离子选择性电极标准加入法的测量误差研究

研究了离子选择性电极标准加入法的测量误差与标准溶液加入量的关系。从理论上导出了离子选择性电极一次标准加入法测量结果的相对误差计算公式。当加入标准溶液使试液增加的浓度等于试液原来的浓度，测量结果的相对误差最小。     

Quantitative study on selective stacking of zwitterions in large-volume sample matrix by moving reaction boundary in capillary electrophoresis

The paper advanced the theoretical procedures for quantitative design on selective stacking of zwitterions in full capillary sample matrix by a cathodic-direction moving reaction boundary (MRB) in capillary electrophoresis (CE) under control of electroosmotic flow (EOF). With the procedures, we conducted the theoretical computations on the selective stacking of two test analytes of L-histidine (His) and L-tryptophan (Trp) by the MRB created with 30 mM pH 3.0 formic acid-NaOH buffer and 2-80 mM sodium formate. The results revealed the following three predictions. At first, the MRB cannot stack His and Trp plugs if less than 12.5 mM sodium formate is used to form the MRB and prepare the sample matrix. Second, the MRB can stack His and/or Trp sample plugs completely if higher than 50 mM sodium formate is chosen to form the MRB. Third, the MRB can only focus His plug completely, but stack Trp plug partially if 20-50 mM sodium formate is used; this implied the complete MRB-induced selective stacking to His rather than Trp. All the three predictions were quantitatively proved by the experiments. With great dilution of sample matrix and control of EOF, controllable, simultaneous and MRB-induced selective stacking and separation of zwitterions were achieved. The theoretical results hold evident significances to the quantitative design of selective stacking conditions and the increase of detection sensitivity of zwitterions in CE. In addition, the control of EOF by cetyltrimethylammonium bromide (CTAB) can evidently improve the stacking efficiency to both His and Trp.     

An integrated procedure of selective injection, sample stacking and fractionation of phosphopeptides for MALDI MS analysis

Protein phosphorylation is one of the most important post-translational modifications (PTM), however, the detection of phosphorylation in proteins using mass spectrometry (MS) remains challenging. This is because many phosphorylated proteins are only present in low abundance, and the ionization of the phosphorylated components in MS is very inefficient compared to the non-phosphorylated counterparts. Recently, we have reported a selective injection technique that can separate phosphopeptides from non-phosphorylated peptides due to the differences in their isoelectric points (pI) [1]. Phosphorylated peptides from α-casein were clearly observed at low femtomole level using MALDI MS. In this work, further developments on selective injection of phosphopeptides are presented to enhance its capability in handling higher sample complexity. The approach is to integrate selective injection with a sample stacking technique used in capillary electrophoresis to enrich the sample concentration, followed by electrophoresis to fractionate the components in preparation for MALDI MS analysis. The effectiveness of the selective injection and stacking was evaluated quantitatively using a synthetic phosphopeptide as sample, with an enrichment factor of up to 600 being recorded. Next, a tryptic digest of α-casein was used to evaluate the separation and fractionation of peptides for MALDI MS analysis. The elution order of phosphopeptides essentially followed the order of decreasing number of phosphates on the peptides. Finally, to illustrate the applicability, the integrated procedure was applied to evaluate the phosphorylation of a highly phosphorylated protein, osteopontin. Up to 41 phosphopeptides were observed, which allowed us to examine the phosphorylation of all 29 possible sites previously reported [2]. A high level of heterogeneity in the phosphorylation of OPN was evident by the multiple-forms of variable phosphorylation detected for a large number of peptides.     

On-line multidimensional supercritical fluid chromatography/capillary gas chromatography

A new analytical technique combining on-line supercritical fluid chromatography with capillary gas chromatography has been developed. The supercritical fluid sample effluent is decompressed through a restrictor directly into a conventional capillary gas chromatographic injection port. This technique allows for not only direct (100%) sample transfer from the supercritical fluid chromatograph to the gas chromatograph but also for selective or multi-step heartcutting of various sample peaks as they elute from the supercritical fluid chromatograph. Heartcut times are determined by monitoring the responses from the flame ionization or ultraviolet absorbance detectors on the supercritical fluid chromatograph. This report describes the operational setup and provides the results of heartcut reproducibility experiments using normal hydrocarbon and aromatic test mixtures. Results from studies where operational parameters were varied, such as GC injector temperature, will also be provided. The potential usefulness of this new technique for selective heartcutting will also be demonstrated using complex hydrocarbon streams.     

