Characterizing unusual metal substrates for gap‐mode tip‐enhanced Raman spectroscopy

In this article, the electromagnetic (EM) field in gap‐mode tip‐enhanced Raman spectroscopy (TERS) is investigated theoretically and experimentally for a range of commonly used and unusual metal and nonmetal substrates. By approaching a metal tip to a substrate, both form a coupled system that confines the EM field created at the tip apex. The influence of the substrate onto the EM field enhancement is observed in a top‐illumination gap‐mode TERS setup for different metal substrates. These include Au, the most commonly used substrate, and also a wide range of rarely or previously unused TERS substrates (Cu, Ag, Al, Pd, Pt, Ni, Ti, Mo, W, stainless steel, Al₂O₃, SiO₂). Self‐assembled monolayers of thiols and brilliant cresyl blue thin film samples are investigated experimentally on nine metal substrates, all showing considerable TERS enhancement. With finite difference time domain and finite element simulations used, the article provides a good estimate of the EM field enhancement for a wide range of substrates for users to estimate how well a substrate of choice will perform in a gap‐mode TERS experiment. The reduction in EM field strength |E²| compared with Au is less than an order of magnitude for many metals (Calculations: Cu 92%, Ag 81%, Ni 53%). This article experimentally shows that a wide variety of conductive substrates can be used, when one is willing to trade a fraction of the EM field enhancement. TERS was seen on all metal substrates including stainless steel, yet quantification was not always possible. These qualitative results were complemented with intensities from calculations. The wider variety of substrates will increase the applicability of TERS and evolve it one step further towards use in standard analytics. Copyright © 2012 John Wiley & Sons, Ltd.     

Chemical analysis of argon–oxygen decarburization slags in stainless steelmaking process by X‐ray fluorescence spectrometry

A quantitative analysis method of fluorine in the slags produced in the stainless argon–oxygen decarburization (AOD) process by X‐ray spectrometry was proposed employing direct analysis technique by pressed pellet. This research investigated the separate quantification of calcium fluoride and calcium oxide contained in AOD slags. X‐ray diffraction measurement was performed to identify the stable phase of fluorine compound, which is primarily present in the slags. The synthetic standards prepared in laboratory were used to construct the X‐ray fluorescence (XRF) calibration curves for F, Ca_tO, SiO₂, MgO, Al₂O₃ and Cr₂O₃, considering the matrix effects and line overlap corrections (t: total). The calibration curves were tested by the quantitative analysis of synthetic standards with satisfactory precision and accuracy. The proposed method might be an alternative solution to the problem with the simple and routine chemical analyses of calcium fluoride in AOD slags of stainless steelmaking process by XRF spectrometry. Copyright © 2010 John Wiley & Sons, Ltd.     

Studies by imaging TOF-SIMS of bone mineralization on porous titanium implants after 1 week in bone

Anodic oxidation was used to grow porous layers on titanium discs. Six different oxidation procedures were used producing six different surfaces. The implants were inserted in rat bone (tibia) for 7 days. After implant retrieval, mineralization (hydroxyapatite formation) on the implant surfaces was investigated using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Bone tissue around the implants was sectioned and stained. The amount of bone in close apposition to the implant was calculated. The porosity showed great variation between the surfaces. Hydroxyapatite was detected on all surfaces. A slight positive correlation between porosity and mineralization was found, although the most porous surface was not the best mineralized one. Bone had formed around all implants after 7 days. The bone-to-metal contact for the porous implants did not differ significantly from the non-porous control. Porosity is known to influence cellular events. The results indicate that porosity could have an initial, positive influence on bone integration of implants, by stimulating the mineralization process. The methods used were found to be suitable tools for investigation of initial healing around implants in bone.     

