气相色谱-质谱法快速检测木制玩具中的邻苯基苯酚

使用气相色谱-质谱法快速、简单、有效检测木制玩具中邻苯基苯酚的含量. 使用甲醇超声萃取,乙酸酐乙酰化对样品预处理,采用气相色谱-质谱技术进行检测. 研究结果显示,方法对邻苯基苯酚的检测线性范围为0.1~4.0 mg/L,检出限为0.01 mg/L,添加回收率为85%~101%,相对标准偏差为3.29%和3.52%. 表明方法不仅可以用于检测木制玩具中邻苯基苯酚,也可以用于其它材料中邻苯基苯酚的分析.     

Multivariate chemical mapping of pigments and binders in easel painting cross-sections by micro IR reflection spectroscopy

Paintings are composed of superimposed layers of inorganic and organic materials (pigments and binders). Knowledge of the stratigraphic sequence of these heterogeneous layers is fundamental for understanding the artist’s painting technique and for conservation issues. In this study, micro-IR mapping experiments in reflection mode have been carried out on cross-sections taken from simulations of ancient easel paintings. The objective was to locate both organic binders and inorganic pigments. Chemical maps have been re-constructed using the common approach based on the integration of specific infrared bands. However, owing to the complexity of painting materials, this approach is not always applicable when dealing with broad and superimposed spectral features and with reststrahlen or derivative-like bands resulting from acquisition in reflection mode. To overcome these limitations, principal-component analysis has been successfully used for the re-construction of the image, extracting the relevant information from the complex full spectral data sets and obtaining reliable chemical distributions of the stratigraphy materials. Different pigment–binder combinations have been evaluated in order to understand limitations and strengths of the approach. Finally, the method has been applied for stratigraphic characterization of a cross-section from a 17th century wooden sculpture identifying both the original paint layer and the several overpaintings constituting the complex stratigraphy.     

Polycyclic Aromatic Hydrocarbons in Wooden Railway Beams Impregnated with Coal Tar: Extraction and Quantification by GC-MS

 An analytical technique for the simultaneous determination of PAHs (polycyclic aromatic hydrocarbons) in wooden railway beams, impregnated with coal tar for their protection, has been developed, based on the effective extraction of the PAHs and their determination by GC-MS. Two extraction techniques, the Soxhlet and the ultrasonic one, using two different solvents, hexane and toluene have been compared for their efficiency for PAHs which can be determined in ppb-ppt range after optimised clean up and enrichment. Several parameters, such as the degree of impregnation of the wooden beams, the effect of sun radiation on the degradation of the PAHs and their migration to the soil have been investigated by following the concentration of the PAHs and that of their methylated products found at various sampling positions. The results are useful for the decision about recycling procedure or their further disposal.     

Differentiation of walnut wood species and steam treatment using ATR-FTIR and partial least squares discriminant analysis (PLS-DA)

Wood is a ubiquitous material used in everyday life. Accurate identification of species can be of importance in a historical context enabling appropriate conservation treatment and adequate choice of material to be applied to historic wooden objects, and in a more modern context, in the identification of forgeries. Wood is also often treated to improve certain physical characteristics, often strength and durability. However, determination of whether or not a piece of wood has been treated can be very difficult. Infrared spectroscopy has previously been applied to differentiate between different wood species or between treated and untreated wood, often in conjunction with chemometric analysis techniques. Here, we report the use of mid-IR spectroscopy, coupled with partial least squares discriminant analysis for the discrimination between two walnut wood species and to differentiate between steam-treated and untreated samples of each of these wood species. We show that the discrimination between species and between steam-treated and non-steam-treated wood from Juglans nigra is very clear and, while analysis of the quality of the discrimination between steam-treated and non-steam-treated J. regia samples is not as good, it is, nevertheless, sufficient for discrimination between the two groups with a statistical significance of P < 0.0001.     

