RESUMO
The activation experiment was performed using the accelerated beam of Phasotron accelerator at the Joint Institute for Nuclear Research (JINR). The natural uranium spallation target QUINTA was irradiated with protons with energy 660â¯MeV. Monte Carlo simulations of neutron production were performed using the Geant4 code. The number of leakage neutrons from the sections of the uranium target surrounded by the lead shielding and the number of leakage neutrons from lead were determined. The total number of fissions in the setup QUINTA was determined. Experimental values of reaction rates for the produced nuclei in the 127I sample were obtained and several values of reaction rates were compared with the results of simulations. Experimentally determined fluence of neutrons in energy interval 10-175â¯MeV using the (n,xn) reactions in the 127I(NaI) sample was compared with the results of simulations. Possibility of transmutation of the long-lived radionuclide 129I in the QUINTA setup was estimated.
RESUMO
In this study, the screening steps of chiral separation strategies with polysaccharide-based chiral stationary phases were applied on boron cluster compounds in normal-phase liquid chromatography (NPLC) and polar organic solvents chromatography (POSC). Since the screening steps were initially developed to analyze organic compounds, their applicability for boron clusters was investigated. Overall, the screening steps in NPLC were applicable for the separation of zwitterions, while for anions mostly no elution was observed. A hypothesis for the latter behavior is precipitation of anions in the nonpolar mobile phases. Ten out of 11 compounds could be partially or baseline separated on the NPLC screening systems. In POSC, all zwitterions were separated on at least one of the screening systems, with an overall lower retention as in NPLC. Anions were detected but not separated in the majority of the experiments. Also their retention on the chiral stationary phases was very limited. This study showed that the chiral discrimination potential of chemically modified polysaccharides is meaningful for chiral separations of structurally chiral boron cluster species, but needs further systematic research, in which recognition mechanisms should be further explored. In addition, some unusual peaks also indicated that conditions with a high separation efficiency must first be searched for some of the tested systems.
Assuntos
Compostos de Boro/isolamento & purificação , Cromatografia Líquida de Alta Pressão/métodos , Adsorção , Compostos de Boro/química , Cromatografia Líquida de Alta Pressão/instrumentação , Estrutura Molecular , Polissacarídeos/química , EstereoisomerismoRESUMO
The synthesis of N,S-heterodisubstituted 1-(2'-pyridyl)-2-SR-1,2-closo-C2B10H10 compounds (R = Et, 2; R = (i)Pr, 3) has been accomplished starting from 1-(2'-pyridyl)-l,2-closo-C2B10H11 (1), and their partial deboronation reaction leading to the structurally chiral [7-(2'-pyridyl)-8-SR-7,8-nido-C2B9H10]-derivatives (R = Et, [4]-; R = (i)Pr, [5]-) has been studied. Capillary electrophoresis combined with the chiral selector alpha-cyclodextrin has permitted the separation of the electrophoretically pure racemic [7-(2'-pyridyl)-8-SR-7,8-nido-C2B9H11]- ions into two peaks each one corresponding to the interaction of one enantiomer with the alpha-cyclodextrin. The N,S-heterodisubstituted o-carborane containing a mercapto group, 1-(2'-pyridyl)-2-SH-1,2-closo-C2B10H10, 1, is one of the two examples of a rigid bidentate chelating (pyridine)N-C-C-C-S(H) motif having been structurally fully characterized. To study the potential of such a binding site, 1 has been tested as a ligand with metal ions requiring different coordination numbers, two (Au(+)) and four (Pd2+ and Rh+). The crystal structures of the Pd(II) and Au(I) complexes are reported. For the Pd(II) complex, 1 acts as a bidentate ligand whereas for Au(I), 1 acts as a monodentate ligand through the thiolate.
