Flow field-flow fractionation and single particle inductively coupled plasma mass spectrometry as a powerful tool for tracking and understanding the sensing mechanism of Ag-Au bimetallic nanoparticles toward cobalt ions.

BACKGROUND: Ag-Au bimetallic nanoparticles (BNPs), synthesized by using citrate reduction of Ag and Au ions, were used as sensor for detection of Co2+. In order to optimize sensing performance, it is necessary to control the particle size and size distribution of the original Ag-Au BNPs. Therefore, analytical methods based on the use of single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) and flow-field flow fractionation (FlFFF)-ICP-MS were developed to track the signal of Ag and Au in bimetallic nanoparticles at each step of the procedure: BNP synthesis, aggregation and sensing in order to understand the sensing mechanism. To better understand colorimetric sensing of Co2+ using Ag-Au BNPs, various solution mixtures were analyzed by using SP-ICP-MS and FlFFF-ICP-MS. RESULTS: SP-ICP-MS provided the information on the core size, size distribution and particle number concentration, as well as the heterogeneity of the particles synthesized by using various citrate concentrations and metal ratios. FlFFF-ICP-MS offered the information on hydrodynamic size as well as the signal intensity ratio of Ag and Au in BNPs and for the understanding of the aggregation of BNPs arising from the [Co(II)(en)3]2+ complex surrounding the surface of the BNPs. Under optimum sensing condition, the use of SP-ICP-MS for BNPs assisted detection of Co2+ improved the sensitivity of Co2+ determination by 20-fold in comparison with the conventional spectrophotometric analysis. SIGNIFICANCE: The information obtained from SP-ICP-MS and FlFFF-ICP-MS can be combinedly used to understand sensing mechanism and to select the best condition for synthesis of BNPs used as sensor. This study illustrates the usefulness of SP-ICP-MS and FlFFF-ICP-MS in the nanoparticle-based sensor development research area.

Quantitative Determination of Iron-Siderophore Complexes in Peat by Isotope-Exchange Size-Exclusion UPLC-Electrospray Ionization High-Resolution Accurate Mass (HRAM) Mass Spectrometry.

A method was developed for the quantification of iron-siderophore complexes by electrospray high-resolution accurate mass (HRAM) mass spectrometry (MS) without the need for authentic standards. The bulk of iron-siderophore complexes was purified by solid-phase extraction (SPE) and concentrated by evaporation. The individual complexes were identified by fast size-exclusion chromatography (FastSEC)-Orbitrap MSn on the basis of the exact molecular mass (±1 ppm) and MS2 or MS3 fragmentation. Their capability to readily exchange the natural 56Fe for the added 58Fe was demonstrated by SEC with ICP MS and ESI MS detection. The method was applied to the analysis of peat sampled in the eastern part of the French Pyrenean mountains. Nineteen siderophores belonging to four different classes were identified and quantified. The results were validated using ICP MS detection of iron by matching the sum of iron complexes determined by isotope exchange-ESI MS within each peak observed by FastSEC-ICP MS.

Microfluidic paper-based analytical devices for simultaneous detection of oxidative potential and copper in aerosol samples.

The potential reach of point-of-care (POC) diagnostics into daily routines for exposure to reactive oxygen species (ROS) and Cu in aerosolized particulate matter (PM) demands that microfluidic paper-based analytical devices (µPADs) take into consideration the simple detection of these toxic PM components. Here, we propose µPADs with a dual-detection system for simultaneous ROS and Cu(II) detection. For colorimetric ROS detection, the glutathione (GSH) assay with a folding design to delay the reaction yielded complete ROS and GSH oxidation, and improved homogeneity of color development relative to using the lateral flow pattern. For electrochemical Cu(II) determination, 1,10-phenanthroline/Nafion modified graphene screen-printed electrodes showed ability to detect Cu(II) down to pg level being low enough to be applied to PM analysis. No intra- and inter-interference affecting both systems were found. The proposed µPADs obtained LODs for 1,4-naphthoquinone (1,4-NQ), used as the ROS representative, and Cu(II) of 8.3 ng and 3.6 pg, respectively and linear working ranges of 20 to 500 ng for ROS and 1 × 10-2 to 2 × 102 ng for Cu(II). Recovery of the method was between 81.4 and 108.3% for ROS and 80.5-105.3% for Cu(II). Finally, the sensors were utilized for simultaneous ROS and Cu(II) determination in PM samples and the results statistically agreed with those using the conventional methods at 95% confidence.

