The structure of the cations from 2– and 4-pyrimidones

An infrared spectral investigation of a number of pyrimidine and pyrimidone hexachloroantimonates is reported. Typical aromatic absorption bands found in pyrimidinium salts were absent in the pyrimidone cations. 2-And 4-Pyrimidone hexachloroantimonates, as well as their N-methyl- and N,N'-dimethyl derivatives, exhibit intense carbonyl absorption bands between 1720–1729 cm^?1 (solid state) which corroborates N-protonation of pyrimidones.     

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”?.     

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.     

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.     

ON THE ACRIDINE AND THIAZINE DYE SENSITIZED PHOTODYNAMIC INACTIVATION OF LYSOZYME—SINGLET OXYGEN SELF-QUENCHING BY THE SENSITIZERS

Abstract— The quantum yield of the photodynamic inactivation of lysozyme increases in the sequence acridine orange, methylene blue, proflavine and acriflavine (1:5:6:12). At least up to protein concentrations of 0.1 m M , singlet oxygen is exclusively responsible for the inactivation of the enzyme. For methylene blue, acriflavine and proflavine the quantum yields decrease considerably with increasing dye concentrations. From measurements in H₂O and D₂O buffer solutions it was concluded that in the case of methylene blue the effect is mainly caused by the quenching of singlet oxygen [rate constant (3–4) × 10⁸ M ⁻¹ s⁻¹]. For the acridine sensitizers both singlet oxygen and dye triplet quenching processes have to be taken into consideration. It has been found that all sensitizers act as competitive inhibitors of the enzymatic reaction of lysozyme. However, the dye-protein interaction near the active center cannot be responsible for the observed dye self-quenching effect.     

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.