Template-Reaktion von Bis(acetylacetonato)-dioxo-molybdän(VI) mit Benzoylhydrazin

Template Reaction of Bis(acetylacetonato)-dioxo-molybdenum(VI) with Benzoylhydrazone By reaction of bis(acetylacetonato)-dioxo-molybdenum(VI) with benzoylhydrazine benzoylhydrazido(2?)-acetylacetonebenzoylhydrazonato(2?)-oxo-molybdenum(VI) was formed beside another species. The compound was characterized by mass spectrometry and X-ray structural analysis. Crystallographic data see ?Inhaltsübersicht”?.     

Ultraviolet emission spectra of sunbeds

It is well known that UV radiation contributes to the development of skin cancer. Exposure to solar radiation is predominantly responsible for the high incidence rate of skin cancer, but there are also indications that sunbeds are involved. The aim of the present investigation was to determine the UV emission spectra of sunbeds. It included the most common sunbed models, which cover more than 50% of the Swiss market. The UV emission spectra of sunbeds have special characteristics and are different from the sun spectrum, which can be seen in high-resolution spectral measurements. Sunbed emission spectra are similar to the sun spectrum in the UVB (280-320 nm) range but reach values 10 to 15 times higher in the UVA (320-400 nm) range. An average erythema-effective irradiance of 0.33 W/m2 was determined for sunbeds. This corresponds to a UV index of 13, which is significantly higher than the UV index of 8.5 of the high summer sun at noon at intermediate latitudes. The measurements were spread over the whole effective area of the sunbeds, and an inhomogeneous distribution of the irradiances with variations of up to 30% from the average value was found.     

Preparation and crystal structure of tetraphenylphosphonium triiodotetrabromide [PPh4][I3Br4

Tetraphenylphosphonium triiodotetrabromide [PPh4][I3Br4] is obtained by the reaction of tetraphenylphosphonium bromide with iodine monobromide. It is the first example of an iodine rich, seven-membered polybromide. [PPh4][I3Br4] crystallizes triclinic in the space group P1 with a = 10.947(1) A, b = 11.945(1) A, c = 12.896(1) A, alpha = 66.80(1) degrees, beta = 77.21(1) degrees, gamma = 85.73(1) degrees, and two formula units per unit cell. The final R indices [I > 4 sigma(I)] are R1 = 0.0362 and wR2 = 0.0944.     

Reactions of aromatic ketones with 3-mercapto-1,2-propanediol. Synthesis of cis- and trans-2-alkyl-2-aryl-(1,3-oxathiolane-5-methanols and 1,3-dioxolane-4-methanethiols)

Aromatic ketones react with 3-mercapto-1,2-propanediol ( 1 ) in refluxing benzene under the catalytic influence of a sulfonic acid and with azeotropic removal of water to yield a mixture comprised predominantly of cis- and trans-2-alkyl-2-aryl-1,3-oxathiolane-5-methanols 7, accompanied by lesser amounts of cis- and trans-2-alkyl-2-aryl-1,3-dioxolane-4-methanethiols 8 (up to 30%). It was discovered that 8 is the kinetic product and is isomerized by 4-toluenesulfonic acid in hot benzene to the thermodynamically more stable 7 . Under these conditions, ortho- and α-substituted aromatic ketones tend to produce more of 8 , which can be attributed to steric hindrance encountered by the thiol as it attacks the ketone. Ketalizations of 1-aryl-2-(1H-imidazol-1-yl)-1- as well as 1-aryl-2-(1,H-1,2,4-triazol-1-yl)-1-ethanones by 1 fail under these conditions, even after 24 hours of reflux in toluene. However, 1-(4-chlorophenyl)-3-(1H-imidazol-1-yl)-1-propanone and 1-(4-bromophenyl)-4-(1H-imidazol-1-yl)-1-butanone are ketalized by 1 as expected. Interestingly, the reaction of 2-bromo-4′-chloroace-tophenone with 1 produces 1-(4-chlorophenyl)-2,8-dioxa-6-thiabicyclo[3.2.1]octane. Characterization of all isomers and separation of some diastereomers is described. Nuclear Overhauser enhancement experiments are utilized to establish the stereochemistry of 1,3-oxathiolanes.     

Electrochemical impedance spectroscopic analysis of dye-sensitized solar cells

Electrochemical impedance spectroscopy (EIS) has been performed to investigate electronic and ionic processes in dye-sensitized solar cells (DSC). A theoretical model has been elaborated, to interpret the frequency response of the device. The high-frequency feature is attributed to the charge transfer at the counter electrode while the response in the intermediate-frequency region is associated with the electron transport in the mesoscopic TiO2 film and the back reaction at the TiO2/electrolyte interface. The low-frequency region reflects the diffusion in the electrolyte. Using an appropriate equivalent circuit, the electron transport rate and electron lifetime in the mesoscopic film have been derived, which agree with the values derived from transient photocurrent and photovoltage measurements. The EIS measurements show that DSC performance variations under prolonged thermal aging result mainly from the decrease in the lifetime of the conduction band electron in the TiO2 film.     

