Self-assembly and alignment of semiconductor nanoparticles on cellulose nanocrystals

The synthesis of cadmium sulfide (CdS), zinc sulfide (ZnS), and lead sulfide (PbS) nanoparticle chains on cellulose nanocrystal (CNC) templates can be accomplished by the reaction of the precursor salts. The use of a cationic surfactant, cetyltrimethylammonium bromide (CTAB), was critical for the synthesis of well-defined semiconductor nanoparticle chains on the surface of the CNCs. The semiconductor nanoparticle particle size and packing density on CNC surface could be controlled by the variation of the precursor concentration and the pH of the salt solution.     

Competitive adsorption of fibronectin and albumin on hydroxyapatite nanocrystals

Abstract

Competitive adsorption of two-component solutions containing fibronectin (Fn) and albumin (Ab) on hydroxyapatite (HAp) nanocrystals was analyzed in situ using the quartz crystal microbalance with dissipation (QCM-D) technique. Adsorption of the one-component protein (Fn or Ab) and the two-component proteins adjusted to different molar ratios of Fn to Ab at a fixed Fn concentration was investigated. The frequency shift (Δf; Hz) and the dissipation energy shift (ΔD) were measured with the QCM-D technique, and the viscoelastic changes of adlayers were evaluated by the saturated ΔD/Δf value and the Voigt-based viscoelastic model. For the adsorption of the one-component protein, the Fn adlayer showed a larger mass and higher viscoelasticity than the Ab adlayer, indicating the higher affinity of Fn on HAp. For the adsorption of the two-component proteins, the viscoelastic properties of the adlayers became elastic with increase in Ab concentration, whereas the adsorption mass was similar to that of Fn in the one-component solution regardless of the Ab concentration. The specific binding mass of the Ab antibody to the adlayers increased with increase in Ab concentration, whereas that of the Fn antibody decreased. Therefore, Fn preferentially adsorbs on HAp and Ab subsequently interacts with the adlayers, indicating that the interfacial viscoelasticity of the adlayers was dominated by the interaction between Fn and Ab.     

Competitive adsorption of fibronectin and albumin on hydroxyapatite nanocrystals

Competitive adsorption of two-component solutions containing fibronectin (Fn) and albumin (Ab) on hydroxyapatite (HAp) nanocrystals was analyzed in situ using the quartz crystal microbalance with dissipation (QCM-D) technique. Adsorption of the one-component protein (Fn or Ab) and the two-component proteins adjusted to different molar ratios of Fn to Ab at a fixed Fn concentration was investigated. The frequency shift (Δf; Hz) and the dissipation energy shift (ΔD) were measured with the QCM-D technique, and the viscoelastic changes of adlayers were evaluated by the saturated ΔD/Δf value and the Voigt-based viscoelastic model. For the adsorption of the one-component protein, the Fn adlayer showed a larger mass and higher viscoelasticity than the Ab adlayer, indicating the higher affinity of Fn on HAp. For the adsorption of the two-component proteins, the viscoelastic properties of the adlayers became elastic with increase in Ab concentration, whereas the adsorption mass was similar to that of Fn in the one-component solution regardless of the Ab concentration. The specific binding mass of the Ab antibody to the adlayers increased with increase in Ab concentration, whereas that of the Fn antibody decreased. Therefore, Fn preferentially adsorbs on HAp and Ab subsequently interacts with the adlayers, indicating that the interfacial viscoelasticity of the adlayers was dominated by the interaction between Fn and Ab.     

Preparation of anatase nanocrystals deposited on hydroxyapatite by hydrothermal treatment

TiO₂-deposited hydroxyapatite (HAp) crystals have been successfully synthesized by hydrothermal treatment of nearly neutral suspension of HAp powders in 10 vol.% of TAS-FINE™ (Titanium amine complex) solutions at 120 or 180 °C. Resultant products were characterized by XRD, SEM–EDX, Vis-Raman and TEM. SEM and TEM observation showed that small rodlike TiO₂, identified as anatase crystals of 100–150 nm in length, were deposited on HAp plates/crystals. The anatase crystals seem to be formed by heterogeneous nucleation on the surfaces of HAp crystals. A higher temperature and a longer reaction period promoted the cystallization of anatase TiO₂.     