An electrochemical paper-based analytical sensor for one-step latex protein detection.

Exposure to natural rubber latex (NRL) can result in sensitivity to NRL protein with resulting allergic reactions. Low-cost, portable, simple, sensitive analytical tools for NRL protein measurements are needed for rapid and accurate assessments of allergenic risks at the point-of-care (POC) instead of using traditional methods that require large and expensive instruments, long-time analysis, and complex sample preparation steps. Here, an electrochemical paper-based analytical device (ePAD) is presented by combining sample preparation and electrochemical detection within a single device to offer a one-step NRL analysis. The lack of antibodies and/or enzymes against NRL makes POC analysis difficult. In this work, detection is based on electrochemical measurement of the remaining Cu after in situ protein complexation instead of more complex biological assays for the first time. Graphene screen-printed electrodes modified with 1,10-phenanthroline and Nafion were used in the ePAD to improve Cu signal 18-fold relative to unmodified carbon screen-printed electrodes. The optimum parameters including 1,10-phenanthroline concentration, reaction time between Cu and protein, and the starting Cu concentration were 5% w/v, 1 min, and 600 µg mL-1, respectively. In addition to short analysis time (4 min), the system selectivity indicated no other interfering species affecting protein detection. The proposed ePAD achieved an LOD of 3.0 mg dL-1 and a linear range of 10.0-200.0 mg dL-1. Finally, the proposed sensors were applied for NRL protein detection and the results were not significantly different from the traditional Lowry method at 95% confidence.

A novel sensor based on bead-counting of purple sweet potato tapioca pearl for freshness monitoring of shrimp.

A novel sensor based on bead-counting of purple sweet potato tapioca pearl for freshness monitoring of shrimp was proposed. The sensor was prepared from commercially available tapioca pearls with purple sweet potato as a natural colorant by using a similar procedure as to prepare "Thai Saku dessert". A novel concept of using five tapioca pearls stacked in a pipette tip was proposed to observe the color change of the pearls by bead counting approach. The color of the tapioca pearl changed from purple to greenish-blue upon the detection of volatile amines and then to green on prolonged exposure to volatile amines. This color change was observed from the first bead and gradually observed on the next beads according to the concept of distance-based colorimetric measurement. This work is the first to demonstrate the use of bead counting as a novel, low-cost sensor technology for estimating the freshness of shrimp.

Use of single particle inductively coupled plasma mass spectrometry for understanding the formation of bimetallic nanoparticles.

