Role of pseudopolymorphism on concentration dependent competitive adsorption at a liquid/solid interface

We present for the first time a peculiar concentration effect on competitive adsorption of a binary mixture at the liquid/solid interface, which we attribute to the existence of pseudopolymorphism and its concentration dependence. These results are helpful for the understanding of phase behavior of multi-component systems at the interface.     

Lewis-Pairing-Induced Electrochemiluminescence Enhancement from Electron Donor-Acceptor Diads Decorated with Tris(pentafluorophenyl)borane as an Electrochemical Protector

This study reports an effective peripheral decoration of organic donor-acceptor diads with B(C₆F₅)₃ for stabilizing electrogenerated radical ions. By employing a common p-type organic semiconductor benzothienobenzothiophene (BTBT) as the donor, tetracoordinate boron complexes showed improved solution electrochemiluminescence (ECL) intensity, reaching a 156-fold increase compared to that of the parent diad. The unprecedented Lewis-pairing-induced ECL enhancement is attributed to the multiple roles of B(C₆F₅)₃: 1) redistributing frontier orbitals, 2) facilitating electrochemical excitation, and 3) restricting molecular motions. Furthermore, B(C₆F₅)₃ converted the molecular arrangement of BTBT from conventional 2D herringbones into 1D π-stacks. This robust, highly ordered columnar nanostructure allowed red-shifting of the crystalline film ECL with electrochemical doping through the electronic coupling pathways of BTBT. Our approach will facilitate the development of elaborate metal-free ECL systems.     

Molecular clusters in two-dimensional surface-confined nanoporous molecular networks: structure, rigidity, and dynamics

The self-assembly of a series of hexadehydrotribenzo[12]annulene (DBA) derivatives has been investigated by scanning tunneling microscopy (STM) at the liquid/solid interface in the absence and presence of nanographene guests. In the absence of appropriate guest molecules, DBA derivatives with short alkoxy chains form two-dimensional (2D) porous honeycomb type patterns, whereas those with long alkoxy chains form predominantly dense-packed linear type patterns. Added nanographene molecules adsorb in the pores of the existing 2D porous honeycomb type patterns or, more interestingly, they even convert the guest-free dense-packed linear-type patterns into guest-containing 2D porous honeycomb type patterns. For the DBA derivative with the longest alkoxy chains (OC20H41), the pore size, which depends on the length of the alkoxy chains, reaches 5.4 nm. Up to a maximum of six nanographene molecules can be hosted in the same cavity for the DBA derivative with the OC20H41 chains. The host matrix changes its structure in order to accommodate the adsorption of the guest clusters. This flexibility arises from the weak intermolecular interactions between interdigitating alkoxy chains holding the honeycomb structure together. Diverse dynamic processes have been observed at the level of the host matrix and the coadsorbed guest molecules.     

Structures of xantholides A and B,two new guaianolides from xanthium canadense mill.

The structures of xantholides A and B were deduced on the basis of IR and NMR spectra, and confirmed by X-ray analysis. Xantholide A inhibited the larval growth of Drosophila melanogaster.     

New insight into the surface denaturation of proteins: electronic sum frequency generation study of cytochrome c at water interfaces

In situ characterization of surface denaturation of a protein was realized by newly developed interface-selective multiplex electronic sum frequency generation spectroscopy. The observed electronic spectra of cytochrome c at the air/water interface exhibited a broad feature, which demonstrated coexistence of the nativelike and denatured protein at the interface. This situation of the mixed conformation at the air/water interface did not change in the acidic condition of pH=2 where the protein was completely denatured in the bulk water. In sharp contrast, only native spectrum was observed at the silica/water interface.     

Excited-state structure and dynamics of 1,3,5-tris(phenylethynyl)benzene as studied by Raman and time-resolved fluorescence spectroscopy

Excited-state structure and dynamics of 1,3,5-tris(phenylethynyl)benzene (TPB) have been studied in n-hexane and n-heptane solutions. Time-resolved fluorescence spectra, fluorescence anisotropy, and lifetime of TPB were recorded with femtosecond to nanosecond time resolution. Raman depolarization ratio was also measured to elucidate a nonplanar structure of the ground state. Two fluorescence components, the short-lived component with 150 fs lifetime and the long-lived component with 10 ns lifetime, were observed. The analysis of the fluorescence anisotropy values combined with the Raman depolarization data has led to a conclusion that TPB is primarily excited to a short-lived excited singlet state with a nonplanar structure, and then it relaxes to a long-lived excited singlet state with a 3-fold axis. A rapid structural change from a nonplanar to a planar structure is suggested to take place in the process of relaxation.