Effect of chondroitin sulfate on osteogenetic differentiation of human mesenchymal stem cells

Chondroitin sulfate (CS) has anti-inflammatory properties and increases the regeneration ability of injured bone. In different in vivo investigations on bone defects the addition of CS to calcium phosphate bone cement has lead to an enhanced bone remodeling and increased new bone formation. The goal of this study was to evaluate the cellular effects of CS on human mesenchymal stem cells (hMSCs). In cell culture experiments hMSCs were incubated on calcium phosphate bone cements with and without CS and cultivated in a proliferation and an osteogenetic differentiation media. Alkaline phosphatase and the proliferation rate were determined on days 1, 7 and 14. Concerning the proliferation rates, no significant differences were detected. On days 1, 7 and 14 a significantly higher activity of alkaline phosphatase, an early marker of osteogenesis, was detected around CS modified cements in both types of media. The addition of CS leads to a significant increase of osteogenetic differentiation of hMSCs. To evaluate the influence of the osteoconductive potency of CS in twelve adult male Wistar rats, the interface reaction of cancellous bone to a nanocrystalline hydroxyapatite cement containing type I collagen (CDHA/Coll) without and with CS (CDHA/Coll/CS) was evaluated. Cylindrical implants were inserted press-fit into a defect of the tibial head. 28 days after the operation the direct bone contact and the percentage of newly formed bone were significantly higher on CDHA/Coll/CS-implants (p < 0.05). The addition of CS appears to enhance new bone formation on CDHA/Coll-composites in the early stages of bone healing. Possible mechanisms are discussed.     

Ionic liquid matrix for direct UV-MALDI-TOF-MS analysis of dermatan sulfate and chondroitin sulfate oligosaccharides

Polyanionic oligosaccharides such as dermatan sulfate (DS) and chondroitin sulfate (CS) exhibit poor ionization efficiencies and tend to undergo thermal fragmentation through the loss of SO(3) under conventional ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI) conditions. A new ionic liquid matrix (ILM), a guanidinium salt of alpha-cyano-4-hydroxycinnamic acid, facilitates direct UV-MALDI mass spectrometric (MS) analysis of underivatized DS and CS oligosaccharides up to a decasaccharide in their common form as sodium salts. The resulting mass spectra show very low extent of fragmentation through an SO(3) loss. The new ILM is suitable for MALDI-MS analysis of mixtures containing oligosaccharides with different numbers of sulfo groups.     

Controllable synthesis of hydroxyapatite nanocrystals via a dendrimer-assisted hydrothermal process

The morphology and size of hydroxyapatite Ca₁₀(PO₄)₆(OH)₂ (denoted HAP) can be controlled under hydrothermal treatment assisted with different dendrimers, such as carboxylic terminated poly(amidoamine) (PAMAM) and polyhydroxy terminated PAMAM. The structure and morphology were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR) and transmission electron microscopy (TEM). IR spectra were also used to investigate the complexation of Ca²⁺ with PAMAM. The results revealed that the inner cores of the PAMAM dendrimers are hydrophilic and potentially open to calcium ions, since interior nitrogen moieties serve as complexation sites, especially in case of the polyhydroxy terminated PAMAM. And the reasonable mechanism of crystallization was proposed that it can be attributed to the localization of nucleation site: external or interior PAMAM. Additionally, the PAMAM dendrimer with carboxylic and polyhydroxy groups has an effective influence on the size and shape of hydroxyapatite (HAP) nanostructures. Different crystal morphology was accomplished by adsorption of different dendrimers onto specific faces of growing crystals, altering the relative growth rates of the different crystallographic faces and leading to different crystal habits.     

Self-assembly of colloidal nanocrystals as route to novel classes of nanostructured materials

Colloidal crystallisation is the only way to obtain three-dimensional ordered materials in which semiconductor, metallic, and magnetic nanocrystals are in close contact. It is expected that the quantum mechanical and dipolar interactions between the nanocrystal units can lead to unseen physical phenomena and materials. Here we review the development of this new and exciting field. We first compare nanocrystal superlattices with regular atomic solids regarding their mechanical strength and opto-electronic properties. We describe how nanocrystal superlattices have been obtained from colloid suspensions in several ways. The thermodynamic driving force for colloidal crystallisation is discussed in terms of inter-particle interactions in a good solvent and entropy. We compare the binary superlattices that have been obtained by solvent evaporation with the predictions of the hard-sphere model and show that semiconductor nanocrystals in a good solvent can behave as hard spheres. Finally, we discuss the quantum mechanical and dipolar interactions in nanocrystal superlattices and review recent studies of the opto-electronic and magnetic properties of novel superlattice materials.     