Bimetallic nanoparticles (NPs), including core-shell structure and bimetallic alloy nanoparticles, were synthesized and characterized using flow field-flow fractionation (FlFFF), single particle inductively coupled plasma mass spectrometry (SP-ICP-MS), and transmission electron microscope (TEM) with energy-dispersive x-ray spectroscopy (EDS). For the core-shell particles, a nominal 80 nm commercial core-shell AuAg bimetallic nanoparticle was used to examine the applicability of SP-ICP-MS to determine the core size of Au and shell thickness of Ag. Then, the method was applied to estimate the core size of Au and shell thickness of Ag for the laboratory synthesized particles. The results were compared with those obtained from TEM-EDS. For the alloy nanoparticles, two synthesis protocols, based on the galvanic replacement of Ag seed particles with Au, were used. One was to prepare a hollow AgAu particle by varying the volume of dissolved Au in basic solution (K-gold) to etch some parts of AgNPs to dissolved ionic silver with the formation of AuNPs covering the remaining AgNPs, producing a hole inside the core nanoparticles. Another protocol was to prepare AgAu alloy nanoparticles. SP-ICP-MS was used in combination with FlFFF to provide information on the changes of particle size with varying volume of K-gold reagent. Hydrodynamic diameter increased with increasing K-gold, as observed by FlFFF. With SP-ICP-MS without prior FlFFF, bimodal distributions were observed in the size distribution of Au and Ag. With prior FlFFF, monomodal distributions were observed by SP-ICP-MS, which allow the use of particle concentration and size to estimate the mass concentration of elements on the fractionated bimetallic nanoparticles. This study illustrates the potential use of SP-ICP-MS for gaining information about particle transformation during the synthesis of bimetallic nanoparticles.

Use of electrical field-flow fractionation for gold nanoparticles after improving separation efficiency by carrier liquid optimization.

Electrical field-flow fractionation (ElFFF) is a useful separation technique for nanoparticles, however, it has been limited by polarization/electrical double layer formation which reduces an effective field for separation. With an appropriate direct current (DC) applied voltage, sodium carbonate, FL-70, Triton X-100 and acetonitrile were explored as additive substances for preparation of carrier liquid used in normal ElFFF to enhance an amplitude of effective field by their ionic redox-active species, ionic and nonionic surfactant and wide electrochemical potential window nonionic organic solvent properties, respectively. Effective field was indirectly measured in each carrier liquid by investigating retention behavior of polystyrene latex nanoparticles and gold nanoparticles. Effective field improvement was observed in all carrier liquid types (except FL-70) by which the highest effective field existed in 16 µM sodium carbonate at 1.70 V and 0.01% (V/V) Triton X-100 and 50% (V/V) acetonitrile at 1.90 V as compared to deionized water at 1.90 V. In addition, those carrier liquids were applied for separation of 5 nm and 15 nm gold nanoparticles mixture by which Triton X-100 exhibited the best separation resolution (Rs = 1.11).

Dietary Intake and Milk Micronutrient Levels in Lactating Women with Full and Partial Breastfeeding.

BACKGROUND: Micronutrient intake and status in lactating women may impact micronutrient levels in milk. OBJECTIVES: This study aimed to determine the micronutrient intake and status in lactating women, and their association with micronutrient levels in human milk. METHODS: Lactating women were enrolled at 4-6 months postpartum. A 24h food recall was examined and nutrient intakes were analyzed using INMUCAL software. Human milk samples were collected to analyze calcium, copper, iron, and zinc levels. Plasma zinc and serum ferritin levels were determined. RESULTS: Thirty-four women participated; 19 were classified as full breastfeeding and 15 as partial breastfeeding. Mean levels of calcium, copper, iron, and zinc in human milk were 243, 0.2, 0.2, and 1.56 mg/L, respectively. The prevalence of zinc deficiency (plasma zinc < 10.7 µmol/L) was 11.8%. No lactating women had iron deficiency. Nutrient intakes were lower than the recommended amounts in 38%-70% of participants, and were not correlated with corresponding nutrient levels in human milk. Multiple linear regression showed significant association between zinc levels in human milk and plasma for lactating women with full breastfeeding (ß = 0.034, 95% confidence interval [0.003, 0.067], p = 0.040). CONCLUSIONS: Lactating women were at risk of micronutrient deficiency. There was an association between zinc levels in human milk and plasma of lactating women with full breastfeeding. As the nutritional status of lactating women influences the quality of human milk, we should encourage good nutrient intake for lactating women.

Novel paper-based colorimetric immunoassay (PCI) for sensitive and specific detection of salbutamol residues in flesh of swine and urine using Ag3 PO4 /Ag nanocomposite as label.

