Development of a novel colorimetric indicator pad for detecting aldehydes

A colorimetric indicator was developed and a colorimetric indicator pad was fabricated for the rapid detection of aldehydes. The detection pad has two sides: an observation side on top and a barrier on the bottom. The top side contains a reagent which reacts directly with aldehydes to produce a color change, while the bottom side is coated with a double-sided plastic tape barrier to prevent the escape of chemicals. Sensitivity of the indicator pads was determined using the vapor sensitive ASTM F739 technique with the presence of the indicator. A significant indicator color change (yellow to red) occurred about 5 min before the infrared analyzer response of the ASTM method. The chemical principle and reaction characterization of the test are described. The stability and potential interferences of the indicator pad were also examined by directly spiking aldehydes and compounds with other functional groups, respectively, onto the indicator pads. The newly developed aldehyde indicator pad should find utility in detecting aldehydes in both liquid and vapor phases and in collecting aldehyde permeation through PPE for further study.     

Effect of TiO2–Ti and TiO2–TiN composite coatings on corrosion behavior of NiTi alloy

Two kinds of biocompatible coatings were produced in order to improve the corrosion resistance of nickel titanium (NiTi) alloy. A titanium oxide–titanium (TiO₂–Ti) composite was coated on NiTi alloy using electrophoretic method. After the coating process, the samples were heat‐treated at 1000 °C in two tube furnaces, the first one in argon atmosphere and the second one in nitrogen atmosphere at 1000 °C. The morphology and phase analysis of coatings were investigated using scanning electron microscopy and X‐ray diffraction analysis, respectively. The electrochemical behavior of the NiTi and coated samples was examined using polarization and electrochemical impedance spectroscopy tests. Electrochemical tests in simulated body fluid demonstrated a considerable increase in corrosion resistance of composite‐coated NiTi specimens compared to the non‐coated one. The heat‐treated composite coating sample in nitrogen atmosphere had a higher level of corrosion resistance compared to the heat‐treated sample in argon atmosphere, which is mainly due to having nitride phases. Copyright © 2014 John Wiley & Sons, Ltd.     

Evaluation of silica gel cartridges coated in situ with acidified 2,4-dinitrophenylhydrazine for sampling aldehydes and ketones in air

A procedure for coating in situ silica gel in prepacked cartridges with 2,4-dinitrophenylhydrazine (DNPH) acidified with hydrochloric acid is described. The coated cartridge was compared with a validated DNPH impinger method for sampling organic carbonyl compounds (aldehydes and ketones) in diluted automotive exhaust emissions and in ambient air for subsequent analysis of the DNPH derivatives by high performance liquid chromatography. Qualitative and quantitative data are presented that show that the two sampling devices are equivalent. The coated cartridge is ideal for long-term sampling of carbonyls at sub to low parts-per-billion level in ambient air or for short-term sampling of carbonyls at low ppb to parts-per-million level in diluted automotive exhaust emissions. An unknown degradation product of acrolein has been tentatively identified as x-acrolein. The disappearance of acrolein in the analytical sample matrix correlates quantitatively almost on a mole for mole basis with the growth of x-acrolein. The sum of the concentration of acrolein and x-acrolein appears to be invariant with time.     

Yttria‐based sol–gel coating for capillary microextraction online coupled to high‐performance liquid chromatography

This work about the development of yttria‐based polymeric coating using [bis(hydroxyethyl) amine] terminated polydimethylsiloxanes and yttrium trimethoxyethoxide inside the capillary. The coated capillary was utilized for online capillary microextraction and high‐performance liquid chromatography analysis. The prepared coating material was characterized using scanning electron microscopy, X‐ray photoelectron spectroscopy, energy dispersive X‐ray spectrometry, and thermogravimetric analysis. The coated capillary with polymer presented better extraction efficiency compared with the pure yttria‐based coated capillary with applicability in extreme pH environments (pH 0–pH 14). Excellent extraction towards polyaromatic hydrocarbons, aldehydes, ketones, alcohols, phenols, and amides was observed with limit of detection ranging from 0.18 to 7.35 ng/mL (S/N = 3) and reproducibility in between 0.6 and 6.8% (n = 3). Capillary‐to‐capillary extraction analysis has presented reproducibility between 4.1 and 9.9%. The analysis provided linear response for seven selected phenols in the range of 5–200 ng/mL with R² values between 0.9971 and 0.9998. The inter‐day, intra‐day, and capillary‐to‐capillary reproducibility for phenols was also <10%. Real sample analysis by spiking 5, 50, and 200 ng/mL of phenols in wastewater and pool‐water produced recovery between 84.7 and 94.3% and reproducibility within 7.6% (n = 3).     

