Tagged-particle motion in glassy systems under shear: Comparison of mode coupling theory and Brownian dynamics simulations

We study the dynamics of a tagged particle in a glassy system under shear. The recently developed integration through transients approach, based on mode coupling theory, is continued to arrive at the equations for the tagged-particle correlators and the mean squared displacements. The equations are solved numerically for a two-dimensional system, including a nonlinear stability analysis of the glass solution, the so called β-analysis. We perform Brownian Dynamics simulations in 2D and compare with theory. After switch on, transient glassy correlation functions show strong fingerprints of the stress overshoot scenario, including, additionally to previously studied superexponential decay, a shoulder-like slowing down after the overshoot. We also find a new type of Taylor dispersion in glassy states which has intriguing similarity to the known low-density case. The theory qualitatively captures most features of the simulations with quantitative deviations concerning the shear-induced time scales. We attribute these deviations to an underestimation of the overshoot scenario in the theory.     

Separating electrophilicity and Lewis acidity: the synthesis, characterization, and electrochemistry of the electron deficient tris(aryl)boranes B(C6F5)(3-n)(C6Cl5)n (n = 1-3)

A new family of electron-deficient tris(aryl)boranes, B(C(6)F(5))(3-n)(C(6)Cl(5))(n) (n = 1-3), has been synthesized, permitting an investigation into the steric and electronic effects resulting from the gradual replacement of C(6)F(5) with C(6)Cl(5) ligands. B(C(6)F(5))(2)(C(6)Cl(5)) (3) is accessed via C(6)Cl(5)BBr(2), itself prepared from donor-free Zn(C(6)Cl(5))(2) and BBr(3). Reaction of C(6)Cl(5)Li with BCl(3) in a Et(2)O/hexane slurry selectively produced B(C(6)Cl(5))(2)Cl, which undergoes B-Cl exchange with CuC(6)F(5) to afford B(C(6)F(5))(C(6)Cl(5))(2) (5). While 3 forms a complex with H(2)O, which can be rapidly removed under vacuum or in the presence of molecular sieves, B(C(6)Cl(5))(3) (6) is completely stable to refluxing toluene/H(2)O for several days. Compounds 3, 5, and 6 have been structurally characterized using single crystal X-ray diffraction and represent the first structure determinations for compounds featuring B-C(6)Cl(5) bonds; each exhibits a trigonal planar geometry about B, despite having different ligand sets. The spectroscopic characterization using (11)B, (19)F, and (13)C NMR indicates that the boron center becomes more electron-deficient as n increases. Optimized structures of B(C(6)F(5))(3-n)(C(6)Cl(5))(n) (n = 0-3) using density functional theory (B3LYP/TZVP) are all fully consistent with the experimental structural data. Computed (11)B shielding constants also replicate the experimental trend almost quantitatively, and the computed natural charges on the boron center increase in the order n = 0 (0.81) < n = 1 (0.89) < n = 2 (1.02) < n = 3 (1.16), supporting the hypothesis that electrophilicity increases concomitantly with substitution of C(6)F(5) for C(6)Cl(5). The direct solution cyclic voltammetry of B(C(6)F(5))(3) has been obtained for the first time and electrochemical measurements upon the entire series B(C(6)F(5))(3-n)(C(6)Cl(5))(n) (n = 0-3) corroborate the spectroscopic data, revealing C(6)Cl(5) to be a more electron-withdrawing group than C(6)F(5), with a ca. +200 mV shift observed in the reduction potential per C(6)F(5) group replaced. Conversely, use of the Guttmann-Beckett and Childs' methods to determine Lewis acidity on B(C(6)F(5))(3), 3, and 5 showed this property to diminish with increasing C(6)Cl(5) content, which is attributed to the steric effects of the bulky C(6)Cl(5) substituents. This conflict is ascribed to the minimal structural reorganization in the radical anions upon reduction during cyclic voltammetric experiments. Reduction of 6 using Na((s)) in THF results in a vivid blue paramagnetic solution of Na(+) [6](?-); the EPR signal of Na(+)[6](?-) is centered at g = 2.002 with a((11)B) 10G. Measurements of the exponential decay of the EPR signal (298 K) reveal [6](?-) to be considerably more stable than its perfluoro analogue.     

Controlled self-assembly of filled micelles on nanotubes

We have used coarse-grained molecular dynamics simulations to show that hydrated lipid micelles of preferred sizes and amounts of filling with hydrophobic molecules can be self-assembled on the surfaces of carbon nanotubes. We simulated micelle formation on a hydrated (40,0) carbon nanotube with an open end that was covered with amphiphilic double-headed CH(3)(CH(2))(14)CH(((CH(2)OCH(2)CH(2))(2)(CH(2)COCH(2)))(2)H)(2) or single-headed CH(3)(CH(2))(14)CH(2)((CH(2)OCH(2)CH(2))(2)(CH(2)COCH(2)))(4)H lipids and filled with hexadecane molecules. Once the hexadecane molecules inside the nanotube were pressurized and the lipids on its surface were dragged by the water flowing around it, kinetically stable micelles filled with hexadecane molecules were sequentially formed at the nanotube tip. We investigated the stability of the thus-formed kinetically stable filled micelles and compared them with thermodynamically stable filled micelles that were self-assembled in the solution.     

Hydrophilic Quaternary Ammonium Ionenes—Is There an Influence of Backbone Flexibility and Topology on Antibacterial Properties?

