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101.
Derivatization of the alkaloids cephaeline, codeine, emetine, ephedrine, morphine, narcotine and others with dansyl chloride has been studied with the aim of developing a sensitive and specific liquid chromatographic method for these substances in complex pharmaceutical dosage forms. While codeine and narcotine do not react, the other compounds form completely substituted derivatives which possess maxima in their fluorescence emission spectra between 470 and 500 nm. The structure of the derivatives has been confirmed by nuclear magnetic resonance spectroscopy. The dansylated compounds have been separated by thin-layer chromatography and high-pressure liquid chromatography. The improved selectivity and sensitivity have permitted an analysis of these substances present in low concentrations in 10- 100-fold excesses of other drugs. Direct derivatization of syrups and aqueous slurries of capsules having a complex excipient and drug composition is feasible and time saving and serves as a pre-clean-up step. Detection limits are in the 1-10-ng range or better, depending on the efficiency of the detection device. The reproducibility of the method is limited by the derivatization step, but a relative standard deviation of less than 2% can be obtained. The analysis time for these pharmaceuticals may be reduced by at least one fifth of that required by conventional techniques. 相似文献
102.
Drug Delivery: Biodegradable Passion Fruit‐Like Nano‐Architectures as Carriers for Cisplatin Prodrug (Part. Part. Syst. Charact. 11/2016)
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103.
Concetta De Santi Bjørn Altermark Marcin Miroslaw Pierechod Luca Ambrosino Donatella de Pascale Nils-Peder Willassen 《BMC biochemistry》2016,17(1):1
Background
The use of metagenomics in enzyme discovery constitutes a powerful approach to access to genomes of unculturable community of microorganisms and isolate novel valuable biocatalysts for use in a wide range of biotechnological and pharmaceutical fields.Results
Here we present a novel esterase gene (lip3) identified by functional screening of three fosmid metagenomic libraries, constructed from three marine sediment samples. The sequenced positive fosmid revealed an enzyme of 281 amino acids with similarity to class 3 lipases. The 3D modeling of Lip3 was generated by homology modeling on the basis of four lipases templates [PDB ID: 3O0D, 3NGM, 3G7N, 2QUB] to unravel structural features of this novel enzyme. The catalytic triad of Lip3 was predicted to be Asp207, His267 and the catalytic nucleophile Ser150 in a conserved pentapeptide (GXSXG). The 3D model highlighted the presence of a one-helix lid able to regulate the access of the substrate to the active site when the enzyme binds a hydrophobic interface. Moreover an analysis of the external surface of Lip3 model showed that the majority of the surface regions were hydrophobic (59.6 %) compared with homologous lipases (around 35 %) used as templates. The recombinant Lip3 esterase, expressed and purified from Escherichia coli, preferentially hydrolyzed short and medium length p-nitrophenyl esters with the best substrate being p-nitrophenyl acetate. Further characterization revealed a temperature optimum of 35 °C and a pH optimum of 8.0. Lip3 exhibits a broad temperature stability range and tolerates the presence of DTT, EDTA, PMSF, β-mercaptoethanol and high concentrations of salt. The enzyme was also highly activated by NaCl.Conclusions
The biochemical characterization and homology model reveals a novel esterase originating from the marine Arctic metagenomics libraries with features of a cold-active, relatively thermostable and highly halotolerant enzyme. Taken together, these results suggest that this esterase could be a highly valuable candidate for biotechnological applications such as organic synthesis reactions and cheese ripening processes.104.
Type I polyketide synthases (PKSs) consist of modules that add two-carbon units in polyketide backbones. Rearranging modules from different sources can yield novel enzymes that produce unnatural products, but the rules that govern module-module communication are still not well known. The construction and assay of hybrid bimodular units with synthetic PKS genes were recently reported. Here, we describe the rational design of trimodular PKSs by combining bimodular units. A cloning-expression system was developed to assemble and test 54 unnatural trimodular PKSs flanked by the loading module and the thioesterase from the erythromycin synthase. Remarkably, 96% of them produced the expected polyketide. The obtained results represent an important milestone toward the ultimate goal of making new bioactive polyketides by rational design. Additionally, these results show a path for the production of customized tetraketides by fermentation, which can be an important source of advanced intermediates to facilitate the synthesis of complex products. 相似文献
105.
