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2020


Interface-mediated spontaneous symmetry breaking and mutual communication between drops containing chemically active particles
Interface-mediated spontaneous symmetry breaking and mutual communication between drops containing chemically active particles

Singh, D., Domínguez, A., Choudhury, U., Kottapalli, S., Popescu, M., Dietrich, S., Fischer, P.

Nature Communications, 11(2210), May 2020 (article)

Abstract
Symmetry breaking and the emergence of self-organized patterns is the hallmark of com- plexity. Here, we demonstrate that a sessile drop, containing titania powder particles with negligible self-propulsion, exhibits a transition to collective motion leading to self-organized flow patterns. This phenomenology emerges through a novel mechanism involving the interplay between the chemical activity of the photocatalytic particles, which induces Mar- angoni stresses at the liquid–liquid interface, and the geometrical confinement provided by the drop. The response of the interface to the chemical activity of the particles is the source of a significantly amplified hydrodynamic flow within the drop, which moves the particles. Furthermore, in ensembles of such active drops long-ranged ordering of the flow patterns within the drops is observed. We show that the ordering is dictated by a chemical com- munication between drops, i.e., an alignment of the flow patterns is induced by the gradients of the chemicals emanating from the active particles, rather than by hydrodynamic interactions.

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link (url) DOI [BibTex]


Spectrally selective and highly-sensitive UV photodetection with UV-A, C band specific polarity switching in silver plasmonic nanoparticle enhanced gallium oxide thin-film
Spectrally selective and highly-sensitive UV photodetection with UV-A, C band specific polarity switching in silver plasmonic nanoparticle enhanced gallium oxide thin-film

Arora, K., Singh, D., Fischer, P., Kumar, M.

Adv. Opt. Mat., March 2020 (article)

Abstract
Traditional photodetectors generally show a unipolar photocurrent response when illuminated with light of wavelength equal or shorter than the optical bandgap. Here, we report that a thin film of gallium oxide (GO) decorated with plasmonic nanoparticles, surprisingly, exhibits a change in the polarity of the photocurrent for different UV bands. Silver (Ag) nanoparticles are vacuum-deposited onto β-Ga2O3 and the AgNP@GO thin films show a record responsivity of 250 A/W, which significantly outperforms bare GO planar photodetectors. The photoresponsivity reverses sign from +157 µA/W in the UV-C band under unbiased operation to -353 µA/W in the UV-A band. The current reversal is rationalized by considering the charge dynamics stemming from hot electrons generated when the incident light excites a local surface plasmon resonance (LSPR) in the Ag nanoparticles. The Ag nanoparticles improve the external quantum efficiency and detectivity by nearly one order of magnitude with high values of 1.2×105 and 3.4×1014 Jones, respectively. This plasmon-enhanced solar blind GO detector allows UV regions to be spectrally distinguished, which is useful for the development of sensitive dynamic imaging photodetectors.

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[BibTex]


Investigating photoresponsivity of graphene-silver hybrid nanomaterials in the ultraviolet
Investigating photoresponsivity of graphene-silver hybrid nanomaterials in the ultraviolet

Deshpande, P., Suri, P., Jeong, H., Fischer, P., Ghosh, A., Ghosh, G.

J. Chem. Phys., 152, pages: 044709, January 2020 (article)

Abstract
There have been several reports of plasmonically enhanced graphene photodetectors in the visible and the near infrared regime but rarely in the ultraviolet. In a previous work, we have reported that a graphene-silver hybrid structure shows a high photoresponsivity of 13 A/W at 270 nm. Here, we consider the likely mechanisms that underlie this strong photoresponse. We investigate the role of the plasmonic layer and examine the response using silver and gold nanoparticles of similar dimensions and spatial arrangement. The effect on local doping, strain, and absorption properties of the hybrid is also probed by photocurrent measurements and Raman and UV-visible spectroscopy. We find that the local doping from the silver nanoparticles is stronger than that from gold and correlates with a measured photosensitivity that is larger in devices with a higher contact area between the plasmonic nanomaterials and the graphene layer.

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link (url) DOI [BibTex]

link (url) DOI [BibTex]


A High-Fidelity Phantom for the Simulation and Quantitative Evaluation of Transurethral Resection of the Prostate
A High-Fidelity Phantom for the Simulation and Quantitative Evaluation of Transurethral Resection of the Prostate

Choi, E., Adams, F., Gengenbacher, A., Schlager, D., Palagi, S., Müller, P., Wetterauer, U., Miernik, A., Fischer, P., Qiu, T.

