E-Mail Alert

Add your e-mail address to receive forthcoming issues of this journal:

Journal Browser

Journal Browser

Special Issue "Applications of Circular Dichroism"

Quicklinks

A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Physical Chemistry, Theoretical and Computational Chemistry".

Deadline for manuscript submissions: closed (31 January 2012)

Special Issue Editor

Guest Editor
Prof. Dr. David Kliger

Department of Chemistry and Biochemistry; University of California, Santa Cruz, Santa Cruz, CA 95064, USA
E-Mail

Special Issue Information

Dear Colleagues,

Chiroptical phenomena have been known for two centuries.  However, new developments over the past 20 – 30 years have greatly expanded the capability and versatility of chiroptical spectroscopy, as evidenced by the articles in this special issue.

Biot first observed optical rotation, and he and Fresnel studied the phenomenon in the early 1800’s.  In the mid 1800’s Pasteur related the phenomenon to molecular asymmetry.  Since that time optical rotation (OR), and the related phenomenon of circular dichroism (CD), have been used in innumerable studies of molecular structures.

Early studies of chiroptical phenomena, of course, did not have the use of electronic devices that we now take for granted, so they involved measurements of optical rotation using null techniques detected visually. This situation changed as photoelectric light detectors were developed along with electronic devices to record light intensities in the twentieth century. With the advent of fast modulators of light polarization and phase sensitive measurement techniques, it became possible to measure differences in the absorption of left and right circularly polarized light with high sensitivity.  CD spectroscopy then became a more common tool for molecular structure determinations since  CD spectra can more easily be correlated with molecular structure than OR spectra and because instruments capable of producing sensitive measurements of visible and ultraviolet CD spectra, became commercially available.

The more recent developments of the past several decades have again expanded the capabilities of chiroptical spectroscopy by opening up access to spectral regions and higher order optical effects sensitive to additional features of molecular structure, by extending time resolution to the very fast time scales of fundamental molecular processes, and by advancing the theoretical understanding needed to interpret the structural implications of chiroptical spectra. Circularly polarized luminescence spectroscopy has increased the sensitivity of CD measurements of emitting chiral molecules.  Structural determinations have been improved by making CD measurements farther into the UV region and even extending CD measurements into the X-ray and IR regions. IR measurements of CD monitor anisotropies of vibrational transitions and are thus particularly sensitive to local structural features. Similar capabilities have also been introduced with the development of Raman optical activity measurements.  Highly sensitive measurements of local structural features around aromatic moieties have also been made possible with the development of magnetic circular dichroism. Techniques have also been developed to measure CD spectra with nanosecond or even picosecond or femtoseconds time resolution. These new developments, and improved theoretical analyses of CD spectra, have brought new capabilities to this old technique, thus made it useful for new applications.  This issue explores a variety of such new applications of CD spectroscopy.

Prof. Dr. David Kliger
Guest Editors

Keywords

  • chiroptical phenomena
  • circular dichroism
  • magnetic circular dichroism
  • optical activity
  • Raman optical activity
  • vibrational circular dichroism
  • structure determination
  • time-resolved circular dichroism

Published Papers (9 papers)

View options order results:
result details:
Displaying articles 1-9
Export citation of selected articles as:

