This paper reports a computational approach for analysis of FTIR spectra where peaks are detected, assigned and matched across samples to produce a peak table with rows corresponding to samples and columns to variables. The algorithm is applied on a dataset of 103 spectra of a broad range of edible oils for exploratory analysis and variable selection using Self Organising Maps (SOMs) and t-statistics, respectively. Analysis on the resultant peak table allows the underlying patterns and the discriminatory variables to be revealed. The algorithm is user-friendly; it involves a minimal number of tunable parameters and would be useful for analysis of a large and complicated FTIR dataset.
A new poly(4-vinyl pyridine) (P4VP) based cadmium (Cd)-ion selective electrode (ISE) was developed. The 4-vinyl pyridine (4VP) was first polymerized electrochemically on the surface of graphite, later characterized by FTIR, SEM/EDX and then optimized as ISE for Cd. At optimal pH 6.4, slope of 27.7±0.8mVdecade(-1), linear concentration range of 1×10(-7) to 1.0×10(-1)M Cd(2+) and limit of detection (S/N=3) of 2.51×10(-8)M were obtained. The ISE was very selective towards Cd(2+), with K(pot)<1×10(-2) in the presence of the usual cations and anions in water samples. Response time and shelf life of less than 1min and 90 days, respectively, were observed. Its application was tested in various types of samples.
Recent advances in microfluidic systems, particularly in the Micro Total Analysis System (μTAS) or Lab On a Chip (LOC), drive the current analysis tools and equipment towards miniaturization, rapid at-line testing and mobility. The state-of-the-art microfluidic technology targets a wider range but smaller volumes of analytes, making the analytical procedure relatively easier and faster. This trend together with faster electronics and modern instrumentation systems will make real-time and in situ analysis a definite possibility. This review focuses on microchip capillary electrophoresis with amperometric detection (MCE-AD) for the detection of DNA and other electroactive analytes. The problems associated with the microchip design, in particular the choice of materials and the configuration of electrodes are discussed thoroughly and solutions are proposed. Significant developments in the related areas are also covered and reviewed critically.
A sorbent material based on a newly synthesized hydrazone ligand, 4-hydroxy-N'-[(E)-(2-hydroxyphenyl)methylidene]benzohydrazide was prepared by immobilizing the ligand into a silica sol-gel matrix. The capability of the sorbent material for the extraction of seven biogenic amines (BAs), i.e., tryptamine (TRY), beta-phenylethylamine (PEA), putrescine (PUT), cadaverine (CAD), histamine (HIS), tyramine (TYR), and spermidine (SPD) was studied. Under the adopted conditions, the sorbent showed good selectivity towards PUT, CAD, HIS and SPD (% extraction (%E)>96) while %E for TYR, TRY and PEA were 82.0, 78.9 and 46.4%, respectively. The sorbent could be used up to six extraction cycles for SPD, CAD and PUT and was applied to the determination of food samples ("budu", ketchup, orange juice, soy sauce) that were spiked with 20 mg L(-1) of the BAs. The extracted analytes were derivatized with dansyl chloride before the HPLC determination. With the exception of HIS and TYR in "budu" sample, reasonable recoveries were found for the other analytes in all the tested food samples.
A reversed-phase high-performance liquid chromatographic method with capacitively coupled contactless conductivity detector (C(4)D) has been developed for the separation and the simultaneous determination of five underivatized long chain fatty acids (FAs), namely myristic, palmitic, stearic, oleic, and linoleic acids. An isocratic elution mode using methanol/1mM sodium acetate (78:22, v/v) as mobile phase with a flow rate of 0.6 mL min(-1) was used. The separation was effected by using a Hypersil ODS C(18) analytical column (250 mm x 4.6 mm x 5 microm) and was operated at 45 degrees C. Calibration curves of the five FAs were well correlated (r(2)>0.999) within the range of 5- 200 microg mL(-1) for stearic acid, and 2-200 microg mL(-1) for the other FAs. The proposed method was tested on four vegetable oils, i.e., pumpkin, soybean, rice bran and palm olein oils; good agreement was found with the standard gas chromatographic (GC) method. The proposed method offers distinct advantages over the official GC method, especially in terms of simplicity, faster separation times and sensitivity.
