Showing posts with label chirality. Show all posts
Showing posts with label chirality. Show all posts

Wednesday, September 11, 2019

Abstract-Terahertz spectroscopy of enantiomeric and racemic pyroglutamic acid



Zhipeng Wu, Zhongjie Zhu, Chao Cheng, Jianbing Zhang, Gong Yan, Mingzhu Xu, Shaoping Lia, Hongwei Zhao,

https://www.sciencedirect.com/science/article/pii/S1386142519308996

The low-frequency vibrational properties of D-, L- and DL-pyroglutamic acid (PGA) have been investigated with the terahertz time-domain spectroscopy (THz-TDS) from 0.5 to 4.5 THz. The enantiomers (D- and L-PGA) present similar absorption spectra, while the spectrum of racemate (DL-PGA) is obviously different. The temperature-dependent THz spectra of different PGA were recorded in the range of 293–83 K. The spectral changes during the cooling process suggest that D- and L-PGA undergo a structural phase transition, and no phase change of DL-PGA was found. The results indicate that THz spectroscopy is highly sensitive to the crystal structure of molecules. The density functional theory (DFT) calculations based on the crystal structures were performed to simulate the sample's THz spectra. It was demonstrated that the characteristic resonant absorption peaks of the enantiomeric and racemic PGA in the low-frequency THz region originate from the different vibrations, which corresponding to the specific structures and intermolecular interactions. The conformational diversity and fluctuation may help to understand the properties of PGA in biochemistry and functional material.

Tuesday, July 2, 2019

Kirigami can spin terahertz rays in real time to peer into biological tissue


https://news.umich.edu/kirigami-can-spin-terahertz-rays-in-real-time-to-peer-into-biological-tissue/

ANN ARBOR—With a light-spinning device inspired by the Japanese art of paper cutting, University of Michigan researchers have detected microscopic twists in the internal structure of plant and animal tissue without harmful X-rays.
The approach is the first that can fully rotate terahertz radiation in real time, and it could open new dimensions in medical imaging, encrypted communications and cosmology. The researchers are most interested in using terahertz rays to identify biological tissues through the twists in their structures—their “chirality.” A tissue’s chirality affects how much it absorbs twisted radiation.
Terahertz radiation is the band of electromagnetic waves that runs from infrared radiation down to the range of the “millimeter scanners” that peer through your clothing at airports. It can travel about a quarter of an inch into the body, but unlike X-rays, it’s non-ionizing—meaning it doesn’t free up potentially damaging electrical charges in the body. 
“Our bodies have a lot of twisted structures that are close enough to the surface for terahertz photons to penetrate: vessels, ligaments, muscle fibers, molecules and even some helical bacteria,” said Nicholas Kotov, the Joseph B. and Florence V. Cejka Professor of Engineering and a corresponding author on the study in Nature Materials.
He believes it may be possible to gain medically relevant information about the working behaviors of these tissues using terahertz imaging. However, as with X-rays, it is difficult to tell the difference between soft tissues in terahertz scans. 
With an eye to exploring how chirality may help distinguish tissues, the team gathered everyday biological materials to look for differences in the absorption of clockwise- or counter-clockwise-rotating radiation in the terahertz spectrum. They studied a maple leaf, a dandelion flower, pork fat and the wing case of an iridescent beetle. While the leaf and fat showed no difference in absorption of clockwise or counter-clockwise radiation, the flower and wing case preferentially absorbed the one over the other, revealing microscopic twists in their structures.
This technique, called circular dichroism spectroscopy, was impractical in the terahertz range until now. Other parts of the electromagnetic spectrum, such as visible light, can be twisted with natural crystals, but the twisting power was limited for terahertz radiation or else it couldn’t be done in real time. 
The new device is a deceptively simple—essentially a plastic ribbon, printed with a gold herringbone pattern and sliced with staggered rows of tiny cuts. The incisions are influenced by the Japanese art of kirigami, which uses arrangements of cuts to create 3D structures from paper.
When the ribbon is stretched, the cuts open up and the slices of ribbon twist. The gold lines then guide the radiation, twisting it in turn. In radiation, twisting is called “circular polarization,” which is the same optical phenomenon that is used in liquid crystal displays (LCDs). 
“We all might have an experience of playing with paper crafting when we were young, but there were no design rules for a 3D chiral optical devices built using only folding and cutting. So, we started from scratch and tested many models through both simulations and experiments,” said Wonjin Choi, a Ph.D. student in materials science and engineering and co-first author on the study.
The team proposes the same design could be scaled for other types of radiation as well, with larger patterns interacting with microwaves or radio waves, or shrinking the pattern down to manipulate infrared light.
Because spinning terahertz light wasn’t widely studied, one of the team’s challenges was figuring out how to see whether the kirigami device worked at all.
“The conventional ways of measuring terahertz radiation are limited to how much energy is lost as it travels through a sample, which is not enough for our case,” said Gong Cheng, a Ph.D. student in physics at U-M and co-first author.
By stacking linear polarizers, rotated with respect to one another, in the path of the beam, they could make measurements to reveal the circular polarization.
In addition to imaging living tissues, terahertz circular dichroism spectroscopy could also aid the development of new medicines based on large biological molecules such as proteins and antibodies. 
Choi anticipates that an early application could be to encrypt and decrypt communications on the terahertz spectrum. And if these kirigami devices were flown on satellites to measure the twist in the terahertz spectrum of the universe’s background radiation, it could tell us more about the earliest stars.
The study was supported by the Defense Advanced Research Projects Agency and the Department of Defense’s Vannevar Bush Fellowship. The chiral kirigami modulator was built in the Lurie Nanofabrication Facility.
Ted Norris, the Gerard A. Mourou Collegiate Professor of Electrical Engineering and Computer Science, is also a corresponding author on the study. Kotov is also a professor of chemical engineering, materials science and engineering and macromolecular science and engineering.

