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2020


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Sliding Mode Control with Gaussian Process Regression for Underwater Robots

Lima, G. S., Trimpe, S., Bessa, W. M.

Journal of Intelligent & Robotic Systems, January 2020 (article)

ics

DOI [BibTex]

2020


DOI [BibTex]


Hierarchical Event-triggered Learning for Cyclically Excited Systems with Application to Wireless Sensor Networks
Hierarchical Event-triggered Learning for Cyclically Excited Systems with Application to Wireless Sensor Networks

Beuchert, J., Solowjow, F., Raisch, J., Trimpe, S., Seel, T.

IEEE Control Systems Letters, 4(1):103-108, January 2020 (article)

ics

arXiv PDF DOI Project Page [BibTex]

arXiv PDF DOI Project Page [BibTex]


Control-guided Communication: Efficient Resource Arbitration and Allocation in Multi-hop Wireless Control Systems
Control-guided Communication: Efficient Resource Arbitration and Allocation in Multi-hop Wireless Control Systems

Baumann, D., Mager, F., Zimmerling, M., Trimpe, S.

IEEE Control Systems Letters, 4(1):127-132, January 2020 (article)

ics

arXiv PDF DOI [BibTex]

arXiv PDF DOI [BibTex]


Spatial Scheduling of Informative Meetings for Multi-Agent Persistent Coverage
Spatial Scheduling of Informative Meetings for Multi-Agent Persistent Coverage

Haksar, R. N., Trimpe, S., Schwager, M.

IEEE Robotics and Automation Letters, 2020 (article) Accepted

ics

DOI [BibTex]

DOI [BibTex]


Event-triggered Learning
Event-triggered Learning

Solowjow, F., Trimpe, S.

Automatica, 2020 (article) Accepted

ics

arXiv PDF Project Page [BibTex]


Safe and Fast Tracking on a Robot Manipulator: Robust MPC and Neural Network Control
Safe and Fast Tracking on a Robot Manipulator: Robust MPC and Neural Network Control

Nubert, J., Koehler, J., Berenz, V., Allgower, F., Trimpe, S.

IEEE Robotics and Automation Letters, 2020 (article) Accepted

Abstract
Fast feedback control and safety guarantees are essential in modern robotics. We present an approach that achieves both by combining novel robust model predictive control (MPC) with function approximation via (deep) neural networks (NNs). The result is a new approach for complex tasks with nonlinear, uncertain, and constrained dynamics as are common in robotics. Specifically, we leverage recent results in MPC research to propose a new robust setpoint tracking MPC algorithm, which achieves reliable and safe tracking of a dynamic setpoint while guaranteeing stability and constraint satisfaction. The presented robust MPC scheme constitutes a one-layer approach that unifies the often separated planning and control layers, by directly computing the control command based on a reference and possibly obstacle positions. As a separate contribution, we show how the computation time of the MPC can be drastically reduced by approximating the MPC law with a NN controller. The NN is trained and validated from offline samples of the MPC, yielding statistical guarantees, and used in lieu thereof at run time. Our experiments on a state-of-the-art robot manipulator are the first to show that both the proposed robust and approximate MPC schemes scale to real-world robotic systems.

am ics

arXiv PDF DOI [BibTex]

arXiv PDF DOI [BibTex]

2015


Enzymatically active biomimetic micropropellers for the penetration of mucin gels
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.

pf

link (url) DOI [BibTex]

2015


link (url) DOI [BibTex]


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Distributed Event-based State Estimation

Trimpe, S.

Max Planck Institute for Intelligent Systems, November 2015 (techreport)

Abstract
An event-based state estimation approach for reducing communication in a networked control system is proposed. Multiple distributed sensor-actuator-agents observe a dynamic process and sporadically exchange their measurements and inputs over a bus network. Based on these data, each agent estimates the full state of the dynamic system, which may exhibit arbitrary inter-agent couplings. Local event-based protocols ensure that data is transmitted only when necessary to meet a desired estimation accuracy. This event-based scheme is shown to mimic a centralized Luenberger observer design up to guaranteed bounds, and stability is proven in the sense of bounded estimation errors for bounded disturbances. The stability result extends to the distributed control system that results when the local state estimates are used for distributed feedback control. Simulation results highlight the benefit of the event-based approach over classical periodic ones in reducing communication requirements.

am ics

arXiv [BibTex]

arXiv [BibTex]


Automatic LQR Tuning Based on Gaussian Process Optimization: Early Experimental Results
Automatic LQR Tuning Based on Gaussian Process Optimization: Early Experimental Results

Marco, A., Hennig, P., Bohg, J., Schaal, S., Trimpe, S.