Three sorbent materials (A18C6-MS, DA18C6-MS and AB18C6-MS) based on the crown ether ligands, 1-aza-18-crown-6, 1,4,10,13-tetraoxa-7,16-diazacyclo octadecane and 4'-aminobenzo-18-crown-6, respectively, were prepared by the chemical immobilization of the ligand onto mesoporous silica support. The sorbents were characterized by FT-IR, scanning electron microscopy-energy dispersive X-ray microanalysis, elemental analysis and nitrogen adsorption-desorption test. The applicability of the sorbents for the extraction of biogenic amines by the batch sorption method was extensively studied and evaluated as a function of pH, biogenic amines concentration, contact time and reusability. Under the optimized conditions, all the sorbents exhibited highest selectivity toward spermidine (SPD) compared to other biogenic amines (tryptamine, putrescine, histamine and tyramine). Among the sorbents, AB18C6-MS offer the highest capacity and best selectivity towards SPD in the presence of other biogenic amines. The AB18C6-MS sorbent can be repeatedly used three times as there was no significant degradation in the extraction of the biogenic amines (%E>85). The optimized procedure was successfully applied for the separation of SPD in food samples prior to the reversed-phase high performance liquid chromatography separation.
A capillary electrophoretic method for the separation of the aminoglutethimide (AGT) enantiomers using methylated-beta-cyclodextrin (M-beta-CD) as chiral selector is described. Several parameters affecting the separation were studied, including the type and concentration of chiral selector, buffer pH, voltage and temperature. Good chiral separation of the racemic mixture was achieved in less than 9 min with resolution factor Rs=2.1, using a fused-silica capillary and a background electrolyte (BGE) of tris-phosphate buffer solution (50 mmol L(-1), pH 3.0) containing 30 mgm L(-1) of M-beta-CD. The separation was carried out in normal polarity mode at 25 degrees C, 16 kV and using hydrostatic injection. Acceptable validation criteria for selectivity, linearity, precision, and accuracy/recovery were included. The proposed method was successfully applied to the assay of AGT enantiomers in pharmaceutical formulations. The computational calculations for the inclusion complexes of the R- and S-AGT-M-beta-CD rationalized the reasons for the different migration times between the AGT enantiomers.
The development of an optical biosensor based on immobilization of 3-methyl-2-benzothiazolinone hydrazone (MBTH) in hybrid nafion/sol-gel silicate film and tyrosinase in chitosan film for the detection of phenolic compounds has been described. Tyrosinase was immobilized in chitosan film deposited on the hybrid nafion/sol-gel silicate film containing MBTH. The enzymatic oxidation product of phenolic compounds were stabilized through formation of adduct with MBTH to produce a maroon color adduct. The color intensity of adduct was found to increase proportionally with the increase of the substrate concentrations after 5min exposure. The linearity of the biosensor towards phenol, catechol and m-cresol were in the respective concentration range of 0.5-7.0, 0.5-10.0 and 1.0-13.0mg/L with detection limit of 0.18, 0.23 and 0.43mg/L, respectively. The biosensor shows a good stability for at least 3 months.
An optical biosensor consisting of a chromoionophore (ETH5294) (CM) doped sol-gel film interfaced with another sol-gel film immobilized with acetylcholinesterase (AChE) was employed to detect the insecticide dichlorvos. The main advantage of this optical biosensor is the use of a sol-gel layer with immobilized CM that possesses lipophilic property. The highly lipophilic nature of the CM and its compatibility with the sol-gel matrix has prevented leaching, which is frequently a problem in optical sensor construction based on pH indicator dyes. The immobilization of the indicator and enzyme was simple and need no chemical modification. The CM layer is pH sensitive and detects the pH changes of the acetylcholine chloride (AChCl) substrate when hydrolyzed by AChE layer deposited above. In the absence of the AChE layer, the pH response of the CM layer is linear from pH 6 to 8 (R(2)=0.98, n=3) and it showed no leaching of the lipophilic chromoionophore. When the AChE layer is deposited on top, the optical biosensor responds to AChCl with a linear dynamic range of 40-90mM AChCl (R(2)=0.984, n=6). The response time of the biosensor is 12min. Based on the optimum incubation time of 15min, a linear calibration curve of dichlorvos against the percentage inhibition of AChE was obtained from 0.5 to 7mg/L of dichlorvos (17-85% inhibition, R(2)=0.991, n=9). The detection limit for dichlorvos was 0.5mg/L. The results of the analysis of 1.7-6.0mg/L of dichlorvos using this optical biosensor agreed well with a gas chromatography-mass spectrometry detection method.
