Novel chemical sensors based on a time-dependent nonlinear response are reviewed. The strategy is to artificially mimic information transduction in living organisms. In taste and olfaction, information of chemical structure and concentration is transformed into nervous impulses in the nervous cell, i.e., time-dependent multi-dimensional information. Because the excitation and pulse generation in the nervous cell are typically nonlinear phenomena, it may be worthwhile to utilize the nonlinearity as the multi-dimensional information for molecular recognition. The principle of a “nonlinear” sensor is that a sinusoidal modulation is applied to a system, and the output signal is analyzed. The output signal of the sensor is characteristically deformed from the sinusoidal input depending on the chemical structure and concentration of the chemical stimuli. The characteristic nonlinear responses to chemical stimuli are discussed in relation to the kinetics of chemical compounds on the sensor surface. As a practical application, we introduced electrochemical sensors based on the differential capacitance, semiconductor gas sensors under the application of sinusoidal temperature or diffusion change, and a chemical sensor based on the spatio-temporal information. We demonstrated that mutli-dimensional information based on nonlinearity can provide quite useful information for the analysis of chemical species, even in the presence of another analyte or an interference with a single detector.
A fluorometric method for the determination of N-nitroso-N-methylurea (NMU) has been developed. It is based on the N-methylation reaction of nicotinamide with NMU and a subsequent condensation reaction with acetophenone, followed by an acid treatment to form a fluorescent 2,7-naphthyridine derivative. This method enabled the determination of NMU in the range 0.05 - 2 nmol/200 µl with a relative standard deviation of ca. 3%. It was applied to the determination of NMU formed from a precursor N-methylurea (MU) under simulated gastric conditions containing nitrite and thiocyanate ions at pH 3.0 in the presence of fresh orange juice and milk. NMU was extracted by an Extrelut 20 column and then determined. The mean recoveries of NMU added to the simulated gastric juice containing water, orange juice and milk were 86.5, 85.1 and 69.8%, respectively. The amounts of NMU formed from MU were found to decrease to below 25% in the presence of orange juice and milk.
A γ-cyclodextrin dimer modified with two pyrene moieties, 6-(2-pyrenebutylate-aminoethyl)pyrenebutylate-amino-6-deoxy-bis-γ-cyclodextrin, has been synthesized in the presence of N,N′-dicyclohexycarbodiimide from γ-cyclodextrin dimer linked with ethylenediamine at an upper rim. The sensing ability and binding property of the titled dimer were investigated for bile acids and endocrine disruptors. This cyclodextrin dimer showed both monomer and excimer fluorescence; the guest-induced emissions were observed as increases or decreases depending on the guest. The values ΔIm/I0m and ΔIex/I0ex, where I0m and Im are fluorescence intensities of monomer emission in the absence and presence of a guest and I0ex and Iex are those of excimer emission and ΔIm and ΔIex were Im - I0m and Iex - I0ex, respectively, were used as a parameter of sensitivity. This host exhibited highly sensitive molecular recognition ability for bile acids and endocrine disruptors, in which the sensing parameters obtained from monomer emission were plus or minus values, whereas the parameters obtained as excimer emission were minus ones. The behavior of the appended moieties of the host during a host-guest complexation was studied by induced circular dichroism (ICD) and fluorescence spectra. The ICD intensities of the titled dimer were decreased upon an addition of a guest. The guest-induced variations in the fluorescence and ICD intensity suggest that the appended moieties move by altering the spatial relationship in the hydrophobic space between two linked cyclodextrins.
A bioaffinity sensor was developed aiming at the detection of estrogen. This biosensor system is based on the specific binding of estrogen to its receptor immobilized on a gold disk electrode. The recombinant DNA encoding human estrogen receptor ligand-binding domain was expressed in bacteria using the histidine-tag fusion system. The expression of the fusion protein was under control of a bacteriophage T7 promoter, and the protein was purified under native conditions by affinity chromatography, which is based on a specific interaction between a histidine-tag, located in the N-terminus of the protein, and the Ni(II) chelate adsorbent. The protein was immobilized on an Au-electrode with Ni(II)-mediated chemisorption using a histidine tag and thiol-modified iminodiacetic acid. Cyclic voltammetric measurements showed that the reversible electrochemical reaction of a ferrocyanide/ferricyanide redox couple was suppressed by the presence of estrogen in a concentration-dependent manner. It seems reasonable to suppose that the electrostatic property of the protein layer on the electrode surface was altered by complexation with estrogen. These data suggest that this biosensor is applicable to the evaluation binding activities of the chemicals toward the human estrogen receptor.
