Synthesis of high surface area hydroxyapatite nanoparticles by mixed surfactant-mediated approach

A new surfactant-mediated approach was developed to synthesize hydroxyapatite (HAp) nanoparticles with high surface areas by calcination of their precursors encapsulated with calcium stearate using mixed surfactant-containing reaction mixtures. Acidic aqueous solution of calcium phosphate was mixed with both or either nonaoxyethylene dodecyl ether (C12EO9) and polyoxyethylene(20) sorbitan monostearate (Tween 60) and then was treated with aqueous ammonium at 25 degrees C. The C12EO9-based single surfactant system yielded an aggregate of platy HAp nanoparticles 20-40 nm in size, whereas the Tween 60-based single and mixed systems led to lath-shaped HAp nanoparticles 2-8 nm wide and encapsulated with calcium stearate. On calcination at 500 degrees C, the stearate-encapsulated HAp nanoparticles in the latter two systems were deorganized into high surface area HAp nanoparticles. Particularly, the HAp nanoparticles in the mixed system exhibited a specific surface area as high as 364 m2 g(-1) that is roughly 3 times larger than 160 m2 g(-1) for those in the single system. The significantly high surface area for the former is attributed to much less adhesion of decapsulated HAp nanoparticles, which originated from the particle-separating effect of the C12EO9 molecules adsorbed on the outer surface of the stearate-encapsulated HAp nanoparticles to inhibit their agglomeration or interfacial coordination. The present results demonstrate that the mixed use of two different surfactants as a source of encapsulating and templating agent and a particle-separating agent is specifically effective for the synthesis of high surface area HAp nanoparticles.     

Formation of Pickering emulsions stabilized via interaction between nanoparticles dispersed in aqueous phase and polymer end groups dissolved in oil phase

The influence of end groups of a polymer dissolved in an oil phase on the formation of a Pickering-type hydroxyapatite (HAp) nanoparticle-stabilized emulsion and on the morphology of HAp nanoparticle-coated microspheres prepared by evaporating solvent from the emulsion was investigated. Polystyrene (PS) molecules with varying end groups and molecular weights were used as model polymers. Although HAp nanoparticles alone could not function as a particulate emulsifier for stabilizing dichloromethane (oil) droplets, oil droplets could be stabilized with the aid of carboxyl end groups of the polymers dissolved in the oil phase. Lower-molecular-weight PS molecules containing carboxyl end groups formed small droplets and deflated microspheres, due to the higher concentration of carboxyl groups on the droplet/microsphere surface and hence stronger adsorption of the nanoparticles at the water/oil interface. In addition, Pickering-type suspension polymerization of styrene droplets stabilized by PS molecules containing carboxyl end groups successfully led to the formation of spherical HAp-coated microspheres.     

Growth of hydroxyapatite nanocrystals on polymer particle surface

In the present paper, we describe the preparation of hybrid particles consisting of polymeric core with deposited hydroxyapatite (HAp) nanocrystals. Polystyrene submicron particles modified by β-diketone groups have been used as templates for the growth of HAp. Hybrid particles with HAp nanocrystal content between 7 and 50 wt% have been prepared. Microscopy studies indicate that hybrid particles exhibit “raspberry” morphology, and HAp nanoparticles are not homogeneously distributed on the polymer particle surface. The increase in the HAp content on the polymer particle surface reduces the colloidal stability of the hybrid particles because of the vanishing of the surface charge.     

Surface modification of hydroxyapatite nanocrystals by grafting polymers containing phosphonic acid groups

A novel approach for the surface modification of hydroxyapatite (HAp) nanocrystals is described by grafting polymerization of vinyl phosphonic acid (VPA) using a redox initiating system in an aqueous media. Fourier transform infrared (FT-IR) and XRD analyses confirmed the modification reaction on HAp surfaces. Inductively coupled plasma mass spectroscopy (ICP MS) showed that the Ca/P molar ratio decreased from 1.67 to 1.36 with increasing the feed VPA amount. Zeta potentials of unmodified HAp and modified HAp in phosphate-buffered saline (PBS) solutions (pH 7.4, ionic strength = 10 mM) were negative and decreased with increasing the amount of grafted PVPA. Transmission electron microscopy (TEM) measurements and time-dependent phase monitoring indicated that the colloidal stability of modified HAp over unmodified HAp in water dramatically increased and tended to exist as single nanocrystals without aggregation.     

