Publications | Max Planck Institute for Intelligent Systems

44 results (View BibTeX file of all listed publications)

2018

Role of symmetry in driven propulsion at low Reynolds number

Sachs, J., Morozov, K. I., Kenneth, O., Qiu, T., Segreto, N., Fischer, P., Leshansky, A. M.

Phys. Rev. E, 98(6):063105, American Physical Society, December 2018 (article)

Abstract

We theoretically and experimentally investigate low-Reynolds-number propulsion of geometrically achiral planar objects that possess a dipole moment and that are driven by a rotating magnetic field. Symmetry considerations (involving parity, $\widehat{P}$, and charge conjugation, $\widehat{C}$) establish correspondence between propulsive states depending on orientation of the dipolar moment. Although basic symmetry arguments do not forbid individual symmetric objects to efficiently propel due to spontaneous symmetry breaking, they suggest that the average ensemble velocity vanishes. Some additional arguments show, however, that highly symmetrical ($\widehat{P}$-even) objects exhibit no net propulsion while individual less symmetrical ($\widehat{C}\widehat{P}$-even) propellers do propel. Particular magnetization orientation, rendering the shape $\widehat{C}\widehat{P}$-odd, yields unidirectional motion typically associated with chiral structures, such as helices. If instead of a structure with a permanent dipole we consider a polarizable object, some of the arguments have to be modified. For instance, we demonstrate a truly achiral ($\widehat{P}$- and $\widehat{C}\widehat{P}$-even) planar shape with an induced electric dipole that can propel by electro-rotation. We thereby show that chirality is not essential for propulsion due to rotation-translation coupling at low Reynolds number.

link (url) DOI Project Page [BibTex]

2018

pf Sachs, J., Morozov, K. I., Kenneth, O., Qiu, T., Segreto, N., Fischer, P., Leshansky, A. M. Role of symmetry in driven propulsion at low Reynolds number Phys. Rev. E, 98(6):063105, American Physical Society, December 2018 (article)

link (url) DOI Project Page [BibTex]

Deep Reinforcement Learning for Event-Triggered Control

Baumann, D., Zhu, J., Martius, G., Trimpe, S.

In Proceedings of the 57th IEEE International Conference on Decision and Control (CDC), pages: 943-950, 57th IEEE International Conference on Decision and Control (CDC), December 2018 (inproceedings)

al ics

arXiv PDF DOI Project Page Project Page [BibTex]

al ics Baumann, D., Zhu, J., Martius, G., Trimpe, S. Deep Reinforcement Learning for Event-Triggered Control In Proceedings of the 57th IEEE International Conference on Decision and Control (CDC), pages: 943-950, 57th IEEE International Conference on Decision and Control (CDC), December 2018 (inproceedings)

arXiv PDF DOI Project Page Project Page [BibTex]

Efficient Encoding of Dynamical Systems through Local Approximations

Solowjow, F., Mehrjou, A., Schölkopf, B., Trimpe, S.

In Proceedings of the 57th IEEE International Conference on Decision and Control (CDC), pages: 6073 - 6079 , Miami, Fl, USA, December 2018 (inproceedings)

ei ics

arXiv PDF DOI Project Page [BibTex]

ei ics Solowjow, F., Mehrjou, A., Schölkopf, B., Trimpe, S. Efficient Encoding of Dynamical Systems through Local Approximations In Proceedings of the 57th IEEE International Conference on Decision and Control (CDC), pages: 6073 - 6079 , Miami, Fl, USA, December 2018 (inproceedings)

arXiv PDF DOI Project Page [BibTex]

Optical and Thermophoretic Control of Janus Nanopen Injection into Living Cells

Maier, C. M., Huergo, M. A., Milosevic, S., Pernpeintner, C., Li, M., Singh, D. P., Walker, D., Fischer, P., Feldmann, J., Lohmüller, T.

Nano Letters, 18, pages: 7935–7941, November 2018 (article) Accepted

Abstract

Devising strategies for the controlled injection of functional nanoparticles and reagents into living cells paves the way for novel applications in nanosurgery, sensing, and drug delivery. Here, we demonstrate the light-controlled guiding and injection of plasmonic Janus nanopens into living cells. The pens are made of a gold nanoparticle attached to a dielectric alumina shaft. Balancing optical and thermophoretic forces in an optical tweezer allows single Janus nanopens to be trapped and positioned on the surface of living cells. While the optical injection process involves strong heating of the plasmonic side, the temperature of the alumina stays significantly lower, thus allowing the functionalization with fluorescently labeled, single-stranded DNA and, hence, the spatially controlled injection of genetic material with an untethered nanocarrier.

link (url) DOI [BibTex]

pf Maier, C. M., Huergo, M. A., Milosevic, S., Pernpeintner, C., Li, M., Singh, D. P., Walker, D., Fischer, P., Feldmann, J., Lohmüller, T. Optical and Thermophoretic Control of Janus Nanopen Injection into Living Cells Nano Letters, 18, pages: 7935–7941, November 2018 (article) Accepted

link (url) DOI [BibTex]

A swarm of slippery micropropellers penetrates the vitreous body of the eye

Wu, Z., Troll, J., Jeong, H. H., Wei, Q., Stang, M., Ziemssen, F., Wang, Z., Dong, M., Schnichels, S., Qiu, T., Fischer, P.

Science Advances, 4(11):eaat4388, November 2018 (article)

Abstract

The intravitreal delivery of therapeutic agents promises major benefits in the field of ocular medicine. Traditional delivery methods rely on the random, passive diffusion of molecules, which do not allow for the rapid delivery of a concentrated cargo to a defined region at the posterior pole of the eye. The use of particles promises targeted delivery but faces the challenge that most tissues including the vitreous have a tight macromolecular matrix that acts as a barrier and prevents its penetration. Here, we demonstrate novel intravitreal delivery microvehicles slippery micropropellers that can be actively propelled through the vitreous humor to reach the retina. The propulsion is achieved by helical magnetic micropropellers that have a liquid layer coating to minimize adhesion to the surrounding biopolymeric network. The submicrometer diameter of the propellers enables the penetration of the biopolymeric network and the propulsion through the porcine vitreous body of the eye over centimeter distances. Clinical optical coherence tomography is used to monitor the movement of the propellers and confirm their arrival on the retina near the optic disc. Overcoming the adhesion forces and actively navigating a swarm of micropropellers in the dense vitreous humor promise practical applications in ophthalmology.

