Setting local rank constraints by orthogonal projections for image resolution analysis: Application to the determination of a low dose pharmaceutical compound

Raman chemical imaging provides chemical and spatial information about pharmaceutical drug product. By using resolution methods on acquired spectra, the objective is to calculate pure spectra and distribution maps of image compounds. With multivariate curve resolution-alternating least squares, constraints are used to improve the performance of the resolution and to decrease the ambiguity linked to the final solution. Non negativity and spatial local rank constraints have been identified as the most powerful constraints to be used.     

Spectral properties of a tight binding Hamiltonian with period doubling potential

We study a one dimensional tight binding hamiltonian with a potential given by the period doubling sequence. We prove that its spectrum is purely singular continuous and supported on a Cantor set of zero Lebesgue measure, for all nonzero values of the potential strength. Moreover, we obtain the exact labelling of all spectral gaps and compute their widths asymptotically for small potential strength.     

Primal cutting plane algorithms revisited

Dual fractional cutting plane algorithms, in which cutting planes are used to iteratively tighten a linear relaxation of an integer program, are well-known and form the basis of the highly successful branch-and-cut method. It is rather less well-known that various primal cutting plane algorithms were developed in the 1960s, for example by Young. In a primal algorithm, the main role of the cutting planes is to enable a feasible solution to the original problem to be improved. Research on these algorithms has been almost non-existent.  In this paper we argue for a re-examination of these primal methods. We describe a new primal algorithm for pure 0-1 problems based on strong valid inequalities and give some encouraging computational results. Possible extensions to the case of general mixed-integer programs are also discussed.     

Konvergente und asymptotische Darstellungen für die Lösungen linearer Differentialgleichungen,deren Koeffizienten Dirichletsche Reihen oder Exponentialpolynome mit komplexen Exponenten sind

Ohne ZusammenfassungDie vorliegende Arbeit wurde von der Mathematisch-naturwissenschaftlichen Fakultät der Universität Jena als Dissertation (D 27) angenommen. nachdem sie vorher einen Fakultätspreis erhalten hatte. Referent war Herr Prof. Hermann Schmidt. Ich möchte ihm auch hier meinen Dank für die Förderung aussprechen, die er mir durch seine vielfachen persönlichen Anregungen zuteil werden ließ.     

Collisional parameters of H2O lines: effects of vibration

A complex semiclassical model for the calculation of line widths and shifts of H₂O broadened by N₂, derived from the Robert and Bonamy approach, is tested by comparisons with measurements for selected transitions in various vibrational bands. The lines retained, which involve rotational states with Kc=J or J−1 have been chosen for two reasons. The first is that they show large variations of the widths with J and thus enable a severe test of the model. The second is that, as explained in this paper, they are well-suited for the study of the effects of vibration on the collisional parameters. The measured values have been extracted from an updated version of a database built years ago (JQSRT 52 (1994) 481) that contains all available measurements. Comparisons between experimental and calculated widths and shifts at room temperature illustrate the quality of the model and clearly demonstrate, for the first time, that there is a vibrational dependence of the broadening. Values of collisional parameters are first studied in fundamental bands. This shows that the theoretical approach accounts for most of the dependence of broadening and shifting on rotational quantum numbers: the variations of γ, which reach a factor of nearly 20 from low to high J values, are correctly accounted for by the model as are some specific features of the shifts δ. Analysis confirms that the bending and stretching vibrations have significantly different effects on δ, due to the vibrational dependence of the intermolecular potential. On the other hand, differences on the widths are rather small with slightly smaller broadening for lines of the bending band. Calculations show that there is a spectroscopic effect, due to the larger rotational constant A in the v₂=1 state. Calculations made for overtone bands involving numerous quanta of the stretching vibration are then presented. They predict that a significant dependence of the width should be observed for high J lines due to the effect of vibration on the interaction potential. This is confirmed by comparisons with measurements for lines involving a change of three and four quanta of stretching vibration.     