Polymeric integrated selective enrichment target (ISET) for solid-phase-based sample preparation in MALDI-TOF MS

A polymer microfabricated proteomic sample preparation and MALDI MS sample presentation device, the integrated selective enrichment target (ISET), comprising an array of perforated nanovials is reported. Each perforated nanovial can be filled with selective extraction media (microbeads) for purification and concentration of protein/peptides prior to matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS). The main areas covered are the influence of the molding-process-induced surface roughness and how to address the lack of inherent conductivity in the polyetheretherketone (PEEK) material for optimal MALDI MS readout. Application of the disposable polymeric ISET devices for solid-phase extraction and phosphopeptide capture is also demonstrated.     

Multivariate selectivity as a metric for evaluating comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry subjected to chemometric peak deconvolution

Two-dimensional gas chromatography (GC x GC) coupled to time-of-flight mass spectrometry (TOFMS) [GC x GC-TOFMS)] is a highly selective technique well suited to analyzing complex mixtures. The data generated is information-rich, making it applicable to multivariate quantitative analysis and pattern recognition. One separation on a GC x GC-TOFMS provides retention times on two chromatographic columns and a complete mass spectrum for each component within the mixture. In this report, we demonstrate how GC x GC-TOFMS combined with trilinear chemometric techniques, specifically parallel factor analysis (PARAFAC) initiated by trilinear decomposition (TLD), results in a powerful analytical methodology for multivariate deconvolution. Using PARAFAC, partially resolved components in complex mixtures can be deconvoluted and identified without requiring a standard data set, signal shape assumptions or any fully selective mass signals. A set of four isomers (iso-butyl, sec-butyl, tert-butyl, and n-butyl benzenes) is used to investigate the practical limitations of PARAFAC for the deconvolution of isomers at varying degrees of chromatographic resolution and mass spectral selectivity. In this report, multivariate selectivity was tested as a metric for evaluating GC x GC-TOFMS data that is subjected to PARAFAC peak deconvolution. It was found that deconvolution results were best with multivariate selectivities over 0.18. Furthermore, the application of GC x GC-TOFMS followed by TLD/PARAFAC is demonstrated for a plant metabolite sample. A region of GC x GC-TOFMS data from a complex natural sample of a derivatized metabolic plant extract from Huilmo (Sisyrinchium striatum) was analyzed using TLD/PARAFAC, demonstrating the utility of this analytical technique on a natural sample containing overlapped analytes without selective ions or peak shape assumptions.     

Detection of environmental polyorganosiloxanes (silicones) by silicon-29 NMR spectroscopy

The utility of ²⁹Si NMR spectroscopy has been demonstrated on sediment-like materials in the quantitative and qualitative determination of polyorganosiloxanes (silicones) in selected environmental samples. This technique is highly selective for polydimethylsiloxanes (PDMS) and is non-destructive to the sample. Also, specific identification of polyorganosiloxanes in sediment is possible, in contrast to previous methods which provided only quantitative information while consuming the sample. The detection limit for a 9 h experiment is approximately 45 ppm.     

Substoichiometry in neutron activation analysis technique

Neutron activation analysis has become one of the most sensitive and selective analytical technique for the determination of trace elements in a wide variety of matrices. Neutron activation involves the irradiation of the test sample and a standard of the element to be determined with thermal neutrons in a reactor, followed by dissolution of the test sample in the presence of carrier of the element to be determined. The carrier and radioisotopes are separated from the bulk of other induced activities (employing precipitation, solvent extraction, ion exchange etc.) and then the activity induced in the sample is measured on a suitable detector. The standard is treated identically. From the ratios of the activity of the sample and standard and the weight of the standard irradiated, the concentration of element in the test sample is calculated. A rapid, selective and sensitive method of radiochemical separation is subtoichiometric extraction in which the same amount of carrier is added to the irradiated test sample and standard. Exactly the same amount of reagent is added to both the sample and standard but in substoichiometric amounts, followed by the separation of the species formed by extracting it with an organic solvent. The activities of the extracts are measured. The amount of element present in the sample is calculated with help of the ratio of the activities and the weight of the standard taken. The advantages of the method are discussed. Application of substoichiometry in neutron activation has been elucidated with reference to the determination of Au in various samples by substoichiometric neutron activation analysis.     

Routine catalytic determination of trace amounts of cobalt in small urine samples

The oxidation of catechol by hydrogen peroxide, catalyzed by cobalt(II), is a highly sensitive and selective reaction. It makes it possible to analyze a small sample of urine (5.0 ml) for cobalt without the need for isolation of the analyte from the matrix. The sample is dried and dry-ashed according to a temperature programme, and the residue is dissolved in hydrochloric acid. After filtration of the solution, acetate buffer and sodium citrate are added and cobalt is determined catalytically in an aliquot of the solution, by the standard-addition method.     

