The refocused INADEQUATE MAS NMR experiment in multiple spin-systems: interpreting observed correlation peaks and optimising lineshapes

The robustness of the refocused INADEQUATE MAS NMR pulse sequence for probing through-bond connectivities has been demonstrated in a large range of solid-state applications. This pulse sequence nevertheless suffers from artifacts when applied to multispin systems, e.g. uniformly labeled (13)C solids, which distort the lineshapes and can potentially result in misleading correlation peaks. In this paper, we present a detailed account that combines product-operator analysis, numerical simulations and experiments of the behavior of a three-spin system during the refocused INADEQUATE pulse sequence. The origin of undesired anti-phase contributions to the spectral lineshapes are described, and we show that they do not interfere with the observation of long-range correlations (e.g. two-bond (13)C-(13)C correlations). The suppression of undesired contributions to the refocused INADEQUATE spectra is shown to require the removal of zero-quantum coherences within a z-filter. A method is proposed to eliminate zero-quantum coherences through dephasing by heteronuclear dipolar couplings, which leads to pure in-phase spectra.     

Diffraction by a wedge at skew incidence: integral representations of Cauchy-Carleman for the electromagnetic fields

An electromagnetic diffraction problem in a wedge shaped region is reduced to a system of coupled functional difference equations by means of Sommerfeld integrals and Malyuzhinets theorem. By introducing an integral operator it is shown that the solutions of this system of functional equations can be defined in terms of integral representations whose kernels are solutions of a singular integral equation of Cauchy-Carleman type for which an explicit solution is given.     

Structural and Magnetic Properties Control of Pr0.7Ba0.3MnO3 with Sr-Doping

Physics of the Solid State - Structural and magnetic properties of Sr-doped Pr0.7Ba0.3MnO3 polycrystallines prepared by solid state reaction are presented. Samples were in monoclinic structure...     

Mass Spectrometric (FAB) Study of Aspartic Acid Side Reactions in Peptide Synthesis

Abstract

We have been interested in the synthesis of branched peptides, by grafting an amine, eg histamine, to the carboxylic group of aspartic acid side chain of Boc-β Ala-Trp-Met-Asp-Phe-NH₂ also called Pentagastrin (or α-PG). Depending on the coupling conditions used, the main product obtained might be either the wanted derivative or a side-product identified a6 amino-succinyl-pentagastrin (or ASC-PG). Acid or base treatment of this product cleaved the amino-succinyl ring and yielded either α-PG or/and (β-Aspartyl)⁴-PC or β-PG. Amino-succinylation being a general problem in peptide synthesis of aspartyl residue containing peptides, synthesis of α-PG, β-PG, Asc-PG and their corresponding C-terminal dipeptide amides were performed to be analyzed by mass spectroscopy.

FAB mass spectra (PI in glycerol) of the free peptides, as well as of their N-Boc derivatives have been recorded and compared to the mono, di, tri and tetra peptide derivatives. The pseudo-molecular ions of Boc-peptides are usually not observed. However, the intense M+1-Boc (? 100 u) ions are present.

Several sequence ions have been identified and compared to the simulation of their spectra according to six fragmentation routes.

The identification of α, β or succinimide structures from FAB spectra has been proposed.     

A study of fused silica micro/nano patterning by focused-ion-beam

A dual-beam scanning electron microscopy (SEM)/focused-ion-beam (FIB) system was used to pattern fused silica substrates coated with a 15 nm thin Cr layer. The dimensions of fabricated features together with their surface morphology and profiles were investigated by SEM and atomic force microscopy (AFM). The study demonstrated that with the increase of the ion beam fluence the sputtering rate of the fused silica decreased non-linearly. Also, it was found that initially the sputtering rate increased with the increase of the beam current, after reaching a maximum value, it started decreasing when further beam current increment was performed. Compared with unprocessed areas, the surface finish of the features fabricated by FIB exhibited a significant improvement, and the ion fluence influence on the surface roughness of trenches with low aspect ratios could be considered as negligible. Using a fine beam probe, nano-gratings in the form of grooves with a width down to 54 nm and an aspect ratio higher than three were fabricated. The study showed that FIB machining could be an alternative technology to e-beam lithography for producing fused silica templates for UV nanoimprinting.     

Stages of melting of graphene model in two-dimensional space

Spontaneous melting of a perfect crystalline graphene model in 2D space is studied via molecular dynamics simulation. Model containing 10⁴ atoms interacted via long-range bond-order potential (LCBOP) is heated up from 50 to 8,450 K in order to see evolution of various thermodynamic quantities, structural characteristics and occurrence of various structural defects. We find that spontaneous melting of our graphene model in 2D space exhibits a first-order behaviour of the transition from solid 2D graphene sheet into a ring-like structure 2D liquid. Occurrence and clustering of Stone–Wales defects are the first step of melting process followed by breaking of C–C bonds, occurrence/growth of various types of vacancies and multi-membered rings. Unlike that found for melting of a 2D crystal with an isotropic bonding, these defects do not occur homogeneously throughout the system, they have a tendency to aggregate into a region and liquid phase initiates/grows from this region via tearing-like or crack-propagation-like mechanism. Spontaneous melting point of our graphene model occurs at T_m = 7,750 K. The validity of classical nucleation theory and Berezinsky–Kosterlitz–Thouless–Nelson–Halperin–Young (BKTNHY) one for the spontaneous melting of our graphene model in strictly 2D space is discussed.     

Laser-induced periodic surface structures formed on the sidewalls of microholes trepanned by a femtosecond laser

Laser-induced periodic surface structures (LIPSSs) were observed on the sidewalls of 300-μm-diameter holes trepanned on cemented tungsten carbide using femtosecond laser pulses at a wavelength of 800 nm. For a circularly polarized beam, LIPSSs were formed at a period of 300 nm and oriented perpendicularly to the plane of incidence on the sidewalls. For a linearly polarized beam, LIPSS formation was dependent on the relative angle α between the polarization direction and the plane of incidence. For relative angles α from 0° to 70° and from 110° to 180°, LIPSS spacing was 300 nm. However, there were two types of LIPSSs coexisting from 70° to 110°. One had a spacing of 120 nm and the other had a spacing that varied from 500 to 760 nm. It was found that the orientation angle of LIPSSs measured between the LIPSS orientation and the plane of incidence had a nonlinear dependence on α. To understand this dependence, a model was proposed in which LIPSSs are assumed to align perpendicularly to the direction of the absorbed electric field lying in the tangent plane of the sidewall of a drilled hole. The calculated results from this model showed good agreement with the experimental results.