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81.
Young-a Lee Sang Myung jung Shin Won kang Ok-sang Jung 《Transition Metal Chemistry》2004,29(7):710-713
A facile procedure for synthesizing the mono(hydroxo)tris(carboxylato)platinum(IV) species has been achieved. The reaction of [PtII(OH)2(dmpda)] (dmpda=2,2-dimethyl-1,3-propanediamine) with a 30% aqueous solution of H2O2 in the presence of a carboxylic acid produces a stable [PtIV(OOCR)3(OH)(dmpda)] (R=Me, Et) complex in high yield. The crystal structures of [PtIV(OOCMe)3(OH)(dmpda)] . H2O (triclinic P1 bar, a=8.761(2) Å, b=9.245(3) Å, c=10.659(2) Å, =106.25(2)°, =93.90(2)°, =98.92(2)°, V=813.1(3) Å3, Z=2, R= 0.0474) and [PtIV(OOCEt)3(OH)(dmpda)] (monoclinic P21/c, a=12.777(4) Å, b=10.514(2) Å, c=14.971(3) Å, =107.40(2)°, V=1919.2(8) Å3, Z=4, R=0.0611) show that the hydroxyl group has been selectively positioned at an axial site. The intramolecular hydrogen bond between the OH and C=O moiety exists (O(H)...=C, 2.83 Å for [PtIV(OOCMe)3(OH)(dmpda)] · H2O; 2.72 Å for [PtIV(OOCEt)3(OH)(dmpda)]. Formation of the axial-mono(hydroxo)tris(carboxylato)platinum(IV) species may be ascribed to a combination of `reactive-equatorial effects' with `cis-addition' in the carboxylic acid. 相似文献
82.
[reaction: see text] A new recyclable supported catalyst system for orthoalkylation was devised using a self-assembly consisting of the barbiturate and 2,4,6-triaminopyrimidine H-bonding motifs. At high temperature, the system is completely homogeneous so as to give an efficient catalytic activity, while it is heterogenized at room temperature to form an insoluble solid phase for the easy recovery of the catalyst after the reaction. 相似文献
83.
A synthetic strategy for the preparation of cyclic peptide mimetics based on SET-promoted photocyclization processes 总被引:2,自引:0,他引:2
Yoon UC Jin YX Oh SW Park CH Park JH Campana CF Cai X Duesler EN Mariano PS 《Journal of the American Chemical Society》2003,125(35):10664-10671
A novel method for the synthesis of cyclic peptide analogues has been developed. The general approach relies on the use of SET-promoted photocyclization reactions of peptides that contain N-terminal phthalimides as light absorbing electron acceptor moieties and C-terminal alpha-amidosilane or alpha-amidocarboxylate centers. Prototypical substrates are prepared by coupling preformed peptides with the acid chloride of N-phthalimidoglycine. Irradiation of these substrates results in the generation of cyclic peptide analogues in modest to good yields. The chemical efficiencies of these processes are not significantly affected by (1) the lengths of the peptide chains separating the phthalimide and alpha-amidosilane or alpha-amidocarboxylate centers and (2) the nature of the penultimate cation radical alpha-heterolytic fragmentation process (i.e., desilylation vs decarboxylation). An evaluation of the effects of N-alkyl substitution on the amide residues in the peptide chain showed that N-alkyl substitution does not have a major impact on the efficiencies of the photocyclization reactions but that it profoundly increases the stability of the cyclic peptide. 相似文献
84.
