A PLS model based on dominant factor for coal analysis using laser-induced breakdown spectroscopy

Thirty-three bituminous coal samples were utilized to test the application of laser-induced breakdown spectroscopy technique for coal elemental concentration measurement in the air. The heterogeneity of the samples and the pyrolysis or combustion of coal during the laser–sample interaction processes were analyzed to be the main reason for large fluctuation of detected spectra and low calibration quality. Compared with the generally applied normalization with the whole spectral area, normalization with segmental spectral area was found to largely improve the measurement precision and accuracy. The concentrations of major element C in coal were determined by a novel partial least squares (PLS) model based on dominant factor. Dominant C concentration information was taken from the carbon characteristic line intensity since it contains the most-related information, even if not accurately. This dominant factor model was further improved by inducting non-linear relation by partially modeling the inter-element interference effect. The residuals were further corrected by PLS with the full spectrum information. With the physical-principle-based dominant factor to calculate the main quantitative information and to partially explicitly include the non-linear relation, the proposed PLS model avoids the overuse of unrelated noise to some extent and becomes more robust over a wider C concentration range. Results show that RMSEP in the proposed PLS model decreased to 4.47% from 5.52% for the conventional PLS with full spectrum input, while R ² remained as high as 0.999, and RMSEC&P was reduced from 3.60% to 2.92%, showing the overall improvement of the proposed PLS model.     

Surface analysis of the size-fractioned urban aerosols by secondary ion mass spectrometry (ToF-SIMS)

The secondary ion mass spectrometry method (ToF-SIMS) has been applied to the analysis of some mineral and organic species on the surface layers of airborne urban particulates. Particulate matter was collected on aluminum sheets of the 8-stage Anderson type cascade impactor from three different sampling sites in the city of Lodz, Poland, which were different in terms of aerosol source apportionment. The obtained results show that vehicle combustion products occur mainly in fine fraction with aerodynamic diameters below 1μm. The main contribution to the mineral components comes from direct and traffic related soil resuspension.      

A genetic factor model for the statistical analysis of multilocus DNA fingerprints.

A novel concept is described for the statistical analysis of multilocus DNA fingerprints. Utilizing this method, it is shown by simulation that the application of multilocus DNA fingerprints to paternity testing is robust against deviations from idealistic assumptions made about underlying models and parameters. Partial homozygosity, allelism and linkage at the DNA loci involved, as well as variations in estimates of band-sharing probabilities were studied for effects on the resulting paternity probabilities. None of the above-mentioned phenomena appear to change these values to an extent relevant for decision making in paternity cases.     

Trace element levels of aerosols at an urban area of Korea by instrumental neutron activation analysis

Instrumental neutron activation analysis was used to measure the concentrations of about 27 elements associated with airborne PM 10 samples that were collected from a roadside sampling station at a moderately polluted urban area of Taejon city, Korea. The magnitude of their concentrations was clearly distinguished and spanned over four orders. If compared in terms of enrichment factors, it was found that certain elements (e.g., As, Br, Cl, Sb, Se, and Zn) are enriched in PM 10 samples of the study site. The factor analysis indicated three factors with statistical significance, which may exert dominant controls on regulating the metal concentration levels in the study area.     

A coded support for use in analysis of aerosols by different spectroscopic methods

A device used for localization of solid atmospheric microparticles on silicon wafers is described. Dimensions of the device are 5.04 mm × 5.0809 mm. This support facilitates the analysis by other instruments of particles previously located by scanning electron microscopy (SEM). The area of the wafer is divided into tables and cells identified by microlithographic alphanumeric characters. These characters are made of an alloy of aluminium, silicon and copper which can be visualized by imaging secondary-ion mass spectrometry (SIMS). The quality of the image produced by SIMS is worse than that obtained with SEM, mainly because of the bigger diameter of the SIMS ion beam, but the symbols and patterns used are still easily legible. Examples are given of images obtained from SEM, SIMS and secondary electron ion-induced microscopy (SEIIM).     

A novel strategy on the spectrochromatographic analysis of a quaternary mixture by parallel factor analysis model

Poor chromatographic resolution is one of the main challenges in chromatographic analysis. Partially separated chromatographic peaks frequently occur, due to the nature of analytes and the demand for fast analysis using high flow rates and shorter columns. Modeling of chromatographic three-way data using suitable chemometric tools enables determining co-eluted peaks without using additional experimental efforts. In this paper, parallel factor analysis (PARAFAC) was applied to chromatographic data for the quantitative resolution of a quaternary mixture at the co-elution condition of acetaminophen, aspirin, ascorbic acid, and guaifenesin in a spectrochromatogram. The spectrochromatograms of the calibration set, validation set, and real samples were arranged as a three-way array. In the next step, the PARAFAC model was implemented to decompose the spectrochromatographic array into trilinear components, corresponding to spectral, chromatographic, and relative concentration profiles of the analytes. The chromatographic and spectral modes were used for the qualitative analysis of components, whereas the analytes in commercial tablets were quantified from their individual profiles in their concentration mode. This study indicated that the application of the PARAFAC model provided a novel strategy for determining overlapping peaks in a chromatogram to perform the analysis of multicomponent mixtures with reduced runtime and without additional efforts.     

