Image or mirror image? Chiral recognition by femtosecond laser

The trick is to replace the individual high-energy photon with three laser photons that excite the molecule through intermediate levels until it releases an electron (this method is known as REMPI, Resonance-Enhanced Multi-Photon Ionization). “It is thus possible to eject electrons with less energetic but more intense light,” explains Thomas Baumert of the University of Kassel.

For the measurements, the light must be circularly polarized. What does this mean? “Ordinary” light consists of waves that oscillate in all spatial directions perpendicular to their direction of travel. If light is linearly polarized, the light waves oscillate exclusively in one plane. When light is circularly polarized, the light wave oscillates in a helical form, because its amplitude describes a circle around the axis of travel – either to the right or the left.

Molecules in the gas phase are randomly oriented and thus encounter the laser light from all possible angles; the ejected electrons also fly off in every possible direction as they leave the molecule. By using both a special configuration for measurement and special calculation processes, the team is able to determine the distribution of the angles of the electrons’ flight paths. In the case of linearly polarized light, the distribution is symmetrical. “However, when the electrons are ejected by circularly polarized light, we find a distinct asymmetry to the angles at which the free electrons are found in relation to the laser beam,” reports Baumert. “This asymmetry is inverted if left circularly polarized light is used instead of right, an effect known as photoelectron circular dichroism. We observe the same effect when we keep the circular polarization the same but change from the “right handed” to the “left handed” structure of the chiral molecule being observed.” The researchers were able to demonstrate this with the chiral compounds camphor and fenchone.

“This circular dichroism effect has previously only been observed with synchrotron radiation. In contrast, our procedure uses a compact laser system, so that this method is not limited to basic laboratory research but, because of the magnitude of the observed effects, may also find its way into analysis,” according to Baumert.

More information: Thomas Baumert, Circular Dichroism in the Photoelectron Angular Distributions of Camphor and Fenchone from Multiphoton Ionization with Femtosecond Laser Pulses, Angewandte Chemie International Edition, http://dx.doi.org/ … ie.201109035

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Metamaterials may advance with new femtosecond laser technique

Researchers in applied physics have cleared an important hurdle in the development of advanced materials, called metamaterials, that bend light in unusual ways.

Working at a scale applicable to infrared light, the Harvard team has used extremely short and powerful laser pulses to create three-dimensional patterns of tiny silver dots within a material. Those suspended metal dots are essential for building futuristic devices like invisibility cloaks.

The new fabrication process, described in the journal Applied Physics Letters, advances nanoscale metal lithography into three dimensions -- and does it at a resolution high enough to be practical for metamaterials.

"If you want a bulk metamaterial for visible and infrared light, you need to embed particles of silver or gold inside a dielectric, and you need to do it in 3D, with high resolution," says lead author Kevin Vora, a graduate student at the Harvard School of Engineering and Applied Sciences (SEAS).

"This work demonstrates that we can create silver dots that are disconnected in x, y, and z," Vora says. "There's no other technique that feasibly allows you to do that. Being able to make patterns of nanostructures in 3D is a very big step towards the goal of making bulk metamaterials."

Vora works in the laboratory of Eric Mazur, Balkanski Professor of Physics and Applied Physics at SEAS. For decades, Mazur has been using a piece of equipment called a femtosecond laser to investigate how very tightly focused, powerful bursts of light can change the electrical, optical, and physical properties of a material.

When a conventional laser shines on a transparent material, the light passes straight through, with slight refraction. The femtosecond laser is special because it emits a burst of photons as bright as the surface of the sun in a flash lasting only 50 quadrillionths (5 × 10-14) of a second. Instead of shining through the material, that energy gets trapped within it, exciting the electrons within the material and achieving a phenomenon known as nonlinear absorption.

Inside the pocket where that energy is trapped, a chemical reaction can take place, permanently altering the internal structure of the material. The process has previously been exploited for 2D and simple 3D metal nanofabrication.