Video: Nanorobots propel through the eye link (url) DOI [BibTex]

pf Wu, Z., Troll, J., Jeong, H. H., Wei, Q., Stang, M., Ziemssen, F., Wang, Z., Dong, M., Schnichels, S., Qiu, T., Fischer, P. A swarm of slippery micropropellers penetrates the vitreous body of the eye Science Advances, 4(11):eaat4388, November 2018 (article)

Video: Nanorobots propel through the eye link (url) DOI [BibTex]

Depth Control of Underwater Robots using Sliding Modes and Gaussian Process Regression

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

In Proceeding of the 15th Latin American Robotics Symposium, João Pessoa, Brazil, 15th Latin American Robotics Symposium, November 2018 (inproceedings)

Abstract

The development of accurate control systems for underwater robotic vehicles relies on the adequate compensation for hydrodynamic effects. In this work, a new robust control scheme is presented for remotely operated underwater vehicles. In order to meet both robustness and tracking requirements, sliding mode control is combined with Gaussian process regression. The convergence properties of the closed-loop signals are analytically proven. Numerical results confirm the stronger improved performance of the proposed control scheme.

ics

[BibTex]

ics Lima, G. S., Bessa, W. M., Trimpe, S. Depth Control of Underwater Robots using Sliding Modes and Gaussian Process Regression In Proceeding of the 15th Latin American Robotics Symposium, João Pessoa, Brazil, 15th Latin American Robotics Symposium, November 2018 (inproceedings)

[BibTex]

Gait learning for soft microrobots controlled by light fields

Rohr, A. V., Trimpe, S., Marco, A., Fischer, P., Palagi, S.

In International Conference on Intelligent Robots and Systems (IROS) 2018, pages: 6199-6206, International Conference on Intelligent Robots and Systems 2018, October 2018 (inproceedings)

Abstract

Soft microrobots based on photoresponsive materials and controlled by light fields can generate a variety of different gaits. This inherent flexibility can be exploited to maximize their locomotion performance in a given environment and used to adapt them to changing environments. However, because of the lack of accurate locomotion models, and given the intrinsic variability among microrobots, analytical control design is not possible. Common data-driven approaches, on the other hand, require running prohibitive numbers of experiments and lead to very sample-specific results. Here we propose a probabilistic learning approach for light-controlled soft microrobots based on Bayesian Optimization (BO) and Gaussian Processes (GPs). The proposed approach results in a learning scheme that is highly data-efficient, enabling gait optimization with a limited experimental budget, and robust against differences among microrobot samples. These features are obtained by designing the learning scheme through the comparison of different GP priors and BO settings on a semisynthetic data set. The developed learning scheme is validated in microrobot experiments, resulting in a 115% improvement in a microrobot’s locomotion performance with an experimental budget of only 20 tests. These encouraging results lead the way toward self-adaptive microrobotic systems based on lightcontrolled soft microrobots and probabilistic learning control.

ics pf

arXiv IEEE Xplore DOI Project Page [BibTex]

ics pf Rohr, A. V., Trimpe, S., Marco, A., Fischer, P., Palagi, S. Gait learning for soft microrobots controlled by light fields In International Conference on Intelligent Robots and Systems (IROS) 2018, pages: 6199-6206, International Conference on Intelligent Robots and Systems 2018, October 2018 (inproceedings)

arXiv IEEE Xplore DOI Project Page [BibTex]

Nanoscale robotic agents in biological fluids and tissues

Palagi, S., Walker, D. Q. T., Fischer, P.

In The Encyclopedia of Medical Robotics, 2, pages: 19-42, 2, (Editors: Desai, J. P. and Ferreira, A.), World Scientific, October 2018 (inbook)

Abstract

Nanorobots are untethered structures of sub-micron size that can be controlled in a non-trivial way. Such nanoscale robotic agents are envisioned to revolutionize medicine by enabling minimally invasive diagnostic and therapeutic procedures. To be useful, nanorobots must be operated in complex biological fluids and tissues, which are often difficult to penetrate. In this chapter, we first discuss potential medical applications of motile nanorobots. We briefly present the challenges related to swimming at such small scales and we survey the rheological properties of some biological fluids and tissues. We then review recent experimental results in the development of nanorobots and in particular their design, fabrication, actuation, and propulsion in complex biological fluids and tissues. Recent work shows that their nanoscale dimension is a clear asset for operation in biological tissues, since many biological tissues consist of networks of macromolecules that prevent the passage of larger micron-scale structures, but contain dynamic pores through which nanorobots can move.

link (url) DOI [BibTex]

pf Palagi, S., Walker, D. Q. T., Fischer, P. Nanoscale robotic agents in biological fluids and tissues In The Encyclopedia of Medical Robotics, 2, pages: 19-42, 2, (Editors: Desai, J. P. and Ferreira, A.), World Scientific, October 2018 (inbook)

link (url) DOI [BibTex]

Fast spatial scanning of 3D ultrasound fields via thermography

Melde, K., Qiu, T., Fischer, P.

Applied Physics Letters, 113(13):133503, September 2018 (article)

Abstract

We propose and demonstrate a thermographic method that allows rapid scanning of ultrasound fields in a volume to yield 3D maps of the sound intensity. A thin sound-absorbing membrane is continuously translated through a volume of interest while a thermal camera records the evolution of its surface temperature. The temperature rise is a function of the absorbed sound intensity, such that the thermal image sequence can be combined to reveal the sound intensity distribution in the traversed volume. We demonstrate the mapping of ultrasound fields, which is several orders of magnitude faster than scanning with a hydrophone. Our results are in very good agreement with theoretical simulations.

link (url) DOI Project Page [BibTex]

pf Melde, K., Qiu, T., Fischer, P. Fast spatial scanning of 3D ultrasound fields via thermography Applied Physics Letters, 113(13):133503, September 2018 (article)

link (url) DOI Project Page [BibTex]

Diffusion Measurements of Swimming Enzymes with Fluorescence Correlation Spectroscopy

Günther, J., Börsch, M., Fischer, P.