N,N-二甲基甲酰胺中电沉积制备镁镍储氢合金

采用恒电位沉积法, 选用适宜的添加剂和络合剂, 成功地从N,N-二甲基甲酰胺(DMF)中沉积出致密的黑色Mg-Ni储氢合金膜. 并初步探讨了其共沉积机理. XRD显示沉积层中含有非晶态Mg-Ni相和微晶态Mg相. SEM图及相应能谱图分析表明合金颗粒以团聚状态存在, 合金成分不是很均匀. AAS分析表明沉积合金中Mg的原子摩尔分数达27.3%. LAND电池测试系统测得所镀合金膜的放电比容量最高为172.4 mAh/g.     

Electrochemical Behavior of Dental Ni‐Cr Wirolloy Coated with Eco‐friendly Films in Artificial Saliva

The electrochemical corrosion behavior of the non‐precious Ni‐Cr Wirolloy, being used in dentistry, was investigated before and after applying of two types of eco‐friendly coatings, polyvinyl silsesquioxane (PVS) and nano‐hydroxyapatite (nHAP) separately in artificial saliva solution at 37 °C for 14 d of immersion. The study aimed to investigate the effectiveness of the introduced coating films in enhancing the corrosion resistance of the alloy, and in decreasing the leaching of the toxic Ni ions from the alloy into the environment. The electrochemical corrosion investigation methods used are; open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. The evaluated results revealed that the electrochemically coated alloy with PVS. prepared at cathodic potential showed higher corrosion resistance and more stable film compared to that prepared by conventional dip‐coating method. At the same time, the nHAP electrochemically coated film provided the best anti‐corrosion properties over all examined time intervals. The obtained results were confirmed via surface analysis, which assured the formation of the prepared coatings on the alloy surface. Chemical analysis of the corrosion product/solutions showed that the effect of electrochemically deposited nHAP and PVS. polymer films in suppression of Ni ions leaching is similar and slightly higher than that of the chemically coated PVS. one; however, all of them are efficient in decreasing the leaching of the risky Ni ions into the solution.     

陶瓷基钯银合金膜制备技术及性能研究

报道采用浆料涂敷与化学镀相结合法在陶瓷支撑上沉积钯银合金膜,采用浆料涂敷法,将含钯银的浆料涂敷在支撑体上,干燥后热分解,使支撑体表面沉积部分钯银。然后,采用化学镀在50℃下沉积钯银膜,热处理后,得到表面较光洁、厚度约为3μm、银含量为23%(原子百分含量)、合金化较完全的钯银合金膜,该膜在压差为0.1MPa,温度为300℃时的渗氢通量达45cm^3(STP)/(cm^2·min),分离因子达500,研究了钯银合金膜中银含量随热处理温度的变化规律,由实验结果发现,银逐渐向表面扩散,并在一定的温度条件达到基本平衡。     

Electrochemical detection of amino acids at carbon nanotube and nickel-carbon nanotube modified electrodes

