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.     

Recent advances on the use of active anodes in environmental electrochemistry

Active anodes, especially those consisting of metal mixed oxides (MMOs) containing Ru and/or Ir oxides, have been applied in the treatment of wastewater, especially when chloride ions are present. Their characteristics continuously drive the study of applications of these materials, be they in the degradation of different organic molecules, the preparation of new electrode materials and in the association of various processes to increase pollutant removal. Thus, this brief review aims to present some of the recent advances in the application of active anode materials in environmental electrochemistry. Focussing on the 2018–2020 period, it is possible to note many applied studies, using commercially available materials, covering a wide range of target pollutants. Still other studies aim to modify the catalyst surfaces to increase the mineralization capacity, and the use of these anodes in the production of free chlorine species to mediate indirect organic reduction is observed.     

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.     

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.     

Carbon-13 NMR evidence for cocrystallization of cellulose as a mechanism for hornification of bleached kraft pulp

Solid-state ¹³C NMR spectroscopy was used to characterize a bleached softwood kraft pulp in the never-dried state and after cycles of drying and remoistening. Changes in NMR signal strengths indicated that growth of crystalline domains involved cocrystallization rather than accretion of cellulose from noncrystalline domains. A cluster of C-4 signals at 89.4 ppm, assigned to the interiors of crystalline domains, grew at the expense of C-4 signals at 84.0 and 84.9 ppm, assigned to the well-ordered surfaces of crystalline domains. Irreversible changes were not detected until the moisture content dropped below 18%. They were enhanced by a second drying/remoistening cycle, but showed little further change on subsequent cycles. The necessary conditions resembled those reported for hornification, suggesting that cocrystallization might provide a mechanism for hornification.     

Solvent‐ and interface‐induced surface segregation in blends of isotactic polypropylene with poly(ethylene‐co‐propylene) rubber

The surface compositions and morphologies of melt‐quenched blends of isotactic polypropylene (iPP) with aspecific poly(ethylene‐co‐propylene) rubber (aEPR) were characterized by atomic force microscopy, optical microscopy, and X‐ray photoelectron spectroscopy. The surface morphologies and compositions formed in the melt are frozen‐in by crystallization of the iPP component and, depending on the processing conditions, are enriched in iPP or aEPR or contain a phase‐separated mix of iPP and aEPR. Enrichment of iPP is observed for blends melted in open air, in agreement with earlier work showing the high surface activity of atactic polypropylene at open interfaces. Surface segregation of iPP is suppressed at confined interfaces. Blends melt‐pressed between hydrophilic and hydrophobic substrates have phase‐separated iPP and aEPR domains present at the surface, which grow in size as the melt time increases. Surface enrichment of aEPR is observed after exposing melt‐pressed blends to n‐hexane vapor, which preferentially solvates aEPR and draws it to the surface. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 421–432, 2004