scholarly journals Platform- and label-free detection of lead ions in environmental and laboratory samples using G-quadraplex probes by circular dichroism spectroscopy

2020 ◽  
Vol 10 (1) ◽  
Author(s):  
Raeyeong Kim ◽  
Young-Sang Youn ◽  
Misook Kang ◽  
Eunjoo Kim
Keyword(s):  
Circular Dichroism ◽  
Treatment Plant ◽  
Polarized Light ◽  
Cd Spectroscopy ◽  
Label Free ◽  
Related Sequence ◽  
Circularly Polarized Light ◽  
Effluent Sample ◽  
Label Free Detection ◽  
Circular Dichroïsm

AbstractGuanine-rich quadruplex (G-QD) are formed by conversion of nucleotides with specific sequences by stabilization of positively charged K+ or Na+. These G-QD structures differentially absorb two-directional (right- and left-handed) circularly polarized light, which can discriminate the parallel or anti-parallel structures of G-QDs. In this study, G-QDs stabilized by Pb2+ were analyzed by a circular dichroism (CD) spectroscopy to determine Pb2+ concentration in water samples. Thrombin aptamer (TBA), PS2.M, human telomeric DNA (HTG), AGRO 100, and telomeric related sequence (T2) were studied to verify their applicability as probes for platform- and label-free detection of Pb2+ in environmental as well as laboratory samples. Among these nucleotides, TBA and PS2.M exhibited higher binding constants for Pb2+, 1.20–2.04 × 106/M at and 4.58 × 104–1.09 × 105/M at 100 micromolar and 100 mM K+ concentration, respectively. They also exhibited excellent selectivity for Pb2+ than for Al3+, Cu2+, Ni2+, Fe3+, Co2+, and Cr2+. When Pb2+ was spiked into an effluent sample from a wastewater treatment plant (WWTP), its existence was detected by CD spectroscopy following a simple addition of TBA or PS2.M. By the addition of TBA and PS2.M, the Pb2+ signals were observed in effluent samples over 0.5 micromolar (100 ppb) concentration. Furthermore, PS2.M caused a Pb2+-specific absorption band in the effluent sample without spiking of Pb2+, and could be induced to G-QD structure by the background Pb2+ concentration in the effluent, 0.159 micromolar concentration (3.30 ppb). Taken together, we propose that TBA and PS2.M are applicable as platform- and label-free detection probes for monitoring Pb2+ in environmental samples such as discharged effluent from local WWTPs, using CD spectroscopy.

scholarly journals Mass-resolved electronic circular dichroism ion spectroscopy

Science ◽  
2020 ◽  
Vol 368 (6498) ◽  
pp. 1465-1468 ◽  
Author(s):  
Steven Daly ◽  
Frédéric Rosu ◽  
Valérie Gabelica
Keyword(s):  
Circular Dichroism ◽  
Three Dimensional ◽  
Polarized Light ◽  
Negative Ions ◽  
Data Interpretation ◽  
Electronic Circular Dichroism ◽  
Circularly Polarized Light ◽  
Chiral Compounds ◽  
Electron Photodetachment ◽  
Circular Dichroïsm

DNA and proteins are chiral: Their three-dimensional structures cannot be superimposed with their mirror images. Circular dichroism spectroscopy is widely used to characterize chiral compounds, but data interpretation is difficult in the case of mixtures. We recorded the electronic circular dichroism spectra of DNA helices separated in a mass spectrometer. We studied guanine-rich strands having various secondary structures, electrosprayed them as negative ions, irradiated them with an ultraviolet nanosecond optical parametric oscillator laser, and measured the difference in electron photodetachment efficiency between left and right circularly polarized light. The reconstructed circular dichroism ion spectra resembled those of their solution-phase counterparts, thereby allowing us to assign the DNA helical topology. The ability to measure circular dichroism directly on biomolecular ions expands the capabilities of mass spectrometry for structural analysis.