Machine Learning in Planning and Control of Robot Motion Workshop at the IEEE/RSJ International Conference on Intelligent Robots and Systems (iROS), pages: , , Machine Learning in Planning and Control of Robot Motion Workshop, October 2015 (conference)

Abstract
This paper proposes an automatic controller tuning framework based on linear optimal control combined with Bayesian optimization. With this framework, an initial set of controller gains is automatically improved according to a pre-defined performance objective evaluated from experimental data. The underlying Bayesian optimization algorithm is Entropy Search, which represents the latent objective as a Gaussian process and constructs an explicit belief over the location of the objective minimum. This is used to maximize the information gain from each experimental evaluation. Thus, this framework shall yield improved controllers with fewer evaluations compared to alternative approaches. A seven-degree-of-freedom robot arm balancing an inverted pole is used as the experimental demonstrator. Preliminary results of a low-dimensional tuning problem highlight the method’s potential for automatic controller tuning on robotic platforms.

am ei ics pn

PDF DOI Project Page [BibTex]

PDF DOI Project Page [BibTex]


The EChemPen: A Guiding Hand To Learn Electrochemical Surface Modifications
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.

pf

DOI [BibTex]

DOI [BibTex]


3D-printed Soft Microrobot for Swimming in Biological Fluids
3D-printed Soft Microrobot for Swimming in Biological Fluids

Qiu, T., Palagi, S., Fischer, P.

In Conf. Proc. IEEE Eng. Med. Biol. Soc., pages: 4922-4925, August 2015 (inproceedings)

Abstract
Microscopic artificial swimmers hold the potential to enable novel non-invasive medical procedures. In order to ease their translation towards real biomedical applications, simpler designs as well as cheaper yet more reliable materials and fabrication processes should be adopted, provided that the functionality of the microrobots can be kept. A simple single-hinge design could already enable microswimming in non-Newtonian fluids, which most bodily fluids are. Here, we address the fabrication of such single-hinge microrobots with a 3D-printed soft material. Firstly, a finite element model is developed to investigate the deformability of the 3D-printed microstructure under typical values of the actuating magnetic fields. Then the microstructures are fabricated by direct 3D-printing of a soft material and their swimming performances are evaluated. The speeds achieved with the 3D-printed microrobots are comparable to those obtained in previous work with complex fabrication procedures, thus showing great promise for 3D-printed microrobots to be operated in biological fluids.

pf

link (url) DOI [BibTex]

link (url) DOI [BibTex]


Direct Loss Minimization Inverse Optimal Control
Direct Loss Minimization Inverse Optimal Control

Doerr, A., Ratliff, N., Bohg, J., Toussaint, M., Schaal, S.

In Proceedings of Robotics: Science and Systems, Rome, Italy, Robotics: Science and Systems XI, July 2015 (inproceedings)

Abstract
Inverse Optimal Control (IOC) has strongly impacted the systems engineering process, enabling automated planner tuning through straightforward and intuitive demonstration. The most successful and established applications, though, have been in lower dimensional problems such as navigation planning where exact optimal planning or control is feasible. In higher dimensional systems, such as humanoid robots, research has made substantial progress toward generalizing the ideas to model free or locally optimal settings, but these systems are complicated to the point where demonstration itself can be difficult. Typically, real-world applications are restricted to at best noisy or even partial or incomplete demonstrations that prove cumbersome in existing frameworks. This work derives a very flexible method of IOC based on a form of Structured Prediction known as Direct Loss Minimization. The resulting algorithm is essentially Policy Search on a reward function that rewards similarity to demonstrated behavior (using Covariance Matrix Adaptation (CMA) in our experiments). Our framework blurs the distinction between IOC, other forms of Imitation Learning, and Reinforcement Learning, enabling us to derive simple, versatile, and practical algorithms that blend imitation and reinforcement signals into a unified framework. Our experiments analyze various aspects of its performance and demonstrate its efficacy on conveying preferences for motion shaping and combined reach and grasp quality optimization.

am ics

PDF Video Project Page [BibTex]

PDF Video Project Page [BibTex]


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LMI-Based Synthesis for Distributed Event-Based State Estimation

Muehlebach, M., Trimpe, S.

In Proceedings of the American Control Conference, July 2015 (inproceedings)

Abstract
This paper presents an LMI-based synthesis procedure for distributed event-based state estimation. Multiple agents observe and control a dynamic process by sporadically exchanging data over a broadcast network according to an event-based protocol. In previous work [1], the synthesis of event-based state estimators is based on a centralized design. In that case three different types of communication are required: event-based communication of measurements, periodic reset of all estimates to their joint average, and communication of inputs. The proposed synthesis problem eliminates the communication of inputs as well as the periodic resets (under favorable circumstances) by accounting explicitly for the distributed structure of the control system.

am ics

PDF DOI Project Page [BibTex]

PDF DOI Project Page [BibTex]


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Guaranteed H2 Performance in Distributed Event-Based State Estimation

Muehlebach, M., Trimpe, S.

