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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]


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Novel plasticity rule can explain the development of sensorimotor intelligence

Der, R., Martius, G.

Proceedings of the National Academy of Sciences, 112(45):E6224-E6232, 2015 (article)

Abstract
Grounding autonomous behavior in the nervous system is a fundamental challenge for neuroscience. In particular, self-organized behavioral development provides more questions than answers. Are there special functional units for curiosity, motivation, and creativity? This paper argues that these features can be grounded in synaptic plasticity itself, without requiring any higher-level constructs. We propose differential extrinsic plasticity (DEP) as a new synaptic rule for self-learning systems and apply it to a number of complex robotic systems as a test case. Without specifying any purpose or goal, seemingly purposeful and adaptive rhythmic behavior is developed, displaying a certain level of sensorimotor intelligence. These surprising results require no system-specific modifications of the DEP rule. They rather arise from the underlying mechanism of spontaneous symmetry breaking, which is due to the tight brain body environment coupling. The new synaptic rule is biologically plausible and would be an interesting target for neurobiological investigation. We also argue that this neuronal mechanism may have been a catalyst in natural evolution.

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link (url) DOI Project Page [BibTex]

link (url) DOI Project Page [BibTex]


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Quantifying Emergent Behavior of Autonomous Robots

Martius, G., Olbrich, E.

Entropy, 17(10):7266, 2015 (article)

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link (url) DOI [BibTex]

link (url) DOI [BibTex]

2010


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Molecular QED of coherent and incoherent sum-frequency and second-harmonic generation in chiral liquids in the presence of a static electric field

Fischer, P., Salam, A.

MOLECULAR PHYSICS, 108(14):1857-1868, 2010 (article)

Abstract
Coherent second-order nonlinear optical processes are symmetry forbidden in centrosymmetric environments in the electric-dipole approximation. In liquids that contain chiral molecules, however, and which therefore lack mirror image symmetry, coherent sum-frequency generation is possible, whereas second-harmonic generation remains forbidden. Here we apply the theory of molecular quantum electrodynamics to the calculation of the matrix element, transition rate, and integrated signal intensity for sum-frequency and second-harmonic generation taking place in a chiral liquid in the presence and absence of a static electric field, to examine which coherent and incoherent processes exist in the electric-dipole approximation in liquids. Third- and fourth-order time-dependent perturbation theory is employed in combination with single-sided Feynman diagrams to evaluate two contributions arising from static field-free and field-induced processes. It is found that, in addition to the coherent term, an incoherent process exists for sum-frequency generation in liquids. Surprisingly, in the case of dc-field-induced second-harmonic generation, the incoherent contribution is found to always vanish for isotropic chiral liquids even though hyper-Rayleigh second-harmonic generation and electric-field-induced second-harmonic generation are both independently symmetry allowed in any liquid.

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DOI [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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2009


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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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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]


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A Sensor-Based Learning Algorithm for the Self-Organization of Robot Behavior

Hesse, F., Martius, G., Der, R., Herrmann, J. M.

Algorithms, 2(1):398-409, 2009 (article)

Abstract
Ideally, sensory information forms the only source of information to a robot. We consider an algorithm for the self-organization of a controller. At short timescales the controller is merely reactive but the parameter dynamics and the acquisition of knowledge by an internal model lead to seemingly purposeful behavior on longer timescales. As a paradigmatic example, we study the simulation of an underactuated snake-like robot. By interacting with the real physical system formed by the robotic hardware and the environment, the controller achieves a sensitive and body-specific actuation of the robot.

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link (url) [BibTex]

link (url) [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]


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Rocking Stamper and Jumping Snake from a Dynamical System Approach to Artificial Life

Der, R., Hesse, F., Martius, G.

Adaptive Behavior, 14(2):105-115, 2006 (article)

Abstract
Dynamical systems offer intriguing possibilities as a substrate for the generation of behavior because of their rich behavioral complexity. However this complexity together with the largely covert relation between the parameters and the behavior of the agent is also the main hindrance in the goal-oriented design of a behavior system. This paper presents a general approach to the self-regulation of dynamical systems so that the design problem is circumvented. We consider the controller (a neural net work) as the mediator for changes in the sensor values over time and define a dynamics for the parameters of the controller by maximizing the dynamical complexity of the sensorimotor loop under the condition that the consequences of the actions taken are still predictable. This very general principle is given a concrete mathematical formulation and is implemented in an extremely robust and versatile algorithm for the parameter dynamics of the controller. We consider two different applications, a mechanical device called the rocking stamper and the ODE simulations of a "snake" with five degrees of freedom. In these and many other examples studied we observed various behavior modes of high dynamical complexity.

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DOI [BibTex]

DOI [BibTex]

2005


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Nonlinear optical spectroscopy of chiral molecules

Fischer, P., Hache, F.

CHIRALITY, 17(8):421-437, 2005 (article)

Abstract
We review nonlinear optical processes that are specific to chiral molecules in solution and on surfaces. In contrast to conventional natural optical activity phenomena, which depend linearly on the electric field strength of the optical field, we discuss how optical processes that are nonlinear (quadratic, cubic, and quartic) functions of the electromagnetic field strength may probe optically active centers and chiral vibrations. We show that nonlinear techniques open entirely new ways of exploring chirality in chemical and biological systems: The cubic processes give rise to nonlinear circular dichroism and nonlinear optical rotation and make it possible to observe dynamic chiral processes at ultrafast time scales. The quadratic second-harmonic and sum-frequency-generation phenomena and the quartic processes may arise entirely in the electric-dipole approximation and do not require the use of circularly polarized light to detect chirality: They provide surface selectivity and their observables can be relatively much larger than in linear optical activity. These processes also give rise to the generation of light at a new color, and in liquids this frequency conversion only occurs if the solution is optically active. We survey recent chiral nonlinear optical experiments and give examples of their application to problems of biophysical interest. (C) 2005 Wiley-Liss, Inc.

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DOI [BibTex]

2005


DOI [BibTex]


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Negative refraction at optical frequencies in nonmagnetic two-component molecular media

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

PHYSICAL REVIEW LETTERS, 95(6), 2005 (article)

Abstract
There is significant motivation to develop media with negative refractive indices at optical frequencies, but efforts in this direction are hampered by the weakness of the magnetic response at such frequencies. We show theoretically that a nonmagnetic medium with two atomic or molecular constituents can exhibit a negative refractive index. A negative index is possible even when the real parts of both the permittivity and permeability are positive. This surprising result provides a route to isotropic negative-index media at optical frequencies.

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DOI [BibTex]

DOI [BibTex]