Reactions between alkaloids and tetraphenylboron and their analytical application : A heterometric study

The reactions between tetraphenylboron (TPB) and acriflavine, rivanol, nitron, cinchonine, quinine, strychnine, papaverine, sparteine, phenanthroline, pyramidon, antipyrine, atropine and oxine were studied heterometrically at pH values 1–9. The reactions were about one third as sensitive as with bismuth nitrate in iodide solution. The sensitivity in the above series decreases from acriflavine to oxine. Precise titrations could always be carried out with TPB. Compounds with two adjacent N atoms gave no precipitation, at pH 5–7. The structures of the compounds and the analytical aspects are discussed and a method of determination is presented.     

Structural variations among the aporphine-benzylisoquinoline dimers

$\text{Thalictrum}$$\text{minus}$ L. var. $\text{microphyllum}$ Boiss. (Ranunculaceae) has yielded (+)-istanbulamine ($\text{5}$) which is the first aporphine-benzylisoquinoline formed from one (+)-reticuline-type unit linked to a (+)-N-methylcoclaurine moiety. Other new dimers also present are (+)-bursanine ($\text{6}$) and (+)-iznikine ($\text{7}$).     

Structural Features of the Unready Ni-A State of [NiFe] Hydrogenase Revealed by X-Ray Crystallography and EPR Spectroscopy

The oxidized “unready” Ni-A state [NiFe] hydrogenases has been the subject of recent investigations by spectroscopic and crystallographic techniques. In the Ni-A state, the enzyme is inhibited and cannot turn over molecular hydrogen. Ideally, if the Ni-A state can be avoided, and if the oxidized enzyme exclusively resides in the “ready” Ni-B state, it can be quickly activated, thus increasing its activity of hydrogen production. In this study, recent observations by electron paramagnetic resonance spectroscopy as well as X-ray crystallography are combined and interpreted. Though it remains a mystery as to which differences exist on the geometric and electronic level between the Ni-A and Ni-B states, and in particular about the exact structure of the active site in the Ni-A state, the recent studies when combined do provide important hints.     

Compact chip-scale filter based on curved waveguide Bragg gratings

We propose a method for miniaturization of filters based on curved waveguide Bragg gratings, so that long structures can be packed into a small area on a chip. This eliminates the stitching errors introduced in the fabrication process, which compromise the performance of long Bragg gratings. Our approach relies on cascading curved waveguide Bragg gratings with the same radius of curvature. An analytical model for the analysis of these devices was developed, and a filter based on this model was designed and fabricated in a silicon on insulator platform. The filter had a total length of 920μm, occupied an area of 190μm×114μm, and exhibited a stop band of 1.7nm at 1.55μm and an extinction ratio larger than 23dB.     

Hydrogen bonding affects the [NiFe] active site of Desulfovibrio vulgaris Miyazaki F hydrogenase: a hyperfine sublevel correlation spectroscopy and density functional theory study

Pulse electron paramagnetic resonance and hyperfine sublevel correlation spectroscopy have been used to investigate nitrogen coordination of the active site of [NiFe] hydrogenase of Desulfovibrio vulgaris Miyazaki F in its oxidized "ready" state. The obtained (14)N hyperfine (A = [+1.32, +1.32, +2.07] MHz) and nuclear quadrupole (e(2)qQ/h = -1.9 MHz, eta = 0.37) coupling constants were assigned to the N(epsilon) of a highly conserved histidine (His88) by studying a hydrogenase preparation in which the histidines were (15)N labeled. The histidine is hydrogen-bonded via its N(epsilon)-H to the nickel-coordinating sulfur of a cysteine (Cys549) that carries an appreciable amount of spin density. Through the hydrogen bond a small fraction of the spin density ( approximately 1%) is delocalized onto the histidine ring giving rise to an isotropic (14)N hyperfine coupling constant of about 1.6 MHz. These conclusions are supported by density functional calculations. The measured (14)N quadrupole coupling constants are related to the polarization of the N(epsilon)-H bond, and the respective hydrogen bond can be classified as being weak.     

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.