Nature's polyoxometalate chemistry: X-ray structure of the Mo storage protein loaded with discrete polynuclear Mo-O clusters

Some N(2)-fixing bacteria prolong the functionality of nitrogenase in molybdenum starvation by a special Mo storage protein (MoSto) that can store more than 100 Mo atoms. The presented 1.6 ? X-ray structure of MoSto from Azotobacter vinelandii reveals various discrete polyoxomolybdate clusters, three covalently and three noncovalently bound Mo(8), three Mo(5-7), and one Mo(3) clusters, and several low occupied, so far undefinable clusters, which are embedded in specific pockets inside a locked cage-shaped (αβ)(3) protein complex. The structurally identical Mo(8) clusters (three layers of two, four, and two MoO(n) octahedra) are distinguishable from the [Mo(8)O(26)](4-) cluster formed in acidic solutions by two displaced MoO(n) octahedra implicating three kinetically labile terminal ligands. Stabilization in the covalent Mo(8) cluster is achieved by Mo bonding to Hisα156-N(ε2) and Gluα129-O(ε1). The absence of covalent protein interactions in the noncovalent Mo(8) cluster is compensated by a more extended hydrogen-bond network involving three pronounced histidines. One displaced MoO(n) octahedron might serve as nucleation site for an inhomogeneous Mo(5-7) cluster largely surrounded by bulk solvent. In the Mo(3) cluster located on the 3-fold axis, the three accurately positioned His140-N(ε2) atoms of the α subunits coordinate to the Mo atoms. The formed polyoxomolybdate clusters of MoSto, not detectable in bulk solvent, are the result of an interplay between self- and protein-driven assembly processes that unite inorganic supramolecular and protein chemistry in a host-guest system. Template, nucleation/protection, and catalyst functions of the polypeptide as well as perspectives for designing new clusters are discussed.     

Fluorinated Copolymer PCPDTBT with Enhanced Open-Circuit Voltage and Reduced Recombination for Highly Efficient Polymer Solar Cells

A novel fluorinated copolymer (F-PCPDTBT) is introduced and shown to exhibit significantly higher power conversion efficiency in bulk heterojunction solar cells with PC(70)BM compared to the well-known low-band-gap polymer PCPDTBT. Fluorination lowers the polymer HOMO level, resulting in high open-circuit voltages well exceeding 0.7 V. Optical spectroscopy and morphological studies with energy-resolved transmission electron microscopy reveal that the fluorinated polymer aggregates more strongly in pristine and blended layers, with a smaller amount of additives needed to achieve optimum device performance. Time-delayed collection field and charge extraction by linearly increasing voltage are used to gain insight into the effect of fluorination on the field dependence of free charge-carrier generation and recombination. F-PCPDTBT is shown to exhibit a significantly weaker field dependence of free charge-carrier generation combined with an overall larger amount of free charges, meaning that geminate recombination is greatly reduced. Additionally, a 3-fold reduction in non-geminate recombination is measured compared to optimized PCPDTBT blends. As a consequence of reduced non-geminate recombination, the performance of optimized blends of fluorinated PCPDTBT with PC(70)BM is largely determined by the field dependence of free-carrier generation, and this field dependence is considerably weaker compared to that of blends comprising the non-fluorinated polymer. For these optimized blends, a short-circuit current of 14 mA/cm(2), an open-circuit voltage of 0.74 V, and a fill factor of 58% are achieved, giving a highest energy conversion efficiency of 6.16%. The superior device performance and the low band-gap render this new polymer highly promising for the construction of efficient polymer-based tandem solar cells.     

Titanium‐Catalyzed Vinylic and Allylic C?F Bond Activation—Scope,Limitations and Mechanistic Insight

The hydrodefluorination (HDF) of fluoroalkenes in the presence of a variety of titanium catalysts was studied with respect to scope, selectivity, and mechanism. Optimization revealed that the catalyst requires low steric bulk and high electron density; secondary silanes serve as the preferred hydride source. A broad range of substrates yield partially fluorinated alkenes, such as previously unknown (Z)‐1,2‐(difluorovinyl)ferrocene. Mechanistic studies indicate a titanium(III) hydride as the active species, which forms a titanium(III) fluoride by H/F exchange with the substrate. The HDF step can follow both an insertion/elimination and a σ‐bond metathesis mechanism; the E/Z selectivity is controlled by the substrate. The catalysts’ ineffieciency towards fluoroallenes was rationalized by studying their reactivity towards Group 6 hydride complexes.     