Chemistry of Natural Compounds - Two new chromanone acid derivatives, calophinophyllins A and B (1 and 2), together with a known one (3), were isolated from Calophyllum inophyllum. The structures... 相似文献
106.
We study self-assembly on a spherical surface of a model for a binary mixture of amphiphilic dimers in the presence of guest particles via Monte Carlo (MC) computer simulation. All particles had a hard core, but one monomer of the dimer also interacted with the guest particle by means of a short-range attractive potential. We observed the formation of aggregates of various shapes as a function of the composition of the mixture and of the size of guest particles. Our MC simulations are a further step towards a microscopic understanding of experiments on colloidal aggregation over curved surfaces, such as oil droplets. 相似文献
107.
Mandal SM Pati BR Ghosh AK Das AK 《European journal of mass spectrometry (Chichester, England)》2007,13(2):165-171
Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI ToF-MS) has been used to identify bacteria on the basis of its spectral nature. Identification of bacteria using MALDI ToF mass spectra depends on instrumental parameters and sample preparation protocol. Here we have optimized the sample preparation protocol for whole cell Rhizobium and evaluated the effect of its different growth phases to find out specific growth periods superior to the taxonomical approach. Sample preparation integrates the most important step influencing the quality and reproducibility of the spectra. The important factors in sample preparation include selection of matrix, solvent and acid concentration. A maximum numbers of peaks have been observed using 2,4- dihydroxy-phenylazobenzoic acid (HABA) rather than the commonly used alpha-cyano-4-hydroxy cinnamic acid (CHCA) or 3, 5-dimethoxy- 4-hydroxycinnamic acid (sinapinic acid) for whole cell Rhizobium identification. A protocol has been optimized after considering different experimental variables including various phases of bacterial growth and late log to stationary phase has been found to be best for identification of whole cell Rhizobium by this method. 相似文献
108.
Sciarrone D Costa R Ragonese C Tranchida PQ Tedone L Santi L Dugo P Dugo G Joulain D Mondello L 《Journal of chromatography. A》2011,1218(1):137-142
109.
Duran-Frigola M Tejedor-Estrada R Sánchez-García D Nonell S 《Physical chemistry chemical physics : PCCP》2011,13(21):10326-10332
The absorption spectrum of the asymmetric 9-amino-2,7,12,17-tetraphenylporphycene shows new, strongly red-shifted bands compared to the symmetric parental 2,7,12,17-tetraphenylporphycene and to the also asymmetric 9-acetoxy-2,7,12,17-tetraphenylporphycene. Dual emission is also observed with relative contributions that depend strongly on the excitation wavelength and temperature. The gap between the two fluorescence bands is 84 nm. Tautomerization in both the ground and excited states is shown to account for these observations, the 9-amino group being particularly able to selectively lower the energy of the first excited singlet state of just one of the trans tautomers. Introduction of amino groups in porphycenes may be a convenient way to gain a deeper insight into the tautomerization mechanisms in this macrocyclic core. 相似文献
110.
Cazzoli G Cludi L Puzzarini C Stoppa P Pietropolli Charmet A Tasinato N Baldacci A Baldan A Giorgianni S Wugt Larsen R Stopkowicz S Gauss J 《The journal of physical chemistry. A》2011,115(4):453-459
A combined microwave, infrared, and computational investigation of CHBrF(2) is reported. For the vibrational ground state, measurements in the millimeter- and sub-millimeter-wave regions for CH(79)BrF(2) and CH(81)BrF(2) provided rotational and centrifugal-distortion constants up to the sextic terms as well as the hyperfine parameters (quadrupole-coupling and spin-rotation interaction constants) of the bromine nucleus. The determination of the latter was made possible by recording of spectra at sub-Doppler resolution, achieved by means of the Lamb-dip technique, and supporting the spectra analysis by high-level quantum chemical calculations at the coupled-cluster level. In this context, the importance of relativistic effects, which are of the order of 6.5% and included in the present work using second-order direct perturbation theory, needs to be emphasized for accurate predictions of the bromine quadrupole-coupling constants. The infrared measurements focused on the ν(4) fundamental band of CH(79)BrF(2). Fourier transform investigations using a synchrotron radiation source provided the necessary resolution for the observation and analysis of the rotational structure. The spectroscopic parameters of the v(4) = 1 state were found to be close to those of the vibrational ground state, indicating that the ν(4) band is essentially unaffected by perturbations. 相似文献