A novel synthetic method for 2-arylmethyl substituted imidazolines and imidazoles from 2-aryl-1,1-dibromoethenes

Various 2-arylmethylimidazolines were prepared by treating readily available 2-aryl-1,1-dibromoethenes with ethylenediamine under mild conditions and further converted into the corresponding imidazoles smoothly with Swern oxidation.     

Characterization of the short-chain branches in poly(vinyl chloride)s by γ irradiation of the reduced polymers

The volatile products from the γ irradiation of samples of poly(vinyl chloride) prepared under different conditions and reduced to the corresponding polyethylenes have been measured quantitatively and compared with those for low- and high-density polyethylenes and copolymers of ethylene with small amounts of α-olefins. The presence of methyl branches is clearly demonstrated and there is also evidence for ethyl and butyl branches, although these had not been considered significant in previous [¹³C] NMR studies. The method is shown to be extremely sensitive to small quantities of residual trialkyl tin hydride reductant occluded in, and possibly also reacted with, the polymer, and to residual chlorine (<0.5%). The yields of alkanes are higher than expected from the branch frequencies determined by i.r. and [¹³C] NMR and results for ethylene-α-olefin copolymers. This difference is apparently due to sensitisation of the radiation degradation by residual chlorine and reductant. Quantitative determinations of branch frequencies by the radiolytic method are unlikely to be obtained until these problems are overcome.     

Relaxation of the optical Kerr effect of anisotropic molecules in mixed liquids

The relaxation time of the Kerr effect of nitrobenzene and m-nitrotoluene in various mixtures with carbon tetrachloride and various alcohols was determined by measuring the kinetics of the Kerr effect using picosecond laser techniques. These measurements yield information on the rotational motion of molecules in liquids. The relaxation time data are interpreted in terms of an effective local viscosity effect, pair correlation, and coupling of rotational motion with shear modes.     

The Photochemistry of Diazomethane the Reactions of Methylene with Toluene and P-Xylene in Liquid Phase (I)

The photochemistry of diazomethane in toluene and p-xylene solutions was investigated. The reactions of methylene with toluene gave eight products. In the diazomethane p-xylene solution, p-ethyltoluene, 1,2,4-trimethylbenzene, 1,4-dimethylcyclohepatriene-1,3,5 and three unidentified compounds were found as products of the reaction of methylene with p-xylene. The relative rates of addition and insertion reaction of methylene with toluene and p-xylene have been calculated.     

Ab initio molecular dynamics simulation of liquid Al88Si12 alloys

First-principles molecular dynamics simulations are carried out to study the structures, dynamics, and electronic properties of liquid Al88Si12 in the temperature ranging from 898 to 1298 K. The temperature dependence of static structure factors, pair correlation functions, and electronic density-of-states are investigated. The structural properties obtained from the simulations are in good agreement with the x-ray diffraction experimental results.     

Electrical conductivity measurements of aqueous sodium chloride solutions to 600°C and 300 MPa

Electrical conductance measurements of dilute (<0.1>^–1) aqueous NaCl solutions were made primarily to quantify the degree of ion association which increases with increasing temperature and decreasing solvent density. These measurements were carried out at temperatures from 100 to 600°C and pressures up to 300 MPa with a modified version of the apparatus used previously in the high temperature study in this laboratory. Particular emphasis was placed on conditions close to the critical temperaturelpressure region of water, i.e., at 5° intervals from 370 to 400°C. The results verify previous findings that the limiting equivalent conductance A_o of NaCl increases linearly with decreasing density from 0.75 to 0.3 g-cm^–1 and also with increasing temperature from 100 to 350°C. Above 350°C. A_o is virtually temperature independent. The logarithm of the molal association constant as calculated exclusively from the data400°C is represented as a function of temperature (Kelvin) and the logarithm of the density of water (g-cm^–3) as follows:

The participation of the anion and alkyl substituent of diaryliodonium salts in photo‐initiated cationic polymerization reactions

