Effect of the type of ion-pairing reagent in reversed-phase ion-pair chromatography

Summary The retention of positively and negatively charged and neutral solutes was studied in an aqueous phosphate buffer eluent, with constant inorganic-counterion concentration, on ODS-Hypersil stationary phase in the presence of various sulfonic acid ion-pairing reagents. The adsorption isotherms of the ion-pairing reagents d-camphor-10-sulfonic acid, sodium cyclohexylsulfamic acid and sodium alkylsulfonates (butyl-, hexyl- and octyl-) were determined by the breakthrough method.Dedicated to Professor J. F. K. Huber on the occasion of his 60th birthday.     

Detection and analysis of cyclotrimethylenetrinitramine (RDX) in environmental samples by surface‐enhanced Raman spectroscopy

Techniques for rapid and sensitive detection of energetics such as cyclotrimethylenetrinitramine (RDX) are needed both for environmental and security screening applications. Here we report the use of surface‐enhanced Raman scattering (SERS) spectroscopy to detect traces of RDX with good sensitivity and reproducibility. Using gold (Au) nanoparticles (∼90–100 nm in diameter) as SERS substrates, RDX was detectable at concentrations as low as 0.15 mg/l in a contaminated groundwater sample. This detection limit is about two orders of magnitude lower than those reported previously using SERS techniques. A surface enhancement factor of ∼6 × 10⁴ was obtained. This research further demonstrates the potential for using SERS as a rapid, in situ field screening tool for energetics detection when coupled with a portable Raman spectrometer. Copyright © 2010 John Wiley & Sons, Ltd.     

Statistical inference of 2-type critical Galton–Watson processes with immigration

In this paper the asymptotic behavior of the conditional least squares estimators of the offspring mean matrix for a 2-type critical positively regular Galton–Watson branching process with immigration is described. We also study this question for a natural estimator of the spectral radius of the offspring mean matrix, which we call criticality parameter. We discuss the subcritical case as well.     

Asymptotic Behavior of Critical Primitive Multi-Type Branching Processes with Immigration

Under natural assumptions a Feller-type diffusion approximation is derived for critical multi-type branching processes with immigration when the offspring mean matrix is primitive (in other words, positively regular). Namely, it is proved that a sequence of appropriately scaled random step functions formed from a sequence of critical primitive multi-type branching processes with immigration converges weakly toward a squared Bessel process supported by a ray determined by the Perron vector of the offspring mean matrix.     

On the exterior algebra method applied to restricted set addition

In 1994 Dias da Silva and Hamidoune solved a long-standing open problem of Erd?s and Heilbronn using the structure of cyclic spaces for derivatives on Grassmannians and the representation theory of symmetric groups. They proved that for any subset A$A$ of the p$p$-element group Z/pZ$\mathbb{Z}/p\mathbb{Z}$ (where p$p$ is a prime), at least min{p,m|A|−m²+1}$min\{p,m\left|A\right|-m^2+1\}$ different elements of the group can be written as the sum of m$m$ different elements of A$A$. In this note we present an easily accessible simplified version of their proof for the case m=2$m=2$, and explain how the method can be applied to obtain the corresponding inverse theorem.     

Structural impact of GTP binding on downstream KRAS signaling

Oncogenic RAS proteins, involved in ∼30% of human tumors, are molecular switches of various signal transduction pathways. Here we apply a new protocol for the NMR study of KRAS in its (inactive) GDP- and (activated) GTP-bound form, allowing a comprehensive analysis of the backbone dynamics of its WT-, G12C- and G12D variants. We found that Tyr32 shows opposite mobility with respect to the backbone of its surroundings: it is more flexible in the GDP-bound form while more rigid in GTP-complexes (especially in WT- and G12D-GTP). Using the G12C/Y32F double mutant, we showed that the presence of the hydroxyl group of Tyr32 has a marked effect on the G12C-KRAS-GTP system as well. Molecular dynamics simulations indicate that Tyr32 is linked to the γ-phosphate of GTP in the activated states – an arrangement shown, using QM/MM calculations, to support catalysis. Anchoring Tyr32 to the γ-phosphate contributes to the capture of the catalytic waters participating in the intrinsic hydrolysis of GTP and supports a simultaneous triple proton transfer step (catalytic water → assisting water → Tyr32 → O1G of the γ-phosphate) leading to straightforward product formation. The coupled flip of negatively charged residues of switch I toward the inside of the effector binding pocket potentiates ligand recognition, while positioning of Thr35 to enter the coordination sphere of the Mg²⁺ widens the pocket. Position 12 mutations do not disturb the capture of Tyr32 by the γ-phosphate, but (partially) displace Gln61, which opens up the catalytic pocket and destabilizes catalytic water molecules thus impairing intrinsic hydrolysis.

Nucleotide exchange to the physiological, activated, GTP-bound form of KRAS results in the anchoring of Tyr32 within the active site.