Self-assembly of uniform polyhedral silver nanocrystals into densest packings and exotic superlattices

Understanding how polyhedra pack into extended arrangements is integral to the design and discovery of crystalline materials at all length scales. Much progress has been made in enumerating and characterizing the packing of polyhedral shapes, and the self-assembly of polyhedral nanocrystals into ordered superstructures. However, directing the self-assembly of polyhedral nanocrystals into densest packings requires precise control of particle shape, polydispersity, interactions and driving forces. Here we show with experiment and computer simulation that a range of nanoscale Ag polyhedra can self-assemble into their conjectured densest packings. When passivated with adsorbing polymer, the polyhedra behave as quasi-hard particles and assemble into millimetre-sized three-dimensional supercrystals by sedimentation. We also show, by inducing depletion attraction through excess polymer in solution, that octahedra form an exotic superstructure with complex helical motifs rather than the densest Minkowski lattice. Such large-scale Ag supercrystals may facilitate the design of scalable three-dimensional plasmonic metamaterials for sensing, nanophotonics and photocatalysis.     

Characterisation of freeze-dried type II collagen and chondroitin sulfate scaffolds

Collagen type-II is the dominant type of collagen in articular cartilage and chondroitin sulfate is one of the main components of cartilage extracellular matrix. Afibrillar and fibrillar type-II atelocollagen scaffolds with and without chondroitin sulfate were prepared using casting and freeze-drying methods. The scaffolds were characterised to highlight the effects of fibrillogenesis and chondroitin sulfate addition on viscosity, pore structure, porosity and mechanical properties. Microstructure analysis showed that fibrillogenesis increased the circularity of pores significantly in collagen-only scaffolds, whereas with it, no significant change was observed in chondroitin sulfate-containing scaffolds. Addition of chondroitin sulfate to afibrillar scaffolds increased the circularity of the pores and the proportion of pores between 50 and 300 μm suitable for chondrocytes growth. Fourier transform infrared spectroscopy explained the bonding between chondroitin sulfate and afibrillar collagen- confirmed with rheology results- which increased the compressive modulus 10-fold to 0.28 kPa. No bonding was observed in other scaffolds and consequently no significant changes in compressive modulus were detected.     

The cross-linkage effect of hydroxyapatite/collagen nanocomposites on a self-organization phenomenon

Hydroxyapatite(HAp)/collagen nanocomposites were prepared by a coprecipitation method controlling the degree of cross-linkage between collagen molecules using glutaraldehyde. The precipitates filtered were dried in a freeze drier or naturally dried in the air at 25 °C. The naturally dried cakes had open channels of 5–15 m in diameters, which were three-dimensionally and regularly developed over the whole samples, and showed a pretty good mechanical strength. The channels that were formed at spaces among the HAp/collagen particles, cross-linked one another, which had been filled up with water before its evaporation. The ordering state of the open channels depended on the degree of cross-linkage with glutaraldehyde; the optimal self-organized state was found when 30 molecules of glutaraldehyde were added per collagen molecule, though an excess amount of glutaraldehyde suppressed the appearance of the ordered state. From SEM and FT-IR measurements, it was indicated that the self-organization in the HAp/collagen nanocompsites continuously occurred during the drying process together with the removal of water and the increase of the density.     

Drug-supported microparticles of calcium carbonate nanocrystals and its covering with hydroxyapatite

Drug-supported spherical microparticles with below 3 microm in diameter of calcium carbonate (CC) nanocrystals were precipitated by a complex decomposition method from Na2CO3 and CaCl2 solutions with hydrocortisone phosphate (HyC). The HyC was completely incorporated into the microparticles and was adsorbed on the surface of nanocrystals. The crystal phases of vaterite and calcite were controlled by the addition of magnesium ions. Spherical microparticles of calcite cores and petal-shaped hydroxyapatite (HAp) outer layers were fabricated by soaking calcite into the SBF, or a supersaturated solution of phosphate ions to enhance the crystal growth of HAp.     

