Solid-phase microextraction Ni–Ti fibers coated with functionalised silica particles immobilized in a sol–gel matrix

One of the possible approaches for the development of novel solid-phase microextraction (SPME) fibers is the physical deposition of porous materials onto a support using high-temperature epoxy glue. However, a major drawback arises from decomposition of epoxy glue at temperatures below 300 °C and instability in some organic solvents. This limitation motivated us to explore the possibility of replacing the epoxy glue with a sol–gel film, thermally more stable and resistant to organic solvents. We found that functionalised silica particles could be successfully attached to a robust Ni–Ti wire by using a UV-curable sol–gel film. The particles were found to be more important than the sol–gel layer during the microextraction process, as shown by competitive extraction trials and by the different extraction profiles observed with differently functionalised particles. If a quality control microscopic-check aiming at the rejection of fibers exhibiting unacceptably low particle load was conducted, acceptable (6–14%) reproducibility of preparation of C₁₈-silica fibers was observed, and a strong indication of the durability of the fibers was also obtained. A cyclohexyldiol-silica fiber was used, as a simple example of applicability, for the successful determination of benzaldehyde, acetophenone and dimethylphenol at trace level in spiked tap water. Recoveries: 95–109%; limits of detection: 2–7 μg/L; no competition effects within the studied range (≤125 μg/L).     

Synthesis of sub-micro-sized solid alpha alumina fibers with smooth surfaces by sol–gel method

Alumina sol containing nano-meter sized Al₂O₃ particles were synthesized using aluminum sec-butoxide and nitric acid as precursor and peptizing agent, respectively. Polyvinylpyrrolidone (PVP) was added to prevent particle growth and adjust sol viscosity. PVP/alumina hybrid fibers were drawn from the sol with a viscosity value in the range of 2,500–3,000 mPa.s. By guided through a temperature gradient tube furnace at a rate of 4 m/min, the wet PVP/alumina hybrid fibers were sufficiently dried. Sub-micro-sized pure alpha alumina fibers were obtained by sintering the dry hybrid fibers at 1,000 °C for 3 h. The organic matters were decomposed within a wide temperature range from 150 to 800 °C allowing the nano Al₂O₃ particles to gradually get together and form solid alumina fibers with smooth surfaces.     

Titanium dioxide fibers prepared by sol–gel process and centrifugal spinning

A new study of the preparation of nanocrystalline titanium dioxide (TiO₂) fibers is reported in the paper, which were prepared by sol–gel process with titanium acetate [Ti(CH₃COO)₄] as precursor. After that, centrifugal spinning and steam atmosphere heat-treatment were used to obtain final fibers. Here, the molecule structure of precursor was analyzed and the TiO₂ fibers obtained were characterized. Additionally, the effects of the silica (SiO₂) doping were discussed in this paper. By the Fourier transformation infrared spectrum analysis, the chain structure of –O–Ti–O–Ti–O– was confirmed in the Ti(CH₃COO)₄ precursor, as a result the precursor spinning solution showed a good spinning performance. And the pyrolysis process of precursor fibers was analyzed with the help of DSC–TG method. The phase of TiO₂ fibers obtained after heat-treatment with steam atmosphere was characterized mainly by the X-ray diffractometer (XRD), from the XRD curves, the result that the SiO₂ doping can efficiently inhibit the grain growth of TiO₂ fibers could also be verified. The microstructure of the TiO₂ fibers was observed by scanning electron microscope, which showed that diameter of TiO₂ fibers obtained with excellent continuity are from 5 to 10 μm. At last, the photocatalytic property of TiO₂ fibers was also tested.     

Role of precursors and coating polymers in sol–gel chemistry toward enhanced selectivity and efficiency in solid phase microextraction