Sunday, October 8, 2017

Abstract-Analysis of the Chirality Effects on the Capacity of Wireless Communication Systems in the THz band


Anna Maria Vegni, Valeria Loscri,


http://ieeexplore.ieee.org/document/8048612/


The potentialities of Terahertz frequency band in the context of nano-scale communications are largely increasing, thanks to specific features that allow to overcome the issues related to the spectrum scarcity and capacity limitation. Apart from high molecular absorption and very high reflection loss that represent the main phenomena in Terahertz (THz) band, in this paper we investigate the chirality effects that affect the propagation medium, in the frequency range (4 􀀀 10) THz. It is observed that in this interval the chiral parameter shows resonance peaks in specific frequencies. In this paper we investigate the channel capacity in a special medium affected by chirality effects, such as biomolecules, DNA chains, etc. Specifically, we analyze the signal propagation in a chiral medium where a Giant Optical Activity (GOA) is present. This effect is typical of the so-called chiral-metamaterials. Through simulation results we distinguish the behavior of a chirality-affected channel with GOA in Line-of-Sight and Non- Line-of-Sight propagations, assuming different power allocation techniques and also comparing the performance to the case of No GOA.

Wednesday, August 3, 2016

Metamolecules That Switch Handedness at Light-Speed


http://newscenter.lbl.gov/2012/07/10/metamolecules-that-switch-handedness-at-light-speed/


(Top) Scanning electron microscopy image of optically switchable chiral THz metamolecules, (Bottom) The purple, blue and tan colors represent the gold meta-atom structures at different layers, with the two silicon pads shown in green. (courtesy of Zhang, et. al)
A multi-institutional team of researchers that included scientists with the U.S. Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) has created the first artificial molecules whose chirality can be rapidly switched from a right-handed to a left-handed orientation with a  beam of light. This holds potentially important possibilities for the application of terahertz technologies across a wide range of fields, including reduced energy use for data-processing, homeland security and ultrahigh-speed communications.
Chirality is the distinct left/right orientation or “handedness” of some types of molecules, meaning the molecule can take one of two mirror image forms. The right-handed and left-handed forms of such molecules, called “enantiomers,” can exhibit strikingly different properties. For example, one enantiomer of the chiral molecule limonene smells of lemon, the other smells of orange. The ability to observe or even switch the chirality of molecules using terahertz (trillion-cycles-per-second) electromagnetic radiation is a much coveted asset in the world of high technology.
“Natural materials can be induced to change their chirality but the process, which involves structural changes to the material, is weak and slow. With our artificial molecules, we’ve demonstrated strong dynamic chirality switching at light-speed,” says Xiang Zhang, one of the leaders of this research and a principal investigator with Berkeley Lab’s Materials Sciences Division.
Working with terahertz (THz) metamaterials engineered from nanometer-sized gold strips with air as the dielectric – Zhang and his colleagues fashioned a delicate artificial chiral molecule which they then incorporated with a photoactive silicon medium. Through photoexcitation of their metamolecules with an external beam of light, the researchers observed handedness flipping in the form of circularly polarized emitted THz light. Furthermore, the photoexcitation enabled this chirality flipping and the circular polarization of THz light to be dynamically controlled.
“In contrast to previous demonstrations where chirality was merely switched on or off in metamaterials using photoelectric stimulation, we used an optical switch to actually reverse the chirality of our THz metamolecules,” Zhang says.
Zhang, who holds the Ernest S. Kuh Endowed Chair Professor of Mechanical Engineering at the University of California (UC)  Berkeley, where he also directs the Nano-scale Science and Engineering Center, is one of three corresponding authors of a paper describing this work in Nature Communications. The paper is titled “Photoinduced handedness switching in terahertz chiral metamolecules.” The other corresponding authors are Shuang Zhang of the University of Birmingham in the United Kingdom, and Antoinette Taylor of DOE’s Los Alamos National Laboratory.
The optically switchable chiral THz metamolecules consisted of  a pair of 3D meta-atoms of opposite chirality made from precisely structured gold strips. Each meta-atom serves as a resonator with a coupling between electric and magnetic responses that produces strong chirality and large circular dichroism at the resonance frequency.
“When two chiral meta-atoms of the same shape but opposite chirality are assembled to form a metamolecule, the mirror symmetry is preserved, resulting in the vanishing of optical activity,” Zhang says. “From a different point of view, the optical activity arising from these two meta-atoms of opposite chirality cancels out each other.”

