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71.
Four novel siloxane polymeric pseudostationary phases with three different ionic head groups have been synthesized and characterized for electrokinetic chromatography. Siloxane polymers are of interest in this application because of the wide range of chemistries that can be developed based on these backbones, including much of the chromatographic stationary phase chemistry developed in the last thirty years. All four of the siloxanes studied were synthesized by modification of a single methylhydrosiloxane polymer with highly acidic anionic functionalities. One of the siloxanes had both ionic groups and alkane chains attached to the siloxane backbone. The electrophoretic mobilities varied from being somewhat less than sodium dodecyl sulfate (SDS) to being much greater than SDS. The siloxanes substituted with ionic groups at all of the silicon sites showed significant nonequilibrium band broadening, severely limiting the efficiencies of these polymers. Substitution of 20% of the silicon sites with an alkyl group improved the efficiency of the separations and the peak symmetry. The chemical selectivities of the siloxane polymers are very different from SDS, but are similar to each other. 相似文献
72.
The syntheses of both diastereoisomers of 5′-ethyl-substituted thymidine dimers, the (5′R)- and (5′S)-configurated 33a and 33b respectively, in which the natural phosphodiester linkage is replaced by an amide group (C(3′)-CH2CONH-CH(5′)(Et)), arc described. Their fully protected derivatives 35a and 35b , respectively, are suitable for incorporation into antisense oligonucleotides. Unexpectedly, an attempted PdII-catalysed aza-Claisen rearrangement of trichloroacetimidate 7 provided the diastereoisomerically pure cyclopropane derivative 17 , whose structure was confirmed by X-ray analysis. 相似文献
73.
Step-scan FTIR time-resolved spectroscopy (S2FTIR TRS) in acetonitrile-d3 has been used to probe the acceptor ligand in metal-to-ligand charge transfer (MLCT) excited states of amide-substituted polypyridyl complexes of RuII and in analogues appended to polystyrene. On the basis of ground-to-excited state shifts in v(C = O) of -31 cm-1 for the amide group in [RuII(bpy)2(bpyCONHEt')]2+ (bpyCONHEt' = 4'-methyl-2,2'-bipyridine-4-carboxamide-Et'; Et' = -CH2CH2BzCH2CH3) (1) and in the derivatized polystyrene abbreviated [PS-[CH2-CH2NHCObpy-RuII(bpy)2]20]40+ (3), the excited-state dipole is directed toward the amide-containing pyridyl group in the polymer side chain. Smaller shifts in v(C = O) of -17 cm-1 in [RuII(4,4'-(CONEt2)2bpy)2-(bpyCONHEt')]2+ (2) and in the derivatized polystyrene abbreviated [PS-[CH2CH2NHCObpy-RuII(4,4'-(CONEt2)2bpy)2]20]40+ (4) indicate that the excited-state dipole is directed toward one of the diamide bpy ligands. The nearly identical results for 1 and 3 and for 2 and 4 show that the molecular and electronic structures of the monomer excited states are largely retained in the polymer samples. These conclusions about dipole orientation in the polymers are potentially of importance in understanding intrastrand energy transfer dynamics. The excited-state dipole in 3 is oriented in the direction of the covalent link to the polymer backbone, and toward nearest neighbors. In 4, it is oriented away from the backbone. 相似文献
74.
Copper is a bioessential element in biology with truly unique chemical characteristics in its two relevant oxidation states +I and +II. Significant progress has been made in recent years in the elucidation of the frequently surprising biochemistry of this trace element. Those advances were especially furthered through mutual stimulation involving results from biochemistry, molecular biology, and medicine on one hand and the synthesis as well as the structural and spectroscopic characterization of low molecular weight model complexes on the other. The most notable features of protein-bound active copper are its almost exclusive function in the metabolism of O2 or N/O compounds (NO, N2O) and its frequent association with oxidizing organic and inorganic radicals such as tyrosyl, semiquinones, superoxide, or nitrosyl. This unique biological role of copper can be rationalized given its chemical and assumed evolutionary background. 相似文献
75.
Nuclear spin-spin coupling constants (1)J(Hg-Hg) in the systems Hg(2)(2+) and Hg(3)(2+) represent the largest coupling constants so far observed in NMR experiments. We have performed a computational study on these ions, on Hg(2)(2+) complexes with 18-crown-6 and 15-crown-5, and on Hg(3)(2+) with solvent molecules and counterions. The results obtained with our recently developed program for the density functional computation of heavy nucleus spin-spin coupling constants are in good agreement with experiments. The data reveal that the bare ions Hg(2)(2+) and Hg(3)(2+) would afford much larger coupling constants than those experimentally observed, with an upper limit of approximately 0.9 MHz for Hg(2)(2+). This limit is much larger than that previously estimated by Hückel theory. It is demonstrated that in solution or due to complexation the experimentally determined values are much smaller than the free ion's coupling constants. With the help of intuitive MO arguments, it is illustrated how the environment strongly reduces the coupling constants in Hg(2)(2+) and Hg(3)(2+). The two-bond coupling constant (2)J(Hg-Hg) in Hg(3)(2+) is also examined. 相似文献
76.