Influence of organic modifiers on morphology and crystallization of poly(ϵ‐caprolactone)/synthetic clay intercalated nanocomposites

ε‐caprolactone was polymerized in the presence of neat montmorillonite or organomontmorillonites to obtain a variety of poly(ε‐caprolactone) (PCL)‐based systems loaded with 10 wt % of the silicates. The materials were thoroughly investigated by different X‐ray scattering techniques to determine factors affecting structure of the systems. For one of the nanocomposites it was found that varying the temperature in the range corresponding to crystallization of PCL causes reversible changes in the interlayer distance of the organoclay. Extensive experimental and literature studies on this phenomenon provided clues indicating that this effect might be a result of two‐dimensional ordering of PCL chains inside the galleries of the silicate. Small angle X‐ray scattering and wide angle X‐ray scattering investigation of filaments oriented above melting point of PCL revealed that polymer lamellae were oriented perpendicularly to particles of unmodified silicate, while in PCL/organoclay systems they were found parallel to clay tactoids. Calorimetric and microscopic studies shown that clay particles are effective nucleating agents. In the nanocomposites, PCL crystallized 20‐fold faster than in the neat polymer. The crystallization rate in nanocomposites was also significantly higher than in microcomposite. Further research provided an insight how the presence of the filler affects crystalline fraction and spherulitic structure of the polymer matrix in the investigated systems. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2350–2367, 2007     

Mineralogical analysis of auriferous ores from the El Diamante mine, Colombia

X-ray diffraction (XRD), Mössbauer spectrometry (MS), secondary ions mass spectroscopy (SIMS) and laser-ablation microprobe–inductively coupled plasma–mass spectrometry (LAM–ICP–MS) were used to study mineral samples of Colombian auriferous ores collected from the “El Diamante” mine, located in the municipality of Guachavez-Nariño, in Colombia. The samples were prepared as polished thin sections and polished sections. From XRD data, quartz, sphalerite and pyrite were detected and their respective cell parameters were estimated. From MS analyses, pyrite, arsenopyrite and chalcopyrite were identified; their respective hyperfine parameters and respective texture were deduced. Multiple regions of approximately 200 × 200 μm in each sample were analyzed with SIMS; the occurrence of “invisible gold” associated mainly with pyrite and secondarily with arsenopyrite could thus be assigned. It was also found that pyrite is of the arsenious type. Spots from 30 to 40 μm in diameter were analyzed with LAM–ICP–MS for pyrite, arsenopyrite and sphalerite; Au is “homogeneously” distributed inside the structure of the arsenious pyrite and the arsenopyrite (not as inclusions); the chemical composition indicates similarities of this “invisible gold”, forming a solid solution with arsenious pyrite and arsenopyrite. One hundred nineteen and 62 ppm of ‘invisible gold’ was quantified in 21 spots analyzed on pyrite and in 14 spots on arsenopyrite, respectively.     

HAC estimation and strong linearity testing in weak ARMA models

In the framework of ARMA models, we consider testing the reliability of the standard asymptotic covariance matrix (ACM) of the least-squares estimator. The standard formula for this ACM is derived under the assumption that the errors are independent and identically distributed, and is in general invalid when the errors are only uncorrelated. The test statistic is based on the difference between a conventional estimator of the ACM of the least-squares estimator of the ARMA coefficients and its robust HAC-type version. The asymptotic distribution of the HAC estimator is established under the null hypothesis of independence, and under a large class of alternatives. The asymptotic distribution of the proposed statistic is shown to be a standard χ² under the null, and a noncentral χ² under the alternatives. The choice of the HAC estimator is discussed through asymptotic power comparisons. The finite sample properties of the test are analyzed via Monte Carlo simulation.     

Constraint incorporation in optimization

Numerical methods for solving constrained optimization problems need to incorporate the constraints in a manner that satisfies essentially competing interests; the incorporation needs to be simple enough that the solution method is tractable, yet complex enough to ensure the validity of the ultimate solution. We introduce a framework for constraint incorporation that identifies a minimal acceptable level of complexity and defines two basic types of constraint incorporation which (with combinations) cover nearly all popular numerical methods for constrained optimization, including trust region methods, penalty methods, barrier methods, penalty-multiplier methods, and sequential quadratic programming methods. The broad application of our framework relies on addition and chain rules for constraint incorporation which we develop here.