The oxidation and enhanced detection of traditionally 'non-electroactive' amino acids at a single-wall carbon nanotube (SWNT) surface and at a nickel hydroxide film electrochemically deposited and generated upon the SWNT layer is reported. Different CNT are compared, with Nafion-dispersed SWNT offering the most favorable layer for constant-potential amperometric detection. Factors affecting the oxidation process, including the pH or applied potential, are assessed. The response of the SWNT-Nafion coated electrode compares favorably with that of copper and nickel disk electrodes under flow injection analysis (FIA) conditions. The electrodeposition of nickel onto the SWNT-Nafion layer (Ni-CNT) led to a dramatic enhancement of the analytical response (vs. that observed at the SWNT or nickel electrodes alone). The oxidative process at the Ni(OH)(2) layer has been studied and the increase in sensitivity rationalized. In the presence of amino acid the Ni-CNT layer undergoes an electrocatalytic process in which the amino acid reduces the newly formed NiO(OH) species. Furthermore, the attractive response of both the CNT and Ni-CNT layers has allowed these electrodes to be used for constant-potential FIA of various amino acids and indicates great promise for monitoring chromatographic effluents. Once again an improved signal was observed at the Ni-CNT electrode compared to nickel deposited upon a bare glassy carbon electrode (Ni-GC).     

Development of a multiresidue method for analyzing herbicide and fungicide residues in bovine milk based on solid-phase extraction and liquid chromatography-tandem mass spectrometry

The adverse effect of reactive chemical residues on the quality of drug products has necessitated the determination of low-molecular-weight aldehydes in pharmaceutical excipients. An analytical methodology for the detection of trace amounts of C1-C8 aliphatic aldehydes and benzaldehyde in excipients is described. The proposed procedure is based on the derivatization of aldehydes in aqueous solution with O-2,3,4,5,6-(pentafluorobenzyl) hydroxylamine hydrochloride (PFBHA), followed by static headspace gas chromatographic (SHS-GC) analysis of PFBHA aldehyde oximes with negative chemical ionization (NCI) MS detection. The method developed was demonstrated to be simple, selective, sensitive, and was successfully applied to the screening of aldehydes at sub-microg/g levels in over 30 typical excipients. The most abundant aldehydes found in the samples were formaldehyde and acetaldehyde, for which a rapid and reliable routine quantification method by readily available SHS-GC instrumentation coupled with flame-ionization detection was also developed and validated.     

Parts per quadrillion level ultra-trace determination of polar and nonpolar compounds via solvent-free capillary microextraction on surface-bonded sol-gel polytetrahydrofuran coating and gas chromatography-flame ionization detection

Sol-gel polytetrahydrofuran (poly-THF) coating was developed for high-sensitivity sample preconcentration by capillary microextraction (CME). Parts per quadrillion (ppq) level detection limits were achieved for both polar and nonpolar analytes through sample preconcentration on sol-gel poly-THF coated microextraction capillaries followed by gas chromatography (GC) analysis of the extracted compounds using a flame ionization detector (FID). The sol-gel coating was in situ created on the inner walls of a fused silica capillary using a sol solution containing poly-THF as an organic component, methyltrimethoxysilane (MTMOS) as a sol-gel precursor, trifluoroacetic acid (TFA, 5% water) as a sol-gel catalyst, and hexamethyldisilazane (HMDS) as a deactivating reagent. The sol solution was introduced into a hydrothermally-treated fused silica capillary and the sol-gel reactions were allowed to take place inside the capillary for 60 min. A wall-bonded coating was formed due to the condensation of silanol groups residing on the capillary inner surface with those on the sol-gel network fragments evolving in close vicinity of the capillary walls. Poly-THF is a medium polarity polymer, and was found to be effective in carrying out simultaneous extraction of both polar and nonpolar analytes. Efficient extraction of a wide range of trace analytes from aqueous samples was accomplished using sol-gel poly-THF coated fused silica capillaries for further analysis by GC. The test analytes included polycyclic aromatic hydrocarbons (PAHs), aldehydes, ketones, chlorophenols, and alcohols. To our knowledge, this is the first report on the use of a poly-THF based sol-gel material in analytical microextraction. Sol-gel poly-THF coated CME capillaries showed excellent solvent and thermal stability (>320 degrees C).     

