Novel method for preparing controllable and stable silver particle films for surface-enhanced Raman scattering spectroscopy

A new surface-enhanced Raman scattering (SERS) active substrate has been developed based on our previous study. Small silver nanoparticles on a quartz slide can be enlarged by using a mixture of commercially available reagents called Silver Enhancer and Initiator. The optical properties and characteristics of the new substrate have been investigated by ultraviolet-visible (UV-Vis) spectroscopy and atomic force microscopy (AFM). The results indicate that the small silver nanoparticles grow and some silver aggregates emerge on the quartz slide after the slide is immersed into the Silver Enhancer and Initiator Mixture (SEIM). The average diameter of the silver nanoparticles on the substrate becomes approximately double after the immersion into SEIM for 20 s. 1,4-bis[2-(4-pyridyl)ethenyl]-benzene (BPENB) was used as a Raman probe to evaluate the enhancement ability of the new silver substrate. It has been found that the SERS intensity can be increased about 10 times by using the substrate treated by SEIM compared with that without being treated by SEIM. Interestingly enough, the SERS enhancement increases with time. This may be due to the reorganization of silver nanoparticles on the quartz surface. The new substrate can remain active for more than 90 days. The adsorption mode of BPENB on the new substrate and the dependence of the BPENB configurations on the concentration of BPENB in methanol solution have also been investigated by SERS or UV-Vis spectroscopy. The SERS spectra of a self-assembled monolayer (SAM) BPENB film adsorbed on a silver substrate treated by SEIM show that BPENB molecules are chemically absorbed through the Ag-N bond. Consequently, a nearly perpendicular orientation of BPENB on the silver surface is proposed. The SERS spectra of BPENB SAMs on the new substrates fabricated from methanol solutions with different concentrations are compared. The concentration dependence of the SERS spectra reveals that the BPENB molecules are adsorbed on the silver film as monomers when the film is prepared from the solution with a lower concentration (<4 x 10(-6) M) and as aggregates when it is prepared from the solution with a higher concentration (>1 x 10(-5) M).     

Application of TiO2 nanoparticles coated multi-wall carbon nanotube to dye-sensitized solar cells

This study uses the sol-gel method to prepare TiO2 nanoparticle, and further applies TiO2 nanoparticle coating on the surface of the multi-wall carbon nanotube (MWCNT). As a result, TiO2-CNT composite nanoparticles are prepared to serve as photoelectrode material in dye-sensitized solar cell (DSSC). First, after acid treatment of MWCNT is used to remove impurities. Then, the sol-gel method is employed to prepare TiO2-CNT composite nanopowder. X-ray diffraction (XRD) pattern shows that after the TiO2 in TiO2-CNT composite nanopowder has been thermally treated at 450 degrees C, it can be completely changed to anatase phase. Furthermore, as shown from the SEM image, TiO2 has been successfully coated on CNT. The photoelectrode of DSSC is prepared using the electrophoretic deposition method (EPD) to mix the Degassa P25 TiO2 nanoparticles with TiO2-CNT powder for deposition on the indium tin oxide (ITO) conductive glass. After secondary EPD, a thin film of TiO2/CNTs with thickness 17 microm can be acquired. For the prepared TiO2-CNT composite nanoparticles, since MWCNT can increase the short-circuit current density of DSSC, the light-to-electricity conversion efficiency of DSSC can be effectively increased. Experimental results show that the photoelectric conversion efficiency of DSSC using CNT/TiO2 photoelectrode and N719 dye is increased by 41% from the original 3.45% to 4.87%.     

Characterization of mono- and multilayered films with Mn-doped ZnS nanoparticles and luminescence properties of the monolayered films prepared by applying magnetic fields

Mn²⁺-doped ZnS (ZnS:Mn) nanoparticles were prepared using bis(2-ethylhexyl) sulfosuccinate (AOT) reversed micelle method. Luminescence at 583-589 nm were observed in the ZnS:Mn nanoparticles and are ascribed to Mn²⁺ ion in the nanoparticles due to energy transfer from ZnS. The luminescence was enhanced by capping with alkanethiol. Mono-and multilayered films with the alkanethiol-capped ZnS:Mn nanoparticles were fabricated on quartz substrates by layer-by-layer method using self-assembled monolayer (SAM) of 1,6-hexanedithiol. The polarization degrees of luminescence for the monolayered films were enhanced by preparation under applying magnetic field. The enhancements are probably caused by magnetic orientation of the ZnS:Mn nanoparticles on the quartz substrates.     