To evaluate the selectivity and efficiency of solid phase microextraction (SPME) fiber coatings, synthesized by sol–gel technology, roles of precursors and coating polymers were extensively investigated. An on-line combination of capillary microextraction (CME) technique and high performance liquid chromatography (HPLC) was set up to perform the investigation. Ten different fiber coatings were synthesized in which five of them contained only the precursor and the rests were prepared using both the precursor and coating polymer. All the coatings were chemically bonded to the inner surface of copper tubes, intended to be used as the CME device and already functionalized by self-assembly monolayers of 3-(mercaptopropyl)trimethoxysilane (3MPTMOS). The selected precursors included tetramethoxysilane (TMOS), 3-(trimethoxysilyl)propylmethacrylate (TMSPMA), 3-(triethoxysilyl)-propylamine (TMSPA), 3MPTMOS, [3-(2,3-epoxypropoxy)-propyl]-trimethoxysilane (EPPTMOS) while poly(ethyleneglycol) (PEG) was chosen as the coating polymer. The effects of different precursors on the extraction efficiency and selectivity, was studied by selecting a list of compounds ranging from non-polar to polar ones, i.e. polycyclic aromatic hydrocarbon, herbicides, estrogens and triazines. The results from CME–HPLC analysis revealed that there is no significant difference between precursors, except TMOS, in which has the lowest extraction efficiency. Most of the selected precursors have rather similar interactions toward the selected analytes which include Van der Walls, dipole–dipole and hydrogen bond while TMOS has only dipole–dipole interaction and therefore the least efficiency. TMOS is silica but the other sorbents are organically modified silica (ORMOSIL). Our investigation revealed that it is rather impossible to prepare a selective coating using conventional sol–gel methodologies. The comparison study performed among the fiber coatings contained only a precursor and those synthesized by a precursor along with coating polymer proved that the extraction efficiency obtained for all coatings are the same. This is an indication that by selecting the appropriate precursor there is no need to use any coating polymer. In overall, a fiber coating in sol–gel process could be synthesize with no coating polymer which leads to faster, easier, cheaper and more controllable synthesis.     

Thermally stable and transparent superhydrophobic sol–gel coatings by spray method

A facile method was developed for the fabrication of the methyltriethoxysilane based transparent and superhydrophobic coating on glass substrates. The transparent and hydrophobic coatings were deposited on the glass substrates, using spray deposition method followed by surface modification process. A spray deposition method generates hierarchical morphology and post surface modification with monofunctional trimethylchlorosilane decreases the surface free energy of coating. These combined effects of synthesis produces bio-inspired superhydrophobic surface. The deposited coating surface shows high optical transparency, micro-nano scale hierarchical structures, improved hydrophobic thermal stability, static water contact angle of about 167° ± 1°, low sliding angle about 2° ± 1° and stable superhydrophobic nature. This paper provides the very simple sol–gel approach to the fabrication of optically transparent, thermally stable superhydrophobic coating on glass substrates. This fabrication strategy may easily extend to the industrial scale up and high-technology fields.     

Comparative study of the sol–gel based solid phase microextraction fibers in extraction of naphthalene, fluorene, anthracene and phenanthrene from saffron samples extractants

We are introducing a method for the determination of some polycyclic aromatic hydrocarbons in aqueous saffron sample by direct immersion solid phase microextraction (SPME) and gas chromatography. A sol–gel technique is used for the preparation of the SPME fibers. Three kinds of sol–gel coatings on the fibers were tested and compared. They are composed of poly(dimethyl siloxane) (PDMS), poly(ethylene glycol) (PEG), and a poly(ethylene glycol) modified with multi-walled carbon nanotubes (PEG/CNTs). The effects of fiber coating, desorption time, desorption temperature, extraction time, stirring speed and salting effect were optimized. Under the optimal conditions, the detection limits (at S/N?=?3) are 7–50, 5–50, and 1–10?pg?mL^–1, respectively, for SPME fibers made from PDMS, PEG and PEG/CNTs. The relative standard deviations for one type of fiber are from 2.1% to 9.6% for all fibers (at n?=?5), and in the range from 1.9% to 9.8% from batch to batch (for n?=?3).

Titanium coated with high-performance nanocrystalline ruthenium oxide synthesized by the microwave-assisted sol–gel procedure

Ruthenium oxide coating on titanium was prepared by the sol–gel procedure from well-defined colloidal oxide dispersions synthesized by the microwave (MW)-assisted hydrothermal route under defined temperature and pressure heating conditions. The dispersions were characterized by dynamic light scattering (DLS) measurements and scanning electron microscopy (SEM). The electrochemical properties were analyzed as capacitive performances gained by cyclic voltammetry and electrochemical impedance spectroscopy and as the electrocatalytic activity for oxygen evolution from acid solution. The obtained dispersions were polydisperse and contained regular particles and agglomerates of increasing surface energy and decreasing particle size as the MW-assisted heating conditions were intensified. Owing to these features of the precursor dispersions, the obtained coatings had considerably improved capacitive performances and good electrocatalytic activity for oxygen evolution at high overpotentials.     

