Separation of tetracyclines by high-speed liquid chromatography.

The separation of tetracycline and its four commoninpurities has been studied by high-speed liquid chromatography. A preliminary study of the effectiveness of ion-exchange, adsorption, liquid-liquid partition and reversed-phase ion-pair chromatography indicated that only the last method showed promise. By developing special hydrocarbon-bonded stationary phases a rapid and complete resolution of all five tetracyclines has been obtained within 10 min. Plate heights using a derivatised 18-mum partisil are in the range 0.15-0.3 mm. The method can be used to quantify the impurities in tetracycline at around the 1% level.     

SINGLET OXYGEN GENERATION BY FUROCOUMARIN TRIPLET STATES—I. LINEAR FUROCOUMARINS (PSORALENS)

Abstract— Triplet extinction coefficients and hence singlet → triplet intersystem crossing quantum yields have been measured in benzene for a number of linear furocoumarins including pseudopsoralen, 5, 8-dimethoxypsoralen, 4, 5', 8-trimethylpsoralen and 3-carbethoxypseudopsoralen. These triplet yields were then used in conjunction with the corresponding quantum yields of singlet oxygen formation, measured in oxygenated solution, to estimate the fractions of furocoumarin triplets which when quenched by ground state oxygen produce singlet excited oxygen, similar data being obtained for psoralen, 5-methoxypsoralen, 8-methoxypsoralen and 3-carbethoxypsoralen. The superoxide anion radical was not detected from these oxygen quenching reactions, nor was a contribution to the singlet oxygen yield found from furocoumarin excited singlet state quenching by oxygen. The fraction of furocoumarin-oxygen quenching interactions leading to singlet oxygen varied between 0.13 (for 5, 8-dimethoxypsoralen) and unity (for 3-carbethoxypsoralen), and thus needs to be taken into account, as well as the triplet quantum yields, in assessing photobiological processes involving singlet oxygen.     

Acidic ent-kauranoids from the metabolism of ent-kaura-2,16-dien-19-ol in gibberella fujikuroi

Three acidic ent-kauranoid metabolites have been obtained as the methyl esters (7, 8, and 9) from incubation of the [17-¹⁴C]-labelled dienol (1) with Gibberella fujikuroi. Spectroscopic studies of the triol ester (7) and chemical degradation of B-ring cleaved products establish the assigned structure (7). The structures of the other two metabolite esters are indicated to be 8 and 9 from the spectroscopic data.     

Proteomic analysis of the Arabidopsis thaliana cell wall

With the completion of the Arabidopsis genome, many hypothetical proteins have been predicted without any information on their expression, subcellular localisation and function. We have performed proteomic analysis of proteins sequentially extracted from enriched Arabidopsis cell wall fractions and separated by two-dimensional gel electrophoresis (2-DE). The proteins were identified by peptide mass fingerprinting using matrix-assisted laser desorption/ionisation-time of flight (MALDI-TOF) mass spectrometry and genomic database searches. This is part of a targeted exercise to establish the entire Arabidopsis secretome database. We report evidence for new proteins of unknown function whose existence had been predicted from genomic sequences and, furthermore, localise them to the cell wall. In addition, we observed an unexpected presence in the cell wall preparations of proteins whose known biochemical activity has never been associated with this compartment hitherto. We discuss the implications of these findings and present results suggesting a possible involvement of cell wall kinases in plant responses to pathogen attack.     

Hydrocarbon metal sulphide complexes : VI. A new type of rearrangement of a cyclopentadienylruthenium complex

The complexes C₅H₅Ru(CO)₂SR (R = C₆F₅ or CH₃) undergo photochemical conversion to binuclear and trinuclear derivatives which exhibit isomerism. A novel rearrangement has been detected for [C₅H₅Ru(CO)(SC₆F₅)]₂.     