Salbutamol (SAL) can cause potential hazards to human health and its use as a growth promoter in meat-producing animals is illegal. This work reports a novel approach for competitive paper-based colorimetric immunoassay (PCI) using the Ag3 PO4 /Ag nanocomposite as label for sensitive and specific determination of SAL in flesh of swine and urine. The Ag3 PO4 /Ag nanocomposite was synthesized by a one-step chemical bath method, which could instantly oxidize a chromogenic substrate for the color development under acidic conditions without the participation of H2 O2 . This approach provides high affinity between the Ag3 PO4 /Ag nanocomposite and the substrate (with the Michaelis-Menten constant of 0.44 mM). In addition, the fabrication process of the PCI was simple and cost-effective. Particularly, the novel PCI also exhibits simplicity and cost-effectiveness of the fabrication process through a simple wax screen-printing, which requires inexpensive equipment and material including a screen, wax, a squeegee, and a hair dryer. Under optimal conditions, the competitive PCI exhibited a linearity range of 0.025 to 1.00 µg/L. The developed approach offers advantages over the conventional ELISA for the purpose of routine use because it requires a shorter incubation time (<1 hr), significantly small volumes of reagents and samples (<100 µL each), and an inexpensive consumer-grade digital camera coupled with a simple gray-scale transformation of the RGB (Red Green Blue) color image for the purpose of quantification of the detection. PRACTICAL APPLICATION: Salbutamol (SAL) can cause potential hazards to human health and the use of which as growth promoter in meat-producing animals is illegal. This work introduces a novel approach for competitive immunoassay on paper-based colorimetric immunoassay using the Ag3 PO4 /Ag nanocomposite as the label (instead of using natural enzyme) for low-cost, sensitive, and specific determination of SAL residues at low level in flesh of swine and urine samples. The proposed approach offers advantages over the conventional ELISA for the purpose of routine use.

Use of flow field-flow fractionation and single particle inductively coupled plasma mass spectrometry for size determination of selenium nanoparticles in a mixture.

Various analytical techniques have been used for size analysis of selenium nanoparticles (SeNPs). These include flow field-flow fractionation (FlFFF), single particle inductively coupled plasma mass spectrometry (SP-ICP-MS), dynamic light scattering (DLS) and transmission electron microscopy (TEM). For hydrodynamic diameter estimation, the FlFFF technique was used and the results were compared with those analyzed by DLS. For core diameter estimation, the results obtained from SP-ICP-MS were compared with those from TEM. Two types of FlFFF channel were employed, i.e., symmetrical FlFFF (Sy-FlFFF) and asymmetrical FlFFF (Asy-FlFFF). Considering the use of FlFFF, optimization was performed on a Sy-FlFFF channel to select the most appropriate carrier liquid and membrane in order to minimize problems due to particle membrane interaction. The use of FL-70 and 10 kDa RC provided an acceptable compromise peak quality and size accuracy for all samples of SeNPs which were coated by proteins (positively charged SeNPs) and sodium dodecyl sulfate (negatively charged SeNPs). FlFFF always yielded the lower estimate of the hydrodynamic size than DLS as a reference method. The results obtained by SP-ICP-MS were consistent with the TEM method for the core diameter estimation. The results from FlFFF and the DLS reference method were significantly different as confirmed by paired t-test analysis, while the results provided by SP-ICP-MS and the TEM reference method were not significantly different. Furthermore, consecutive size analysis by SP-ICP-MS for the fractions collected from FlFFF was proposed for sizing of SeNP mixtures. The combined technique helps to improve the size analysis in the complex samples and shows more advantages than using only SP-ICP-MS.

Exploring the applicability of nano-selenium for capture of mercury vapor: Paper based sorbent and a chemical modifier in graphite furnace atomic absorption spectrometry.