Applying pyrolysis-gas chromatography/mass spectrometry to the identification of oriental lacquers: study of two lacquered shields

Oriental lacquers have been used as coating materials for thousands of years for wooden, ceramics, leather and metal objects. Lacquers are natural polymers obtained from three species growing in different regions of Asia: Rhus vernicifera (China, Japan and Korea); Rhus succedanea (Vietnam and Taiwan); and Melanorrhoea usitate (Myanmar and Thailand). The identification of lacquer films is important for conservation and restoration purposes, as well as for art history studies because it may help in determining the origin of the lacquered objects. In this work, pyrolysis-gas chromatography/mass spectrometry using a filament-type pyrolyser was successfully applied to the characterization of oriental lacquers. A method to identify the three kinds of lacquer was developed and applied to the study of two lacquered shields imported from Asia in the sixteenth century. The materials that constitute the shields were also examined by Fourier-transform infrared microspectroscopy and details of the lacquering technique are reported.     

A description of an automatic continuous equilibrium system for the measurement of dissolved gaseous mercury

A novel continuous equilibrium system with high time resolution, i.e. every ten minutes, was developed to sample and determine dissolved gaseous mercury (DGM) in natural surface waters. The system is based on the opposite flow principle, can be connected to a ship’s bow water system, and can be applied under most ambient conditions, such as high wind speeds and onboard a moving ship. For the DGM determination the system uses the measured equilibrium concentration of mercury established between the aqueous and gaseous phases, i.e. DGM = Hg_extr / k _H′, where Hg_extr is the measured mercury concentration in the outgoing gas phase and k_H′ is the dimensionless Henry’s Law constant at the desired temperature and salinity. The efficiency of the system was investigated via theoretical calculations and by comparing the continuous equilibrium system with discrete samples. The measurements obtained by the continuous equilibrium system agree within 13% at the 95% confidence level with the measurements of discrete samples obtained by the traditional technique. The theoretical calculations estimated that the continuous equilibrium system described here had an efficiency of 99% for determining the DGM concentration.     

Monitoring of pigmented and wooden surfaces in accelerated ageing processes by FT-Raman spectroscopy and multivariate control charts

Two of the most suitable analytical techniques used in the field of cultural heritage are NIR (near-infrared) and Raman spectroscopy. FT-Raman spectroscopy coupled to multivariate control charts is applied here for the development of a new method for monitoring the conservation state of pigmented and wooden surfaces. These materials were exposed to different accelerated ageing processes in order to evaluate the effect of the applied treatments on the goods surfaces. In this work, a new approach based on the principles of statistical process control (SPC) to the monitoring of cultural heritage, has been developed: the conservation state of samples simulating works-of-art has been treated like an industrial process, monitored with multivariate control charts, owing to the complexity of the spectroscopic data collected.The Raman spectra were analysed by principal component analysis (PCA) and the relevant principal components (PCs) were used for constructing multivariate Shewhart and cumulative sum (CUSUM) control charts. These tools were successfully applied for the identification of the presence of relevant modifications occurring on the surfaces. CUSUM charts however proved to be more effective in the identification of the exact beginning of the applied treatment. In the case of wooden boards, where a sufficient number of PCs were available, simultaneous scores monitoring and residuals tracking (SMART) charts were also investigated. The exposure to a basic attack and to high temperatures produced deep changes on the wooden samples, clearly identified by the multivariate Shewhart, CUSUM and SMART charts. A change on the pigment surface was detected after exposure to an acidic solution and to the UV light, while no effect was identified on the painted surface after the exposure to natural atmospheric events.     

Characterisation of steroids in wooden crates of veal calves by accelerated solvent extraction (ASE®) and ultra-high performance liquid chromatography coupled to triple quadrupole mass spectrometry (U-HPLC-QqQ-MS-MS)

