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2015


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Exploiting Object Similarity in 3D Reconstruction

Zhou, C., Güney, F., Wang, Y., Geiger, A.

In International Conference on Computer Vision (ICCV), December 2015 (inproceedings)

Abstract
Despite recent progress, reconstructing outdoor scenes in 3D from movable platforms remains a highly difficult endeavor. Challenges include low frame rates, occlusions, large distortions and difficult lighting conditions. In this paper, we leverage the fact that the larger the reconstructed area, the more likely objects of similar type and shape will occur in the scene. This is particularly true for outdoor scenes where buildings and vehicles often suffer from missing texture or reflections, but share similarity in 3D shape. We take advantage of this shape similarity by locating objects using detectors and jointly reconstructing them while learning a volumetric model of their shape. This allows us to reduce noise while completing missing surfaces as objects of similar shape benefit from all observations for the respective category. We evaluate our approach with respect to LIDAR ground truth on a novel challenging suburban dataset and show its advantages over the state-of-the-art.

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pdf suppmat [BibTex]

2015


pdf suppmat [BibTex]


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FollowMe: Efficient Online Min-Cost Flow Tracking with Bounded Memory and Computation

Lenz, P., Geiger, A., Urtasun, R.

In International Conference on Computer Vision (ICCV), International Conference on Computer Vision (ICCV), December 2015 (inproceedings)

Abstract
One of the most popular approaches to multi-target tracking is tracking-by-detection. Current min-cost flow algorithms which solve the data association problem optimally have three main drawbacks: they are computationally expensive, they assume that the whole video is given as a batch, and they scale badly in memory and computation with the length of the video sequence. In this paper, we address each of these issues, resulting in a computationally and memory-bounded solution. First, we introduce a dynamic version of the successive shortest-path algorithm which solves the data association problem optimally while reusing computation, resulting in faster inference than standard solvers. Second, we address the optimal solution to the data association problem when dealing with an incoming stream of data (i.e., online setting). Finally, we present our main contribution which is an approximate online solution with bounded memory and computation which is capable of handling videos of arbitrary length while performing tracking in real time. We demonstrate the effectiveness of our algorithms on the KITTI and PETS2009 benchmarks and show state-of-the-art performance, while being significantly faster than existing solvers.

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pdf suppmat video project [BibTex]

pdf suppmat video project [BibTex]


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Enzymatically active biomimetic micropropellers for the penetration of mucin gels

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

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

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

pf

link (url) DOI [BibTex]

link (url) DOI [BibTex]


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Towards Probabilistic Volumetric Reconstruction using Ray Potentials

(Best Paper Award)

Ulusoy, A. O., Geiger, A., Black, M. J.

In 3D Vision (3DV), 2015 3rd International Conference on, pages: 10-18, Lyon, October 2015 (inproceedings)

Abstract
This paper presents a novel probabilistic foundation for volumetric 3-d reconstruction. We formulate the problem as inference in a Markov random field, which accurately captures the dependencies between the occupancy and appearance of each voxel, given all input images. Our main contribution is an approximate highly parallelized discrete-continuous inference algorithm to compute the marginal distributions of each voxel's occupancy and appearance. In contrast to the MAP solution, marginals encode the underlying uncertainty and ambiguity in the reconstruction. Moreover, the proposed algorithm allows for a Bayes optimal prediction with respect to a natural reconstruction loss. We compare our method to two state-of-the-art volumetric reconstruction algorithms on three challenging aerial datasets with LIDAR ground truth. Our experiments demonstrate that the proposed algorithm compares favorably in terms of reconstruction accuracy and the ability to expose reconstruction uncertainty.

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code YouTube pdf suppmat DOI Project Page [BibTex]

code YouTube pdf suppmat DOI Project Page [BibTex]


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The EChemPen: A Guiding Hand To Learn Electrochemical Surface Modifications

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

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

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

pf

DOI [BibTex]

DOI [BibTex]


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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]


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Displets: Resolving Stereo Ambiguities using Object Knowledge

Güney, F., Geiger, A.

In IEEE Conf. on Computer Vision and Pattern Recognition (CVPR) 2015, pages: 4165-4175, IEEE International Conference on Computer Vision and Pattern Recognition (CVPR), June 2015 (inproceedings)

Abstract
Stereo techniques have witnessed tremendous progress over the last decades, yet some aspects of the problem still remain challenging today. Striking examples are reflecting and textureless surfaces which cannot easily be recovered using traditional local regularizers. In this paper, we therefore propose to regularize over larger distances using object-category specific disparity proposals (displets) which we sample using inverse graphics techniques based on a sparse disparity estimate and a semantic segmentation of the image. The proposed displets encode the fact that objects of certain categories are not arbitrarily shaped but typically exhibit regular structures. We integrate them as non-local regularizer for the challenging object class 'car' into a superpixel based CRF framework and demonstrate its benefits on the KITTI stereo evaluation.

