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2015


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Enzymatically active biomimetic micropropellers for the penetration of mucin gels

Walker (Schamel), D., Käsdorf, B. T., Jeong, H. H., Lieleg, O., Fischer, P.

Science Advances, 1(11):e1500501, December 2015 (article)

Abstract
In the body, mucus provides an important defense mechanism by limiting the penetration of pathogens. It is therefore also a major obstacle for the efficient delivery of particle-based drug carriers. The acidic stomach lining in particular is difficult to overcome because mucin glycoproteins form viscoelastic gels under acidic conditions. The bacterium Helicobacter pylori has developed a strategy to overcome the mucus barrier by producing the enzyme urease, which locally raises the pH and consequently liquefies the mucus. This allows the bacteria to swim through mucus and to reach the epithelial surface. We present an artificial system of reactive magnetic micropropellers that mimic this strategy to move through gastric mucin gels by making use of surface-immobilized urease. The results demonstrate the validity of this biomimetic approach to penetrate biological gels, and show that externally propelled microstructures can actively and reversibly manipulate the physical state of their surroundings, suggesting that such particles could potentially penetrate native mucus.

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link (url) DOI [BibTex]

2015


link (url) DOI [BibTex]


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The EChemPen: A Guiding Hand To Learn Electrochemical Surface Modifications

Valetaud, M., Loget, G., Roche, J., Hueken, N., Fattah, Z., Badets, V., Fontaine, O., Zigah, D.

J. of Chem. Ed., 92(10):1700-1704, September 2015 (article)

Abstract
The Electrochemical Pen (EChemPen) was developed as an attractive tool for learning electrochemistry. The fabrication, principle, and operation of the EChemPen are simple and can be easily performed by students in practical classes. It is based on a regular fountain pen principle, where the electrolytic solution is dispensed at a tip to locally modify a conductive surface by triggering a localized electrochemical reaction. Three simple model reactions were chosen to demonstrate the versatility of the EChemPen for teaching various electrochemical processes. We describe first the reversible writing/erasing of metal letters, then the electrodeposition of a black conducting polymer "ink", and finally the colorful writings that can be generated by titanium anodization and that can be controlled by the applied potential. These entertaining and didactic experiments are adapted for teaching undergraduate students that start to study electrochemistry by means of surface modification reactions.

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DOI [BibTex]

DOI [BibTex]


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Optimal Length of Low Reynolds Number Nanopropellers

Walker (Schamel), D., Kuebler, M., Morozov, K. I., Fischer, P., Leshansky, A. M.

Nano Letters, 15(7):4412-4416, June 2015 (article)

Abstract
Locomotion in fluids at the nanoscale is dominated by viscous drag. One efficient propulsion scheme is to use a weak rotating magnetic field that drives a chiral object. Froth bacterial flagella to artificial drills, the corkscrew is a universally useful chiral shape for propulsion in viscous environments. Externally powered magnetic micro- and nanomotors have been recently developed that allow for precise fuel-free propulsion in complex media. Here, we combine analytical and numerical theory with experiments on nanostructured screw-propellers to show that the optimal length is surprisingly short only about one helical turn, which is shorter than most of the structures in use to date. The results have important implications for the design of artificial actuated nano- and micropropellers and can dramatically reduce fabrication times, while ensuring optimal performance.

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DOI [BibTex]

DOI [BibTex]


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A theoretical study of potentially observable chirality-sensitive NMR effects in molecules

Garbacz, P., Cukras, J., Jaszunski, M.

