Controlled hydrothermal synthesis of strontium-substituted hydroxyapatite nanorods and their application as a drug carrier for proteins

Without the addition of any organic additives, both undoped hydroxyapatite (HAp) and different strontium (Sr)-substituted hydroxyapatite (SrHAp) samples with amounts from 1 to 20?mol.% were synthesized via hydrothermal route. The crystal texture, chemical functional group and microstructure were well characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and inductively coupled plasma (ICP), respectively. And the protein adsorption and release properties of bovine serum albumin (BSA) and lysozyme (LYS) were investigated on the samples to search for a well protein drug delivery vehicle. The results revealed that the pure HAp consisted of uniform nanobelts and all SrHAp samples had a rod-like morphology. The lattice parameters of SrHAp were larger than HAp, while they had similar crystal structure. The protein adsorption and release tests indicated that the incorporation of Sr into HAp lattice could increase the amounts of BSA and LYS adsorption. The BSA adsorption capacity of 1SrHAp was found to be 55.52?mg/g, which was about 14.64% higher than that of HAp. The 15SrHAp possessed the highest LYS loading amount of 90.54?mg/g, which was about three times that of HAp. And SrHAp exhibited sustained protein release capability.     

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.     

Synthesis of mercaptothiadiazole-functionalized gold nanoparticles and their self-assembly on Au substrates

Gold nanoparticles (AuNPs) stabilized with mercaptothiadiazole ligands, 2,5-dimercapto-1,3,4-thiadiazole (DMT), 5-amino-2-mercapto-1,3,4-thiadiazole (AMT) and 5-methyl-2-mercapto-1,3,4-thiadiazole (MMT), were prepared by the reaction of the respective ligands with HAuCl(4) and NaBH(4) in an aqueous medium. TEM images show that the average size of AuNPs was 6.5 ± 0.5?nm, irrespective of the capping ligands. The colloidal solution of both DMT-capped AuNPs (DMT-AuNPs) and AMT-capped AuNPs (AMT-AuNPs) were highly stable for several months. However, several changes were noticed for MMT-capped AuNPs (MMT-AuNPs) after 2?h from its formation. The SPR band intensity at 518?nm decreases and the narrow SPR absorption band slowly changes into a flat absorption pattern with a broad peak from 518 to 1000?nm which was accompanied by a colour change of the solution from red to purple and then blue and thereafter unchanged. The TEM image of MMT-AuNPs after 96?h shows that most of the spherical shape of the AuNPs assembled to form a nanowire-like structure. The observed changes may be due to the absence of a strong stabilizing force on the surface of the MMT-AuNPs. The amino and thiolate groups on the surface of the AMT-AuNPs and DMT-AuNPs, respectively, were directly self-assembled on Au electrodes. They exhibit excellent electrocatalytic activity towards the oxidation of AA by enhancing its oxidation current twice in addition to more than 200?mV negative shift in the oxidation potential in contrast to bare Au electrode.     

Self-assembly phenomenon of hydroxyapatite nanocrystals on chondroitin sulfate

Self-assembly phenomenon of hydroxyapatite (HAp) nanocrystals on chondroitin sulfate (ChS) templates was investigated. A HAp/ChS hybrid was synthesized through a precipitation method with a calcium hydroxide suspension and phosphoric acid solution containing the ChS. The preferential alignment of the crystallographic c-axis of the HAp crystals parallel to the long axis direction of the ChS templates was observed to occur with the chemical interactions between the HAp crystals and the functional groups of the ChS. This phenomenon was interpreted by the crystallochemical specific nucleation and growth of the HAp crystals regulated by the pre-organized functional groups of the ChS template. Practical implication may involve a biomimetic artificial bone or cartilage can be made through a precipitation method with suitable bio-organics.     