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pdf abstract suppmat [BibTex]

pdf abstract suppmat [BibTex]


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Object Scene Flow for Autonomous Vehicles

Menze, M., Geiger, A.

In IEEE Conf. on Computer Vision and Pattern Recognition (CVPR) 2015, pages: 3061-3070, IEEE, IEEE International Conference on Computer Vision and Pattern Recognition (CVPR), June 2015 (inproceedings)

Abstract
This paper proposes a novel model and dataset for 3D scene flow estimation with an application to autonomous driving. Taking advantage of the fact that outdoor scenes often decompose into a small number of independently moving objects, we represent each element in the scene by its rigid motion parameters and each superpixel by a 3D plane as well as an index to the corresponding object. This minimal representation increases robustness and leads to a discrete-continuous CRF where the data term decomposes into pairwise potentials between superpixels and objects. Moreover, our model intrinsically segments the scene into its constituting dynamic components. We demonstrate the performance of our model on existing benchmarks as well as a novel realistic dataset with scene flow ground truth. We obtain this dataset by annotating 400 dynamic scenes from the KITTI raw data collection using detailed 3D CAD models for all vehicles in motion. Our experiments also reveal novel challenges which can't be handled by existing methods.

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pdf abstract suppmat DOI [BibTex]

pdf abstract suppmat DOI [BibTex]


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Optimal Length of Low Reynolds Number Nanopropellers

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

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

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

pf

DOI [BibTex]

DOI [BibTex]


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

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

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

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

pf

DOI [BibTex]

DOI [BibTex]


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Dynamic Inclusion Complexes of Metal Nanoparticles Inside Nanocups

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

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

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

pf

DOI [BibTex]

DOI [BibTex]


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Surface roughness-induced speed increase for active Janus micromotors

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

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

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

pf

DOI [BibTex]

DOI [BibTex]


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Active colloidal microdrills

Gibbs, J. G., Fischer, P.

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

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

pf

DOI [BibTex]

DOI [BibTex]


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Joint 3D Object and Layout Inference from a single RGB-D Image

(Best Paper Award)

Geiger, A., Wang, C.

In German Conference on Pattern Recognition (GCPR), 9358, pages: 183-195, Lecture Notes in Computer Science, Springer International Publishing, 2015 (inproceedings)

Abstract
Inferring 3D objects and the layout of indoor scenes from a single RGB-D image captured with a Kinect camera is a challenging task. Towards this goal, we propose a high-order graphical model and jointly reason about the layout, objects and superpixels in the image. In contrast to existing holistic approaches, our model leverages detailed 3D geometry using inverse graphics and explicitly enforces occlusion and visibility constraints for respecting scene properties and projective geometry. We cast the task as MAP inference in a factor graph and solve it efficiently using message passing. We evaluate our method with respect to several baselines on the challenging NYUv2 indoor dataset using 21 object categories. Our experiments demonstrate that the proposed method is able to infer scenes with a large degree of clutter and occlusions.

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pdf suppmat video project DOI [BibTex]

pdf suppmat video project DOI [BibTex]


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Selectable Nanopattern Arrays for Nanolithographic Imprint and Etch-Mask Applications

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

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

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

pf

link (url) DOI [BibTex]

link (url) DOI [BibTex]


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Discrete Optimization for Optical Flow

Menze, M., Heipke, C., Geiger, A.

In German Conference on Pattern Recognition (GCPR), 9358, pages: 16-28, Springer International Publishing, 2015 (inproceedings)

Abstract
We propose to look at large-displacement optical flow from a discrete point of view. Motivated by the observation that sub-pixel accuracy is easily obtained given pixel-accurate optical flow, we conjecture that computing the integral part is the hardest piece of the problem. Consequently, we formulate optical flow estimation as a discrete inference problem in a conditional random field, followed by sub-pixel refinement. Naive discretization of the 2D flow space, however, is intractable due to the resulting size of the label set. In this paper, we therefore investigate three different strategies, each able to reduce computation and memory demands by several orders of magnitude. Their combination allows us to estimate large-displacement optical flow both accurately and efficiently and demonstrates the potential of discrete optimization for optical flow. We obtain state-of-the-art performance on MPI Sintel and KITTI.

