含芴共轭单元的超支化聚合物的合成及表征

以芴和季戊四醇为初始物,分别合成了具有芴共轭单元和季戊四醇多臂结构的两种聚合单体,进一步采用Suzuki反应合成出一种结构新颖的部分共轭结构的超支化聚合物.利用紫外吸收光谱和荧光发射光谱对聚合物予以表征,结果表明,超支化聚合物具有与模型化合物分子相似的发光行为,既可以发出纯正的蓝光,又表现出支化结构对荧光发射的影响.差...     

ortho‐Fluoroazobenzenes: Visible Light Switches with Very Long‐Lived Z Isomers

Improving the photochemical properties of molecular photoswitches is crucial for the development of light‐responsive systems in materials and life sciences. ortho‐Fluoroazobenzenes are a new class of rationally designed photochromic azo compounds with optimized properties, such as the ability to isomerize with visible light only, high photoconversions, and unprecedented robust bistable character. Introducing σ‐electron‐withdrawing F atoms ortho to the N?N unit leads to both an effective separation of the n→π* bands of the E and Z isomers, thus offering the possibility of using these two transitions for selectively inducing E/Z isomerizations, and greatly enhanced thermal stability of the Z isomers. Additional para‐electron‐withdrawing groups (EWGs) work in concert with ortho‐F atoms, giving rise to enhanced separation of the n→π* transitions. A comprehensive study of the effect of substitution on the key photochemical properties of ortho‐fluoroazobenzenes is reported herein. In particular, the position, number, and nature of the EWGs have been varied, and the visible light photoconversions, quantum yields of isomerization, and thermal stabilities have been measured and rationalized by DFT calculations.     

From workplace air measurement results toward estimates of exposure? Development of a strategy to assess exposure to manufactured nano-objects

In the past few years, an increasing number of studies on workplace air measurements on manufactured nano-materials and -objects have been published. Most of the studies had a more explorative character, so a direct interpretation to workers” exposure for a given exposure situation, activity, or process is not a straight-forward process. In general, the studies use a quite similar package of devices for near real-time monitoring of particle number- and mass concentration in size ranges <100 nm up to 10 μm, and the collection of samples for off-line characterization of air samples. Various approaches for addressing background concentrations and its use to indicate the potential for exposure to nano-objects could be observed. Within the EU-sponsored NANOSH project, a harmonized approach for measurement strategy, data analysis and reporting was developed. In addition to time/activity–concentration profiles as reported by most studies, this approach enables a first step to estimate the potential for exposure to manufactured nano-objects, more quantitatively. The NANOSH data will be collated into a base, which may form the starting point for a harmonized database facilitating overall analysis in near future, to derive estimates for exposure for several exposure situations.     

Combinatorial Chemistry for Ligand Development in Catalysis: Synthesis and Catalysis Screening of Peptidosulfonamide Tweezers on the Solid Phase

On the basis of a pyrrolidine tweezer 1, a library of peptidosulfonamide tweezers (15a-e, 16a-e) was synthesized on the solid phase. This library was screened in a simultaneous substrate screening procedure for the ability to enantioselectively catalyze the Ti(O-i-Pr)(4)-mediated addition of diethylzinc to aldehydes. One of the best solid-phase tweezer catalyst (i.e., 16d, giving an ee of 32% in solid-phase catalysis) was resynthesized in solution (compounds 20 and 21). The now homogeneous solution-phase catalysis showed even better enantioselectivity (i.e., up to 66%).     

The uniqueness of the near hexagon on 729 points

We prove that any regular near hexagon with 729 vertices and lines of size 3 is derived from the ternary Golay code, thus settling the last case in doubt among the regular near hexagons with lines of size 3.     

Heteronuclear decoupling interference during symmetry-based homonuclear recoupling in solid-state NMR

We examine the influence of continuous-wave heteronuclear decoupling on symmetry-based double-quantum homonuclear dipolar recoupling, using experimental measurements, numerical simulations, and average Hamiltonian theory. There are two distinct regimes in which the heteronuclear interference effects are minimized. The first regime utilizes a moderate homonuclear recoupling field and a strong heteronuclear decoupling field; the second regime utilizes a strong homonuclear recoupling field and a weak or absent heteronuclear decoupling field. The second regime is experimentally accessible at moderate or high magic-angle-spinning frequencies and is particularly relevant for many realistic applications of solid-state NMR recoupling experiments to organic or biological materials.     

Universal gap fluctuations in the superconductor proximity effect

Random-matrix theory is used to study the mesoscopic fluctuations of the excitation gap in a metal grain or quantum dot induced by the proximity to a superconductor. We propose that the probability distribution of the gap is a universal function in rescaled units. Our analytical prediction for the gap distribution agrees well with exact diagonalization of a model Hamiltonian.     

Reflection and transmission of waves near the localization threshold

A theory is presented for propagation of waves in bounded media near the mobility edge, based on the self-consistent theory for localization. It predicts a spatially inhomogeneous diffusion constant that leads to scale dependence in enhanced backscattering and transmission.     

Density of states in coupled chains with off-diagonal disorder

We compute the density of states rho(varepsilon) in N coupled chains with random hopping. At zero energy, rho(varepsilon) shows a singularity that strongly depends on the parity of N. For odd N, rho(varepsilon) approximately 1/|varepsilonln (3)varepsilon|, with and without time-reversal symmetry. For even N, rho(varepsilon) approximately |lnvarepsilon| in the presence of time-reversal symmetry, while there is a pseudogap, rho(varepsilon) approximately |varepsilonlnvarepsilon|, in the absence of time-reversal symmetry.     

Carbon-13 and fluorine-19 NMR spectroscopy of the supramolecular solid p-tert-butylcalix(4)arene.alpha,alpha,alpha-trifluorotoluene

The supramolecular 1:1 host-guest inclusion compound, p-tert-butylcalix[4]arene x alpha,alpha,alpha-trifluorotoluene, 1, is characterized by 19F and 13C solid-state NMR spectroscopy. Whereas the 13C NMR spectra are easily interpreted in the context of earlier work on similar host-guest compounds, the 15F NMR spectra of solid 1 are, initially, more difficult to understand. The 19F[1H] NMR spectrum obtained under cross-polarization and magic-angle spinning conditions shows a single isotropic resonance with a significant spinning sideband manifold. The static 19F[1H] CP NMR spectrum consists of a powder pattern dominated by the contributions of the anisotropic chemical shift and the homonuclear dipolar interactions. The 19F MREV-8 experiment, which minimizes the 19F-19F dipolar contribution, helps to identify the chemical shift contribution as an axial lineshape. The full static 19F[1H] CP NMR spectrum is analysed using subspectral analysis and subsequently simulated as a function of the 19F-19F internuclear distance (D(FF) = 2.25 +/- 0.01 A) of the rapidly rotating CF3 group without including contributions from additional libration motions and the anisotropy in the scalar tensor. The shielding span is found to be 56 ppm. The width of the centerband in the 19F[1H] sample-spinning CP NMR spectrum is very sensitive to the angle between the rotor and the magnetic field. Compound 1 is thus an attractive standard for setting the magic angle for NMR probes containing a fluorine channel with a proton-decoupling facility.