The chiral coating on an achiral nanostructure by the secondary effect in focused ion beam induced deposition

2021 ◽  
Author(s):  
Chen Fang ◽  
Qing Chai ◽  
Ye Chen ◽  
Yan Xing ◽  
Zai-fa Zhou
Keyword(s):  
Circular Dichroism ◽  
Focused Ion Beam ◽  
Ion Beam ◽  
Polarized Light ◽  
Localized Surface Plasmon ◽  
Light Illumination ◽  
Secondary Effect ◽  
Circularly Polarized Light ◽  
Optical Metamaterials ◽  
Circular Dichroïsm

Abstract Optical metamaterials are widely used in electromagnetic wave modulation due to their sub-wavelength feature sizes. In this paper, a method to plate an achiral nanopillar array with chiral coating by the secondary effect in focused ion beam induced deposition is proposed. Guided by the pattern defined in a bitmap with variable residence time, the beam scan strategy suppresses the interaction between adjacent nanostructures. A uniform chiral coating is formed on the target nanostructure without affecting the adjacent nanostructure, under carefully selected beam parameters and the rotation angle of the sample stage. Energy Dispersive X-Ray Spectroscopy results show that the chiral film has high purity metal, which enables the generation of localized surface plasmon resonances and causes the circular dichroism under circularly polarized light illumination. Finally, the tailorable circular dichroism spectrum of the coated array is verified by the Finite Difference Time Domain method.

Correction for Unequal Intensities of Left and Right Circularly Polarized Light in Steady-State and Lifetime-Resolved Fluorescence-Detected Circular Dichroism

1994 ◽  
Vol 48 (2) ◽  
pp. 167-175 ◽  
Author(s):  
Lei Geng ◽  
Linda B. McGown
Keyword(s):  
Circular Dichroism ◽  
Steady State ◽  
General Scheme ◽  
Multicomponent System ◽  
Polarized Light ◽  
Circularly Polarized Light ◽  
Circularly Polarized ◽  
Experimental Approaches ◽  
Total Absorbance ◽  
Circular Dichroïsm

A major difficulty in fluorescence-detected circular dichroism (FDCD) and lifetime-resolved fluorescence-detected circular dichroism (LRFDCD) is the generation of equal excitation intensities of left circularly polarized light (LCPL) and right circularly polarized light (RCPL). In the presence of unequal intensities, the observed FDCD signal of an optically active sample, or the resolved FDCD signals of a multicomponent system in the case of LRFDCD, will be contaminated by a factor that is the ratio of the two unequal intensities. For optically inactive samples, a sample-independent, artifactual, nonzero signal of constant magnitude is observed. A general scheme is presented for the correction of these inaccuracies caused by unequal intensities of LCPL and RCPL. Large differences between LCPL and RCPL excitation intensities were artificially introduced in steady-state FDCD measurements, and the artifact was accurately corrected by the scheme. Corrected results for the different experimental approaches that have been described for LRFDCD showed similarly good accuracy. In a related consideration, inclusion of the total absorbance and absorption circular dichroism of the sample in the calculation of the FDCD signal is shown to be essential for samples with high absorbances.

Philip John Stephens. 9 October 1940 — 31 July 2012

2013 ◽  
Vol 59 ◽  
pp. 359-382 ◽  
Author(s):  
Andrew J. Thomson ◽  
Laurence D. Barron
Keyword(s):  
Circular Dichroism ◽  
Density Functional ◽  
Magnetic Circular Dichroism ◽  
Polarized Light ◽  
Deep Understanding ◽  
Chiral Drugs ◽  
Widespread Application ◽  
Circularly Polarized Light ◽  
Circularly Polarized ◽  
Circular Dichroïsm

Philip J. Stephens was a theoretical chemist who brought to fruition two new forms of optical spectroscopy, using circularly polarized light, for the determination of electronic structure and molecular stereochemistry. The first was magnetic circular dichroism (MCD), the wavelength dependence of the differential absorption of left and right circularly polarized light induced by a magnetic field applied parallel to the light beam. Stephens established a methodology for extracting from MCD spectra the angular momentum characteristics of ground and excited electronic states and demonstrated applications to the assignment of the optical spectra of coordination complexes of transition metals and to metalloproteins. In the second half of his career Stephens led the field of vibrational circular dichroism (VCD), the measurement of the natural circular dichroism (CD) arising from the vibrational transitions of chiral molecules. He developed instrumental techniques to measure this weak dichroism over a wide frequency range with high sensitivity. Subsequently he developed a quantum-mechanical method that yielded reliable calculations of VCD spectra by using density functional theory. Thus absolute configurations of all the chiral centres in an organic molecule are readily established. Given the increasing importance of enantiomerically pure chiral drugs, VCD has found widespread application in the pharmaceutical industry. Philip had not only a deep understanding of chemical theory but also a thorough grasp of experiments. His lectures on theoretical topics were models of clarity. He was also an accomplished pianist in demand, when a student at Oxford University, as an accompanist and for chamber concerts.

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