Phys. Chem. Chem. Phys., 17(35):22642-22651, May 2015 (article)

Abstract
Two recently predicted nuclear magnetic resonance effects, the chirality-induced rotating electric polarization and the oscillating magnetization, are examined for several experimentally available chiral molecules. We discuss in detail the requirements for experimental detection of chirality-sensitive NMR effects of the studied molecules. These requirements are related to two parameters: the shielding polarizability and the antisymmetric part of the nuclear magnetic shielding tensor. The dominant second contribution has been computed for small molecules at the coupled cluster and density functional theory levels. It was found that DFT calculations using the KT2 functional and the aug-cc-pCVTZ basis set adequately reproduce the CCSD(T) values obtained with the same basis set. The largest values of parameters, thus most promising from the experimental point of view, were obtained for the fluorine nuclei in 1,3-difluorocyclopropene and 1,3-diphenyl-2-fluoro-3-trifluoromethylcyclopropene.

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DOI [BibTex]

DOI [BibTex]


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Dynamic Inclusion Complexes of Metal Nanoparticles Inside Nanocups

Alarcon-Correa, M., Lee, T. C., Fischer, P.

Angew. Chem. Int. Ed., 54(23):6730-6734, May 2015, Featured cover article. (article)

Abstract
Host-guest inclusion complexes are abundant in molecular systems and of fundamental importance in living organisms. Realizing a colloidal analogue of a molecular dynamic inclusion complex is challenging because inorganic nanoparticles (NPs) with a well-defined cavity and portal are difficult to synthesize in high yield and with good structural fidelity. Herein, a generic strategy towards the fabrication of dynamic 1: 1 inclusion complexes of metal nanoparticles inside oxide nanocups with high yield (> 70%) and regiospecificity (> 90%) by means of a reactive double Janus nanoparticle intermediate is reported. Experimental evidence confirms that the inclusion complexes are formed by a kinetically controlled mechanism involving a delicate interplay between bipolar galvanic corrosion and alloying-dealloying oxidation. Release of the NP guest from the nanocups can be efficiently triggered by an external stimulus. Featured cover article.

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DOI [BibTex]

DOI [BibTex]


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Surface roughness-induced speed increase for active Janus micromotors

Choudhury, U., Soler, L., Gibbs, J. G., Sanchez, S., Fischer, P.

Chem. Comm., 51(41):8660-8663, April 2015 (article)

Abstract
We demonstrate a simple physical fabrication method to control surface roughness of Janus micromotors and fabricate self-propelled active Janus microparticles with rough catalytic platinum surfaces that show a four-fold increase in their propulsion speed compared to conventional Janus particles coated with a smooth Pt layer.

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DOI [BibTex]

DOI [BibTex]


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Active colloidal microdrills

Gibbs, J. G., Fischer, P.

Chem. Comm., 51(20):4192-4195, Febuary 2015 (article)

Abstract
We demonstrate a chemically driven, autonomous catalytic microdrill. An asymmetric distribution of catalyst causes the helical swimmer to twist while it undergoes directed propulsion. A driving torque and hydrodynamic coupling between translation and rotation at low Reynolds number leads to drill-like swimming behaviour.

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DOI [BibTex]

DOI [BibTex]


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Selectable Nanopattern Arrays for Nanolithographic Imprint and Etch-Mask Applications

Jeong, H. H., Mark, A. G., Lee, T., Son, K., Chen, W., Alarcon-Correa, M., Kim, I., Schütz, G., Fischer, P.

Adv. Science, 2(7):1500016, 2015, Featured cover article. (article)

Abstract
A parallel nanolithographic patterning method is presented that can be used to obtain arrays of multifunctional nanoparticles. These patterns can simply be converted into a variety of secondary nanopatterns that are useful for nanolithographic imprint, plasmonic, and etch-mask applications.

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link (url) DOI [BibTex]

link (url) DOI [BibTex]

2014


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Nanopropellers and Their Actuation in Complex Viscoelastic Media

Schamel, D., Mark, A. G., Gibbs, J. G., Miksch, C., Morozov, K. I., Leshansky, A. M., Fischer, P.