Synthesis, characterization and in vitro cytotoxicity assessment of hydroxyapatite from different bioresources for tissue engineering application

In the present study, hydroxyapatite (HAp) is synthesized from different biosources like eggshell, fish scale and bovine bone in a cost effective and ecofriendly way. HAp materials were synthesized from eggshell by wet precipitation method whereas thermal decomposition method was applied in case of fish scale and bovine bone. The phase purity and crystallinity of different calcined HAp powder were determined by XRD and FTIR analyses. The thermogravimetric analysis was carried out to show thermal stability of HAp powder. Average grain sizes of sintered samples were in submicron range. The morphology of the powders were observed under scanning electron microscopy (SEM). The dried powders were wet ball milled for several hours and surfactants like Triton-X small fillers (2 / 4 mm long rod-shaped) were made for in vitro testing. In order to verify the biocompatibility of HAp powders, cytotoxicity evaluation was carried out in RAW macrophage like cell line media for an incubation period of 72 h. The cell attachment studies on HAp compacts show an excellent affinity between cells and compact surface. These results proved high biocompatibility of HAp powders obtained from different biosources for tissue engineering applications.     

ZnO nanoparticles: hydrothermal synthesis and 4-nitrophenol sensing property

In this paper reports a facile hydrothermal synthesis, characterization and sensing application of zinc oxide (ZnO) nanostructures. ZnO nanostructures were synthesized by mixing triethylamine (TEA) with zinc nitrate at 60?°C followed by calcination at 650?°C for 6 h. The detailed characterizations conformed the synthesized ZnO nanostructures. Powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and Raman spectral analysis confirmed the formation of hexagonal ZnO. Band gap of the ZnO nanoparticles was determined by UV–visible absorption spectroscopy. Morphology and size of the sample was examined by field emission scanning electron microscopy (FE-SEM) and high resolution transmission electron microscopy (HR-TEM). It shows that the sample has rod and hexagonal morphology. Elemental composition was determined by energy dispersive X-ray (EDX) spectroscopy. The ZnO was coated on glassy carbon electrode (ZnO/GCE) and it was utilized as an electrochemical sensor for 4-nitrophenol (4-Np). Sensitivity and detection limit of ZnO/GCE towards 4-Np was found to be 0.04 µA/mM and 2.09?×?10^?5 M. The result suggests that ZnO has suitable sensor detection of 4-Np.     

A composite prepared from covalent organic framework and gold nanoparticles for the electrochemical determination of enrofloxacin

A high conductivity composite based on covalent organic frameworks/gold nanoparticles (TAPB-PDA-COFs/AuNPs, TAPB: 3,5-tris(4-aminophenyl)benzene, PDA: p-phthalaldehyde) was prepared by a simple in-situ synthesized method and a novel electrochemical sensor based on TAPB-PDA-COFs/AuNPs was constructed for detection of Enrofloxacin (ENR). A variety of different characterization techniques including ultraviolet‐visible spectrophotometer (UV–vis), fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the TAPB-PDA-COFs/AuNPs. ENR was detected by square wave stripping voltammetry (SWV) according to the relationship between the ENR concentration and the oxidation peak current. The result showed that TAPB-PDA-COFs/AuNPs was synthesized successfully. The electrochemical sensor showed two linear ranges in the range of 0.05–10 μmol L^?1 and 10–120 μmol L^?1 with the limit of detection of 0.041 μmol L^?1 (S/N = 3). The good recoveries (96.7–102.2%) and low RSDs (0.9–6.4%) indicated the possibility of using this sensor for actual sample detection. Therefore, TAPB-PDA-COFs/AuNPs-based electrochemical sensor showed good performance in detecting ENR, and would be a potential candidate for the development of fluoroquinolones determination.     

Synthesis of organic derived hydroxyapatite scaffold from pig bone waste for tissue engineering applications

Micro porous hydroxyapatite (HAp) had drawn great attention in the field of tissue engineering due to its numerous applications such as tissue regeneration, dental, drug delivery, and adsorption and desorption of substances etc. The chemical synthesis of HAp is often faced with the high cost of starting materials and often lacks the presence of beneficial ions which can promote biological reactions. This paper examined a novel application of pig bone waste for the synthesis of HAp via heat treatment between 600 and 1000 °C. Thus synthesized powder was characterized by X-ray diffraction (XRD), Fourier transform infra-red spectroscopy (FT-IR), Thermogravimetric analysis (TGA), Scanning electron microscopy (SEM), Energy dispersive X-ray analysis (EDX) and Transmission electron microscopy (TEM). XRD results revealed the main characteristic peaks of single phase HAp powder, while the presence of various functional groups such as PO₄^3?, CO₃^2? and OH^? corresponding to HAp were observed by FT-IR analysis. The elemental composition of as-synthesized HAp powder as observed by EDX showed the presence of Ca and P in addition to some beneficial metals such as Na, K, Mg and Si which plays vital roles in biological applications. SEM and TEM observation confirmed the microscopic sctructure of the as-synthesized HAp to be rod-like morphology with 38–52 nm in length. Porous HAp scaffold up to 65% porosity could be prepared using ammonium bicarbonate as pore forming agent. Therefore, bio-waste such as pig bones can be utilized in the synthesis of porous hydroxyapatite scaffold which can serve as an alternative for the conventional chemical method.     