The antimicrobial properties of polycations are strongly affected by the structural features such as the backbone flexibility and topology (isomerism) through the polymer ability to attain proper conformation in interaction with the cell membrane. In this paper, a synthesis and biocidal properties evaluation of ionenes characterized by different backbone topology (isomerism) and flexibility are presented. The findings reveal influence of variation in topology on activity against different microorganisms, and general positive effect of improved flexibility. Furthermore, one of the obtained ionenes displays degradable properties in near physiological environment (phosphate‐buffered saline pH 7.4, 37 °C). The degradation proceeds via Hofmann elimination reaction and the products are not of acidic character. For the first time a new class of degradable ionenes with a high antimicrobial potential is presented.     

Effect of multivalent cations,temperature, and aging on SOM thermal properties

Multivalent cations are suggested to influence the supramolecular structure of soil organic matter (SOM) via inter- and intra-molecular interactions with SOM functional groups. In this study, we tested the combined effect of cations, temperature treatment, and isothermal aging on SOM matrix properties. Samples from a peat and a mineral soil were either enriched with Na, Ca, and Al or desalinated in batch experiments. After treatment at 25, 40, 60, and 105 °C and after different periods of aging at 19 °C and 31 % relative humidity, we investigated the physicochemical matrix stability and the thermal stability against combustion. We hypothesized that multivalent cations stabilize the SOM matrix, that these structures disrupt at elevated temperatures, and that aging leads to an increase in matrix stability. The results show that cation-specific effects on matrix rigidity started to evolve in the peat only after 8 weeks of aging and were significantly lower than the temperature effects. Temperature treatment above 40 °C caused a non (or not immediately) reversible loss of water molecule bridges (WaMB) and above 60 °C a partly reversible melting process probably of semi-crystalline poly(methylene). Thermal stability increased with increasing cation valence and degree of protonation and was much less affected by temperature. Generally, Na-treated and control samples revealed lower thermal stability and lower increase in matrix rigidity with aging than those treated with Ca, Al, and H. We conclude that drying at elevated temperatures (>40 °C) may irreversibly change SOM structure via disruption of labile cross-links and melting of semi-crystalline domains.     

Iron(II) Spin‐Crossover Complexes in Ultrathin Films: Electronic Structure and Spin‐State Switching by Visible and Vacuum‐UV Light

The electronic structure of the iron(II) spin crossover complex [Fe(H₂bpz)₂(phen)] deposited as an ultrathin film on Au(111) is determined by means of UV‐photoelectron spectroscopy (UPS) in the high‐spin and in the low‐spin state. This also allows monitoring the thermal as well as photoinduced spin transition in this system. Moreover, the complex is excited to the metastable high‐spin state by irradiation with vacuum‐UV light. Relaxation rates after photoexcitation are determined as a function of temperature. They exhibit a transition from thermally activated to tunneling behavior and are two orders of magnitude higher than in the bulk material.     

Density functional study on structures, stabilities, and electronic properties of size-selected Pd n Si q (n = 1–7 and q = 0, +1, −1) clusters

The density functional theory (DFT) calculations within the framework of generalized gradient approximation have been employed to systematically investigate the geometrical structures, stabilities, and electronic properties of Pd _n Si ^q (n = 1–7 and q = 0, +1, ?1) clusters and compared them with the pure ${\text{Pd}}_{n + 1}^{q}$ (n = 1–7 and q = 0, +1, ?1) clusters for illustrating the effect of doping Si atom into palladium nanoclusters. The most stable configurations adopt a three-dimensional structure for both pure and Si-doped palladium clusters at n = 3–7. As a result of doping, the Pd _n Si clusters adopt different geometries as compared to that of Pd _n+1. A careful analysis of the binding energies per atom, fragmentation energies, second-order difference of energies, and HOMO–LUMO energy gaps as a function of cluster size shows that the clusters ${\text{Pd}}_{4}^{ + }$ , ${\text{Pd}}_{4}$ , ${\text{Pd}}_{8}^{ - }$ , ${\text{Pd}}_{5} {\text{Si}}^{0, + , - }$ , and ${\text{Pd}}_{7} {\text{Si}}^{0, + , - }$ possess relatively higher stability. There is enhancement in the stabilities of palladium frameworks due to doping with an impurity atom. In addition, the charge transfer has been analyzed to understand the effect of doped atom and compared further.     

An Organometallic Inhibitor for the Human Repair Enzyme 7,8‐Dihydro‐8‐oxoguanosine Triphosphatase

The probe‐based discovery of the first small‐molecule inhibitor of the repair enzyme 8‐oxo‐dGTPase (MTH1) is presented, which is an unconventional cyclometalated ruthenium half‐sandwich complex. The organometallic inhibitor with low‐nanomolar activity displays astonishing specificity, as verified in tests with an extended panel of protein kinases and other ATP binding proteins. The binding of the organometallic inhibitor to MTH1 is investigated by protein crystallography.     

Total Synthesis of (R,R,R)‐α‐Tocopherol Through Asymmetric Cu‐Catalyzed 1,4‐Addition

By introducing a disposable activating substituent at C‐3, the asymmetric 1,4‐addition to a notoriously unreactive 2‐substituted chromenone was achieved with high levels of (2R)‐stereoselectivity in the presence of a chiral Cu^I‐phosphoramidite complex as a catalyst. This paved the way for an efficient and conceptually novel synthesis of (R,R,R)‐α‐tocopherol from readily available starting materials.