Simultaneous determination of HCHO,CH3CHO and O(x) in ambient air by hydrazine reagent and hplc

Formaldehyde, acetaldehyde, ozone and nitrogen dioxide in ambient air are simultaneously collected on silica gel cartridges coated with 1-methyl-1-(2,4-dinitrophenyl)hydrazine (MDNPH), where the two aldehydes are derivatized to their respective hydrazones, while the two oxidants are converted into N-methyl-2,4-dinitroaniline (MDNA). The three products are then separated and quantified by HPLC with UV detection at 360 nm. The stoichiometric factors of the MDNPH reactions with O3 and NO2 in laboratory tests correspond to 2.0 +/- 0.1 moles of MDNA per mole of O(x) (O3 + NO2). The limits of detection (LOD) are 0.7 ppbv HCHO, 0.8 ppbv CH3CHO and 1.6 ppbv O(x) for 30 L (1 h) air sampled. The sampling performance is insensitive to relative humidities encountered in real atmospheres. When compared with Sep-Pak DNPH silica cartridges as well as with ozone photometric and nitrogen dioxide chemiluminescent analyzers, the proposed chromatographic method demonstrates a very good accuracy (12% for HCHO, 14% for CH3CHO and 7% for O(x), on the average) under field sampling conditions at concentrations lower than 3 and 1 ppbv, for HCHO and CH3CHO, respectively and ranging from 28 to 62 ppbv for O(x).     

A fast CE method for the achiral separation of methadone and its major metabolites, 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine and 2-ethyl-5-methyl-3,3-diphenyl-1-pyrroline

The utilization of dynamic doubly coated capillaries for a fast separation of methadone and its two major metabolites, 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP) and 2-ethyl-5-methyl-3,3-diphenyl-1-pyrroline (EMDP) was investigated. The coated capillaries were prepared using a polycation of poly(diallyldimethylammonium chloride) and a polyanion of dextran sulfate. A fast achiral separation was developed using the coated capillaries with a BGE of 100 mM phosphate buffer at pH 2.6. Complete achiral separation of methadone, EDDP and EMDP was achieved, with migration times of approximately 4 min. The method offers considerable advantages with respect to BGE simplicity and analysis time compared to previously published CE methods for methadone and its related analytes.     

Transient isotachophoresis of highly saline trace metals under strong electroosmotic flow conditions

Transient isotachophoresis (TITP) is usually performed under low-electroosmotic flow (EOF) conditions using a coated capillary or a low pH background electrolyte. We used a bare fused-silica capillary for TITP stacking of anionic complexes of some heavy metals under high-EOF conditions (pH 9.0). The sample component chloride as a leading electrolyte induced stacking by an isotachophoretic mechanism and the complexing agent 4-(2-pyridylazo) resorcinol (PAR) acted as a terminating electrolyte. The optimized background electrolyte was composed of 150 mM N-tris(hydroxymethyl)methyl-3-aminopropanesulfonic acid, 127 mM triethylamine, and 0.1 mM PAR at pH 9.0. The strong EOF at pH 9.0 pulled the analytes against their mobilities toward the outlet side, allowing a separation in the normal polarity mode. The stacking efficiency, reproducibility, analysis time, and sample loading capacity in coated and bare capillaries were compared. The stacking efficiency and reproducibility were higher and the analysis time was shorter in the coated capillary. However, a larger volume of a sample could be injected in the bare capillary to achieve detection limits comparable to those for the coated one without compromising the resolution between the analyte peaks. The limits of detection (S/N = 3) were in the sub-ppb range for the selected metals (Fe2+, 0.3 ppb; Ni2+, 0.16 ppb; and Zn2+, 0.8 ppb) in a standard saline sample with 250 mM NaCl matrix. The proposed method was successfully applied to the analysis of reference urine samples and human urine samples.     

The evolution of growth morphology and corrosion behavior of electrodeposited Ni–P coatings on alumina borate whisker‐reinforced pure aluminum composite

The Ni–P alloy coatings were obtained on alumina borate whisker‐reinforced pure aluminum composite by electro‐deposition. The initial electro‐deposition behavior of the Ni–P alloys on the composite and pure aluminum was studied, respectively. It was found that the composition and the morphology of materials had a distinct effect on the initial electro‐deposition behavior of the Ni–P alloys. The Ni–P alloy coatings preferred to nucleate at the composite as compared with the pure aluminum. Moreover, the Ni–P particles were prone to deposit at the whisker/Al interface in the composite. The Ni–P coatings were barely depositing upon the surface of whisker during the plating process. As the deposition time increased, the Ni–P particles that were deposited on the surface of the composite grew gradually. These Ni–P particles linked to each other and eventually covered the whisker surface. Moreover, it can be found that the surfaces of the composite were gradually covered by Ni–P coatings and the anticorrosion performance of the coated composite increased remarkably with the increase in the deposition time. When the deposition time is 60 min, only the Ni–P diffraction peak could be detected. In this case, the coated composite had significantly better corrosion resistant, which is attributed to the surface of composite was perfectly covered by the Ni–P coatings. Copyright © 2012 John Wiley & Sons, Ltd.     

