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51.
52.
Many biologically active natural products are constrained by macrocyclization and modified with carbohydrates. These two types of modifications are essential for their biological activities. Here we report a chemoenzymatic approach to make carbohydrate-modified cyclic peptide antibiotics. Using a thioesterase domain from the decapeptide tyrocidine synthetase, 13 head-to-tail cyclized tyrocidine derivatives were obtained with one to three propargylglycines incorporated at positions 3-8. These cyclic peptides were then conjugated to 21 azido sugars via copper(I)-catalyzed cycloaddition. Antibacterial and hemolytic assays showed that the two best glycopeptides, Tyc4PG-14 and Tyc4PG-15, have a 6-fold better therapeutic index than the natural tyrocidine. We believe this method will also be useful for modifying other natural products to search for new therapeutics. 相似文献
53.
Nonribosomal peptide synthetases (NRPS) are multimodular biocatalysts that bacteria and fungi use to assemble many complex peptides with broad biological activities. The same modular enzymatic assembly line principles are found in fatty acid synthases (FAS), polyketide synthases (PKS), and most recently in hybrid NRPS/PKS multienzymes. FAS as well as PKS are known to function as homodimeric enzyme complexes, raising the question of whether NRPS may also act as homodimers. To test this hypothesis, biophysical methods (size exclusion chromatography, analytical equilibrium ultracentrifugation, and chemical crosslinking) and biochemical methods (two-affinity-tag-system and complementation studies with enzymes being inactivated in different catalytic domains) were applied to NRPS subunits from the gramicidin S (GrsA-ATE), tyrocidine (TycB(1)-CAT and TycB(2-3)-AT.CATE), and enterobactin (EntF-CATTe) biosynthetic systems. These methods had revealed the dimeric structure of FAS and PKS previously, but all three NRPS systems investigated are functionally active as monomers. 相似文献
54.
Robin Zuluaga Jean-Luc Putaux Adriana Restrepo Iñaki Mondragon Piedad Gañán 《Cellulose (London, England)》2007,14(6):585-592
Cellulose microfibrils have been prepared from banana rachis using a combination of chemical and mechanical treatments. The
morphology and structure of the samples were characterized using transmission electron microscopy, atomic force microscopy,
and X-ray diffraction. Fourier-transformed infrared spectroscopy (FTIR) was used to characterize the chemical modifications
of the samples after each treatment. Suspensions of bundled or individualized 5-nm-wide microfibrils were obtained after homogenization
(PH) whereas an organosolv (PO) treatment resulted in shorter aggregates of parallel cellulose microcrystallites. The sharper
rings in the X-ray diffraction pattern of the PO-treated sample suggest a higher crystallinity due to a more efficient removal
of hemicelluloses and dissolution of amorphous zones by the acid treatment. Both microfibrils and microcrystals prepared by
both methods can be used as reinforcing filler in nanocomposite materials. 相似文献
55.
Chromatography has been an important tool in marine laboratories. Since the 1960s, marine laboratories have been involved in the analysis of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and brominated flame retardants (BFRs). Column chromatography and liquid chromatography (LC) techniques have been used, mainly in the clean-up phase, while gas chromatography (GC) has been used extensively in the final determination of these contaminants. Developments have been observed from the use of packed GC columns, via capillary columns to the use of heart-cut multi-dimensional GC and comprehensive multi-dimensional GC. The progress made in interlaboratory studies and the availability of certified reference materials are discussed. 相似文献
56.
We show that the two-photon resonances in the third-order susceptibility can be exploited to yield two-photon spectra of molecular gases at moderately high spectral resolution. This form of spectroscopy does not depend on the occurrence of processes (such as fluorescence of photoionization) leading to indirect methods of two-photon absorption. The method is direct and leads in principle to values for a two-photon cross section. Comparisons of two-photon and coherent anti-Stokes Raman resonances leads to ratios of Raman and two-proton cross sections independent of the laser powers and spatial characteristics. The technique is documented with rotationally resolved spectra of SO2 and NO. A value for |αxxαyy| of 1.5 × 10?52 cm6 was measured for the O12 (6) component of the (A)2Σ ← (X)2 Π transition of nitric oxide. 相似文献
57.
Amaresh RR Lakshmikantham MV Baldwin JW Cava MP Metzger RM Rogers RD 《The Journal of organic chemistry》2002,67(8):2453-2458
3,4-Cyanomethyl substituted thiophenes reacted with thionyl chloride in the presence of base to give dicyano substituted thieno(3,4-c)thiophenes. The use of selenium oxychloride furnished the corresponding cyano substituted seleno(3,4-c)thiophene. 1,2-Phenylenediacetonitriles gave the corresponding cyano substituted benzo(c)thiophenes and benzo(c)selenenophenes, respectively, upon reaction with thionyl chloride and selenium oxychloride in the presence of base. 相似文献
58.
Functional-based screening of crude β-galactosidase activities from 42 yeast strains resulted in the selection of a single
enzyme of potential interest as a digestive supplement. β-Galactosidase produced by Kluyveromyces marxianus DSM5418 was purified to homogeneity by a combination of gel filtration, ion-exchange, and hydroxylapatite chromatographies.
The denatured (123 kDa) and native molecular masses (251 kDa) suggest that the enzyme is a homodimer. The optimum pH and temperature
of the purified enzyme were 6.8 and 37°C, respectively. The unpurified β-galactosidase in particular displayed a high level
of stability when exposed to simulated intestinal conditions in vitro for 4 h. Matrix-assisted laser desorption ionization
mass sectrometry analysis revealed that the enzyme's trypsin-generated peptide mass fingerprint shares several peptide fragment
hits with β-galactosidases from Kluyveromyces lactis. This confirms the enzyme's identity and indicates that significant sequence homology exists between these enzymes. 相似文献
59.
The dipole strengths of the 4A2 → 4T1(F), 4T1(P), d-electron transitions of the cobalt(II) tetrahalides are found to decrease with an increase in temperature, in agreement with a dynamic ligand-polarisation model for the absorption mechanism. The reduction in dipole strength is accounted for by a decrease in the coulombic coupling between the quadrupole moment of the d-electron transition of the metal ion and the transient electric dipole moment induced in the ligands, due to the anharmonic increase in the mean bond length and the progressively larger mean-square amplitudes of the bending modes of the complex ion in its ground electronic state as the temperature is raised. 相似文献
60.
Bedford RB 《Chemical communications (Cambridge, England)》2003,(15):1787-1796
Palladacycles are amongst the most active catalysts in Heck-type carbon-carbon bond formation and related carbon-heteroatom bond forming reactions. For instance they have recently emerged as showing the highest activity in the Suzuki coupling of electronically challenging aryl chloride substrates. In addition to the high activity they display, their ease of synthesis, facile modification and comparative stability all act to enhance their appeal. 相似文献