Steady-state and dynamic rheology of poly(1-olefin) melts

The steady-state and dynamic melt rheology for a series of poly(1-olefins) has been investigated. The series includes poly(1-butene), poly(1-hexene), poly(1-heptene), poly(1-octene), Poly(1-undecene), poly(1-tridecene), poly(1-hexadecene), and poly(1-octadecene). The flow behavior was investigated by use of a Weissenberg rheogoniometer. Measurements on poly(1-butene) were also made using an Instron capillary rheometer. The empirical relationship developed by Cox and Merz was obeyed for the entire series of poly(1-olefins) at all temperatures investigated. Graessley's theory was used to calculate the flow curves for the poly(1-olefins) from the measured molecular weight distributions. The purpose was to investigate the effect of polymer composition on the shear rate dependence of viscosity. It was found that all experimental flow curves except those for poly(1-hexene) can be fitted with the calculated curves from the individual molecular weight distributions. The conclusion is made that flow curves of poly(1-olefins) depend predominately on molecular weight distribution and are essentially independent of side-chain length even for poly(1-olefins) with pendant groups as long as 16 carbon atoms. The low-shear limiting Newtonian viscosity η₀ for all poly(1-olefins) was expressed by, η₀ = KM? or by η₀ = K′P? where M?_w is the weight-average molecular weight and P?_w is the weight-average degree of polymerization. The K and K′ values obtained decrease systematically as the side chain is increased.     

Self-starting passive harmonic mode-locked femtosecond Yb3+-doped fiber laser at 1030 nm

We demonstrate, for the first time to our knowledge, a self-starting passive harmonic mode-locked femtosecond Yb3+-doped fiber laser with a scalable repetition rate of up to 585 MHz and >45 dB of supermode suppression. Pulse-to-pulse jitter of approximately 14 ps is measured by optical cross correlation at the ninth harmonic, and radiofrequency (RF) spectrum measurements show that certain correlations exist between pulses in harmonic mode. Our results suggest that one of the proposed passive harmonic mode-locking mechanisms may be dominant for this laser.     

Soliton self-frequency shift in a short tapered air-silica microstructure fiber

We report a soliton self-frequency shift of more than 20% of the optical frequency in a tapered air-silica microstructure fiber that exhibits a widely flattened large anomalous dispersion in the near infrared. Remarkably, the large frequency shift was realized in a fiber of length as short as 15 cm, 2 orders of magnitude shorter than those reported previously with similar input pulse duration and pulse energies, owing to the small mode size and the large and uniform dispersion in the tapered fiber. By varying the power of the input pulses, we generated compressed sub-100-fs soliton pulses of ~1-nJ pulse energy tunable from 1.3 to 1.65 mum with greater than 60% conversion efficiency.     

Generation of 90-nJ pulses with a 4-MHz repetition-rate Kerr-lens mode-locked Ti:Al(2)O(3) laser operating with net positive and negative intracavity dispersion

We demonstrate the generation of high-energy pulses by using a low-repetition-rate Kerr-lens mode-locked laser. Repetition rates as low as 4 MHz were achieved with a long, multiple-pass cavity and a semiconductor saturable Bragg reflector. The laser generated pulses of 55-fs duration with a pulse energy of 48 nJ when it was mode locked in the net negative dispersion regime. Mode locking in the positive dispersion regime reduces instabilities and enables pulses to have durations of 80 fs and energies as high as 90 nJ. This is, to our knowledge, the highest pulse energy and the lowest repetition rate ever generated directly from a femtosecond laser resonator without cavity dumping.     

Characterizing the peak in the cosmic microwave background angular power spectrum

A peak has been unambiguously detected in the cosmic microwave background angular spectrum. Here we characterize its properties with fits to phenomenological models. We find that the TOCO and BOOM/NA data determine the peak location to be in the range 175-243 and 151-259, respectively (at 95% confidence) and determine the peak amplitude to be between approximately 70 and 90 &mgr;K. The peak shape is consistent with inflation-inspired flat, cold dark matter plus cosmological constant models of structure formation with adiabatic, nearly scale invariant initial conditions. It is inconsistent with open models and presents a great challenge to defect models.