The photo‐initiated cationic polymerization (PCP) of epoxides using diaryliodonium salt photoacid generators (PAGs) bearing alkyl groups and anions was investigated. The properties and reactivities of a series of iodonium salts containing various cations and anions were compared in the context of a PCP reaction. The products from the decomposition of the cations of these salts were analyzed using gas chromatography‐mass spectrometry (GC‐MS) spectra. The relationship between the molecular structure of the salts and their reaction mechanism in the PCP reaction was investigated. Based on the results of the investigation, it was concluded that the structures of the cations and anions of theiodonium salts affect the PCP reaction rate, which was controlled by the products from the diaryliodonium salts. As part of an additional investigation, the diaryliodonium salts‐epoxide materials were applied to 254 nm‐photo‐patterning. Copyright © 2006 John Wiley & Sons, Ltd.     

A mesoporous Pt/TiO2 nanoarchitecture with catalytic and photocatalytic functions

A novel metal/semiconductor nanocomposite with catalytic and photocatalytic functions has been prepared. The new material consists of highly dispersed platinum (Pt) nanoparticles embedded in a cubic mesoporous nanocrystalline anatase (meso-nc-TiO2) thin film. The porous thin film possesses a narrow pore-size distribution and a large surface area. The diameter of the Pt cluster can be controlled to below 5 nm, and the high dispersion of these clusters gives rise to catalytic activity for the oxidation of carbon monoxide, an important reaction for automobile exhaust treatment. This novel ordered mesoporous Pt/TiO2 nanoarchitecture is also a promising photochemical material, as demonstrated by the photo-driven killing of Micrococcus lylae cells on the film.     

Reaction of azole condensed quinoxaline N-oxides with acetic anhydride

The reaction of 7-chlorotetrazolo[1,5-α]quinoxaline 5-oxide 6a with acetic anhydride gave 7-chloro-5-(7-chlorotetrazolo[1,5-α]quinoxalin-4-yl)-4,5-dihydro-4-oxotetrazolo[1,5-α]quinoxaline 7a , while the reaction of 7-chloro-1,2,4-triazolo[4,3-α]quinoxaline 5-oxide 6b with acetic anhydride afforded 7-chloro-5-(7-chloro-1,2,4-triazolo[4,3-α]quinoxalin-4-yl)-4,5-dihydro-4-oxo-1,2,4-triazolo[4,3-α]quinoxaline 7b and 7-chloro-4,5-dihydro-4-oxo-1,2,4-triazolo[4,3-α]quinoxaline 8b . The reaction of compound 6a or 6b with acetic anhydride/acetic acid provided 7-chloro-4,5-dihydro-4-oxo-tetrazolo[1,5-α]quinoxaline 8a or compound 8b , respectively.     

Cancer cells undergoing epigenetic transition show short-term resistance and are transformed into cells with medium-term resistance by drug treatment

To elucidate the epigenetic mechanisms of drug resistance, epigenetically reprogrammed H460 cancer cells (R-H460) were established by the transient introduction of reprogramming factors. Then, the R-H460 cells were induced to differentiate by the withdrawal of stem cell media for various durations, which resulted in differentiated R-H460 cells (dR-H460). Notably, dR-H460 cells differentiated for 13 days (13dR-H460 cells) formed a significantly greater number of colonies showing drug resistance to both cisplatin and paclitaxel, whereas the dR-H460 cells differentiated for 40 days (40dR-H460 cells) lost drug resistance; this suggests that 13dR-cancer cells present short-term resistance (less than a month). Similarly, increased drug resistance to both cisplatin and paclitaxel was observed in another R-cancer cell model prepared from N87 cells. The resistant phenotype of the cisplatin-resistant (CR) colonies obtained through cisplatin treatment was maintained for 2–3 months after drug treatment, suggesting that drug treatment transforms cells with short-term resistance into cells with medium-term resistance. In single-cell analyses, heterogeneity was not found to increase in 13dR-H460 cells, suggesting that cancer cells with short-term resistance, rather than heterogeneous cells, may confer epigenetically driven drug resistance in our reprogrammed cancer model. The epigenetically driven short-term and medium-term drug resistance mechanisms could provide new cancer-fighting strategies involving the control of cancer cells during epigenetic transition.Subject terms: Tumour heterogeneity, Epigenetics