The ability of the selenium nanoparticles (SeNPs) to capture mercury (Hg) is a subject of interest as this concept can be applied to reduce mercury poisoning cases to certain extent. In this work, SeNPs were fabricated on a paper and used as sorbent for capturing mercury vapor. The formation of the stable HgSe on the paper sorbent after the sequestration was visible to the naked eye for mercury concentration of higher than 200 µg L-1, corresponding with the discoloration of the paper sorbent from dark orange to gray color. The gray color was more intense with increasing Hg concentrations from 200 to 300, 500, and 1000 µg L-1. Therefore, color analysis software was used as a semi-quantitative technique for mercury analysis. The mercury captured was also analyzed with the inductively coupled plasma mass spectrometry (ICP-MS). After confirming that SeNPs helps capture mercury, it was further applied as a chemical modifier in graphite furnace atomic absorption spectrometry (GFAAS) for mercury determination. The SeNPs (410 mg L-1) allowed the use of pyrolysis temperature up to 300 °C with adequate sensitivity. Calibration curve was constructed from 100 to 500 µg L-1 with good linearity (R2 = 0.9968). With the use of SeNPs, 15 times sensitivity improvement was obtained compared to that without the use of any chemical modifier. The detection limit (N = 10 at 3σ) was calculated at 2 µg L-1 for the Hg standard. The proposed modifier was used for analyzing mercury in the saliva sample. Apart from minimizing extensive sample pretreatment process, the recovery percentage of Hg from the spiked sample was found to be approximately 90% (RSD 0-2%) with the help of the SeNPs modifier. This work exhibits multi-dimensional applications of SeNPs towards mercury analysis.

Performance evaluation of flow field-flow fractionation and electrothermal atomic absorption spectrometry for size characterization of gold nanoparticles.

Flow field-flow fractionation (Fl-FFF) coupled off-line with electrothermal atomic absorption spectrometry (ETAAS) was applied for particle size characterization of gold nanoparticles (AuNPs). Effects of carrier liquid and membranes on the Fl-FFF separation performance were studied in order to achieve the best separation condition for AuNPs before ETAAS analysis. The separation of AuNPs was investigated with the use of 10 kDa regenerated cellulose (RC) and 10 kDa polyethersulfone (PES) membrane and three types of carrier solution including deionized water (DI water), 0.05% SDS (sodium dodecyl sulfate), and 0.02% FL-70 with 0.02% NaN3. Using DI water with 10 kDa RC membrane provided the best separation performance for AuNPs. Fractions eluted from Fl-FFF were collected and introduced into ETAAS for gold detection. With ETAAS, the time at the maximum absorbance increased when the particle size increased. The in-house synthesized AuNPs were characterized by using Fl-FFF with ETAAS, dynamic light scattering (DLS), and transmission electron microscopy (TEM) technique and the results obtained were in good agreement. Statistical comparison between Fl-FFF and DLS (texperiment = 1.02), ETAAS after Fl-FFF and TEM (texperiment = 0.96) showed no significant difference using paired t-test with the critical value of t as 4.30 (P = 0.05). The experimental results indicated that the size of AuNPs from two methods, Fl-FFF with DLS for hydrodynamic diameter and ETAAS with TEM for core size, were not significantly different at P = 0.05.

Screen-printed microfluidic paper-based analytical device (µPAD) as a barcode sensor for magnesium detection using rubber latex waste as a novel hydrophobic reagent.

This work reports the first use of cis-1,4-polyisoprene obtained from rubber latex (RL) waste as the hydrophobic reagent for the fabrication of a microfluidic paper-based analytical device (µPAD), providing a user-friendly means for magnesium detection. The µPAD was fabricated using a screen printing technique and the barcode-like paper sensor was then used for the detection of Mg(II) ions in RL and water samples. Using different types of paper media (paper towel, Whatman No.1 and Whatman No.4), the results indicate that the key factors in optimizing the quality of the fabricated µPAD include the viscosity of cis-1,4-polyisoprene solution which could be adjusted using different solvents and heating temperatures, the mesh screen size, the pore size of the paper substrates, and the dimension of the sample zone. The fabricated µPAD, which showed high chemical resistance, durability and design flexibility, was tested for the detection of Mg(II) ions using the reaction based on complexometric titration with EDTA where Eriochrome Black T was used as an indicator. An Android application "UBU OMg Sensor" was also developed to provide a simple, fast, and accurate means for end-users to interpret results generated by our developed µPAD.