Research

Jump to: Review

Open AccessArticle First Insights on Organic Cosolvent Effects on FhuA Wildtype and FhuA Δ1-159
Int. J. Mol. Sci. 2012, 13(2), 2459-2471; doi:10.3390/ijms13022459
Received: 6 January 2012 / Revised: 9 February 2012 / Accepted: 13 February 2012 / Published: 22 February 2012
Cited by 7 | PDF Full-text (376 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Circular dichroism (CD) and deconvolution were used to study the structural integrity of a “plugged” and an “open” FhuA transmembrane channel protein in the presence of varied concentrations of tetrahydrofuran (THF), ethanol (EtOH) and chloroform/methanol (C/M). FhuA is an Escherichia coli outer membrane
[...] Read more.
Circular dichroism (CD) and deconvolution were used to study the structural integrity of a “plugged” and an “open” FhuA transmembrane channel protein in the presence of varied concentrations of tetrahydrofuran (THF), ethanol (EtOH) and chloroform/methanol (C/M). FhuA is an Escherichia coli outer membrane protein (78.9 kDa) consisting of 22 β-sheets and an internal globular cork domain which acts as an iron transporter. FhuA and the deletion variant FhuA Δ1-159 showed comparable and remarkable resistance in the presence of THF (≤40 vol%) and EtOH (≤10 vol%). In C/M, significant differences in structural resistance were observed (FhuA stable ≤10 vol%; FhuA Δ1-159 ≤1 vol%). Deconvolution of CD-spectra for FhuA and FhuA Δ1-159 yielded β-sheet contents of 61 % (FhuA) and 58% (FhuA Δ1-159). Interestingly, FhuA and FhuA Δ1-159 had comparable β-sheet contents in the presence and absence of all three organic cosolvents. Additionally, precipitated FhuA and FhuA Δ1-159 (in 40 vol% C/M or 65 vol% THF) redissolved by supplementing the detergent n-octyl-oligo-oxyethylene (oPOE). Full article
(This article belongs to the Special Issue Applications of Circular Dichroism)
Open AccessArticle Nanosecond T-Jump Experiment in Poly(glutamic acid): A Circular Dichroism Study
Int. J. Mol. Sci. 2012, 13(2), 2239-2248; doi:10.3390/ijms13022239
Received: 5 January 2012 / Revised: 2 February 2012 / Accepted: 13 February 2012 / Published: 17 February 2012
Cited by 9 | PDF Full-text (215 KB) | HTML Full-text | XML Full-text
Abstract
Poly(glutamic acid) has been studied with a nanosecond T-jump experiment. A new experimental set-up based on the frequency-quadrupling of an 82 MHz Titanium-Sapphire laser allows rapid CD measurements to be performed. Combining time-resolved absorption and circular dichroism at 204 and 220 nm, we
[...] Read more.
Poly(glutamic acid) has been studied with a nanosecond T-jump experiment. A new experimental set-up based on the frequency-quadrupling of an 82 MHz Titanium-Sapphire laser allows rapid CD measurements to be performed. Combining time-resolved absorption and circular dichroism at 204 and 220 nm, we are able to measure precisely the unfolding relaxation time as well as the helical fraction evolution. We show that only CD at 220 nm is relevant to observe the unfolding of an alpha helix whereas no change is observed for CD at 204 nm. Conversely, both absorptions yield information on the dynamics of the process. Full article
(This article belongs to the Special Issue Applications of Circular Dichroism)
Open AccessArticle 3,3′-Diethylthiatricarbocyanine Iodide: A Highly Sensitive Chiroptical Reporter of DNA Helicity and Sequence
Int. J. Mol. Sci. 2011, 12(11), 8052-8062; doi:10.3390/ijms12118052
Received: 21 October 2011 / Revised: 2 November 2011 / Accepted: 7 November 2011 / Published: 16 November 2011
Cited by 5 | PDF Full-text (1148 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Using UV-vis absorption and circular dichroism (CD) spectroscopies, we explored the binding interactions of 3,3′-diethylthiatricarbocyanine iodide (Cy7) with polynucleotides of different sequences and helicity. CD showed to be a very diagnostic tool giving different spectroscopic chiroptical signatures for all explored DNA
[...] Read more.
Using UV-vis absorption and circular dichroism (CD) spectroscopies, we explored the binding interactions of 3,3′-diethylthiatricarbocyanine iodide (Cy7) with polynucleotides of different sequences and helicity. CD showed to be a very diagnostic tool giving different spectroscopic chiroptical signatures for all explored DNA sequences upon Cy7 binding. Cy7 was able to spectroscopically discriminate between the right handed B-DNA of poly(dG-dC)2 and its left handed Z-DNA counterpart induced by spermine or Co(III)hexamine via nearly opposite induced circular dichroic signal. Full article
(This article belongs to the Special Issue Applications of Circular Dichroism)
Figures