Probing Adsorption Behaviors of BSA onto Chiral Surfaces of Nanoparticles

Chiral properties of nanoscale materials are of importance as they dominate interactions with proteins in physiological environments; however, they have rarely been investigated. In this study, a systematic investigation is conducted for the adsorption behaviors of bovine serum albumin (BSA) onto the chiral surfaces of gold nanoparticles (AuNPs), involving multiple techniques and molecular dynamic (MD) simulation. The adsorption of BSA onto both L‐ and D‐chiral surfaces of AuNPs shows discernible differences involving thermodynamics, adsorption orientation, exposed charges, and affinity. As a powerful supplement, MD simulation provides a molecular‐level understanding of protein adsorption onto nanochiral surfaces. Salt bridge interaction is proposed as a major driving force at protein–nanochiral interface interaction. The spatial distribution features of functional groups (? COO^?, ? NH₃⁺, and ? CH₃) of chiral molecules on the nanosurface play a key role in the formation and location of salt bridges, which determine the BSA adsorption orientation and binding strength to chiral surfaces. Sequentially, BSA corona coated on nanochiral surfaces affects their uptake by cells. The results enhance the understanding of protein corona, which are important for biological effects of nanochirality in living organisms.     

Achievement of 4.7% conversion efficiency in ZnO dye-sensitized solar cells fabricated by spray deposition using hydrothermally synthesized nanoparticles

ZnO-based dye-sensitized solar cells (DSSCs) have been fabricated using hydrothermally synthesized ZnO nanoparticles by spray deposition. The effect of self-assembled nanostructures in ZnO photoelectrodes, due to the electric field during spray deposition, has been studied. Thickness of the photoelectrode is found to play a role on the cell performance, the cell with nanocrystalline film thickness of ～4.3?μm yielding an efficiency of ～2.8% for a cell area of ～3.2?cm(2). On the other hand, the cell with ZnO nanostructures is found to yield an efficiency of 4.7% (enhancement of ～60%) which is highest for the cell with area>1?cm(2) having a photoelectrode thickness of ～4.5?μm. Increased surface area due to the presence of ZnO nanostructures in the photoelectrode film helps in the adsorption of more dye molecules to the ZnO surface, which contributes to the better cell performance. The improved dye-sensitized solar cell performance is also explained with the help of light scattering by the ZnO nanostructures through extending the distance traveled by light so as to increase the light-harvesting efficiency of the photoelectrode film.     

Sensitive chemiluminescence immunoassay by capillary electrophoresis with gold nanoparticles

This technical note describes a new chemiluminescence immunoassay hyphenated to capillary electrophoresis (CE-based CL-IA) with gold nanoparticles (AuNPs) technique for biological molecules determination. AuNPs were used as a protein label reagent in the light of its excellent catalytic effect to the CL reaction of luminol and hydrogen peroxide. AuNPs conjugate with antibody (Ab) to form tagged antibody (Ab*), and then Ab* link to antigen (Ag) to produce an Ab*-Ag complex by a noncompetitive immunoreaction. The mixture of the excess Ab* and the Ab*-Ag complex was baseline separated and detected within 5 min under the optimized conditions. This new protocol was evaluated with human immunoglobulin G (IgG) as the target molecule. The calibration curve of IgG was in the range of 0.008-5 μg/mL with a correlation coefficient of 0.995. The detection limit (S/N = 3) of IgG was 1.14 × 10(-3) μg/mL (7.1 pmol/L, 0.39 amol). The proposed AuNPs enhanced CE-based CL-IA method was successfully applied for the quantification of IgG in human sera from patients. It proves that the present method could be developed into a new and sensitive biochemical analysis technique.     