Flow field-flow fractionation for hydrodynamic diameter estimation of gold nanoparticles with various types of surface coatings.

Flow field-flow fractionation (FlFFF) with inductively coupled plasma mass spectrometric (ICP-MS) detection was applied for estimating the hydrodynamic diameter of gold nanoparticles (AuNPs). Hydrodynamic diameters of AuNPs of the same core diameter but with different surface coatings were different because the coating agents and their properties were different. The challenge of this work is due to the fact that AuNPs with various types of surface coatings exhibited different interactions in the FlFFF channel, leading to different retention behaviors. Therefore, we are interested in finding suitable FlFFF conditions for estimating the hydrodynamic diameter of AuNPs with various types of electrostatic stabilizing agents [tannic acid (TA) and citrate (CT)] and steric stabilizing agents [polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), and branched polyethylene imine (BPEI)]. Different types of carrier liquids (DI water, 0.02% FL-70, 0.05% SDS, and 30 mM Tris buffer) and membrane materials [regenerated cellulose (RC) and polyethersulfone (PES) membranes] were investigated. Generally, FlFFF was applied for size characterization of nanoparticles based on FlFFF theory but the interactions between AuNPs and membrane affected the retention and the experimentally obtained hydrodynamic diameters of AuNPs from the FlFFF system. With DI water as a carrier liquid with RC or PES membranes, the hydrodynamic diameters of negatively charged particles (TA-, CT-, PVP-, and PEG-stabilized AuNPs) from FlFFF corresponded well with the hydrodynamic diameters from dynamic light scattering (DLS). Interestingly, it was possible to estimate hydrodynamic diameters of AuNPs in the mixture by using FlFFF whereas it was not possible with the use of DLS within the size range studied. This work summarized the possible interactions between AuNPs with various coating agents and membrane materials in different carrier liquids to give guidelines on the suitable conditions of FlFFF for further applications on AuNP hydrodynamic diameter estimation.

Alternative Patterning Methods for Paper-based Analytical Devices Using Nail Polish as a Hydrophobic Reagent.

A rapid, easy, and cost effective fabrication method for paper-based analytical devices (PADs) is described. This newly developed method is based on the use of nail polish as an alternative hydrophobic reagent, and the nail polish was resistant to basic and organic solvents. Three approaches for fabrication of paper-based analytical devices (PADs) were investigated, namely writing, stamping, and spraying. The writing approach was carried out by drawing the hydrophobic area of a pre-designed pattern on filter paper with a simple lab-made pen filled with nail polish as the hydrophobic agent. The stamping and spraying approaches required the use of a designed mask, which was made by laser cutting of the magnet rubber sheet. With laser cutting, two types of templates were made, i.e., positive and negative counterparts. The positive counterpart was the inside pattern and the negative counterpart was the outside pattern of the magnet sheets. For the stamping approach, the negative counterpart of the magnet rubber mask was attached onto a simple rubber stamper that was then stamped onto filter paper after loading with nail polish solution. With the spraying method, the positive counterpart was used to cover the hydrophilic area on the paper. Then, the nail polish solution was used with an air brush and sprayed on the paper covered with the magnet rubber mask. All approaches were cost effective and required neither extra equipment nor any pretreatment step. Among all three methods, however, the spraying method was found most suitable for mass production and provided the best resolution when compared with the other two approaches. With this approach, the actual channel widths obtained were similar to the designed widths, with the narrowest possible channel width of 650 µm. Furthermore, a nail polish-treated PAD was prepared by soaking the paper in the nail polish solution. The ability of the nail polish-treated PAD was examined for its resistance to a strong basic solution and an organic solvent (up to 30% ethanol and dichloromethane). The nail polish-treated paper also showed the potential to be used as an organic-aqueous separator.