A multielement determination of major-to-trace elements in black tea leaves and their tea infusions was carried out by ICP-AES (inductively coupled plasma atomic emission spectrometry) and ICP-MS (inductively coupled plasma mass spectrometry). Tea infusions were prepared as usual tea beverage by brewing black tea leaves in boiling water for 5 min. About 40 elements in tea leaves and tea infusions could be determined over the wide concentration range in 8 orders of magnitude. The extraction efficiency of each element was estimated as the ratio of its concentration in tea infusions to that in tea leaves. From the experimental results for the extraction efficiencies, the elements in black tea leaves were classified into three characteristic groups: (i) highly-extractable elements (>55%): Na, K, Co, Ni, Rb, Cs and Tl, (ii) moderately-extractable elements (20 - 55%): Mg, Al, P, Mn and Zn, and (iii) poorly-extractable elements (<20%): Ca, Fe, Cu, Sr, Y, Zr, Mo, Sn, Ba and lanthanoid elements. Furthermore, speciation of major-to-trace elements in tea infusions was performed by using a combined system of size exclusion chromatography (SEC) and ICP-MS (or ICP-AES). As a result, many diverse elements were found to be present as complexes associated with large organic molecules in tea infusions.
Multielement monitoring of the concentrations of trace metals dissolved in surface seawater collected at sampling stations along the ferry track between Osaka and Okinawa was performed by ICP-MS (inductively coupled plasma mass spectrometry). The surface seawater samples were collected by an automated sampling system for on-board sampling, which was installed on the bottom of a ferryboat. A part of each seawater sample was filtered with a membrane filter (pore size of 0.45 µm) immediately after sampling. Both filtered and non-filtered seawater samples were acidified to pH ca. 1 by adding conc. HNO3, and were subjected to chelating resin preconcentration for the determination of trace metals by ICP-MS, where the concentrations of analyte metals in the filtered and non-filtered seawater samples were referred to as the dissolved and total concentrations, respectively. According to the thus-obtained results, it was found that most trace metals, especially below the 0.01 µg l-1 as the dissolved and total concentrations, sensitively reflected the environmental pollution in the Osaka Bay and Seto Inland Sea area, as well as near to the Bungo Canal and the outlet of Kagoshima Bay.
Depth profiling of Ar in Ar-implanted tungsten (W) films with an excellent detection limit was investigated by secondary ion mass spectrometry (SIMS). Depth profiles of Ar with the detection of Ar+ and ArCs+ secondary ions, which were produced by O2+ and Cs+ primary ions, respectively, were compared in view of the detection limit and the depth resolution. The detection limit of Ar monitoring Ar+ was limited by the carbon- and oxygen-containing molecular ion (C2O+) in the sample as well as in the SIMS instrument. It was observed that some of the Ar+ ions were produced in the vacuum above the sample surfaces, whereas the ionization of almost all C2O+ occurred at the samples. By using different energy spectra between Ar+ and C2O+, we showed that the energy-filtering technique is advantageous for suppressing C2O+ ion detection. It is also confirmed that the ArCs+ secondary ion is only slighting by the C2OCs+ mass-interference ion. A detection limit of 4 × 1018 cm-3 for monitoring Ar+ and 3 × 1016 cm-3 for monitoring ArCs+ was achieved under a primary-ion current density of 0.16 mA/cm2. The detection of ArCs+ ion rather than Ar+ was found to be superior in the detection limit and the depth resolution. We conclude that SIMS is useful for the determination of the Ar depth distribution in W films.
Theophylline derivatives with some kinds of alkyl chains were synthesized and used in extraction experiments involving metal ions. Theophylline derivatives have exhibited a high selectivity for palladium over other precious metals and base metals. The extraction of palladium from acidic chloride media has been investigated using theophylline derivatives (= RN) as extractants. Palladium(II) was found to be extracted with 7-octyltheophylline according to the following reaction: PdCl2 + 2RN ⇔ PdCl2(RN)2. The extraction equilibrium constant was determined to be K = 2.67 × 108 (mol dm-3)-2. In addition, the stripping of palladium was performed to an extent of 100% by a single batchwise treatment with a 1.0 mol dm-3 ammonia solution. The stoichiometric relation in the extraction of palladium was supported by an analysis using mass spectrometry.
The distribution of formic, benzoic and 4-methylbenzoic acids between a 0.1 mol dm-3 (Na+, H+)ClO4- solution and octanol and carbon tetrachloride was studied at five different temperatures of 10 - 30°C. The thermodynamic parameters for the transfer process of monomeric acid between two phases and for the dimerization of monomeric acid in carbon tetrachloride (ΔH and ΔS) were evaluated from the van’t Hoff isochore. The free-energy change for the transfer of a methylene group from water to organic solvents was entropically controlled, irrespective of the organic solvents. The distribution constants of formic and benzoic acids were larger than those expected from the distribution constants of acetic and phenylacetic acids, respectively. The free-energy change for all solutes, except for benzoic and 4-methylbenzoic acids, was also entirely entropically controlled in the case of octanol as a solvent. The enthaly-entropy compensation for the dimerization constant of acids in carbon tetrachloride was observed.