Distribution and incorporation of zinc in biological calcium phosphates

Human dental calculi are biological calcium phosphates, which consist of an organic phase and an inorganic or mineral phase. In the latter phase, spectrochemical analyses have revealed the presence of several different magnesium and calcium phosphates. As the crystalline structure of the calculus passes through several stages during its allocation in the mouth, special attention is paid to some elements, such as zinc, that can modify the mineralization process. Several in vitro studies relating to the dental calculus mineralization process have been performed so far, but there is a lack of data obtained from biologically synthesized samples. The knowledge of the zinc distribution and incorporation in biological calcium phosphates is of great interest in providing more information about the biological process of calculus formation. In this paper we present surveys of the elemental distribution and incorporation of zinc in human dental calculus, by using a combination of different techniques: x‐ray microfluorescence using synchrotron radiation, scanning electron microscopy and x‐ray absorption spectroscopy. One‐dimensional x‐ray microfluorescence of zinc and magnesium measurement shows that there is a high accumulation of both elements in the sub‐gingival region of the calculus and a strong correlation of their spatial distribution. Experimental Ca/P molar ratios were determined by energy‐dispersive spectroscopy to identify different calcium phosphate phases, the sub‐gingival region being composed of a mixture of highly and poorly calcified phosphates and the supra‐gingival region composed mainly of carbonated hydroxyapatite. Finally, x‐ray absorption measurements were carried out at the zinc K edge on synthetic and biological samples. The Zn—O distance and coordination number of the synthetic samples and the supra‐gingival calculus show that zinc is adsorbed on these structures, whereas in the sub‐gingival samples it is allocated in a cation site. The results are indicative of the active participation of zinc in the calcification process of sub‐gingival calculus. Copyright © 2003 John Wiley & Sons, Ltd.     

Nanoscale characterization of the interface between bone and hydroxyapatite implants and the effect of silicon on bone apposition

Silicon plays an important role in bone mineralization and formation and is therefore incorporated into a wide variety of medical implants and bone grafts used today. The significance of silicon (Si) can be understood through an analysis of the mechanisms of bone bonding to calcium containing biomaterials and through comparisons of hydroxyapatite (HA) and silicon-substituted hydroxyapatite (Si–HA). The addition of Si to HA causes a decrease in grain size that subsequently affects surface topography, dissolution–reprecipitation rates and the bone apposition process. Through the use of high-resolution transmission electron microscopy (HR-TEM) studies, the interactions between bone and silicon hydroxyapatite (Si–HA) at interfaces are reviewed and related to their impact on bone apposition and ultimately the performance of medical implants.     

Comparative study of hydroxyapatite and octacalcium phosphate coatings deposited on metallic implants by PLD method

The aim of the presented study was an analysis of two apatite coatings: hydroxyapatite (HA) and octacalcium phosphate (OCP) as coatings materials for metallic implants. Both layers were deposited by means of the PLD method. As a target material, synthetic, powdered and pressed hydroxyapatite was used. HA was deposited on 316L steel substrate in two temperature ranges for obtaining different coatings: 150±30°C and 430±30°C for OCP and HA, respectively. As an intermediate layer, the nanocrystalline diamond layer (NCD) was deposited. Examined calcium phosphate layers were tested for adhesion of osteoblast cell culture (MG-63). Analytical methods (AFM, FTIR) showed the usefulness of the PLD method for deposition of the apatite layers on metallic implants. Both examined layers showed biocompatibility with human osteoblast cells and presented favorable conditions for their proliferation.     

Surface characterisation and electrochemical behaviour of porous titanium dioxide coated 316L stainless steel for orthopaedic applications

Porous titanium dioxide was coated on surgical grade 316L stainless steel (SS) and its role on the corrosion protection and enhanced biocompatibility of the materials was studied. X-ray diffraction analysis (XRD), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) were carried out to characterise the surface morphology and also to understand the structure of the as synthesised coating on the substrates. The corrosion behaviour of titanium dioxide coated samples in simulated body fluid was evaluated using polarisation and impedance spectroscopy studies. The results reveal that the titanium dioxide coated 316L SS exhibit a higher corrosion resistance than the uncoated 316L SS. The titanium dioxide coated surface is porous, uniform and also it acts as a barrier layer to metallic substrate and the porous titanium dioxide coating induces the formation of hydroxyapatite layer on the metal surface.     

