Effect of montmorillonite on morphology, glass transition and crystallinity of the xylitol-plasticized bionanocomposites.

High amylose based nanocomposites plasticized by xylitol were prepared via twin-screw extrusion. The synergistic interaction in the xylitol-plasticized nanocomposite was studied via various characterization methods and the unique behavior of the xylitol-plasticized nanocomposite had been discussed. As revealed in the XRD and TEM results, good intercalated/exfoliated morphology had been achieved in all the nanocomposites. Furthermore, the expansion of nanoclay basal spacing was related to the xylitol/nanoclay ratio. DSC analysis clearly proved the unique crystallization process of xylitol-plasticized samples. Moreover, in the crystallization domain results, two domains sized at approximately 93.7 Å and 346 Å were found. This observation points to a two-level complex effect from two aggregate domains; one, the re-aggregation of certain number of silicate layers into domains which trap some of the amylose polymer chains, and two, the bulk drying process which combines smaller amylose crystalline domains within a larger amorphous high amylose matrix.

Cancer therapy and fluorescence imaging using the active release of doxorubicin from MSPs/Ni-LDH folate targeting nanoparticles.

Hierarchical structured nanomaterials with diverse functionality, such as magnetic susceptibility, stimuli-responsiveness, environmental sensing and biocompatibility, are highly sought after for biomedicine and biodetection alike. In this study, we designed and fabricated a new kind of multifunctional core/shell nanospheres as biodegradable targeted drug carriers, the controlled drug release progress and therapeutic effect were monitored in-situ by the fluorescent state of the cells. Firstly, the core/shell nanospheres with biodegradability were synthesized using magnetic supraparticles (MSPs) as core and the layered double hydroxide (LDH) as shell via a hydrothermal route, the reaction parameters were well investigated to obtain the desired structure of the LDH shell. The anti-cancer drug doxorubicin was modified with carboxyl group (DOX-COOH) and loaded in the shell of MSPs/LDH nanospheres via an anion-exchange intercalation. To endow the nanospheres with tumor-targeting capability, IDA (iminodiacetic acid)-modified folate was successfully immobilized onto the surface of LDH shell using chelating interaction. These nanospheres behaved as multifunctional carriers for targeted delivery of anti-cancer drug, doxorubicin (DOX), within Hela cells and thus, these nano-drugs exhibited clear cytotoxicity and inhibition toward Hela cells as compared to normal cell-lines of HEK 293T cells. Interestingly, after the internalization of these nano-drugs, there was a sharp contrast in illumination between the tumorous Hela cells and the normal HEK 293T cells, the acidic cytoplasm of Hela cell stimulated DOX-COOH in LDH shell quickly degraded into positive-charged DOX, and then rapidly escaped from the positive-charged intercalation of LDH shell by strong repulsive interaction, the released DOX rapidly lit up the whole tumor cells in a short time, but only very weak light was found in HEK 293T cells.

Ultrasonic treatment and synthesis of sugar alcohol modified Na+-montmorillonite clay.

Na(+)-montmorillonite clay (generally referred to as MMT) is very useful for reinforcing polymeric matrix at very low concentrations (typically, 2-5% wt). These clay particles are typically exfoliated before they can demonstrate the significant gains in heat deflection temperature, modulus, and elongation properties. In the case of hydrophilic biopolymer based matrices, such as carbohydrates and chitosan, exfoliating these nanoclay particles needs greater attention because the exfoliation is typically carried out using hydrophobic oligomers through ion-exchange. This study reports a new method of synthesizing completely hydrophilic MMT-assemblages using hydrophilic plasticizers for biopolymers. We used sugar alcohols (glycerol, xylitol with 3 and 5 hydroxyl groups) and polysaccharide maltodextrin to exfoliate the MMT. Sonication was conducted for MMT nanoclay and plasticizers at different weight ratios. It was confirmed that all plasticizer/modifier led to expansion of MMT gallery spacing (d-spacing) and the change in d-spacing could be related to the molecular structure of the plasticizer. Meanwhile, the extent of exfoliation was maximum with maltodextrin (fully exfoliation with 1:10 and 1:20 ratio of MMT:plasticizer) across all test samples and interestingly, glycerol and xylitol samples quickly established within the MMT galleries and exhibited minimal influence with further increase in relative concentrations.

Investigation on the phase behaviour of gelatin/agarose mixture in an environment of reduced solvent quality.

Investigation on the phase behaviour of a biopolymer mixture has been performed using 7.5% (w/w) gelatin and 1.5% (w/w) agarose in the presence of variable amounts of polydextrose as the co-solute from low to high levels of total solids. Mechanical observation of the system was performed using small deformation dynamic oscillation in shear along with thermal studies using modulated differential scanning calorimetry. Micrographs provided images of the changing morphology of the network with the addition of co-solute. Agarose and gelatin form non-interactive bicontinuous phases in the aqueous environment. Systematic increase in the concentration of polydextrose prevents the formation of a stable agarose network, with the polysaccharide chains dispersing in the high solids environment. Gelatin, on the other hand, retains its conformational stability even at a saturating co-solute environment through enhanced protein structuring. Vitrification studies on the high solids system at subzero temperatures provides information on the structural and molecular relaxation identified as a glass transition phenomenon. Fourier transform infrared spectroscopy was used to analyse potential direct interaction between polymers and co-solute. The extent of amorphicity in the system was confirmed using wide angle X-ray diffraction.