Ultrastable Au nanocatalyst supported on surface-modified TiO2 nanocrystals

The surfaces of TiO2 nanocrystals were modified with amorphous aluminum-oxide layers using a surface sol-gel process to control the interaction between supports and metal particles. Ultrastable Au nanocatalysts were prepared by the deposition of Au nanoparticles on the surface-modified TiO2 nanocrystals using a deposition-precipitation (DP) method. The TEM analysis showed that the Au nanoparticles on the surface-modified nanocrystal supports were highly stable with a sinter-resistant capability during high-temperature calcination. The HRTEM analysis revealed that the surface of the TiO2 nanocrystals was covered by an amorphous aluminum-oxide layer and the Au nanoparticles were primarily anchored to this amorphous layer. This amorphous aluminum-oxide layer played an extremely important role in the stabilization of the supported Au nanoparticles without affecting catalytic activities. The surface modification of nanocrystal supports highlights new opportunities in tailoring the stability and activity of supported nanocatalyst systems.     

Tuning the solubility of TiO2 nanoparticles in apolar solvents by doping with Co2+

Anatase Co-doped TiO2 nanoparticles capped by oleic acid with a wide range of dopant concentrations (0-23.27%) were synthesized. The surface chemistry of the doped nanoparticles was probed by Fourier transform infrared spectroscopy and thermogravimetric analyses. An interesting effect of doping was discovered: doping with Co2+ at the nanocrystal surface significantly improves the solubility and dispersibility of the nanocrystals in apolar solvents, which can originate in the change in the self-assembled structure of the surface ligand from the weakly hydrophobic quasibilayer in undoped TiO2 nanorods to the strongly hydrophobic monolayer in Co-doped TiO2 nanocrystals.     

Biocomposites of nanohydroxyapatite with collagen and poly(vinyl alcohol)

Biocomposites of hydroxyapatite, HAp, in conjunction with various binders including poly(vinyl alcohol), PVA, and collagen have the potential of serving in various tissue engineering applications, such as in bone repair and reconstruction tasks, especially if the nanoparticles of hydroxyapatite are used. Here, hydroxyapatite nanoparticles (n-HAp) were synthesized at the ultimate size range of 10-50 nm and then incorporated into PVA or in situ synthesized in collagen/PVA. The biocomposites of HAp with PVA exhibited relatively high elasticity (as revealed by the linear viscoelastic material functions, characterized upon small-amplitude oscillatory shear) especially upon cryogenic treatment. The incorporation of the collagen into the PVA/HAp biocomposite provided internal porosity to the biocomposite with the pores in the 50-100 nm range for collagen/HAp and 50-500 nm for the collagen/HAp/PVA.     

A solid-state NMR investigation of the structure of nanocrystalline hydroxyapatite

Nanocrystalline hydroxyapatite (HAp) prepared by a precipitation route was investigated. The X-ray diffraction (XRD) powder patterns of the elongated nanocrystals with a typical diameter of about 10 nm and length of 30-50 nm (by transmission electron microscopy (TEM)) revealed the presence of HAp with significantly broadened XRD reflections. However, Ca deficiency was found, as the Ca/P ratio was 1.5 only (so-called calcium-deficient hydroxyapatite (CDHA)), and not 1.67. This Ca deficiency of nanocrystalline HAp is explained using NMR. It is shown unambiguously that (i) the nanocrystals consist of a crystalline core and a (disordered) surface region with a relative phosphate content of about 1:1, (ii) the crystalline core is HAp, and (iii) the surface region is dominated by hydrogen phosphate anions (with no hydroxyapatite-like structural motif) and structural water (hydrate). From the relative phosphate content and taking into account the crystal shape, the thickness of the surface layer along the main crystal axis could be estimated to be about 1 nm, and the average chemical composition of the surface layer has been determined. Finally, a Ca/P ratio of 1.52 was estimated from the NMR data that compares well with the value of 1.51 from chemical analysis. The important consequences are that the surface of nanocrystalline HAp has nothing in common with the bulk composition and that the chemistry of such materials (e.g. the binding of protein molecules to phosphate surfaces) must be reconsidered.     