Study of the effects of unsupervised over‐the counter whitening products on dental enamel using μ‐Raman and μ‐EDXRF spectroscopies

The purpose of this in vitro study was to assess whether the mineralization degree and elemental content in tooth enamel are altered when bleaching the teeth with two different over‐the‐counter bleaching gels, exceeding the recommendations of the manufacturer. In order to perform this evaluation, 12 healthy teeth were used, six samples were treated with Teeth Whitening Home Kit, and the other six samples were treated with WHITE! (Bingo‐UK) bought in online shopping sites, for the period of 39 days. The pH of each product and the elemental content of each sample, before and after, were obtained by energy dispersive X‐ray spectrometry and phosphate (PO₄^3‐) profile was evaluated with Raman spectroscopy. Data was analyzed accordingly to a pre‐established plan with a mixed‐model ANOVA for repeated measures, significance was set at 5%. Both products were markedly acidic and below enamel critical level of 5.5. Moreover, seven days after treatment, demineralization was significant, wherein at the end of the study the degree of demineralization seems to be permanent. Copyright © 2015 John Wiley & Sons, Ltd.     

Distribution of selected elements in atherosclerotic plaques of apoE/LDLR‐double knockout mice assessed by synchrotron radiation‐induced micro‐XRF spectrometry

Apolipoprotein E and LDL receptor double‐knockout (apoE/LDLR^?/?) mice represent a reliable experimental model of atherosclerosis. The aim of the present study was to examine the elemental content of atherosclerotic plaques using synchrotron radiation‐induced micro x‐ray fluorescence (XRF) spectrometry. Numerous essential and trace elements were detected in cross‐sections of aortic roots collected from 6‐month‐old apoE/LDLR^?/? mice fed with chow diet. Two‐dimensional maps of the elemental distribution and point recordings were compared with images of consecutive sections stained histologically, allowing precise localization of the analyzed elements in morphologically defined areas of aortic lesion. The sulphur was detected in areas occupied by macrophages and smooth muscle cells. Iron was observed in high concentrations in cardiac and smooth muscle, blood clots and in adjacent coronary vessels. Lower concentrations of iron were seen in the regions of plaques rich in macrophages and lipids. Copper was detected in higher amounts only in cardiac muscle and its concentration in plaques was very low. There was a quite high content of calcium in aortic plaque areas containing lipids and macrophages. Much higher concentrations of calcium were observed in mineral deposits, mostly located in the aortic media. Similar distribution was also characteristic for phosphorus. Zinc was observed in moderately low concentrations in atheromas. Higher content of zinc was seen in smooth musculature, in cardiac muscle and in mineral concretions. The presented results provide a substantial morphological and physicochemical background for further investigations aiming to evaluate pharmacological and dietary treatment of atherosclerosis in an apoE/LDLR^?/? mouse model. Copyright © 2008 John Wiley & Sons, Ltd.     

A comparative study of surface‐enhanced Raman scattering from silver‐coated anodic aluminum oxide and porous silicon

Three types of Ag‐coated arrays from porous anodic aluminum oxide (AAO) were prepared and studied as substrates for surface‐enhanced Raman scattering (SERS). They were compared with Ag‐coated porous silicon (PSi) samples. AAO‐based substrates were prepared by the vapor deposition of silver directly onto the surface of porous AAO with different morphologies of the pores, whereas SERS‐active island films on the PSi were prepared by immersion plating. The resulting metallic nanostructures were characterized by UV‐vis absorption spectroscopy and scanning electron microscopy (SEM). Thermal evaporation leads to the formation of granular arrays of Ag nanoparticles on the surface of AAO. SERS activity of the substrates was tested using water‐soluble cationic Zn(II)‐tetrakis (4‐N‐methylpyridyl) porphyrin (ZnTMPyP4) as a probe molecule. The results indicate that all AAO‐based substrates studied here exhibit some degree of SERS activity. Noteworthy, for excitation at 532 nm, signals from AAO‐based substrates were comparable with those from the PSi‐based ones, whereas for 441.6 nm excitation they were about twice higher. The strongest SERS‐enhancement at 441.6 nm excitationwas provided by the AAO substrates with silver deposited on the monolith (originally nonporous) side of AAO. Preferential SERS‐enhancement of the bands ascribed to the vibrations of the N‐methylpyridinium group of ZnTMPyP4 when going to blue excitation was found. Copyright © 2010 John Wiley & Sons, Ltd.     

