A novel scandium ortho-methoxynitrosobenzene-dimer complex: mechanistic implications for the nitroso-Diels-Alder reaction

Arylnitroso dienophiles exist in equilibrium with their dimeric counterparts, which in turn form stable bidentate complexes with scandium(III) triflate and react with cyclohexadiene to give the corresponding Diels-Alder adduct at the same rate as the normal thermal process.     

Mechanisms of sulfanyl (RS) migrations: synthesis of heterocycles

Thiiranium (episulfonium) ions had been acknowledged as reaction intermediates for many years, but it was not until 1977 that Nicolaou demonstrated systematically that these reactive heterocyclic cations could be trapped by carboxylic acids to give lactones. In the years that followed this report, extensive research greatly extended the scope of this reaction, particularly with regard to the methods for generating thiiranium ions, the types of nucleophiles that are compatible with this reaction, and the selectivity involved in the cyclization reactions. For many years we have been using thiiranium ions for the synthesis of saturated heterocycles. Whereas Nicolaou's method relied on electrophilic sulfenylation of alkenes, we have generated thiiranium ions by displacement of a leaving group with neighboring-group participation by a sulfanyl group. Many of the examples we have reported are of cyclizations that are reversible and so where two (and in some cases more) products can result, the outcome of the reactions provides fundamental information about the relative stability of different heterocyclic ring systems. This Review will begin with a brief introduction to sulfanyl participation as a method for generating thiiranium (and thiolanium) ions, and will go on to explore the idea of using sulfanyl migrations in synthesis. Initially, emphasis will be placed on mechanisms of [1,2] sulfanyl migrations: we will look specifically at [1,2] sulfanyl migrations (usually PhS) with elimination, substitution, and cyclization. Emphasis will then shift to the factors that affect the outcome of cyclization reactions. In particular, we will cover cyclizations with hydroxy nucleophiles and examine situations in which there are more than one hydroxy nucleophile present. We will also examine cyclizations with other nucleophiles, namely amines and sulfides. After our discussion of [1,2] sulfanyl migrations, we will look very briefly at the scope of [1,4] sulfanyl participation, before finally drawing up some guidelines that (we hope) will help other organic chemists take advantage of the rearrangement reactions that the sulfanyl group has to offer.     

Further study of Saint-Venant's principle in linear viscoelasticity

Summary For a viscoelastic beam loaded at one end and otherwise traction-free, it is shown that a certain integral measure of the strain in that portion of the beam at a distance greater than or equal tos decays exponentially with increasings. This is a different integral decay estimate from that obtained previously by Edelstein [2] and leads immediately to a pointwise decay estimate for strains.

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Zusammenfassung Für einen viskoelastischen Balken, der am einen Ende belastet ist, wird gezeigt, dass ein gewisses Integralmass der Verzerrung in Entfernungen, die grösser oder gleichs sind, mit zunehmendems exponentiell abnimmt. Es handelt sich dabei um eine andere Integral-Abschätzung, als sie früher von Edelstein [2] aufgestellt wurde. Sie führt direkt zu einer punktweisen Abschätzung für die Verzerrungen.

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Submitted by R.E.N. as a partial fulfillment of the requirements for the Ph.D. degree at Illinois Institute of Technology, Chicago, Illinois 60616.     

Strings with dimension-dependent intercept

By changing the boundary conditions of the relativistics string in extra dimensions, the intercept α(0) is lowered to $\text{1 ?}\text{1}\text{16}\text{(26 ?D}{}_0\text{)}$ in the modified orbital model, where D₀ is the dimensionality of the Poincaré-invariant subspace of space-time. In the modified model of the spinning string, the boson intercept becomes $\text{1}\text{2}\text{?}\text{1}\text{8}\text{(10 ? D}{}_{\mathrm{o}}\text{)}$, while the fermion intercept stays at zero. The projective invariance of the ground state is broken, giving the “photon” mass by a Higgs-like mechanism. Unfortunately, the strings have a negative “G parity”, so the usual, unshifted strings appear as intermediate states in the scattering amplitudes. Also, some of the amplitudes are not dual.     

Characterization of pure high-grade DCIS on magnetic resonance imaging using the evolving breast MR lexicon terminology: can it be differentiated from pure invasive disease?

Magnetic resonance imaging (MRI) is now a recognized method of imaging the breast. Unfortunately, there is lack of standardization in the MRI terminology used to characterize the appearance of breast lesions. Moreover, cases of mixed histologies are often imaged. We retrospectively identified cases of pure high-grade ductal carcinoma in situ (DCIS) using the recently introduced breast MRI lexicon and characterized the lesions in order to try and identify features that might distinguish high-grade DCIS from invasive disease. Five-year review of our institution's database revealed 637 patients underwent gadolinium-enhanced breast MRI examination. Twenty patients had histologically proven pure high-grade DCIS. After excluding patients with previous chemotherapy or inadequate MRI examination, 13 patients were analyzed and compared to the 13 most recent cases of pure invasive breast carcinoma. The morphological and dynamic features were then compared. High-grade DCIS cases were significantly more likely to show focal branching pattern (P=.03) and to have an irregular contour (P=.03), compared with invasive disease. Although of marginal statistical significance, DCIS lesions are more likely to have a lower morphological score than invasive carcinoma (P=.06), whilst the latter is more likely to show ring enhancement (P=.07). Use of breast MRI for staging at our institution shows that pure DCIS and pure invasive cancers are both rare entities. Despite the relatively limited numbers, we identified features that would help to differentiate high-grade DCIS from invasive carcinoma on MRI.