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11.
The first total synthesis of (±)-cyclooroidin, a member of the pyrrole-imidazole alkaloid family recently isolated from the sponge Agelas oroides in optically pure form, is described. The synthesis was achieved in nine linear steps, with an overall yield of 10%. Key step was a Wolff bromoketone synthesis performed on the intermediate longamide B. 相似文献
12.
Concetta?De?Stefano Antonio?Gianguzza Daniela?Piazzese Silvio?SammartanoEmail author 《Analytical and bioanalytical chemistry》2003,375(7):956-967
The binding ability of diethylene triamine pentaacetate (dtpa(5-)) and triethylene tetraamine hexaacetate (ttha(6-)) ligands towards major components, H(+), Na(+), Mg(2+) and Ca(2+), of natural waters was studied in both single and mixed ionic media at different ionic strengths and at T=25 degrees C. Some measurements, performed in Mg(2+)-Ca(2+) mixtures, allowed us to find the formation of new mixed species MgCa(dtpa), MgCa(ttha) and MgCaH(ttha), here reported for the first time. All the complexes formed in the various systems were characterized in terms of both stoichiometry and stability, and an attempt was made to find general rules for the stability of mixed metal complexes in comparison with that of simple species. To obtain quantitative information on the complexing ability of dtpa and ttha in seawater, measurements have been carried out in artificial seawater ionic medium (Na(+), K(+), Ca(2+), Mg(2+), Cl(-) and SO(4)(2-)). Calculations, performed by considering the salt mixture as single salt BA, allowed us to find some quite stable B(i)H(j)L species. Under the natural seawater conditions [S(salinity)=35], we found for the most important species logbeta( B(dtpa))=9.64 and. Literature data comparison is also reported. 相似文献
13.
The formation and stability of protonated diamines-carboxylic ligand complexes was studied potentiometrically (H(+)-glass electrode). Species formed are ALH(r) (A=cadaverine, putrescine, L=acetate, malate, tartrate, malonate, citrate, 1,2,3-propanetricarboxylate, 1,2,3,4-butanetetracarboxylate and glutamate; r=1...m+1, where m is the maximum degree of protonation of the carboxylic ligand), and their stability is a function of charges involved in the formation reaction. For the equilibrium H(i)A(i+)+H(j)L((j-z))=ALH((i+j-z))(i+j) the following linear relationships can be written: logK(1j)=-0.25+0.75 |j-z|, logK(2j)=0.50+0.90 |j-z| (by also considering some ethylenediamine and 1,2-diaminopropane complexes). Medium effects were considered. Comparison was made with analogous inorganic polyanion complexes. The simplest relationships -DeltaG(0)=6.5+/-0.3 and -DeltaG(0)=7.9+/-0.6 kJ mol(-1)n(-1) (n=number of possible salt bridges) were found for carboxylic and inorganic anions, respectively. 相似文献
14.
Young PM Price R Lewis D Edge S Traini D 《Journal of colloid and interface science》2003,262(1):298-302
Drug particulate interactions in pressurized metered dose inhalers (pMDI) may lead to a decrease in aerosolization efficiency and subsequent efficacy in patient treatment. The interactions between salbutamol sulfate (commonly used in Ventolin pMDIs) and a series of pMDI canister materials were investigated using the atomic force microscope (AFM) colloid probe technique. Approximately 4000 individual force-distance curves were determined for a drug probe and three surfaces (10 x 10 mum areas) in situ, in a model propellant. The area under each force-distance curve was integrated to obtain separation energy values. Median separation energy values followed the rank order borosilicate glass > aluminum > PTFE, suggesting PTFE to be the most suitable canister coating. 相似文献
15.
Zamfir A Seidler DG Kresse H Peter-Katalinić J 《Rapid communications in mass spectrometry : RCM》2002,16(21):2015-2024
An analytical approach based on high-performance capillary electrophoresis (CE) in conjunction with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (ESI-QTOF-MS/MS) has been developed for providing the basis to obtain new insights into the domain structure of the glycosaminoglycan (GAG) moiety of proteoglycans. The feasibility and performance of the off-line CE/ESI-QTOF-MS approach in GAG oligosaccharide analysis were assessed by screening a chondroitin/dermatan sulfate (DS) oligosaccharide mixture obtained from bovine aorta by enzymatic depolymerization by chondroitin B lyase. The CS/DS mixture was analyzed by CE using 50 mM ammonium acetate, pH 12.0, dissolved in aqueous methanol (2:3; v/v), as a CE carrier. Structural identification of the GAG components was achieved using off-line CE/nanoESI-QTOF-MS and-MS/MS experiments. ESI-QTOF instrumental parameters were found to play an important role in the MS screening of the CE-separated GAG species. By optimizing the ESI conditions, oligosaccharides differing in chain length and degree of sulfation could be detected. The building block composition, the size of the carbohydrate chain, as well as structural features of the repeating HexA-GalNAc, HexA-GalNAc(S) units, have been determined using MS/MS by applying collision-induced dissociation at low energies. Cleavage of GAG chains by chondroitin B lyase occurs with formation of structural markers useful for identification of IdoA-containing domains. 相似文献
16.