ACS Nano, 8(9):8794-8801, June 2014, Featured cover article. (article)

Abstract
Tissue and biological fluids are complex viscoelastic media with a nanoporous macromolecular structure. Here, we demonstrate that helical nanopropellers can be controllably steered through such a biological gel. The screw-propellers have a filament diameter of about 70 nm and are smaller than previously reported nanopropellers as well as any swimming microorganism. We show that the nanoscrews will move through high-viscosity solutions with comparable velocities to that of larger micropropellers, even though they are so small that Brownian forces suppress their actuation in pure water. When actuated in viscoelastic hyaluronan gels, the nanopropellers appear to have a significant advantage, as they are of the same size range as the gel’s mesh size. Whereas larger helices will show very low or negligible propulsion in hyaluronan solutions, the nanoscrews actually display significantly enhanced propulsion velocities that exceed the highest measured speeds in Newtonian fluids. The nanopropellers are not only promising for applications in the extracellular environment but small enough to be taken up by cells.

Featured cover article.

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Video - Helical Micro and Nanopropellers for Applications in Biological Fluidic Environments link (url) DOI [BibTex]


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Circular polarization interferometry: circularly polarized modes of cholesteric liquid crystals

Sanchez-Castillo, A., Eslami, S., Giesselmann, F., Fischer, P.

OPTICS EXPRESS, 22(25):31227-31236, 2014 (article)

Abstract
We describe a novel polarization interferometer which permits the determination of the refractive indices for circularly-polarized light. It is based on a Jamin-Lebedeff interferometer, modified with waveplates, and permits us to experimentally determine the refractive indices n(L) and n(R) of the respectively left- and right-circularly polarized modes in a cholesteric liquid crystal. Whereas optical rotation measurements only determine the circular birefringence, i.e. the difference (n(L) - n(R)), the interferometer also permits the determination of their absolute values. We report refractive indices of a cholesteric liquid crystal in the region of selective (Bragg) reflection as a function of temperature. (C) 2014 Optical Society of America

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DOI [BibTex]

DOI [BibTex]


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Self-Propelling Nanomotors in the Presence of Strong Brownian Forces

Lee, T., Alarcon-Correa, M., Miksch, C., Hahn, K., Gibbs, J. G., Fischer, P.

NANO LETTERS, 14(5):2407-2412, 2014 (article)

Abstract
Motility in living systems is due to an array of complex molecular nanomotors that are essential for the function and survival of cells. These protein nanomotors operate not only despite of but also because of stochastic forces. Artificial means of realizing motility rely on local concentration or temperature gradients that are established across a particle, resulting in slip velocities at the particle surface and thus motion of the particle relative to the fluid. However, it remains unclear if these artificial motors can function at the smallest of scales, where Brownian motion dominates and no actively propelled living organisms can be found. Recently, the first reports have appeared suggesting that the swimming mechanisms of artificial structures may also apply to enzymes that are catalytically active. Here we report a scheme to realize artificial Janus nanoparticles (JNPs) with an overall size that is comparable to that of some enzymes similar to 30 nm. Our JNPs can catalyze the decomposition of hydrogen peroxide to water and oxygen and thus actively move by self-electrophoresis. Geometric anisotropy of the Pt-Au Janus nanoparticles permits the simultaneous observation of their translational and rotational motion by dynamic light scattering. While their dynamics is strongly influenced by Brownian rotation, the artificial Janus nanomotors show bursts of linear ballistic motion resulting in enhanced diffusion.

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DOI [BibTex]


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Shape control in wafer-based aperiodic 3D nanostructures

Hyeon-Ho, J., Mark, A. G., Gibbs, J. G., Reindl, T., Waizmann, U., Weis, J., Fischer, P.

NANOTECHNOLOGY, 25(23), 2014, Cover article. (article)

Abstract
Controlled local fabrication of three-dimensional (3D) nanostructures is important to explore and enhance the function of single nanodevices, but is experimentally challenging. We present a scheme based on e-beam lithography (EBL) written seeds, and glancing angle deposition (GLAD) grown structures to create nanoscale objects with defined shapes but in aperiodic arrangements. By using a continuous sacrificial corral surrounding the features of interest we grow isolated 3D nanostructures that have complex cross-sections and sidewall morphology that are surrounded by zones of clean substrate.

