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.     

Review of recent developments in OR/MS research in disaster operations management

Potential consequences of disasters involve overwhelming economic losses, large affected populations and serious environmental damages. Given these devastating effects, there is an increasing interest in developing measures in order to diminish the possible impact of disasters, which gave rise to the field of disaster operations management (DOM). In this paper we review recent OR/MS research in DOM. Our work is a continuation of a previous review from Altay and Green (2006). Our purpose is to evaluate how OR/MS research in DOM has evolved in the last years and to what extent the gaps identified by Altay and Green (2006) have been covered. Our findings show no drastic changes or developments in the field of OR/MS in DOM since the publication of Altay and Green (2006). Additionally to our comparative analysis, we present an original evaluation about the most common assumptions in recent OR/MS literature in DOM. Based on our findings we provide future research directions in order to make improvements in the areas where lack of research is detected.     

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.     

Synthesis of 4-unsubstituted 2H-1,2,3-benzothiadiazine 1,1-dioxides via ortho lithiation of protected benzaldehyde derivatives

Variously substituted 2-phenyl-1,3-dioxolanes and 2-(2-bromophenyl)-1,3-dioxolanes, prepared from the corresponding benzaldehydes, were lithiated ortho to the acetal group. Reaction of the lithio derivatives with sulfur dioxide led to the lithium sulfinate salts, which gave, upon oxidative chlorination with sulfuryl chloride, the corresponding benzenesulfonyl chlorides. Then, depending on the aromatic substitution pattern of the molecule, several protocols were elaborated for the functional group transformations leading to the target compounds. Ring closure was performed with hydrazine hydrate or acetylhydrazine, in the latter case with one-pot removal of the acetyl group. The 4-unsubstituted 2H-1,2,3-benzothiadiazine 1,1-dioxides thus obtained are potential drug candidates based on their structural similarity to biologically active phthalazinones.