Pulsed electron-electron double resonance (PELDOR) distance measurements in detergent micelles

Pulsed electron-electron double resonance (PELDOR) spectroscopy is a powerful tool for measuring nanometer distances in spin-labeled systems. A common approach is doubly covalent spin-labeling of a macromolecule and measurement of the inter-spin distance, or to use singly-labeled components of a system that forms aggregates or oligomers. This situation has been described as a spin-cluster. The PELDOR signal, however, does not only contain the desired dipolar coupling between the spin-labels of the molecule or cluster under study. In samples of finite concentration the dipolar coupling between the spin-labels of the randomly distributed molecules or spin-clusters also contributes significantly. In homogeneous frozen solutions or lipid vesicle membranes this second contribution can be considered to be an exponential or stretched exponential decay, respectively. In this study, we show that this assumption is not valid in detergent micelles. Spin-labeled fatty acids that are randomly partitioned into different detergent micelles give rise to PELDOR time traces which clearly deviate from stretched exponential decays. The obtained signals can be modeled quantitatively based on the size of the micelles, their aggregation number, the spin-label concentration and the degree of spin-labeling. As a main conclusion a PELDOR signal deviating from a stretched exponential decay does not necessarily prove the observation of specific distance information on the molecule or cluster. These results are important for the interpretation of PELDOR experiments on membrane proteins or lipophilic peptides solubilized in detergent micelles or small vesicles, which often do not show pronounced dipolar oscillations in their time traces.     

PELDOR measurements on a nitroxide-labeled Cu(II) porphyrin: orientation selection, spin-density distribution, and conformational flexibility

Metal ions are functionally or structurally important centers in metalloproteins or RNAs, which makes them interesting targets for spectroscopic investigations. In combination with site-directed spin labeling, pulsed electron-electron double resonance (PELDOR or DEER) could be a well-suited method to characterize and localize them. Here, we report on the synthesis, full characterization, and PELDOR study of a copper(II) porphyrin/nitroxide model system. The X-band PELDOR time traces contain besides the distance information a convolution of orientational selectivity, conformational flexibility, exchange coupling, and spin density distribution, which can be deconvoluted by experiments with different frequency offsets and simulations. The simulations are based on the known experimental and spin Hamiltonian parameters and make use of a geometric model as employed for structurally similar bis-nitroxides and spin density parameters as obtained from density functional theory calculations. It is found that orientation selection with respect to dipolar angles is only weakly resolvable at X-band frequencies due to the large nitrogen hyperfine coupling of the copper porphyrin. On the other hand, the PELDOR time traces reveal a much faster oscillation damping than observed for structurally similar bis-nitroxides, which is mainly assigned to a small distribution in exchange couplings J. Taking the effects of orientation selectivity, distribution in J, and spin density distribution into account leads finally to a narrow distance distribution caused solely by the flexibility of the structure, which is in agreement with distributions from known bis-nitroxides of similar structure. Thus, X-band PELDOR measurements at different frequency offsets in combination with explicit time trace simulations allow for distinguishing between structural models and quantitative interpretation of copper-nitroxide PELDOR data gives access to localization of copper(II) ions.     

Synthesis and evaluation of a novel natural-based phosphine antioxidant for the thermal stabilization of polyethylene

Journal of Thermal Analysis and Calorimetry - A new phosphine-type potential secondary stabilizer was synthesized successfully with large natural raw material content. The stabilizer is a waxy...     

Zwitterionic Polymeric Sulfur Ylides with Minimal Charge Separation Open a New Generation of Antifouling and Bactericidal Materials**

Zwitterionic polymers are widely employed hydrophilic building blocks for antifouling coatings with numerous applications across a wide range of fields, including but not limited to biomedical science, drug delivery and nanotechnology. Zwitterionic polymers are considered as an attractive alternative to polyethylene glycol because of their biocompatibility and effectiveness to prevent formation of biofilms. To this end, zwitterionic polymers are classified in two categories, namely polybetaines and polyampholytes. Yet, despite a fundamental interest to drive the development of new antifouling materials, the chemical composition of zwitterionic polymer remains severely limited. Here, we show that poly(sulfur ylides) that belong to the largely overlooked class of poly(ylides), effectively prevent the formation of biofilms from pathogenic bacteria. While surface energy analysis reveals strong hydrogen-bond acceptor capabilities of poly(sulfur ylide), membrane damage of pathogenic bacteria induced by poly(sulfur ylides) indicates toxicity towards bacteria while not affecting eucaryotic cells. Such synergistic effect of poly(sulfur ylides) offers distinct advantages over polyethylene glycol when designing new antifouling materials. We expect that our findings will pave the way for the development of a range of ylide-based materials with antifouling properties that have yet to be explored, opening up new directions at the interface of chemistry, biology, and material science.     

Diverse Imprecise Goal Programming Model Formulations

The goal programming (GP) model is probably the best known in mathematical programming with multiple objectives. Available in various versions, GP is one of the most powerful multiple objective methods which has been applied in much varied fields. It has also been the target of many criticisms among which are those related to the difficulty of determining precisely the goal values as well as those concerning the decision-maker's near absence in this modelling process. In this paper, we will use the concept of indifference thresholds for modelling the imprecision related to the goal values. Many classical imprecise and fuzzy GP model formulations can be considered as a particular case of the proposed formulation.     

On a Non-Periodic Modified Euler Equation: Well-Posedness and Quasi-Invariant Measures

Potential Analysis - We consider a modified Euler equation on $mathbb {R}^{2}$ . We prove existence of weak global solutions for bounded (and fast decreasing at infinity) initial conditions and...     

Generalized stochastic flows and applications to incompressible viscous fluids

We introduce a notion of generalized stochastic flows on manifolds, that extends to the viscous case the one defined by Brenier for perfect fluids. Their kinetic energy extends the classical kinetic energy to Brownian flows, defined as the L²$L^2$ norm of their drift. We prove that there exists a generalized flow which realizes the infimum of the kinetic energy among all generalized flows with prescribed initial and final configuration. We also construct generalized flows with prescribed drift and kinetic energy smaller than the L²$L^2$ norm of the drift.