Detection of Chemical Warfare Nerve Agents via a Beckmann Fragmentation of Aldoxime

Abstract

A new (E)-pyrene-1-carbaldehyde O-tert-butyldimethylsilyl oxime 3 was synthesized for the detection of chemical warfare nerve agents, O-isopropyl methylphosphonofluoridate (GB) and O-pinacolyl methylphosphonofluoridate (GD). ¹H NMR spectrum showed that the tert-butyldimethylsilyl (TBDMS) group was deprotected using TBAF and the oximate supernucleophile was made. Upon addition of chemical warfare agents (GB and GD) (50 mol%), the reaction was completely finished within 5 min and also the color change of reaction mixture was observed under a hand-held UV lamp with the naked eye.     

An Improved Direct Oxidation of Alkyl Halides to Aldehydes

The oxidation of alkyl chlorides and bromides with dimethyl sulfoxide has been performed in the presence of sodium iodide. This method allows a convenient one-step procedure for the preparation of aldehydes from alkyl chlorides and bromides.     

Chrysin Derivative CM1 and Exhibited Anti-Inflammatory Action by Upregulating Toll-Interacting Protein Expression in Lipopolysaccharide-Stimulated RAW264.7 Macrophage Cells

Although our previous study revealed that gamma-irradiated chrysin enhanced anti-inflammatory activity compared to intact chrysin, it remains unclear whether the chrysin derivative, CM1, produced by gamma irradiation, negatively regulates toll-like receptor (TLR) signaling. In this study, we investigated the molecular basis for the downregulation of TLR4 signal transduction by CM1 in macrophages. We initially determined the appropriate concentration of CM1 and found no cellular toxicity below 2 μg/mL. Upon stimulation with lipopolysaccharide (LPS), CM1 modulated LPS-stimulated inflammatory action by suppressing the release of proinflammatory mediators (cytokines TNF-α and IL-6) and nitric oxide (NO) and downregulated the mitogen-activated protein kinase (MAPK) and nuclear factor-κB (NF-κB) signaling pathways. Furthermore, CM1 markedly elevated the expression of the TLR negative regulator toll-interacting protein (Tollip) in dose- and time-dependent manners. LPS-induced expression of cell surface molecules (CD80, CD86, and MHC class I/II), proinflammatory cytokines (TNF-α and IL-6), COX-2, and iNOS-mediated NO were inhibited by CM1; these effects were prevented by the knockdown of Tollip expression. Additionally, CM1 did not affect the downregulation of LPS-induced expression of MAPKs and NF-κB signaling in Tollip-downregulated cells. These findings provide insight into effective therapeutic intervention of inflammatory disease by increasing the understanding of the negative regulation of TLR signaling induced by CM1.     

Weak-type normal families of holomorphic mappings in Banach spaces and characterization of the Hilbert ball by its automorphism group

We present a characterization of the open unit ball in a separable infinite dimensional Hilbert space by the property of automorphism orbits among the domains that are not necessarily bounded. This generalizes the recent work of Kim and Krantz [6]. Key new features of this article include: a lower bound estimate of the Kobayashi metric and distance near a pluri-subharmonic peak boundary point of the domains in Banach spaces, an effective localization argument, and an improvement of weak-type convergence of sequences of biholomorphic mappings of domains in Banach spaces.     

Upregulation of extracellular matrix metalloproteinase inducer (EMMPRIN) and gelatinases in human atherosclerosis infected with Chlamydia pneumoniae: the potential role of Chlamydia pneumoniae infection in the progression of atherosclerosis

Chlamydia pneumoniae infection implicated as an important etiologic factor of atherosclerosis, especially in coronary artery disease (CAD), was found in vitro to be associated with the induction of matrix metalloproteinases (MMPs). An extracellular matrix metalloproteinase inducer (EMMPRIN)/ membrane-type 1 matrix metalloproteinase (MT1-MMP) system which induces and activates MMPs, is suggested to be functional and were upregulated in the failing myocardium. However, the upstream regulation of MMPs by C. pneumoniae within atheroma itself remains unclear. We evaluated the seroepidemiologic study of C. pneumoniae infection in CAD patients (n= 391) and controls (n=97) and performed histopathological and in vitro analysis in atherosclerotic vascular tissues obtained from patients with seropositive to C. pneumoniae (n=20), by using immunochemistry for C. pneumoniae, EMMPRIN/MT1-MMP, MMP-2, and MMP-9. The seropositive rates of both anti-C. pneumoniae IgG and IgA were 56.7% in CAD group and 43.3% in control group (P=0.033). Seropositive rate was increased in subgroups of CAD patients without conventional coronary risk factors compared to those with conventional risk factors. Immunoreactivities of EMMPRIN, MT1-MMP, MMP-2, and MMP-9 were increased in the atheromatous plaque itself, predominantly in immunoreactive macrophages/mononuclear cells to C. pneumoniae. Furthermore, Western blot analysis showed that EMMPRIN and MMP-2 were detected more prominently in atherosclerotic tissues infected with C. pneumoniae compared to control tissues. Zymographic analysis revealed that activities of MMP-2 and MMP-9 were more increased in atherosclerotic tissues infected with C. pneumoniae compared to control tissues. The present study demonstrated upstream regulation of MMPs can be induced by C. pneumoniae within atheromatous plaque itself. These findings help to understand the potential role of C. pneumoniae in the progression of atherosclerosis.     

Tangent Bundle of a Manifold and its Homotopy Type

There is a homotopy equivalence :MM' between closed smooth manifoldsof an odd dimension such that *TM', TM are stably isomorphicbut not isomorphic to each other.     

Gradient estimates for elliptic systems with measurable coefficients in nonsmooth domains

We consider an elliptic system in divergence form with measurable coefficients in a nonsmooth bounded domain to find a minimal regularity requirement on the coefficients and a lower level of geometric assumption on the boundary of the domain for a global W ^1,p , 1 < p < ∞, regularity. It is proved that such a W ^1,p regularity is still available under the assumption that the coefficients are merely measurable in one variable and have small BMO semi-norms in the other variables while the domain can be locally approximated by a hyperplane, a so called δ-Reifenberg domain, which is beyond the Lipschitz category. This regularity easily extends to a certain Orlicz-Sobolev space.     

Gradient estimates in Orlicz space for nonlinear elliptic equations

In this paper we generalize gradient estimates in Lp space to Orlicz space for weak solutions of elliptic equations of p-Laplacian type with small BMO coefficients in δ-Reifenberg flat domains. Our results improve the known results for such equations using a harmonic analysis-free technique.