High Urinary Iodine Concentration Among Breastfed Infants and the Factors Associated with Iodine Content in Breast Milk.

Iodine deficiency in infants leads to delayed growth and development. Some studies have reported iodine deficiency among infants and lactating women. We assessed iodine status in infants and lactating women, as well as the iodine content in breast milk. A cross-sectional study enrolled mother-infant pairs (infants aged 4-6 months), who visited Well Child Clinic at Ramathibodi Hospital, Bangkok, Thailand. Infants were classified by feeding type as breastfed (BF), mixed breastfed and formula-fed (MF), and formula-fed (FF). Demographic and perinatal data were collected. The urinary iodine concentration (UIC) of infants and lactating women, and breast milk iodine concentration (BMIC) were analyzed. Seventy-one infants were enrolled. The median UIC of infants was 282 mcg/L. Breastfed infants had higher median UIC than formula-fed infants (553 vs. 192 mcg/L; p = 0.002). Forty-eight percent of infants had a UIC more than 300 mcg/L. The median UIC and BMIC of lactating women were 149 and 255 mcg/L, respectively. Among the BF group, the infant UIC was correlated with maternal UIC (rs = 0.857, p = 0.014). Multiple linear regression showed the BMIC to be associated with maternal UIC (ß = 4.03, 95% CI [1.34, 6.71]) and maternal weight (ß = 8.26, 95%CI [2.76, 13.77]). Iodine nutrition among our study population was adequate. The median UIC of infants and lactating mothers were 282 and 149 mcg/L, respectively. Breastfed infants had a significantly higher median UIC than formula-fed infants. The BMIC was associated with maternal UIC and maternal weight.

Complexometric and argentometric titrations using thread-based analytical devices.

This work describes analytical approaches based on simple complexometric and argentometric titrations leading to the color change of a novel microfluidic thread-based analytical device (µTAD). The device was fabricated from a cotton thread (15 cm) treated with indicator solution, providing an easy-to-use platform for rapid measurement of analyte concentration in aqueous solution. The thread was immobilized onto a support, being a polypropylene sheet or box platform, to facilitate loading of liquid samples. Interaction between the deposited reagents and analytes in the samples then occurred within a few minutes. This resulted in zones of color change with different lengths along the thread depending on the analyte concentration. The interaction zones can be analyzed by human eyes based on comparison of the zone lengths with the printed scales which are correlated with the analyte concentrations. Complexometric titration using µTADs was initially investigated for Mg(II) determination in water and rubber latex samples. These devices consisted of two threads which were pretreated with Eriochrome Black T (EBT) and then treated with ethylenediaminetetraacetic acid (EDTA) in N-cyclohexyl-3-aminopropanesulfonic acid (CAPS) buffer at pH 10. Both threads were tied together with a central knot before being attached to the box platform prior to the analysis. Load of sample solution (6 µL) resulted in the length of red-violet color product on the threads being proportional to the concentration of Mg(II) in waters and rubber latex samples with the working concentration range of 25-1000 mg L-1. In addition, µTAD with a supporting polypropylene sheet consisting of several threads treated with AgNO3 and K2CrO4 indicators was applied for argentometric titration of chloride ion in water and food seasoning samples. After sample loading (3 µL), the initially red-brown threads turned into white corresponding to formation of AgCl(s) on the threads with a working concentration range of 75-600 mg L-1. Greater selectivity towards Mg(II) and chloride compared with potential interference ions was also observed. All the developed µTADs were applied for analysis of real samples which showed results being in agreement with those obtained by classical titrations.