In Proceeding of the First International Conference on Event-based Control, Communication, and Signal Processing, June 2015 (inproceedings)

am ics

PDF DOI Project Page [BibTex]

PDF DOI Project Page [BibTex]


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On the Choice of the Event Trigger in Event-based Estimation

Trimpe, S., Campi, M.

In Proceeding of the First International Conference on Event-based Control, Communication, and Signal Processing, June 2015 (inproceedings)

am ics

PDF DOI Project Page [BibTex]

PDF DOI Project Page [BibTex]


Optimal Length of Low Reynolds Number Nanopropellers
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.

pf

DOI [BibTex]

DOI [BibTex]


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

pf

DOI [BibTex]

DOI [BibTex]


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Event-based Estimation and Control for Remote Robot Operation with Reduced Communication

Trimpe, S., Buchli, J.

In Proceedings of the IEEE International Conference on Robotics and Automation, May 2015 (inproceedings)

Abstract
An event-based communication framework for remote operation of a robot via a bandwidth-limited network is proposed. The robot sends state and environment estimation data to the operator, and the operator transmits updated control commands or policies to the robot. Event-based communication protocols are designed to ensure that data is transmitted only when required: the robot sends new estimation data only if this yields a significant information gain at the operator, and the operator transmits an updated control policy only if this comes with a significant improvement in control performance. The developed framework is modular and can be used with any standard estimation and control algorithms. Simulation results of a robotic arm highlight its potential for an efficient use of limited communication resources, for example, in disaster response scenarios such as the DARPA Robotics Challenge.

am ics

PDF DOI Project Page [BibTex]

PDF DOI Project Page [BibTex]


Dynamic Inclusion Complexes of Metal Nanoparticles Inside Nanocups
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.

pf

DOI [BibTex]

DOI [BibTex]


Surface roughness-induced speed increase for active Janus micromotors
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.

pf

DOI [BibTex]

DOI [BibTex]


Active colloidal microdrills
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.

pf

DOI [BibTex]

DOI [BibTex]


Selectable Nanopattern Arrays for Nanolithographic Imprint and Etch-Mask Applications
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.

pf

link (url) DOI [BibTex]

link (url) DOI [BibTex]


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A New Perspective and Extension of the Gaussian Filter

Wüthrich, M., Trimpe, S., Kappler, D., Schaal, S.

In Robotics: Science and Systems, 2015 (inproceedings)

Abstract
The Gaussian Filter (GF) is one of the most widely used filtering algorithms; instances are the Extended Kalman Filter, the Unscented Kalman Filter and the Divided Difference Filter. GFs represent the belief of the current state by a Gaussian with the mean being an affine function of the measurement. We show that this representation can be too restrictive to accurately capture the dependencies in systems with nonlinear observation models, and we investigate how the GF can be generalized to alleviate this problem. To this end we view the GF from a variational-inference perspective, and analyze how restrictions on the form of the belief can be relaxed while maintaining simplicity and efficiency. This analysis provides a basis for generalizations of the GF. We propose one such generalization which coincides with a GF using a virtual measurement, obtained by applying a nonlinear function to the actual measurement. Numerical experiments show that the proposed Feature Gaussian Filter (FGF) can have a substantial performance advantage over the standard GF for systems with nonlinear observation models.

am ics

Web PDF Project Page [BibTex]

2007


Frequency-domain displacement sensing with a fiber ring-resonator containing a variable gap
Frequency-domain displacement sensing with a fiber ring-resonator containing a variable gap

Vollmer, F., Fischer, P.

SENSORS AND ACTUATORS A-PHYSICAL, 134(2):410-413, 2007 (article)

Abstract
Ring-resonators are in general not amenable to strain-free (non-contact) displacement measurements. We show that this limitation may be overcome if the ring-resonator, here a fiber-loop, is designed to contain a gap, such that the light traverses a free-space part between two aligned waveguide ends. Displacements are determined with nanometer sensitivity by measuring the associated changes in the resonance frequencies. Miniaturization should increase the sensitivity of the ring-resonator interferometer. Ring geometries that contain an optical circulator can be used to profile reflective samples. (c) 2006 Elsevier B.V. All rights reserved.

pf

DOI [BibTex]

2007


DOI [BibTex]


Observation of the Faraday effect via beam deflection in a longitudinal magnetic field
Observation of the Faraday effect via beam deflection in a longitudinal magnetic field

Ghosh, A., Hill, W., Fischer, P.

