Influence of water content on the acidities in acetonitrile. Quantifying charge delocalization in anions

The effect of traces of water on the relative strengths of acids (ΔpK(a) values) in acetonitrile was quantitatively evaluated experimentally and computationally (COSMO-RS). Water affects first of all the anions by selective solvation. Expectedly, the more localized is the charge in acid anions the higher is the effect of water. The energetic effect of increasing water content from 0 to ca. 10,000 ppm on solvation enthalpies of anions ranged from 0.2-0.4 kcal mol?1 (anions with delocalized charges) to 15 kcal mol?1 in the case of the highly charge-localized acetate ion. In the case of ΔpK(a) values the change ranges from 0.01 to ca. 1.7 pK(a) units (acid pair involving acetic acid). The COSMO-RS method was found to satisfactorily describe the trends in ΔpK(a) values. To quantify the extent of charge localization/delocalization in anions a parameter, weighted average positive σ (WAPS), was introduced, which can be conveniently computed using the COSMO approach. WAPS characterizes the distribution of charge density across the molecular surface and was found to correlate well with the extent of water influence on the dissociation of the respective acid.     

ATR-FT-IR spectroscopy in the region of 550–230 cm−1 for identification of inorganic pigments

A comprehensive study of ATR-FT-IR spectra of 40 inorganic pigments of different colours widely used in historical paintings has been carried out in the low wave number spectral range (550–230 cm^?1). The infrared spectra were recorded from mixtures of pigment and linseed oil. It is demonstrated that this spectral range – essentially devoid of absorption peaks of the common binder materials – can be well used for identification of inorganic pigments in paint samples thereby markedly extending the possibilities of pigment identification/confirmation by ATR-IR spectroscopy into the realm of pigments having no absorptions in the mid-IR region. In some cases the method can be used alone for pigment identification and in many cases it provides useful additional evidence for pigment identification using other instrumental techniques (electron microprobe analysis, XRF, optical microscopy). Together with earlier work this study provides a comprehensive overview of the pigment identification possibilities using ATR-FT-IR as well as a collection of reference spectra and is expected to be a useful reference for conservation practitioners.     

A review of analytical techniques for determination of Sudan I–IV dyes in food matrixes

Sudan dyes are a family of lipophilic azo dyes, extensively used in industrial and scientific applications but banned for use as food colorants due to their carcinogenicity. Due to the continuing illicit use of Sudan dyes as food colorants their determination in different food matrices – especially in different chilli and tomato sauces and related products – has during the recent years received increasing attention all over the world. This paper critically reviews the published determination methods of Sudan I–IV dyes. LC–UV–vis and LC–MS are the dominating methods for analysis of Sudan I–IV dyes. Sudan dyes are usually found in food at mg kg⁻¹ levels at which it may be necessary to use a preconcentration step in order to attain the desired detection limits. Liquid–solid extraction is the dominating sample preparation procedure. In recent years it has been supplemented by ultrasonic-assisted extraction and pressurized liquid extraction. Various solid phase extraction types have been used for sample cleanup. The large majority of works use conventional C18 columns and conventional LC eluents. Traditionally the UV–vis absorbance detection has been the most frequently used. In the recent years MS detection is applied more and more often as it offers more reliable identification possibilities.     

The M/M/c with critical jobs

We consider theM/M/c queue, where customers transfer to a critical state when their queueing (sojourn) time exceeds a random time. Lower and upper bounds for the distribution of the number of critical jobs are derived from two modifications of the original system. The two modified systems can be efficiently solved. Numerical calculations indicate the power of the approach.     

Adaptive discretization of convex multistage stochastic programs

We propose a new scenario tree reduction algorithm for multistage stochastic programs, which integrates the reduction of a scenario tree into the solution process of the stochastic program. This allows to construct a scenario tree that is highly adapted on the optimization problem. The algorithm starts with a rough approximation of the original tree and locally refines this approximation as long as necessary. Promising numerical results for scenario tree reductions in the settings of portfolio management and power management with uncertain load are presented.     

The Mössbauer spectrum of synthetic hureaulite: Fe5 2+(H2O)4(PO4H)2(PO4)2

The crystal structure of synthetic ferrous hureaulite, Fe₅ ²⁺ (H₂O)₄(PO₄H)₂(PO₄)₂, was refined from single-crystal X-ray data. It is monoclinic, space group C2/c, with a=17.487(4), b=9.017(2), c=9.338(2) Å, β=96.27(3)°, V=1463.6(6) Å³, Z=4 and D _calc=3.327 g/cm³. This end member of the hureaulite series was crystallized under distinctly acidic conditions, by a method that gives perfect crystals, large enough for X-ray single crystal studies. The main feature of the hureaulite structure is that it has an equal number of normal (PO₄)³⁺ and acid (PO₄H)²⁺ tetradentate groups. These are centered on Fe²⁺ atoms and share corners with edge-linked octahedra, forming pentamer units. The five Fe²⁺ atoms are distributed on three distinct sites in these units. This can be directly observed in the Mössbauer spectrum at 295 K, which contains three doublets whose relative intensities correspond to the 1:2:2 distributions of crystallographic sites.     

Algorithms for separable nonlinear least squares with application to modelling time-resolved spectra

The multiexponential analysis problem of fitting kinetic models to time-resolved spectra is often solved using gradient-based algorithms that treat the spectral parameters as conditionally linear. We make a comparison of the two most-applied such algorithms, alternating least squares and variable projection. A numerical study examines computational efficiency and linear approximation standard error estimates. A new derivation of the Fisher information matrix under the full Golub-Pereyra gradient allows a numerical comparison of parameter precision under variable projection variants. Under the criteria of efficiency, quality of standard error estimates and parameter precision, we conclude that the Kaufman variable projection technique performs well, while techniques based on alternating least squares have significant disadvantages for application in the problem domain.