Development of pure certified reference material of stevioside.

Pure stevioside was extracted from leaves of Stevia rebaudiana (Bertoni) to be used as a reference material in the instrument calibration or method validation process. The mass fraction was determined by comparison between the mass balance method and quantitative nuclear magnetic resonance (qNMR) spectroscopy. The impurities in the sample were analyzed by Karl Fischer titration for moisture content and thermogravimetric analysis for inorganic residue. Homogeneity, together with short term and long term stability, were also studied and the uncertainty was reported. The certified value of this mass fraction is 0.986 ±â€¯0.0019 (k = 2) with 1 year stability.

Use of electrothermal atomic absorption spectrometry for size profiling of gold and silver nanoparticles.

Electrothermal atomic absorption spectrometry (ETAAS) was applied to investigate the atomization behaviors of gold nanoparticles (AuNPs) and silver nanoparticles (AgNPs) in order to relate with particle size information. At various atomization temperatures from 1400 °C to 2200 °C, the time-dependent atomic absorption peak profiles of AuNPs and AgNPs with varying sizes from 5 nm to 100 nm were examined. With increasing particle size, the maximum absorbance was observed at the longer time. The time at maximum absorbance was found to linearly increase with increasing particle size, suggesting that ETAAS can be applied to provide the size information of nanoparticles. With the atomization temperature of 1600 °C, the mixtures of nanoparticles containing two particle sizes, i.e., 5 nm tannic stabilized AuNPs with 60, 80, 100 nm citrate stabilized AuNPs, were investigated and bimodal peaks were observed. The particle size dependent atomization behaviors of nanoparticles show potential application of ETAAS for providing size information of nanoparticles. The calibration plot between the time at maximum absorbance and the particle size was applied to estimate the particle size of in-house synthesized AuNPs and AgNPs and the results obtained were in good agreement with those from flow field-flow fractionation (FlFFF) and transmission electron microscopy (TEM) techniques. Furthermore, the linear relationship between the activation energy and the particle size was observed.

Rapid characterization of trace aflatoxin B1 in groundnuts, wheat and maize by dispersive liquid-liquid microextraction followed by direct electrospray probe tandem mass spectrometry.

RATIONALE: Aflatoxins are poisonous and cancer-related chemical compounds commonly found in crops and plants. Aflatoxin B1 is the most toxic compound among aflatoxins and has been classified as group 1 carcinogenic to humans, especially in liver cancer. Herein, an ambient mass spectrometric method was developed for rapid characterization of trace aflatoxin B1 in peanuts. METHODS: Direct electrospray probe tandem mass spectrometry (DEP-MS/MS) was used to detect aflatoxin B1 in peanuts. To avoid the matrix effect, the aflatoxin B1 in the samples was extracted and concentrated by dispersive liquid-liquid microextraction. The mass spectrometer was operated in the positive ion mode to monitor the intact molecular ion (m/z 313, MH+ ) and product ion (m/z 241) of aflatoxin B1 using multiple reaction monitoring. RESULTS: Since no clean-up procedure of the sample was required, the sampling step and the subsequent mass spectrometric detection of the aflatoxin B1 was completed in less than 5 min. The limit of detection of aflatoxin B1 is at the sub-ppb level. The results obtained by DEP-MS/MS were also validated by liquid chromatography/tandem mass spectrometry (LC/MS/MS). Recovery of aflatoxin B1 in the sample was evaluated by analyzing spiked aflatoxin B1 with LC/MS/MS to be 85% and DEP-MS/MS to be 84%. CONCLUSIONS: DEP-MS/MS combined with a simple dispersive liquid-liquid microextraction procedure was successfully used for the quantitative analysis of AFB1 in nut samples. Due to its high efficiency, it is promising in providing important toxicological information for food safety in the real world. Copyright © 2017 John Wiley & Sons, Ltd.