Micro arc oxidized HAp-TiO2 nanostructured hybrid layers-part I: Effect of voltage and growth time

Micro arc oxidation was employed to grow hydroxyapatite-TiO₂ nanostructured porous composite layers. The layers were synthesized on the titanium substrates in the electrolytes consisting of calcium acetate and sodium β-glycerophosphate salts under different applied voltages for various times. SEM and AFM investigations revealed a porous structure and rough surface where the pores size and the surface roughness were respectively determined as 70-650 nm and 9.8-12.7 nm depending on the voltage and time. Chemical composition and phase structure of the layers were evaluated using EDX, XPS, and XRD methods. The layers consisted of the hydroxyapatite, anatase, α-TCP, and calcium titanatephases with a varying fraction depending on the growth conditions. The hydroxyapatite crystalline size was also determined as ∼42 nm. The sample fabricated under the voltage of 350 V for 3 min exhibited the most appropriate Ca/P ratio (∼1.60) as well as the highest amount of the hydroxyapatite phase. This sample had a fine surface morphology and a high pores density.     

Effect of gamma irradiation on X‐ray absorption and photoelectron spectroscopy of Nd‐doped phosphate glass

X‐ray absorption near‐edge structure (XANES) and X‐ray photoelectron spectroscopy (XPS) of Nd‐doped phosphate glasses have been studied before and after gamma irradiation. The intensity and the location of the white line peak of the L₃‐edge XANES of Nd are found to be dependent on the ratio O/Nd in the glass matrix. Gamma irradiation changes the elemental concentration of atoms in the glass matrix, which affects the peak intensity of the white line due to changes in the covalence of the chemical bonds with Nd atoms in the glass (structural changes). Sharpening of the Nd 3d_5/2 peak profile in XPS spectra indicates a deficiency of oxygen in the glasses after gamma irradiation, which is supported by energy‐dispersive X‐ray spectroscopy measurements. The ratio of non‐bridging oxygen to total oxygen in the glass after gamma radiation has been found to be correlated to the concentration of defects in the glass samples, which are responsible for its radiation resistance as well as for its coloration.     

TOF-SIMS analysis of the interface between bone and titanium implants—Effect of porosity and magnesium coating

Implant healing was studied with regard to the mineralization of the implant-tissue interface. Titanium discs were surface-modified and implanted in rat tibia for 4 weeks. After implantation, the bone was embedded in resin and cross sections of bone and implant were made using a low speed saw equipped with a diamond wafering blade. The sections were analyzed with imaging TOF-SIMS using a Bi₃⁺ cluster ion source. This ion source has recently been shown to enable identification of hydroxyapatite (HA) fragments in bone samples. The area within 40 μm from the implant surface was selected for analysis, corresponding to bone-implant interface, from which positive spectra were recorded. In conclusion, differences were observed between the implants tested regarding signal intensity of fragments specific for HA. Coating of the implants with magnesium and porosity were shown to influence the mineral content of the bone-implant interface. This technique might be useful for biocompatibility assessment and for studying the mineralization process at implant surfaces.     

