‘Total fluorine’ analysis of seed of Australian Gastrolobium spp. showing temporal, spatial and morphological variation

Alkali-fusion in conjunction with a fluoride selective electrode were used to quantify ‘total fluorine’, being organic fluorine + inorganic fluoride, for the seed of 13 species of Gastrolobium from south-west Western Australia. Intact seed covering spatial and temporal distributions, as well as G. bilobum, G. calycinum and G. parviflorum seed dissected into cotyledons and testa + aril, were analysed. Analysis found significant intra-and inter-species variation, both temporally and spatially, with intact seed concentrations ranging from 1.6 ± 0.3 mg kg⁻¹ in G. spinosum from Mundaring to 1063.9 ± 77.8 mg kg⁻¹ for G. cuneatum from Torbay. Approximately 87% of the ‘total fluorine’ was found to be in the seed cotyledons. Additional analysis detected little inorganic fluoride, indicating the majority of fluorine in the seed is organically bound. Parent compound(s) of the fluorine, seed toxicity and the implications of the results for seed chemical defense are discussed.     

Photochemistry of 1,3-dimethyluracil. A novel photochemical ring-opening leading to an enamine

Besides known reduction and solvent addition products, the photolysis of 1,3-dimethyluracil in methanol resulted in formation of the enamine 2-methoxycarbonyl-N-methyl-3-methylaminopropenamide (5) $\text{via}$ a novel ring-opening reaction. A mechanism for the formation of 5 is suggested and its structure was confirmed by an independent synthesis.     

The synthesis of macrocyclic polyether-diester compounds with a pyridine subcyclic unit

Two new series of macrocyclic polyether-diester ligands ( 4-15 ) containing a pyridine subcyclic unit have been prepared by treating various oligoethylene glycols and sulfur-containing oligo-ethylene glycols with 2,6- and 3,5-pyridine dicarbonyl chlorides. The compounds prepared from 2,6-pyridine dicarbonyl chloride were: 3,6,9,12-tetraoxa-18-azabicyclo[12.3.1 ]oetadeca-1(18), 14,16-triene-2,13-dione ( 4 ); 3,6,9,12,15-pentaoxa-21-azabieyclo[15.3.1]heneicosa-1(21),17,19-triene-2,16-dione ( 5 ); 3,6,12,15-tetraoxa-9-thia-21-azabicyclo[15.3.1 ]heneicosa-1(21),17,19-tri-ene-2,16-dione( 6 ); 3,9,15-trioxa-6,12-dithia-21-azabicyclo[15.3.1]heneicosa-1(21),17,19-triene-2,16-dione ( 7 ); 3,6,9,12,15,18-hexaoxa-24-azabicyclo[18.3.1 ]tetracosa-1(24),20,22-triene-2,19-dione ( 8 ); 3,6,9,12,15,18,21-heptaoxa-27-azabicyclo[21.3.1]heptacosa-1(27),23,25-triene-2,22-dione ( 9 ); and the corresponding analogues from 3,5-pyridine dicarbonyl chloride ( 10-15 ). The solid potassium thiocyanate complex of compound 5 was also prepared.     

Cyclodextrins containing an acetone bridge. Synthesis and study as epoxidation catalysts

Three cyclodextrine derivatives (6A,6D-di-O-(prop-2-one-1,3-dienyl)-alpha-cyclodextrin (1), 6-O-(prop-2-one-1-yl)-alpha-cyclodextrin (2) and 6A,6D-di-O-(prop-2-one-1,3-dienyl)-beta-cyclodextrin (3)) were synthesised and investigated as epoxidation catalysts. The three compounds were synthesised from the corresponding perbenzylated cyclodextrins which were mono- or didebenzylated in the 6-position using Sina?'s method. Reaction with NaH and methallyl chloride in the case of 2, or methallyl dichloride in the case of 1 and 3, followed by dihydroxylation, periodate cleavage and protection group removal gave the target compounds. All three compounds catalysed, in the presence of oxone, the epoxidation of a series of alkenes. Epoxidation was compared to the reaction catalysed by simple ketones and inhibition was studied.     

The enumeration of shift register sequences

A study is made of the number of cycles of length k which can be produced by a general n-stage feedback shift register. This problem is equivalent to finding the number of cycles of length k on the so-called de Bruijn-Good graph (Proc. K. Ned. Akad. Wet.49 (1946), 758–764; J. London Math. Soc.21 (3) (1946), 169–172). The number of cycles of length k in such a graph is denoted by β(n, k). From the-de Bruijn-Good graph, it can be shown that β(n, k) is also the number of cyclically distinct binary sequences of length k which have all k successive sets of n adjacent digits (called “n windows”) distinct (the sequence to be considered cyclically). After listing some known results for β(n, k), we show that

$\text{β(k?3, k)=β(k, k)?2φ}{}_{\mathrm{k,\; 2}}\text{+2}\text{for}\text{k?5}$

, where $\text{φ}{}_{\mathrm{k,\; r}}\text{?}$ the number of integers l ? k such that (k, l) ? r, and (k, l) denotes the greatest common divisor of k and l. From the results of several computer programs, it is conjectured that

$\text{β(k?4, k)=β(k, k)?4φ}{}_{\mathrm{k,\; 3}}\text{?2(k, 2)+10 (k?8)}$

,

$\text{β(k?5, k)=β(k, k)?8φ}{}_{\mathrm{k,\; 4}}\text{?(k, 3)+19 (k?11)}$

$\text{β(k?6, k)=β(k, k)?16φ}{}_{\mathrm{k,\; 5}}\text{?4(k, 2)?2(k, 3)+48 (k?15)}$

     

Excitation spectroscopy of retinal and related polyenes

Abstract— Fluorescence excitation spectra of all-trans retinal and the related polyene hydrocarbons anhydrovitamin A and diphenyloctatetraene show that only retinal has a wavelength-dependent fluorescence quantum yield. Three possibilities for the unusual quantum yield behavior of retinal are considered. We conclude that competition between a fast radiationless process (perhaps of photochemical origin) and internal conversion between ¹ππ* states and a low-lying ¹nπ* state provides the best rationalization for the data now in hand.