Illegal steroid administration to enhance growth performance in veal calves has long been, and still is, a serious issue facing regulatory agencies. Over the last years, stating undisputable markers of illegal treatment has become complex because of the endogenous origin of several anabolic steroids. Knowledge on the origin of an analyte is therefore of paramount importance. The present study shows the presence of steroid analytes in wooden crates used for housing veal calves. For this purpose, an analytical procedure using accelerated solvent extraction (ASE®), solid-phase extraction (SPE) and ultra-high performance liquid chromatography coupled to triple quadrupole mass spectrometry (U-HPLC-MS-MS) is developed for the characterisation of androstadienedione (ADD), boldenone (bBol), androstenedione (AED), β-testosterone (bT), α-testosterone (aT), progesterone (P) and 17α-hydroxy-progesterone (OH-P) in wood samples. In samples of wooden crates used for housing veal calves, ADD, AED, aT and P could be identified. Using the standard addition approach concentrations of these analytes were determined ranging from 20?±?4 ppb to 32?±?4 ppb for ADD, from 19?±?5 ppb to 44?±?17 ppb for AED, from 11?±?6 ppb to 30?±?2 ppb for aT and from 14?±?1 ppb to 42?±?27 ppb for P, depending on the sample type. As exposure of veal calves to steroid hormones in their housing facilities might complicate decision-making on illegal hormone administration, inequitable slaughter of animals remains possible. Therefore, complete prohibition of wooden calf accommodation should be considered.     

Terminal and Penultimate Reactivity Ratios in the Styrene-Acrylonitrile Free-Radical Copolymerization System in Bulk

ABSTRACT

The terminal and penultimate model reactivity ratios for the styrene-acrylonitrile monomer system in bulk have been investigated by the simplex and scanning method. It has been shown that Mayo-Lewis equation has an unique solution when determining the reactivity ratios according to the terminal model while for the penultimate model the non-uniqueness in determination of the reactivity ratios has been found. The numerical values of the penultimate r-parameters calculated with the simplex method depend on the initial guess for r-parameters.

Several sets of penultimate reactivity ratios for the styrene-acrylonitrile system in bulk have been found to be equal from mathematical point of view. The reactivity ratios with comparable standard deviation have an equivalent graphical representation on the copolymerization diagragm. It has been also confirmed that the penultimate model is a more appropriate of the models considered to describe the variation of the copolymer composition with the monomer feed. Taking into account previous results for the styrene-methyl methacrylate system in bulk it is thereby assumed that the occurrence non-uniqueness in determination of the penultimate model reactivity ratios does not depend on the monomer system.     

Cutting boards in Salmonella cross-contamination

Cutting boards are commonly perceived as important fomites in cross-contamination of foods with agents such as Salmonella spp., despite the lack of supporting epidemiological data. A variety of woods and plastics have been used to make work surfaces for cutting. In general, wood is said to dull knives less than plastic, and plastic is seen as less porous than wood. Research to model the hypothetical cross-contamination has been done in a variety of ways and has yielded a variety of results. At least some of the work with knife-scarred plastic indicates that the surface is very difficult to clean and disinfect, although this may vary among the polymers used. High-density polyethylene, which is most used in commercial applications, has been shown to delaminate in response to knife scarring. Wood is intrinsically porous, which allows food juices and bacteria to enter the body of the wood unless a highly hydrophobic residue covers the surface. The moisture is drawn in by capillary action until there is no more free fluid on the surface, at which point immigration ceases. Bacteria in the wood pores are not killed instantly, but neither do they return to the surface. Destructive sampling reveals infectious bacteria for hours, but resurrection of these bacteria via knife edges has not been demonstrated. Small plastic cutting boards can be cleaned in a dishwasher (as can some specially treated wooden boards), but the dishwasher may distribute the bacteria onto other food-contact surfaces. Most small wooden boards (i.e., those with no metal joiners in them) can be sterilized in a microwave oven, but this should be unnecessary if accumulation of food residues is prevented. However, 2 epidemiological studies seem to show that cutting board cleaning habits have little influence on the incidence of sporadic salmonellosis. Further, one of these studies indicated that use of plastic cutting boards in home kitchens is hazardous, whereas use of wooden cutting boards is not.     

Evaluation of the humidity state of glued wooden constructions during monitoring

The work presents the research method for determining the humidity of wood in glued structures during their exploitation. The conductometric method serves a basis for the above-mentioned technique, but instead of regular sensors of humidity meter, we suggest the use of special sensors with electrodes of different lengths. It has been shown that the developed method has a number of advantages compared to the gravimetric method for determining wood humidity and can be used to monitor wooden structures during their exploitation with minimal time and labor inputs.     

