Synthesis and Photophysical Properties of a Sc3N@C80‐Corrole Electron Donor–Acceptor Conjugate

Embedding endohdedral metallofullerenes (EMFs) into electron donor–acceptor systems is still a challenging task owing to their limited quantities and their still largely unexplored chemical properties. In this study, we have performed a 1,3‐dipolar cycloaddition reaction of a corrole‐based precursor with Sc₃N@C₈₀ to regioselectively form a [5,6]‐adduct ( 1 ). The successful attachment of the corrole moiety was confirmed by mass spectrometry. In the electronic ground state, absorption spectra suggest sizeable electronic communications between the electron acceptor and the electron donor. Moreover, the addition pattern occurring at a [5,6]‐bond junction is firmly proven by NMR spectroscopy and electrochemical investigations performed with 1 . In the electronically excited state, which is probed in photophysical assays with 1 , a fast electron‐transfer yields the radical ion pair state consisting of the one‐electron‐reduced Sc₃N@C₈₀ and of the one‐electron‐oxidized corrole upon its exclusive photoexcitation. As such, our results shed new light on the practical work utilizing EMFs as building blocks in photovoltaics.     

Light and heat control over secondary structure and amyloid-like fiber formation in an overcrowded-alkene-modified Trp zipper

The external photocontrol over peptide folding, by the incorporation of molecular photoswitches into their structure, provides a powerful tool to study biological processes. However, it is limited so far to switches that exhibit only a rather limited geometrical change upon photoisomerization and that show thermal instability of the photoisomer. Here we describe the use of an overcrowded alkene photoswitch to control a model β-hairpin peptide. This photoresponsive unit undergoes a large conformational change and has two thermally stable isomers which has major influence on the secondary structure and the aggregation of the peptide, permitting the phototriggered formation of amyloid-like fibrils.     

T1Effects in Sequential Dynamic Susceptibility Contrast Experiments

Residual effects of an initial bolus of gadolinium contrast agent have been previously demonstrated in sequential dynamic susceptibility contrast MR experiments. While these residual effects quickly reach a saturation steady state, their etiology is uncertain, and they can lead to spurious estimates of hemodynamic parameters in activation experiments. The possible influence ofT₁effects is now investigated with experiments in whichT₁weighting is varied as well as with serial regionalT₁measurements. Little evidence for significant residualT₁effects is found, suggesting instead that susceptibility effects underlie these observations. An initial saturation dose of contrast agent minimizes this effect.     

Controlling an oscillating Jackson-type network having state-dependent service rates

We consider a Jackson-type network comprised of two queues having state-dependent service rates, in which the queue lengths evolve periodically, exhibiting noisy cycles. To reduce this noise a certain heuristic, utilizing regions in the phase space in which the system behaves almost deterministically, is applied. Using this heuristic, we show that in order to decrease the probability of a customers overflow in one of the queues in the network, the server in that same queue – contrary to intuition – should be shut down for a short period of time. Further noise reduction is obtained if the server in the second queue is briefly shut down as well, when certain conditions hold.     

Spectral action and big desert

The values of the Higgs mass are obtained for two possibilities of extending the standard model in a way compatible with the existence of a noncommutative structure at high energies. We assume the existence of a big desert between the low energy electroweak scale and the high energy scale Λ=1.1×10¹⁷ GeV, where noncommutative features become relevant. We conclude that it is extremely difficult to depart from the Higgs mass value obtained from noncommutative geometry for the standard model with three generations only.     

Property (<Emphasis Type="Italic">T</Emphasis>) and rigidity for actions on Banach spaces

We study property (T) and the fixed-point property for actions on L ^p and other Banach spaces. We show that property (T) holds when L ² is replaced by L ^p (and even a subspace/quotient of L ^p ), and that in fact it is independent of 1≤p<∞. We show that the fixed-point property for L ^p follows from property (T) when 1<p< 2+ε. For simple Lie groups and their lattices, we prove that the fixed-point property for L ^p holds for any 1< p<∞ if and only if the rank is at least two. Finally, we obtain a superrigidity result for actions of irreducible lattices in products of general groups on superreflexive spaces. Bader partially supported by ISF grant 100146; Furman partially supported by NSF grants DMS-0094245 and DMS-0604611; Gelander partially supported by NSF grant DMS-0404557 and BSF grant 2004010; Monod partially supported by FNS (CH) and NSF (US).