Cover article.

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DOI [BibTex]

DOI [BibTex]


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Swimming by reciprocal motion at low Reynolds number

Qiu, T., Lee, T., Mark, A. G., Morozov, K. I., Muenster, R., Mierka, O., Turek, S., Leshansky, A. M., Fischer, P.

NATURE COMMUNICATIONS, 5, 2014, Max Planck Press Release. (article)

Abstract
Biological microorganisms swim with flagella and cilia that execute nonreciprocal motions for low Reynolds number (Re) propulsion in viscous fluids. This symmetry requirement is a consequence of Purcell's scallop theorem, which complicates the actuation scheme needed by microswimmers. However, most biomedically important fluids are non-Newtonian where the scallop theorem no longer holds. It should therefore be possible to realize a microswimmer that moves with reciprocal periodic body-shape changes in non-Newtonian fluids. Here we report a symmetric `micro-scallop', a single-hinge microswimmer that can propel in shear thickening and shear thinning (non-Newtonian) fluids by reciprocal motion at low Re. Excellent agreement between our measurements and both numerical and analytical theoretical predictions indicates that the net propulsion is caused by modulation of the fluid viscosity upon varying the shear rate. This reciprocal swimming mechanism opens new possibilities in designing biomedical microdevices that can propel by a simple actuation scheme in non-Newtonian biological fluids.

Max Planck Press Release.

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Video - A Swimming Micro-Scallop Video - Winner of the Micro-robotic Design Challenge in Hamlyn Symposium on Medical Robotics DOI [BibTex]

Video - A Swimming Micro-Scallop Video - Winner of the Micro-robotic Design Challenge in Hamlyn Symposium on Medical Robotics DOI [BibTex]


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Nanohelices by shadow growth

Gibbs, J. G., Mark, A. G., Lee, T., Eslami, S., Schamel, D., Fischer, P.

NANOSCALE, 6(16):9457-9466, 2014 (article)

Abstract
The helix has remarkable qualities and is prevalent in many fields including mathematics, physics, chemistry, and biology. This shape, which is chiral by nature, is ubiquitous in biology with perhaps the most famous example being DNA. Other naturally occurring helices are common at the nanoscale in the form of protein secondary structures and in various macromolecules. Nanoscale helices exhibit a wide range of interesting mechanical, optical, and electrical properties which can be intentionally engineered into the structure by choosing the correct morphology and material. As technology advances, these fabrication parameters can be fine-tuned and matched to the application of interest. Herein, we focus on the fabrication and properties of nanohelices grown by a dynamic shadowing growth method combined with fast wafer-scale substrate patterning which has a number of distinct advantages. We review the fabrication methodology and provide several examples that illustrate the generality and utility of nanohelices shadow-grown on nanopatterns.

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Video - Fabrication of Designer Nanostructures DOI [BibTex]


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Chiral Nanomagnets

Eslami, S., Gibbs, J. G., Rechkemmer, Y., van Slageren, J., Alarcon-Correa, M., Lee, T., Mark, A. G., Rikken, G. L. J. A., Fischer, P.

ACS PHOTONICS, 1(11):1231-1236, 2014 (article)

Abstract
We report on the enhanced optical properties of chiral magnetic nanohelices with critical dimensions comparable to the ferromagnetic domain size. They are shown to be ferromagnetic at room temperature, have defined chirality, and exhibit large optical activity in the visible as verified by electron microscopy, superconducting quantum interference device (SQUID) magnetometry, natural circular dichroism (NCD), and magnetic circular dichroism (MCD) measurements. The structures exhibit magneto-chiral dichroism (MChD), which directly demonstrates coupling between their structural chirality and magnetism. A chiral nickel (Ni) film consisting of an array of nanohelices similar to 100 nm in length exhibits an MChD anisotropy factor g(MChD) approximate to 10(-4) T-1 at room temperature in a saturation field of similar to 0.2 T, permitting polarization-independent control of the film's absorption properties through magnetic field modulation. This is also the first report of MChD in a material with structural chirality on the order of the wavelength of light, and therefore the Ni nanohelix array is a metamaterial with magnetochiral properties that can be tailored through a dynamic deposition process.

