Characterisation of flavonols in broccoli (Brassica oleracea L. var. italica) by liquid chromatography-uV diode-array detection-electrospray ionisation mass spectrometry

The flavonoid composition of broccoli inflorescences has been studied by LC/UV-DAD/ESI-MSn. A large number of hydroxycinnamic acid esters of kaempferol and quercetin glucosides has been characterised. The structures of the flavonoid glycosides were analysed after alkaline hydrolysis, and were identified as 3-sophoroside/sophorotrioside-7-glucoside/sophoroside of kaempferol, quercetin and isorhamnetin (this last found in trace amount). These complex quercetin and isorhamnetin glucosides have not been previously characterised in nature. In addition, several less complex glucosides based on the same aglycones have been identified. The effect of sugar substitution and acylation on chromatographic mobility and ESI ionisation and fragmentation are discussed.     

Sensitive determination of diquat by a kinetic method using the stopped-flow mixing technique

A simple, sensitive, selective, fast and inexpensive assay for the determination of diquat is proposed. The method is based on the reduction of the herbicide to a strongly fluorescent monocation radical with sodium dithionite. The initial rate of this reaction is directly proportional to the diquat concentration. The stopped-flow mixing technique was used because the kinetic data can be obtained in only 7 s, meaning that the method can be automated. The calibration graph is linear over the range 5-500 ng ml-1 and the precision (RSD) is close to 1.2%. The applicability of the method was demonstrated by determining the herbicide in different kinds of samples.     

EXCITATION ENERGY TRANSFER IN THE CRYPTOPHYTES. FLUORESCENCE EXCITATION SPECTRA AND PICOSECOND TIME-RESOLVED EMISSION SPECTRA OF INTACT ALGAE AT 77 K

Excitation spectra of chlorophyll- a (Chl- a ) fluorescence in intact cells of Cryptomonas ovata, Chroomonas pauciplastida and Chroomonas salina were determined at 77 K. For all species the excitation spectra for emission from Chl- a associated with photosystem II (PSII) showed increased contributions by a carotenoid (493 nm) and phycobiliproteins, and decreased contributions by carotenoid (417 nm, 505 nm) and Chl- a (445 nm) as compared to excitation spectra for emission from Chl- a associated with photosystem I (PSI). Excitation spectra of C. salina and C. ovata showed an increased contribution by Chl- c ² to PSII Chl- a fluorescence emission. In all three species the absorbance band positions of Chl- a , as determined from the excitation spectra, were similar to those previously described in green plants. green algae and phycobilisome-containing organisms. Time-resolved 77 K fluorescence emission spectra of C. ovata and C. salina showed successive emission from both phycoerythrin and Chl- c ², PSII Chl- a , and PSI Chl- a. C. pauciplastida showed successive emission from phycocyanin, PSII Chl- a , and PSI Chl- a. Spectral red-shifts with time were observed for the phycobiliprotein peaks in all three species. The fluorescence decay of phycoerythrin in C. ovata and C. salina was faster than that of phycocyanin in C. pauciplastida. The results are discussed in relation to the organization of the antenna pigments of PSII and PSI in the cryptophyte algae.     

ortho-metallation reactions involving some triphenyl phosphite complexes of osmium

Osmium triphenylphosphine complexes, OsH₄(PPh₃)₃, OsH₂ (CO)(PPh₃)₃ and OsHCl(CO)(PPh₃)₃ react with triphenyl phosphite in boiling organic solvents to yield triphenyl phosphite derivatives which subsequently undergo ortho-metallation reactions.     

Mechanism of silver-mediated di-tert-butylsilylene transfer from a silacyclopropane to an alkene

Kinetic studies of the reactions of cyclohexene silacyclopropane 1 and monosubstituted alkenes in the presence of 5 mol % of (Ph3P)2AgOTf suggested a possible mechanism for silver-mediated di-tert-butylsilylene transfer. The kinetic order in cyclohexene silacyclopropane 1 was determined to be one. Inverse kinetic saturation behavior (rate inhibition) was observed in monosubstituted alkene and cyclohexene concentrations. Saturation kinetic behavior in catalyst concentration was observed. A reactive intermediate, a silylsilver complex, was observed using low temperature 29Si NMR spectroscopy. Competition experiments between substituted styrenes and a deficient amount of 1 correlated well with the Hammett equation and provided a rho value of -0.62 +/- 0.02 using sigmap constants. These data support a mechanism involving reversible silver-promoted di-tert-butylsilylene extrusion from 1 followed by irreversible concerted electrophilic attack of the silylsilver intermediate on the alkene.     

6-Magnesiated purines: preparation and reaction with aldehydes

[reaction: see text] Halogen-metal exchange reaction of 9-benzyl-6-iodopurine with iPrMgCl in toluene at -80 degrees C proceeds almost quantitatively. Such a purine-derived Grignard reagent reacts selectively with aldehydes in toluene, giving the corresponding alcohols in 25-62% yield, while other functional groups such as ketones, esters, and nitriles do not react under these conditions. The reaction can be extended to protected 6-iodopurine ribonucleoside.     

Elektronenreiche übergangsmetallkomplexe : II. Nitril-phosphan-molybdändicarbonyle: Farbe und solvatochromie

Complexes of aromatic or α,β-unsaturated nitriles YCN of the type (YCN)₂(PR₃)₂Mo(CO)₂ and (YCN)(PR₃)₃Mo(CO)₂ are new chromophores. Their intense electronic absorption band in the visible spectrum is strongly influenced by substituents and solvent polarity. Acceptor properties of nitriles are discussed on the basis of CNDO-calculations. CT-character and solvato-chromism can be interpreted in terms of the back-bonding ability of the nitriles in electron-rich metal complexes.