Biological applications of resonance Raman spectroscopy: haem proteins

Resonance Raman spectroscopy involves laser excitation within an absorption band of the sample. Certain vibrational modes, those which couple to the electronic transition, exhibit greatly increased Raman scattering in the resulting spectrum. Sensitivity approaches that of absorption spectrophotometry, while the high resolution characteristic of vibrational spectroscopy is preserved, even in solution at room temperature. If the resonant electronic transition is associated with a site of biological activity, then the technique offers a sensitive probe for structural features of the site. Haem proteins afford particularly informative resonance Raman spectra, with a rich assortment of porphyrin ring vibrations, which can be classified and analysed via their symmetry properties. Certain of these frequencies are sensitive to the structural concomitants of spin- and oxidation-state changes of the haem group. These can be used to monitor the structural consequences of ligation or electron transfer in haem proteins.

1999 ◽  
Vol 19 (1-4) ◽  
pp. 71-74 ◽  
Author(s):  
Xuming Zheng ◽  
David Lee Phillips

We have obtained A-band absorption resonance Raman spectra of 1-chloro-2- iodoethane in cyclohexane solution. We have done preliminary time-dependent wavepacket calculations to simulate the resonance Raman intensities and absorption spectrum in order to learn more about the short-time photodissociation dynamics. We compare our preliminary results for 1-chloro-2-iodoethane with previous resonance Raman results for iodoethane and find that there appears to be more motion along non- C—I stretch modes for 1-chloro-2-iodoethane than for iodoethane. This is consistent with results of TOF photofragment spectroscopy experiments which indicate much more internal excitation of the photoproducts from 1-chloro-2-iodoethane photodissociation than the photoproducts from iodoethane photodissociation.


1999 ◽  
Vol 19 (1-4) ◽  
pp. 311-316 ◽  
Author(s):  
Susan M. Tavender ◽  
Steven A. Johnson ◽  
Daniel Balsom ◽  
Anthony W. Parker ◽  
Roger H. Bisby

The carbonate radical (Co3−·) is of biological significance acting as an intermediate in free radical-mediated damage and is capable of oxidising amino acids and proteins. In order to distinguish between the four possible structures of Co3−·, nanosecond timeresolved resonance Raman (TR3) experiments were undertaken. Photolysis of persulphate at 250 nm generated the So4−· radical which then oxidised sodium carbonate. Resonance Raman spectra of the resulting Co3−· radical were obtained using a probe wavelength of 620 nm. Point group theory calculations and interpretation of the TR3 spectra suggest that the radical has C2v molecular symmetry.


2021 ◽  
Vol 50 (6) ◽  
pp. 2233-2242
Author(s):  
Elizabeth S. Carlton ◽  
Joshua J. Sutton ◽  
Ariel G. Gale ◽  
George C. Shields ◽  
Keith C. Gordon ◽  
...  

Augmented with TDDFT, solvatochromism and resonance Raman spectroscopy of RCp2Ti(C2Fc)2 complexes are consistent with the characterization of the lowest-energy electronic transition as a delocalized ethynylferrocene to TiIV charge transfer.


2012 ◽  
Vol 35 (1) ◽  
pp. 11-18 ◽  
Author(s):  
Magdalena Laskowska ◽  
Łukasz Laskowski ◽  
Kazimierz Dzilinski

Abstract Mesoporous silica SBA-15 functionalized by (1,4,8,11-tetraazacyclotetradecane) cyclam groups containing nickel ions (Ni-cyclam) was synthesized by two different approaches, and investigated by resonance Raman spectroscopy. Vibrational features of organometallic moleculess are analyzed for (Ni-cyclam) groups grafted in the silica pores. An assignment of bands in resonance Raman spectra was done to monitor the structure and properties of the mesoporous silica material with regard to the methods of synthesis used in this study. It was shown, that Raman scattering can be useful for probing of functionalization's efficiency of mesoporous silica. On the base of the resonance investigation: Raman and EPR spectroscopy, distribution of the functional groups inside pores can be determined. In the present article the Raman spectroscopy is treat as a complementary research to EPR investigation. It was shown that a clustering of the active groups alter significantly the resonance Raman spectra through broadening and shifts of the corresponding bands in comparison with separated molecules. Results obtained from the analysis of the resonance Raman spectra indicate significant differences between the samples prepared by the two procedures. The discussion of the Raman results was referred to EPR results, and on the base of this authors concluded about correct achievement of the functionalization.


1980 ◽  
Vol 35 (10) ◽  
pp. 1272-1273 ◽  
Author(s):  
Robin J. H. Clark ◽  
Mohamedally Kurmoo ◽  
K. D. Buse ◽  
H. J. Keller

Abstract The partially oxidized cis-Pt(NH3)2(SCN)2I has been studied by resonance Raman spectroscopy. A progression in the symmetric I-PtIV-I vibration (v1 = 120.1 cm-1), reaching as far as 8 v1, has been observed. The compound Pt(NH3)2(SCN)2I could be identified as a mixed valence solid with neutral, linear PtII···I-PtIV chains.


2002 ◽  
Vol 06 (04) ◽  
pp. 301-302 ◽  
Author(s):  
Teizo Kitagawa

The main topics in resonance Raman spectroscopy presented at ICPP-2 in Kyoto are briefly discussed. These include: (i) coherent spectroscopy and low frequency vibrations of ligand-photodissociated heme proteins, (ii) vibrational relaxation revealed by time-resolved anti-Stokes Raman spectroscopy, (iii) electron transfer in porphyrin arrays, (iv) vibrational assignments of tetraazaporphyrins and (v) resonance Raman spectra of an NO storing protein, nitrophorin.


1979 ◽  
Vol 34 (7) ◽  
pp. 986-988 ◽  
Author(s):  
G. C. Papavassiliou ◽  
T. Theophanides

Abstract The partially oxidized form of Magnus' salt has been studied by resonance Raman spectroscopy (RRS) and it has been established that the oxidized form is a chlorine bridged chain polymer. The spectra show intense progressions, υν, where ν, is the symmetric ···X-Pt(IV)-X··· stretching mode, and v the quantum number


Holzforschung ◽  
2004 ◽  
Vol 58 (1) ◽  
pp. 82-90 ◽  
Author(s):  
A.-M. Saariaho ◽  
A.-S. Jääskelinen ◽  
P. Matousek ◽  
M. Towrie ◽  
A. W. Parker ◽  
...  

Abstract Raman spectroscopy using 400 nm excitation was successfully applied to chemical pulp samples and the fluorescence background that usually limits the application of this method to such samples was effectively suppressed. This enabled the detection of much weaker Raman bands from the pulps. The rejection ratio of the fluorescence background to Raman scattering was estimated to be about 250. The resonance Raman spectra of peroxide bleached chemical pulps had chromophoric lignin bands at 1605 and 1655 cm−1, whereas the chlorine dioxide bleached pulps had only the aromatic band at 1605 cm−1. The square root of the aromatic chromophore band relative to cellulose band correlated linearly with the brightness which is in accordance with the Kubelka-Munk theory. This correlation indicated that the resonance enhanced Raman bands were mainly due to chromophoric lignin structures. Chlorine dioxide and peroxide bleached pulps gave different correlations to brightness, which was an indication of different kinds of chromophores in these pulps. The intensity of the aromatic band relative to the cellulose band was about 20 times higher with the ultraviolet (257 nm) than with the visible (400 nm) excitation. This clearly illustrated the importance of working with different excitation wavelengths. On one hand the UV excitation is more sensitive towards aromatic residual lignin in pulp, and on the other hand the visible excitation enables the selective detection of chromophoric lignin structures.


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