"Normally, when people use femtosecond lasers in fabrication, they're creating a wood pile structure: something stacked on something else, being supported by something else," explains Mazur.

"If you want to make an array of silver dots, however, they can't float in space."

In the new process, Vora, Mazur, and their colleagues combine silver nitrate, water, and a polymer called PVP into a solution, which they bake onto a glass slide. The solid polymer then contains ions of silver, which are photoreduced by the tightly focused laser pulses to form nanocrystals of silver metal, supported by the polymer matrix.

The need for this particular combination of chemicals, at the right concentrations, was not obvious in prior work. Researchers sometimes combine silver nitrate with water in order to create silver nanostructures, but that process provides no structural support for a 3D pattern. Another process combines silver nitrate, water, PVP, and ethanol, but the samples darken and degrade very quickly by producing silver crystals throughout the polymer.

With ethanol, the reaction happens too quickly and uncontrollably. Mazur's team needed nanoscale crystals, precisely distributed and isolated in 3D.

"It was just a question of removing that reagent, and we got lucky," Vora says. "What was most surprising about it was how simple it is. It was a matter of using less."

SeungYeon Kang, a graduate student at SEAS, and Shobha Shukla, a former postdoctoral fellow, coauthored the paper. The work was supported by the Air Force Office of Scientific Research.

Story Source:

The above story is reprinted from materials provided by Harvard School of Engineering and Applied Sciences, via AlphaGalileo.

Note: Materials may be edited for content and length. For further information, please contact the source cited above.

Journal Reference:

Kevin Vora, SeungYeon Kang, Shobha Shukla, Eric Mazur. Fabrication of disconnected three-dimensional silver nanostructures in a polymer matrix. Applied Physics Letters, 2012; 100 (6): 063120 DOI: 10.1063/1.3684277

Proteins in focus: Adjustable protein microlenses made by femtosecond laser direct writing

Proteins are potentially useful as “building materials” for microcomponents because they are readily available, inexpensive, and biocompatible. They can also change their properties in response to external stimuli, which makes them an interesting material for use in adjustable microlenses. However, lenses must be extremely precise in order to meet optical requirements—something difficult to achieve with proteins. In addition, they must be fast, simple, and inexpensive to produce.

The Chinese researchers have now met this challenge: They used a laser to “write” the desired micrometer-sized lens shape out of a solution of bovine serum albumin, a protein. Methylene blue acts as a photosensitizer, which captures the light energy like an antenna and triggers a crosslinking reaction of the protein molecules. Driven by a computer, the laser cuts out the desired three-dimensional form voxel by voxel. A voxel is a three-dimensional pixel, a tiny segment of volume. The irradiation used is in femtosecond pulses, which lasts on the order of 10-13 seconds. The crosslinking reaction only takes place in the locations that are irradiated. After the reaction, the protein molecules that have not reacted can simply be rinsed away. What stays behind is a cross-linked, aqueous protein gel in the shapes of micrometer-sized lenses.

Direct writing with lasers usually results in structures that have too rough a surface for optical applications. By optimizing the duration of the laser pulse, the pulse intensity, and the protein concentration, Sun and his team obtained lenses with outstanding optical properties.

The special trick in this case is that the amount of liquid absorbed by the protein gel depends on the pH value of the solution. Increasing the pH causes the lens to swell. If the increase in thickness is limited by a glass surface, the lens primarily grows in width and becomes flatter. If the pH value is reduced, the gel shrinks and the lens is more curved. Because the radius of curvature determines the focal length of the lens, this method can be used to focus the microlenses.

Because the protein lenses are biocompatible, they may be used in optical analytical systems for medical diagnostics or lab-on-a-chip technology.

More information: Hong-Bo Sun, Dynamically Tunable Protein Microlenses, Angewandte Chemie International Edition, http://dx.doi.org/ … ie.201105925

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