Self-assembled networks highly responsive to hydrocarbons

Rheological studies were performed with aqueous salt solutions of anionic surfactant potassium oleate and its mixtures with hydrophobically modified polyacrylamide. Semidilute solutions of the surfactant in the presence of salt (KCl) demonstrate viscoelastic properties due to the formation of a transient network of entangled wormlike micelles. These systems are highly responsive to hydrocarbons: the addition of n-heptane or n-dodecane reduces the viscosity of solutions by up to 4 to 5 orders of magnitude, thus inducing the transition of a gellike system to a fluid one. It is the transformation of cylindrical surfactant micelles into spherical ones upon absorption of hydrocarbon that disrupts the network. The addition of a small amount (0.5 wt %) of associating polymer leads to up to a 5000-fold increase in the zero-shear viscosity and enhances the susceptibility to hydrocarbons. SANS data show that independently of the presence of polymer the radius of wormlike micelles is roughly equal to the length of a surfactant molecule, whereas the radius of spheres formed upon the absorption of hydrocarbon is 2-2.5-fold higher. A possible structure of the spherical micelles is discussed.     

Magnetic properties of bulk BiCrO3 studied with dc and ac magnetization and specific heat

Single-phased powder BiCrO(3) sample was prepared at 6 GPa and 1653 K. Its magnetic properties were investigated by dc/ac magnetization, magnetic relaxation, and specific heat measurements. Four anomalies of magnetic origin were found near 40, 75, 109, and 111 K. The long-range antiferromagnetic order with weak ferromagnetism occurs at T(N) = 109 K. The ac susceptibilities showed that the transition near T(N) is a two-step transition. Additional frequency-independent broad anomalies were observed on the real part of the ac susceptibilities near 75 K, likely, caused by the change in the magnetic easy axis. The dc magnetic susceptibilities also had anomalies at 75 K, and the isothermal magnetization curves and relaxation curves changed their behavior below 75 K. Below 40 K, frequency-dependent anomalies with very large temperature shifts were observed on both the real and imaginary parts of the ac susceptibilities. The monoclinic-to-orthorhombic structural phase transition near 420 K was investigated by magnetization and differential scanning calorimetry measurements.     

Amine nitrosation via NO reduction of the polyamine copper(II) complex Cu(DAC)2+

The reaction of the fluorescent macrocyclic ligand 1,8-bis(anthracen-9-ylmethyl)-1,4,8,11-tetraazacyclotetradecane with copper(II) salts leads to formation of the Cu(DAC)2+ cation (I), which is not luminescent. However, when aqueous methanol solutions of I are allowed to react with NO, fluorescence again develops, owing to the formation of the strongly luminescent N-nitrosated ligand DAC-NO (II), which is released from the copper center. This reaction is relatively slow in neutral media, and kinetics studies show it to be first order in the concentrations of NO and base. In these contexts, it is proposed that the amine nitrosation occurs via NO attack at a coordinated amine that has been deprotonated and that this step occurs with concomitant reduction of the Cu(II) to Cu(I). DFT computations at the BP/LACVP* level support these mechanistic arguments. It is further proposed that such nitrosation of electron-rich ligands coordinated to redox-active metal centers is a mechanistic pathway that may find greater generality in the biochemical formation of nitrosothiols and nitrosoamines.     

Origin of the monoclinic-to-monoclinic phase transition and evidence for the centrosymmetric crystal structure of BiMnO3

Structural properties of polycrystalline single-phased BiMnO3 samples prepared at 6 GPa and 1383 K have been studied by selected area electron diffraction (SAED), convergent beam electron diffraction (CBED), and the Rietveld method using neutron diffraction data measured at 300 and 550 K. The SAED and CBED data showed that BiMnO3 crystallizes in the centrosymmetric space group C2/c at 300 K. The crystallographic data are a = 9.5415(2) A, b = 5.61263(8) A, c = 9.8632(2) A, beta = 110.6584(12) degrees at 300 K and a = 9.5866(3) A, b = 5.59903(15) A, c = 9.7427(3) A, beta = 108.601(2) degrees at 550 K, Z = 8, space group C2/c. The analysis of Mn-O bond lengths suggested that the orbital order present in BiMnO3 at 300 K melts above TOO = 474 K. The phase transition at 474 K is of the first order and accompanied by a jump of magnetization and small changes of the effective magnetic moment and Weiss temperature, mueff = 4.69 microB and theta = 138.0 K at 300-450 K and mueff = 4.79 microB and theta = 132.6 K at 480-600 K.     