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DOI [BibTex]

DOI [BibTex]


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Wireless powering of e-swimmers

Roche, J., Carrara, S., Sanchez, J., Lannelongue, J., Loget, G., Bouffier, L., Fischer, P., Kuhn, A.

SCIENTIFIC REPORTS, 4, 2014 (article)

Abstract
Miniaturized structures that can move in a controlled way in solution and integrate various functionalities are attracting considerable attention due to the potential applications in fields ranging from autonomous micromotors to roving sensors. Here we introduce a concept which allows, depending on their specific design, the controlled directional motion of objects in water, combined with electronic functionalities such as the emission of light, sensing, signal conversion, treatment and transmission. The approach is based on electric field-induced polarization, which triggers different chemical reactions at the surface of the object and thereby its propulsion. This results in a localized electric current that can power in a wireless way electronic devices in water, leading to a new class of electronic swimmers (e-swimmers).

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DOI [BibTex]

DOI [BibTex]


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Swelling and shrinking behaviour of photoresponsive phosphonium-based ionogel microstructures

Czugala, M., O’Connell, C., Blin, C., Fischer, P., Fraser, K. J., Benito-Lopez, F., Diamond, D.

SENSORS AND ACTUATORS B-CHEMICAL, 194, pages: 105-113, 2014 (article)

Abstract
Photoresponsive N-isopropylacrylamide ionogel microstructures are presented in this study. These ionogels are synthesised using phosphonium based room temperature ionic liquids, together with the photochromic compound benzospiropyran. The microstructures can be actuated using light irradiation, facilitating non-contact and non-invasive operation. For the first time, the characterisation of the swelling and shrinking behaviour of several photopatterned ionogel microstructures is presented and the influence of surface-area-to-volume ratio on the swelling kinetics is evaluated. It was found that the swelling and shrinking behaviour of the ionogels is strongly dependent on the nature of the ionic liquid. In particular, the {[}P-6,P-6,P-6,P-14]{[}NTf2] ionogel exhibits the greatest degree of swelling, reaching up to 180\% of its initial size, and the fastest shrinkage rate (k(sh) = 29 +/- 4 x 10(-2) s(-1)). (C) 2014 Elsevier B. V. All rights reserved.

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DOI [BibTex]

DOI [BibTex]

2012


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Fourier-transform photocurrent spectroscopy using a supercontinuum light source

Petermann, C., Beigang, R., Fischer, P.

APPLIED PHYSICS LETTERS, 100(6), 2012 (article)

Abstract
We demonstrate an implementation of frequency-encoded photocurrent spectroscopy using a super-continuum light source. The spectrally broad light is spatially dispersed and modulated with a special mechanical chopper design that permits a continuous wavelength-dependent modulation. After recombination, the light beam contains a frequency encoded spectrum which enables us to map the spectral response of a given sample in 60 ms and with a lateral resolution of 10 mu m. (C) 2012 American Institute of Physics.

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DOI [BibTex]

2012


DOI [BibTex]


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Eine neue Form von Cavity Enhanced Absorption Spectroscopy

Petermann, C., Fischer, P.

DE Gruyter, 79(1), 2012, Best paper award OPTO 2011 (article)

Abstract
Wir stellen eine Kopplungsmethode für resonatorgestützte Absorptionsmessungen vor, bei der Licht durch einen im Resonator platzierten akustooptischen Modulator aktiv ein- und ausgekoppelt wird. Dies ermöglicht es Cavity-Ring-Down-Spektroskopie (CRDS) mit breitbandigen und zeitlich inkohärenten Lichtquellen niedriger spektraler Leistungsdichte durchzuführen. Das Verfahren wird zum ersten Mal mit einer breitbandigen Superkontinuum-Quelle demonstriert.