Annals of Biomed. Eng., 48, pages: 437-446, January 2020 (article)

Abstract
Transurethral resection of the prostate (TURP) is a minimally invasive endoscopic procedure that requires experience and skill of the surgeon. To permit surgical training under realistic conditions we report a novel phantom of the human prostate that can be resected with TURP. The phantom mirrors the anatomy and haptic properties of the gland and permits quantitative evaluation of important surgical performance indicators. Mixtures of soft materials are engineered to mimic the physical properties of the human tissue, including the mechanical strength, the electrical and thermal conductivity, and the appearance under an endoscope. Electrocautery resection of the phantom closely resembles the procedure on human tissue. Ultrasound contrast agent was applied to the central zone, which was not detectable by the surgeon during the surgery but showed high contrast when imaged after the surgery, to serve as a label for the quantitative evaluation of the surgery. Quantitative criteria for performance assessment are established and evaluated by automated image analysis. We present the workflow of a surgical simulation on a prostate phantom followed by quantitative evaluation of the surgical performance. Surgery on the phantom is useful for medical training, and enables the development and testing of endoscopic and minimally invasive surgical instruments.

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link (url) DOI [BibTex]

link (url) DOI [BibTex]


Interactive Materials – Drivers of Future Robotic Systems
Interactive Materials – Drivers of Future Robotic Systems

Fischer, P.

Adv. Mat., January 2020 (article)

Abstract
A robot senses its environment, processes the sensory information, acts in response to these inputs, and possibly communicates with the outside world. Robots generally achieve these tasks with electronics-based hardware or by receiving inputs from some external hardware. In contrast, simple microorganisms can autonomously perceive, act, and communicate via purely physicochemical processes in soft material systems. A key property of biological systems is that they are built from energy-consuming ‘active’ units. Exciting developments in material science show that even very simple artificial active building blocks can show surprisingly rich emergent behaviors. Active non-equilibrium systems are therefore predicted to play an essential role to realize interactive materials. A major challenge is to find robust ways to couple and integrate the energy-consuming building blocks to the mechanical structure of the material. However, success in this endeavor will lead to a new generation of sophisticated micro- and soft-robotic systems that can operate autonomously.

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link (url) DOI [BibTex]


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Analytical classical density functionals from an equation learning network

Lin, S., Martius, G., Oettel, M.

The Journal of Chemical Physics, 152(2):021102, 2020, arXiv preprint \url{https://arxiv.org/abs/1910.12752} (article)

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Preprint_PDF DOI [BibTex]

Preprint_PDF DOI [BibTex]

2016


Wireless actuation with functional acoustic surfaces
Wireless actuation with functional acoustic surfaces

Qiu, T., Palagi, S., Mark, A. G., Melde, K., Adams, F., Fischer, P.

Appl. Phys. Lett., 109(19):191602, November 2016, APL Editor's pick. APL News. (article)

Abstract
Miniaturization calls for micro-actuators that can be powered wirelessly and addressed individually. Here, we develop functional surfaces consisting of arrays of acoustically resonant microcavities, and we demonstrate their application as two-dimensional wireless actuators. When remotely powered by an acoustic field, the surfaces provide highly directional propulsive forces in fluids through acoustic streaming. A maximal force of similar to 0.45mN is measured on a 4 x 4 mm(2) functional surface. The response of the surfaces with bubbles of different sizes is characterized experimentally. This shows a marked peak around the micro-bubbles' resonance frequency, as estimated by both an analytical model and numerical simulations. The strong frequency dependence can be exploited to address different surfaces with different acoustic frequencies, thus achieving wireless actuation with multiple degrees of freedom. The use of the functional surfaces as wireless ready-to-attach actuators is demonstrated by implementing a wireless and bidirectional miniaturized rotary motor, which is 2.6 x 2.6 x 5 mm(3) in size and generates a stall torque of similar to 0.5 mN.mm. The adoption of micro-structured surfaces as wireless actuators opens new possibilities in the development of miniaturized devices and tools for fluidic environments that are accessible by low intensity ultrasound fields.

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link (url) DOI Project Page [BibTex]

2016


link (url) DOI Project Page [BibTex]


Nanomotors
Nanomotors

Alarcon-Correa, M., Walker (Schamel), D., Qiu, T., Fischer, P.

Eur. Phys. J.-Special Topics, 225(11-12):2241-2254, November 2016 (article)

Abstract
This minireview discusses whether catalytically active macromolecules and abiotic nanocolloids, that are smaller than motile bacteria, can self-propel. Kinematic reversibility at low Reynolds number demands that self-propelling colloids must break symmetry. Methods that permit the synthesis and fabrication of Janus nanocolloids are therefore briefly surveyed, as well as means that permit the analysis of the nanocolloids' motion. Finally, recent work is reviewed which shows that nanoagents are small enough to penetrate the complex inhomogeneous polymeric network of biological fluids and gels, which exhibit diverse rheological behaviors.

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DOI [BibTex]

DOI [BibTex]


Structured light enables biomimetic swimming and versatile locomotion of photoresponsive soft microrobots
Structured light enables biomimetic swimming and versatile locomotion of photoresponsive soft microrobots

Palagi, S., Mark, A. G., Reigh, S. Y., Melde, K., Qiu, T., Zeng, H., Parmeggiani, C., Martella, D., Sanchez-Castillo, A., Kapernaum, N., Giesselmann, F., Wiersma, D. S., Lauga, E., Fischer, P.

