The Au(n) cluster probe in secondary ion mass spectrometry: influence of the projectile size and energy on the desorption/ionization rate from biomolecular solids

A Au-Si liquid metal ion source which produces Au(n) clusters over a large range of sizes was used to study the dependence of both the molecular ion desorption yield and the damage cross-section on the size (n = 1 to 400) and on the kinetic energy (E = 10 to 500 keV) of the clusters used to bombard bioorganic surfaces. Three pure peptides with molecular masses between 750 and 1200 Da were used without matrix. [M+H](+) and [M+cation](+) ion emission yields were enhanced by as much as three orders of magnitude when bombarding with Au(400) (4+) instead of monatomic Au(+), yet very little damage was induced in the samples. A 100-fold increase in the molecular ion yield was observed when the incident energy of Au(9) (+) was varied from 10 to 180 keV. Values of emission yields and damage cross-sections are presented as a function of cluster size and energy. The possibility to adjust both cluster size and energy, depending on the application, makes the analysis of biomolecules by secondary ion mass spectrometry an extremely powerful and flexible technique, particularly when combined with orthogonal time-of-flight mass spectrometry that then allows fast measurements using small primary ion beam currents.     

The electrical resistance of some lithium-magnesium alloys near the martensitic transformation

The electrical resistivity of four lithium-magnesium alloys with magnesium concentrations of 1.0, 5.0, 10 and 20 atomic percent has been measured as the specimens were slowly cooled from 300 K to ～3 K and warmed again to 300 K. From a hysteresis in the resistivity in the region of the martensitic transformation the M_s temperatures were found. M_s increases ～5 K per atomic percent of added magnesium and, while in agreement with Dugdale and Gugan the martensite in the dilute alloy is less resistive than the high temperature (bcc) phase, it has a larger resistivity in three less dilute alloys.     

High-resolution spectroscopy of SO2 using a frequency-doubled,continuous-wave dye laser

The SO₂ molecule is of considerable interest in the context of atmospheric pollution, and in many laser monitoring techniques the ultraviolet absorption band at 300 nm is used to determine SO₂ concentrations in the atmosphere. Recent laboratory experiments with a resolution of 2 × 10^-3 nm showed that variations could occur in absorption cross-section measurements made with different laser bandwidths due to unresolved fine structure. We have investigated absorption spectra with a line width of 3 × 10^-6 nm, using a frequency-doubled continuous-wave dye laser, and have confirmed the existence of fine structure in the absorption even when collisionally broadened with an atmosphere of nitrogen. These measurements provide a data base from which valid absorption cross sections may be calculated for all monitoring laser bandwidths. We estimate the pressure broadening coefficient for nitrogen in this wavelength region as 83 ± 38 kHz Pa^-1 (11 ± 5 MHz torr^-1). The temperature dependence of the absorption cross-section was also investigated.     

Multipole pairing states and the correspondence between two- and four-particle transfer reactions

Data for the ^58,60Ni(⁶Li, d) ^62,64Zn reactions, together with an analysis in terms of a simple multipole pairing model, indic that two-phonon states are extremely weakly excited. This result arises from the dominance of monopole pairing correlations in four-particle transfer reactions and explains the observed correspondence between two- and four-particle transfer reactions populating the same final nucleus.     

The first-to-zero-sound transition in non-superfluid liquid 4He

Neutron inelastic scattering from ⁴He at T = 2.3 K shows that for Q ? 2 nm^?1 “sound-wave” excitations propagate with the characteristics of ordinary or first sound while for Q ? 3 nm^?1 they propagate with the characteristics of zero sound.     

Copula‐based robust optimal block designs

Blocking is often used to reduce known variability in designed experiments by collecting together homogeneous experimental units. A common modeling assumption for such experiments is that responses from units within a block are dependent. Accounting for such dependencies in both the design of the experiment and the modeling of the resulting data when the response is not normally distributed can be challenging, particularly in terms of the computation required to find an optimal design. The application of copulas and marginal modeling provides a computationally efficient approach for estimating population‐average treatment effects. Motivated by an experiment from materials testing, we develop and demonstrate designs with blocks of size two using copula models. Such designs are also important in applications ranging from microarray experiments to experiments on human eyes or limbs with naturally occurring blocks of size two. We present a methodology for design selection, make comparisons to existing approaches in the literature, and assess the robustness of the designs to modeling assumptions.     

Embedded cluster modeling of excited chromium impurities in halide elpasolites

Abstract

Embedded cluster calculations performed on both ground (⁴A_2g) and excited (⁴T_2g) states of substitutional Cr³⁺ in halide elpasolites account successfully for the pressure dependence of photoluminescence spectra.     

Specificity of Furanoside–Protein Recognition through Antibody Engineering and Molecular Modeling

Recognition of furanosides (five‐membered ring sugars) by proteins plays important roles in host–pathogen interactions. In comparison to their six‐membered ring counterparts (pyranosides), detailed studies of the molecular motifs involved in the recognition of furanosides by proteins are scarce. Here the first in‐depth molecular characterization of a furanoside–protein interaction system, between an antibody (CS‐35) and cell wall polysaccharides of mycobacteria, including the organism responsible for tuberculosis is reported. The approach was centered on the generation of the single chain variable fragment of CS‐35 and a rational library of its mutants. Investigating the interaction from various aspects revealed the structural motifs that govern the interaction, as well as the relative contribution of molecular forces involved in the recognition. The specificity of the recognition was shown to originate mainly from multiple CH–π interactions and, to a lesser degree, hydrogen bonds formed in critical distances and geometries.     

A Traveling Wave Ion Mobility Spectrometry (TWIMS) Study of the Robo1-Heparan Sulfate Interaction

Roundabout 1 (Robo1) interacts with its receptor Slit to regulate axon guidance, axon branching, and dendritic development in the nervous system and to regulate morphogenesis and many cell functions in the nonneuronal tissues. This interaction is known to be critically regulated by heparan sulfate (HS). Previous studies suggest that HS is required to promote the binding of Robo1 to Slit to form the minimal signaling complex, but the molecular details and the structural requirements of HS for this interaction are still unclear. Here, we describe the application of traveling wave ion mobility spectrometry (TWIMS) to study the conformational details of the Robo1-HS interaction. The results suggest that Robo1 exists in two conformations that differ by their compactness and capability to interact with HS. The results also suggest that the highly flexible interdomain hinge region connecting the Ig1 and Ig2 domains of Robo1 plays an important functional role in promoting the Robo1-Slit interaction. Moreover, variations in the sulfation pattern and size of HS were found to affect its binding affinity and selectivity to interact with different conformations of Robo1. Both MS measurements and CIU experiments show that the Robo1-HS interaction requires the presence of a specific size and pattern of modification of HS. Furthermore, the effect of N-glycosylation on the conformation of Robo1 and its binding modes with HS is reported.

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