The Sherman equations as a nonlinear Perron eigenvalue problem

When a chemical sample composed of N elements is analyzed using sequential selective excitation by a tunable polyenergetic X-ray beam and selective measurement of the characteristic X-rays, the production of secondary fluorescence does not interfere with the measurements. This experimental situation leads to a particular case of the Sherman equations which can be written as a set of non-linear equations. The same kind of equations are also obtained when we excite a chemical sample with a polyenergetic X-ray beam and neglect the production of secondary fluorescence. This set of equations can be regarded as a non-linear eigenvalue problem. A non-linear extension of the Perron Frobenious theorem ensures that there is one and only one physically acceptable solution, and also leads to a method to obtaining it. The propagation off measurements errors of sample fluorescence to errors in the calculated sample concentrations, has been simulated, and the results show that the solution is well conditioned. The case of production of secondary fluorescence can not be treated, in general, as a nonlinear Perron eigenvalue problem, but it has been shown that it is rather plausible that Sherman equations corresponding to the actual chemical elements and that include the production of secondary fluorescence have one and only one physically acceptable solution. An exhaustive search could elucitate the existence and unicity of solutions for the equations corresponding to the actual chemical elements.     

Comparison of near-infrared and Raman spectroscopy for the determination of the density of polyethylene pellets

In this study, we compare near-infrared (NIR) and Raman spectroscopy for the determination of the density of linear low density polyethylene (PE) (in a pellet form). As generally known, Raman spectral features are more selective than those of NIR for most chemical samples. NIR spectroscopy has been more extensively used for the quantitative analysis of polymers, but Raman spectroscopy is the better choice as long as the problem of reproducibility of Raman measurements (especially for solid samples), mostly resulting from insufficient sample representation due to probing only localized chemical information and the sensitivity of sample placement with regard to the focal plane, can be overcome. To improve sample representation and reproducibility of Raman measurements, we have employed the wide area illumination (WAI) Raman scheme, capable of illuminating a laser onto a large sample area (28.3 mm²) for Raman spectral collection (a 6-mm laser spot with a focal length of 248 mm). Diffuse reflectance NIR spectra of PE pellets were collected using a sample moving system which allowed for the scanning of large areas. The prediction error was 0.0008 g cm⁻³ for Raman spectroscopy and 0.0011 g cm⁻³ for NIR spectroscopy. The harmonization of inherently selective Raman features and a reproducible spectral collection with correct sample representations using the WAI scheme led to an accurate determination of the density of the PE pellets.     

Determination of glyphosate as cross-contaminant in a commercial herbicide by capillary electrophoresis-electrospray ionization-mass spectrometry

Capillary electrophoresis combined with mass spectrometry (CE-MS) was used for the rapid determination of the negatively charged herbicide, Glyphosate, in a selective dried granule (DG) formulation. The CE-MS method was required to ensure product safety from the risk of cross contamination of a selective herbicide formulation. Glyphosate separation was achieved by using a bare fused-silica capillary column, operated in the reversed-polarity mode, using ammonium formate buffer, pH 2.5. The total CE-MS analysis time was under 10 min and the limit of detection was 10 ng/mL. The CE-MS analysis of Glyphosate was simple, rapid, and selective. The method involved minimal sample handling and was proven to be ideal for cross-contamination investigations in manufacturing samples.     

Bioinspired NC Coated BM-ZIF for Electrochemical Monitoring of Adrenaline from Blood and Pharmaceutical Samples

Herein, we have developed highly sensitive and selective non-enzymatic bioinspired polydopamine derived nitrogen rich carbon (NC) coated bimetallic zeolitic imidazolate framework (BM-ZIF) electrochemical sensor via simple hydrothermal approach for monitoring adrenaline (AD) from COVID-19 quarantined person blood and pharmaceutical sample. The designed NC-BM-ZIF electrode shows excellent sensitive and selective performance towards AD monitoring with detection limit (LOD) of 0.01 nM and 0.1931 μA/nM/cm² sensitivity over a wide linear range of 50–1625 nM. To the best of our knowledge, this is the first study of using of NC-BM-ZIF electrode for the electrochemical sensing of AD from quarantined person blood and pharmaceutical sample.     