RESUMO
Electrophoretic and photometric experiments strongly indicate that monovalent anions, which arise by deprotonation of the nitrogen atom in zwitterionic Good's buffers 3-(cyclohexylamino)-2-hydroxy-1-propanesulfonic acid (CAPSO) and 3-morpholinopropanesulfonic acid (MOPS), spontaneously aggregate. Cationic migration of sanguinarine (SA) and chelerythrine (CHE) in highly alkaline 1,3-bis[tris(hydroxymethyl)methylamino]propane (Bis-Tris-propane), in which the concentration of cations of both alkaloids is negligible, may be explained by the existence of an aggregate, which contains uncharged sanguinarine or chelerythrine and one monovalent cation of Bis-Tris-propane at least. Tendency of tris(hydroxymethyl)aminomethane (Tris), bis (2-hydroxyethyl)iminotris(hydroxymethyl)methane (Bis-Tris) and Bis-Tris-propane cations to ion pairing with synthetic cluster borane anions and with fused silica markedly rises up with the size and charge of these cations. The drop in mobility of cluster borane compounds sometimes exceeds 50% of their mobility found at identical pH and ionic strength in buffers with sodium cation. The electroosmosis drop approached 70% if background electrolyte contained Bis-Tris-propane cations instead of sodium cations. Nitrate, taken as a model inorganic ion, and four randomly chosen organic anions interacted markedly less with Tris, Bis-Tris and Bis-Tris-propane cations than cluster borane anions. 2-(N-morpholino)ethanesulfonic (MES) acid anions present in background electrolyte affect the ion pairing of Tris, Bis-Tris and Bis-Tris-propane cations with anionic analytes and, in this way influence also mobilites of these anionic analytes. Limited hydrophilicity at least one of interacting species appears to be the most probable cause of observed intermolecular interactions of biological buffers.
Assuntos
Alcaloides/química , Eletroforese Capilar/métodos , Fenantridinas/química , Espectrofotometria Ultravioleta/métodos , Benzofenantridinas , Soluções Tampão , IsoquinolinasRESUMO
A method for the pKa determination, based on mobility data measured by capillary zone electrophoresis, was applied to cytokinins and their analogs. The combination of charged mobility standards with an uncharged electroosmosis marker, injected in the uncoated capillary simultaneously with the measured substances, allows one to minimize the number of runs, reduce their duration and, in addition, to inform on the run-to-run stability of electroosmosis and on contingent side-effects. pKa values of investigated cytokinins and their analogs ranged from 2.8 to 4.0 at 25 degrees C in the phosphate and acetate buffers of ionic strength 0.015 M. Standard deviations of the constants, obtained by the non-linear fitting of equations for the pKa calculation, were 3-5-times lower than standard deviations from the linear fitting or from the point-to-point calculation utilizing the Hendersson-Haselbalch equation. The equation of Boltzman sigmoid offers two checks on reliability of effective mobilities that serve as the raw data in the pKa calculation.
Assuntos
Citocininas/química , Eletroforese Capilar/métodosRESUMO
Interactions of chiral selectors with enantiomers or with other chiral analytes, underlying their electrophoretic separations, are particular cases of interactions of dissolved species. The interaction model that describes these reversible, fast interactions is simple. Equations describing the model are also simple and applying equations for the calculation of respective equilibrium constants to experimental data is easy using computers. Obtaining the experimental mobility data, necessary for the calculation, is the critical step on the way to stability constants quantitating the strengths of interactions of chiral selectors with enantiomers and other analytes. These data are decisive for both the accuracy and precision of the calculated constants. The meaning and applicability of the particular constant depend on the type of the constant. The common method for the determination of stability constants from electrophoretic migration data is reasonable for low and medium stability constants. For stronger complexing, characterised by stability constants of the order of 10(4) l/mol, typical of affinity chiral selectors, the method becomes unreliable. For strong complexing giving constants of the order of 10(5) or higher of or higher the method is not applicable in its commonly used form.