Graphitized carbon LC-MS characterization of the chondroitin sulfate oligosaccharides of aggrecan

A novel in-gel endoglycosidase technique to study oligosaccharides with graphitized carbon LC-MS has revealed differences in the sulfation profile between the linkage and repeat regions of chondroitin sulfate on aggrecan. Bovine articular cartilage aggrecan was isolated in a composite agarose PAGE gel or diluted in ammonium acetate buffer and was digested overnight with chondroitinase ABC. Including a chemical release/reduction protocol after digestion, we could separate and detect three differentially sulfated chondroitin sulfate disaccharides of the repeat region (DeltaUA1-3GalNAc0/4/6S-ol) from the three differentially sulfated linkage region hexasaccharides (DeltaUA1-3GalNAc0/4/6Sbeta1-4GlcAbeta1-3Galbeta1-3Galbeta1-4Xylitol). Graphitized carbon LC-MS in the negative ion mode was able to resolve isomeric disaccharides and linkage region hexasaccharides. Specific MS2 and MS3 enabled us to confirm the sulfate location on all oligosaccharides by comparing their fragmentation with sulfated disaccharide standards. The presence of unsulfated, 6-sulfated, and 4-sulfated linkage regions was correlated with positive Western blot staining with the respective CS linkage region neoepitope antibodies (1B5, 3B3, 2B6) on digested aggrecan. Our strategy of examining linkage region and repeat region profiles is applicable to screening GAGs from various biological samples in order to detect differences between normal and disease states.     

Self-assembly of CdTe nanocrystals at the water/oil interface by amphiphilic hyperbranched polymers

A general strategy for realizing the self-assembly of aqueous CdTe nanocrystals (NCs) at the water/oil interface by means of an amphiphilic core-shell hyperbranched polymer has been proposed. Aqueous CdTe NCs were firstly transferred into the chloroform phase in the presence of palmityl chloride functionalized hyperbranched poly(amidoamine) (HPAMAM-PC), and then self-assembled at the water/chloroform interface by decreasing the pH value of the aqueous phase or introducing α-CDs to the aqueous phase. The resulting CdTe/HPAMAM-PC self-assembly film was characterized by fluorescence microscopy, UV-vis, PL, TEM, EDS, FT-IR, DSC and TGA.     

In vivo estimation of calcium phosphate cements containing chondroitin sulfate in subcutis

Calcium phosphate cements using an equimolar mixture of tetracalcium phosphate and dicalcium phosphate dihydrate (TeDCPD) for the powder phase were experimentally developed for use in endodontic treatment. The fundamental cement is comprised of TeDCPD kneaded with modified McIlvain's buffer solution containing calboxymethyl cellulose sodium salt (CEM-1). In the liquid phase of the modified one (CEM-2), chondroitin sulfate (CS) was added in place of the salt. The final concentration of CS in CEM-2 is 1%. Another one (CEM-3) contained 2% CS finally in place of the salt. X-ray diffract meter (XRD) was used to examine the crystalline phases of the cements. The tissue compatibility of the cements was examined histologically in the subcutaneous tissue using rats. The XRD results showed no dibasic calcium phosphate phase to be traced in CS containing two cements after 1 day of kneading. There were more multinucleated giant cells appearing around CEM-1 than around CEM-2 or CEM-3 after 4 weeks. Fibroblasts, collagen fibers and small vessels infiltrated into the internal porous structure of CEM-3. Excluding CEM-3, two cements were encapsulated with a dense fibrous connective tissue layer. We conclude that CS, in the experimentally developed cement, contributed to biocompatibility and bioactivity of the cement.     

Influence of fluorine substitution on the morphology and structure of hydroxyapatite nanocrystals prepared by hydrothermal method

Hydroxyapatite (HAp) nanocrystals with different levels of fluorine substitution (P/F = 0, 6, 4 and 2) on the OH sites were produced via hydrothermal method. The fluorine substitution was found to alter the morphology of crystals appreciably. The aspect ratio and the crystallinity of HAp crystals increased with increasing fluorine substitution. The presence of broad ring and hallow ring patterns in electron diffraction suggests the low-crystalline nature of HAp crystals. With increasing fluorine substitution, the diffraction patterns exhibited discrete rings and numerous diffraction spots, implying the increased crystallinity. Raman spectra from the HAp nanoparticles also support the less-crystalline nature of the pristine HAp and the enhanced crystallization by fluorine substitution. In HAp crystals processed with no fluorine substitution, surface energy and planar Ca²⁺ density are less sensitive to the crystallographic orientation because of its low-crystalline nature, favoring equi-axed or slightly elongated particles. The addition of fluorine apparently increased the crystallinity, enhancing the orientation dependent growth and accordingly the aspect ratio. Osteoblast proliferation was observed to be enhanced by fluorine substitution in HAp. In vitro biological data support that the excellent osteoblastic cell viability and functional activity of the fluoridated apatite.