Accounts of Chemical Research, 51(9):1911-1920, August 2018 (article)

Abstract

Self-propelled chemical motors are chemically powered micro- or nanosized swimmers. The energy required for these motors’ active motion derives from catalytic chemical reactions and the transformation of a fuel dissolved in the solution. While self-propulsion is now well established for larger particles, it is still unclear if enzymes, nature’s nanometer-sized catalysts, are potentially also self-powered nanomotors. Because of its small size, any increase in an enzyme’s diffusion due to active self-propulsion must be observed on top of the enzyme’s passive Brownian motion, which dominates at this scale. Fluorescence correlation spectroscopy (FCS) is a sensitive method to quantify the diffusion properties of single fluorescently labeled molecules in solution. FCS experiments have shown a general increase in the diffusion constant of a number of enzymes when the enzyme is catalytically active. Diffusion enhancements after addition of the enzyme’s substrate (and sometimes its inhibitor) of up to 80\% have been reported, which is at least 1 order of magnitude higher than what theory would predict. However, many factors contribute to the FCS signal and in particular the shape of the autocorrelation function, which underlies diffusion measurements by fluorescence correlation spectroscopy. These effects need to be considered to establish if and by how much the catalytic activity changes an enzyme’s diffusion.We carefully review phenomena that can play a role in FCS experiments and the determination of enzyme diffusion, including the dissociation of enzyme oligomers upon interaction with the substrate, surface binding of the enzyme to glass during the experiment, conformational changes upon binding, and quenching of the fluorophore. We show that these effects can cause changes in the FCS signal that behave similar to an increase in diffusion. However, in the case of the enzymes F1-ATPase and alkaline phosphatase, we demonstrate that there is no measurable increase in enzyme diffusion. Rather, dissociation and conformational changes account for the changes in the FCS signal in the former and fluorophore quenching in the latter. Within the experimental accuracy of our FCS measurements, we do not observe any change in diffusion due to activity for the enzymes we have investigated.We suggest useful control experiments and additional tests for future FCS experiments that should help establish if the observed diffusion enhancement is real or if it is due to an experimental or data analysis artifact. We show that fluorescence lifetime and mean intensity measurements are essential in order to identify the nature of the observed changes in the autocorrelation function. While it is clear from theory that chemically active enzymes should also act as self-propelled nanomotors, our FCS measurements show that the associated increase in diffusion is much smaller than previously reported. Further experiments are needed to quantify the contribution of the enzymes’ catalytic activity to their self-propulsion. We hope that our findings help to establish a useful protocol for future FCS studies in this field and help establish by how much the diffusion of an enzyme is enhanced through catalytic activity.

link (url) DOI [BibTex]

pf Günther, J., Börsch, M., Fischer, P. Diffusion Measurements of Swimming Enzymes with Fluorescence Correlation Spectroscopy Accounts of Chemical Research, 51(9):1911-1920, August 2018 (article)

link (url) DOI [BibTex]

Uphill production of dihydrogen by enzymatic oxidation of glucose without an external energy source

Suraniti, E., Merzeau, P., Roche, J., Gounel, S., Mark, A. G., Fischer, P., Mano, N., Kuhn, A.

Nature Communications, 9(1):3229, August 2018 (article)

Abstract

Chemical systems do not allow the coupling of energy from several simple reactions to drive a subsequent reaction, which takes place in the same medium and leads to a product with a higher energy than the one released during the first reaction. Gibbs energy considerations thus are not favorable to drive e.g., water splitting by the direct oxidation of glucose as a model reaction. Here, we show that it is nevertheless possible to carry out such an energetically uphill reaction, if the electrons released in the oxidation reaction are temporarily stored in an electromagnetic system, which is then used to raise the electrons' potential energy so that they can power the electrolysis of water in a second step. We thereby demonstrate the general concept that lower energy delivering chemical reactions can be used to enable the formation of higher energy consuming reaction products in a closed system.

link (url) DOI [BibTex]

pf Suraniti, E., Merzeau, P., Roche, J., Gounel, S., Mark, A. G., Fischer, P., Mano, N., Kuhn, A. Uphill production of dihydrogen by enzymatic oxidation of glucose without an external energy source Nature Communications, 9(1):3229, August 2018 (article)

link (url) DOI [BibTex]

Chemical micromotors self-assemble and self-propel by spontaneous symmetry breaking

Yu, T., Chuphal, P., Thakur, S., Reigh, S. Y., Singh, D. P., Fischer, P.

Chem. Comm., 54, pages: 11933-11936, August 2018 (article)

Abstract

Self-propelling chemical motors have thus far required the fabrication of Janus particles with an asymmetric catalyst distribution. Here, we demonstrate that simple, isotropic colloids can spontaneously assemble to yield dimer motors that self-propel. In a mixture of isotropic titanium dioxide colloids with photo-chemical catalytic activity and passive silica colloids, light illumination causes diffusiophoretic attractions between the active and passive particles and leads to the formation of dimers. The dimers constitute a symmetry-broken motor, whose dynamics can be fully controlled by the illumination conditions. Computer simulations reproduce the dynamics of the colloids and are in good agreement with experiments. The current work presents a simple route to obtain large numbers of self-propelling chemical motors from a dispersion of spherically symmetric colloids through spontaneous symmetry breaking.

link (url) DOI [BibTex]

pf Yu, T., Chuphal, P., Thakur, S., Reigh, S. Y., Singh, D. P., Fischer, P. Chemical micromotors self-assemble and self-propel by spontaneous symmetry breaking Chem. Comm., 54, pages: 11933-11936, August 2018 (article)

link (url) DOI [BibTex]

Learning-Based Robust Model Predictive Control with State-Dependent Uncertainty

Soloperto, R., Müller, M. A., Trimpe, S., Allgöwer, F.

In Proceedings of the IFAC Conference on Nonlinear Model Predictive Control (NMPC), Madison, Wisconsin, USA, 6th IFAC Conference on Nonlinear Model Predictive Control, August 2018 (inproceedings)

ics

PDF [BibTex]

ics Soloperto, R., Müller, M. A., Trimpe, S., Allgöwer, F. Learning-Based Robust Model Predictive Control with State-Dependent Uncertainty In Proceedings of the IFAC Conference on Nonlinear Model Predictive Control (NMPC), Madison, Wisconsin, USA, 6th IFAC Conference on Nonlinear Model Predictive Control, August 2018 (inproceedings)

PDF [BibTex]

A machine from machines

Fischer, P.