斜投影-不展开薄层色谱法对废木料液化产物乙酰丙酸的过程分析

采用多波长薄层色谱扫描法,不经过传统的薄层色谱展开步骤实现混合体系的快速定量。废木料液化过程产物为混合体系,分别将不同液化反应时间点所取样品点样于硅胶板上。仅对液化过程终点的样本点进行一次展开,分离斜投影建模所需的反射光谱,切割出目标产物(乙酰丙酸)和背景光谱,构造斜投影算子;对其他液化过程中的样品点不展开,采集混合光谱,经斜投影算法分离出其中的目标产物纯光谱,从而实现定量。将该方法的定量结果与高效液相色谱法的定量结果对比,得到两种方法测定乙酰丙酸的相对误差小于3.27%,表明两种方法具有良好的一致性。     

A Tucker model based approach for analysis of complex oil biodegradation data

A novel method based on gas chromatography–mass spectrometry in selected ion monitoring mode (GC–MS/SIM) and Tucker models is developed to evaluate the effects of oil type, microbial treatments and incubation time on the biodegradation of petroleum hydrocarbons. The data set consists of sections of the m/z 180, 192 and 198 GC–MS/SIM chromatograms of oil extracts from a biodegradation experiment where four oil types were exposed to four microbial treatments over a period of one year. The chosen sections, which are specific to methylfluorenes, phenanthrenes and dibenzothiophenes, were combined in a 4-way array (incubation time × oil type × treatment × combined chromatographic retention times) that was analyzed using both principal component analysis and the Tucker model. Several conclusions could be reached: the light fuel oil was the least degradable of those tested, 2- and 3-methyl isomers were more easily degraded compared to the 4-methyl isomers, the mixture of surfactant producers and PAC degraders provided the most effective degradation and the largest part of the degradation occurred between 54 and 132 days.     

Absolute modelling of urban aerosol elemental composition by factor analysis

Data on the elemental composition of urban aerosols from a Danish city are treated by R-mode factor analysis to identify and quantify contributions from different sources. The analysis produced a 6-factor solution. If it is assumed that all sources contributing to the total suspended particulates were determined, absolute calculations of emission profiles and source contributions are possible.     

Calibration model transfer for near-infrared spectra based on canonical correlation analysis

In order to solve the calibration transformation problem in near-infrared (NIR) spectroscopy, a method based on canonical correlation analysis (CCA) for calibration model transfer is developed in this work. Two real NIR data sets were tested. A comparative study between the proposed method and piecewise direct standardization (PDS) was conducted. It is shown that the transfer results obtained with the proposed method based on CCA were better than those obtained by PDS when the subset had sufficient samples.     

A catenated anion receptor based on indolocarbazole

A catenated anion receptor 7 comprising two indolocarbazole units was prepared by olefin ring-closing metathesis using Grubbs’ catalyst. Receptor 7 possesses a cage-like cavity where anions are encapsulated by forming four hydrogen bonds in the order of Cl⁻ > AcO⁻ >  >  > Br⁻ >  > I⁻ ≈  in 1% H₂O/acetone.     

A model of cooperativity based on restricted binding: kinetic and thermodynamic analysis

Cooperative protein–ligand binding is an essential biochemical process. In this work, we introduce a model that can simulate the emergence of such phenomenon in the binding kinetics. It is based on the inability of the ligand molecules to fully utilize all the available binding sites due to some restriction, realized here in terms of a model parameter, called the restriction parameter. The theory is developed at the level of a single oligomeric protein molecule interacting with a ligand, maintained at a constant concentration, using a chemical master equation. The model provides stepwise binding constants related to the restriction parameter. The relative magnitudes of these constants, when compared to the Hill coefficients measuring cooperativity, give a physical insight in the development of the cooperative behavior and can also act as a reference frame. This can be useful for an alternative theoretical characterization of cooperativity in oligomeric proteins with large number of binding sites and arbitrary binding constants. We establish this point here by taking a tetrameric protein as a case study. A stochastic thermodynamic analysis is also performed, highlighting the energy–entropy contribution to the overall free energy change due to protein–ligand interaction for various cases of restricted binding.     

