Gln-Gly cleavage: a dominant dissociation site in the fragmentation of protonated peptides

An understanding of the gas-phase dissociation of protonated peptides within the mass spectrometer is essential for automated high-throughput protein identification. In this communication we describe a facile cleavage of the Gln-Gly peptide bond under low-collisional energy conditions. A variety of synthetic peptides have been analysed where key amino acids have been substituted within the sequence PQGPPQQGGR, which is a consensus repeat present in the tryptic peptides of acidic proline-rich protein 1 (PRP-1). The collision-induced dissociation spectra obtained from the PRP-1 tryptic peptides and the synthetic peptides indicate that facile Gln-Gly cleavage occurs when an X-Gln-Gly-Y sequence is present in a peptide, where X is any amino acid and Y any amino acid other than Gly.     

A general,recursive, and open‐ended response code

We present a new implementation of a recent open‐ended response theory formulation for time‐ and perturbation‐dependent basis sets (Thorvaldsen et al., J. Chem. Phys. 2008, 129, 214108) at the Hartree–Fock and density functional levels of theory. A novel feature of the new implementation is the use of recursive programming techniques, making it possible to write highly compact code for the analytic calculation of any response property at any valid choice of rule for the order of perturbation at which to include perturbed density matrices. The formalism is expressed in terms of the density matrix in the atomic orbital basis, allowing the recursive scheme presented here to be used in linear‐scaling formulations of response theory as well as with two‐ and four‐component relativistic wave functions. To demonstrate the new code, we present calculations of the third geometrical derivatives of the frequency‐dependent second hyperpolarizability for HSOH at the Hartree–Fock level of theory, a seventh‐order energy derivative involving basis sets that are both time and perturbation dependent. © 2014 Wiley Periodicals, Inc.     

Experimental validation of corrections factors for γ–γ and γ–X coincidence summing of 133Ba, 152Eu,and 125Sb in volume sources

True coincidence summing correction factors for ¹³³Ba, ¹⁵²Eu and ¹²⁵Sb were determined experimentally for a small volume source and compared with correction factors obtained with three softwares (EFFTRAN-X, GESPECOR and VGSL). The radionuclides investigated have a relatively challenging decay scheme and their spectra are known to suffer from losses due to summation (γ–γ, γ–X and X–X) when measured at close distances on a HPGe detector sensitive to low energy photons. This study shows that the softwares were in good agreement with each other and the experimental data and the calculated activity was consistent with the activity in the volume source.

     

Thiol–ene coupling reaction of fatty acid monomers

The reactivities and reaction rates of the thiol–ene coupling reaction of 2‐ethyl‐(hydroxymethyl)‐1,3‐propanediol trimercapto acetate and 2‐ethyl‐(hydroxymethyl)‐1,3‐propanediol trimercapto propionate with two common unsaturated fatty acid methyl esters (methyl oleate and methyl linoleate) were evaluated. The reactions were monitored with real‐time IR and ¹H NMR, which both showed that the mercapto acetate was more reactive than the mercapto propionate. Both thiols were more prone to add to the monounsaturated methyl oleate than to methyl linoleate, which contained two unconjugated double bonds. According to bond energy calculations, the thiol hydrogen of mercapto acetate was somewhat more difficult to abstract than the hydrogen of mercapto propionate. Consequently, the formed S? C bond in the acetate case was stronger than in the propionate case, and so the equilibrium was more shifted toward the addition products. The real‐time IR measurements also showed that the cis unsaturation in methyl oleate isomerized much more quickly than that in methyl linoleate, and this also had an impact on the overall addition rate of the thiols because a trans unsaturation was more reactive than a cis unsaturation. The higher isomerization rates in the oleate systems, compared with those of the linoleate systems, was suggested to be due to a more restricted rotation along the C? C bond of the reacted unsaturation in linoleate. This study showed the importance of trans unsaturations in obtaining reasonable reaction rates in thiol–ene reactions with fatty acid derivatives. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6346–6352, 2004     

Hedgehogs in a three-dimensional anisotropic spin system

We study a continuum version of a classical anisotropic spin model in three dimensions with three component spins. We prove the existence of topological defects, called hedgehogs, which are analogous to the vortices in the two-dimensionalxy-model and have a logarithmically divergent action. Bounds for the interaction energy of a hedgehog and an antihedgehog are derived.     

