Stable (amino)(phosphino)carbenes: difunctional molecules

(Amino)(phosphino)carbenes are stable due to the donation of the nitrogen lone pair, the phosphino group remains strongly pyramidalized. Reactions can be performed selectively at the carbene center, but also at the phosphorus center leading to new stable carbenes. These difunctional molecules can be considered as hybrid ligands.     

Total synthesis of deamido bleomycin a(2), the major catabolite of the antitumor agent bleomycin

Metabolic inactivation of the antitumor antibiotic bleomycin is believed to be mediated exclusively via the action of bleomycin hydrolase, a cysteine proteinase that is widely distributed in nature. While the spectrum of antitumor activity exhibited by the bleomycins is believed to reflect the anatomical distribution of bleomycin hydrolase within the host, little has been done to characterize the product of the putative inactivation at a chemical or biochemical level. The present report describes the synthesis of deamidobleomycin demethyl A(2) (3) and deamido bleomycin A(2) (4), as well as the respective aglycones. These compounds were all accessible via the key intermediate N(alpha)-Boc-N(beta)-[1-amino-3(S)-(4-amino-6-carboxy-5-methylpyrimidin-2-yl)propion-3-yl]-(S)-beta-aminoalanine tert-butyl ester (16). Synthetic deamido bleomycin A(2) was shown to be identical to the product formed by treatment of bleomycin A(2) with human bleomycin hydrolase, as judged by reversed-phase HPLC analysis and (1)H NMR spectroscopy. Deamido bleomycin A(2) was found to retain significant DNA cleavage activity in DNA plasmid relaxation assays and had the same sequence selectivity of DNA cleavage as bleomycin A(2). The most significant alteration of function noted in this study was a reduction in the ability of deamido bleomycin A(2) to mediate double-strand DNA cleavage, relative to that produced by BLM A(2).     

Description of pulse propagation in a dispersive medium by use of a pulse quality factor

We investigated how the duration of short laser pulses evolves in a dispersive material, using rms widths and a propagation law based on a pulse quality factor. Experiments were carried out with femtosecond pulses (10 to 25fs at the temporal waist) propagating in bulk fused silica. Excellent agreement was found between theory and experiment. This approach does not require complete characterization of laser pulses and eliminates the need for any assumption regarding the interpretation of autocorrelation traces. The method is of general validity, and it can be applied to pulses of arbitrary shape.     

Resin dynamics contributes to the NMR line broadening of organic molecules grafted onto a polystyrene resin

Despite the use of high resolution magic angle spinning NMR, the NMR linewidth of anchored molecules on the commonly used Merrifield solid phase resins remains larger than that of the corresponding molecules in solution. We investigate the different mechanisms that might be at the origin of this line broadening. Experimentally, we use the CPMG method to determine the (15)N relaxation times of a tethered tripeptide and show that the slow resin dynamics significantly contributes to the transverse relaxation.     

Semi-explicit solutions for M/PH/1-like queuing systems

A large class of queuing systems have a stationary probability vector of matrix-geometric form. The essential step in the computation algorithm is the evaluation of a matrix R, the unique nonnegative solution of a matrix quadratic equation. The matrix R is usually determined by successive approximations.An explicit form of R is proposed, for systems that resemble the M/PH/1 queue.     

Collective features of gravitational light focusing

A distribution of matter described by a continuous density function of spherical symmetry is shown to behave as a stigmatic lens whose focal length and aberrations are calculated. We suggest that a statistically spherical cluster of stars has similar optical properties. The close ray — particle (star) interactions are described as scattering losses for the collective lens effect due to the averaged long range interactions.     

The vacuum UV photolysis of various C4 and C5 olefins: The energy content of the α- and β-methallyl fragments

In recent publications from this laboratory, we have shown that the fragmentation of photoexcited olefinic molecules in the vacuum UV region leads mainly to the cleavage of a C—C bond located in the ß position relative to the double bond. The allyl fragment bears away part of the excess energy of the photon. At low pressure, this excited radical is capable of undergoing further decomposition. From the pressure effect, we were able to measure the first order rate constant for this secondary fragmentation. In this paper we shall use RRKM calculations in order to get a better idea on how the energy is distributed among the primary fragments. In cases where α- and β;-methallyl radicals were involved, the results show that an important part of the excess energy is located in the methallyl fragment in the 7.1 and 7.6 eV photolysis of 3-methyl-1-butene, 2-methyl-1-butene, and cis-2-pentene.