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Rapid scanning spectroscopy stopped flow

Problem 8.28 Consider styrene polymerization by triflic (trifluoroethanesul-fonic) acid in 1,2-dichloroethane at 20°C where is 4.2x10 mol/L (23]. For experiments performed (using stopped-flow rapid scan spectroscopy) at a styrene concentration of 0.397 M and acid concentration of 4.7x10 M at 20°C, the maximum concentration of cationic ends (both free ions and ion pairs) was found [23] to be 1.4x10 M, indicating that the initiator efficiency is 0.030. At 20°C, kf / is reported [23] to be 12. [Pg.729]

Optical Spectroscopy General principles and overview, 246, 13 absorption and circular dichroism spectroscopy of nucleic acid duplexes and triplexes, 246, 19 circular dichroism, 246, 34 bioinorganic spectroscopy, 246, 71 magnetic circular dichroism, 246, 110 low-temperature spectroscopy, 246, 131 rapid-scanning ultraviolet/visible spectroscopy applied in stopped-flow studies, 246, 168 transient absorption spectroscopy in the study of processes and dynamics in biology, 246, 201 hole burning spectroscopy and physics of proteins, 246, 226 ultraviolet/visible spectroelectrochemistry of redox proteins, 246, 701 diode array detection in liquid chromatography, 246, 749. [Pg.6]

The chromophoric pyridoxal phosphate coenzyme provides a useful spectrophotometric probe of catalytic events and of conformational changes that occur at the pyridoxal phosphate site of the P subunit and of the aiPi complex. Tryptophan synthase belongs to a class of pyridoxal phosphate enzymes that catalyze /3-replacement and / -elimination reactions.3 The reactions proceed through a series of pyridoxal phosphate-substrate intermediates (Fig. 7.6) that have characteristic spectral properties. Steady-state and rapid kinetic studies of the P subunit and of the aiPi complex in solution have demonstrated the formation and disappearance of these intermediates.73-90 Fig. 7.7 illustrates the use of rapid-scanning stopped-flow UV-visible spectroscopy to investigate the effects of single amino acid substitutions in the a subunit on the rate of reactions of L-serine at the active site of the P subunit.89 Formation of enzyme-substrate intermediates has also been observed with the 012P2 complex in the crystalline state.91 ... [Pg.133]

Silverman s studies on mechanism based MAO inactivation have provided overwhelming support for the role of electron transfer in the MAO catalyzed dealkylation of amines. It must be mentioned however that spectroscopic attempts for detecting the radical ion intermediates have hitherto been unsuccessful. Yasanobu and coworkers could not find EPR spectral evidence for radical intermediates in MAO-catalyzed oxidation of benzylamine [205]. Miller et al. failed to observe the flavin semiquinone or an amine-flavin adduct in rapid-scan-stopped flow spectroscopy [206]. The only time-dependent absorption change observed in this study was the bleaching of the oxidized flavin. Furthermore, no influence of a magnetic field up to 6500 G was observed on the rate of MAO B reduction. The reaction rates of systems with kinetically significant radical pair intermediates are known to be altered... [Pg.1072]

Applications of Rapid-Scanning, Stopped-Flow (RSSF) UV-Visible Spectroscopy to the Study of Biological Systems... [Pg.191]

APPLICATIONS OF RAPID-SCANNING, STOPPED-FLOW (RSSF) UV-VISIBLE SPECTROSCOPY TO THE STUDY OF BIOLOGICAL SYSTEMS... [Pg.193]

Dunn, Michael, Rapid-Scanning Stopped-Flow Spectroscopy. 37 191... [Pg.302]

Rapid-Scanning Stopped-Flow Spectroscopy Peter S. Brzovic and... [Pg.333]

Rapid-Scanning Ultraviolet/Visible Spectroscopy Applied in Stopped-Flow Studies... [Pg.168]

If the investigation of the chemical mechanisms of enzyme-catalyzed reactions is to be successful, then detection and identification of transient intermediates along the reaction path are essential components. The application of rapid-scanning stopped-flow (RSSF) UV/visible spectroscopy to the study of enzyme catalysis may be of considerable significance in certain instances as a tool for both the direct detection and the identification of transient chemical intermediates. [Pg.168]

Significant Applications Use of Rapid-Scanning Stopped-Flow Spectroscopy to Investigate Enzyme Structure-Function Relationships... [Pg.180]

Reback, M.L., Roske, C.W., Bitterwolf, T.E., Griffiths, P.R. and Manning, C.J. (2010) Stopped-flow ultra-rapid-scanning Fourier transform infrared spectroscopy on the millisecond time scale. Appl. Spectrosc., 64,907-911. [Pg.303]


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See also in sourсe #XX -- [ Pg.191 ]




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