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A new coupling scheme for cavity enhanced absorption spectroscopy makes use of an intracavity acousto-optical modulator to actively switch light into (and out of) a resonator. This allows cavity ringdown spectroscopy (CRDS) to be implemented with broadband temporally incoherent light sources with low spectral power densities. The method is demonstrated for the first time using a broadband supercontinuum source. Best paper award OPTO 2011.

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link (url) [BibTex]

link (url) [BibTex]

2009


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Full phase and amplitude control in computer-generated holography

Fratz, M., Fischer, P., Giel, D. M.

OPTICS LETTERS, 34(23):3659-3661, 2009 (article)

Abstract
We report what we believe to be the first realization of a computer-generated complex-valued hologram recorded in a single film of photoactive polymer. Complex-valued holograms give rise to a diffracted optical field with control over its amplitude and phase. The holograms are generated by a one-step direct laser writing process in which a spatial light modulator (SLM) is imaged onto a polymer film. Temporal modulation of the SLM during exposure controls both the strength of the induced birefringence and the orientation of the fast axis. We demonstrate that complex holograms can be used to impart arbitrary amplitude and phase profiles onto a beam and thereby open new possibilities in the control of optical beams. (C) 2009 Optical Society of America

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[BibTex]

2009


[BibTex]


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Digital polarization holograms with defined magnitude and orientation of each pixel’s birefringence

Fratz, M., Giel, D. M., Fischer, P.

OPTICS LETTERS, 34(8):1270-1272, 2009 (article)

Abstract
A new form of digital polarization holography is demonstrated that permits both the amplitude and the phase of a diffracted beam to be independently controlled. This permits two independent intensity images to be stored in the same hologram. To fabricate the holograms, a birefringence with defined retardance and orientation of the fast axis is recorded into a photopolymer film. The holograms are selectively read out by choosing the polarization state of the read beam. Polarization holograms of this kind increase the data density in holographic data storage and allow higher quality diffractive optical elements to be written. (C) 2009 Optical Society of America

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[BibTex]


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Controlled Propulsion of Artificial Magnetic Nanostructured Propellers

Ghosh, A., Fischer, P.

NANO LETTERS, 9(6):2243-2245, 2009, Featured highlight ‘Nanotechnology: The helix that delivers’ Nature 459, 13 (2009). (article)

Abstract
For biomedical applications, such as targeted drug delivery and microsurgery, it is essential to develop a system of swimmers that can be propelled wirelessly in fluidic environments with good control. Here, we report the construction and operation of chiral colloidal propellers that can be navigated in water with micrometer-level precision using homogeneous magnetic fields. The propellers are made via nanostructured surfaces and can be produced in large numbers. The nanopropellers can carry chemicals, push loads, and act as local probes in rheological measurements.

Featured highlight ‘Nanotechnology: The helix that delivers’ Nature 459, 13 (2009).

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Video - Nanospropellers DOI [BibTex]

Video - Nanospropellers DOI [BibTex]


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Absolute Asymmetric Reduction Based on the Relative Orientation of Achiral Reactants

Kuhn, A., Fischer, P.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 48(37):6857-6860, 2009 (article)

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DOI [BibTex]

DOI [BibTex]

2006


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Chiral molecules split light: Reflection and refraction in a chiral liquid

Ghosh, A., Fischer, P.

PHYSICAL REVIEW LETTERS, 97(17), 2006, Featured highlight ‘Fundamental optical physics: Refraction’ Nature Photonics, Nov. 2006. (article)

Abstract
A light beam changes direction as it enters a liquid at an angle from another medium, such as air. Should the liquid contain molecules that lack mirror symmetry, then it has been predicted by Fresnel that the light beam will not only change direction, but will actually split into two separate beams with a small difference in the respective angles of refraction. Here we report the observation of this phenomenon. We also demonstrate that the angle of reflection does not equal the angle of incidence in a chiral medium. Unlike conventional optical rotation, which depends on the path-length through the sample, the reported reflection and refraction phenomena arise within a few wavelengths at the interface and thereby suggest a new approach to polarimetry that can be used in microfluidic volumes.

