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21.
Synthetic erythropoietic proteins: tuning biological performance by site-specific polymer attachment
Chen SY Cressman S Mao F Shao H Low DW Beilan HS Cagle EN Carnevali M Gueriguian V Keogh PJ Porter H Stratton SM Wiedeke MC Savatski L Adamson JW Bozzini CE Kung A Kent SB Bradburne JA Kochendoerfer GG 《Chemistry & biology》2005,12(3):371-383
Chemical synthesis in combination with precision polymer modification allows the systematic exploration of the effect of protein properties, such as charge and hydrodynamic radius, on potency using defined, homogeneous conjugates. A series of polymer-modified synthetic erythropoiesis proteins were constructed that had a polypeptide chain similar to the amino acid sequence of human erythropoietin but differed significantly in the number and type of attached polymers. The analogs differed in charge from +5 to -26 at neutral pH and varied in molecular weight from 30 to 54 kDa. All were active in an in vitro cell proliferation assay. However, in vivo potency was found to be strongly dependent on overall charge and size. The trends observed in this study may serve as starting points for the construction of more potent synthetic EPO analogs in the future. 相似文献
22.
In this paper we suggest to consider the spatial distribution of the Born-Oppenheimer nonadiabatic coupling terms as fields which are created by sources, located at degeneracy points, and which can be derived using the ordinary mathematical tools of field theory. It is shown that the curl-divergence equations as formed within a given Hilbert space [M. Baer, Chem. Phys. Lett. 35, 112 (1975)] can be converted into a set of inhomogeneous coupled Poisson equations which are solved for a given set of boundary conditions. The method is applied to the three-state Hilbert subspace of the H(3) system. The numerical results are compared with ab initio calculations for which a very encouraging fit is found. 相似文献
23.
Procedures are proposed for the determination of phosphorus and silicon in the ppM range, by extraction of phosphomolybdic and silicomolybdic acids with organic solvent, decomposition of the complex and spectrophotometric determination of its molybdenum content. 相似文献
24.
Pablo Wessig Philipp Wettstein Bernd Giese Markus Neuburger Margaretha Zehnder 《Helvetica chimica acta》1994,77(3):829-837
The chiral N-(2-benzoylethyl)-N-tosylglycinamides 1a-c were prepared from the C2-symmetric pyrrolidines 5a-c . Irradiation of these ketones 1a-c gave cis-3-hydroxyprolinamides 10-12 in moderate to good yields (Scheme 3). The de of the photocyclizations depended on the size of the substituents in positions C(2) and C(5) of the chiral pyrrolidine auxiliaries. In addition, the de varied with the reaction temperature, allowing the determination of activation-parameter differences. The structure of products 10-12 were established by NMR and X-ray analyses. 相似文献
25.
The addition of possible oxidation and/or isomerization products (butadiene, water, isomeric n-butenes) resulted in neither promotion nor inhibition in the oxidative dehydrogenation of n-butenes over tin-antimony mixed oxide catalysts. On the basis of these and other information on the influence of products an interpretation has been given to complete the reaction mechanism more realistic than those based on previous experimental results.
(, ) ( -) , . , , .相似文献
26.
Haiss W Raisch P Schiffrin DJ Bitsch L Nichols RJ 《Faraday discussions》2002,(121):167-80; discussion 229-51
In situ FTIR spectroscopy has been used in the attenuated total reflectance (ATR) mode to investigate the surface chemistry of etching Si(100) surfaces in aqueous KOH. The effect of solution concentration and electrode potential on the Si-H vibrations has been explored and the experimental results compared with density functional theory calculations. In addition. the kinetics of surface passivation of n-Si(100) has been investigated using FTIR spectroscopy. 相似文献
27.
Increased structural complexity leads to higher activity: peptides as efficient and versatile catalysts for asymmetric aldol reactions 总被引:3,自引:0,他引:3
[reaction: see text] Peptides containing a secondary amine and a carboxylic acid in a specific orientation to each other are presented as highly efficient catalysts for asymmetric aldol reactions: (1) their activity is considerably higher compared to that of proline, and (2) the enantioselectivity of the peptidic catalysts can be changed from (R)- to (S)-selectivity by simple modifications of the secondary structure. 相似文献
28.
29.
E. Kuzmann Z. Homonnay A. Vértes I. Halász J. Bánkuti I. Kirschner 《Journal of Radioanalytical and Nuclear Chemistry》1989,135(5):373-380
151Eu,119Sn and57Fe Mössbauer spectroscopy was used to study high Tc superconductors. Mössbauer spectra of Sn substituted EuBa2Cu3O7–y, YBa2Cu3O7–y and TlBaCaCuO4.5+y as well as of Fe Substituted TlBaCaCuO4.5+y were compared. The Sn and Fe ions replace the regular Cu positions in the YBa2Cu3O7–y and in TlBaCaCuO4.5+y materials, fespectively, while the localization of tin atoms in both the119Sn doped EuBa2Cu3O7–y and TlBaCaCuO4.5+y superconductors is different from that of previous cases. Up to our knowledge, this is the first publication on a Mössbauer study of a Tl-containing superconductor. 相似文献
30.
M. Jayakannan Paul A. Van Hal Ren A. J. Janssen 《Journal of polymer science. Part A, Polymer chemistry》2002,40(14):2360-2372
Novel alternating conjugated copolymers ( P1–P6 ) consisting of an electron‐deficient benzothiadiazole and a variety of electron‐rich thiophene‐arene‐thiophene units were synthesized by palladium‐catalyzed polycondensations (Stille and Suzuki reactions), aiming at processable materials with a reduced optical band gap. The structures of P1–P6 were confirmed by 1H NMR and 13C NMR, and their molecular weights were determined by size exclusion chromatography. In the Suzuki polycondensation, the role of the catalyst [Pd(PPh3)4 and Pd(OAc)2] on the resulting molecular weight was investigated. Pd(OAc)2 enhances the molecular weight of the polymers for both thiophene and phenylene bis‐boronic esters as compared with Pd(PPh3)4. The optical properties of the polymers were examined in solution and the solid state. The polymers with n‐octyl substituents ( P1 , P4 , P5 , and P6 ) on the thiophene rings possessed less‐planar structures as a result of torsional steric hindrance, and their absorption spectra appeared blueshifted as compared with their unsubstituted analogues ( P2 and P3 ). The electrochemical properties of the polymers were studied using cyclic voltammetry. Although the alkyl substitution affects the oxidation potential, only marginal differences in the reduction potentials were observed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2360–2372, 2002 相似文献