Synthesis of a dialuminum-substituted silicotungstate and the diastereoselective cyclization of citronellal derivatives

A novel dialuminum-substituted silicotungstate TBA(3)H[gamma-SiW(10)O(36){Al(OH(2))}(2)(mu-OH)(2)] x 4 H(2)O (1, TBA = tetra-n-butylammonium) was synthesized by the reaction of the potassium salt of [gamma-SiW(10)O(36)](8-) (SiW10) with 2 equiv of Al(NO(3))(3) in an acidic aqueous medium. It was confirmed by the X-ray crystallographic analysis that compound 1 was a monomer of the gamma-Keggin dialuminum-substituted silicotungstate with the {Al(2)(mu-OH)(2)} diamond core. The cluster framework of 1 maintained the gamma-Keggin structure in the solution states. The reaction of 1 with pyridine yielded TBA(3)[(C(5)H(5)N)H][gamma-SiW(10)O(36){Al(C(5)H(5)N)}(2)(mu-OH)(2)] x 2 H(2)O (2), and the molecular structure was successfully determined by the X-ray crystallographic analysis. In compound 2, two of three pyridine molecules coordinated to the axial positions of aluminum centers and one of them existed as a pyridinium cation, showing that compound 1 has two Lewis acid sites and one Br?nsted acid site. Compound 1 showed high catalytic activity for the intramolecular cyclization of citronellal derivatives such as (+)-citronellal (3) and 3-methylcitronellal (4) without formation of byproduct resulting from etherification and dehydration. For the 1-catalyzed cyclization of 3, the diastereoselectivity toward (-)-isopulegol (3a) reached ca. 90% and the value was the highest level among those with reported systems so far. The reaction rate for the 1-catalyzed cyclization of 3 decreased by the addition of pyridine, and the cyclization hardly proceeded in the presence of 2 equiv of pyridine with respect to 1. On the other hand, the reaction rate and diastereoselectivity to 3a in the presence of 2,6-lutidine were almost the same as those in the absence. Therefore, the present cyclization is mainly promoted by the Lewis acid sites (aluminum centers) in 1. DFT calculations showed that the formation of the transition state to produce 3a is sterically and electronically more favorable than the other three transition states for the present 1-catalyzed cyclization of 3.     

Disilane- and siloxane-bridged biphenyl and bithiophene derivatives as electron-transporting materials in OLEDs

Optical, electrochemical, and electron-transporting properties of disilane- and siloxane-bridged biphenyl and bithiophene derivatives were investigated, in comparison with those of the monosilane-bridged analogues (siloles). The UV spectra and cyclic voltammograms indicated that elongation of the silicon bridge suppresses the π-conjugation, in accordance with the results of DFT calculations. The DFT calculations indicated also that the disilane-bridged biphenyl and siloxane-bridged bithiophene should have the low-lying HOMOs and LUMOs. The electron-transporting properties were evaluated by the performance of triple-layered OLEDs having vapor-deposited films of the Si-bridged compound, Alq₃, and TPD, as the electron-transport, emitter, and hole-transport, respectively. Of these, the device with a disilane-bridged biphenyl exhibited the high performance with the maximum current density of 590 mA/cm² at the applied electric field of 12 × 10⁷ V/m (applied bias voltage = 13 V) and the maximum luminance of 22 000 cd/m² at 13 × 10⁷ V/m.     

Dissociation of DNA from histone by reaction of anti-cancer drug cis-diamminedichloroplatinum(II) with DNA-histone complexes used as cellular model

Although both cis-diamminedichloroplatinum(II) (cisplatin or cis-DDP) and trans-diamminedichloroplatinum(II) bind to DNA, only cis-DDP is widely used as a chemotherapeutic agent; the stereoisomer trans-DDP is inactive. DNA, generally, is wound around the histone core in the nucleus of living cells and forms the nucleosome structure. To understand the essentially different anticancer activities of cis-DDP and trans-DDP, it is necessary to investigate the interaction of cis-DDP (or trans-DDP) with DNA around the histone in the nucleosome. Here, we used psiX174DNA-histone(LNCaP) complexes prepared by the reaction of psiX174DNA with histone(LNCaP) extracted from LNCaP cells. We first show that the ability of cis-DDP to dissociate the DNA from psiX174DNA-histone(LNCaP), as a nucleosome model, is much stronger than that of trans-DDP. As a result of the action of cis-DDP, the DNA in the nucleosome is rendered naked, and the naked DNA is vulnerable to cis-DDP (or other drugs). This study describes a new model showing that the difference in the activities of cis-DDP and trans-DDP is related to the difference in their abilities to dissociate the DNA from the nucleosome.     

Synthesis of rigidly-linked vancomycin dimers and their in vivo efficacy against resistant bacteria

A novel and efficient avenue for the preparation of dimeric vancomycins is described, and the dimers exhibited excellent antibacterial activities in the murine infection model.     

The size and mass distribution of firebrands collected from ignited building components exposed to wind

Wildfires that spread into communities, commonly referred to as Wildland-Urban Interface fires (WUI), are a significant international problem. Post-fire damage studies have suggested for some time that firebrands are a significant cause of structure ignition in WUI fires, yet little research has been conducted to investigate firebrand production from burning vegetation and structures. To this end, firebrand production from real-scale building components under well-controlled laboratory conditions was investigated. Specifically, wall and re-entrant corner assemblies were ignited and during the combustion process, firebrands were collected to determine the size/mass distribution generated from such real-scale building components under varying wind speed. Finally, the size and mass distributions of firebrands collected in this study were compared with the data from an actual full-scale structure burn to determine if simple component tests such as these can provide insights into firebrand generation data from full-scale structures. The results are presented and discussed.     

Light source spectrum strongly influences the in vitro estimation of sun protection factor

Irradiation from an artificial solar simulator that matches the relative cumulative erythema effectiveness (RCEE) of sunlight is used for in vivo sun protection factor (SPF) testing, whereas irradiation that matches the spectrum of natural sunlight (NS) is generally used for in vitro SPF testing. This study was designed to clarify whether this difference is important. Eight sunscreens spread on artificial substrates and several optical filters as sunscreen mimics were used. Their in vitro SPF values were evaluated using RCEE-compliant and NS spectrum-matching light sources in calculation. The calculated in vitro SPF values obtained using NS light (SPF [NS]) were lower than those obtained using RCEE light (SPF [RCEE]). The in vitro SPF (RCEE) values showed a better correlation and better agreement with in vivo SPF values, as compared with the in vitro SPF (NS) values. A marked difference between in vitro SPF values obtained with the two light sources in calculation was found for sunscreens showing low transmittance in the ultraviolet B region. To obtain in vitro SPF values that correspond well to in vivo SPF values measured with currently accepted methodology, it is important to use an RCEE-compliant light source.