Featured highlight ‘Fundamental optical physics: Refraction’ Nature Photonics, Nov. 2006.

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DOI [BibTex]

2006


DOI [BibTex]


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Direct chiral discrimination in NMR spectroscopy

Buckingham, A., Fischer, P.

CHEMICAL PHYSICS, 324(1):111-116, 2006 (article)

Abstract
Conventional nuclear magnetic resonance spectroscopy is unable to distinguish between the two mirror-image forms (enantiomers) of a chiral molecule. This is because the NMR spectrum is determined by the chemical shifts and spin-spin coupling constants which - in the absence of a chiral solvent - are identical for the two enantiomers. We discuss how chirality may nevertheless be directly detected in liquid-state NMR spectroscopy: In a chiral molecule, the rotating nuclear magnetic moment induces an electric dipole moment in the direction perpendicular to itself and to the permanent magnetic field of the spectrometer. We present computations of the precessing electric polarization following a pi/2 pulse. Our estimates indicate that the electric polarization should be detectable in favourable cases. We also predict that application of an electrostatic field induces a chirally sensitive magnetization oscillating in the direction of the permanent magnetic field. We show that the electric-field-perturbed chemical shift tensor, the nuclear magnetic shielding polarizability, underlies these chiral NMR effects. (c) 2005 Elsevier B.V. All rights reserved.

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DOI [BibTex]

DOI [BibTex]


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Ring-resonator-based frequency-domain optical activity measurements of a chiral liquid

Vollmer, F., Fischer, P.

OPTICS LETTERS, 31(4):453-455, 2006 (article)

Abstract
Chiral liquids rotate the plane of polarization of linearly polarized light and are therefore optically active. Here we show that optical rotation can be observed in the frequency domain. A chiral liquid introduced in a fiber-loop ring resonator that supports left and right circularly polarized modes gives rise to relative frequency shifts that are a direct measure of the liquid's circular birefringence and hence of its optical activity. The effect is in principle not diminished if the circumference of the ring is reduced. The technique is similarly applicable to refractive index and linear birefringence measurements. (c) 2006 Optical Society of America.

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DOI [BibTex]


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Sign of the refractive index in a gain medium with negative permittivity and permeability

Chen, Y., Fischer, P., Wise, F.

JOURNAL OF THE OPTICAL SOCIETY OF AMERICA B-OPTICAL PHYSICS, 23(1):45-50, 2006 (article)

Abstract
We show how the sign of the refractive index in any medium may be derived using a rigorous analysis based on Einstein causality. In particular, we consider left-handed materials, i.e., media that have negative permittivities and permeabilities at the frequency of interest. We find that the consideration of gain in such media can give rise to a positive refractive index. (c) 2006 Optical Society of America.

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DOI [BibTex]

DOI [BibTex]

1998


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Surface second-order nonlinear optical activity

Fischer, P., Buckingham, A.

JOURNAL OF THE OPTICAL SOCIETY OF AMERICA B-OPTICAL PHYSICS, 15(12):2951-2957, 1998 (article)

Abstract
Following the recent observation of a large second-harmonic intensity difference from a monolayer of chiral molecules with left and right circularly polarized light, the scattering theory is generalized and extended to predict linear and circular intensity differences for the more Versatile sum-frequency spectroscopy. Estimates indicate that intensity differences should be detectable for a typical experimental arrangement. The second-order nonlinear surface susceptibility tensor is given for different surface point groups in the electric dipole approximation; it is shown that nonlinear optical activity phenomena unambiguously probe molecular chirality only for molecular monolayers that are symmetric about the normal. Other surface symmetries can give rise to intensity differences from monolayers composed of achiral molecules. A water surface is predicted to show Linear and nonlinear optical activity in the presence of an electric field parallel to the surface. (C) 1998 Optical Society of America {[}S0740-3224(98)01311-3] OCIS codes: 190.0190, 190.4350, 240.6490.

