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111.
Malkinson JP Anim MK Zloh M Searcey M Hampshire AJ Fox KR 《The Journal of organic chemistry》2005,70(19):7654-7661
[reaction: see text] In this article, the first solid-phase-based total synthesis of TANDEM, a synthetic analogue of triostin A, is described. In initial studies, the synthesis incorporated depsipeptide formation, introduction of chromophores, and disulfide bond formation on the solid phase, prior to a final solution-phase macrolactamization, to give the target molecule. Although pure TANDEM was obtained in an overall yield comparable to those for all syntheses to date, the yield of the final cyclization was low (11%). A more efficient approach involved removal from the solid phase prior to disulfide bond formation. The resulting linear peptide underwent macrolactamization under mild conditions and high dilution. Final disulfide bond formation was essentially quantitative and gave the target molecule, TANDEM, in an overall yield of 18%. The final compound was assessed for its ability to bind to 5'-TpA sequences on DNA by DNase I footprinting. This efficient synthesis sets the stage for a study of the structure-activity relationship of TANDEM and the natural product triostin A, with analogues containing "point mutations" at every site within the cyclic compounds. 相似文献
112.
It is shown that a thiolamide antioxidant, 4-mercaptoacetamido diphenylamine (MADA) can be reacted with both polypropylene and polyethylene in a mechanochemical process. The resulting bound antioxidant concentrates (MADA-B) can be used for the thermal and photostabilisation of the parent polymers. The adduct is very stable to solvent extraction and is also very effective as a high temperature antioxidant for polypropylene subjected to water leaching.The uv stabilising mechanism of MADA-B is believed to be related to the regenerative process involved in the mechanism of stabilisation by hindered nitroxyl radicals. 相似文献
113.
114.
Applied Biochemistry and Biotechnology - 相似文献
115.
Applied Biochemistry and Biotechnology - 相似文献
116.
An expert system for classifying and identifying low-resolution mass spectra of toxic and related compounds was developed with an expert shell program. The shell system used was an inexpensive, rule-building software package with an implementation of the ID3 algorithm. Seventy-eight target compounds were used to establish classes previously found by SIMCA class modeling. The six classes included nonhalobenzenes; chlorobenzenes; bromoalkanes and bromoalkenes; mono- and di-chloroalkanes and the analogous alkenes; tri-, tetra- and penta-chloroalkanes and the analogous alkenes; and unknowns. Identification modules for the target compounds were forward-chained to the classification modules. An expert system based on binary-encoded mass spectra, with 17 masses selected on the basis of information content, gave 97 and 86% classification accuracy for training and test spectra, respectively. Identification accuracy was 77 and 80%, respectively. An expert system was also developed which was based on ternary encoding of the mass spectra of 108 training compounds using 25 masses. Ternary encoding has many of the advantages of binary encoding, without the disadvantages. This latter system was tested with the spectra of thirty compounds found in field samples or potential air pollutants. The classification accuracy for training and test spectra was 99 and 97%, respectively. The identification accuracy was 96 and 93%, respectively. With proper precautions, the rule-building expert system can be very effective in spectral classification and identification problems. 相似文献
117.
The synthesis and characterization of cationic platinum complexes of the type [(R(2)PC(2)H(4)PR(2))PtMe(OEt(2))]BAr(F) (R = Cy, Et) are reported. These electrophilic platinum cations are found to react quantitatively with arenes (benzene, toluene) at room temperature by undergoing intermolecular C-H activation with concomitant C-C coupling to generate complexes of the type [[Pt(R(2)PC(2)H(4)PR(2))](2)(mu-eta(3):eta(3)-biaryl)][BAr(F)](2). The dianionic biaryl ligands in these compounds exhibit a rare mu-eta(3):eta(3)-bis-allyl bonding mode and can be removed from the complex with stoichiometric oxidants to generate the free biaryl and [(R(2)PC(2)H(4)PR(2))Pt(mu-X)](2)[BAr(F)](2) (R = Cy, Et; X = Cl, I). The cationic platinum complexes [(R(2)PC(2)H(4)PR(2))PtMe(OEt(2))]BAr(F) (R = Cy, Et) are also quite reactive with water, forming the bridging hydroxide complexes [(R(2)PC(2)H(4)PR(2))Pt(mu-OH)](2)[BAr(F)](2) (R = Cy, Et). A possible mechanism is proposed for the C-C coupling reaction based upon the structures of these bridging biphenyl complexes, which provides a new perspective for the related palladium-catalyzed oxidative coupling of arenes to form biaryls. 相似文献
118.
119.
Palladium catalysis has been found to offer an effective solution-phase alternative to gas-phase flash vacuum pyrolysis as a method for converting the planar ring system of 7, 10-di(2-bromophenyl)fluoranthene (4) to that of the C(28)H(14) bowl-shaped fullerene fragment dibenzo[a,g]corannulene (5). 相似文献
120.
Yan B Collins N Wheatley J Irving M Leopold K Chan C Shornikov A Fang L Lee A Stock M Zhao J 《Journal of combinatorial chemistry》2004,6(2):255-261
We have developed a high-throughput purification system to purify combinatorial libraries at a 50-100-mg scale with a throughput of 250 samples/instrument/day. We applied an accelerated retention window method to shorten the purification time and targeted one fraction per injection to simplify data tracking, lower QC workload, and simplify the postpurification processing. First, we determined the accurate retention time and peak height for all compounds using an eight-channel parallel LC/UV/MS system, and calculated the specific preparative HPLC conditions for individual compounds. The preparative HPLC conditions include the compound-specific gradient segment for individual compounds with a fixed gradient slope and the compound-specific UV or ELSD threshold for triggering a fraction collection device. A unique solvent composition or solvent strength was programmed for each compound in the preparative HPLC in order to elute all compounds at the same target time. Considering the possible deviation of the predicted retention time, a 1-min window around the target time was set to collect peaks above a threshold based on UV or ELSD detection. Dual column preparative instruments were used to maximize throughput. We have purified more than 500 000 druglike compounds using this system in the past 3 years. We report various components of this high-throughput purification system and some of our purification results. 相似文献