Materials,Furnaces, and Texts: How to Write About Making Glass Colours in the Seventeenth Century

Johann Kunckel's Ars Vitraria Experimentalis (1679) is arguably the most important text on seventeenth-century glassmaking. As an augmented German translation of Italian (1612) and English (1662) editions, Kunckel presented a complex and layered text that contained a plethora of recipes, elaborate commentaries and annotations, and various appendices dealing with glass-related technologies and arts. We reworked four recipes for rosichiero glass (a transparent red glass) in Kunckel's book to discover what strategies Kunckel employed to help readers engage with the recipes and to make the recipes work in the specificity of their own workshop. We learned that Kunckel regularly neglected to test the Italian recipes, and that not all of his corrections are improvements, thereby specifying our understanding of the “codification of error” as a strategy to write down colour-making knowledge. Instead, Kunckel made the choice to educate his readers on the very mechanisms of glass colouring to allow them to intervene to influence the colour of the glass and to gain further control over the making process. He argued that the colour of glass is sensitive to the manner in which ingredients are sourced and processed, and emphasised the importance of furnace management in optimising the colour of glass.     

Catalytic Asymmetric Torgov Cyclization: A Concise Total Synthesis of (+)‐Estrone

An asymmetric Torgov cyclization, catalyzed by a novel, highly Brønsted acidic dinitro‐substituted disulfonimide, is described. The reaction delivers the Torgov diene and various analogues with excellent yields and enantioselectivity. This method was applied in a very short synthesis of (+)‐estrone.     

Chemoselective Catalysis with Organosoluble Lewis Acidic Polyoxotungstates

The preparation of new organosoluble Lewis acidic polyoxometalates (POMs) is reported. These complexes were prepared by the incorporation of Zr, Sc, and Y atoms into the corresponding monolacunary Dawson [P₂W₁₇O₆₁]^10? and Keggin [PW₁₁O₃₉]^7? polyoxotungstates. The catalytic activity of these compounds was evaluated for C? C bond formation in the Diels–Alder, Mannich, and Mukaiyama‐type reactions. Comparisons with previously described Lewis acidic POMs are reported. Competitive reactions between imines and aldehydes or between various imines demonstrated that fine tuning of the reactivity could be reached by varying the metal atom incorporated into the polyanionic framework. A series of experiments that employed pyridine derivatives allowed us to distinguish between the Lewis and induced Brønsted acidity of the POMs. These catalysts activate imines in a Lewis acidic way, whereas aldehydes are activated by indirect Brønsted catalysis.     

High-resolution IR cavity ring-down spectroscopy of jet-cooled free radicals and other species

Initial spectral results are reported from a newly constructed cavity ringdown spectrometer. The apparatus incorporates a slit-jet expansion, with or without a discharge, to produce cold sample molecules. High spectral resolution in both the near- and mid-IR is obtained by using stimulated Raman scattering of the pulsed amplified output of a cw Ti:Sa ring laser. Molecular spectra presented include the electronic near-IR transitions a (1)Delta(g)(-)<-- X (3)Sigma(g)(-) of O(2) and B (3)Pi(g)<-- A (3)Sigma(u)(+) of metastable N(2) and vibrational overtones of H(2)O (polyad 2) and the OH radical. Fundamental vibrational transitions of CH(3) (nu(3)) in the mid-IR are also observed. This apparatus has demonstrated the potential for obtaining high-resolution spectra of both reactive and non-reactive species throughout the entire IR region.     

Differential Algebras with Banach-Algebra Coefficients II: The Operator Cross-Ratio Tau-Function and the Schwarzian Derivative

Several features of an analytic (infinite-dimensional) Grassmannian of (commensurable) subspaces of a Hilbert space were developed in the context of integrable PDEs (KP hierarchy). We extended some of those features when polarized separable Hilbert spaces are generalized to a class of polarized Hilbert modules and then consider the classical Baker and τ-functions as operator-valued. Following from Part I we produce a pre-determinant structure for a class of τ-functions defined in the setting of the similarity class of projections of a certain Banach *-algebra. This structure is explicitly derived from the transition map of a corresponding principal bundle. The determinant of this map leads to an operator τ-function. We extend to this setting the operator cross-ratio which had previously been used to produce the scalar-valued τ-function, as well as the associated notion of a Schwarzian derivative along curves inside the space of similarity classes of a given projection. We link directly this cross-ratio with Fay’s trisecant identity for the τ-function. By restriction to the image of the Krichever map, we use the Schwarzian to introduce the notion of an operator-valued projective structure on a compact Riemann surface: this allows a deformation inside the Grassmannian (as it varies its complex structure). Lastly, we use our identification of the Jacobian of the Riemann surface in terms of extensions of the Burchnall–Chaundy C*-algebra (Part I) provides a link to the study of the KP hierarchy.     

Characterization of the surface of positive electrodes for Li-ion batteries using 7Li MAS NMR

The growth and evolution of the interphase, due to contact with the ambient atmosphere or electrolyte, are followed using ⁷Li magic-angle spinning nuclear magnetic resonance (MAS NMR) in the case of two materials amongst the most promising candidates for positive electrodes for lithium batteries: LiFePO₄ and LiMn_0.5Ni_0.5O₂. The use of appropriate experimental conditions to acquire the NMR signal allows observing only the «diamagnetic» lithium species at the surface of the grains of active material. The reaction of LiMn_0.5Ni_0.5O₂ with the ambient atmosphere or LiPF₆ (1 M in Ethylene Carbonated/DiMéthyl Carbonate (EC/DMC)) electrolyte is extremely fast and leads to an important amount of lithium-containing diamagnetic species compared to what can be observed in the case of LiFePO₄. The two studied materials display a completely different surface chemistry in terms of reactivity and/or kinetics of the surface towards electrolyte. Moreover, these results show that MAS NMR is a very promising tool to monitor phenomena taking place at the interface between electrode and electrolyte.     

Demodulation of Spatial Carrier Images: Performance Analysis of Several Algorithms Using a Single Image

Optical full-field techniques have a great importance in modern experimental mechanics. Even if they are reasonably spread among the university laboratories, their diffusion in industrial companies remains very narrow for several reasons, especially a lack of metrological performance assessment. A full-field measurement can be characterized by its resolution, bias, measuring range, and by a specific quantity, the spatial resolution. The present paper proposes an original procedure to estimate in one single step the resolution, bias and spatial resolution for a given operator (decoding algorithms such as image correlation, low-pass filters, derivation tools …). This procedure is based on the construction of a particular multi-frequential field, and a Bode diagram representation of the results. This analysis is applied to various phase demodulating algorithms suited to estimate in-plane displacements.