Rapid identification of common hexapyranose monosaccharide units by a simple TOCSY matching approach

Solution NMR spectroscopy is a well established technique for non-destructive characterization of the structures and conformations of complex oligo- and polysaccharides. One of the key experiments involves the use of 2D TOCSY to collect the 1H spins into groups that can be associated with the individual saccharide units that are present in the molecule under study. It is well known that the magnetization transfer rate through the 1H spin system during the TOCSY spin lock period is sensitive to the intervening 3J(H,H) scalar couplings, and therefore also to the saccharide stereochemistry. Here, we have investigated the potential to extract information on the stereochemistry of hexapyranose monosaccharide units directly from TOCSY spectra. Through a systematic experimental investigation of the magnetization transfer initiated from the anomeric 1H resonance in D-glucose, D-galactose and D-mannose it is shown that a 100 ms spin lock time provides optimal spectroscopic discrimination between these three commonly occurring building blocks. A simple matching scheme is proposed as a new tool for rapid attribution of the TOCSY traces originating from the anomeric 1H resonances towards the underlying monosaccharide type. The scheme appears robust with regard to structural variations and fairly tolerant to incidental overlap. Its application provides useful guidance during the subsequent NMR assignment process, as demonstrated with the PS7F polysaccharide from Streptococcus pneumonia. In addition, we show that our scheme affords a clear-cut distinction between the alpha- and beta-epimers of D-mannose-type units, which can be difficult to discriminate by NMR analysis. Application to the N-glycan 100.2 demonstrates the potential and wide applicability of this new discrimination approach.     

Assessing weak intramolecular donor-acceptor interactions using 1H-117Sn J-HMQC spectroscopy

It is demonstrated that long-range nJ(1H,117Sn) coupling constants down to 0.3 Hz, can be accurately quantified from non-linear fitting of the sine modulation of the associated 1H-117Sn correlation cross-peak intensities sampled as a function of the heteronuclear antiphase coherence preparation time in the 1H-117Sn J-HMQC pulse sequence. The contribution of additional, undesired modulations is illustrated and assessed using the product operator formalism, and is traced back to contributions that arise from miss-setting of the wandering 180 degrees pulse angle in the constant time period. The power of the method and its use in the characterization of weak intramolecular donor-acceptor interactions are illustrated by the determination of long-range nJ(1H,117Sn) coupling constants of bis[3-(dimethylamino)propyl]tin derivatives, [Me2N(CH2)3]2SnR2 (', R = Me; 3, R = Ph; 4, R = t-Bu). By comparing these with the values found for the corresponding bis(4-methylpentyl)tin derivatives, [Me2CH(CH2)3]2SnR2 (2', R = Me; 3', R = Ph), which lack such interactions, the use of long-range coupling constants to detect intramolecular donor-acceptor interactions is evaluated. It is concluded that nJ(1H,117Sn) couplings up to six bonds through an organic carbon chain can be quantified, whether donor-acceptor interactions are present or not. Furthermore, evidence is presented that, when two scalar coupling pathways co-exist, the pathway involving an intramolecular donor-acceptor interaction can have opposite sign, thus decreasing the overall coupling constant to a value smaller than that actually measured in the absence of a donor-acceptor interaction, where only one coupling pathway is active. There is nevertheless clear numerical value discrimination in the series of compounds investigated between long-range couplings in derivatives without weak intramolecular donor-acceptor interactions and those where such interactions can exist.     