Thiol‐modified gold‐coated glass as an efficient hydrophobic substrate for drop coating deposition Raman (DCDR) technique

In this paper we report an easy and low‐cost way to prepare a hydrophobic substrate for drop coating deposition Raman (DCDR) spectroscopy. This substrate is formed by a thiol‐modified Au‐coated glass and provides the Raman spectra with the same quality as the commercial Teflon‐coated stainless steel substrate (SpectRIM™, Tienta Sciences, Inc.) for model molecular systems – albumin solution and liposome suspension. Gold layer, similarly to polished steel in the commercial substrate, served as a highly refractive layer strongly increasing the Raman signal. The main advantage of introduced substrate is that it is simple and a low‐cost preparation easily manageable in every standard laboratory. Thus, it represents a promising alternative to commercial Teflon‐coated stainless steel substrate. Copyright © 2016 John Wiley & Sons, Ltd.     

Nanoporous Ag–GaN thin films prepared by metal‐assisted electroless etching and deposition as three‐dimensional substrates for surface‐enhanced Raman scattering

Three‐dimensional (3D) nanoporous gallium nitride (PGaN) scaffolds are fabricated by Pt‐assisted electroless hydrofluoric acid (HF) etching of crystalline GaN followed by in situ electroless deposition of Ag nanostructures onto the interior surfaces of the nanopores, yielding a large surface area substrate for surface‐enhanced Raman scattering (SERS). The resulting 3D SERS‐active substrates have been optimized by varying reaction parameters and starting material concentration, exhibiting enhanced Raman signals 10–100× more intense than either (1) sputtered Ag‐coated porous GaN or (2) Ag‐coated planar GaN. The increase in SERS signal is attributed to a combination of the large surface area and the inherent transparency of PGaN in the visible spectral region. Overall, Ag‐decorated PGaN is a promising platform for high sensitivity SERS detection and chemical analysis, particularly for reaction and metabolic products that can be trapped inside the highly anisotropic nanoscale pores of PGaN. The potential of this sampling mode is illustrated by the ability to acquire Raman spectra of adenine down to 5 fmol. Additionally, correlated SERS and laser desorption/ionization mass spectrometry spectra can be acquired from same sample spot without further preparation, opening new possibilities for the investigation of surface‐bound molecules with substantially enhanced information content. Copyright © 2012 John Wiley & Sons, Ltd.     

Beamline BL‐07 at Indus‐2: a facility for microfabrication research

The X‐ray lithography beamline on Indus‐2 is now operational, with two modes of operation. With a pair of X‐ray mirrors it is possible to tune the energy spectrum between 1 and 20 keV with a controlled spectral bandwidth. In its `no optics' mode, hard X‐rays up to 40 keV are available. Features and performance of the beamline are presented along with some example structures. Structures fabricated include honeycomb structures in PMMA using a stainless steel stencil mask and a compound refractive X‐ray lens using a polyimide–gold mask in SU‐8.     

Thermomagnetically Responsive γ‐Fe2O3@Wax@SiO2 Sub‐Micrometer Capsules

A three steps synthesis route is proposed to generate thermosensitive and magnetically responsive γ‐Fe₂O₃@Wax@SiO₂ sub‐micrometer capsules with a paraffinic core and a solid and brittle shell. The process integrates Pickering‐based emulsions, inorganic and sol–gel chemistries to promote monodisperse in size wax droplets, γ‐Fe₂O₃ nanoparticles and mineralization of the wax/water interfaces. Hybrid capsules are obtained with an average size around 800 nm, representing the first example of sub‐micrometer capsules generated employing Pickering emulsions as templates. Cetyltrimethylammonium bromide (CTAB) cationic surfactant added during mineralization at concentrations between 0.17 and 1.0 wt% impacts the shell density. The shell density seems to improve its mechanical strength while affording a low wax expansion volume without breaking for CTAB concentrations above 1.0 wt%. At lower CTAB concentration (0.17 wt%), the silica shell becomes less bulky and cannot resist the wax dilatation induced by the solid‐to‐liquid phase transition imposed by hyperthermia. The magnetically induced heating provided by the internal magnetic moments is sufficient to melt the wax core, expanding its volume, inducing thereby the surrounding silica shell rupture. Such γ‐Fe₂O₃@Stearic Acid@Wax@SiO₂ sub‐micrometer capsules allow a sustained wax release with time, whereby 20% of the wax is released after 50 min of alternating magnetic field treatment.     