Force-induced prolyl cis-trans isomerization in elastin-like polypeptides

Elastin-like polypeptides (ELPs) are stimulus-responsive polymers that contain repeats of five amino acids, Val-Pro-Gly-Xaa-Gly (VPGXG), where Xaa is a guest residue that can be any amino acid with the exception of proline. While studying the conformational mechanics of ELPs over a range of solvent conditions by single-molecule force spectroscopy, we noticed that some force-extension curves showed temperature-independent, extensional transitions that could not be fitted with a freely jointed chain or worm-like chain model. Here we show that the observed molecular elongation results from the force-induced peptidyl-prolyl cis-trans isomerization in prolines, which are repeated every fifth residue in the main chain of ELPs. Control experiments with poly(L-proline) demonstrate the similarity of the conformational transition between poly(L-proline) and ELPs. In contrast, the force-extension behavior of poly(L-lysine) showed no deviation in the relevant force range. Force-extension curves in hysteresis experiments showed an elongational difference between extension and relaxation pathways that suggests that the cis conformational state of the prolines could be exhausted on the time scale of the experiment. We present further computational evidence for this mechanism by Monte Carlo simulation of the force-extension behavior using an elastically coupled, two-state model. We believe ours is the first demonstration of force-induced prolyl cis-trans isomerization in proline-containing polypeptides. Our results suggest that single-molecule force spectroscopy could provide an alternate means to assay this important conformational transition in polypeptides.     

Molecular bottle brushes in a solution of semiflexible polyelectrolytes and block copolymers with an oppositely charged block: a molecular dynamics simulation

Using a coarse-grained model, we performed molecular dynamics simulations of the electrostatically driven self-assembly of strongly charged polyelectrolytes and diblock copolymers composed of oppositely charged and neutral blocks. Stoichiometric micelle-like complexes formed in a dilute solution represent cylindrical brushes whose conformation is determined by the linear charge density on the polyelectrolyte and by temperature. The core-shell morphology of the cylindrical brushes is proven. The core of these anisotropic micelles consists of an insoluble complex coacervate formed by the ionic chains and a shell made up of the neutral solvophilic blocks. As the concentration of macromolecules increases, the orientational ordering of ionic micelles takes place. The complexation can induce effective steric stiffening of the polyelectrolyte chains.     

Electronic to vibrational energy transfer assisted by interacting transition dipole moments: a quantum model for the nonadiabatic I2(E) + CF4 collisions

We report a theoretical study of nonadiabatic transitions within the first-tier ion-pair states of molecular iodine induced by collisions with CF(4). We propose a model that treats the partner as a spherical particle with internal vibrational structure. Potential energy surfaces and nonadiabatic matrix elements for the I(2)-CF(4) system are evaluated using the diatomics-in-molecule perturbation theory. A special form of the intermolecular perturbation theory for quasi-degenerate electronic states is implemented to evaluate the corrections to the long-range interaction of transition dipole moments of colliding molecules. The collision dynamics is studied by using an approximate quantum scattering approach that takes into account the coupling of electronic and vibrational degrees of freedom. Comparison with available experimental data on the rate constants and product state distributions demonstrates a good performance of the model. The interaction of the transition dipole moments is shown to induce very efficient excitation of the dipole-allowed upsilon(3) and upsilon(4) modes of the CF(4) partner. These transitions proceed predominantly through the near-resonant E-V energy transfer. The resonant character of the partner's excitation and the large mismatch in vibrational frequencies allow one to deduce the partner's vibrational product state distributions from the distributions measured for the molecule. The perspectives of the proposed theoretical model for treating a broad range of molecular collisions involving the spherical top partners are discussed.     