Cross sections and isomeric ratios in the photoproduction of 44Sc from heavier nuclei

The yields and isomeric yield ratios in the photoproduction of⁴⁴Sc from ⁴⁵Sc, ⁵⁵Mn, Fe, ⁵⁹Co and ⁷⁵As have been measured by activation methods in the energy region 100–800 MeV. Mean cross sections and isomeric cross-section ratios in the energy region 250–800 MeV have been deduced and the number of valence neutrons available for the (γ, n) reaction estimated. The experimental cross sections are compared both to cascade-evaporation calculations based upon the free-nucleon photopion cross sections and to cross sections calculated with a semi-empirical formula. The isomeric cross-section ratios are compared to calculations based on the statistical formalism by Huizenga and Vandenbosch together with cascade-evaporation theory.     

0+ states and E0 and E2 transition rates in even Sn nuclei

0⁺ states and their depopulating E0 and E2 transitions have been studied in ^112–124Sn. Several methods of γ-ray and electron spectrometry have been employed, including special coincidence techniques for lifetime, conversion electron and double Coulomb excitation measurements. For ^114–118Sn the E2 transition probabilities from the first excited 0⁺states (0₂⁺) are about 20 W.u., which is compatible with a vibrational two-phonon character. Also the E0 transition probabilities from these states are within a factor of two from the vibrational values. For the second excited 0⁺ states (0₃⁺) the corresponding E2 and E0 transition probabilities are considerably smaller. A total of 12 E0 transitions have been observed. The 0₃⁺ → 0₂⁺ transition is observed in ^114–120Sn and has in ¹¹⁶Sn a reduced transition probability 1–2 orders of magnitude larger than those of the groundstate E0 transitions, which indicates that the 0₃⁺ and 0₂⁺ states are strong mixtures of components with different 〈r²〉. The 0⁺ states in ¹¹⁶Sn are discussed as possible rotational band heads associated with a deformation β₂ ≈ 0.2. The Coulomb excitation cross section of the 0₂⁺ state is found to be sensitive to an interference term including matrix elements with the 2₂⁺ state. The relative sign of this term has been determined.     

Continuous separation of lipid particles from erythrocytes by means of laminar flow and acoustic standing wave forces

Improved continuous acoustic particle separation (separation efficiency close to 100%) and separation of erythrocytes (red blood cells) from lipid microemboli in whole blood is reported.     

Haar wavelets of higher order on fractals and regularity of functions

Wavelets of Haar type of higher order m on self-similar fractals were introduced by the author in J. Fourier Anal. Appl. 4 (1998) 329-340. These are piecewise polynomials of degree m instead of piecewise constants. It was shown that for certain totally disconnected fractals, spaces of functions defined on the fractal may be characterized by means of the magnitude of the wavelet coefficients of the functions. In this paper, the study of these wavelets is continued. It is shown that also in the case when the fractals are not totally disconnected, the wavelets can be used to study regularity properties of functions. In particular, the self-similar sets considered can be, e.g., an interval in or a cube in . It turns out that it is natural to use Haar wavelets of higher order also in these classical cases, and many of the results in the paper are new also for these sets.     

Protein adsorption onto silica nanoparticles: conformational changes depend on the particles' curvature and the protein stability

We have analyzed the adsorption of protein to the surfaces of silica nanoparticles with diameters of 6, 9, and 15 nm. The effects upon adsorption on variants of human carbonic anhydrase with differing conformational stabilities have been monitored using methods that give complementary information, i.e., circular dichroism (CD), nuclear magnetic resonance (NMR), analytical ultracentrifugation (AUC), and gel permeation chromatography. Human carbonic anhydrase I (HCAI), which is the most stable of the protein variants, establishes a dynamic equilibrium between bound and unbound protein following mixture with silica particles. Gel permeation and AUC experiments indicate that the residence time of HCAI is on the order of approximately 10 min and slowly increases with time, which allows us to study the effects of the interaction with the solid surface on the protein structure in more detail than would be possible for a process with faster kinetics. The effects on the protein conformation from the interaction have been characterized using CD and NMR measurements. This study shows that differences in particle curvature strongly influence the amount of the protein's secondary structure that is perturbed. Particles with a longer diameter allow formation of larger particle-protein interaction surfaces and cause larger perturbations of the protein's secondary structure upon interaction. In contrast, the effects on the tertiary structure seem to be independent of the particles' curvature.