PHYSICAL REVIEW A, 76(5), 2007 (article)

Abstract
We show that magnetic-field-induced circular differential deflection of light can be observed in reflection or refraction at a single interface. The difference in the reflection or refraction angles between the two circular polarization components is a function of the magnetic-field strength and the Verdet constant, and permits the observation of the Faraday effect not via polarization rotation in transmission, but via changes in the propagation direction. Deflection measurements do not suffer from n-pi ambiguities and are shown to be another means to map magnetic fields with high axial resolution, or to determine the sign and magnitude of magnetic-field pulses in a single measurement.

pf

DOI [BibTex]


Circular differential double diffraction in chiral media
Circular differential double diffraction in chiral media

Ghosh, A., Fazal, F. M., Fischer, P.

OPTICS LETTERS, 32(13):1836-1838, 2007 (article)

Abstract
In an optically active liquid the diffraction angle depends on the circular polarization state of the incident light beam. We report the observation of circular differential diffraction in an isotropic chiral medium, and we demonstrate that double diffraction is an alternate means to determine the handedness (enantiomeric excess) of a solution. (c) 2007 Optical Society of America.

pf

DOI [BibTex]

DOI [BibTex]

2005


Nonlinear optical spectroscopy of chiral molecules
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.

pf

DOI [BibTex]

2005


DOI [BibTex]


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

pf

DOI [BibTex]

DOI [BibTex]

2002


Chirality-specific nonlinear spectroscopies in isotropic media
Chirality-specific nonlinear spectroscopies in isotropic media

Fischer, P., Albrecht, A.

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 75(5):1119-1124, 2002, 10th International Conference on Time-Resolved Vibrational Spectroscopy (TRVS 2001), OKAZZAKI, JAPAN, MAY 21-25, 2001 (article)

Abstract
Sum or difference frequency generation (SFG or DFG) in isotropic media is in the electric-dipole approximation only symmetry allowed for optically active systems. The hyperpolarizability giving rise to these three-wave mixing processes features only one isotropic component. It factorizes into two terms, an energy (denominator) factor and a triple product of transition moments. These forbid degenerate SFG, i.e., second harmonic generation, as well as the existence of the linear electrooptic effect (Pockels effect) in isotropic media. This second order response also has no static limit, which leads to particularly strong resonance phenomena that are qualitatively different from those usually seen in the ubiquitous even-wave mixing spectroscopies. In particular, the participation of two (not the usual one) excited states is essential to achieve dramatic resonance enhancement, We report our first efforts to see such resonantly enhanced chirality specific SFG.

pf

DOI [BibTex]

2002


DOI [BibTex]


The chiral specificity of sum-frequency generation in solutions
The chiral specificity of sum-frequency generation in solutions

Fischer, P., Beckwitt, K., Wise, F., Albrecht, A.

CHEMICAL PHYSICS LETTERS, 352(5-6):463-468, 2002 (article)

Abstract
Sum-frequency generation in isotropic media is in the electric-dipole approximation the only symmetry allowed for chiral systems. We demonstrate that the sum-frequency intensity from an optically active liquid depends quadratically on the difference in concentration of the two enantiomers. The dominant contribution to the signal is found to be due to the chirality specific electric-dipolar three-wave mixing nonlinearity. Selecting the polarization of all fields allows the chiral electric-dipolar contributions to the bulk sum-frequency signal to be discerned from any achiral magnetic-dipolar and electric-quadrupolar contributions. (C) 2002 Published by Elsevier Science B.V.

pf

DOI [BibTex]

DOI [BibTex]


On optical rectification in isotropic media
On optical rectification in isotropic media

Fischer, P., Albrecht, A.

LASER PHYSICS, 12(8):1177-1181, 2002 (article)

Abstract
Coherent nonlinear optical processes at second-order are only electric-dipole allowed in isotropic media that are optically active. Sum-frequency generation in chiral liquids has recently been observed, and difference-frequency and optical rectification have been predicted to exist in isotropic chiral media. Both Rayleigh-Schrodinger perturbation theory and the density matrix approach are used to discuss the quantum-chemical basis of optical rectification in optically active liquids. For pinene we compute the corresponding orientationally averaged hyperpolarizability, and estimate the light-induced dc electric polarization and the consequent voltage across a measuring capacitor it may give rise to near resonance.

pf

[BibTex]

[BibTex]

1998


Surface second-order nonlinear optical activity
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.

pf

DOI [BibTex]

1998


DOI [BibTex]


Linear electro-optic effect in optically active liquids
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.

pf

DOI [BibTex]

DOI [BibTex]


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

pf

DOI [BibTex]

DOI [BibTex]


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

pf

DOI [BibTex]

DOI [BibTex]