Open AccessArticle Environmental Dependence of Artifact CD Peaks of Chiral Schiff Base 3d-4f Complexes in Soft Mater PMMA Matrix
Int. J. Mol. Sci. 2011, 12(10), 6966-6979; doi:10.3390/ijms12106966
Received: 13 September 2011 / Revised: 10 October 2011 / Accepted: 14 October 2011 / Published: 19 October 2011
Cited by 6 | PDF Full-text (721 KB) | HTML Full-text | XML Full-text
Abstract
Four chiral Schiff base binuclear 3d-4f complexes (NdNi, NdCu, GdNi, and GdCu) have been prepared and characterized by means of electronic and CD spectra, IR spectra, magnetic measurements, and X-ray crystallography (NdNi). A so-called artifact peak of solid state CD spectra, which was
[...] Read more.
Four chiral Schiff base binuclear 3d-4f complexes (NdNi, NdCu, GdNi, and GdCu) have been prepared and characterized by means of electronic and CD spectra, IR spectra, magnetic measurements, and X-ray crystallography (NdNi). A so-called artifact peak of solid state CD spectra, which was characteristic of oriented molecules without free molecular rotation, appeared at about 470 nm. Magnetic data of the complexes in the solid state (powder) and in PMMA cast films or solutions indicated that only GdCu preserved molecular structures in various matrixes of soft maters. For the first time, we have used the changes of intensity of artifact CD peaks to detect properties of environmental (media solid state (KBr pellets), PMMA cast films, concentration dependence of PMMA in acetone solutions, and pure acetone solution) for chiral 3d-4f complexes (GdCu). Rigid matrix keeping anisotropic orientation exhibited a decrease in the intensity of the artifact CD peak toward negative values. The present results suggest that solid state artifact CD peaks can be affected by environmental viscosity of a soft mater matrix. Full article
(This article belongs to the Special Issue Applications of Circular Dichroism)
Open AccessArticle Role of α-Helical Structure in Organic Solvent-Activated Homodimer of Elastase Strain K
Int. J. Mol. Sci. 2011, 12(9), 5797-5814; doi:10.3390/ijms12095797
Received: 18 July 2011 / Revised: 5 August 2011 / Accepted: 11 August 2011 / Published: 9 September 2011
Cited by 4 | PDF Full-text (483 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Recombinant elastase strain K overexpressed from E. coli KRX/pCon2(3) was purified to homogeneity by a combination of hydrophobic interaction chromatography and ion exchange chromatography, with a final yield of 48% and a 25-fold increase in specific activity. The purified protein had exhibited a
[...] Read more.
Recombinant elastase strain K overexpressed from E. coli KRX/pCon2(3) was purified to homogeneity by a combination of hydrophobic interaction chromatography and ion exchange chromatography, with a final yield of 48% and a 25-fold increase in specific activity. The purified protein had exhibited a first ever reported homodimer size of 65 kDa by SDS-PAGE and MALDI-TOF, a size which is totally distinct from that of typically reported 33 kDa monomer from P. aeruginosa. The organic solvent stability experiment had demonstrated a stability pattern which completely opposed the rules laid out in previous reports in which activity stability and enhancement were observed in hydrophilic organic solvents such as DMSO, methanol, ethanol and 1-propanol. The high stability and enhancement of the enzyme in hydrophilic solvents were explained from the view of alteration in secondary structures. Elastinolytic activation and stability were observed in 25 and 50% of methanol, respectively, despite slight reduction in α-helical structure caused upon the addition of the solvent. Further characterization experiments had postulated great stability and enhancement of elastase strain K in broad range of temperatures, pHs, metal ions, surfactants, denaturing agents and substrate specificity, indicating its potential application in detergent formulation. Full article
(This article belongs to the Special Issue Applications of Circular Dichroism)