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DOI [BibTex]

1998


DOI [BibTex]


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Linear electro-optic effect in optically active liquids

Buckingham, A., Fischer, P.

CHEMICAL PHYSICS LETTERS, 297(3-4):239-246, 1998 (article)

Abstract
A linear effect of an electrostatic field F on the intensity of sum- and difference-frequency generation in a chiral liquid is predicted. It arises in the electric dipole approximation. The effect changes sign with the enantiomer and on reversing the direction of the electrostatic field. The sum-frequency generator chi(alpha beta gamma)((2)) (-omega(3);omega(1),omega(2)), where omega(3) = omega(1) + omega(2), and the electric field-induced sum-frequency generator chi(alpha beta gamma delta)((3))(-omega(3);omega(1),omega(2),0)F-delta interfere and their contributions to the scattering power can be distinguished. Encouraging predictions are given for a typical experimental arrangement. (C) 1998 Elsevier Science B.V. All rights reserved.

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DOI [BibTex]

DOI [BibTex]


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Monolayers of hexadecyltrimethylammonium p-tosylate at the air-water interface. 1. Sum-frequency spectroscopy

Bell, G., Li, Z., Bain, C., Fischer, P., Duffy, D.

JOURNAL OF PHYSICAL CHEMISTRY B, 102(47):9461-9472, 1998 (article)

Abstract
Sum-frequency vibrational spectroscopy has been used to determine the structure of monolayers of the cationic surfactant, hexadecyltrimethylammonium p-tosylate (C(16)TA(+)Ts(-)), at the surface of water. Selective deuteration of the cation or the anion allowed the separate detection of sum-frequency spectra of the surfactant and of counterions that are bound to the monolayer. The p-tosylate ions an oriented with their methyl groups pointing away from the aqueous subphase and with the C-2 axis tilted, on average, by 30-40 degrees from the surface normal. The vibrational spectra of C(16)TA(+) indicate that the number of gauche defects in the monolayer does not change dramatically when bromide counterions are replaced by p-tosylate. The ends of the hydrocarbon chains of C16TA+ are, however, tilted much further from the surface normal in the presence of p-tosylate than in the presence of bromide. A quantitative analysis of the sum-frequency spectra requires a knowledge of the molecular hyperpolarizability tensor: the role of ab initio calculations and Raman spectroscopy in determining the components of this tensor is discussed.

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DOI [BibTex]

DOI [BibTex]


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Ultraviolet resonance Raman study of drug binding in dihydrofolate reductase, gyrase, and catechol O-methyltransferase

Couling, V., Fischer, P., Klenerman, D., Huber, W.

BIOPHYSICAL JOURNAL, 75(2):1097-1106, 1998 (article)

Abstract
This paper presents a study of the use of ultraviolet resonance Raman (UVRR) spectroscopic methods as a means of elucidating aspects of drug-protein interactions. Some of the RR vibrational bands of the aromatic amino acids tyrosine and tryptophan are sensitive to the microenvironment, and the use of UV excitation radiation allows selective enhancement of the spectral features of the aromatic amino acids, enabling observation specifically of their change in microenvironment upon drug binding. The three drug-protein systems investigated in this study are dihydrofolate reductase with its inhibitor trimethoprim, gyrase with novobiocin, and catechol O-methyltransferase with dinitrocatechol. It is demonstrated that UVRR spectroscopy has adequate sensitivity to be a useful means of detecting drug-protein interactions in those systems for which the electronic absorption of the aromatic amino acids changes because of hydrogen bonding and/or possible dipole-dipole and dipole-polarizability interactions with the ligand.

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DOI [BibTex]

DOI [BibTex]