Influence of ensemble surrogate models and sampling strategy on the solution quality of algorithms for computationally expensive black-box global optimization problems

This paper examines the influence of two major aspects on the solution quality of surrogate model algorithms for computationally expensive black-box global optimization problems, namely the surrogate model choice and the method of iteratively selecting sample points. A random sampling strategy (algorithm SO-M-c) and a strategy where the minimum point of the response surface is used as new sample point (algorithm SO-M-s) are compared in numerical experiments. Various surrogate models and their combinations have been used within the SO-M-c and SO-M-s sampling frameworks. The Dempster–Shafer Theory approach used in the algorithm by Müller and Piché (J Glob Optim 51:79–104, 2011) has been used for combining the surrogate models. The algorithms are numerically compared on 13 deterministic literature test problems with 2–30 dimensions, an application problem that deals with groundwater bioremediation, and an application that arises in energy generation using tethered kites. NOMAD and the particle swarm pattern search algorithm (PSWARM), which are derivative-free optimization methods, have been included in the comparison. The algorithms have also been compared to a kriging method that uses the expected improvement as sampling strategy (FEI), which is similar to the Efficient Global Optimization (EGO) algorithm. Data and performance profiles show that surrogate model combinations containing the cubic radial basis function (RBF) model work best regardless of the sampling strategy, whereas using only a polynomial regression model should be avoided. Kriging and combinations including kriging perform in general worse than when RBF models are used. NOMAD, PSWARM, and FEI perform for most problems worse than SO-M-s and SO-M-c. Within the scope of this study a Matlab toolbox has been developed that allows the user to choose, among others, between various sampling strategies and surrogate models and their combinations. The open source toolbox is available from the authors upon request.     

Diffusion of n-pentane in the zeolite ZK5 studied by high-temperature configuration-space exploration

The extremely slow diffusion of the molecule n-pentane caused by the hopping from cage-to-cage in zeolite ZK5 has been investigated by transition state theory (TST). Such slow diffusion cannot be accessed by usual molecular dynamics simulation techniques. The calculation of the partition function ratio needed for TST was enabled by a recently developed method, the so-called high-temperature configuration-space exploration (HTCE). Dynamical corrections for recrossing events have also been taken into account. The obtained intra-zeolite self-diffusion constant between 247 and 317 K of 10⁻¹⁶–10⁻¹⁵ m² s⁻¹ falls in the range of 10⁻¹⁸–10⁻¹⁵ m² s⁻¹ observed experimentally. The calculated energetic barrier between two neighboring cages of 29 kJ mol⁻¹ is in good agreement with that of 28 ± 5 kJ mol⁻¹ obtained from NMR measurement.     

Skew-Self-Adjoint Dirac System with a Rectangular Matrix Potential: Weyl Theory, Direct and Inverse Problems

A non-classical Weyl theory is developed for skew-self-adjoint Dirac systems with rectangular matrix potentials. The notion of the Weyl function is introduced and direct and inverse problems are solved. A Borg?CMarchenko type uniqueness result and the evolution of the Weyl function for the corresponding focusing nonlinear Schr?dinger equation are also derived.     

Titanium-catalyzed vinylic and allylic cf bond activation-scope, limitations and mechanistic insight

The hydrodefluorination (HDF) of fluoroalkenes in the presence of a variety of titanium catalysts was studied with respect to scope, selectivity, and mechanism. Optimization revealed that the catalyst requires low steric bulk and high electron density; secondary silanes serve as the preferred hydride source. A broad range of substrates yield partially fluorinated alkenes, such as previously unknown (Z)-1,2-(difluorovinyl)ferrocene. Mechanistic studies indicate a titanium(III) hydride as the active species, which forms a titanium(III) fluoride by H/F exchange with the substrate. The HDF step can follow both an insertion/elimination and a σ-bond metathesis mechanism; the E/Z selectivity is controlled by the substrate. The catalysts' ineffieciency towards fluoroallenes was rationalized by studying their reactivity towards Group?6 hydride complexes.     

StavroX—A Software for Analyzing Crosslinked Products in Protein Interaction Studies

Chemical crosslinking in combination with mass spectrometry has matured into an alternative approach to derive low-resolution structural information of proteins and protein complexes. Yet, one of the major drawbacks of this strategy remains the lack of software that is able to handle the large MS datasets that are created after chemical crosslinking and enzymatic digestion of the crosslinking reaction mixtures. Here, we describe a software, termed StavroX, which has been specifically designed for analyzing highly complex crosslinking datasets. The StavroX software was evaluated for three diverse biological systems: (1) the complex between calmodulin and a peptide derived from Munc13, (2) an N-terminal ß-laminin fragment, and (3) the complex between guanylyl cyclase activating protein-2 and a peptide derived from retinal guanylyl cyclase. We show that the StavroX software is advantageous for analyzing crosslinked products due to its easy-to-use graphical user interface and the highly automated analysis of mass spectrometry (MS) and tandem mass spectrometry (MS/MS) data resulting in short times for analysis. StavroX is expected to give a further push to the chemical crosslinking approach as a routine technique for protein interaction studies.     

Photoexcitation of K-shell and L-shell hollow beryllium

We have observed K-shell and L-shell hollow beryllium atoms (2s(2)2p3s and 1s3s(2)3p) created by photoexcitation using synchrotron radiation. Resonance shapes were fitted to the Fano profile and the parameters were deduced. A Dirac-Fock calculation was performed to identify the configuration of the peaks and to predict other hollow atomic peaks. The results of the calculation were in good agreement with the experimental data. The comparison of the transition strength has revealed that the three-electron photoexcitation to the 1s3s(2)3p configuration is stronger than the two-electron photoexcitation to the 2s(2)2p3s configuration. This is attributed to the large overlap between the 2s orbital of the ground state (1s(2)2s(2)) with the orbital of the L-shell hollow state (1s3s(2)3p).     

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