Nature Physics, 14, pages: 1072–1073, July 2018 (misc)

Abstract

Building spinning microrotors that self-assemble and synchronize to form a gear sounds like an impossible feat. However, it has now been achieved using only a single type of building block -- a colloid that self-propels.

link (url) DOI [BibTex]

pf Fischer, P. A machine from machines Nature Physics, 14, pages: 1072–1073, July 2018 (misc)

link (url) DOI [BibTex]

Chemotaxis of Active Janus Nanoparticles

Popescu, M. N., Uspal, W. E., Bechinger, C., Fischer, P.

Nano Letters, 18(9):5345–5349, July 2018 (article)

Abstract

While colloids and molecules in solution exhibit passive Brownian motion, particles that are partially covered with a catalyst, which promotes the transformation of a fuel dissolved in the solution, can actively move. These active Janus particles are known as “chemical nanomotors” or self-propelling “swimmers” and have been realized with a range of catalysts, sizes, and particle geometries. Because their active translation depends on the fuel concentration, one expects that active colloidal particles should also be able to swim toward a fuel source. Synthesizing and engineering nanoparticles with distinct chemotactic properties may enable important developments, such as particles that can autonomously swim along a pH gradient toward a tumor. Chemotaxis requires that the particles possess an active coupling of their orientation to a chemical gradient. In this Perspective we provide a simple, intuitive description of the underlying mechanisms for chemotaxis, as well as the means to analyze and classify active particles that can show positive or negative chemotaxis. The classification provides guidance for engineering a specific response and is a useful organizing framework for the quantitative analysis and modeling of chemotactic behaviors. Chemotaxis is emerging as an important focus area in the field of active colloids and promises a number of fascinating applications for nanoparticles and particle-based delivery.

link (url) DOI [BibTex]

pf Popescu, M. N., Uspal, W. E., Bechinger, C., Fischer, P. Chemotaxis of Active Janus Nanoparticles Nano Letters, 18(9):5345–5349, July 2018 (article)

link (url) DOI [BibTex]

Learning an Approximate Model Predictive Controller with Guarantees

Hertneck, M., Koehler, J., Trimpe, S., Allgöwer, F.

IEEE Control Systems Letters, 2(3):543-548, July 2018 (article)

Abstract

A supervised learning framework is proposed to approximate a model predictive controller (MPC) with reduced computational complexity and guarantees on stability and constraint satisfaction. The framework can be used for a wide class of nonlinear systems. Any standard supervised learning technique (e.g. neural networks) can be employed to approximate the MPC from samples. In order to obtain closed-loop guarantees for the learned MPC, a robust MPC design is combined with statistical learning bounds. The MPC design ensures robustness to inaccurate inputs within given bounds, and Hoeffding’s Inequality is used to validate that the learned MPC satisfies these bounds with high confidence. The result is a closed-loop statistical guarantee on stability and constraint satisfaction for the learned MPC. The proposed learning-based MPC framework is illustrated on a nonlinear benchmark problem, for which we learn a neural network controller with guarantees.

ics

arXiv PDF DOI [BibTex]

ics Hertneck, M., Koehler, J., Trimpe, S., Allgöwer, F. Learning an Approximate Model Predictive Controller with Guarantees IEEE Control Systems Letters, 2(3):543-548, July 2018 (article)

arXiv PDF DOI [BibTex]

Probabilistic Recurrent State-Space Models

Doerr, A., Daniel, C., Schiegg, M., Nguyen-Tuong, D., Schaal, S., Toussaint, M., Trimpe, S.

In Proceedings of the International Conference on Machine Learning (ICML), International Conference on Machine Learning (ICML), July 2018 (inproceedings)

Abstract

State-space models (SSMs) are a highly expressive model class for learning patterns in time series data and for system identification. Deterministic versions of SSMs (e.g., LSTMs) proved extremely successful in modeling complex time-series data. Fully probabilistic SSMs, however, unfortunately often prove hard to train, even for smaller problems. To overcome this limitation, we propose a scalable initialization and training algorithm based on doubly stochastic variational inference and Gaussian processes. In the variational approximation we propose in contrast to related approaches to fully capture the latent state temporal correlations to allow for robust training.

am ics

arXiv pdf Project Page [BibTex]

am ics Doerr, A., Daniel, C., Schiegg, M., Nguyen-Tuong, D., Schaal, S., Toussaint, M., Trimpe, S. Probabilistic Recurrent State-Space Models In Proceedings of the International Conference on Machine Learning (ICML), International Conference on Machine Learning (ICML), July 2018 (inproceedings)

arXiv pdf Project Page [BibTex]

Event-triggered Learning for Resource-efficient Networked Control

Solowjow, F., Baumann, D., Garcke, J., Trimpe, S.

In Proceedings of the American Control Conference (ACC), pages: 6506 - 6512, American Control Conference, June 2018 (inproceedings)

ics

arXiv PDF DOI Project Page [BibTex]

ics Solowjow, F., Baumann, D., Garcke, J., Trimpe, S. Event-triggered Learning for Resource-efficient Networked Control In Proceedings of the American Control Conference (ACC), pages: 6506 - 6512, American Control Conference, June 2018 (inproceedings)

arXiv PDF DOI Project Page [BibTex]

Colloidal Chemical Nanomotors

Alarcon-Correa, M.

Colloidal Chemical Nanomotors, pages: 150, Cuvillier Verlag, MPI-IS , June 2018 (phdthesis)

Abstract

Synthetic sophisticated nanostructures represent a fundamental building block for the development of nanotechnology. The fabrication of nanoparticles complex in structure and material composition is key to build nanomachines that can operate as man-made nanoscale motors, which autonomously convert external energy into motion. To achieve this, asymmetric nanoparticles were fabricated combining a physical vapor deposition technique known as NanoGLAD and wet chemical synthesis. This thesis primarily concerns three complex colloidal systems that have been developed: i)Hollow nanocup inclusion complexes that have a single Au nanoparticle in their pocket. The Au particle can be released with an external trigger. ii)The smallest self-propelling nanocolloids that have been made to date, which give rise to a local concentration gradient that causes enhanced diffusion of the particles. iii)Enzyme-powered pumps that have been assembled using bacteriophages as biological nanoscaffolds. This construct also can be used for enzyme recovery after heterogeneous catalysis.

