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.     

Onset of crater formation during short pulse laser ablation

We report morphologic changes of metallic surfaces at the onset of ablation, starting from gentle ablation to the emergence of ablation craters. The evolution of both observed melting zones and of ablation craters therein are investigated in dependence of the ablation laser fluence for nanosecond ultraviolet laser pulses. Further, consequences of crater formation for cluster synthesis within the released atomic vapor are pointed out. PACS 52.38.Mf; 79.20.Ds; 65.40.De     

Piecewise Deterministic Markov Control Processes with Feedback Controls and Unbounded Costs

The control of piecewise-deterministic processes is studied where only local boundedness of the data is assumed. Moreover the discount rate may be zero. The value function is shown to be solution to the Bellman equation in a weak sense; however the solution concept is strong enough to generate optimal policies. Continuity and compactness conditions are given for the existence of nonrelaxed optimal feedback controls.     

Determination of platinum and biologically important trace elements in structure-activity relationship studies on platinum-containing anti-cancer drugs. Special procedures for removing32P as well as for the estimation of99 Mo and199Au

As part of an examination of the cytostatic effects of 1,2-diarylethylenediamine-platinum(II)-complexes the contents of platinum and biologically essential trace elements of tumour tissue and different organs were determined. The activation analysis procedure — separation of³²P, isolation of¹⁹⁹Au and⁹⁹Mo — is described. In the course of a pharmakokinetical experiment with tumourbearing rats (DMBA induced hormone-dependent tumours) the desired enrichment of the administered drug in the tumour tissue was found. Changes of the trace element level of tumour tissue were found for hormone-dependent MXT-mammary tumours on mice.     

A systematic elimination procedure for Ito stochastic differential equations and the adiabatic approximation

We study a class of nonlinear Ito stochastic differential equations (with possibly state dependent diffusion coefficients), in which the variables can be divided into linearly damped (slaved) variables s and linearly undamped variablesu (order parameters). We devise a systematic and constructive procedure to eliminate the slaved variables. We take explicit time and chance dependence of the slaved variables into account, the latter via a family of diffusion processesZ _t ^(v) . These act as fluctuating coefficients of the Center Manifolds _t=s(u _t, t,Z _t ^(v) (v=2, 3, ...)) and appear explicitly in the elimination procedure. We show how in the Ito calculus fluctuating and deterministic coefficients of the Center Manifold are more completely separated than in the previously treated Stratonovich case [1]. The adiabatic approximation is defined as a partial summation of the elimination expansion and the stochastic generalization ofs=0 is derived. We show how thus ambiguity of stochastic calculi is removed. Closed form summations are given in two examples. We briefly indicate the potential use of perturbation theory techniques in the systematic elimination procedure.