Lee JS Kim DH Liu KH Oh TK Lee CH 《Rapid communications in mass spectrometry : RCM》2005,19(23):3539-3548
Searchable MS/MS spectra libraries, constructed using the results of liquid chromatography coupled with electrospray ionization (ESI) tandem mass spectrometry (LC/MS/MS) with data-dependent acquisition on an ion trap mass spectrometer, are presented with regard to the identification and confirmation of a variety of closely related flavonoids in a set of biological samples. Flavonoids were found to exhibit a maximum amount of structurally specific MS/MS spectra at 45% of normalized collision energy on the instrument used, without wideband activation. These MS/MS spectra were then searched automatically against a 297-substance MS/MS library that contains many previously acquired spectra of standard flavonoids. The possible applications of this powerful technique to biological samples are also discussed. Daidzein and genistein were identified through the MS/MS spectra library while searching through LC/MS/MS data for plant and microbial extracts. Moreover, these compounds proved completely distinguishable from other flavonoids of closely related structures in the MS/MS spectra library, using the NIST MS search program. The applicability of the library-searchable spectra at low concentrations was demonstrated by successful identification of daidzein and genistein at 0.05 and 0.5 microg/mL, respectively. 相似文献
85.
Seung‐Chul Choi Jaejung Ko Sang Ook Kang Won‐Sik Han Ki‐Young Choi 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(3):m85-m87
The copper(II) ion in the syn–anti carboxylate‐bridged one‐dimensional zigzag chain title complex, {[Cu(C16H18N3O2)]ClO4}n, exhibits a distorted trigonal–bipyramidal environment. Two N atoms and one carboxylate O atom of the ligand form the basal plane, while the axial positions are filled by an N atom of the ligand and one O atom belonging to the carboxylate group of an adjacent molecule. The crystal packing is enhanced by C—H⋯O(perchlorate) hydrogen bonds. 相似文献
86.
A sequential injection analysis (SIA) system was developed to monitor the concentration of l-cysteine in biological processes on-line. It is based on the redox reaction of l-cysteine with iron(III) in the presence of 1,10-phenanthroline (phen) and the detection of the red-iron(II)-phen complex with a spectrophotometry. The system was fully automated using software written in the LabVIEW™ development environment. A number of system variables such as the flow rate of the carrier buffer solution, the volume ratio of the sample to the reagents, and the reaction coil length, etc., were evaluated to increase the sensitivity and performance of the SIA system. Under partially optimized operating conditions the performance of the SIA system was linear up to a concentration of l-cysteine of 1 mM (R2 = 0.998) with a detection limit of 0.005 mM and a sample frequency of 15 hr−1. The SIA system was employed to monitor the concentration of l-cysteine on-line in a continuously stirred reactor and a fermentation process of Saccharomyces cerevisiae. The on-line monitored data were in good agreement with the off-line data measured by a HPLC with a fluorescence detector (n = 15, R2 = 09899). 相似文献
87.
Xanthine Sensors Based on Anodic and Cathodic Detection of Enzymatically Generated Hydrogen Peroxide
A xanthine biosensor was fabricated by the covalent immobilization of xanthine oxidase (XO) onto a functionalized conducting polymer (Poly‐5, 2′: 5′, 2″‐terthiophine‐3‐carboxylic acid), poly‐TTCA through the formation of amide bond between carboxylic acid groups of poly‐TTCA and amine groups of enzyme. The immobilization of XO onto the conducting polymer (XO/poly‐TTCA) was characterized using cyclic voltammetry, quartz crystal microbalance (QCM), and X‐ray photoelectron spectroscopy (XPS) techniques. The direct electron transfer of the immobilized XO at poly‐TTCA was found to be quasireversible and the electron transfer rate constant was determined to be 0.73 s?1. The biosensor efficiently detected xanthine through oxidation at +0.35 V and reduction at ?0.25 V (versus Ag/AgCl) of enzymatically generated hydrogen peroxide. Various experimental parameters, such as pH, temperature, and applied potential were optimized. The linear dynamic ranges of anodic and cathodic detections of xanthine were between 5.0×10?6?1.0×10?4 M and 5.0×10?7 to 1.0×10?4 M, respectively. The detection limits were determined to be of 1.0×10?6 M and 9.0×10?8 M with anodic and cathodic processes, respectively. The applicability of the biosensor was tested by detecting xanthine in blood serum and urine real samples. 相似文献
88.