Collagen immobilization on 316L stainless steel surface with cathodic deposition of calcium phosphate

Collagen fibril/(calcium phosphate and carbonate) composite coatings on 316L stainless steel were developed with a cathodic deposition technique. The response of SaOS-2 osteoblast-like cells to the collagen/calcium salt-coated 316L steel was investigated. The collagen fibrils were self-assembled on the 316L steel surface and immobilized by their partial incorporation into a calcium salt layer electrodeposited cathodically in Hanks’ solution. The amount of calcium salt depended on the applied cathodic potential. The mineralization of collagen fibrils was observed. The collagen coverage localized and the composition of calcium salts varied on the same specimen. Such non-uniform surfaces affected the cell response. The observed outlines of cell bodies and nuclei on the thin collagen coating were clearer than those on the thick collagen coating in most cases. The collagen coating did not significantly influence the mean viability of cells on the whole specimen surface. Interestingly, the alkaline phosphatase activity per cell on the collagen/calcium salt-coated specimens was higher than that on the as-received specimen. It was revealed that cathodic deposition is an effective technique to immobilize collagen fibrils on a 316L steel surface.     

Effect of electrodeposition modes on surface characteristics and corrosion properties of fluorine-doped hydroxyapatite coatings on Mg-Zn-Ca alloy

The microstructure, morphology and composition highly determine the corrosion resistance and bioactivity of coating. In traditional cathodic electrodeposition process, because of the unfavorable effects of the polarization of concentration difference and H₂ evolution, fluorine-doped hydroxyapatite coating was loose and porous. This coating could not ensure the long-term stability of the Mg alloy implants. In order to improve the corrosion resistance and bioactivity of coating, pulse electrodeposition and H₂O₂ were introduced into the electrodeposition to deposit fluorine-doped hydroxyapatite coating. As a comparative study, microstructure, corrosion resistance properties and bioactivity of traditional cathodic electrodeposition coating and pulse electrodeposition coating were investigated, respectively. The results revealed that nano fluorine-doped hydroxyapatite coating could be prepared by pulse electrodeposition, and the coating was dense and uniform. The potentiodynamic polarization experiment indicated that the dense and uniform coating could effectively protect Mg alloy substrate from corrosion. Immersion testing was performed in simulated body fluid. It was found that pulse electrodeposition coating could more effectively induce the precipitation of Mg²⁺, Ca²⁺ and PO₄³⁻ in comparison with traditional cathodic electrodeposition coating, because the nano phase had comparatively high specific surface area. Thus magnesium alloy coated with fluorine-doped nano-hydroxyapatite coating may be a promising candidate as biodegradable bone implants, and was worthwhile to further investigate the in vivo degradation behavior.     

Amorphous silicon solar cells on nano‐imprinted commodity paper without sacrificing efficiency

Paper is a cheap substrate which is in principle compatible with the process temperature applied in the plasma enhanced chemical vapour deposition (PECVD) and hot wire CVD (HWCVD) of thin film silicon solar cells. The main drawback of paper for this application is the porosity due to its fibre like structure. The feature size (micrometre scale) is larger than the thickness of the applied photovoltaic layers. To overcome this problem, UV curable lacquer was used to planarize the surface. Plain 80 grams printer paper was taken as a substrate and the lacquer smoothens the rough surface of the paper such that a designed nanostructure can be imprinted for light scattering. In this manner single junction amorphous silicon solar cells with a HWCVD deposited intrinsic layer were processed on paper, without any concessions to the process temperature of 200 °C. The cell performance is comparable to that of reference cells grown on stainless steel, proving that solar cells can be deposited on paper substrates without sacrificing performance. PV on paper could be applied as ”disposable” power source for gadgets, electronic labelling, remote sensing systems, etc. (Internet of Things). (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)