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251.
Xu M Brahmachary E Janco M Ling FH Svec F Fréchet JM 《Journal of chromatography. A》2001,928(1):25-40
Uniformly sized macroporous polymer beads, which can be used as chiral stationary phase (CSP), have been prepared by the staged templated suspension polymerization process using chiral monomer as one of the copolymerization components. This approach enables the preparation of CSPs for which properties such as pore size, pore volume, surface area, chemistry, and chiral ligands can be tuned over a broad range. Several types of well-defined chiral monomers were prepared and allowed to assess synergistic effect of multiple selectors attached to a branched linker as well as the effect of the length and chemistry of the linker. Microscale batch screening was used for simple and rapid evaluation of selectivity. The most promising candidate CSPs were prepared on a larger scale and packed into HPLC columns. Their performance was demonstrated on the separation of racemic N-(3,5-dinitrobenzoyl)-alpha-amino acid alkylamides. The highest separation factors alpha of up to 27 were observed for CSPs prepared from monomers containing the branched spacer. These highly selective CSPs also enabled the separation of larger amounts of the target racemates upon column overload conditions. 相似文献
252.
B. W. Wenclawiak Torsten Hees Corinna E. Z?ller Hans-Peter Kabus 《Fresenius' Journal of Analytical Chemistry》1997,358(4):471-474
An on-line system of supercritical fluid extraction (SFE) and high performance liquid chromatography (HPLC) via solid phase
extraction (SPE) is described for the determination of palladium and rhodium 2,2,6,6-tetramethyl-3,5-heptanedione-(thd) as
well as rhodium-acetylacetonate-(acac) and benzylacetonate-(bzac) chelates. The chelates were extracted with supercritical
CO2 from sand and humic acid, concentrated on SPE cartridges and analysed with HPLC. Two cartridge materials were tested and
compared to off-line trapping. The percentage of the breakthrough and cartridge retained material were measured in liquid
dichloromethane. The SFE conditions could be optimized to separate metal chelates during the extraction. The supercritical
fluid (SF) behaviour of different ligands on rhodium were investigated.
Received: 19 July 1996/Revised: 11 December 1996/Accepted: 14 December 1996 相似文献
253.
Arsenic (As) is a toxic trace element that occurs naturally in groundwater and soils. Understanding the reactions of arsenite
(As(III)) and arsenate (As(V)) with soil and mineral surfaces is critical for predicting the fate and transport of As in the
environment and developing better ways to remediate As-contaminated areas. This investigation uses X-ray absorption near edge
spectroscopy (XANES) to evaluate the solid phase oxidation state and mineral surface binding sites in three agricultural soil
samples from California, USA by fitting linear combinations of XANES spectra derived from several synthetic and well characterized
As(III)- and As(V)-treated model compounds (Fe and Al metal hydroxides and aluminosilicate illite clay mineral). The results
suggest that As(III) is either partially or completely oxidized to As(V) when reacted with soil in an aqueous, batch reaction.
The As(III)-treated Aiken soil was composed of 60% As(III) attached to surfaces similar to lepidocrocite (γ-FeOOH)) and 40%
As(V) attached to aluminosilicate (illite). The Fallbrook soil completely oxidized As(III) and the product was As(V) adsorbed
on Al hydroxide (gibbsite, γ-Al(OH)3) (62%), illite (16%), and lepidocrocite (γ-FeOOH) (22%). The reaction of As(III) with Wyo soil resulted in 42% As(III) adsorbed
on surface similar to goethite and 58% As(V) adsorbed on lepidocrocite. Arsenic(V) adsorption on soil resulted in stable As(V)
surface complexes that were well described by XANES spectra from As(V) adsorption complexes on gibbsite, illite, and lepidocrocite. 相似文献
254.
Ioannis?Z.?EmirisEmail author Theodoros?G.?Nikitopoulos 《Journal of mathematical chemistry》2005,37(3):233-253
Three-dimensional molecular structure is fundamental in chemical function identification and computer-aided drug design. The enumeration of a small number of feasible conformations provides a rigorous way to determine the optimal or a few acceptable conformations. Our contribution concerns a heuristic enhancement of a method based on distance geometry, typically in relation with experiments of the NMR type. Distance geometry has been approached by different viewpoints; ours is expected to help in several subtasks arising in the process that determines 3D structure from distance information. More precisely, the input to our algorithm consists of a set of approximate distances of varying precision; some are specified by the covalent structure and others by Nuclear Magnetic Resonance (NMR) experiments (or X-ray crystallography which, however, requires crystallization). The output is a valid tertiary structure in a specified neighborhood of the input. Our approach should help in detecting outliers of the NMR experiments, and handles inputs with partial information. Moreover, our technique is able to bound the number of degrees of freedom of the conformation manifold. We have used numerical linear algebra algorithms for reasons of speed, and because they are well-implemented, fully documented and widely available. Our main tools include, besides distance matrices, structure-preserving matrix perturbations for minimizing singular values. Our MATLAB (or SCILAB) implementation is described and illustrated.AMS subject Classification: 92E10 Molecular structure, 92C40 Biochemistry, molecular biology, 65F15 Eigenvalues, eigenvectors, 15A18 Eigenvalues, singular values, and eigenvectors 相似文献
255.