Surface characterization and dissolution study of biodegradable calcium metaphosphate coated by sol–gel method

Coatings of biomedical implant surfaces by a bioactive calcium phosphate film render bioactivity to the implant surface and shorten the healing time. In this present study, calcium metaphosphate (CMP) sol was synthesized by sol–gel method and coated onto the titanium alloys (Ti-6Al-4V). CMP sol was first synthesized by reacting Ca(NO₃)₂4H₂O (Sigma–Aldrich 99%, USA) with (OC₂H₅)₃P (Fluka 97%, Japan) in methyl alcohol. A stoichiometric Ca/P ratio of 0.5 was obtained by varying the amounts of the reactants. Sol was then coated on Ti-6Al-4V substrates by spin coating. The coated-specimens were then dried at 70 °C for 24 h, followed by a heat treatment at 650 °C for 1 h. Structural and chemical properties of the coatings were evaluated using XRD, SEM, and EPMA. The dissolution property of the coated-CMP layer was investigated by immersing the samples in the simulated body fluid (SBF) for 1, 3, 7 and 21 days. The concentration of Ca²⁺ released was measured using ICP. After heat treatment, SEM indicated a smooth and uniform CMP layer, with CMP grains of approximately 100 nm. The CMP phase was identified with δ-CMP (JCPDS #9-363). After immersion in SBF, coatings were observed to be roughened and porous. The concentration of Ca²⁺ in SBF was observed to increase over time, indicating continuous dissolution. The presence of titanium oxide phosphate compounds were also observed on CMP surfaces after immersion. It was thus concluded that the ability to control coating properties as well as the need for low heat treatment temperature offers advance for the use of CMP coating by sol–gel process on Ti-6Al-4V implant surfaces.     

Synthesis of hybrid polymeric fibers of different functionalized alkoxysilane coupling agents obtained via sol–gel and electrospinning technique: effect on the morphology by addition of PVA

Journal of Sol-Gel Science and Technology - Hybrid functionalized alkoxysilane/PDMS-OH and alkoxysilane/PDMS-OH/PVA polymers were synthesized through acid catalysis sol–gel technique and...     

Aptamer-functionalized solid phase microextraction–liquid chromatography/tandem mass spectrometry for selective enrichment and determination of thrombin

In this publication, a novel solid phase microextraction (SPME) coating functionalized with a DNA aptamer for selective enrichment of a low abundance protein from diluted human plasma is described. This approach is based on the covalent immobilization of an aptamer ligand on electrospun microfibers made with the hydrophilic polymer poly(acrylonitrile-co-maleic acid) (PANCMA) on stainless steel rods. A plasma protein, human α-thrombin, was employed as a model protein for selective extraction by the developed Apt-SPME probe, and the detection was carried out with liquid chromatography/tandem mass spectrometry (LC–MS/MS). The SPME probe exhibited highly selective capture, good binding capacity, high stability and good repeatability for the extraction of thrombin. The protein selective probe was employed for direct extraction of thrombin from 20-fold diluted human plasma samples without any other purification. The Apt-SPME method coupled with LC–MS/MS provided a good linear dynamic range of 0.5–50 nM in diluted human plasma with a good correlation coefficient (R² = 0.9923), and the detection limit of the proposed method was found to be 0.30 nM. Finally, the Apt-SPME coupled with LC–MS/MS method was successfully utilized for the determination of thrombin in clinical human plasma samples. One shortcoming of the method is its reduced efficiency in undiluted human plasma compared to the standard solution. Nevertheless, this new aptamer affinity-based SPME probe opens up the possibility of selective enrichment of a given targeted protein from complex sample either in vivo or ex vivo.     

Preconcentration and determination of naproxen in water samples by functionalized multi-walled carbon nanotubes hollow fiber solid phase microextraction—HPLC

A simple, sensitive and selective solid phase microextraction with hollow fiber-supported multi-walled carbon nanotube functionalization reinforced sol–gel combined HPLC method was proposed for the determination of naproxen in tap, well and river water samples. In this method, functionalized multi-walled carbon nanotubes (MWCNTs) were prepared and held in pores of hollow fiber with sol–gel technology by immersion of polypropylene hollow fiber segment into the sol of the functionalized MWCNTs/silica composite and ultrasonically treated at room temperature. Effect of main parameters such as volume of donor phase, pH, extraction time, desorption time, type of desorption solvent, sample ionic strength and stirring rate were studied. Under optimum conditions, linearity was observed in the range of 0.03–500 ng/mL, with correlation coefficients of 0.997. The relative standard deviation for three replicate determinations of 50 ng/mL of naproxen was 4.3%. Limit of detection and pre-concentration factor were 0.008 ng/mL and 198, respectively. In order to check the applicability of the proposed method, it was used to determine trace levels of naproxen in different water samples.     

