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Smith BM Lappi SE Brewer SH Dembowy S Belyea J Franzen S 《Langmuir : the ACS journal of surfaces and colloids》2004,20(4):1184-1188
The surface of a germanium internal reflectance element (IRE) was modified to bind 6X-histidine (his)-tagged biomolecules. The step-by-step surface modification was monitored via single-pass attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FT-IR). Initially an adlayer of 7-octenyltrimethoxysilane (7-OTMS) was formed on the Ge crystal through the surface hydroxyl groups, which were produced via ozonolysis of the Ge surface. The vinyl moiety of 7-OTMS was oxidized to a carboxylic acid, which was activated by 1,1'-carbonydiimidazole (CDI) to produce a labile imidazole. The labile imidazole that resulted from the CDI coupling was then displaced by the primary amine of nitrilotriacetic acid (NTA). Nickel sulfate was added to the system, and it coordinated with the three carbonyl groups and the nitrogen on NTA, thus leaving the ability of Ni to coordinate with two adjacent histidine residues. Binding of his-tagged biotin to nickel nitrilotriacetic acid (Ni-NTA) was observed by ATR-FT-IR spectroscopy. The surface modification method presented in this paper had minimal nonspecific binding, the Ni-NTA surface was reusable if stored properly, and complete removal of the organic surface was achievable. 相似文献
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Utko J Przybylak S Jerzykiewicz LB Mierzwicki K Latajka Z Sobota P 《Inorganic chemistry》2003,42(2):267-269
The reaction of [Ti4(OMe)14Cl2] (1) with an excess of AlMe3 gave the cocrystallite [Ti2(mu-OMe)2(mu-Cl)Cl3(thf)3].[Ti2(mu-OMe)3Cl3(thf)3] (2.3) species in a 1:1 ratio. Similar to 2, [Ti2(mu-OEt)2(mu-Cl)Cl3-(thf)3] (4) was obtained in the reaction of an equimolar mixture of TiCl4 and Ti(OEt)4 with Al/AlMe3. The short distance [2.543(1)av A in 2.3 and 2.599(1) A in 4] between "Ti(+3)" atoms, their diamagnetism, and ELF analysis indicate the presence of a Ti-Ti bond. 相似文献
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Development of a capillary electrophoretic method for the analysis of amino acids containing tablets 总被引:6,自引:0,他引:6
Ketosteril is an enteral medicinal product indicated for prevention and therapy in chronic renal insufficiency in connection with a low protein diet. Tablets of Ketosteril contain five essential amino acids like: Lys, His, Thr, Trp, Tyr and another five amino acids in the form of their hydroxy and keto analogues as calcium salts, that are: alpha-ketoleucine, alpha-ketoisoleucine, alpha-ketovaline, alpha-ketophenylalanine and alpha-hydroxymethionine. The composition of Ketosteril tablets is routinely tested with three LC methods. Capillary electrophoretic method seems to be a good alternative for amino acids and their analogues determination in multicomponent pharmaceuticals because of short analysis time and the possibility to assay all components during a single run without any pretreatment. Electrophoresis was performed in 50 microm I.D. fused-silica capillaries with 65 cm distance to the detector. Capillaries were installed in Waters Quanta 4000 electrophoretic equipment with a positive power supply and on-line UV detection at 214 nm. Separations were done in a buffer containing 40 mM Tris and 160 mM boric acid titrated with NaOH to pH 10. The method developed allows the separation of all investigated analytes with an efficiency of n = 230,000 and 20 min analysis time. The method was applied for determination of all components of Ketosteril in commercial tablets. 相似文献
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Doust AB van Stokkum IH Larsen DS Wilk KE Curmi PM van Grondelle R Scholes GD 《The journal of physical chemistry. B》2005,109(29):14219-14226
We report ultrafast femtosecond transient absorption measurements of energy-transfer dynamics for the antenna protein phycoerythrin 545, PE545, isolated from a unicellular cryptophyte Rhodomonas CS24. The phycoerythrobilins are excited at both 485 and 530 nm, and the spectral response is probed between 400 and 700 nm. Room-temperature measurements are contrasted with measurements at 77 K. An evolution-associated difference spectra (EADS) analysis is combined with estimations of bilin spectral positions and energy-transfer rates to obtain a detailed kinetic model for PE545. It is found that sub pulse-width dynamics include relaxation between the exciton states of a chromophore dimer (beta 50/60) located in the core of the protein. Energy transfer from the lowest exciton state of the phycoerythrobilin (PEB) dimer to one of the periphery 15,16-dihydrobiliverdin (DBV) bilins is found to occur on a time scale of 250 fs at room temperature and 960 fs at 77 K. A host of energy-transfer dynamics involving the beta 158, beta 82, and alpha 19 bilins occur on a time scale of 2 ps at room temperature and 3 ps at 77 K. A final energy transfer occurs between the red-most DBV bilins with a time scale estimated to be approximately 30 ps. The role of the centrally located phycoerythrobilin dimer is seen as crucial-spectrally as it expands the cross-section of absorption of the protein; structurally as it sits in the middle of the protein acting as an intermediary trap; and kinetically, as the internal conversion and subsequent red-shift of the excitation is extremely fast. 相似文献