磷灰石包覆金红石型TiO2纳米粉体的制备及表征

将金红石型TiO₂纳米粉体浸泡在模拟体液中, 于37℃经过不同时间, 制备出磷灰石包覆金红石型TiO₂纳米粉体. 用XRD、SEM、TEM、EDX、FTIR、ICP AES和BET方法对复合粉体进行了表征, XRD结果表明,磷灰石的含量可随着金红石型TiO2在模拟体液中浸泡时间的延长而增加. FTIR结果中显示了磷灰石的O-H和PO₄^3-吸收峰, 说明复合粉体中有磷灰石存在. ICP-AES结果表明溶液中Ca和P浓度随浸泡时间延长而下降, 表明时间延长后更多的Ca和P被消耗. TEM和EDX结果证明了金红石型TiO₂表面有磷灰石存在, HRTEM结果显示磷灰石（211）面的晶格间距为0.27nm, 晶粒尺寸约为40nm.     

Modified multistep electrophoretic deposition of TiO2 nanoparticles to prepare high quality thin films for dye-sensitized solar cell

In this study, a modified procedure is introduced which consists of multistep process for improving the structure of mesoporous TiO₂ films. The films were prepared by electrophoretic deposition (EPD) on FTO (F-SnO₂ coated glass). It is shown that high quality TiO₂ film can be produced by multistep EPD method. The effect of EPD time on the thickness and density of the films have been investigated. The performance of dye-sensitized solar cells (DSSCs) that were fabricated by improved layer are tested under AM 1.5 simulated sunlight. Finally, the structure and effective parameters of DSSCs that were fabricated by one step and multistep EPD are investigated precisely, using electrochemical impedance spectroscopy.     

A study on mineralization behavior of amino-terminated hyperbranched polybenzimidazole membranes

Amino-bearing polymers, coated with apatite or similar minerals, have attracted significant attention for their potential in medical applications. In this study, an amino-terminated hyperbranched polybenzimidazole (HBPBI) membrane was used as a substrate for apatite growth. The membrane was soaked in solutions of CaCl₂, Na₂HPO₄ and SBF to yield an apatite coating. The structure and morphology of the layers were characterized by FTIR-ATR, XRD and FESEM. The results indicate that the high densities of amino, imide and imidazole groups on the amino-terminated HBPBI membrane provide active sites for the growth of apatite.     

Fabrication of a surface plasmon resonance biosensor based on gold nanoparticles chemisorbed onto a 1,10-decanedithiol self-assembled monolayer

We have investigated the fabrication of surface plasmon resonance (SPR) biosensors using self-assembled monolayers (SAMs) and adsorbed gold nanoparticles. The SAM of 1,10-decanedithiol was first fabricated onto a gold substrate. Gold nanoparticles were then chemisorbed onto the SAM surface by bonding with the terminal thiol groups, forming a sensor that can be used to immobilize proteins. Bovine serum albumin (BSA) was used as a test protein in this study. Several spectroscopic and microscopic techniques were used to investigate both the SAM and the chemisorption of gold nanoparticles at the SAM surface. Our results confirm the covalent bonding of the gold nanoparticles onto the SAM. Surface plasmon resonance (SPR) was used to study both the adsorption of BSA to the SAM surface and to the gold nanoparticle-coated SAM. For SAM surfaces with adsorbed gold nanoparticles a larger SPR response to BSA than to the sensors with a bare SAM is observed.     