Synthesis and characterization of hydroxyapatite obtained from different organic precursors by sol–gel method

The synthesis of four types of hydroxyapatite synthesized from calcium chloride and four different organic phosphites is presented. The method of synthesis chosen is the sol–gel route, which has a number of advantages compared to other methods, like the intimate contact between reactants and the milder synthesis conditions. The samples were thermally treated, the TG/DTG/DTA curves being obtained at four heating rates, namely: 7, 10, 12 and 15 °C min⁻¹. The samples were characterized before and after the thermal treatment using FT-IR analysis. The FT-IR spectra certified that the formed compounds represent hydroxyapatite. Based on the information from the TG curves and IR spectra interpretation, a reaction mechanism was proposed.     

Development and application of a new solid-phase microextraction fiber by sol–gel technology on titanium wire

Novel solid-phase microextraction fibers were prepared based on sol–gel technique. Commonly used fused silica substrate was replaced by titanium wire which provided high strength and longer fiber life cycle. Titanium isopropoxide was employed as the precursor which provides a sol solution containing Ti–OH groups and shows more tendencies to the molecularly similar group on the substrate. Three different polymers, poly (dimethylsiloxane) (PDMS), poly(ethylenepropyleneglycol)-monobutyl ether (Ucon) and polyethylene glycol (PEG) were employed as coating polymer in preparing three different fibers. The applicability of these fibers was assessed for the headspace SPME (HS-SPME) of benzene, toluene, ethylbenzene and xylenes (BTEX) from water sample followed by gas chromatography–mass spectrometry (GC–MS). Effects of different parameters such as fiber coating type, extraction condition, desorption condition were investigated and optimized. Under the optimized conditions, LODs and LOQs of 0.75–10 μg L⁻¹ (S/N = 3) and 1–20 μg L⁻¹ (S/N = 10) were respectively obtained. The method showed linearity in the range of 10–25,000 μg L⁻¹ with correlation coefficient of >0.99. The relative standard deviation was less than 8%.     

Analysis of capsaicin and dihydrocapsaicin in peppers and pepper sauces by solid phase microextraction–gas chromatography–mass spectrometry

A simple method for the analysis of capsaicin and dihydrocapsaicin in peppers and pepper sauces by solid phase microextraction–gas chromatography–mass spectrometry has been developed. A novel device was designed for direct extraction solid phase microextraction in order to avoid damage to the fiber. The analysis was performed without derivatization for the gas chromatography–mass spectrometry analysis. Selection fiber, extraction temperature, extraction time and pH, were optimized. The method was linear in the range 0.109–1.323 μg/mL for capsaicin and 0.107–1.713 μg/mL for dihydrocapsaicin with correlation coefficient up to r = 0.9970 for both capsaicinoids. The precision of the method was less than 10%. The method was applied to the analysis of 11 varieties of peppers and four pepper sauces. A broad range of capsaicin (55.0–25 459 μg/g) and dihydrocapsaicin (93–1 130 μg/g) was found in the pepper and pepper sauces samples (4.3–717.3 and 1.0–134.8 μg/g), respectively.     

Studies on the phase behavior and solubilization of the microemulsion formed by surfactant-like ionic liquids with ɛ–β-fish-like phase diagram

The phase behavior and the solubilization of the microemulsion systems surfactant-like ionic liquids 1-hexadecyl-3-methylimidazolium bromide (C₁₆mimBr), 1-tetradecyl-3-methylimidazolium bromide (C₁₄mimBr), or 1-dodecyl-3-methylimidazolium bromide (C₁₂mimBr)/alcohol/alkane/brine have been studied with ɛ–β-fish-like phase diagram method at 40 °C and an oil-to-water mass ratio of 1:1. From the ɛ–β-fish-like phase diagram, the physicochemical parameters, such as the mass fraction of alcohol in the hydrophile–lipophile-balanced interfacial layer (A ^S), and the solubilities of ionic liquid (S ^O) and alcohol (A ^O) in alkane phase, were calculated. The solubilization of the microemulsion system has been discussed based on the ɛ–β-fish-like phase diagram. The smaller the oil molecule, the longer the alcohol chain length, and the larger the NaCl concentration in water, the larger the solubilization of the microemulsion system. In this paper, the solubilization of the microemulsion stabilized by both C₁₂mimBr and sodium dodecyl sulfonate (sodium dodecyl sulfate) was also investigated with the ɛ–β-fish-like phase diagram. The unequimolar composite of anionic and cationic surfactants can avoid the sedimentation aroused by the strong electrostatic attraction, and an obvious synergism effect in solubilization was obtained.     