A total of seven pesticides and eight alkylphenols were monitored using this method for the determination of their trace levels in human cord blood. The pesticides are lindane, diazinon, alpha-endosulfan, beta-endosulfan, endosulfan sulfate, chlorpyrifos and endrin; while the alkylphenols are 4-n-butylphenol, 4-n-pentylphenol, 4-n-hexylphenol, 4-t-octylphenol, 4-n-heptylphenol, nonylphenol, 4-n-octylphenol and bisphenol A. The pesticides and alkylphenols in the cord blood samples were extracted with solid phase extraction IST C18 cartridges and analyzed by selected ion monitoring mode using quadrapole detector in Shimadzu QP-5000 gas chromatograph-mass spectrometer. Trace levels of pesticide and alkylphenols in the range of non-detectable to 15.17 ng ml(-1), were detected in the human cord blood samples. This technique of monitoring the levels of endocrine-disruptors in blood samples is consistent, reliable and cost effective while reducing wastage of time and solvents.
A flow injection potentiometric method for the rapid determination of paraquat in herbicide formulations and biological samples is described. It is based on the utilization of a flow-through potentiometric detector containing polyvinyl chloride-immobilised octamethylcyclotetrasiloxane, a lipophilic plasticizer (tetra-n-undecyl 3,3',4,4'-benzophenone tetracarboxylate) and membrane additive potassium tetrakis(4-chlorophenyl)borate. The detector was minimally interfered by the presence of constituents such as Na(+), K(+), Ca(2+), Mg(2+), glucose, urea, lactic and citric acids at physiological levels, respectively. Good correlation between results of the proposed method and HPLC for the formulation samples was found, while results for the determination of paraquat in biological samples such as urine, vomitus and stomach washout was less satisfactory.
An optical sensor for Hg(II) monitoring using a complex of zinc dithizonate immobilised on XAD 7 which is based on reflectance spectrophotometry has been developed in this study. Measurements were made using a kinetic approach whereby the reflectance signal is measured at a fixed time of 5 min. The sensor could be regenerated using a saturated solution of KCl in 1 M sulphuric acid. The sensor was found to have an optimum response at pH 3.0 with respective measurement repeatability and probe-to-probe reproducibility of 1.53% and 5.26%. A linear response was observed in the Hg(II) concentration range of 0.0-180.0 ppm with a calculated limit of detection (LOD) of 0.05 ppm. The results obtained for aqueous Hg(II) determination using this probe were found to be comparable with the well-established method of atomic absorption spectrometry.
A flow injection (FI) method with on-line preconcentration using a mini-column loaded with 8-hydroxyquinoline immobilized on controlled pore glass (CPG-8HQ) is described for the determination of trace metals by ion chromatography (IC) with pyridine-2-6-dicarboxylic acid (PDCA) as the eluent. Copper, cadmium, lead, zinc, nickel and iron were determined at ppb level after post-column derivatization with 4-(2-pyridylazo)-resorcinol (PAR). The detection limits (3sigma) for the FI/IC system were 8.27, 0.89, 0.09, 0.06, 0.09 and 0.07 g l(-1) for Pb(2+), Cd(2+), Cu(2+) Ni(2+), Zn(2+) and Fe(3+), respectively, using 5 ml sample volume. The method was applied to the analysis of Malaysian natural waters.
Gallocynin immobilized in chitosan membrane has been studied as a sensor element of an optical sensor for lead using a flowing system. By using this set up, lead in solution has been determined in the concentration range from 1.0x10(-1) to 1.0x10(3) ppm with a detection limit of 0.075 ppm. The standard deviation of the method for the repeatability of lead detection at a concentration of 100 ppm was found to be 2.10%. The response of the sensor was reproducible and can be regenerated by using acidified saturated KNO(3) solution. Interference from foreign ions was also studied at 1:1 mole ratio of Pb(II):foreign ions.
This paper describes the preparation of and experimentation undertaken by heterogeneous chitosan membrane as ion selective electrode for glutamate ion. The linearity response was obtained in the range of 1.0x10(-5) to 1.0x10(-1)M with a detection limit of 1.0x10(-6)M. The performance of the electrode was found in the pH range of 4.0-8.0 at temperature 25+/-3 degrees C. The response time was at 5-35s and was useful for a period of more than 4 months. The selectivity values towards some anions indicates good selectivity over a number of interfering anions. No significant improvement of membrane performance over additional of plasticizers such as 2-NPOE, BEHA and DOPP. The electrodes gave sufficient Nernstian responses with the exception of membrane with 2-NPOE.
In this report, silver nanoparticles (Ag NPs) were successfully deposited on graphene oxide (GO) sheets to form GO-Ag nanocomposite using garlic extract and sunlight and the nanocomposite modified glassy carbon (GC) electrode was applied as an electrochemical sensor for the detection of nitrite ions. The formation of GO-Ag nanocomposite was confirmed by using UV-visible absorption spectroscopy, TEM, XRD and FTIR spectroscopy analyses. Further, TEM pictures showed a uniform distribution Ag on GO sheets with an average size of 19 nm. The nanocomposite modified electrode produced synergistic catalytic current in nitrite oxidation with a negative shift in overpotential. The limit of detection (LOD) values were found as 2.1 µM and 37 nM, respectively using linear sweep voltammetry (LSV) and amperometric i-t curve techniques. The proposed sensor was stable, reproducible, sensitive and selective toward the detection nitrite and could be applied for the detection of nitrite in real water sample.