Even if the first protein therapeutics are now for more than 20 years on the market the selection of suitable adsorbents for the preparative downstream processing (DSP) of these biomolecules as well as the method development towards process conditions are still based mainly on 'trial and error'. Therefore, theses processes are not perfectly efficient, but indeed very time consuming and laborious. In this study a novel systematic method is introduced to find a suitable adsorbent (not necessarily the best one) with appropriate separation parameters for a specific separation with reduced effort. Following this strategy, the adsorbents must first be packed into columns under preparative conditions and then characterized completely with regard to, e.g. pressure drop, k'-values, plate heights (HETP curves), selectivity and capacity by using test substances, which are similar in their characteristics (molecular mass, size, charge distribution, hydrophobicity) to the target proteins. With the database once determined, a preselection of most suitable adsorbents including separation parameters is made regarding chromatographic and also economical properties. After this, preparative experiments must be conducted with a reduced number of adsorbents to figure out the individual influence of side components. This approach is demonstrated for the separation of an exemplary industrial protein mixture using cation-exchange chromatography (CEX). Characterization of different weak CEX-adsorbents is illustrated. After comparing these phases with each other, a first preselection and a prediction of suitable adsorbents is made. In the following preparative separation conditions (load, velocity, gradient) are determined for the preparative separations using the database and results of some additional experiments. The final comparison of separation performance in preparative scale confirms this selection and so the applicability of the new method. 相似文献
77.
New antimalarial drugs 总被引:6,自引:0,他引:6
Wiesner J Ortmann R Jomaa H Schlitzer M 《Angewandte Chemie (International ed. in English)》2003,42(43):5274-5293
Approximately 40% of the world population live in areas with the risk of malaria. Each year, 300-500 million people suffer from acute malaria, and 0.5-2.5 million die from the disease. Although malaria has been widely eradicated in many parts of the world, the global number of cases continues to rise. The most important reason for this alarming situation is the rapid spread of malaria parasites that are resistant to antimalarial drugs, especially chloroquine, which is by far the most frequently used. The development of new antimalarial drugs has been neglected since the 1970s owing to the end colonialism, changes in the areas of military engagement, and the restricted market potential. Only in recent years, in part supported by public funding programs, has interest in the development of antimalarial drugs been renewed. New data available from the recently sequenced genome of the malaria parasite Plasmodium falciparum and the application of methods of modern drug design promise to bring significant development in the fight against this disease. 相似文献
78.
Richard M. Kettler Donald A. Palmer David J. Wesolowski 《Journal of solution chemistry》1995,24(1):65-87
The first and second molal dissociation quotients of succinic acid were measured potentiometrically with a hydrogen-electrode, concentration cell. These measurements were carried out from 0 to 225°C over 25° intervals at five ionic strengths ranging from 0.1 to 5.0 molal (NaCl). The dissociation quotients from this and two other studies were combined and treated with empirical equations to yield the following thermodynamic quantities for the first acid dissociation equilibrium at 25°C: log K1a=–4.210±0.003; H
1a
0
=2.9±0.2 kJ-mol–1; S
1a
0
=–71±1 J-mol–1-K–1; and C
p1a
0
=–98±3 J-mol–1-K–1; and for the second acid dissociation equilibrium at 25°C: log K2a=–5.638±0.001; H
2a
0
= –0.5±0.1 kJ-mol–1; S
2a
0
=–109.7±0.4 J-mol–1-K–1; and C
p2a
0
= –215±8 J-mol–1-K–1. 相似文献
79.
C. Kourkoumelis L. K. Resvanis T. A. Filippas E. Fokitis A. M. Chops S. Iwata R. B. Palmer D. C. Rahm P. Rehak I. Stumer C. W. Fabjan T. Fields D. Lissauer I. Mannelli P. Mouzourakis A. Nappi W. J. Willis 《Zeitschrift fur Physik C Particles and Fields》1980,5(2):95-104
The inclusive cross-section for π0 production near 90° inpp collisions at the CERN Intersecting Storage Rings has been studied for thep T range 3<p T <16GeV/c at four different centre-of-mass energies ( \(\sqrt s = 30.6\) , 44.8, 52.7, and 62.8 GeV). In this experiment the two photons from the π0→yy decay were resolved and measured separately forp T values up to 10 GeV/c. Results indicate an agreement with thep T ?8 behaviour for the lower values ofp T and a slower decrease of the cross-section for the higher values ofp T . The high-p T data deviate from the scaling expressionp T ?n F(x T ), which holds for the lowerp T values (p T <8GeV/c). 相似文献
80.
Determination of heavy metal complexes with humic substances by HPLC/ICP-MS coupling using on-line isotope dilution technique 总被引:3,自引:0,他引:3
An isotope dilution mass spectrometric (IDMS) method has been developed for the simultaneous determination of the complexes
of 11 heavy metals (Ag, Cd, Cu, Mo, Ni, Pb, Tl, U, W, Zn and Zr) with humic substances (HS) by coupling HPLC with ICP-MS and
applying the on-line isotope dilution technique. The HPLC separation was carried out with size exclusion chromatography. This
HPLC/ICP-IDMS method was applied to samples from a brown water, ground water, sewage and seepage water as well as for a sample
containing isolated fulvic acids. The total contents of heavy metals and of their complexes were analyzed in these samples
with detection limits in the range of 5–110 ng/L. The analysis of heavy metal/HS complexes from the different waters resulted
in characteristic fingerprints of the distribution pattern of heavy metals in the separated HS fractions. A comparison between
the total heavy metal concentrations and their portions bound to humic substances showed distinct differences for the various
metals. Simultaneous 12C detection was used for the characterization of HS complexes not identified by UV detection and for the determination of
relative DOC concentrations of chromatographic peaks.
Received: 21 February 1997 / Revised: 27 May 1997 / Accepted: 28 May 1997 相似文献