Determination of pesticides by solid phase extraction followed by gas chromatography with nitrogen–phosphorous detection in natural water and comparison with solvent drop microextraction

The European Union specificies that drinking water can contain pesticide residues at concentrations of up to 0.1 μg/L each and 0.5 μg/L in total, and that 1–3 μg/L of pesticides can be present in surface water, but the general idea is to keep discharges, emissions and losses of priority hazardous substances close to zero for synthetic substances. Therefore, in order to monitor pesticide levels in water, analytical methods with low quantification limits are required. The method proposed here is based on solid phase extraction (SPE) followed by gas chromatography with a nitrogen–phosphorous detector (GC-NPD). During method development, six organophosphate pesticides (azinphos-ethyl, chlorfenvinphos, chlorpyriphos, ethoprophos, fenamiphos and malathion) and two organonitrogen pesticides (alachlor and deltamethrin) were considered as target analytes. Elution conditions that could influence the efficiency of the SPE were studied. The optimized methodology exhibited good linearity, with determination coefficients of better than 0.996. The analytical recovery for the target analytes ranged from 70 to 100%, while the within-day precision was 4.0–11.5 %. The data also showed that the nature of the aqueous matrice (ultrapure, surface or drinking water) had no significant effect on the recovery. The quantification limits for the analytes were found to be 0.01–0.13 μg/L (except for deltamethrin, which was 1.0 μg/L). The present methodology is easy, rapid and gives better sensitivity than solvent drop microextraction for the determination of organonitrogen and organophosphate pesticides in drinking water at levels associated with the legislation.     

Photocatalytic activity of CaTiO3 synthesized by solid state,sol–gel and hydrothermal methods

Journal of Sol-Gel Science and Technology - The structures and compositions of CaTiO3 samples synthesized by solid state, sol–gel, and hydrothermal methods were characterized by various means...     

Synthesis and characterization of sol–gel derived ZrV2O7 fibers with negative thermal expansion property

Novel ZrV₂O₇ fibers with negative thermal expansion were prepared via combination of sol–gel process and thermal decomposition. The as-prepared fibers were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy and Raman spectroscopy. The results showed that the synthetic pH value had little influence on the crystal structure of products while showed significant effect on morphology. The fibers obtained at pH = 9 exhibited cylindrical morphology and its mean diameter was about 1 μm. The thermal expansion property of the as-prepared fibers was investigated by in situ XRD and thermal mechanical analyzer. All of the as-prepared fibers showed positive thermal expansion first and then negative thermal expansion, resulting from a phase transition from 3 × 3 × 3 superstructure to 1 × 1 × 1 cubic structure. The macro thermal expansion coefficients of ZrV₂O₇ ceramic rods increased with decreasing of fiber diameter. The mechanism of the phase transition was also discussed.     

Preparation of sol–gel materials doped with ionic liquid and extractant for cerium(III) extraction

Silica materials (ILDEHPASGs) consisting of ionic liquids and di-(2-ethylhexyl)phosphoric acid (DEHPA) for Ce(III) extraction was prepared by a sol–gel method using the hydrophobic ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate ([C₈mim]PF₆) as porogen and solvent medium. The ILDEHPASGs were characterized by scanning electron microscopy, Brunauer–Emmett–Teller surface area, Fourier transform infrared, and thermogravimetric analyses. The results indicated the doping of DEHPA and [C₈mim]PF₆ in ILDEHPASG-3 would evidently affect the formation of porous structure of sol–gel materials. ILDEHPASG-3 also possessed more channels and macropores than the blank sorbent; the surface area and pore volume of ILDEHPASG-3 were 409 m² g^?1 and 0.444 cm³ g^?1, respectively. [C₈mim]PF₆ and DEHPA were only physically confined or entrapped in the growing covalent silica network rather than chemically bound to the inorganic matrix. The majority of [C₈mim]PF₆ and DEHPA were stably immobilized in the gel. Then, the effects of contact time and pH were determined. The results showed the sorption of Ce(III) strongly depended on the contact time and pH, and ILDEHPASGs had high sorption ability for Ce(III). The results were analyzed by both Langmuir and Freundlich adsorption isotherm models, and the latter was found to give a better fit.