Solvent Influence on Cellulose 1,4‐β‐Glycosidic Bond Cleavage: A Molecular Dynamics and Metadynamics Study

We explore the influence of two solvents, namely water and the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate (EmimAc), on the conformations of two cellulose models (cellobiose and a chain of 40 glucose units) and the solvent impact on glycosidic bond cleavage by acid hydrolysis by using molecular dynamics and metadynamics simulations. We investigate the rotation around the glycosidic bond and ring puckering, as well as the anomeric effect and hydrogen bonds, in order to gauge the effect on the hydrolysis mechanism. We find that EmimAc eases hydrolysis through stronger solvent–cellulose interactions, which break structural and electronic barriers to hydrolysis. Our results indicate that hydrolysis in cellulose chains should start from the ends and not in the centre of the chain, which is less accessible to solvent.     

Temperature dependence of hyperfine fields in intermediate valent140CeLa and140CeLu

The hyperfine fields for the systems¹⁴⁰CeLa and¹⁴⁰CeLu have been determined by time differential perturbed angular correlations (TDPAC) in the temperature range 4.2 K≤T≤330 K. Magnitude and temperature dependence of the paramagnetic enhancement factor β indicate that cerium in either system is of intermediate valence. This behaviour is discussed in terms of a theory proposed by Ramakrishnan et al. [1–3].     

Image Formation in Low Vacuum SEM

The role of positive gaseous ions in the formation of secondary electron images in low vacuum scanning electron microscopes is discussed. This paper describes the charging processes and related effects that occur during high vacuum imaging of insulators and then discusses the influence of ions on those processes. The ions are responsible for a number of phenomena, including distortion of the electric field above and below the specimen surface due to space charge, removal of excess negative charge from the specimen, alteration of the specimen surface barrier, and scavenging/filtering of the secondary electron emission. The resulting electron-specimen-ion interactions can give rise to interesting contrast effects that are unique to this class of instruments.     

Monitoring genomic alterations with a panel of oligonucleotide probes specific for various simple repeat motifs

Germline and somatic instability of the human genome was studied, using synthetic oligonucleotides specific for simple repeat motifs. The following probes were used: (GTG)5, (GACA)4, (GATA)4, (CT)8, (TTAGGG)3, (GT)8, (GAA)6 and (GGAT)4. Each of them is unique with respect to the target regions recognized in the genome. Thus compilation of the various fingerprint data provides a complex map of the genome (and its deviations). While the fingerprints of differentiated somatic tissues never showed any alterations, in tumor tissues (namely gliomas) many changes could be detected. Most of the latter reflect secondary karyological aberrations. In nearly one third of the gliomas, drastically amplified and apparently monomorphic DNA fragments were identified. This marker should make it possible to deal with causal pathogenetic mechanisms as well as novel diagnostic strategies.     

Synchronization Analysis of Coupled Noncoherent Oscillators

We present two different approaches to detect and quantify phase synchronization in the case of coupled non-phase coherent oscillators. The first one is based on the general idea of curvature of an arbitrary curve. The second one is based on recurrences of the trajectory in phase space. We illustrate both methods in the paradigmatic example of the R?ssler system in the funnel regime. We show that the second method is applicable even in the case of noisy data. Furthermore, we extend the second approach to the application of chains of coupled systems, which allows us to detect easily clusters of synchronized oscillators. In order to illustrate the applicability of this approach, we show the results of the algorithm applied to experimental data from a population of 64 electrochemical oscillators.     

XPS investigations of ink‐jet printed paper

Different ink‐jet printed paper materials were investigated using X‐ray photoelectron spectroscopy (XPS) yielding the elemental composition of the near‐surface region of the papers. We found significant differences with respect to the detected elements and their atomic concentrations in the different inks studied here. Two different groups of inks could be identified by means of a lower ratio of the O and C atomic concentrations and lower concentrations in specific trace elements like Mg, Na and Si. High‐resolution spectra of C 1s and O 1s core levels allowed a detailed determination of the chemical state of the respective elements. On the basis of a detailed deconvolution of these XPS signals, significant differences between all the investigated ink‐jet printed papers were found, thereby allowing their discrimination. The applicability of the measurements and, more generally, the XPS technique for forensic investigations of paper are discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

The Equilibrium Structure of Methyl Fluoride

The equilibrium structure of CH₃F has been determined using new sets of accurate rotational constants that have been determined by taking into account all the interactions between the excited vibrational states. This experimental structure is in excellent agreement with the equilibrium geometry calculated at the CCSD(T) level of theory with the cc-pV(5, Q)Z basis set (including corrections for the core correlation and for the effect of diffuse functions on fluorine). Finally, the experimental and ab initio structures have been combined by a least-squares analysis. The results are , and L _e(HCH) = 110.2 (1)°, where the uncertainties shown in parentheses correspond to three standard deviations.     

New features in the catalytic cycle of cytochrome P450 during the formation of compound I from compound 0

Density functional theory (DFT) is applied to the dark section of the catalytic cycle of the enzyme cytochrome P450, namely, the formation of the active species, Compound I (Cpd I), from the ferric-hydroperoxide species (Cpd 0) by a protonation-assisted mechanism. The chosen 96-atom model includes the key functionalities deduced from experiment: Asp(251), Thr(252), Glu(366), and the water channels that relay the protons. The DFT model calculations show that (a) Cpd I is not formed spontaneously from Cpd 0 by direct protonation, nor is the process very exothermic. The process is virtually thermoneutral and involves a significant barrier such that formation of Cpd I is not facile on this route. (b) Along the protonation pathway, there exists an intermediate, a protonated Cpd 0, which is a potent oxidant since it is a ferric complex of water oxide. Preliminary quantum mechanical/molecular mechanical calculations confirm that Cpd 0 and Cpd I are of similar energy for the chosen model and that protonated Cpd 0 may exist as an unstable intermediate. The paper also addresses the essential role of Thr(252) as a hydrogen-bond acceptor (in accord with mutation studies of the OH group to OMe).     

Comparative investigation of ruthenium-based metathesis catalysts bearing N-heterocyclic carbene (NHC) ligands

Exchange of one PCy3 unit of the classical Grubbs catalyst 1 by N-heterocyclic carbene (NHC) ligands leads to "second-generation" metathesis catalysts of superior reactivity and increased stability. Several complexes of this type have been prepared and fully characterized, six of them by X-ray crystallography. These include the unique chelate complexes 13 and 14 in which the NHC- and the Ru-CR entities are tethered to form a metallacycle. A particularly favorable design feature is that the reactivity of such catalysts can be easily adjusted by changing the electronic and steric properties of the NHC ligands. The catalytic activity also strongly depends on the solvent used; NMR investigations provide a tentative explanation of this effect. Applications of the "second-generation" catalysts to ring closing alkene metathesis and intramolecular enyne cycloisomerization reactions provide insights into their catalytic performance. From these comparative studies it is deduced that no single catalyst is optimal for different types of applications. The search for the most reactive catalyst for a specific transformation is facilitated by IR thermography allowing a rapid and semi-quantitative ranking among a given set of catalysts.