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Adam Sokoowski Jan Chlebicki Kazimiera A. Wilk 《Colloids and surfaces. A, Physicochemical and engineering aspects》1993,80(2-3):243-249
The surface tension isotherms for pure oligooxypropylenated piperidine and morpholine at the aqueous solution—air interface were determined and interpreted. The surface excess concentration, Γ, the surface area per molecule, A, and the standard free energy of adsorption, ΔG°, were calculated according to a new empirical adsorption equation. The standard free energy contribution for the oxypropylene group (PO) in morpholine derivatives,ΔG° (PO) = −3.34 kJ mol−1, is substantially lower than that for the PO group located in the piperidine derivatives, i.e. ΔG° (PO)= −3.12 kJ mol−1. 相似文献
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Wilk A Grajkowski A Bull TE Dixon AM Freedberg DI Beaucage SL 《Journal of the American Chemical Society》2002,124(7):1180-1181
The determination of the absolute configuration of deoxyribonucleoside cyclic N-acylphosphoramidites at phosphorus toward the synthesis of P-stereodifined phosphorothioated oligodeoxyribonucleotides is easily accomplished with computer-assisted molecular modeling and M-GOESY NMR spectroscopy. Specifically, computer-modeling diasteromeric phosphoramidite 3 has identifed a proximal (2.55 A) through-space interaction between benzylic H-5 and sugar H-2' ', which can predictably be detected by M-GOESY NMR in SP-3 but not in RP-3 because of being too distant (5.85 A). Consistent with computer-assisted modeling predictions, M-GOESY NMR spectra of SP-3 and RP-3 revealed NOE signals generated from nuclei near the selectively excited H-2' ' that are common to both SP-3 and RP-3, namely those of H-2', H-4', H-3', and H-1'. In addition, a diagnostic NOE signal at 5.5 ppm (benzylic H-5) is, as predicted, only detected in SP-3 and thus provides an unequivocal assessment of the configuration of the diastereomer at phosphorus. M-GOESY NMR data also confirm that the condensation of deoxyribonucleoside cyclic N-acylphosphoramidites with base-activated nucleosidic or nucleotidic 5'-hydroxyls proceeds via a single nucleophilic event. 相似文献
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Encouraging results obtained for modulation of gene expression by antisense oligonucleotides and their analogues have kindled hopes for a new generation of therapeutics against viral infections, cancer, and many other diseases. Among such analogues, oligo(nucleoside phosphorothioate)s (Oligo-S) have generally shown the highest efficacy in inhibiting the biosynthesis of “unwanted” proteins. The first clinical trials of antisense agents are now in progress using Oligo-S against genital warts and acute myeloid leukemia, and tests of Oligo-S against AIDS should follow soon. Nevertheless, their mechanism of action, internalization, cellular trafficking, subcellular localization, and interaction with cellular proteins is still poorly understood. It is assumed a priori that application involves rapid and efficient molecular recognition of target RNA by Oligo-S; however, the effects of the chirality of Oligo-S have so far been unappreciated, because Oligo-S has not yet been synthesized with stereocontrol. Indeed, the diastereomeric composition of Oligo-S has never been determined, primarily because of the lack of appropriate analytical methods. Since each of the diastereomers is a stereochemically unique chemical entity, questions arise as to which diastereomer is responsible for an observed biological response, including positive (curative) or possibly negative (toxic) side effects. In this review we intend provide a perhaps somewhat speculative assessment of the problems associated with the stereo-controlled synthesis of Oligo-S and to discuss the state-of-the-art in this field including strategies that may lead to Oligo-S of predetermined chirality. This article is not intended to discourage researchers from further studies of dia-steromeric mixtures of Oligo-S as potential pharmaceuticals. Throughout the history of medicinal chemistry numerous useful medicines were discovered, developed, and employed without the detailed knowledge of their structure. Indeed, the composition of the vaccines discovered by Pasteur is a subject of vigorous study still today. 相似文献