Marimganti S Yasmeen S Fischer D Maier ME 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(22):6687-6700
The synthesis of the omega-amino acid 4 is described utilizing a two-dimensional synthesis strategy combined with an enzymatic differentiation of homotopic ester groups. The amino acid 4 features two non-bonded interactions that result in conformational constraints on a cyclic construct. This amino acid was incorporated into the four macrolactams 17, 22, 31, and 37. The ring in 17 and 22 is 18-membered, whereas 31 and 37 have a 19-membered ring. The pairs with the same ring size differ in a N-methyl group. For the larger macrolactams (31 and 37) conformational analysis showed that the macrocyclic rings are somewhat more rigid than in the natural lead, the depsipeptide jasplakinolide. Nevertheless, their conformations are comparable to the natural product. There are no intramolecular hydrogen bonds, neither is the cis-rotamer populated in the N-methyl compound 37. Due to the increased flexibility of the smaller macrolactams 17 and 22 and signal overlap, a distinct solution structure could not be obtained for these compounds. The amino acid 4 should be useful for restricting the conformation of other small peptides. 相似文献
17.
The influence of the cross-linker (concentration), the porogen (lyotrophic salt) and the solvent type as well as the type and concentration of up to three "functional", i.e., interactive monomers on the morphology and the chromatographic properties of acrylamide-based hydrophilic monoliths are investigated. High total monomer concentrations favored polymers with a rigid rather than gel-like structure. High cross-linker concentrations also favor the formation of a nodular structure. The addition of a lyotrophic salt favors the formation of small nodules especially at higher monomer concentration; the pore size of the polymer can also be modulated through the salt concentration. Suitable monoliths were further investigated as potential stationary phases for capillary electrochromatography (CEC). Depending on the type and concentration of the monomers, plate numbers between 50,000 and 100,000 were routinely obtained. The standard deviation of the run-to-run reproducibility was below 2% and that of the batch-to-batch reproducibility below 5%. A set of nine hydrophobic and polar aromatic compounds (all noncharged) was used to investigate the retention mechanism. Possible candidates for chromatographic interaction and retention in these monoliths are the hydrophobic polymer backbone itself and the alkyl, carbonyl, hydroxy, amino, amide, and charged groups introduced by the various functional monomers. Judging from our results, the carbonyl and the hydroxy functions, as well as the hydrophobic polymer backbone can be supposed to be the main sites of interaction. The charged but also the alkyl functions seem to be less important in this regard. The polymerization conditions and especially the composition of the reaction mixture have a strong influence on the behavior of the final column. 相似文献
18.
Summary Using the X-ray crystal structure of the human topoisomerase I (top1) – DNA cleavable complex and the Sybyl software package, we have developed a general model for the ternary cleavable complex formed with four protoberberine alkaloids differing in the substitution on the terminal phenyl rings and covering a broad range of the top1-poisoning activities. This model has the drug intercalated with its planar chromophore between the −1 and +1 base pairs flanking the cleavage site, with the nonplanar portion pointing into the minor groove. The ternary complexes were geometry-optimized and relative interaction energies, computed by using the Tripos force field, were found to rank in correct order the biological potency of the compounds; in addition, the model is also consistent with the top1-poisoning inactivity of berberine, a major prototype of the protoberberine alkaloids. The model might serve as a rational basis for elaboration of the most active compound as a lead structure, in order to develop more potent top1 poisons as next generation anti-cancer drugs. 相似文献
19.
Daniela Walterová Zdeně;K Stránský Vladimír Preininger Prof. Dr. Vilím Šimánek 《Electrophoresis》1985,6(3):128-132
The isotachophoretic behavior of quaternary benzo/c/phenanthridine, protoberberine and aporphine alkaloids in different electrolyte systems is described. The concentration of the leading ion and the pH value of the leading electrolyte affect the relative effective mobilities of the alkaloids. The system of pH 4.7, containing the leading ion K+ (0.005 M) counter ion acetate, and the terminating ion β-alanine (0.02 M), has been selected for the quantitative determination of the studied alkaloids in model mixtures and plant extracts. 相似文献
20.
Marchese S Curini R Gentili A Perret D Rocca LM 《Rapid communications in mass spectrometry : RCM》2004,18(3):265-272
A simple and rapid method using reversed-phase liquid chromatography/tandem mass spectrometry (LC/MS/MS) for the simultaneous determination of the urinary metabolites of benzene, toluene, xylene and styrene in human urine specimens and standard solutions is described. A hybrid quadrupole/time-of-flight (QqTOF) mass spectrometer was compared for the determination of metabolite of aromatic solvents in urine samples. The metabolites selected were: trans,trans-muconic acid, hippuric acid, o-, m- and p-methylhippuric acid and phenylglyoxylic acid. The compounds were well separated from each other on narrow-bore 1-mm i.d. reversed-phase LC C-18 columns. Average recoveries for loading 100 microL of urine samples varied from 88-110% and the quantification limits were less than 30 ng/mL for each analyte (3 ng/mL for trans,trans-muconic acid). The qualitative information obtained (mass accuracy, resolution and full-scan spectra) with the QqTOF mass spectrometer allows a secure identification of analytes in biological matrices. 相似文献