Designed synthesis of hydroxyapatite nanostructures: bullet-like single crystal and whiskered hollow ellipsoid

Hydroxyapatite (HAp) nanostructures of whiskered hollow ellipsoid and bullet-like single crystal were synthesized under mild reaction conditions by using a template-free “one pot” synthetic method. Immersing calcium carbonate precursor into ammonium phosphate solution resulted in the HAp phase. Formed HAp crystals were characterized by X-ray diffraction and transmission electron microscopy techniques. The stability and phase composition of calcium carbonate influenced the morphology and crystallinity of HAp. The transformation of the most stable calcite precursor yielded the bullet-like HAp single crystal of 300–600 nm in length, ~40 nm in tip diameter and ~80 to ~100 nm in bottom diameter. The metastable vaterite precursor showed the formation of the whiskered hollow ellipsoid nanostructures composed of HAp nanorods of ~10 nm in diameter. The driving force for the whole transformation process was the difference in solubility of calcium carbonate and HAp. At the same time, Kirkendall effect and Ostwald ripening played important roles in the formation of the different HAp nanostructures.     

Synthesis and characterization of sol-gel silica films doped with size-selected gold nanoparticles

Homogeneous nanocomposite silica films uniformly doped with size-selected gold nanoparticles (AuNPs) have been prepared by a combined use of colloidal chemistry and the sol-gel process. For this purpose, stable thiol-functionalized AuNPs (DDT-AuNPs) were first synthesized by a two-phase aqueous/organic system and, subsequently, dispersed in an acid-catalysed sol-gel silica solution. The microstructural morphology of the samples was investigated by x-ray diffraction and field emission scanning electron microscopy. X-ray photoelectron spectroscopy (XPS) and UV-vis optical spectrophotometry were instead employed to investigate the elemental chemical behaviour and the evolution of the surface plasmon resonance (SPR) band of the AuNPs from their synthesis up to the formation of the Au-doped silica films. The results show that the size, shape and crystalline domains of the AuNPs remain unchanged during the entire preparation process, indicating that their aggregation or decomposition was prevented. XPS results show that the DDT-AuNPs lose the capping shells and oxidize themselves when dispersed in acid-catalysed sol-gel solutions, and that bare AuNPs are embedded in the SiO(2) films. A large broadening of the SPR band, observed for systems with DDT-AuNPs, suggests the presence of interface effects which cause a surface electron density lowering. Thiol chain detachment from the AuNPs determines an increase of the SPR peak intensity while the oxidation of the Au surfaces causes a red shift of its position. The latter is no longer observed in doped films, suggesting that no interfacial effects between bare AuNPs and the host medium are present.     

Synthesis of CdS-Au2S-Au hybrid dendritic nanostructures

The hybrid CdS-Au₂S-Au dendritic nanocrystals were synthesized in toluene solution at 70 °C. UV-vis and photoluminescence (PL) spectra recorded the optical properties of hybrid nanostructures, which showed an obvious blue shift relative to the absorption peak of CdS dendritic nanocrystals. The initial CdS dendritic nanocrystals exhibited band gap and trap state emission, both of which were quenched by Au parts. Analysis of the hybrid nanostructures by XRD shows the presence of appreciable amounts of Au₂S, indicating that the chemical process involving cation exchanges between Au⁺ ions and Cd²⁺ ions was found.     

Surface modification of poly(l-lactide) electrospun fibers with nanocrystal hydroxyapatite for engineered scaffold applications

The hydrophobicity of the poly(l-lactide) (PLLA) surface was modified by incorporating hydroxyapatite (HAp) nanocrystalline particles during the electrospinning process for the engineered scaffold applications. The HAp nanocrystals were synthesized with 30 nm in diameter and 100–120 nm in length, which subsequently formed micrometer-sized agglomerates in the range of 2.5 μm. The synthesized HAp agglomerates were electrospun in the PLLA solution, and the HAp nanocrystals were desirably exposed on the surface of the electrospun PLLA fibers to give higher surface energy and lower contact angles with water. The surface-exposed hydrophilic HAp nanocrystals substantially increased the precipitation of various salts on the HAp/PLLA fiber surfaces in a buffer solution due to the hydrophilic nature and ionic affinity of HAp. Finally, the developed HAp/PLLA fibers desirably sustained the fibrous structural integrity during the accelerated-aging test in water, which was not the case with the pristine PLLA fibers.     

