PRIMARY PHOTOCHEMICAL PROCESSES OF CATIONIC ACRIDINE ORANGE IN AQUEOUS SOLUTION STUDIED BY FLASH PHOTOLYSIS

Abstract— A transformation system in Escherichia coli was employed to verify the extent of the lesions caused by ultraviolet (UV) and ionizing radiations. DNA inactivated at 280 nm could be reactivated to some extent by exposing the transforming DNA solutions at 240 nm. This reactivation has been tested using more than one strain of E. coli as recipient. Transforming DNA inactivated by ionizing radiations (⁹⁰Sr beta rays and ⁶⁰Co gamma rays) was not reactivable. Low doses of beta rays, however, reactivated the DNA inactivated by 280 nm UV to a slight but significant extent.     

Enantioselective Synthesis of Both Enantiomers of a Isoproterenol Analogue and of Di-O-pivaloylepinephrine

An asymmetric synthesis of the analogue 4a of isoproterenol and of di-o-pyvaloylepinephrine 3 which provides both enantiomers in optically pure state is reported. The key step of the method is the highly diastereo-selective reduction (using DIBAL or DIBAL/ZnCl₂) of a β-ketosulfoxide 7 which leads, as desired, to the (S)- or the (R)-configuration at C(1) (Schemes 4 and 5).     

The Absolute Configuration of β-Bisabolol

From bergamot oil (Citrus bergamia RISSO), (?)-(4S, 8R)-8-epi-α-bisabolol ( 2 ) and (?)-(4R, 8S)-4-epi-β-bisabolol ( 3 ) were isolated. The absolute configuration of their stereoisomers 4 and 5 was established by an enantioselective synthesis starting from (?)-(S)-p-mentha-1,8-dien-4-ol.     

The Reaction of Bicyclo [3.2.1] octenyl Halides with Metal Hydrides

Reduction of 2-phenyl- and 2-methyl-exo-3,4-dichlorobicyclo[3.2.1]oct-2-enes with lithium aluminium hydride (LAH) or tributyltin hydride (TBTH) gave endo-2-phenyl-3-chlorobicyclo[3.2.1]oct-3-ene, 2-phenyl-3-chlorobicyclo[3.2.1]oct-2-ene and their methyl analogues. The action of both reagents on 2-phenyl-exo-3, 4-dibromobicyclo[3.2.1]oct-2-ene similarly resulted in reductive monodebromination to give normal and allylically rearranged products. Additionally, further reduction occurred to give endo-2-phenylbicyclo[3.2.1]oct-3-ene and 2-phenylbicyclo[3.2.1]-oct-2-ene. In all cases, LAH gave mainly the allylic rearrangement product whereas TBTH gave mostly unrearranged product. The reason for these differences could have been due either to the intervention of allylic radicals in the TBTH reduction or to differences in nucleophilicity. The results also show that LAH is equally efficaceous as TBTH in the reduction of these allylic halides and equally selective in the reduction of the vinyl bromides. The stereochemistry of the allylic rearrangement was shown to be synfacial in that hydride replaced halide on the same face of the molecule.     

Non-singular space-times with a negative cosmological constant: V. Boson stars

We prove existence of large families of solutions of Einstein-complex scalar field equations with a negative cosmological constant, with a stationary or static metric and a time-periodic complex scalar field.     

Engyodontochones,Antibiotic Polyketides from the Marine Fungus Engyodontium album Strain LF069

Six new ( 2 , 4 – 8 ) and two known polyketides with a basic structure of an anthraquinone‐xanthone were isolated from mycelia and culture broth of the fungus Engyodontium album strain LF069. The structures and relative configurations of these compounds were established by spectroscopic means, and their absolute configurations were defined mainly by comparison of quantum chemical TDDFT calculated and experimental ECD spectra. Compounds 2 and 4 – 8 were given the trivial names engyodontochone A ( 2 ) and B–F ( 4 – 8 ). Compounds 5 – 8 represent the first example of a 23,28 seco‐beticolin carbon skeleton. The relative and absolute configurations of two known substances JBIR‐97/98 ( 1 ) and JBIR‐99 ( 3 ) were determined for the first time. All isolated compounds were subjected to bioactivity assays. Compounds 1 – 4 exhibited inhibitory activity against methicillin‐resistant Staphylococcus aureus (MRSA) that was 10‐fold stronger than chloramphenicol.     

Enriched 13C NMR of a metallated α-sulphinyl ester; temperature effect

Lithium and magnesium enolates of an α-sulphinyl ester 83% ¹³C enriched at C-1 and C-2 are studied by ¹³C NMR at different temperatures. It is shown that two metaliated species are present in the case of lithium which exchange at ?60°C, ΔG≠ ?60° = 37.8 KJ mol^?1 (9.05 Kcal mol^?1) and that there is no rapid exchange between the non-metallated ester and the metallated species (on the NMR time scale). In the case of magnesium, two or three metallated species are formed, according to the temperature which do not exchange up to 0 °C.     

1H and 13C NMR studies of two monosubstituted [2.2]paracyclophanes

250 MHz ¹H NMR of two monosubstituted [2.2]paracyclophanes shows that whether the substituent is an electron releasing group, OMe, or a withdrawing group, CO₂Me, the transannular effect is deshielding. 62.86 MHz ¹³C NMR shows that among the six transannular effects, only one has a sign which changes with the nature of the substituent (–4.6 ppm for OMe but +3.3 ppm for CO₂Me).     

Reduction of β-ketosulfoxides : a highly efficient asymmetric synthesis of both enantiomers of methyl carbinols from the corresponding esters

It is shown that reductions of β-ketosulfoxides of identical chirality (R) at sulfur, lead to reduction products of opposite stereochemistry according to the reducing agent used. The high enantiomeric excesses obtained (80 to 100%) provide a general route to both enantiomers of methylcarbinols from the corresponding esters.