Polymerization of acrylonitrile. Kinetics of the reaction initiated by the Ce(IV)/thioacetamide redox system

Vinyl polymerization of acrylonitrile initiated by the Ce(IV)/thioacetamide redox system has been investigated in aqueous sulfuric acid in the temperature range of 10–20°C. The rate of polymerization (R_p) and the rate of Ce(IV) disappearance (?R_Ce) were measured. The effect of certain water-soluble organic solvents, added electrolytes, and aromatic and heterocyclic organic nitrogen compounds on the rate of polymerization has been investigated. Depending on the experimental results, we have suggested a suitable reaction scheme for the system which involves the production of initiating radicals from the oxidation of thioacetamide (TAm) by ceric ion and the termination of the polymer chain by metal ions.     

Study on the impregnation of archaeological waterlogged wood with consolidation treatments using synchrotron radiation microtomography

In favourable conditions of low temperature and low oxygen concentration, archaeological waterlogged wooden artefacts, such as shipwrecks, can survive with a good state of preservation. Nevertheless, anaerobic bacteria can considerably degrade waterlogged wooden objects with a significant loss in polysaccharidic components. Due to these decay processes, wood porosity and water content increase under ageing. In such conditions, the conservation treatments of archaeological wooden artefacts often involve the replacement of water with substances which fill the cavities and help to prevent collapse and stress during drying. The treatments are very often expensive and technically difficult, and their effectiveness very much depends on the chemical and physical characteristics of the substances used for impregnation. Also important are the degree of cavity-filling, penetration depth and distribution in the structure of the wood. In this study, the distribution in wood cavities of some mixtures based on polyethylene glycols and colophony, used for the conservation of waterlogged archaeological wood, was investigated using synchrotron radiation X-ray computed microtomography (SR-μCT). This non-destructive imaging technique was useful for the study of the degraded waterlogged wood and enabled us to visualise the morphology of the wood and the distribution of the materials used in the wood treatments. The study has shown how deposition is strictly related to the dimension of the wooden cavities. The work is currently proceeding with the comparison of synchrotron observations with the data of the solutions viscosity and with those of the properties imparted to the wood by the treatments.     

UV‐Visible Spectroelectrochemical Detection of Side‐Reactions in the Hexacyanoferrate(III)/(II) Electrode Process

Hexacyanoferrate(III)/(II) system has been studied by UV‐visible long‐pathway spectroelectrochemistry. Three different methodologies, based on potentiodynamic techniques, have been successfully used in the thermodynamic characterization of the system. Formation of soluble Prussian Blue has been detected during the electrode process. The values of the formal potential (E^0′=0.200 V) and the electron stoichiometry of this side‐reaction (n=0.5) have been obtained.     

Analytical Properties of Solid-substrate Electrospray Ionization Mass Spectrometry

Conventional electrospray ionization mass spectrometry (ESI-MS) uses a capillary for sample loading and ionization. Along with the development of ambient ionization techniques, ESI-MS using noncapillary emitters has attracted more interest in recent years. Following our recent report on ESI-MS using wooden tips (Anal. Chem. 83, 8201–8207 (2011)), the technique was further investigated and extended in this study. Our results revealed that the wooden tips could serve as a chromatographic column for separation of sample components. Sequential and exhaustive ionization was observed for proteins and salts on wooden tips with salts ionized sooner and proteins later. Nonconductive materials that contain microchannels/pores could be used as tips for ESI-MS analysis with sample solutions loaded to the sharp-ends only, since rapid diffusion of sample solutions by capillary action would enable the tips to become conductive. Tips of inert materials such as bamboo, fabrics, and sponge could be used for sample loading and ionization, while samples such as tissue, mushroom, and bone could form tips to induce ionization for direct analysis with application of a high voltage.

