cysteine gold electrode, Osteryoung square wave voltammetric determination of Cu(II) with a detection limit below 5 ppb has been demonstrated.

Synthesis, characterization, and multilayer assembly of pH sensitive graphene−polymer nanocomposites

pH sensitive graphene−polymer composites have been prepared by the modification of graphene basal planes with pyrene-terminated poly(2-N,N′-(dimethyl amino ethyl acrylate) (PDMAEA) and poly(acrylic acid) (PAA) via π−π stacking. The pyrene-terminal PDMAEA and PAA were synthesized using reversible addition−fragmentation chain transfer (RAFT) polymerization with a pyrene-functional RAFT agent. The graphene−polymer composites were found to demonstrate phase transfer behavior between aqueous and organic media at different pH values. Atomic force microscopy (AFM) analysis revealed that the thicknesses of the graphene−polymer sheets were approximately 3.0 nm when prepared using PDMAEA (M_n: 6800 and PDI: 1.12). The surface coverage of polymer chains on the graphene basal plane was calculated to be 5.3 × 10⁻¹¹ mol cm⁻² for PDMAEA and 1.3 × 10⁻¹⁰ mol cm⁻² for PAA. The graphene−polymer composites were successfully characterized using X-ray photoelectron spectroscopy (XPS), attenuated total reflection infrared (ATR-IR) spectroscopy, and thermogravimetric analysis (TGA). Self-assembly of the two oppositely charged graphene−polymer composites afforded layer-by-layer (LbL) structures as evidenced by high-resolution scanning electron microscopy (SEM) and quartz crystal microbalance (QCM) measurements.

Attachment of magnetic molecules on a nanoSQUID

A novel procedure combining monolayer self-assembly with electron beam lithography has been developed for attaching ferritin nanoparticles to a submicron thin-film SQUID (superconducting quantum interference device). After opening a window in the PMMA (polymethylmethacrylate) resist, organic linker molecules are used to attach ferritin to the exposed parts of the gold overlayer of a Nb nanoSQUID. This allows the magnetic nanoparticles to be located optimally as far as magnetic coupling to the nanoSQUID is concerned.

Structure and properties of self-assembled narural rubber/multi-walled carbon nanotube composites

Natural rubber (NR)/multi-walled carbon nanotube (MWCNTs) composites were prepared bycombining self-assembly and latex compounding techniques. The acid-treated MWCNTs (H2SO4: HNO3=3:1,volume ratio) were self-assembled with poly (diallyldimethylammonium chloride) (PDDA) through electrostaticadhesion. In the second assembling, NR/MWCNTs composites were developed by mixing MWCNTs/PDDAsolution with NR latex. The results show that MWCNTs are homogenously distributed throughout the NRmatrix as single tube and present a great interfacial adhesion with NR phase when MWCNTs contents areless than 3 wt%. Moreover, the addition of the MWCNTs brings about the remarkable enhancement in tensilestrength and crosslink density compared with the NR host, and the data peak at 2 wt% MWCNTs loadings.When more MWCNTs are loaded, aggregations of MWCNTs are gradually generated, and the tensile strengthand crosslink both decrease to a certain extent.

Reduced graphene oxide/ZnO composite : reusable adsorbent for pollutant management

Reduced graphene oxide (RGO) coated with ZnO nanoparticles (NPs) was synthesized by a self-assembly and in situ photoreduction method, and then their application for removing organic pollutant from water was investigated. The RGO@ZnO composite nanomaterial has unique structural features including well-dispersed NPs on the surface and dense NPs loading. This composite exhibited a greatly improved Rhodamine B (RhB) adsorption capacity and an improved photocatalytic activity for degrading RhB compared to neat ZnO NPs. These properties made RGO@ZnO reusable for pollutant adsorbent. The composite showed an excellent cycling performance for organic pollutant removal up to 99% recovery over several cycles via simulated sunlight irradiation.

Fmoc-diphenylalanine self assembles to a hydrogel via a novel architecture based on π-π interlocked β-sheets

The self assembly of peptide hydrogelators that carry aromatic substituents can be modeled by a novel nanocylindrical architecture. The proposed model suggests that the nanocylinders are formed by anti-parallel β-sheets interlocked by the π-stacking interactions of fluorenyl groups and phenyl rings. This explanation is consistent with the structures observed in TEM and the data obtained by a variety of spectroscopic techniques.