SiO2 coated Fe3O4 magnetic nanoparticle dispersed multiwalled carbon nanotubes based amperometric glucose biosensor

A new type of amperometric glucose biosensor based on silicon dioxide coated magnetic nanoparticle decorated multiwalled carbon nanotubes (Fe₃O₄@SiO₂/MWNTs) on a glassy carbon electrode (GCE) has been developed. MWNTs have been synthesized by catalytic chemical vapour decomposition (CCVD) of acetylene over rare earth (RE) based AB₃ alloy hydride catalyst. The as-grown MWNTs have been purified and further functionlized. Functionalized MWNTs have been decorated with magnetic Fe₃O₄ nanoparticles which have been uniformly coated with biocompatible SiO₂ using a simple chemical reduction method. The characterization of magnetic nanoparticle modified MWNTs have been done by X-ray diffraction (XRD), Fourier transform infra red spectroscopy (FT-IR), scanning electron microscope (SEM), transmission electron microscope (TEM), vibrating sample magnetometer (VSM), energy dispersive X-ray analysis (EDX) and UV-vis spectroscopy. Amperometric biosensor has been fabricated by the deposition of glucose oxidase (GOD) over Nafion-solubilized Fe₃O₄@SiO₂/MWNTs electrode. The resultant bioelectrode retains its biocatalytic activity and offers fast and sensitive glucose quantification. The performance of the biosensor has been studied using cyclic voltammetry and amperometry and the results have been discussed. The fabricated glucose biosensor exhibits a linear response from 1 μM to 30 mM with an excellent detection limit of 800 nM indicating the potential applications in food industries.     

Electropolymerization of Mefenamic Acid on Copper and Copper Based Alloy as a New Strategy to Control the Release of Copper Ions from Copper Containing Devices

Poly-2-(2,3-dimethylanilino) benzoic acid (PMF) coatings on copper and brass alloy were synthesized by electrochemical oxidation of 2-(2,3-dimethylanilino) benzoic acid in the presence of oxalic acid as the reaction medium. Electrodeposition was carried out using the cyclic voltammetry technique using a silver/silver-chloride standard electrode, with a scan rate of 600 mV min^–1. Smooth and well adhered PMF coatings were electrosynthesized during sequential scanning of the potential in the range–500 mV to 1400 mV on copper and brass alloy. The electrodeposited coatings were characterized by recording the oxidation peaks at 122 mV for Cu and–0.7 mV for brass, in cyclic voltammetry and using scanning electron microscopy (SEM). Corrosion inhibition efficiency of coated copper and brass alloy was investigated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. The impedance results showed that the inhibition efficiency of coated copper is 89% and for coated brass 79.4% compared to the uncoated copper and brass in 0.1 M H₂SO₄.

     

Analysis of aldehydes in excipients used in liquid/semi-solid formulations by gas chromatography-negative chemical ionization mass spectrometry

Monitoring of low-molecular-weight aldehyde levels in excipients used in liquid/semi-solid based capsule (LFC) dosage forms plays a critical role in the development of these pharmaceutical products. A simple, sensitive and specific method based on gas chromatography coupled with mass spectrometry (GC-MS) utilizing an Rtx-5MS capillary column was developed and validated for the detection and quantification of C1-C8 aliphatic aldehydes in LFC excipients at sub-microg/g levels. The proposed procedure is based on the derivatization of aldehydes in 10:1 (v/v) acetonitrile:water with O-2,3,4,5,6-(pentafluorobenzyl) hydroxylamine hydrochloride (PFBHA), followed by direct GC analysis of aldehyde-PFBHA-oxime derivatives with negative chemical ionization (NCI) MS detection. The method developed was successfully applied to the analysis of short chain aldehydes in 30 typical LFC excipients. An example case study on the formation and growth of aldehydes in these excipients under accelerated storage conditions is also reported.     