[BibTex]

pf Alarcon-Correa, M. Colloidal Chemical Nanomotors Colloidal Chemical Nanomotors, pages: 150, Cuvillier Verlag, MPI-IS , June 2018 (phdthesis)

[BibTex]

Oncilla robot: a versatile open-source quadruped research robot with compliant pantograph legs

Sproewitz, A., Tuleu, A., Ajallooeian, M., Vespignani, M., Moeckel, R., Eckert, P., D’Haene, M., Degrave, J., Nordmann, A., Schrauwen, B., Steil, J., Ijspeert, A. J.

Frontiers in Robotics and AI, 5(67), June 2018, arXiv: 1803.06259 (article)

Abstract

We present Oncilla robot, a novel mobile, quadruped legged locomotion machine. This large-cat sized, 5.1 robot is one of a kind of a recent, bioinspired legged robot class designed with the capability of model-free locomotion control. Animal legged locomotion in rough terrain is clearly shaped by sensor feedback systems. Results with Oncilla robot show that agile and versatile locomotion is possible without sensory signals to some extend, and tracking becomes robust when feedback control is added (Ajaoolleian 2015). By incorporating mechanical and control blueprints inspired from animals, and by observing the resulting robot locomotion characteristics, we aim to understand the contribution of individual components. Legged robots have a wide mechanical and control design parameter space, and a unique potential as research tools to investigate principles of biomechanics and legged locomotion control. But the hardware and controller design can be a steep initial hurdle for academic research. To facilitate the easy start and development of legged robots, Oncilla-robot's blueprints are available through open-source. [...]

dlg

link (url) DOI Project Page [BibTex]

dlg Sproewitz, A., Tuleu, A., Ajallooeian, M., Vespignani, M., Moeckel, R., Eckert, P., D’Haene, M., Degrave, J., Nordmann, A., Schrauwen, B., Steil, J., Ijspeert, A. J. Oncilla robot: a versatile open-source quadruped research robot with compliant pantograph legs Frontiers in Robotics and AI, 5(67), June 2018, arXiv: 1803.06259 (article)

link (url) DOI Project Page [BibTex]

Learning from Outside the Viability Kernel: Why we Should Build Robots that can Fail with Grace

Heim, S., Sproewitz, A.

Proceedings of SIMPAR 2018, pages: 55-61, IEEE, 2018 IEEE International Conference on Simulation, Modeling, and Programming for Autonomous Robots (SIMPAR), May 2018 (conference)

dlg

link (url) DOI Project Page [BibTex]

dlg Heim, S., Sproewitz, A. Learning from Outside the Viability Kernel: Why we Should Build Robots that can Fail with Grace Proceedings of SIMPAR 2018, pages: 55-61, IEEE, 2018 IEEE International Conference on Simulation, Modeling, and Programming for Autonomous Robots (SIMPAR), May 2018 (conference)

link (url) DOI Project Page [BibTex]

Bioinspired microrobots

Palagi, S., Fischer, P.

Nature Reviews Materials, 3, pages: 113–124, May 2018 (article)

Abstract

Microorganisms can move in complex media, respond to the environment and self-organize. The field of microrobotics strives to achieve these functions in mobile robotic systems of sub-millimetre size. However, miniaturization of traditional robots and their control systems to the microscale is not a viable approach. A promising alternative strategy in developing microrobots is to implement sensing, actuation and control directly in the materials, thereby mimicking biological matter. In this Review, we discuss design principles and materials for the implementation of robotic functionalities in microrobots. We examine different biological locomotion strategies, and we discuss how they can be artificially recreated in magnetic microrobots and how soft materials improve control and performance. We show that smart, stimuli-responsive materials can act as on-board sensors and actuators and that ‘active matter’ enables autonomous motion, navigation and collective behaviours. Finally, we provide a critical outlook for the field of microrobotics and highlight the challenges that need to be overcome to realize sophisticated microrobots, which one day might rival biological machines.

link (url) DOI [BibTex]

pf Palagi, S., Fischer, P. Bioinspired microrobots Nature Reviews Materials, 3, pages: 113–124, May 2018 (article)

link (url) DOI [BibTex]

Soft Miniaturized Linear Actuators Wirelessly Powered by Rotating Permanent Magnets

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

In 2018 IEEE International Conference on Robotics and Automation (ICRA), pages: 3595-3600, May 2018 (inproceedings)

Abstract

Wireless actuation by magnetic fields allows for the operation of untethered miniaturized devices, e.g. in biomedical applications. Nevertheless, generating large controlled forces over relatively large distances is challenging. Magnetic torques are easier to generate and control, but they are not always suitable for the tasks at hand. Moreover, strong magnetic fields are required to generate a sufficient torque, which are difficult to achieve with electromagnets. Here, we demonstrate a soft miniaturized actuator that transforms an externally applied magnetic torque into a controlled linear force. We report the design, fabrication and characterization of both the actuator and the magnetic field generator. We show that the magnet assembly, which is based on a set of rotating permanent magnets, can generate strong controlled oscillating fields over a relatively large workspace. The actuator, which is 3D-printed, can lift a load of more than 40 times its weight. Finally, we show that the actuator can be further miniaturized, paving the way towards strong, wirelessly powered microactuators.

link (url) DOI [BibTex]

pf Qiu, T., Palagi, S., Sachs, J., Fischer, P. Soft Miniaturized Linear Actuators Wirelessly Powered by Rotating Permanent Magnets In 2018 IEEE International Conference on Robotics and Automation (ICRA), pages: 3595-3600, May 2018 (inproceedings)

link (url) DOI [BibTex]

Impact of Trunk Orientation for Dynamic Bipedal Locomotion

Drama, O.