铅分子印迹聚合物合成及在痕量测量中的应用

以对乙烯基苯甲酸钠(VBA-Na)为功能单体,铅离子为模板分子,对乙烯基苯(DVB)为交联剂,采用预组装方法结合表面印迹技术合成得到铅的分子印迹聚合物(Pb-MIPS)。研究了该聚合物对铅的吸附和选择识别能力,并对其进行了结构表征。结果表明,所合成的Pb-MIPS对铅离子具有良好的吸附和选择识别能力,最大吸附量为725μg/g。Pb-MIPS应用于地表水样中痕量铅的测定,显著地提高了石墨炉原子吸收光谱仪对铅的检出能力。     

Programmed cold sample introduction and multidimensional preparative capillary gas chrornatography. Part I: Introduction,design and operation of a new mass flow controlled multidimensional GC system

A new design of a mass-flow controlled multidimensional switching system for capillary gas chromatography is introduced and discussed. Large sample amounts can be introduced with a required input band width onto the first column. A combination of cold sample introduction and successive high speed programmed heating of the injector liner is used for this purpose. The potential of such an approach for selective and fast high resolution separations with series coupled wide bore, thick film columns is emphasized, and illustrated for various concentrations.     

Effect of solvents on the selectivity of terbutylazine imprinted polymer sorbents used in solid-phase extraction

A solid-phase extraction sample preparation method using a molecularly imprinted polymer (MIP) selective for the triazine type pesticide terbutylazine has been developed. The method involves preconcentration from large volumes of water samples on a C18 disk coupled to selective clean-up on the MIP. The method has been optimised by studying the recovery and retention of terbutylazine and some other structurally related triazine derivates as a function of the selective washing solvent used. The effect of the water content of the selective washing solvent was also investigated on the recovery of the MIP. River water samples were analysed with the coupled technique, and efficient clean-up of the samples was observed.     

Gas chromatographic column for the storage of sample profiles

The concept of a sample retention column that preserves the true time profile of an analyte of interest is studied. This storage system allows for the detection to be done at convenient times, as opposed to the nearly continuous monitoring that is required by other systems to preserve a sample time profile. The sample storage column is essentially a gas chromatography column, although its use is not the separation of sample components. The functions of the storage column are the selective isolation of the component of interest from the rest of the components present in the sample and the storage of this component as a function of time. Using octane as a test substance, the sample storage system was optimized with respect to such parameters as storage and readout temperature, flow rate through the storage column, column efficiency and storage time. A 3-h sample profile was collected and stored at 30 degrees C for 20 h. The profile was then retrieved, essentially intact, in 5 min at 130 degrees C.     

Immunochemical applications in environmental science

Immunochemical methods are based on selective antibodies combining with a particular target analyte or analyte group. The specific binding between antibody and analyte can be used to detect environmental contaminants in a variety of sample matrixes. Immunoassay methods provide cost-effective, sensitive, and selective analyses for many compounds of environmental and human health concern. Immunoaffinity chromatography methods have been integrated with chromatographic methods and are also being used as efficient sample preparations prior to immunochemical or instrumental detection. Immunosensors show promise in obtaining rapid online analyses. These and other advancements in immunochemical methods continue the expansion of their role from field screening methods to highly quantitative procedures that can be easily integrated into the environmental analytical laboratory.     

The Determination of Sodium in Alumina Using a Sodium Selective Ion Electrode

Abstract

A method has been developed for the determination of sodium in alumina using a selective ion electrode. The alumina sample is dissolved in ammonium hydrogen fluoride in platinum crucibles or sintered with boric acid using either platinum, nickel, or zirconium crucibles. Either dissolution technique completely extracts all available sodium. After dissolution, and in the presence of citrate to prevent aluminum hydroxide precipitation, the pH is adjusted to 8.7 with ammonium hydroxide, and the sodium concentration is determined by a sodium selective ion electrode.     

Thin‐Layer Chemical Modulations by a Combined Selective Proton Pump and pH Probe for Direct Alkalinity Detection

We report a general concept based on a selective electrochemical ion pump used for creating concentration perturbations in thin layer samples (～40 μL). As a first example, hydrogen ions are released from a selective polymeric membrane (proton pump) and the resulting pH is assessed potentiometrically with a second membrane placed directly opposite. By applying a constant potential modulation for 30 s, an induced proton concentration of up to 350 mM may be realized. This concept may become an attractive tool for in situ titrations without the need for sampling, because the thin layer eventually re‐equilibrates with the contacting bulk sample. Acid–base titrations of NaOH and Na₂CO₃ are demonstrated. The determination of total alkalinity in a river water sample is carried out, giving levels (23.1 mM ) comparable to that obtained by standard methods (23.6 mM ). The concept may be easily extended to other ions (cations, anions, polyions) and may become attractive for environmental and clinical applications.