Mg0.9Ti0.1Ni0.85Co0.15合金的石墨粉及镍粉球磨表面包覆性能

选用非晶态的Mg0.9Ti0.1Ni0.85Co0.15合金粉末与石墨粉及镍粉进行球磨表面包覆。SEM分析结果表明,己包覆石墨和镍粉的合金表面上吸附着一层小的颗粒,形成薄层将原来的合金表面包覆起来。使用XPS分析了合金表面元素。结果表明,包覆石墨粉后,合金表面碳元素的质量分数和原子分数均增加,Mg的质量分数从22.74%减小至22.23%,原子分数从36.43%减小到32.94%,从而减小了Mg在碱液中的腐蚀几率,提高合金的抗腐蚀性能;包覆镍粉后,合金表面Ni的质量分数由59.89%增加到60.04%,原子分数由40.63%增加到41.02%,形成合金表面富Ni的保护层,提高了合金的抗腐蚀性能。充放电循环测试表明,循环30周后,包覆石墨粉的合金电极容量保持率为32.05%,包覆镍粉的合金电极容量保持率为41.26%,而未包覆的电极容量保持率仅为17.88%。合金电极极化曲线测试结果表明,石墨或镍粉的包覆提高了Mg0.9Ti0.1Ni0.85Co0.15合金电极的循环稳定性和在KOH碱液中的抗腐蚀性能。     

Detection of polymerase chain reaction fragments using a conducting polymer-modified screen-printed electrode in a microfluidic device

A simple and fast method for electrochemical detection of amplified fragments by PCR was successfully developed using CE in a microfluidic device with a modified screen-printed carbon electrode (SPCE). The surfaces of the SPCE were modified with poly-5,2'-5',2'-terthiophene-3'-carboxylic acid, which improves the analysis performance by lowering the detection potential, enhancing the S/N characteristics, and avoiding electrode poisoning. DNA fragments amplified by PCR were separated within 210 s in a 75.5 mm-long coated-separation channel at a separation field strength of -200 V/cm. To minimize the sample adsorption into the inner surface of the capillary wall, which disturbs the separation, a dynamically coated capillary with an acrylamide solution was used. Furthermore, the analysis procedure was simplified and rendered reproducible by using 0.50% w/v hydroxyethylcellulose as a separation matrix in a coated channel. The reproducibility of the analysis employing the coated channel yielded RSD of 4.3% for the peak areas and 1.4% for the migration times in eight repetitive measurements at a modified electrode, compared with 21.3 and 9.4% for a bare electrode. The sensitivity of the assay was 18.74 pAs/(pg/microL) with a detection limit of 584.31 +/- 1.3 fg/microL.     

Electrocatalytic detection of insulin at RuOx/carbon nanotube-modified carbon electrodes

A bilayer surface coating, prepared by electrodepositing ruthenium oxide (RuOx) onto a carbon nanotube (CNT) layer, offers dramatic improvements in the stability and sensitivity of voltammetric and amperometric measurements of insulin compared to the individual (CNT or RuOx) coated electrodes. The enhanced electrocatalytic activity towards insulin is indicated from lowering the potential of the oxidation process (starting around 0.35 versus Ag/AgCl) and the substantially higher sensitivity over the entire potential range. A wide linear dynamic range (10-800 nM) was achieved with a detection limit of 1 nM. The marked electrocatalytic activity of the RuOx/CNT coating towards insulin is coupled with a greatly enhanced stability. For example, the insulin amperometric response of the RuOx/CNT-coated electrodes is highly stable, with 97% of the initial activity remaining after 60 min stirring of 2 × 10⁻⁶ M solution (compared to significantly faster current diminutions at the RuOx- or CNT-coated surfaces). The results suggest great promise for miniaturized sensors and detectors for monitoring insulin.