Structures of small mixed krypton-xenon clusters

Structures of small mixed krypton-xenon clusters of different compositions with an average size of 30-37 atoms are investigated. The Kr 3d(5/2) and Xe 4d(5/2) surface core level shifts and photoelectron intensities originating from corner, edge, and face/bulk sites are analyzed by using soft x-ray photoelectron spectroscopy. Structural models are derived from these experiments, which are confirmed by theoretical simulation taking induced dipole interactions into account. It is found that one or two small Xe cores are partly embedded in the surface of the Kr clusters. These may grow and merge leading to a phase separation between the two rare gas moieties in mixed clusters with increasing the Xe content.     

The magnetic field effect in the presence of the electric field on fluorescence of a methylene-linked compound of pyrene and n,n-dimethylaniline doped in a polymer film

Recent experimental data by Mizoguchi and Ohta are analyzed under the assumption of fast equilibrium between the locally excited (LE), radical-ion-pair (RIP), and exciplex states. In the absence of the equilibrium, no magnetic field effect on the LE fluorescence would be observed. Owing to the equilibrium, the relative electric-field-induced changes of the quantum yields of the LE and exciplex emissions as functions of the magnetic field are linearly connected to each other. The electric field shifts the equilibrium from the LE state toward the RIP state. Predictions are made for the magnetic field effect on the fluorescence kinetics.     

A stable neutral stannaaromatic compound: synthesis, structure and complexation of a kinetically stabilized 2-stannanaphthalene

A kinetically stabilized 2-stannanaphthalene, the first example of a stable, neutral aromatic compound containing a tin atom, has been synthesized and fully characterized. The results of spectroscopic and crystallographic structural analyses of the compound and theoretical calculations using model compounds strongly suggest that it has a delocalized 10pi-electron ring system as does naphthalene. In addition, it was found to behave as an eta6-arene ligand in the ligand exchange reaction with [Cr(CH3CN)3(CO)3] giving the first stable eta6-2-stannanaphthalene chromium complex.     

Asteropine A, a sialidase-inhibiting conotoxin-like peptide from the marine sponge Asteropus simplex

Marine sponges contain structurally intriguing and biologically active peptides of nonribosomal peptide synthase origin, often containing amino acids with novel structures. Here we report the discovery of asteropine A (APA), a cystine knot to be isolated from marine sponges. The solution structure of APA as determined by NMR belongs to the four-loop class of cystine knots similar to those of some conotoxins and spider toxins. However, the highly negatively charged surface of APA is uncommon among other cystine knots. APA competitively inhibits bacterial sialidases, but not a viral sialidase. APA was inactive against all other enzymes tested and did not have any apparent antitumor activity. Our data suggest that APA and other knotting peptides may be important leads for antibacterial and even antiviral drug development.     

Unusual carbon-sulfur bond cleavage in the reaction of a new type of bulky hexathioether with a zerovalent palladium complex

The reaction of a bulky hexathioether, TbtS(o-Phen)S(o-Phen)SS(o-Phen)S(o-Phen)STbt (o-Phen = o-phenylene, Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl) (1), with 3 molar amounts of Pd(PPh3)4 afforded trinuclear palladium complex bridged by two benzenedithiolato ligands via a three-step palladium insertion reaction into one sulfur-sulfur and two carbon-sulfur bonds of 1.     

Optically pure fullerodendron formed by diastereoselective Diels-Alder reaction

The Diels-Alder reaction between C₆₀ and anthryl glycodendron, which has d- or l-gluconamides at the terminals, gave a new fullerene glycodendron conjugate. Interestingly, the diastereoselective cycloaddition reaction proceeded upon the treatment of C₆₀ with the anthryl dendron 3. Furthermore, optical pure fullerodendrons (−)-4L and (+)-4D, which were confirmed by ¹H and ¹³C NMR spectroscopy, FT-IR, MALDI-TOF mass spectroscopic analysis, were isolated from the mixture of diastereomers. And their absolute configurations were predicted by the use of CD spectra.     

Visible-to-UV Photon Upconversion in Nanostructured Chromophoric Ionic Liquids

Visible-to-ultraviolet (vis-to-UV) triplet-triplet annihilation based photon upconversion (TTA-UC) is achieved in a non-volatile chromophoric ionic liquid (IL) for the first time. A novel IL is synthesized by combining UV-emitting anion 4-(2-phenyloxazol-5-yl)benzenesulfonate (PPOS) and trihexyltetradecylphosphonium cation (P₆₆₆₁₄). The nanostructured organization of chromophoric anions is demonstrated by synchrotron X-ray and optical measurements. When the IL is doped with a triplet sensitizer tris(2-phenylpyridinato)iridium(III) (Ir(ppy)₃), the visible-to-UV TTA-UC with a relatively low threshold excitation intensity of 61 mW cm⁻² is achieved. This is due to a large triplet diffusion coefficient in the IL (1.4×10⁻⁷ cm² s⁻¹) as well as a high absorption coefficient 15 cm⁻¹ and a long PPOS triplet lifetime of 1.55 ms, all implemented in the condensed IL system. This work demonstrates the unique potential of ILs to control chromophore arrangements for desired functions.