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
256.
Frank Sobott Andreas Wattenberg Wolfgang Kleinekofort Anja Pfenninger Bernhard Brutschy 《Analytical and bioanalytical chemistry》1998,360(7-8):745-749
A recently developed soft desorption method for mass spectrometry is presented, which is called Laser Induced Liquid Beam
Ionization/Desorption (LILBID). Analyte ions are desorbed from a thin jet of analyte solution directly into vacuum by means
of an IR laser pulse, which has been tuned to a vibrational resonance of the solvent. A comparative experiment with ammonium
chloride and aniline hydrochloride shows that ion formation via proton transfer takes place in the solution. Thermally unstable
compounds, as well as supra- and biomolecular complexes, can be detected intact and mass analyzed in a reflectron time-of-flight
(Re-TOF) mass spectrometer. During the desorption process, noncovalent interactions and some solvation characteristics are
preserved. Three examples for the capacity of LILBID are given in this short overview: (a) ion-solvent interactions with the formation of a clathrate structure Cs+(H2O)20, (b) host-guest interactions with the K+ selectivity of valinomycin, and (c) noncovalent interactions with the dimerization of gramicidin.
Received: 29 July 1997 / Revised: 4 September 1997 / Accepted: 12 September 1997 相似文献
257.
The free radical polymerization of ethyl acrylate was investigated in benzene and dimethyl formamide solutions at 50°. The effects of initiator and monomer concentration were studied over a wide range. The overall rate of polymerization was proportional to (initiator concentration) but not to the concentration of the monomer. We attempted to interpret this solvent effect on the basis of (i) the diffusion theory, (ii) the theory of charge transfer complexes and (iii) the theory of hot radicals. Our experimental results could only be explained quantitatively in terms of hot radicals. 相似文献
258.
Vladislav?Tomi?i?Email author Vjekoslav?Butorac Jadranka?Viher Vladimir?Simeon 《Journal of solution chemistry》2005,34(6):613-616
The effect of temperature on the π∗←π transition band in the UV absorption spectrum of NO3−(aq) centered at ≈200 nm was studied in the temperature range 10–70 ∘C. The observed temperature independence of this band was in contrast to the significant influence of temperature on the nitrate π∗←n transition reported recently by us. However, taking into account the electronic states involved in both the transitions, it was concluded that this finding was in accordance with our previous assumption that interconversion between spectrally distinct (with respect to π∗←n band) nitrate species included the rupture/formation of hydrogen bond(s) in the hydration shell of the nitrate ion. 相似文献
259.
Jin-Woong?Kim Jin-Gyu?Park Jee-Hyun?Ryu Ih-Seop?Chang Kyung-Do?SuhEmail author 《Colloid and polymer science》2005,283(11):1233-1240
This study presents a method to produce monodisperse chloromethyl-functionalized macroporous poly(styrene-co-divinylbenzene) polymer particles by seeded polymerization in aqueous media. We observed that the molecular structure of
polystyrene seed particles, the composition of the secondary monomer mixtures, and the type of solvents were very important
factors that determine the morphology and porosity of the final particles. This study proposes that the molecular chemistry
of polystyrene seed polymers, increasing molecular weight or crosslinking, is another factor that can control the porosity
of the final particles. Also, the selection of a poor solvent was effective in forming the larger surface area. In this study,
it was confirmed that the chloromethyl groups introduced on the surface of porous particles were quantified chemically and
their effective incorporation had a close relationship with the surface area. 相似文献
260.
Paavo?Mansikkam?ki Manu?Lahtinen Kari?RissanenEmail author 《Cellulose (London, England)》2005,12(3):233-242
The completeness of mercerisation can be evaluated by investigating the changes in the crystalline regions of cellulose from
cellulose I (C-I) to cellulose II (C-II) by the X-ray powder diffraction method. Mercerisation experiments in four different
solution systems: ethanol/water, acetone, DMSO and xylene, are reported. Also the effect of some additives, external pressure,
treatment time and alkalisation temperature were studied. In two-phase solvent systems, structural changes of cellulose crystallites
depended primarily on the distribution and solubility of sodium hydroxide in the solvent phases. The sodium hydroxide concentration
in the hydrophilic phase must exceed 7–8 w/w-% before complete crystal change from C-I to C-II can occur. The precipitation
of sodium hydroxide due to high concentration prevents the successful use of one-phase ethanol/water system in slurry process.
On the contrary, the 2-propanol/water/sodium hydroxide system separates into two layers; to the water-rich lower layer and
the 2-propanol-rich upper layer, where the sodium hydroxide remains mainly in the water-rich lower layer. This prevents the
precipitation of sodium hydroxide and promotes the alkalisation of cellulose. Ammonium chloride and ammonium hydroxide clearly
had a positive effect by promoting the crystal changes, however, the urea concentration used in this study was obviously too
small. In the advantageous two-phase 2-propanol/water systems, the alkalisation time was only 15 min when the treatment temperature
was kept between 0 and 10 °C. Reduced external pressure was found to have a small but still detectable positive effect on
cellulose alkalisation while over-pressure prevented crystal changes. 相似文献