Experimental and DFT studies: novel structural modifications greatly enhance the solvent sensitivity of live cell imaging dyes

Structural modifications of previously reported merocyanine dyes (Toutchkine, A.; Kraynov, V.; Hahn, K. J. Am. Chem. Soc. 2003, 125, 4132-4145) were found to greatly enhance the solvent dependence of their absorbance and fluorescence emission maxima. Density functional theory (DFT) calculations have been performed to understand the differences in optical properties between the new and previously synthesized dyes. Absorption and emission energies were calculated for several new dyes using DFT vertical self-consistent reaction field (VSCRF) methods. Geometries of ground and excited states were optimized with a conductor-like screening model (COSMO) and self-consistent field (SCF) methods. The new dyes have enhanced zwitterionic character in the ground state and much lower polarity in the excited state, as shown by the DFT-VSCRF calculations. Consistently, the position of the absorption bands are strongly blue-shifted in more polar solvent (methanol compared to benzene), as predicted by the DFT spectral calculations. Inclusion of explicit H-bonding solvent molecules within the quantum model further enhances the predicted shifts and is consistent with the observed spectral broadening. Smaller but significant spectral shifts in polar versus nonpolar solvent are predicted and observed for emission bands. The new dyes show large fluorescence quantum yields in polar hydrogen-bonding solvents; qualitatively, the longest bonds along the conjugated chain at the excited S1 state minimum are shorter in the more polar solvent, inhibiting photoisomerization. The loss of photostability of the dyes is a consequence of the reaction with and electron transfer to singlet oxygen, starting oxidative dye cleavage. The calculated vertical ionization potentials of three dyes I-SO, AI-SO(4), and AI-BA(4) in benzene and methanol are consistent with their relative photobleaching rates; the charge distributions along the conjugated chains for the three dyes are similarly predictive of higher reaction rates for AI-SO(4) and AI-BA(4) than for I-SO. Time-dependent DFT calculations were also performed on AI-BA(4); these were less accurate than the VSCRF method in predicting the absorption energy shift from benzene to methanol.     

Sn(20.5) square(3.5)As(22)I(8): a largely disordered cationic clathrate with a new type of superstructure and abnormally low thermal conductivity

Sn(20.5)As(22)I(8), a new cationic clathrate, has been prepared by using an ampoule technique. According to the X-ray powder diffraction data, it crystallizes in the face-centered cubic space group F23 or Fm(-)3 with a unit-cell parameter of a=22.1837(4) A. Single-crystal X-ray data allowed solution of the crystal structure in the subcell with a unit-cell parameter of a(0)=11.092(1) A and the space group Pm(-)3n (R=5.7 %). Sn(20.5)As(22)I(8) (or Sn(20.5) square(3.5)As(22)I(8), accounting for the vacancies in the framework) possesses the clathrate-I type crystal structure, with iodine atoms occupying the cages of the cationic framework composed of tin and arsenic atoms. The crystal structure is strongly disordered. The main features are a random distribution of vacancies, and shifts of the tin and arsenic atoms away from their ideal positions. The coordination of the tin atoms has been confirmed by using (119)Sn M?ssbauer spectroscopy. Electron diffraction and high-resolution electron microscopy (HREM) analyses have confirmed the presence of the superstructure ordering, which results in a doubling of the unit-cell parameter and a change of the space group from Pm(-)3n to either F23 or Fm(-)3. Analysis of the crystal structure has led to the construction of four ordering models for the superstructure, which have been corroborated by HREM, and has also led to the identification of disordered regions originating from overlap of the different types of ordered domains. Sn(20.5)As(22)I(8) is a diamagnetic semiconductor with an estimated band gap of 0.45 eV; it displays abnormally low thermal conductivity, with the room temperature value being just 0.5 W m(-1) K(-1).     

The Boundary Control Approach to the Titchmarsh-Weyl <Emphasis Type="Italic">m</Emphasis>–Function. I. The Response Operator and the <Emphasis Type="Italic">A</Emphasis>–Amplitude

We link the Boundary Control Theory and the Titchmarsh-Weyl Theory. This provides a natural interpretation of the A?amplitude due to Simon and yields a new efficient method to evaluate the Titchmarsh-Weyl m?function associated with the Schrödinger operator H = ?? _x ²  + q(x) on L ₂(0, ∞) with Dirichlet boundary condition at x = 0.