Electrophoretic deposition of polyetheretherketone (PEEK) and PEEK/Bioglass® coatings on NiTi shape memory alloy wires

Polyetheretherketone (PEEK) and PEEK/Bioglass® coatings were produced on shape memory alloy (NiTi, Nitinol®) wires using electrophoretic deposition (EPD). Best results were achieved with suspensions of PEEK powders in ethanol in the range (1–6 wt%), using a deposition time of 5 minutes and applied voltage of 20 Volts. EPD using these parameters led to high quality PEEK coatings with a homogeneous microstructure along the wire length and a uniform thickness of up to 15 μm without development of cracks or the presence of large voids. Suspensions of PEEK powders in ethanol with addition of Bioglass® particles (0.5–2 wt%) (size < 5 μm) were used to produce PEEK/Bioglass® coatings. Sintering was carried out as a post EPD process in order to densify the coatings and to improve the adhesion of the coatings to the substrate. The sintering temperature was 340 °C, sintering time 20 min and heating rate 300 °C/h. Sintering led to uniform and dense PEEK and PEEK/Bioglass® coatings without any cracks. The bioactive behaviour of PEEK/Bioglass® composite coatings was investigated by immersion in acellular simulated body fluid (SBF) for up to two weeks. As expected, hydroxyapatite crystals formed on the surface of the coated wires after 1 week in SBF, confirming the bioactive character of the coatings. The results have demonstrated for the first time that EPD is a very convenient method to obtain homogeneous and uniform bioactive PEEK and PEEK/Bioglass® coatings on Nitinol® wires for biomedical applications.     

Histomorphometric evaluation of implants coated with enamel or dentine derived fluoride-substituted apatite

Objectives The aim of this study was to compare osseous healing characteristics of titanium implants coated with enamel-derived fluoride-substituted apatite (EFSA) or dentin-derived fluoride-substituted apatite (DFSA). Methods Fluoride-substituted apatite was derived from extracted human teeth with calcination method at 850 °C. DFSA and EFSA were separated and carefully ground with a blade grinder. Twenty-four titanium implants were prepared from a 99.99% pure titanium bar. EFSA and DFSA powders were sprayed separately on implants. As control group, unsprayed and sandblasted pure titanium implants were used. Eight adult rams were used in the study. One EFSA coated, 1 DFSA coated and 1 control implants were placed into right tibia of each rams. The rams were sacrificed after 6 months of healing. Undecalcified sections were prepared according to Donath’s method and histomorphometric evaluation of implants was made. Results The mean bone contact percentage of DFSA-coated, EFSA-coated and control implants was 89.88% ± 2.34, 70.19% ± 13.11 and 53.12% ± 5.76 respectively. This study suggests that DFSA-coated implants achieved better bone contact than EFSA-coated implants (P < 0.05). Also study groups presented better bone contact than control group (P < 0.05). Conclusions The results of this study show that although DFSA-coated implants achieved better bone contact, both DFSA and EFSA can be considered as appropriate coating materials.     

Feasibility of TEOS coated CoFe2O4 nanoparticles to a GMR biosensor agent for single molecular detection

Magnetic properties of 200 nm ferrimagnetic CoFe2O4 nanoparticles before and after coating with TEOS were explored and compared to soft ferrimagnetic MgFe2O4 nanoparticles (200 nm) to evaluate the feasibility as an in-vitro GMR SV (giant magnetoresistance spin-valve) biosensor agent for single molecular detection (SMD). It was found that the magnetic degradation (or variation) of TEOS coated CoFe2O4 and MgFe2O4 nanoparticles are dominantly affected by the chemical dispersion process, which is carried out in the oleic acid (OA), oleylamine (OL), or OA+OL surfactant, before starting major coating process. In addition, the TEOS coating thickness controlled by TEOS concentration and pH level in the buffer solution prominently influenced on the magnetic degradation of TEOS coated nanoparticles. According to the experimental analysis results, the magnetic degradation of TEOS coated nanoparticles is mainly attributed to the variation of particle dipole interaction caused by the degree of particle aggregation depending on TEOS coating process conditions. The TEOS coated CoFe2O4 nanoparticles exhibited a higher magnetic stability for a GMR biosensor agent, e.g., small variation of remnant magnetization, saturation magnetization and magnetic coercivity, than that of MgFe2O4 nanoparticles at the different coating process conditions. The physical and chemical analysis confirmed that this is primarily due to its higher magnetic anisotropy. The experimentally verified high biocompatibility as well as the stably maintained magnetic properties of TEOS coated CoFe2O4 nanoparticles demonstrate that CoFe2O4 nanoparticles can be considered as one of the promising ferrimagnetic nanoparticle sensor agent for an SMD GMR SV biosensor.     