Ahn YH Park EJ Cho K Kim JY Ha SH Ryu SH Yoo JS 《Rapid communications in mass spectrometry : RCM》2004,18(20):2495-2501
The enrichment of phosphopeptides using immobilized metal ion affinity chromatography (IMAC) and subsequent mass spectrometric analysis is a powerful protocol for detecting phosphopeptides and analyzing their phosphorylation state. However, nonspecific binding peptides, such as acidic, nonphosphorylated peptides, often coelute and make analyses of mass spectra difficult. This study used a partial chemical tagging reaction of a phosphopeptide mixture, enriched by IMAC and contaminated with nonspecific binding peptides, following a modified beta-elimination/Michael addition method, and dynamic mass analysis of the resulting peptide pool. Mercaptoethanol was used as a chemical tag and nitrilotriacetic acid (NTA) immobilized on Sepharose beads was used for IMAC enrichment. The time-dependent dynamic mass analysis of the partially tagged reaction mixture detected intact phosphopeptides and their mercaptoethanol-tagged derivatives simultaneously by their mass difference (-20 Da for each phosphorylation site). The number of new peaks appearing with the mass shift gave the number of multiply phosphorylated sites in a phosphopeptide. Therefore, this partial chemical tagging/dynamic mass analysis method can be a powerful tool for rapid and efficient phosphopeptide identification and analysis of the phosphorylation state concurrently using only MS analysis data. 相似文献
89.
End-labeled free-solution electrophoresis of DNA 总被引:1,自引:0,他引:1
Meagher RJ Won JI McCormick LC Nedelcu S Bertrand MM Bertram JL Drouin G Barron AE Slater GW 《Electrophoresis》2005,26(2):331-350
DNA is a free-draining polymer. This subtle but "unfortunate" property of highly charged polyelectrolytes makes it impossible to separate nucleic acids by free-flow electrophoresis. This is why one must typically use a sieving matrix, such as a gel or an entangled polymer solution, in order to obtain some electrophoretic size separation. An alternative approach consists of breaking the charge to friction balance of free-draining DNA molecules. This can be achieved by labeling the DNA with a large, uncharged molecule (essentially a hydrodynamic parachute, which we also call a drag-tag) prior to electrophoresis; the resulting methodology is called end-labeled free-solution electrophoresis (ELFSE). In this article, we review the development of ELFSE over the last decade. In particular, we examine the theoretical concepts used to predict the ultimate performance of ELFSE for single-stranded (ssDNA) sequencing, the experimental results showing that ELFSE can indeed overcome the free-draining issue raised above, and the technological advances that are needed to speed the development of competitive ELFSE-based sequencing and separation technologies. Finally, we also review the reverse process, called free-solution conjugate electrophoresis (FSCE), wherein uncharged polymers of different sizes can be analyzed using a short DNA molecule as an electrophoretic engine. 相似文献
90.
Won Young Jung Seung Hee Baek Seong Soo Park Gun-Dae Lee Euh Duck Jeong Hyun Gyu Kim Seong-Soo Hong 《Reaction Kinetics and Catalysis Letters》2007,91(2):233-240
The nanosized titania and TiO2/SiO2 particles were prepared by the microwave-hydrothermal method. The effect of physical properties TTIP/TEOS ratio and calcination
temperature has been investigated. The major phase of the pure TiO2 particle is of the anatase structure, and a rutile peak was observed above 800°C. In TiO2/SiO2 particles, however, no significant rutile phase was observed, although the calcination temperature was 900°C. No peaks for
the silica crystal phase were observed at either silica/titania ratio. The crystallite size of TiO2/SiO2 particles decreases as compared to pure TiO2 at high calcination temperatures. The TiO2/SiO2 particles show higher activity on the photocatalytic decomposition of orange II as compared to pure TiO2 particles. 相似文献