Application of Electrospray Ionization Mass Spectrometry to the Elucidation of the Primary Structure of Lignin

Electrospray ionization mass spectrometry (ESI‐MS) was successfully applied to the structural analysis of lignin. The structure of oligomers fractionated from Eucalyptus globulus dioxane lignin was elucidated using tandem mass spectrometry, and the information on fragmentation patterns was provided by experiments on dimeric model compounds. Data obtained revealed a significant abundance in the lignin macromolecules of linear fragments that were composed of 8‐O‐4′‐linked syringyl/guaiacyl units and syringaresinol.

The proposed linear fragment of the E. globulus lignin molecule.     

Magneto-Raman scattering of graphene on graphite: electronic and phonon excitations

Magneto-Raman-scattering experiments from the surface of graphite reveal novel features associated to purely electronic excitations which are observed in addition to phonon-mediated resonances. Graphene-like and graphite domains are identified through experiments with ～1 μm spatial resolution performed in magnetic fields up to 32 T. Polarization resolved measurements emphasize the characteristic selection rules for electronic transitions in graphene. Graphene on graphite displays the unexpected hybridization between optical phonon and symmetric across the Dirac point inter Landau level transitions. The results open new experimental possibilities--to use light scattering methods in studies of graphene under quantum Hall effect conditions.     

Spectroscopic and theoretical studies on solid 1,2-ethylenediamine dihydrochloride salt.

A structural study of [H3N(CH2)2NH3)]2+.2Cl-, the smallest element of the homologous series of the alpha,omega-diamine dihydrochlorides, was carried out by means of Raman and FTIR spectroscopy coupled to ab initio molecular orbital (MO) calculations. As a primary concern, an adequate molecular model for the representation of these solid amine salts was chosen. Thus, several models, varying in the number and position of the counterions as well as in the number of diamine units, were considered. It was found that the best molecular system (i.e., that yielding the best compromise between accuracy and computational requirements) consists of one ethylenediamine cation surrounded by six chloride ions in an arrangement based on the crystal structure reported in the literature for [H3N(CH2)2NH3)]2+.2Cl-. This conclusion will hopefully allow for a better understanding of the conformational preferences, in the solid state, of these biologically relevant linear polyamines.     

Momentum distributions in the nucleus

The nuclear form factor F(q) and one particle momentum distribution p(q) can be shown to have a power law decrease for large momenta. For the form factor F(q) we show that it is q/A that must be large for this asymptotic behavior to be important. For only q large the form factor, in a simple model, is shown to decrease exponentially in q. A similar behavior for p(q) is proposed.     

Fractional Hamiltonian systems with positive semi-definite matrix

We study the existence of solutions for the following fractional Hamiltonian systems $$ \left\{ \begin{array}{ll} - _tD^{\alpha}_{\infty}(_{-\infty}D^{\alpha}_{t}u(t))-\lambda L(t)u(t)+\nabla W(t,u(t))=0,\\[0.1cm] u\in H^{\alpha}(\mathbb{R},\mathbb{R}^n), \end{array} \right. ~~~~~~~~~~~~~~~~~(FHS)_\lambda $$ where $\alpha\in (1/2,1)$, $t\in \mathbb{R}$, $u\in \mathbb{R}^n$, $\lambda>0$ is a parameter, $L\in C(\mathbb{R},\mathbb{R}^{n^2})$ is a symmetric matrix, $W\in C^1(\mathbb{R} \times \mathbb{R}^n,\mathbb{R})$. Assuming that $L(t)$ is a positive semi-definite symmetric matrix, that is, $L(t)\equiv 0$ is allowed to occur in some finite interval $T$ of $\mathbb{R}$, $W(t,u)$ satisfies some superquadratic conditions weaker than Ambrosetti-Rabinowitz condition, we show that (FHS)$_\lambda$ has a solution which vanishes on $\mathbb{R}\setminus T$ as $\lambda \to \infty$, and converges to some $\tilde{u}\in H^{\alpha}(\R, \R^n)$. Here, $\tilde{u}\in E_{0}^{\alpha}$ is a solution of the Dirichlet BVP for fractional systems on the finite interval $T$. Our results are new and improve recent results in the literature even in the case $\alpha =1$.     

Electronic states of on- and off-center donors in quantum rings of finite width

The electronic states of a hydrogenic donor in two-dimensional quantum rings are calculated by taking into account the finite width of the potential well in the ring. In addition, a strong magnetic field is applied perpendicular to the quantum ring. Using the effective-mass approximation at the Γ valley, the radial Hamiltonian for the envelope-function is exactly diagonalized in the case of on-center donors. The corresponding energy levels for different angular momenta are studied as a function of the applied magnetic field. In the case of off-center donors, a perturbation approach is considered and its limitations are discussed. Finally, we calculate the absorption spectra and oscillator strength for different intraband transitions, specifically for on-center donors.     

High-impact polystyrene/polyaniline membranes for acid solution treatment by electrodialysis: preparation, evaluation, and chemical calculation

In this study different membranes were produced, aiming to evaluate their use in electrodialysis. These membranes were produced using conventional polymer (high-impact polystyrene) and polyaniline. The membrane characterization was done by FTIR spectroscopy, scanning electron microscopy (SEM), and thermogravimetry (TGA). The studies of the zinc and proton extraction ionic transport through the membranes were evaluated using a three-compartment cell. The results obtained using the produced membranes were compared to the results obtained with the commercial membrane Nafion 450. It was found that a synthesized membrane can be used to recover zinc in acid media. In addition, a preliminary computational essay about the structures of PAni and CSA is presented.     

Secondary ion yields produced by keV atomic and polyatomic ion impacts on a self-assembled monolayer surface

A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd.     

Effect of hydrogen bonding in the vibrational spectra of trans‐cinnamic acid

A computationally‐assisted methodology to assign the vibrational spectra of molecular materials (PiMM) has been successfully applied to the Raman and infrared (IR) spectra of trans‐cinnamic acid (t‐CIA) in the solid state. The effects of molecular association through O H···O hydrogen‐bonding in both the wavenumber and the intensity of the bands are accurately described by a single dimer structure. This supports the discrimination between the possible conformers in the solid, the complete evaluation of hydrogen‐bonding effects, and the full assignment of the vibrational spectra of t‐CIA. Copyright © 2008 John Wiley & Sons, Ltd.     

Hydrogen bonding in nitrofurantoin polymorphs: a computation‐assisted spectroscopic study

The importance of hydrogen‐bond formation in the molecular packing arrangements of two anhydrous forms of nitrofurantoin is investigated, combining computational methods and spectroscopic data. The overall results indicate, as expected, that the vibrational modes related to the CO, N H and C H groups are strongly affected by intermolecular hydrogen‐bond formation. Moreover, the importance of weak C‐H···O interactions in conferring additional stability to molecular associations in biological systems is evidenced in this study. The complete assignment of the Raman and infrared spectra of both polymorphs is accomplished by means of a computationally based methodology, which accounts for the effects of intermolecular interactions in the crystal. The vibrational shifts due to crystal packing interactions are evaluated from DFT calculations for a set of suitable molecular pairs, using the B3LYP/6‐31G* approach. This methodology provides an answer to the current demand for a reliable and complete assignment of the vibrational spectra of pharmaceutically active compounds such as nitrofurantoin. Copyright © 2009 John Wiley & Sons, Ltd.