Enhanced field emission from injector-like ZnO nanostructures with minimized screening effect

Injector-like zinc oxide (ZnO) nanostructures have been synthesized on Si substrate by the vapour phase transport method. Samples with different areal densities were obtained by controlling the temperature. The field emission properties of the injector-like ZnO nanostructures showed a clear dependence on the areal density of the nanostructures, which is due to the screening effect. The samples with a needle length of 850?nm and an areal density of 1 × 10(8)?cm(-2) showed the lowest field emission turn-on field of 1.85?V?μm(-1) at a current density of 10?μA?cm(-2), and the current density reaches 1?mA?cm(-2) at an applied field of 4.7?V?μm(-1).     

Growth of hydroxyapatite on physiologically clotted fibrin capped gold nanoparticles

The growth of hydroxyapatite (HAp) on physiologically clotted fibrin (PCF)-gold nanoparticles is presented for the first time by employing a wet precipitation method. Fourier transform infrared (FTIR) spectroscopy confirmed the characteristic functionalities of PCF and HAp in the PCF-Au-HAp nanocomposite. Scanning electron microscopy (SEM) images have shown cuboidal nanostructures having a size in the range of 70-300?nm of HAp, whereas 2-50?nm sized particles were visualized in high-resolution transmission electron microscopy (TEM). Energy-dispersive x-ray (EDX) and x-ray diffraction (XRD) studies have confirmed the presence of HAp. These results show that gold nanoparticles with PCF acted as a matrix for the growth of HAp, and that PCF-Au-HAp nanocomposite is expected to have better osteoinductive properties.     

Adsorption of gum Arabic on bioceramic nanoparticles

Surface modification agents can be used to tailor the surface chemistry and biological activity of bioceramic nanoparticles in very intriguing ways. However, the specific modes of interactions between macromolecules and nanoparticles can be difficult to characterize. The aim of this study was to investigate the adsorption of gum Arabic on hydroxyapatite (HAp) and magnetic nanoparticles (MNP) using the bicinchoninic acid (BCA) test. Gum Arabic (GA) is a natural gum that has been widely used as an emulsifying agent and shows promise for dispersing nanoparticles in aqueous solutions. The adsorption of GA onto HAp nanoparticles followed a Langmuir isotherm with an adsorption plateau occurring at 0.2 g GA/g HAp. The adsorption of GA onto MNP attained a maximum value of 0.6 g GA/g MNP, after which it decreased to approximately 0.2 g GA/g MNP. The maximum adsorption density of GA on both MNP and HAp is equivalent when normalized to the specific surface area (4 × 10^− 3 g GA/m²). Adsorbed GA molecules were displaced from the surface of HAp and MNP in the presence of phosphate ions.     

4-Aminophenyl boronic acid modified gold platforms for influenza diagnosis

As a potential pandemic threat to human health, there has been an urgent need for rapid, sensitive, simpler and less expensive detection method for the highly pathogenic influenza A virus. For this purpose, Quartz Crystal Microbalance (QCM) and Surface Plasmon Resonance (SPR) sensors have been developed for the recognition of hemagglutinin (HA) which is a major protein of influenza A virus. 4-Aminophenyl boronic acid (4-APBA) has been synthesized and used as a new ligand for binding of sialic acid (SA) via boronic acid–sugar interaction. SA has an important role in binding of HA. QCM and SPR sensor surfaces have been modified with thiol groups and then 4-APBA and SA have been immobilized on sensor surfaces, respectively. Sensor surfaces have been screened with AFM and used for the determination of HA from aqueous solution. The selective recognition of the QCM and SPR sensors toward Concanavalin A has been reported in this work. Also, the binding capacity and detection limits of QCM and SPR sensors have been calculated and detection limits were found to be 4.7 × 10^? 2 μM, (0.26 μg ml^? 1) and 1.28 × 10^? 1 μM, (0.72 μg ml^? 1) in the 95% confidence interval, respectively.