Wavelet formulation of the polarizable continuum model

The first implementation of a wavelet discretization of the Integral Equation Formalism (IEF) for the Polarizable Continuum Model (PCM) is presented here. The method is based on the application of a general purpose wavelet solver on the cavity boundary to solve the integral equations of the IEF‐PCM problem. Wavelet methods provide attractive properties for the solution of the electrostatic problem at the cavity boundary: the system matrix is highly sparse and iterative solution schemes can be applied efficiently; the accuracy of the solver can be increased systematically and arbitrarily; for a given system, discretization error accuracy is achieved at a computational expense that scales linearly with the number of unknowns. The scaling of the computational time with the number of atoms N is formally quadratic but a N^1.5 scaling has been observed in practice. The current bottleneck is the evaluation of the potential integrals at the cavity boundary which scales linearly with the system size. To reduce this overhead, interpolation of the potential integrals on the cavity surface has been successfully used. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Synchronism in the Diels-Alder reaction

Defined as the formation of two new bonds of equal length at the same time, synchronism has been shown to be not possible for the Diels-Alder reaction when the products are not of strict C_s symmetry. This has been done in two steps. First, the SCF -MO transition-state structures for the cyclization reactions of ethylene with cyclopentadiene and furan have been calculated. The activation energies (and heat of reaction) with the STO -3G, 3-21G, and 4-31G basis sets are as follows: with cyclopentadiene 35.0 (?80.7), 30.0 (?32.0), 38.4 (?19.9) kcal/mol; with furan 33.4 (?66.4), 34.6 (?16.5), 42.1 (?8.8) kcal/mol. Then, using a bond-order-bond-length relationship, a value for the tendency toward asynchronism has been calculated for substituted reactants where the two new bonds are arbitrarily held equal. This tendency has been shown in all cases which break strict C_s symmetry. Further, inspection of the atomic-orbital coefficients showed that the substituents cannot be considered as mere perturbations on the pi system in many cases.     

Inhibitory Effects by Ascorbic Acid on the Oscillations of the Briggs?Rauscher Reaction

The Briggs? Rauscher oscillating reaction (in batch mode) has been shown to be sensitive to various antioxidants, some of which cause cessation of oscillations for a period of time, before a restart occurs. The length of time before oscillations restart is related to the type of antioxidant and its concentration. Procedures have been devised to apply this method as a tool for measuring antioxidant activities of pure compounds and of extracts of natural sources. The antioxidant activity in the Briggs? Rauscher system has been generally related to the reaction of an antioxidants with hydroperoxy radicals (HOO^.) present in the oscillating system. Thereby, at low concentration (<2×10^?4 M ), ascorbic acid is known to have a little effect on the reaction. However, there is a concentration range, where a nearly linear relation is observed between ascorbic acid concentration and inhibition time. We were able to model this type of inhibition by the reducing power of ascorbic acid without invoking a reaction with HOO^..     

Spectrophotometric Determination of Dissociation Constants of Thiovioluric Acid and the Stability Constant of its Fe(II) Complex

Spectrophotometric studies of Fe(II)-thiovioluric acid system indicates the presence of a 1:2 complex in the pH range 4.0–6.5. The apparent equilibrium constant (K′₁) has been determined by general absorbance-extinction concentration scheme. The first and second dissociation constants of the acid have been studied at an ionic strength of 0.1 M while the third dissociation constant has been determined at I = 1 M. The effects of sudden pH change and buffer compositions on the dissociations have also been investigated. The stability constant of the complex has been calculated from the apparent equilibrium constant at ionic strength of 0.1 M. The stability constant works out to be 15.67 at pH 5.5.     

Determination of intrinsic properties of immobilized enzymes

Staphylococcal nuclease has been insolubilized, directly through its amino groups, on CNBr-activated Sepharose 2B. For kinetic studies, a small substrate (thymidine 5′-(p-nitrophenyl phosphate) 3′-phosphate) has been used to measure the hydrolytic activity. With this system the absence of diffusional limitation has been proven. Eadie-Hofstee analysis of the data has been employed to determine the intrinsic kinetic constants of the insolubilized enzyme. Thek _cat-pH andK _M−pH profiles and the activation energies are similar for the soluble and for the insolubilized nuclease. At the same time conditions are established in which a stirred batch reactor containing particles of insolubilized nuclease behaves as an open system.