Dynamic Walking Conference, May 2018 (talk)

Abstract

Impact of trunk orientation for dynamic bipedal locomotion My research revolves around investigating the functional demands of bipedal running, with focus on stabilizing trunk orientation. When we think about postural stability, there are two critical questions we need to answer: What are the necessary and sufficient conditions to achieve and maintain trunk stability? I am concentrating on how morphology affects control strategies in achieving trunk stability. In particular, I denote the trunk pitch as the predominant morphology parameter and explore the requirements it imposes on a chosen control strategy. To analyze this, I use a spring loaded inverted pendulum model extended with a rigid trunk, which is actuated by a hip motor. The challenge for the controller design here is to have a single hip actuator to achieve two coupled tasks of moving the legs to generate motion and stabilizing the trunk. I enforce orthograde and pronograde postures and aim to identify the effect of these trunk orientations on the hip torque and ground reaction profiles for different control strategies.

dlg

Impact of trunk orientation for dynamic bipedal locomotion [DW 2018] link (url) Project Page [BibTex]

dlg Drama, O. Impact of Trunk Orientation for Dynamic Bipedal Locomotion Dynamic Walking Conference, May 2018 (talk)

Impact of trunk orientation for dynamic bipedal locomotion [DW 2018] link (url) Project Page [BibTex]

Shaping in Practice: Training Wheels to Learn Fast Hopping Directly in Hardware

Heim, S., Ruppert, F., Sarvestani, A., Sproewitz, A.

In Proceedings of the IEEE International Conference on Robotics and Automation (ICRA) 2018, pages: 5076-5081, IEEE, International Conference on Robotics and Automation, May 2018 (inproceedings)

Abstract

Learning instead of designing robot controllers can greatly reduce engineering effort required, while also emphasizing robustness. Despite considerable progress in simulation, applying learning directly in hardware is still challenging, in part due to the necessity to explore potentially unstable parameters. We explore the of concept shaping the reward landscape with training wheels; temporary modifications of the physical hardware that facilitate learning. We demonstrate the concept with a robot leg mounted on a boom learning to hop fast. This proof of concept embodies typical challenges such as instability and contact, while being simple enough to empirically map out and visualize the reward landscape. Based on our results we propose three criteria for designing effective training wheels for learning in robotics.

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Video Youtube link (url) Project Page [BibTex]

dlg Heim, S., Ruppert, F., Sarvestani, A., Sproewitz, A. Shaping in Practice: Training Wheels to Learn Fast Hopping Directly in Hardware In Proceedings of the IEEE International Conference on Robotics and Automation (ICRA) 2018, pages: 5076-5081, IEEE, International Conference on Robotics and Automation, May 2018 (inproceedings)

Video Youtube link (url) Project Page [BibTex]

Graphene-silver hybrid devices for sensitive photodetection in the ultraviolet

Paria, D., Jeong, H. H., Vadakkumbatt, V., Deshpande, P., Fischer, P., Ghosh, A., Ghosh, A.

Nanoscale, 10, pages: 7685-7693, April 2018 (article)

Abstract

The weak light-matter interaction in graphene can be enhanced with a number of strategies, among which sensitization with plasmonic nanostructures is particularly attractive. This has resulted in the development of graphene-plasmonic hybrid systems with strongly enhanced photodetection efficiencies in the visible and the IR, but none in the UV. Here, we describe a silver nanoparticle-graphene stacked optoelectronic device that shows strong enhancement of its photoresponse across the entire UV spectrum. The device fabrication strategy is scalable and modular. Self-assembly techniques are combined with physical shadow growth techniques to fabricate a regular large-area array of 50 nm silver nanoparticles onto which CVD graphene is transferred. The presence of the silver nanoparticles resulted in a plasmonically enhanced photoresponse as high as 3.2 A W-1 in the wavelength range from 330 nm to 450 nm. At lower wavelengths, close to the Van Hove singularity of the density of states in graphene, we measured an even higher responsivity of 14.5 A W-1 at 280 nm, which corresponds to a more than 10 000-fold enhancement over the photoresponse of native graphene.

link (url) DOI [BibTex]

pf Paria, D., Jeong, H. H., Vadakkumbatt, V., Deshpande, P., Fischer, P., Ghosh, A., Ghosh, A. Graphene-silver hybrid devices for sensitive photodetection in the ultraviolet Nanoscale, 10, pages: 7685-7693, April 2018 (article)

link (url) DOI [BibTex]

Nanoparticles on the move for medicine

Fischer, P.

Physics World Focus on Nanotechnology, pages: 26028, (Editors: Margaret Harris), IOP Publishing Ltd and individual contributors, April 2018 (article)

Abstract

Peer Fischer outlines the prospects for creating “nanoswimmers” that can be steered through the body to deliver drugs directly to their targets Molecules don’t move very fast on their own. If they had to rely solely on diffusion – a slow and inefficient process linked to the Brownian motion of small particles and molecules in solution – then a protein molecule, for instance, would take around three weeks to travel a single centimetre down a nerve fibre. This is why active transport mechanisms exist in cells and in the human body: without them, all the processes of life would happen at a pace that would make snails look speedy.

link (url) [BibTex]

pf Fischer, P. Nanoparticles on the move for medicine Physics World Focus on Nanotechnology, pages: 26028, (Editors: Margaret Harris), IOP Publishing Ltd and individual contributors, April 2018 (article)

link (url) [BibTex]

Poster Abstract: Toward Fast Closed-loop Control over Multi-hop Low-power Wireless Networks

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

Proceedings of the 17th ACM/IEEE Conference on Information Processing in Sensor Networks (IPSN), pages: 158-159, Porto, Portugal, April 2018 (poster)

ics

DOI Project Page [BibTex]

ics Mager, F., Baumann, D., Trimpe, S., Zimmerling, M. Poster Abstract: Toward Fast Closed-loop Control over Multi-hop Low-power Wireless Networks Proceedings of the 17th ACM/IEEE Conference on Information Processing in Sensor Networks (IPSN), pages: 158-159, Porto, Portugal, April 2018 (poster)

DOI Project Page [BibTex]

Evaluating Low-Power Wireless Cyber-Physical Systems

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

In Proceedings of the IEEE Workshop on Benchmarking Cyber-Physical Networks and Systems (CPSBench), pages: 13-18, IEEE Workshop on Benchmarking Cyber-Physical Networks and Systems (CPSBench), April 2018 (inproceedings)

ics

arXiv PDF DOI Project Page [BibTex]

ics Baumann, D., Mager, F., Singh, H., Zimmerling, M., Trimpe, S. Evaluating Low-Power Wireless Cyber-Physical Systems In Proceedings of the IEEE Workshop on Benchmarking Cyber-Physical Networks and Systems (CPSBench), pages: 13-18, IEEE Workshop on Benchmarking Cyber-Physical Networks and Systems (CPSBench), April 2018 (inproceedings)

arXiv PDF DOI Project Page [BibTex]

Photogravitactic Microswimmers

Singh, D. P., Uspal, W. E., Popescu, M. N., Wilson, L. G., Fischer, P.