Hollow-core magnetic colloidal nanocrystal clusters with ligand-exchanged surface modification as delivery vehicles for targeted and stimuli-responsive drug release.

The fabrication of hierarchical magnetic nanomaterials with well-defined structure, high magnetic response, excellent colloidal stability, and biocompatibility is highly sought after for drug-delivery systems. Herein, a new kind of hollow-core magnetic colloidal nanocrystal cluster (HMCNC) with porous shell and tunable hollow chamber is synthesized by a one-pot solvothermal process. Its novelty lies in the "tunability" of the hollow chamber and of the pore structure within the shell through controlled feeding of sodium citrate and water, respectively. Furthermore, by using the ligand-exchange method, folate-modified poly(acrylic acid) was immobilized on the surface of HMCNCs to create folate-targeted HMCNCs (folate-HMCNCs), which endowed them with excellent colloidal stability, pH sensitivity, and, more importantly, folate receptor-targeting ability. These assemblages exhibited excellent colloidal stability in plasma solution. Doxorubicin (DOX), as a model anticancer agent, was loaded within the hollow core of these folate-HMCNCs (folate-HMCNCs-DOX), and drug-release experiments proved that the folate-HMCNCs-DOX demonstrated pH-dependent release behavior. The folate-HMCNCs-DOX assemblages also exhibited higher potent cytotoxicity to HeLa cells than free doxorubicin. Moreover, folate-HMCNCs-DOX showed rapid cell uptake apart from the enhanced cytotoxicity to HeLa cells. Experimental results confirmed that the synthesized folate-HMCNCs are smart nanovehicles as a result of their improved folate receptor-targeting abilities and also because of their combined pH- and magnetic-stimuli response for applications in drug delivery.

Analysis on the effectiveness of co-solute on the network integrity of high methoxy pectin.

Co-solute requirements for high methoxy pectin gelation were observed by the addition of glucose syrup and polydextrose at concentrations varying from 50% to 78% (w/w). Pectin content was fixed at 2% (w/w) in formulations. Studies from small deformation dynamic oscillation in shear, modulated differential scanning calorimetry and environmental scanning electron microscopy are reported. Structural properties of pectin preparations were recorded in relation to the molecular weight and concentration of added co-solute in an acidic environment (pH ∼3.0). High levels of co-solute induce formation of weak pectin gels at elevated temperatures (even at 95°C), which upon subsequent cooling exhibit increasing strength and convert to a clear glass at subzero temperatures. Fourier Transform Infrared Spectroscopy and wide angle X-ray diffraction were practised to examine the nature of interactions between polymer and co-solute and the extent of amorphicity of preparations. Glucose syrup is an efficient plasticiser leading to a reduction in the glass transition temperature (T(g)) of the pectin network, whereas polydextrose assists in the formation of stronger pectin gels in the rubbery state.

Doxorubicin-conjugated mesoporous magnetic colloidal nanocrystal clusters stabilized by polysaccharide as a smart anticancer drug vehicle.

Fabrication of magnetic nanocarriers that demonstrate enhanced biocompatibility and excellent colloidal stability is critical for the application of magnetic-motored drug delivery, and it remains a challenge. Herein, a novel approach to synthesize mesoporous magnetic colloidal nanocrystal clusters (MMCNCs) that are stabilized by agarose is described; these clusters demonstrate high magnetization, large surface area and pore volume, excellent colloidal stability, enhanced biocompatibility, and acid degradability. The hydroxyl groups of agarose, which cover the surface of the magnetic nanocrystals, are modified with vinyl groups, followed by click reaction with mercaptoacetyl hydrazine to form the terminal hydrazide (-CONHNH(2)). The anticancer agent doxorubicin (DOX) is then conjugated to MMCNCs through a hydrazone bond. The resulting hydrazone is acid cleavable, thereby providing a pH-sensitive drug release capability. This novel carrier provides an important step towards the construction of a new family of magnetic-motored drug-delivery systems. The experimental results show that the release rate of DOX from the DOX-conjugated MMCNCs (MMCNCs-DOX) is dramatically improved at low pH (tumor cell: pH 4-5 in the late stage of endolysosome and pH 5-6 from the early to late endosome), while almost no DOX is released at neutral pH (blood plasma). The cell cytotoxicity of the MMCNCs-DOX measured by MTT assay exhibits a comparable antitumor efficacy but lower cytotoxicity for normal cell lines, when measured against the free drug, thus achieving the aim of reducing side effects to normal tissues associated with controlled drug release.

Phase behaviour of gelatin/polydextrose mixtures at high levels of solids.

This investigation focuses on understanding the phase behaviour of gelatin when mixed with polydextrose (co-solute) primarily at high solid concentrations. The experimental work was carried out using small deformation dynamic oscillation in shear, modulated differential scanning calorimetry, Fourier transform infrared spectroscopy, wide angle X-ray diffraction and environmental scanning electron microscopy. A progression in the mechanical strength and thermal stability of the gelatin network was observed with the addition of polydextrose to the system. Combined thermomechanical and microscopy evidence argues for the development of phase separation phenomenon between protein and co-solute in high-solid preparations, where gelatin maintains helical conformation to provide network integrity as well as glassy consistency at subzero temperature. At the high solids regime, glassy consistency was treated with theoretical frameworks from the synthetic polymer research to pinpoint the glass transition temperature of the system.