Mechanisms for the Oxonolysis of Ethene and Propene: Reliability of Quantum Chemical Predictions

Reactions of ozone with ethene and propene leading to primary ozonide (concerted and stepwise ozonolysis) or epoxide and singlet molecular oxygen (partial ozonolysis) are studied theoretically. The mechanism of concerted ozonolysis proceeds via a single transition structure which is a partial diradical. The transition structures and intermediates in the stepwise ozonolysis and partial ozonolysis mechanisms are singlet diradicals. Spin-restricted and unrestricted density functional methods are employed to calculate the structures of the closed-shell and diradical species. Although the partial diradicals exhibit moderate to pronounced instability in their RDFT and RHF solutions, RDFT is required to locate the transition structure for concerted ozonolysis. Spin projected fourth-order Møller–Plesset theory (PMP4) was used to correct the DFT energies. The calculated pre-exponential factors and activation energies for the concerted ozonolysis of ethene and propene are in good agreement with experimental values. However, the PMP4//DFT procedure incorrectly predicts the stepwise mechanism as the favored channel. UCCSD(T) predicts the concerted mechanism as the favored channel but significantly overestimates the activation energies. RCCSD(T) is found to be more accurate than UCCSD(T) for the calculation of the concerted mechanism but is not applicable to the diradical intermediates. The major difficulty in accurate prediction of the rate constant data for these reactions is the wide range of spin contamination for the reference UHF wave functions and UDFT solutions across the potential energy surface. The possibility of the partial ozonolysis mechanism being the source of epoxide observed in some experiments is discussed

Perfect countably infinite Steiner triple systems

We use a free construction to prove the existence of perfect Steiner triple systems on a countably infinite point set. We use a specific countably infinite family of partial Steiner triple systems to start the construction, thus yielding 2ℵ0 non-isomorphic perfect systems

Status of Supersymmetric Grand Unified Theories

We begin with a brief discussion of the building blocks of supersymmetric grand unified theories. We recall some of the compelling theoretical reasons for viewing supersymmetric grand unification as an attractive avenue for physics beyond the standard model. This is followed by a discussion of some of the circumstantial evidence for these ideas.Comment: 12 pages plain LaTeX to be run twice. Invited talk at the XII DAE Symposium on High Energy Physics, Guwahati, India, Dec. 26, 1996 - Jan. 1, 199

NGC1052 - A study of the pc-scale twin jet

We present results of a VLBA multi-frequency study of the pc-scale twin jet in NGC1052. We observed this object at epoch 1998.99 with the VLBA at 5, 8.4, 22 and 43 GHz both in total and linearly polarized intensity. The spectral analysis confirms the necessity of a free-free absorbing medium, obscuring the innermost part of both jets. At 5 GHz we found a compact linearly polarized emission region at the base of the eastern jet with a degree of polarization of 1.5%. At higher frequencies there is no evidence for polarization in our data. A core shift analysis constrains the position of the central engine to ~0.03 pc. The shift rates of the apparent core position with frequency confirm the strong influence of free-free absorption in conjunction with steep pressure gradients at the bases of both jets.Comment: Proceedings of the conference "SRT: the impact of large antennas on Radio Astronomy and Space Science", Cagliari, Italy, 7-10 November 2001, in press; 6 pages, 5 figures, needs srt_style.st

Demonstration of single-shot picosecond time-resolved MeV electron imaging using a compact permanent magnet quadrupole based lens

We present the results of an experiment where a short focal length (~ 1.3 cm) permanent magnet electron lens is used to image micron-size features of a metal sample in a single shot, using an ultra- high brightness ps-long 4 MeV electron beam from a radiofrequency photoinjector. Magnifcation ratios in excess of 30x were obtained using a triplet of compact, small gap (3.5 mm), Halbach-style permanent magnet quadrupoles with nearly 600 T/m field gradients. These results pave the way to- wards single shot time-resolved electron microscopy and open new opportunities in the applications of high brightness electron beams.Comment: 5 pages, 6 figure

Verification of a localization criterion for several disordered media

We analytically compute a localization criterion in double scattering approximation for a set of dielectric spheres or perfectly conducting disks uniformly distributed in a spatial volume which can be either spherical or layered. For every disordered medium, we numerically investigate a localization criterion, and examine the influence of the system parameters on the wavelength localization domains.Comment: 30 pages, LateX, amstex, revtex styles, 20 figure

Science and technology

노트 : Evaluation period: 1 Jul 1975-1 Sep 197

Inhibition of Nuclear Factor of Activated T-Cells (NFAT) Suppresses Accelerated Atherosclerosis in Diabetic Mice

OBJECTIVE OF THE STUDY: Diabetic patients have a much more widespread and aggressive form of atherosclerosis and therefore, higher risk for myocardial infarction, peripheral vascular disease and stroke, but the molecular mechanisms leading to accelerated damage are still unclear. Recently, we showed that hyperglycemia activates the transcription factor NFAT in the arterial wall, inducing the expression of the pro-atherosclerotic protein osteopontin. Here we investigate whether NFAT activation may be a link between diabetes and atherogenesis. METHODOLOGY AND PRINCIPAL FINDINGS: Streptozotocin (STZ)-induced diabetes in apolipoprotein E(-/-) mice resulted in 2.2 fold increased aortic atherosclerosis and enhanced pro-inflammatory burden, as evidenced by elevated blood monocytes, endothelial activation- and inflammatory markers in aorta, and pro-inflammatory cytokines in plasma. In vivo treatment with the NFAT blocker A-285222 for 4 weeks completely inhibited the diabetes-induced aggravation of atherosclerosis, having no effect in non-diabetic mice. STZ-treated mice exhibited hyperglycemia and higher plasma cholesterol and triglycerides, but these were unaffected by A-285222. NFAT-dependent transcriptional activity was examined in aorta, spleen, thymus, brain, heart, liver and kidney, but only augmented in the aorta of diabetic mice. A-285222 completely blocked this diabetes-driven NFAT activation, but had no impact on the other organs or on splenocyte proliferation or cytokine secretion, ruling out systemic immunosuppression as the mechanism behind reduced atherosclerosis. Instead, NFAT inhibition effectively reduced IL-6, osteopontin, monocyte chemotactic protein 1, intercellular adhesion molecule 1, CD68 and tissue factor expression in the arterial wall and lowered plasma IL-6 in diabetic mice. CONCLUSIONS: Targeting NFAT signaling may be a novel and attractive approach for the treatment of diabetic macrovascular complications