Assuntos
Eletroforese/métodos , Modelos Químicos , EstereoisomerismoRESUMO
The marked increase in the number of communications on the utilization of electrophoresis for practical chiral separations within the last three years is the most evident, and the most important fact. It reveals that the basic period of intensive research in the field is finished. The search for chiral selectors discriminating racemates in a reasonably analytical manner and the study of both the mechanism and physicochemical aspects of the chiral discrimination process were the main features of that period. Here, we review the state of the art in the field and state the references of the related literature up to the end of 1998.
Assuntos
Eletroforese Capilar/métodos , EstereoisomerismoRESUMO
An equation for the calculation of electrophoretic mobility of kinetically labile complexes originating in solutions during the chiral discrimination process is derived. The mobility of the complex is calculated from that of a fully ionized racemic compound, measured in absence of the chiral selector, and from the effective mobilities of its enantiomers, corresponding to the concentration of the chiral selector causing their maximum difference. Correct values of stoichiometric stability constants of both enantiomers may be calculated from the mobility of the complex obtained in this way. Both the mobility and the stability values hold only for the experimental conditions used and the selected background electrolyte. The proposed method is demonstrated for the separation of the fully ionized N-t-BOC-DL-tryptophan with beta-cyclodextrin in 20 mM aqueous solution of alpha-hydroxyisobutyric acid, adjusted with NaOH to pH 4.5. Mobility of the complex is 8.4 X 10(-9) m2V[-1]s(-1) at 25 degrees C. The stability constants of D- and L-enantiomers of N-t-BOC-DL-tryptophan with beta-cyclodextrin, KD and KL obtained from migration data using this mobility of the complex, are 374+/-37 M(-1) and 336+/-31 M(-1), respectively. The geometrical mean value of calculated stability constants, 355 M(-1), agrees perfectly with the value of 350 M(-1), calculated from the same experimental data by another procedure recently.
Assuntos
Ciclodextrinas/química , Eletroforese Capilar , Triptofano/análogos & derivados , beta-Ciclodextrinas , Ciclodextrinas/isolamento & purificação , Eletroquímica , Modelos Químicos , Soluções , Triptofano/química , Triptofano/isolamento & purificaçãoRESUMO
The properties of the macrocyclic antibiotic vancomycin, used as a chiral selector, were studied with aminoquinolycarbamate derivatives of amino acids, containing sulfur and selenium, as well as with other organic ions. Vancomycin combines the ability to resolve fully ionized anionic enantiomers, typical of proteins, with excellent separation efficiency, exceeding that of cyclodextrins. It allows better than baseline chiral separations of several anionic analytes within 3-5 min. The resolving power of vancomycin results from its great skill in discriminating enantiomers rather than from high affinities to the separated enantiomers. The association constants of vancomycin are of the same order of magnitude, 10(2) L/mol, as that found for beta-cyclodextrin (beta-CD). The difference in association constants of separated cystine enantiomers with vancomycin, 2 x 10(2) L/mol, is one order of magnitude higher than that of enantiomers separated with beta-CD. Analytically convenient mobility differences up to 1-2 x 10(9) m2V-1s-1, with only one of the enantiomers appreciably decelerated, are obtained at submillimolar vancomycin concentrations. Typical separation efficiencies are close to 250,000 theoretical plates per meter of capillary. Deceleration of various organic ions by millimolar vancomycin implies that chiral separations with vancomycin need not be restricted to carboxylic acids. The vancomycin-analyte interactions are strongly affected by the chemical composition and concentration of the buffer. An additional experimental variable, highly effective in manipulating the separation selectivity of analytes, is the buffer pH.