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pdf suppmat project DOI [BibTex]

pdf suppmat project DOI [BibTex]


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Joint 3D Estimation of Vehicles and Scene Flow

Menze, M., Heipke, C., Geiger, A.

In Proc. of the ISPRS Workshop on Image Sequence Analysis (ISA), 2015 (inproceedings)

Abstract
Three-dimensional reconstruction of dynamic scenes is an important prerequisite for applications like mobile robotics or autonomous driving. While much progress has been made in recent years, imaging conditions in natural outdoor environments are still very challenging for current reconstruction and recognition methods. In this paper, we propose a novel unified approach which reasons jointly about 3D scene flow as well as the pose, shape and motion of vehicles in the scene. Towards this goal, we incorporate a deformable CAD model into a slanted-plane conditional random field for scene flow estimation and enforce shape consistency between the rendered 3D models and the parameters of all superpixels in the image. The association of superpixels to objects is established by an index variable which implicitly enables model selection. We evaluate our approach on the challenging KITTI scene flow dataset in terms of object and scene flow estimation. Our results provide a prove of concept and demonstrate the usefulness of our method.

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PDF [BibTex]

PDF [BibTex]

2010


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Magnetic Nanostructured Propellers

Fischer, P., Ghosh, A.

July 2010 (patent)

pf

[BibTex]

2010


[BibTex]


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

Fischer, P., Salam, A.

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

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

pf

DOI [BibTex]

2001


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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.

pf

DOI [BibTex]

2001


DOI [BibTex]


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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.

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DOI [BibTex]

2000


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Phenomenological damping in optical response tensors

Buckingham, A., Fischer, P.

PHYSICAL REVIEW A, 61(3), 2000 (article)

Abstract
Although perturbation theory applied to the optical response of a molecule or material system is only strictly valid far from resonances, it is often applied to ``near-resonance{''} conditions by means of complex energies incorporating damping. Inconsistent signs of the damping in optical response tensors have appeared in the recent literature, as have errors in the treatment of the perturbation by a static held. The ``equal-sign{''} convention used in a recent publication yields an unphysical material response, and Koroteev's intimation that linear electro-optical circular dichroism may exist in an optically active liquid under resonance conditions is also flawed. We show that the isotropic part of the Pockels tensor vanishes.

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DOI [BibTex]

2000


DOI [BibTex]


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Ab initio investigation of the sum-frequency hyperpolarizability of small chiral molecules

Champagne, B., Fischer, P., Buckingham, A.

CHEMICAL PHYSICS LETTERS, 331(1):83-88, 2000 (article)

Abstract
Using a sum-over-states procedure based on configuration interaction singles /6-311++G{*}{*}, we have computed the sum-frequency hyperpolarizability beta (ijk)(-3 omega; 2 omega, omega) Of two small chiral molecules, R-monofluoro-oxirane and R-(+)-propylene oxide. Excitation energies were scaled to fit experimental UV-absorption data and checked with ab initio values from time-dependent density functional theory. The isotropic part of the computed hyperpolarizabilities, beta(-3 omega; 2 omega, omega), is much smaller than that reported previously from sum-frequency generation experiments on aqueous solutions of arabinose. Comparison is made with a single-centre chiral model. (C) 2000 Elsevier Science B.V. All rights reserved.

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DOI [BibTex]

DOI [BibTex]


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Three-wave mixing in chiral liquids

Fischer, P., Wiersma, D., Righini, R., Champagne, B., Buckingham, A.

PHYSICAL REVIEW LETTERS, 85(20):4253-4256, 2000 (article)

Abstract
Second-order nonlinear optical frequency conversion in isotropic systems is only dipole allowed for sum- and difference-frequency generation in chiral media. We develop a single-center chiral model of the three-wave mixing (sum:frequency generation) nonlinearity and estimate its magnitude. We also report results from ab initio calculations and from three- and four-wave mixing experiments in support of the theoretical estimates. We show that the second-order susceptibility in chiral liquids is much smaller than previously thought.

pf

DOI [BibTex]

DOI [BibTex]

1998


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Surface second-order nonlinear optical activity

Fischer, P., Buckingham, A.

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

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

pf

DOI [BibTex]

1998


DOI [BibTex]


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Linear electro-optic effect in optically active liquids

Buckingham, A., Fischer, P.

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

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

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DOI [BibTex]

DOI [BibTex]


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

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

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

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

pf

DOI [BibTex]

DOI [BibTex]


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

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

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

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

pf

DOI [BibTex]

DOI [BibTex]