Aqueous microgels for the growth of hydroxyapatite nanocrystals

In present article, we demonstrate that aqueous microgels can be used as containers for the in-situ synthesis of hydroxyapatite. The hydroxyapatite nanocrystals (HAp NCs) become integrated into microgels forming hybrid colloids. The HAp NCs loaded in the microgel can be varied over a broad range. The HAp NCs are localized within the microgel corona. The deposition of the inorganic nanocrystals decreases the colloidal stability of the microgels and leads to particle aggregation at high HAp NCs loading. Because of the strong interactions between HAp NCs and polymer chains, the swelling degree of microgels decreases, and temperature-sensitive properties disappear at high loading of the inorganic component. We demonstrate that hybrid colloids can be used as building blocks for the preparation of nanostructured films on solid substrates.     

First direct visualization of spillover species emitted from pt nanoparticles

We studied the methanol adsorption behavior of Pt nanoparticles that were vacuum-deposited on a TiO(2)(110) surface at room temperature by using an ultrahigh vacuum (UHV) scanning tunneling microscope (STM). A large number of bright spots were observed on fivefold-coordinated Ti (Ti(5c)) rows of the TiO(2)(110) surface after exposure of the Pt/TiO(2)(110) to methanol vapor. We assigned the bright spots to methoxy species. These were mobile and were found to hop along the Ti(5c) rows. In situ time-resolved STM observations of the formation and migration of the bright spots on the Pt/TiO(2)(110) were carried out in the presence of methanol. The bright spots were produced at the periphery of the Pt nanoparticles and migrated to the substrate Ti(5c) rows. We discuss the spillover process and behavior of the methoxy species on the Pt/TiO(2)(110).     

Preparation and applications of novel fluoroalkyl end‐capped vinyltrimethoxysilane oligomer/hydroxyapatite nanocomposites

Novel fluoroalkyl end‐capped vinyltrimethoxysilane oligomer/hydroxyapatite (HAp) nanocomposites were prepared by the reaction of calcium nitrate tetrahydrate and phosphoric acid in the presence of the corresponding oligomer. These fluorinated oligomer/HAp composites thus obtained are nanometer size‐controlled fine particles (83–173 nm), and were found to exhibit good dispersibility in methanol, ethanol, and isopropyl alcohol. These fluorinated HAp nanocomposites were applied to the surface modification of glass and poly(methyl methacrylate) (PMMA) to exhibit good hydro‐ and oleophobic characteristics imparted by fluorine on their surface. In addition, the surface structural changes of the modified polyethylene terephtalate and PMMA films treated with these fluorinated nanocomposites before and after soaking in a simulated body fluid (SBF) were analyzed by using SEM, XRD, and EDX to observe the formation of spherical HAp deposits on the surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Nanocrystalline hydroxyapatite: micelle templated synthesis and characterization

Nanocrystalline calcium phosphate based inorganic, hydroxyapatite (HAp), was synthesized using the dodecyl phosphate micelle system. The surfactant concentration during synthesis played an important role on the final properties of these HAp nanoparticles. A surfactant concentration close to the critical micelle concentration produced the nanoparticles with the highest surface area, with porous less agglomerated morphology. Compacts made of these nanopowders showed between 97 and 98% theoretical density of phase-pure HAp and promoted cell-material interaction when cytotoxicity tests were performed.     

Hydroxyapatite nanoparticles as stimulus-responsive particulate emulsifiers and building block for porous materials

Hydroxyapatite (HAp) nanoparticles with spherical, rod-shaped or fiber-shaped morphologies were synthesized by wet chemical method in aqueous media. Scanning electron microscopy, dynamic light scattering, helium pycnometry, and aqueous electrophoresis techniques were used to characterize the nanoparticles in terms of their particle size and morphology, density and zeta potential, respectively. Stable "Pickering-type" emulsions were prepared using the HAp nanoparticles as a particulate emulsifier and methyl myristate as an oil phase above pH 7.7, but not below pH 6.1. These emulsions were characterized in terms of their emulsion type, mean droplet diameter and morphology using electrical conductivity, light diffraction and optical microscopy. Rapid demulsification could be induced by lowering the solution pH: addition of acid led to dissolution of the HAp nanoparticles attached on oil-water interface and the emulsion was destabilized. HAp nanoparticles precipitated by addition of base to the aqueous phase after demulsification and the HAp particles precipitated worked as an effective particulate emulsifier. This emulsification-demulsification cycle was reversible. Sintering of methyl myristate-in-water emulsion stabilized with the HAp nanoparticles led to a porous HAp material.     