Synthesis of Catechol Derived Rosamine Dyes and Their Reactivity toward Biogenic Amines

Functional organic dyes play a key role in many fields, namely in biotechnology and medical diagnosis. Herein, we report two novel 2,3- and 3,4-dihydroxyphenyl substituted rosamines (3 and 4, respectively) that were successfully synthesized through a microwave-assisted protocol. The best reaction yields were obtained for rosamine 4, which also showed the most interesting photophysical properties, specially toward biogenic amines (BAs). Several amines including n- and t-butylamine, cadaverine, and putrescine cause spectral changes of 4, in UV–Vis and fluorescence spectra, which are indicative of their potential application as an effective tool to detect amines in acetonitrile solutions. In the gas phase, the probe response is more expressive for spermine and putrescine. Additionally, we found that methanolic solutions of rosamine 4 and n-butylamine undergo a pink to yellow color change over time, which has been attributed to the formation of a new compound. The latter was isolated and identified as 5 (9−aminopyronin), whose solutions exhibit a remarkable increase in fluorescence intensity together with a shift toward more energetic wavelengths. Other 9-aminopyronins 6a, 6b, 7a, and 7b were obtained from methanolic solutions of 4 with putrescine and cadaverine, demonstrating the potential of this new xanthene entity to react with primary amines.     

Calibration transfer employing univariate correction and robust regression

This paper proposes a new method for calibration transfer, which was specifically designed to work with isolated variables, rather than the full spectrum or spectral windows. For this purpose, a univariate procedure is initially employed to correct the spectral measurements of the secondary instrument, given a set of transfer samples. A robust regression technique is then used to obtain a model with low sensitivity with respect to the univariate correction residuals. The proposed method is employed in two case studies involving near infrared spectrometric determination of specific mass, research octane number and naphthenes in gasoline, and moisture and oil in corn. In both cases, better calibration transfer results were obtained in comparison with piecewise direct standardization (PDS). The proposed method should be of a particular value for use with application-targeted instruments that monitor only a small set of spectral variables.     

Tunneling rate for superparamagnetic particles by the instanton method

We derive the tunneling rate for paramagnetic molecules in the context of a collective spin model. By means of path integral methods, an analytical expression is derived. Given the very large spins in question (s3000), the observation of magnetization changes due to pure unitary tunnel effects is unlikely.     

Eigenvalues of matrix commutators

We characterize the eigenvalues of [X,A]=XA-AX, where A is an n by n fixed matrix and X runs over the set of the matrices of the same size.     

Monadic dynamic algebras

The main purpose of this work is to introduce the class of the monadic dynamic algebras (dynamic algebras with one quantifier). Similarly to a theorem of Kozen we establish that every separable monadic dynamic algebra is isomorphic to a monadic (possibly non‐standard) Kripke structure. We also classify the simple (monadic) dynamic algebras. Moreover, in the dynamic duality theory, we analyze the conditions under which a hemimorphism of a dynamic algebra into itself defines a quantifier. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The algebraic Bethe ansatz for rational braid-monoid lattice models

In this paper we study isotropic integrable systems based on the braid-monoid algebra. These systems constitute a large family of rational multistate vertex models and are realized in terms of the B_n, C_nand D_n Lie algebra and by the superalgebra Osp(n||2m). We present a unified formulation of the quantum inverse scattering method for many of these lattice models. The appropriate fundamental commutation rules are found, allowing us to construct the eigenvectors and the eigenvaluesof the transfer matrix associated to the B_n, C_n, D_n, Osp(2nt-1||2), Osp(2||2nt-2), Osp(2nt-2||2) and Osp(1||2n) models. The corresponding Bethe ansatz equations can be formulated in terms of the root structure of the underlying algebra.     

High precision analysis of finlines on semiconductor substrate

In this study, the effect of the metallization thickness in finlines on semiconcuctor substrate is researched. The propagation parameters are computed to measure the inluence of the metallization. The theory and numerical results are presented to the propagation constant and characteristic impedance of the bilateral and unilateral finlines. The full wave analysis of the transverse transmission line — TTL method is used to determine the electromagnetic fields of the structure in Fourier transform domain — FTD. Applying the suitable boundary conditions, the moment method and expanding the fields in a set of suitable bases functions, a homogeneous matrix system is obtained and the propagation constant is computed. The characteristic impedance is obtained using the relation of the voltage in the slot and the transmitted power by the structure.Computational programs are developed to obtain numerical results to the propagation parameters composed by the propagation constant and characteristic impedance.This work received financial support by CAPES and CNPq.