ABSTRACT
A new synthetic method to access α-nitroso pyrroles is presented. This method utilises the nitrosonium salt NOBF4, enabling short reaction times (<10 minutes) and avoiding the harsh acidic conditions usually associated with pyrrole nitrosation. Application of this procedure to diarylated pyrroles yielded several novel nitroso-pyrroles. Modifications to the method, through exclusion of air and inclusion of a mild base, allowed for the nitrosation of pyrroles bearing aryl groups substituted with electron-donating groups. Attempts to nitrosylate pyrroles bearing alkyl substituents resulted in the formation of a dimeric material composed of a pyrrolic unit and a 2-hydroxyimino-protected 1,5-dihydro-2H-pyrrol-2-one.
ABSTRACT
A series of synthetic analogs of the tripyrrolic natural product prodigiosin were complexed with boron trifluoride to generate the corresponding F-BODIPYs. The maximum wavelengths of absorption and emission of the pyrrolyldipyrrin F-BODIPYs were tuned through variation of the substituents about the pyrrolyldipyrrinato core. The limited variation of substituents on the C-ring did not significantly affect absorption and emission. However, variation of substituents on the B-ring and A-ring resulted in a corresponding red-shift in absorption and emission reaching maximum wavelengths of 600 nm. The presence of electron donating substituents on the B-ring caused a decrease in the Stokes shift, while the presence of electron-withdrawing substituents caused an increase, ranging from 3-25 nm. Stokes shifts were solvent-dependant for some compounds. The inclusion of a dimethylamino group resulted in photo-induced electron transfer and thus quenched fluorescence which was restored upon protonation.
ABSTRACT
An asymmetric meso-H dipyrrin featuring a conjugated terminal alkyne substituent was converted to its corresponding difluoro boron complex, and the extent of π-conjugation was extended using Sonogashira cross-coupling. Treatment of the alkyne-substituted dipyrrin with BF3·OEt2 and NEt3 revealed the reactivity of the conjugated terminal alkyne toward Lewis-activated electrophilic substitution and led to the isolation of F-BODIPYs bearing terminal bromovinyl and enol substituents.
ABSTRACT
OBJECTIVES: To categorize interval cancers, and thus identify false-negatives, following prevalent and incident screens in the Welsh breast screening programme. SETTING: Breast Test Wales (BTW) Llandudno, Cardiff and Swansea breast screening units. METHODS: Five hundred and sixty interval breast cancers identified following negative mammographic screening between 1989 and 1997 were reviewed by eight screening radiologists. The blind review was achieved by mixing the screening films of women who subsequently developed an interval cancer with screen negative films of women who did not develop cancer, in a ratio of 4 to 1. Another radiologist used patients' symptomatic films to record a reference against which the reviewers' reports of the screening films were compared. Interval cancers were categorized as 'true', 'occult', 'false-negative' or 'unclassified' interval cancers or interval cancers with minimal signs, based on the National Health Service breast screening programme (NHSBSP) guidelines. RESULTS: Of the classifiable interval films, 32% were false-negatives, 55% were true intervals and 12% occult. The proportion of false-negatives following incident screens was half that following prevalent screens (P = 0.004). Forty percent of the seed films were recalled by the panel. CONCLUSIONS: Low false-negative interval cancer rates following incident screens (18%) versus prevalent screens (36%) suggest that lower cancer detection rates at incident screens may have resulted from fewer cancers than expected being present, rather than from a failure to detect tumours. The panel method for categorizing interval cancers has significant flaws as the results vary markedly with different protocol and is no more accurate than other, quicker and more timely methods.