Mesoporous TiO2 nanostructures: a route to minimize Pt loading on titania photocatalysts for hydrogen production

Mesostructured TiO(2) nanocrystals have been prepared using Pluronic F127 as the structure-directing agent. Platinum nanoparticles at different contents (0.1-1.0 wt%) have been photochemically deposited onto the mesoporous TiO(2). TEM investigation of 0.2 wt% Pt/TiO(2) calcined at 450 °C reveals that the TiO(2) particles are quite uniform in size and shape with the particle sizes of TiO(2) and Pt being 10 and 3 nm, respectively. The photocatalytic activities of the Pt loaded TiO(2) have been assessed and compared with those of nonporous commercial Pt/TiO(2)-P25 by determining the rates and the photonic efficiencies of molecular hydrogen production from aqueous methanol solutions. The results show that the amount of hydrogen evolved on Pt/TiO(2)-450 at low Pt loading (0.2 wt%) is three times higher than that evolved on Pt/TiO(2)-P25 and twelve times higher than that evolved on Pt/TiO(2)-350. Despite the BET surface area of the TiO(2)-450 photocatalyst being 3.5 times higher than that of TiO(2)-P25, a 60% smaller amount of the Pt co-catalyst is required to obtain the optimum photocatalytic hydrogen production activity. The reduced Pt loading on the mesoporous TiO(2) will be important both from a commercial and an ecological point of view.     

Redispersible rutile TiO2 nanocrystals in organic media by surface chemical modification with an inorganic barium hydroxide

The present paper describes the synthesis of the redispersible rutile TiO2 nanocrystals in organic media by surface chemical modification reaction in an aqueous barium hydroxide solution. In our facile surface modification reactions, the surfaces of the TiO2 nanocrystals are coated by bimetallic TiOBa spices and saturated with BaOH terminal groups. The inherent characteristics such as morphology, size, crystallinity, and color of the nanocrystals remained almost unchanged after surface-treatment, but their dispersibility in organic media such as methanol and DMF were remarkably enhanced. It is ascribed that BaOH groups in the surface of the TiO2 nanocrystals prevented the formation of covalently bound agglomerates through Ti-O-Ti condensation reaction among the nanocrystals during the purification and water-elimination procedures.     

Biomimetic approach towards the preparation of hydroxyapatite and hydroxyapatite/chitosan/β-cyclodextrin nanoparticles: application to controlled drug release

Hydroxyapatite (HAp) and hydroxyapatite/chitosan/β-cyclodextrin (HAp/CS/β-CD) nanoparticles were successfully prepared in the modified simulated body fluid (SBF) solution at the physiological conditions (pH 7.4, temperature?=?37 °C). CS/β-CD nanoparticles acted as templates for the synthesis of HAp/CS/β-CD nanoparticles to improve the nanoarchitecture of HAp and its crystallinity.The nanoparticles were characterized by FT-IR spectroscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD). Kneading and coprecipitation methods were applied to prepare the inclusion complex involving β-CD and p-THPP (5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin), a photosensitizer for anti-cancer drugs. The 1:1 stoichiometric ratio of the formed inclusion complex was characterized by a formation constant of 7.216?×?10² mol^?1 dm³ and analyzed by ¹H NMR, FTIR, and UV–Vis. The p-THPP delivery release in vitro was in this order: HAp/CS/β-CD?<?CS/β-CD?<?<?HAp/β-CD?<?β-CD, hinting at a better controlled release by HAp/CS/β-CD nanoparticles.     

A study on the melting and crystallization of polyoxymethylene‐copolymer/hydroxyapatite nanocomposites