Schematic shows the chirality switching metamolecule consists of four chiral resonators with fourfold rotational symmetry. An external beam of light instantly reverses the metamolecule’s chirality from right-handed to left-handed. (courtesy of Zhang, et. al)
Silicon pads were introduced to each chiral meta-atom in the metamolecule but at different locations. In one meta-atom, the silicon pad bridged two gold strips, and in the other meta-atom, the silicon pad replaced part of a gold strip. The silicon pads broke the mirror symmetry and induced chirality for the combined metamolecule. The pads also functioned as the optoelectronic switches that flipped the chirality of the metamolecule under  photoexcitation.
Says corresponding author Shuang Zhang, “Our scheme relies on the combination of two meta-atoms with opposite properties, in which one is functional while the other is inactive within the frequency range of interest. With suitable design, the two meta-atoms respond oppositely to an external stimulus, that is, the inactive one becomes functional and vice versa.”
THz electromagnetic radiation – also known as T-rays – falls within the frequency range of molecular vibrations, making it an ideal none-invasive tool for analyzing the chemical constituents of organic and non-organic materials. Being able to flip the handedness of chiral metamolecules and control the circular polarization of THz light could be used to detect toxic and explosive chemicals, or for wireless communication and high-speed data processing systems. As most biological molecules are chiral, including DNA, RNA and proteins, THz-based polarimetric devices should also benefit medical researchers and developers of pharmaceutical drugs among others.
“The switchable chirality we can engineer into our metamaterials provides a viable approach towards creating high performance polarimetric devices that are largely not available at terahertz frequencies,” says corresponding author Antoinette Taylor. “This frequency range is particularly interesting because it uniquely reveals information about physical phenomena such as the interactions between or within biologically relevant molecules. It may enable control of electronic states in novel material systems, such as cyclotron resonances in graphene and topological insulators.”
Taylor and her co-authors say that the general design principle of their optically switchable chiral THz metamolecules is not limited to handedness switching but could also be applied to the dynamic reversing of other electromagnetic properties.
In addition to the corresponding authors, other authors of the Nature Communications paper were Jiangfeng Zhou, Yong-Shik Park, Junsuk Rho, Ranjan Singh, Sunghyun Nam, Abul Azad, Hou-Tong Chen and Xiaobo Yin.
This research was primarily supported by the DOE Office of Science.
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Lawrence Berkeley National Laboratory addresses the world’s most urgent scientific challenges by advancing sustainable energy, protecting human health, creating new materials, and revealing the origin and fate of the universe. Founded in 1931, Berkeley Lab’s scientific expertise has been recognized with 13 Nobel prizes. The University of California manages Berkeley Lab for the U.S. Department of Energy’s Office of Science. For more, visit www.lbl.gov.
Los Alamos National Laboratory, a multidisciplinary research institution engaged in strategic science on behalf of national security, is operated by Los Alamos National Security, LLC, a team composed of Bechtel National, the University of California, The Babcock & Wilcox Company, and URS for the Department of Energy’s National Nuclear Security Administration. Los Alamos enhances national security by ensuring the safety and reliability of the U.S. nuclear stockpile, developing technologies to reduce threats from weapons of mass destruction, and solving problems related to energy, environment, infrastructure, health, and global security concerns. For more information visit http://www.lanl.gov/
DOE’s Office of Science is the single largest supporter of basic research in the physical sciences in the United States, and is working to address some of the most pressing challenges of our time.  For more information, please visit science.energy.gov.
Additional Information
For more information about the research of Xiang Zhang visit http://xlab.me.berkeley.edu/