Octylgermane on gold: synthesis, oxidation, and pattern formation

Chemisorbed monolayers of octylgermane (C8H17GeH3) on gold have been formed by vapor deposition in ultrahigh vacuum. The monolayer has been characterized by X-ray photoelectron and reflection absorption infrared spectroscopies (XPS and RAIRS) and scanning tunneling microscopy (STM). XPS data indicate the monolayer can be oxidized by exposure to ozone. STM images exhibit a complex pattern which can be modeled as strain-mediated spinodal decomposition.     

Synthesis and structures of cis- and trans-bis(alkyneselenolato)platinum(II) complexes

The reaction of 2 equiv of LiSeCC-n-C(5)H(11) (1) with cis-PtCl(2)(Ph(3)P)(2) (2) gives a mixture of the cis and trans isomers of Pt(Ph(3)P)(2)(SeCC-n-C(5)H(11))(2) (3), which slowly isomerizes in CH(2)Cl(2) to the preferred trans form trans-3. The closely related cis-[Pt(dppf)(2)(SeCC-n-C(5)H(11))(2)] (4) (dppf = bis(diphenylphosphino)ferrocene) was prepared by a similar metathetical reaction using the platinum chloride complex of the chelating dppf to impose the cis geometry. The structures of the cis and trans complexes have been investigated in solution by heteronuclear NMR ((31)P, (77)Se, and (195)Pt) and, in the cases of trans-3 and 4, characterized in the solid state by single-crystal X-ray diffraction. Changing the coordination geometry from cis to trans induces significant changes in the structural and spectroscopic parameters, which do not comply with the previously anticipated donor-acceptor properties of selenolate ligands.     

Nucleic acid analysis using an expanded genetic alphabet to quench fluorescence

Organic chemistry has made possible the synthesis of molecules that expand on Nature's genetic alphabet. Using the previously described nonstandard DNA base pair constructed from isoguanine and 5-methylisocytosine, we report a highly specific and sensitive method that allows for the fast and specific quantitation of genetic sequences in a closed tube format. During PCR amplification, enzymatic site-specific incorporation of a quencher covalently linked to isoguanine allows for the simultaneous detection and identification of multiple targets. The specificity of method is then established by analysis of thermal denaturation or melting of the amplicons. The appropriate functions of all reactions are further verified by incorporation of an independent target into the reaction mixture. We report that the method is sensitive down to the single copy level, and specificity is demonstrated by multiplexed end-point genotypic analysis of four targets simultaneously using four separate fluorescent reporters. The method is general enough for quantitative and qualitative analysis of both RNA and DNA using previously developed primer sets. Though the method described employs the commonly used PCR, the enzymatic incorporation of reporter groups into DNA site-specifically should find broad utility throughout molecular biology.     

Small-angle static light scattering of concentrated silica suspensions during in situ destabilization

The aggregation of concentrated aqueous silica suspensions is characterized by means of static light scattering. We use an in situ destabilization mechanism based on the enzyme-catalyzed hydrolysis of urea. This method enables us to continuously and homogeneously change the interparticle potential from repulsive to attractive without disturbing the aggregation process. Moreover, our electrostatically stabilized suspensions can be destabilized by two different methods. In the first method, the pH is shifted toward the isoelectric point of the particles ( Delta pH method), thereby leading to a decrease of their surface charge. In the second method, the ionic strength is continuously increased at constant pH ( Delta I method), leading to a compression of the electrical double layer around the charged particles. A laboratory-built flat-cell light-scattering instrument is used, which allows fast data acquisition and an adjustment of the sample cell thickness. To circumvent multiple scattering effects, we use a very small sample thickness ( approximately 13 microm). In addition, the refractive index difference between the aqueous phase and the particles is reduced by adding sucrose to the liquid phase of our suspensions. We are able to characterize the structural changes at the very early stages of the destabilization process, where no significant effects are yet detected in macroscopic rheological measurements. While during the Delta pH destabilization, the scattering curve shows significant changes only after some characteristic delay time, it changes continuously during the Delta I destabilization. The latter is attributed to the formation of a weak pre-gel structure in the suspensions, as a shallow secondary minimum appears in the interparticle potential. Data are evaluated by using a HMSA square-well structure factor model. Results are in good agreement with those predicted from DLVO theory.     

Synthesis and reactivity of silyl vinylketenes: a formal interrupted Dötz benzannulation with unexpected silyl migration

[reaction: see text]. An efficient method for the generation of silyl vinylketenes from the thermal reaction of Fischer carbene complexes with silyl-substituted phenylacetylenes is described. Although the silyl vinylketene products are highly stable, conditions have been identified to induce a benzannulation/silyl migration process, providing aromatic silyl ethers.