Adv. Func. Mat., 28, pages: 1706660, Febuary 2018 (article)

Abstract

Abstract Phototactic microorganisms are commonly observed to respond to natural sunlight by swimming upward against gravity. This study demonstrates that synthetic photochemically active microswimmers can also swim against gravity. The particles initially sediment and, when illuminated at low light intensities exhibit wall‐bound states of motion near the bottom surface. Upon increasing the intensity of light, the artificial swimmers lift off from the wall and swim against gravity and away from the light source. This motion in the bulk has been further confirmed using holographic microscopy. A theoretical model is presented within the framework of self‐diffusiophoresis, which allows to unequivocally identify the photochemical activity and the phototactic response as key mechanisms in the observed phenomenology. Since the lift‐off threshold intensity depends on the particle size, it can be exploited to selectively address particles with the same density from a polydisperse mixture of active particles and move them in or out of the boundary region. This study provides a simple design strategy to fabricate artificial microswimmers whose two‐ or three‐dimensional swimming behavior can be controlled with light.

link (url) DOI [BibTex]

pf Singh, D. P., Uspal, W. E., Popescu, M. N., Wilson, L. G., Fischer, P. Photogravitactic Microswimmers Adv. Func. Mat., 28, pages: 1706660, Febuary 2018 (article)

link (url) DOI [BibTex]

Chiral Plasmonic Hydrogen Sensors

Matuschek, M., Singh, D. P., Hyeon-Ho, J., Nesterov, M., Weiss, T., Fischer, P., Neubrech, F., Na Liu, L.

Small, 14(7):1702990, Febuary 2018 (article)

Abstract

In this article, a chiral plasmonic hydrogen‐sensing platform using palladium‐based nanohelices is demonstrated. Such 3D chiral nanostructures fabricated by nanoglancing angle deposition exhibit strong circular dichroism both experimentally and theoretically. The chiroptical properties of the palladium nanohelices are altered upon hydrogen uptake and sensitively depend on the hydrogen concentration. Such properties are well suited for remote and spark‐free hydrogen sensing in the flammable range. Hysteresis is reduced, when an increasing amount of gold is utilized in the palladium‐gold hybrid helices. As a result, the linearity of the circular dichroism in response to hydrogen is significantly improved. The chiral plasmonic sensor scheme is of potential interest for hydrogen‐sensing applications, where good linearity and high sensitivity are required.

link (url) DOI [BibTex]

pf Matuschek, M., Singh, D. P., Hyeon-Ho, J., Nesterov, M., Weiss, T., Fischer, P., Neubrech, F., Na Liu, L. Chiral Plasmonic Hydrogen Sensors Small, 14(7):1702990, Febuary 2018 (article)

link (url) DOI [BibTex]

Acoustic Fabrication via the Assembly and Fusion of Particles

Melde, K., Choi, E., Wu, Z., Palagi, S., Qiu, T., Fischer, P.

Advanced Materials, 30(3):1704507, January 2018 (article)

Abstract

Acoustic assembly promises a route toward rapid parallel fabrication of whole objects directly from solution. This study reports the contact-free and maskless assembly, and fixing of silicone particles into arbitrary 2D shapes using ultrasound fields. Ultrasound passes through an acoustic hologram to form a target image. The particles assemble from a suspension along lines of high pressure in the image due to acoustic radiation forces and are then fixed (crosslinked) in a UV-triggered reaction. For this, the particles are loaded with a photoinitiator by solvent-induced swelling. This localizes the reaction and allows the bulk suspension to be reused. The final fabricated parts are mechanically stable and self-supporting.

link (url) DOI Project Page [BibTex]

pf Melde, K., Choi, E., Wu, Z., Palagi, S., Qiu, T., Fischer, P. Acoustic Fabrication via the Assembly and Fusion of Particles Advanced Materials, 30(3):1704507, January 2018 (article)

link (url) DOI Project Page [BibTex]

Distributed Event-Based State Estimation for Networked Systems: An LMI Approach

Muehlebach, M., Trimpe, S.

IEEE Transactions on Automatic Control, 63(1):269-276, January 2018 (article)

am ics

arXiv (extended version) DOI Project Page [BibTex]

am ics Muehlebach, M., Trimpe, S. Distributed Event-Based State Estimation for Networked Systems: An LMI Approach IEEE Transactions on Automatic Control, 63(1):269-276, January 2018 (article)

arXiv (extended version) DOI Project Page [BibTex]

Untersuchung und Charakterisierung von Teilelementen der Modifikation im Lumbosacralbereich von Vögeln

Richter, J.

Hochschule Harz, 2018 (thesis)

dlg

[BibTex]

dlg Richter, J. Untersuchung und Charakterisierung von Teilelementen der Modifikation im Lumbosacralbereich von Vögeln Hochschule Harz, 2018 (thesis)

[BibTex]

Nanorobots propel through the eye

Zhiguang Wu, J. T. H. J. Q. W. M. S. F. Z. Z. W. M. D. S. S. T. Q. P. F.