Fabrication of conducting polymer micro/nanostructures coated with Au nanoparticles for electrochemical sensors

Polypyrrole (PPy) micro/nanostructures coated with Au nanoparticles were prepared by electropolymerization and electro-deposition. Two types of PPy structures, micro-embossed and nanowire forest, were synthesized on patterned gold electrodes using different aqueous solutions, and Au nanoparticles were coated onto the PPy micro/nanostructure surface. The size of the Au nanoparticles ranged from 10 to 100 nm, and the maximum density of the nanoparticles was 73 particles/microm2. The small size and high density of the Au nanoparticles were achieved by optimizing the deposition time and chloroauric acid (HAuCl4) concentration. Cyclic voltammograms of ferrocyanide oxidation showed that the PPy micro/nanostructures coated with Au nanoparticles exhibit good electrochemical activity. These high-performance electrodes can be used in electrochemical sensors because the Au nanoparticles enhance electron transfer and provide a binding site for biomarker molecules, such as DNA, protein, and aptamers.     

The preparation, cytocompatibility, and in vitro biodegradation study of pure β-TCP on magnesium

Biodegradable and bioactive β-tricalcium phosphate (β-TCP) coatings were prepared on magnesium (Mg) in order to improve its biocompatibility by a chemical method. The tensile bonding strength of β-TCP coating and Mg substrate was measured by the standard adhesion test (ISO 13779-4). And the cytocompatibility of β-TCP coated Mg was studied by using human osteoblast-like MG63 cells. It was found that the MG63 cells could grow well on the surface of β-TCP coated Mg and the cell viability on β-TCP coated Mg was above 80% during the cocultivation of MG63 cells and β-TCP coated Mg for 10 days, indicating no cytotoxicity. It was concluded that the β-TCP coated Mg had good cytocompatibility. The degradation of Mg substrate with β-TCP coating in vitro was studied in detail by XRD, EDX, SEM, and ICP. The results showed that a bone-like apatite continually formed on the surface of the sample with the degradation of both Mg substrate and β-TCP coating in Hank’s solution (a simulated body fluid). The biodegradation mechanism was preliminarily analyzed in the paper.     

Urea sensing characteristics of titanate nanotubes deposited by electrophoretic deposition method

Urea sensing properties of titanate nanotubes (TNT) are presented here. TNT films were deposited by electrophoretic deposition (EPD) method on aluminum substrate. Prior to EPD, commercial nanoparticles of TiO2 were hydrothermally treated at 70 degrees C for 48 h after sonicating the solution for 8 h. Hydrothermal method resulted in the conversion of particles to tubular structure following the established method. Urease was covalently attached with TNT (by soaking in urease solution for 3 h). In general, conductivity of film increases after urease immobilization. The urease immobilized films were characterized for urea sensing in the concentration range of 1 mM to 500 mM. Three different sensitivity regions are observed viz. (i) lower concentrations (below 10 mM); (ii) linear region up to 100 mM and a (iii) saturation region above 100 mM. Sensors are extremely sensitive in region (i). From the elemental analyses of the films after urease immobilization, urease was found attached with TiO2, as evident by N 1s peak in the photoelectron spectra. Cyclic voltammetric studies indicated surface-confined redox couple is responsible for sensing behavior. A possible sensing mechanism is presented and discussed.     