A pharmacophore model for dopamine D4 receptor antagonists

A pharmacophore model for dopamine D₄ antagonists has been developed on the basis of a previously reported dopamine D₂ model. By using exhaustive conformational analyses (MM3^* force field and the GB/SA hydration model) and least-squares molecular superimposition studies, a set of eighteen structurally diverse high affinity D₄ antagonists have successfully been accommodated in the D₄ pharmacophore model. Enantioselectivities may be rationalized by conformational energies required for the enantiomers to adopt their proposed bioactive conformations. The pharmacophore models for antagonists at the D₄ and D₂ receptor subtypes have been compared in order to get insight into molecular properties of importance for D₂/D₄ receptor selectivity. It is concluded that the bioactive conformations of antagonists at the two receptor subtypes are essentially identical. Receptor essential volumes previously identified for the D₂ receptor are shown to be present also in the D₄ receptor. In addition, a novel receptor essential volume in the D₄ receptor, not present in the D₂ receptor, has been identified. This feature may be exploited for the design of D₄ selective antagonists. However, it is concluded that the major determinant for D₂/D₄ selectivity is the nature of the interactions between the receptor and aromatic ring systems. The effects of the electronic properties of these ring systems on the affinities for the two receptor subtypes differ substantially.     

Identification of secondary organic aerosols based on aerosol mass spectrometry

Secondary organic aerosol (SOA) is one of the major components of aerosols in the atmosphere and has not been well understood so far. Due to the complex chemical composition of organic aerosols, the identification of SOA has been a hotspot and difficult issue in the field of aerosol study. This study attempts to quantitatively identify SOA in winter of Shenzhen based on positive matrix factorization (PMF) analysis. Major sources were resolved and SOA was identified subsequently according to the characteristic ion fragments measured by highly time-resolved aerosol mass spectrometer measurement. It showed that in the winter of Shenzhen the average SOA concentration was 9.41 ± 6.33 μg/m³, accounting for 39.9 ± 21.8% of the total organic mass. Compared with primary organic aerosol (POA), the SOA concentrations had no large variation, suggestive of characteristics of regional secondary pollutants. The ratio of SOA/BC had pronounced diurnal variation, similar to that of O _x (O₃+NO₂), indicating SOA formation was significantly controlled by activity of photochemistry in the atmosphere. The most effective period for SOA formation was from 9 am ～3 pm since the SOA/BC ratio increased by 122% during this period. This study provides a new technical method and a new idea for SOA investigation.     

A quinoline based bis-urea receptor for anions: a selective receptor for hydrogen sulfate

A dipodal bis-urea receptor has been synthesized from the reaction of 8-amino quinoline and 1,4-phenylene diisocyanate in dichloromethane, and the anion binding ability of the receptor has been studied using fluoride, chloride, bromide, iodide, perchlorate, nitrate, dihydrogen phosphate and hydrogen sulfate by UV-Vis titrations in DMSO. The results show that the receptor binds each of the anions with a 1:1 stoichiometry, showing high affinity and moderate selectivity for hydrogen sulfate among the anions studied. Ab initio calculations based on density functional theory (DFT) suggest that an anion (X(-)) is bonded within the cleft formed by the two arms of the receptor through two NH...X(-) and two aromatic CH...X(-) interactions. The results from solution and theoretical studies suggest that binding is predominantly influenced by hydrogen bonding interactions and the basicity of anions.     

Development of a sequential supercritical fluid extraction method for the analysis of nitrated and oxygenated derivatives of polycyclic aromatic hydrocarbons in urban aerosols

A two-step supercritical fluid extraction (SFE) method has been developed for the analysis of oxygenated and nitrated polycyclic aromatic hydrocarbons (oxy- and nitro-PAHs, respectively) present in urban aerosol samples. The proposed SFE procedure first involves an extraction step using pure CO2 in order to remove the less polar compounds from the matrix and a second consecutive step using toluene-modified CO2. The oxy- and nitro-PAHs are obtained in the second step. Parameters affecting both collection efficiencies and the selective extraction of oxy- and nitro-PAHs in the second SFE step were optimised. Analysis of the extracts was performed using gas chromatography with electron-capture detection and coupled to mass spectrometry. The proposed SFE method was compared with a conventional extraction technique such as sonication and good agreement in the results was obtained. Nevertheless, clean up of sonication extracts was needed, whereas no purification was necessary for SFE extracts. The SFE method was applied to the analysis of oxy- and nitro-PAHs in urban aerosol samples and 9-fluorenone, 9,10-anthraquinone, 2-methyl-9,10-anthraquinone, benzanthrone, benz[a]anthracene-7,12-dione and 1-nitropyrene were identified at concentrations ranging between 15 and 364 pg m(-3).