Max Planck Society, 2018 (mpi_year_book)

Abstract

Scientists at the Max Planck Institute for Intelligent Systems in Stuttgart developed specially coated nanometer-sized robots that could be moved actively through dense tissue like the vitreous of the eye. So far, the transport of such nano-vehicles has only been demonstrated in model systems or biological fluids, but not in real tissue. Our work constitutes one step further towards nanorobots becoming minimally-invasive tools for precisely delivering medicine to where it is needed.

link (url) [BibTex]

pf Zhiguang Wu, J. T. H. J. Q. W. M. S. F. Z. Z. W. M. D. S. S. T. Q. P. F. Nanorobots propel through the eye Max Planck Society, 2018 (mpi_year_book)

link (url) [BibTex]

2003

New electro-optic effect: Sum-frequency generation from optically active liquids in the presence of a dc electric field

Fischer, P., Buckingham, A., Beckwitt, K., Wiersma, D., Wise, F.

PHYSICAL REVIEW LETTERS, 91(17), 2003 (article)

Abstract

We report the observation of sum-frequency signals that depend linearly on an applied electrostatic field and that change sign with the handedness of an optically active solute. This recently predicted chiral electro-optic effect exists in the electric-dipole approximation. The static electric field gives rise to an electric-field-induced sum-frequency signal (an achiral third-order process) that interferes with the chirality-specific sum-frequency at second order. The cross-terms linear in the electrostatic field constitute the effect and may be used to determine the absolute sign of second- and third-order nonlinear-optical susceptibilities in isotropic media.

DOI [BibTex]

2003

pf Fischer, P., Buckingham, A., Beckwitt, K., Wiersma, D., Wise, F. New electro-optic effect: Sum-frequency generation from optically active liquids in the presence of a dc electric field PHYSICAL REVIEW LETTERS, 91(17), 2003 (article)

DOI [BibTex]

Chiral and achiral contributions to sum-frequency generation from optically active solutions of binaphthol

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

JOURNAL OF PHYSICAL CHEMISTRY A, 107(40):8232-8238, 2003 (article)

Abstract

The nonlinear sum- and difference-frequency generation spectroscopies can be probes of molecular chirality in optically active systems. We present a tensorial analysis of the chirality-specific electric-dipolar sum-frequency-generation susceptibility and the achiral electric-quadrupolar and magnetic-dipolar nonlinearities at second order in isotropic media. The chiral and achiral contributions to the sum-frequency signal from the bulk of optically active solutions of 1,1'-bi-2-naphthol (2,2'-dehydroxy-1,1'-binaphthyl) can be distinguished, and the former dominates. Ab initio computations reveal the dramatic resonance enhancement that the isotropic component of the electric-dipolar three-wave mixing hyperpolarizability experiences. Away from resonance its magnitude rapidly decreases, as-unlike the vector component-it is zero in the static limit. The dispersion of the first hyperpolarizability is computed by a configuration interaction singles sum-over-states approach with explicit regard to the Franck-Condon active vibrational substructure for all resonant electronic states.

DOI [BibTex]

pf Fischer, P., Wise, F., Albrecht, A. Chiral and achiral contributions to sum-frequency generation from optically active solutions of binaphthol JOURNAL OF PHYSICAL CHEMISTRY A, 107(40):8232-8238, 2003 (article)

DOI [BibTex]

2001

Isotropic second-order nonlinear optical susceptibilities

Fischer, P., Buckingham, A., Albrecht, A.

PHYSICAL REVIEW A, 64(5), 2001 (article)

Abstract

The second-order nonlinear optical susceptibility, in the electric dipole approximation, is only nonvanishing for materials that are noncentrosymmetric. Should the medium be isotropic, then only a chiral system. such as an optically active liquid, satisfies this symmetry requirement. We derive the quantum-mechanical form of the isotropic component of the sum- and difference-frequency susceptibility and discuss its unusual spectral properties. We show that any coherent second-order nonlinear optical process in a system of randomly oriented molecules requires the medium to be chiral. and the incident frequencies to be different and nonzero. Furthermore, a minimum of two nondegenerate excited molecular states are needed for the isotropic part of the susceptibility to be nonvanishing. The rotationally invariant susceptibility is zero in the static field limit and shows exceptionally sensitive resonance and dephasing effects that are particular to chiral centers.

DOI [BibTex]

2001

pf Fischer, P., Buckingham, A., Albrecht, A. Isotropic second-order nonlinear optical susceptibilities PHYSICAL REVIEW A, 64(5), 2001 (article)

DOI [BibTex]

Reply to “Comment on ‘Phenomenological damping in optical response tensors’”

Buckingham, A., Fischer, P.

PHYSICAL REVIEW A, 63(4), 2001 (article)

Abstract

We show that damping factors must not be incorporated in the perturbation of the ground state by a static electric field. If they are included, as in the theory of Stedman et al. {[}preceding Comment. Phys. Rev. A 63, 047801 (2001)], then there would be an electric dipole in the y direction induced in a hydrogen atom in the M-s = + 1/2 state by a static electric field in the x direction. Such a dipole is excluded by symmetry.

DOI [BibTex]

pf Buckingham, A., Fischer, P. Reply to “Comment on ‘Phenomenological damping in optical response tensors’” PHYSICAL REVIEW A, 63(4), 2001 (article)

DOI [BibTex]

1998

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.

DOI [BibTex]

1998

pf Fischer, P., Buckingham, A. Surface second-order nonlinear optical activity JOURNAL OF THE OPTICAL SOCIETY OF AMERICA B-OPTICAL PHYSICS, 15(12):2951-2957, 1998 (article)

DOI [BibTex]

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.

DOI [BibTex]

pf Buckingham, A., Fischer, P. Linear electro-optic effect in optically active liquids CHEMICAL PHYSICS LETTERS, 297(3-4):239-246, 1998 (article)

DOI [BibTex]

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.

DOI [BibTex]

pf Bell, G., Li, Z., Bain, C., Fischer, P., Duffy, D. Monolayers of hexadecyltrimethylammonium p-tosylate at the air-water interface. 1. Sum-frequency spectroscopy JOURNAL OF PHYSICAL CHEMISTRY B, 102(47):9461-9472, 1998 (article)

DOI [BibTex]

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.

DOI [BibTex]

pf Couling, V., Fischer, P., Klenerman, D., Huber, W. Ultraviolet resonance Raman study of drug binding in dihydrofolate reductase, gyrase, and catechol O-methyltransferase BIOPHYSICAL JOURNAL, 75(2):1097-1106, 1998 (article)

DOI [BibTex]