Detection of gold nanoparticles using an immunoglobulin-coated piezoelectric sensor

Since the existence of nanoparticles in our environment has already attracted considerable attention due to their possible toxic impact on biological systems, the field detection of nanoparticles is becoming a technology that will be much in need. We have constructed a piezoelectric sensor with an antibody-coated electrode. The antiserum can bind gold nanoparticles with a high degree of selectivity and sensitivity. The biosensor thus constructed can detect 4, 5, or 6?nm gold nanoparticles (GNPs) depending on the coated antiserum. The sensitivity for the detection of 5?nm GNPs was 10.3 ± 0.9?ng?Hz(-1), with the low limit of detection at 5.5?ng. A quartz crystal microbalance (QCM) sensor was capable of detecting GNPs and other types of nanoparticle, such as ZnO, or Fe(3)O(4). The current study provides, for the first time, a platform for detecting nanoparticles in a convenient, economical manner.     

Morphologies of nano-sized apatite formed on titanium substrate by biomimetic process

The apatite was formed on the titanium plates with NaOH and heat treatments by biomimetic process. The influence of titanium surface microstructure on the apatite formation onto titanium substrate in SBF solution was investigated. After biomimetic process, nano-sized apatite layers were found on the Ti plates with NaOH and heat treatments. However, the morphologies of formed apatite on substrate had different shapes such as coated, load-like, and linked. The morphology of apatite formed by biomimetic process would be affected by alkaline treatment, and substrate morphology and phase.     

自组装法制备中空二氧化硅纳米粒子减反射薄膜

以正硅酸乙酯(TEOS)为壳层材料, 聚丙烯酸(PAA)为核材料, 以传统的Stöber水解法为基础制备得到结构规整的中空二氧化硅纳米粒子, 并采用自组装法制备单层减反射薄膜和宽波段双层减反射薄膜。主要研究中空二氧化硅纳米粒子的结构调控方法; 自组装次数和中空二氧化硅纳米粒子分散液的pH值对减反射薄膜透光率的影响规律, 以及具有渐变折射率的双层减反射薄膜的制备。研究结果表明: 通过调节PAA和TEOS的用量可精确调控中空二氧化硅纳米粒子的粒径和空腔体积分率, 进而可精确调控减反射薄膜的厚度和折射率; 通过酸洗工艺, 将自组装次数由10次减少为2次, 简化了涂膜的工艺条件, 在最佳工艺条件下所制备的单层减反射薄膜在350~800 nm波长范围内可显著提高玻璃的透光率, 在最佳波长(λ=520 nm)处将玻璃的透光率由91.6%提高至98.1%; 双层减反射薄膜可在更宽的波段范围内提高基材的透光率, 在400~1500 nm波长范围内将玻璃的透光率提高了5%以上。     

Fabrication of Coated/Uncoated Magnetic Nanoparticles to Determine Their Surface Properties

Fabrication of coated and uncoated magnetic nanoparticles (MNPs) was achieved in the present study. The preparation and characterization of MNPs were confirmed by Fourier transform infrared spectroscopy (FTIR) spectroscopy, streaming potential (SP), and magnetic force microscopy (MFM) techniques. Coated and uncoated nanoparticles were analyzed by dynamic light scattering method to obtain the mean size of nanoparticles. The SP was used to record the electrical surface charge of nanoparticles. The results obtained revealed that the bare nanoparticles were negative charged at higher pH (pH > 6.0) while coated nanoparticles were positive charged at lower pH (pH < 6.0). The porosity of surface of bare and coated nanoparticles was shown by MFM.     

Bioactivity of CaSiO<Subscript>3</Subscript>/poly-lactic acid (PLA) composites prepared by various surface loading methods of CaSiO<Subscript>3</Subscript> powder