Assuntos
Aminoácidos/isolamento & purificação , Eletroforese Capilar/métodos , Vancomicina , beta-Ciclodextrinas , Soluções Tampão , Ciclodextrinas , Estabilidade de Medicamentos , Concentração de Íons de Hidrogênio , Indicadores e Reagentes , Solubilidade , Estereoisomerismo , Vancomicina/químicaRESUMO
The maximum in the dependence of the separation selectivity on the concentration of cyclodextrin may be utilized for the determination of the mean value of host-guest interaction constants of the separated enantiomers. For the hosting of N-t-BOC-DL-tryptophan by beta-cyclodextrin, the mean value of these constants, found by drop line estimated from the cyclodextrin concentration corresponding at the maximum, is 350 L.mol-1. The separation at this concentration of cyclodextrin offers the highest resolution in the shortest separation time. It is shown that commonly used simple preliminary experiments, testing the capability of a cyclodextrin to resolve chiral compounds, and based on relatively high cyclodextrin concentrations, may easily lead to incorrect conclusions in cases of enantiomers strongly interacting with the cyclodextrin used.
Assuntos
Ciclodextrinas/química , Eletroforese/métodos , Triptofano/química , Eletroforese/instrumentação , Estereoisomerismo , Relação Estrutura-AtividadeRESUMO
Sensitivity and applicability of commonly used indirect photometric detection in the UV region can be adversely affected by the absorption of the UV light by detected solutes and/or by matrix constituents migrating with them. If the visible light is exploited instead of the UV light, both these disadvantages may be for the most part eliminated, and, moreover, the indirect photometric detection will extend its versatility and sensitivity. Prospects as well as main problems of the approach were tested using inorganic ions as analytes. If organic dyes with a molar light absorption coefficient of the order of 10(6) mol-1 L m-1 was selected as the light-absorbing constituents of the background electrolyte, detection sensitivity comparable with the best reported results was reached for anions; for cations, the detection limit was even lower by two orders of magnitude.
Assuntos
Eletroforese/métodos , Espectrofotometria/métodos , Ânions , Cátions , Corantes/química , Índigo Carmim/química , Luz , Verde de Metila/química , Raios UltravioletaRESUMO
Capillary electrophoresis is a powerful tool for chiral separation of ionogenic enantiomers in solutions. This article brings an overview of the theory of electrophoretic separations with special emphasis on enantiomer-chiral selector equilibria, followed by a survey of indirect separations, based on formation of diastereomers with different electrophoretic mobilities, and a comprehensive appraisal of direct separations when the chiral recognition stems from (i) host-guest interactions using cyclodextrins and crown ethers as hosting agents, (ii) ligand exchange mechanism, (iii) affinity interactions or (iv) a combination of solute-chiral selector interactions with micellar electrophoretic transport. Finally, some trends in chiral separations by capillary electrophoresis are discussed.
Assuntos
Eletroforese/métodos , Ciclodextrinas/isolamento & purificação , Éteres Cíclicos/isolamento & purificação , Cinética , Ligantes , Polissacarídeos/isolamento & purificação , Ligação Proteica , EstereoisomerismoRESUMO
A procedure is proposed for the calculation of the actual effective mobility of a zone from its migration time. It is based on the use of internal standards with known mobilities; the use of two internal standards provides reliable mobility data even if the magnitudes of the effects of sample composition, capillary temperature, capillary length, migration distance, used voltage, as well as the tube length occupied by the injected sample are unknown. Formulas have been derived for the calculation of the actual mobilities, and their experimental verification has been carried out by using a model set of anionic solutes with mobilities ranging from -56 to -20 x 10(-9) m2V-1s-1 and chloride as the ion modelling the effect of the sample matrix.
Assuntos
Eletroforese/métodos , Eletrólitos , Modelos Químicos , Osmose , Cloreto de Sódio , Espectrofotometria Ultravioleta , TemperaturaRESUMO
HPLC separation of pilocarpine from its degradation products (isopilocarpine, pilocarpic acid and isopilocarpic acid) was studied on unmodified silica gel stationary phase. An acidified aqueous solution of inorganic salts with addition of methanol served as the mobile phase. The influence of silica gel used, methanol content, mobile phase pH, anion of acids and/or inorganic salts and column temperature on solute retention, separation selectivity as well as peak shape was studied and partly explained. A significant dependence of the properties of the resulting separation system on the silica gel used was found. A test was proposed for evaluation of silica gel suitability.