Review

Jump to: Research

Open AccessReview Conformational Changes in DNA upon Ligand Binding Monitored by Circular Dichroism
Int. J. Mol. Sci. 2012, 13(3), 3394-3413; doi:10.3390/ijms13033394
Received: 21 January 2012 / Revised: 22 February 2012 / Accepted: 24 February 2012 / Published: 12 March 2012
Cited by 45 | PDF Full-text (728 KB) | HTML Full-text | XML Full-text
Abstract
Circular dichroism (CD) spectroscopy is an optical technique that measures the difference in the absorption of left and right circularly polarized light. This technique has been widely employed in the studies of nucleic acids structures and the use of it to monitor conformational
[...] Read more.
Circular dichroism (CD) spectroscopy is an optical technique that measures the difference in the absorption of left and right circularly polarized light. This technique has been widely employed in the studies of nucleic acids structures and the use of it to monitor conformational polymorphism of DNA has grown tremendously in the past few decades. DNA may undergo conformational changes to B-form, A-form, Z-form, quadruplexes, triplexes and other structures as a result of the binding process to different compounds. Here we review the recent CD spectroscopic studies of the induction of DNA conformational changes by different ligands, which includes metal derivative complex of aureolic family drugs, actinomycin D, neomycin, cisplatin, and polyamine. It is clear that CD spectroscopy is extremely sensitive and relatively inexpensive, as compared with other techniques. These studies show that CD spectroscopy is a powerful technique to monitor DNA conformational changes resulting from drug binding and also shows its potential to be a drug-screening platform in the future. Full article
(This article belongs to the Special Issue Applications of Circular Dichroism)
Open AccessReview Probing Kinetic Mechanisms of Protein Function and Folding with Time-Resolved Natural and Magnetic Chiroptical Spectroscopies
Int. J. Mol. Sci. 2012, 13(1), 683-697; doi:10.3390/ijms13010683
Received: 23 December 2011 / Revised: 5 January 2012 / Accepted: 5 January 2012 / Published: 10 January 2012
PDF Full-text (223 KB) | HTML Full-text | XML Full-text
Abstract
Recent and ongoing developments in time-resolved spectroscopy have made it possible to monitor circular dichroism, magnetic circular dichroism, optical rotatory dispersion, and magnetic optical rotatory dispersion with nanosecond time resolution. These techniques have been applied to determine structural changes associated with the function
[...] Read more.
Recent and ongoing developments in time-resolved spectroscopy have made it possible to monitor circular dichroism, magnetic circular dichroism, optical rotatory dispersion, and magnetic optical rotatory dispersion with nanosecond time resolution. These techniques have been applied to determine structural changes associated with the function of several proteins as well as to determine the nature of early events in protein folding. These studies have required new approaches in triggering protein reactions as well as the development of time-resolved techniques for polarization spectroscopies with sufficient time resolution and sensitivity to probe protein structural changes. Full article
(This article belongs to the Special Issue Applications of Circular Dichroism)
Open AccessReview Chiral Vibrational Structures of Proteins at Interfaces Probed by Sum Frequency Generation Spectroscopy
Int. J. Mol. Sci. 2011, 12(12), 9404-9425; doi:10.3390/ijms12129404
Received: 8 November 2011 / Revised: 13 December 2011 / Accepted: 13 December 2011 / Published: 16 December 2011
Cited by 37 | PDF Full-text (963 KB) | HTML Full-text | XML Full-text
Abstract
We review the recent development of chiral sum frequency generation (SFG) spectroscopy and its applications to study chiral vibrational structures at interfaces. This review summarizes observations of chiral SFG signals from various molecular systems and describes the molecular origins of chiral SFG response.
[...] Read more.
We review the recent development of chiral sum frequency generation (SFG) spectroscopy and its applications to study chiral vibrational structures at interfaces. This review summarizes observations of chiral SFG signals from various molecular systems and describes the molecular origins of chiral SFG response. It focuses on the chiral vibrational structures of proteins and presents the chiral SFG spectra of proteins at interfaces in the C-H stretch, amide I, and N-H stretch regions. In particular, a combination of chiral amide I and N-H stretches of the peptide backbone provides highly characteristic vibrational signatures, unique to various secondary structures, which demonstrate the capacity of chiral SFG spectroscopy to distinguish protein secondary structures at interfaces. On the basis of these recent developments, we further discuss the advantages of chiral SFG spectroscopy and its potential application in various fields of science and technology. We conclude that chiral SFG spectroscopy can be a new approach to probe chiral vibrational structures of protein at interfaces, providing structural and dynamic information to study in situ and in real time protein structures and dynamics at interfaces. Full article
(This article belongs to the Special Issue Applications of Circular Dichroism)
Figures

Open AccessReview X-Ray Detected Magnetic Resonance: A Unique Probe of the Precession Dynamics of Orbital Magnetization Components
Int. J. Mol. Sci. 2011, 12(12), 8797-8835; doi:10.3390/ijms12128797
Received: 11 October 2011 / Revised: 12 November 2011 / Accepted: 15 November 2011 / Published: 2 December 2011
Cited by 5 | PDF Full-text (608 KB) | HTML Full-text | XML Full-text
Abstract
X-ray Detected Magnetic Resonance (XDMR) is a novel spectroscopy in which X-ray Magnetic Circular Dichroism (XMCD) is used to probe the resonant precession of local magnetization components in a strong microwave pump field. We review the conceptual bases of XDMR and recast them
[...] Read more.
X-ray Detected Magnetic Resonance (XDMR) is a novel spectroscopy in which X-ray Magnetic Circular Dichroism (XMCD) is used to probe the resonant precession of local magnetization components in a strong microwave pump field. We review the conceptual bases of XDMR and recast them in the general framework of the linear and nonlinear theories of ferromagnetic resonance (FMR). Emphasis is laid on the information content of XDMR spectra which offer a unique opportunity to disentangle the precession dynamics of spin and orbital magnetization components at given absorbing sites. For the sake of illustration, we focus on selected examples in which marked differences were found between FMR and XDMR spectra simultaneously recorded on ferrimagnetically ordered iron garnets. With pumping capabilities extended up to sub-THz frequencies, high-field XDMR should allow us to probe the precession of orbital magnetization components in paramagnetic organometallic complexes with large zero-field splitting. Even more challenging, we suggest that XDMR spectra might be recorded on selected antiferromagnetic crystals for which orbital magnetism is most often ignored in the absence of any supporting experimental evidence. Full article
(This article belongs to the Special Issue Applications of Circular Dichroism)

Journal Contact

MDPI AG
IJMS Editorial Office
St. Alban-Anlage 66, 4052 Basel, Switzerland
ijms@mdpi.com
Tel. +41 61 683 77 34
Fax: +41 61 302 89 18
Editorial Board
Contact Details Submit to IJMS
Back to Top