Mixing bioactive ceramic powders with polymers is an effective method for generating bioactivity to the polymer-matrix composites but it is necessary to incorporate up to 40 vol% of bioactive ceramic powder. However, such a high mixing ratio offsets the advantages of the flexibility and formability of polymer matrix and it would be highly advantageous to lower the mixing ratio. Since surface loading of ceramic powders in the polymer is thought to be an effective way of reducing the mixing ratio of the ceramic powder while maintaining bioactive activity, CaSiO₃/poly-lactic acid (PLA) composites were prepared by three methods; (1) casting, (2) spin coating and (3) hot pressing. In methods (1) and (2), a suspension was prepared by dissolving PLA in chloroform and dispersing CaSiO₃ powder in it. The suspension was cast and dried to form a film in the case of method (1) while it was spin-coated on a PLA substrate in method (2). In method (3), CaSiO₃ powder was surface loaded on to a PLA substrate by hot-pressing. The bioactivity of these samples was investigated in vitro using simulated body fluid (SBF). Apatite formation was not observed in the samples prepared by method (1) but some apatite formation was achieved by mixing polyethylene glycol (PEG) with the PLA, producing a porous polymer matrix. In method (2), apatite was clearly observed after soaking for 7 days. Enhanced apatite formation was observed in method (3), the thickness of the resulting apatite layers becoming about 20 μm after soaking for 14 days. Since the amount of CaSiO₃ powder used in these samples was only ≤0.4 vol%, it is concluded that this preparation method is very effective in generating bioactivity in polymer-matrix composites by loading with only very small amounts of ceramic powder.     

Microstructural development of woven mullite fibre-reinforced mullite ceramic matrix composites by infiltration processing

Mullite fibre (Nextel 720?)-reinforced mullite ceramic matrix composites (CMCs) with zirconia weak interface were fabricated from heterocoagulated nano-size boehmite/amorphous silica powder particles dispersed in water, using electrophoretic deposition (EPD) and pressure filtration (PF). The nano-size mullite precursor was first prepared and characterised in terms of short-range particle–particle interactions and particle size distribution. Woven Nextel 720 mullite fibres were first desized and then coated with hydrothermally derived zirconia using dip-coating. EPD was performed under constant voltage conditions with varying deposition times, to infiltrate the dispersed powder suspensions into mullite fibre preforms, enabling the parameters necessary for good deposition of stoichiometric mullite to be established. EPD formed bodies were further consolitated using PF. The EPD/PF prepared green body specimens were dried under controlled atmosphere conditions before being sintered at 1200°C for 2 h in air. Mullite fibre mats were fully infiltrated using EPD parameters of 12 V DC applied voltage with 4 min deposition time, then eight EPD infiltrated fibre mats were further consolidated together using PF. The resulting CMC produced contained 35 vol% fibre loading and showed 81% theoretical density aftersintering at 1200°C for 2 h.     

A study on the electrophoretic deposition of 8YSZ coating using mixture of acetone and ethanol solvents

Electrophoretic deposition (EPD) was carried out on nickel metal sheets using acetone and ethanol mixtures. The ratios of the organic solvents in the suspension was varied to arrive at the optimum ratio of solvents and experimental conditions suitable for getting adherent and crack-free yttria-stabilized zirconia (YSZ) coatings. The volume ratios of acetone to ethanol used in the present study were 100:0 mL (4A:0E), 75:25 mL (3A:1E), 50:50 mL (2A:2E), 25:75 mL (1A:3E) and 0:100 mL (0A:4E). Iodine was used as an additive to charge the YSZ particles. The applied dc voltage was varied from 10 to 40 V cm⁻¹ and also the deposition time was varied 4, 6 and 8 min. The effect of applied dc voltage during EPD on the weight of the deposit and in turn on the thickness of the coating obtained was studied. The YSZ deposits were viewed under a metallurgical microscope to determine the presence of cracks or other defects in the as deposited coatings after initial drying. Attempts were made to understand the observed behavior of different solvent ratios with the number of protons released. This study facilitated to arrive at the optimum solvent ratio (3A:1E and 2A:2E) and the experimental conditions required for getting smooth, homogeneous, crack-free YSZ coatings by EPD on nickel substrates. Using the optimized condition of 2A:2E, lanthanum-doped strontium manganite (LSM) tube which acts as cathode in tubular solid oxide fuel cells (SOFCs) was coated with 8YSZ using EPD. The electrophoretically coated YSZ coating on sintering showed a dense microstructure.