Comprehensive Synthesis of Monohydroxy-Cucurbit[n]urils (n=5, 6, 7, 8): High Purity and High Conversions

We describe a photochemical method to introduce a single alcohol function directly on cucurbit[n]urils (n = 5, 6, 7, 8) with conversions of the order 95-100% using hydrogen peroxide and UV light. The reaction was easily scaled up to 1 g for CB[6] and CB[7]. Spin trapping of cucurbituril radicals combined with MS experiments allowed us to get insights about the reaction mechanism and characterize CB [5], CB[6], CB[7], and C13[8] monofunctional compounds. Experiments involving O-18 isotopically labeled water indicated that the mechanism was complex and showed signs of both radical and ionic intermediates. DFT calculations allowed estimating the Bond Dissociation Energies (BDEs) of each hydrogen atom type in the CB series, providing an explanation of the higher reactivity of the "equatorial" C-H position of CB[n] compounds. These results also showed that, for CB [8], direct functionalization on the cucurbituril skeleton is more difficult because one of the methylene hydrogen atoms (H-b) has its BDE lowering within the series and coming close to that of H-c, thus opening the way to other types of free radicals generated on the CB[8] skeleton leading to several side products. Yet CB[5]-(OH)(1) and CB[8]-(OH)(1), the first CB[8] derivative, were obtained in excellent yields thanks to the soft method presented here

Testing the Elliott-Yafet spin-relaxation mechanism in KC8; a model system of biased graphene

Temperature dependent electron spin resonance (ESR) measurements are reported on stage 1 potassium doped graphite, a model system of biased graphene. The ESR linewidth is nearly isotropic and although the g-factor has a sizeable anisotropy, its majority is shown to arise due to macroscopic magnetization. Albeit the homogeneous ESR linewidth shows an unusual, non-linear temperature dependence, it appears to be proportional to the resistivity which is a quadratic function of the temperature. These observations suggests the validity of the Elliott-Yafet relaxation mechanism in KC8 and allows to place KC8 on the empirical Beuneu-Monod plot among ordinary elemental metals.Comment: 6 pages, 4 figures, submitted to Phys. Rev.

Diversification of EPR signatures in site directed spin labeling using a beta-phosphorylated nitroxide

Site Directed Spin Labeling (SDSL) combined with EPR spectroscopy is a very powerful approach to investigate structural transitions in proteins in particular flexible or even disordered ones. Conventional spin labels are based on nitroxide derivatives leading to classical 3-line spectra whose spectral shapes are indicative of the environment of the labels and thus constitute good reporters of structural modifications. However, the similarity of these spectral shapes precludes probing two regions of a protein or two partner proteins simultaneously. To overcome the limitation due to the weak diversity of nitroxide label EPR spectral shapes, we designed a new spin label based on a β-phosphorylated nitroxide giving 6-line spectra. This paper describes the synthesis of this new spin label, its grafting at four different positions of a model disordered protein able to undergo an induced α-helical folding and its characterization by EPR spectroscopy. For comparative purposes, a classical nitroxide has been grafted at the same positions of the model protein. The ability of the new label to report on structural transitions was evaluated by analyzing the spectral shape modifications induced either by the presence of a secondary structure stabilizer (trifluoroethanol) or by the presence of a partner protein. Taken together the results demonstrate that the new phosphorylated label gives a very distinguishable signature which is able to report from subtle to larger structural transitions, as efficiently as the classical spin label. As a complementary approach, molecular dynamics (MD) calculations were performed to gain further insights into the binding process between the labeled NTAIL and PXD. MD calculations revealed that the new label does not disturb the interaction between the two partner proteins and reinforced the conclusion on its ability to probe different local environments in a protein. Taken together this study represents an important step forward in the extension of the panoply of SDSL-EPR approaches. This journal is © 2014 the Owner Societies

Multipurpose High Frequency Electron Spin Resonance Spectrometer for Condensed Matter Research

We describe a quasi-optical multifrequency ESR spectrometer operating in the 75-225 GHz range and optimized at 210 GHz for general use in condensed matter physics, chemistry and biology. The quasi-optical bridge detects the change of mm wave polarization at the ESR. A controllable reference arm maintains a mm wave bias at the detector. The attained sensitivity of 2x10^10 spin/G/(Hz)1/2, measured on a dilute Mn:MgO sample in a non-resonant probe head at 222.4 GHz and 300 K, is comparable to commercial high sensitive X band spectrometers. The spectrometer has a Fabry-Perot resonator based probe head to measure aqueous solutions, and a probe head to measure magnetic field angular dependence of single crystals. The spectrometer is robust and easy to use and may be operated by undergraduate students. Its performance is demonstrated by examples from various fields of condensed matter physics.Comment: submitted to Journal of Magnetic Resonanc