The coextraction of water with benzo-15-crown-5 (B15C5), benzo-18-crown-6 (B18C6) and the B18C6-K+ complex into seven low-polar solvents, i.e., carbon tetrachloride (CTC), chloroform (CF), dichloromethane (DCM), 1,2-dichloroethane (1,2-DCE), benzene (BZ), chlorobenzene (CB) and o-dichlorobenzene (o-DCB), has been investigated. The mean hydration number, nH2O, of these solutes in the water-saturated organic solvents was determined. There is a trend that the nH2O values for any solutes increase with increasing the water concentration in the solvents. Those of B18C6 and B15C5 converge at almost 0.8 for B18C6 and 0.4 - 0.5 for B15C5 in the solvents with the relatively high water concentration, i.e., CF, 1,2-DCE, DCM, and nitorobenzene (NB). The nH2O value of B15C5 is about one-half of that of B18C6 for a given organic solvent. The dominant species of the B18C6-K+ complex in these solvents is non-hydrated. From these results, the hydration equilibrium constants, KH2O,o, in the organic solvents were estimated.
A method for thallium determination in some sulfide minerals (sphalerite, galena, orpiment and realgar) by electrothermal atomic absorption spectrometry has been proposed. Mineral samples were dissolved in a mixture of HNO3 and HCl. The effect of interfering elements (Zn, Pb and As) on the determination of Tl in the investigated minerals was studied. These investigations show that it is not possible to determine thallium directly from solutions obtained by dissolution of minerals in mineral acids, because these matrix elements tend to decrease the absorbance of thallium. Also, it was found that the investigated minerals contain iron that tends to increase the absorbance of thallium. Therefore, a method for extraction of thallium with isoamyl acetate from 10 mol/l HCl media was proposed. In these conditions, Zn, Pb and As remain in the inorganic phase, but iron and thallium are extracted into organic phase. Reextraction of iron from the organic layer was performed with 4 mol/l H2SO4. The determination of thallium was performed in the organic phase using Pd as modifier. The investigated sulfide minerals originated from different mines from the Republic of Macedonia. The relative standard-deviation range was between 2.20 to 3.92%. The detection limit of the method (calculated as 3SD of the blank) was found to be 0.05 µg/g.
Previously, we developed a reversed-phase HPLC method compatible to high performance liquid chromatography diffuse reflectance Fourier-transform infrared (HPLC-FTIR) thermospray interface for the analysis of dyes. Dye separation achieved with a mixed-mode (SCX-ODS) column using a small gradient (90 to 80% water with acetic acid) and pH 3.25; 10 to 20% acetonitrile was considered to be suitable for HPLC-FTIR. A constant-voltage setting for the thermospray temperature (227°C) was successfully used for this gradient condition. The HPLC-separated components deposited as a series of concentrated spots on a moving tape were scanned by specially developed HPLC-FTIR software. Excellent repeatability of the thermospray deposition FTIR chromatograms and IR spectra was obtained. The interface-derived spectra of the separated components of formulated and purified reactive dyes were compared and differences in spectral features were observed.
A kinetic spectrophotometric method for measuring thiocyanate is described. The proposed method is based on the inhibitory effect of thiocyanate on the oxidation of Methyl Red by bromate in the presence of nitrite, which was monitored at 520 nm. The variables affecting the rate of the reaction were investigated and the optimum conditions were established. Thiocyanate can be measured in the range of 0.05 - 1.1 µg ml-1 with a detection limit of 0.025 µg ml-1. This method has been used to determine trace thiocyanate in urine and tap water samples.
A rapid, simple, sensitive and selective spectrophotometric determination of nitrite using new diazotizing and coupling reagents is described. The method is based on a diazotization-coupling reaction between dapsone and iminodibenzyl in a hydrochloric acid medium. The molar absorptivity and Sandell’s sensitivity were found to be 7.5 × 104 l mol-1 cm-1 and 0.000613 µg ml-1, respectively. The interference effects of various cations and anions were also studied and reported. This method has been found to be applicable for the determination of nitrite in various water samples.
A simple colorimetric flow-injection system for the determination of Cu(II) based on a complexation reaction with nitroso-R salt is described. The chemical and FIA variables were established using the univariate and simplex methods. A small volume of Cu(II) was mixed with merged streams of nitroso-R salt and acetate buffer solutions. The absorbance of the complex was continuously monitored at 492 nm. The calibration curve over the concentration range 1.0 - 7.0 µg ml-1 was obtained. The relative standard deviation for determining 4.0 µg ml-1 Cu(II) was 0.47% (n = 11). The detection limit (3σ) was 0.68 µg ml-1 and the sample throughput was 150 h-1. The validity of the method has been satisfactorily examined for the determination of Cu(II) in wastewater and copper ore samples. The accuracy was found to be high, because the student t-values were calculated to be less than the theoretical values when the results were compared with those obtained by FAAS.
The second-harmonic generation of a cyanine dye in an LB film was investigated by varying the incident angle of the excitation laser. There was a clear dependence on the incident angle, which was simulated by a simple model. Thus, a highly sensitive determination should be carried out at such an angle where the efficiency of the second-harmonic generation shows its maximum.