In this work, isothermal crystallization kinetics of polyoxymethylene copolymer (POM) in POM/hydroxyapatite (HAp) nanocomposites has been investigated. Melting behavior and crystalline structure formation were studied using TOPEM DSC, positron lifetime spectroscopy (PALS), atomic force microscopy (AFM) and ¹³C and ³¹P solid‐state NMR. The highest degree of crystallinity was found for POM/0.5% HAp nanocomposite and the lowest for POM/2.5% HAp. Isothermal crystallization analysis showed that an introduction of HAp nanoparticles led to effective heterogeneous nucleation and formation of crystals with higher Avrami exponent. Besides, changes in overall crystallization rate were observed – the highest overall crystallization rate was found for POM/0.5% HAp sample, while the lowest for POM/2.5% HAp was observed. Generally, for POM in POM/HAp nanocomposites, a significant decrease in nucleation activation energy (K_g), and the fold surface free energy (σ_e) was found. For nanocomposite containing 2.5% HAp, heterogeneous nucleation takes place as well, but too high concentration of nanoparticles hinders POM crystallization and enhances formation of more defected crystals as confirmed by AFM data. The presence of HAp nanoparticles in the POM matrix was confirmed by ³¹P MAS‐NMR, but their influence on the crystallization process was not observed in the ¹³C CP‐MAS‐NMR spectra. Copyright © 2012 John Wiley & Sons, Ltd.     

Interplay of three-dimensional morphologies and photocarrier dynamics of polymer/TiO2 bulk heterojunction solar cells

In this study, we investigated the interplay of three-dimensional morphologies and the photocarrier dynamics of polymer/inorganic nanocrystal hybrid photoactive layers consisting of TiO(2) nanoparticles and nanorods. Electron tomography based on scanning transmission electron microscopy using high-angle annular dark-field imaging was performed to analyze the morphological organization of TiO(2) nanocrystals in poly(3-hexylthiophene) (P3HT) in optimal solar cell devices. The Three-dimensional (3D) morphologies of these hybrid films were correlated with the photocarrier dynamics of charge separation, transport, and recombination, which were comprehensively probed by various transient techniques. Visualization of these 3D bulk heterojunction morphologies clearly reveals that elongated and anisotropic TiO(2) nanorods in P3HT not only can significantly reduce the probability of the interparticle hopping transport of electrons by providing better connectivity with respect to the TiO(2) nanoparticles, but also tend to form a large-scale donor-acceptor phase-separated morphology, which was found to enhance hole transport. The results support the establishment of a favorable morphology for polymer/inorganic hybrid solar cells due to the presence of the dimensionality of TiO(2) nanocrystals as a result of more effective mobile carrier generation and more efficient and balanced transport of carriers.     

羟基磷灰石负载放射性18F作为分子影像纳米探针在生物医学中的应用

采用简便有效的方法,制备了生物兼容性强、放射性标记羟基磷灰石(HAp)纳米粒子的正电子发射计算机断层显像(PET)纳米探针。在合成HAp纳米粒子的过程中,放射性的~(18)F作为掺杂剂,占据HAp晶格中羟基位置,在短时间内牢固地标记到HAp上。~(18)F不仅标记在纳米粒子的表面,而且还通过强的化学键标记在纳米颗粒的内部。以达到提高标记量并防止辐射泄漏的目的。设计的高标记量的放射性纳米探针应用于动物实验并靶向到达脏器器官。     

反应介质pH值和前驱体用量对PSt/TiO_2复合微球结构形态及TiO_2空心微球形貌的影响

首先用聚乙烯亚胺(PEI)对粒径为360 nm的单分散无皂聚苯乙烯(PSt)乳胶粒进行修饰,得到表面荷正电的PSt种子乳液,然后将其滴加到溶有钛酸正丁酯(TBT)的乙醇与水的混合介质中,通过溶胶-凝胶(sol-gel)法制备出了核壳结构PSt/TiO2复合微球,系统研究了体系pH和TBT用量对复合微球结构形态的影响.研究表明,酸性条件不利于核壳结构PSt/TiO2复合微球的形成;当体系pH值为7.2时,可得到包覆完整、TiO2壳层厚度均一的PSt/TiO2复合微球,此后随着体系pH值的升高,包覆厚度逐渐提高;当pH值升高到11.0时,壳层厚度达到最大,但出现了包覆层不完整的复合微球.在固定聚合体系pH为8.5,EtOH/H2O质量比为100/6,表面修饰PSt种子乳液用量为0.5 g(固含量为4%)的条件下,随着TBT用量从0.01 g增加到0.16 g,复合微球壳层厚度从约0 nm逐渐增加到60 nm;当TBT用量增加到0.32 g时,壳层厚度迅速降至12nm,微球表面变得粗糙,并出现大量未包覆微粒;此后随着TBT用量的增加,包覆层厚度逐渐减少,未包覆微球逐渐增多.结果显示,当复合微球中TiO2包覆层达到一定厚度时,经煅烧后才能得到形貌完整的TiO2中空微球.