In this study, a sensitive and cost-effective electrochemically reduced graphene oxide (ErGO) on graphite reinforced carbon (GRC) was developed for the detection of lead (Pb(II)) ions present in the real-life samples. A film of graphene oxide (GO) was drop-casted on GRC and their electrochemical properties were investigated using cyclic voltammetry (CV), amperometry and square wave voltammetry (SWV). Factors influencing the detection of Pb(II) ions, such as grades of GRC, constant applied cathodic potential (CACP), concentration of hydrochloric acid and drop-casting drying time were optimised. GO is irreversibly reduced in the range of -0.7 V to -1.6 V vs Ag/AgCl (3 M) in acidic condition. The results showed that the reduction behaviour of GO contributed to the high sensitivity of Pb(II) ions detection even at nanomolar level. The ErGO-GRC showed the detection limit of 0.5 nM and linear range of 3-15 nM in HCl (1 M). The developed electrode has potential to be a good candidate for the determination of Pb(II) ions in different aqueous system. The proposed method gives a good recovery rate of Pb(II) ions in real-life water samples such as tap water and river water.
Lateral flow assays (LFAs) hold great promise for point-of-care testing, especially in resource-poor settings. However, the poor sensitivity of LFAs limits their widespread applications. To address this, we developed a novel device by integrating dialysis-based concentration method into LFAs. The device successfully achieved 10-fold signal enhancement in Human Immunodeficiency Virus (HIV) nucleic acid detection with a detection limit of 0.1nM and 4-fold signal enhancement in myoglobin (MYO) detection with a detection limit of 1.56ng/mL in less than 25min. This simple, low-cost and portable integrated device holds great potential for highly sensitive detection of various target analytes for medical diagnostics, food safety analysis and environmental monitoring.
A new, rapid and sensitive microextraction technique named vortex-assisted liquid-liquid-liquid microextraction (VALLLME) is proposed. The complete extraction process involves two steps. First, a vortex-assisted liquid-liquid microextraction (VALLME) procedure was used to extract the analytes from a relatively large volume of sample (donor phase) to a small volume of organic solvent (intermediate phase). Next, a micro-vortex-assisted liquid-liquid extraction (µ-VALLE) was used to extract the target analytes from the intermediate phase to a smaller volume of aqueous solution (acceptor phase). The final extract (acceptor phase) can be directly injected into the high performance liquid chromatography or capillary electrophoresis units without any further treatments. The selection of the intermediate phase and the manipulation of pH are key parameters that ensure good extraction efficiency of the technique. The proposed technique has been successfully applied for the determination of carvedilol (used as model analyte) in biological fluid samples. The optimum extraction conditions were: toluene as intermediate phase (150 μL); pH of the donor phase, 9.5; vortex time of the VALLME, 45 s (maximum speed, 2500 rpm); 0.1M HCl (15 μL) as acceptor phase; vortexing time of the µ-VALLME, 75 s (maximum stirring speed, 2500 rpm) and salt concentration in the donor phase, 5% (w/v). Under these conditions, enrichment factors of 51- and 418-fold for VALLME step and VALLLME procedure, respectively, were achieved.
Vibrio cholerae is a Gram-negative bacterium that causes cholera, a diarrheal disease. Cholera is widespread in poor, under-developed or disaster-hit countries that have poor water sanitation. Hence, a rapid detection method for V. cholerae in the field under these resource-limited settings is required. In this paper, we describe the development of an electrochemical genosensor assay using lyophilized gold nanoparticles/latex microsphere (AuNPs-PSA) reporter label. The reporter label mixture was prepared by lyophilization of AuNPs-PSA-avidin conjugate with different types of stabilizers. The best stabilizer was 5% sorbitol, which was able to preserve the dried conjugate for up to 30 days. Three methods of DNA hybridization were compared and the one-step sandwich hybridization method was chosen as it was fastest and highly specific. The performance of the assay using the lyophilized reagents was comparable to the wet form for detection of 1aM to 1fM of linear target DNA. The assay was highly specific for V. cholerae, with a detection limit of 1fM of PCR products. The ability of the sensor is to detect LAMP products as low as 50ngµl(-1). The novel lyophilized AuNPs-PSA-avidin reporter label with electrochemical genosensor detection could facilitate the rapid on-site detection of V. cholerae.