Nature Materials, 15(6):647–653, November 2016, Max Planck press release, Nature News & Views. (article)

Abstract
Microorganisms move in challenging environments by periodic changes in body shape. In contrast, current artificial microrobots cannot actively deform, exhibiting at best passive bending under external fields. Here, by taking advantage of the wireless, scalable and spatiotemporally selective capabilities that light allows, we show that soft microrobots consisting of photoactive liquid-crystal elastomers can be driven by structured monochromatic light to perform sophisticated biomimetic motions. We realize continuum yet selectively addressable artificial microswimmers that generate travelling-wave motions to self-propel without external forces or torques, as well as microrobots capable of versatile locomotion behaviours on demand. Both theoretical predictions and experimental results confirm that multiple gaits, mimicking either symplectic or antiplectic metachrony of ciliate protozoa, can be achieved with single microswimmers. The principle of using structured light can be extended to other applications that require microscale actuation with sophisticated spatiotemporal coordination for advanced microrobotic technologies.

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Video - Soft photo Micro-Swimmer DOI [BibTex]

Video - Soft photo Micro-Swimmer DOI [BibTex]


Capture of 2D Microparticle Arrays via a UV-Triggered Thiol-yne ``Click{''} Reaction
Capture of 2D Microparticle Arrays via a UV-Triggered Thiol-yne “Click” Reaction

Walker (Schamel), D., Singh, D. P., Fischer, P.

Advanced Materials, 28(44):9846-9850, September 2016 (article)

Abstract
Immobilization of colloidal assemblies onto solid supports via a fast UV-triggered click-reaction is achieved. Transient assemblies of microparticles and colloidal materials can be captured and transferred to solid supports. The technique does not require complex reaction conditions, and is compatible with a variety of particle assembly methods.

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DOI [BibTex]


Magnesium plasmonics for UV applications and chiral sensing
Magnesium plasmonics for UV applications and chiral sensing

Jeong, H. H., Mark, A. G., Fischer, P.

Chem. Comm., 52(82):12179-12182, September 2016 (article)

Abstract
We demonstrate that chiral magnesium nanoparticles show remarkable plasmonic extinction- and chiroptical-effects in the ultraviolet region. The Mg nanohelices possess an enhanced local surface plasmon resonance (LSPR) sensitivity due to the strong dispersion of most substances in the UV region.

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DOI [BibTex]

DOI [BibTex]


Holograms for acoustics
Holograms for acoustics

Melde, K., Mark, A. G., Qiu, T., Fischer, P.

Nature, 537, pages: 518-522, September 2016, Max Planck press release, Nature News & Views, Nature Video. (article)

Abstract
Holographic techniques are fundamental to applications such as volumetric displays(1), high-density data storage and optical tweezers that require spatial control of intricate optical(2) or acoustic fields(3,4) within a three-dimensional volume. The basis of holography is spatial storage of the phase and/or amplitude profile of the desired wavefront(5,6) in a manner that allows that wavefront to be reconstructed by interference when the hologram is illuminated with a suitable coherent source. Modern computer-generated holography(7) skips the process of recording a hologram from a physical scene, and instead calculates the required phase profile before rendering it for reconstruction. In ultrasound applications, the phase profile is typically generated by discrete and independently driven ultrasound sources(3,4,8-12); however, these can only be used in small numbers, which limits the complexity or degrees of freedom that can be attained in the wavefront. Here we introduce monolithic acoustic holograms, which can reconstruct diffraction-limited acoustic pressure fields and thus arbitrary ultrasound beams. We use rapid fabrication to craft the holograms and achieve reconstruction degrees of freedom two orders of magnitude higher than commercial phased array sources. The technique is inexpensive, appropriate for both transmission and reflection elements, and scales well to higher information content, larger aperture size and higher power. The complex three-dimensional pressure and phase distributions produced by these acoustic holograms allow us to demonstrate new approaches to controlled ultrasonic manipulation of solids in water, and of liquids and solids in air. We expect that acoustic holograms will enable new capabilities in beam-steering and the contactless transfer of power, improve medical imaging, and drive new applications of ultrasound.

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Video - Holograms for Sound DOI Project Page [BibTex]

Video - Holograms for Sound DOI Project Page [BibTex]


A loop-gap resonator for chirality-sensitive nuclear magneto-electric resonance (NMER)
A loop-gap resonator for chirality-sensitive nuclear magneto-electric resonance (NMER)

Garbacz, P., Fischer, P., Kraemer, S.

J. Chem. Phys., 145(10):104201, September 2016 (article)

Abstract
Direct detection of molecular chirality is practically impossible by methods of standard nuclear magnetic resonance (NMR) that is based on interactions involving magnetic-dipole and magnetic-field operators. However, theoretical studies provide a possible direct probe of chirality by exploiting an enantiomer selective additional coupling involving magnetic-dipole, magnetic-field, and electric field operators. This offers a way for direct experimental detection of chirality by nuclear magneto-electric resonance (NMER). This method uses both resonant magnetic and electric radiofrequency (RF) fields. The weakness of the chiral interaction though requires a large electric RF field and a small transverse RF magnetic field over the sample volume, which is a non-trivial constraint. In this study, we present a detailed study of the NMER concept and a possible experimental realization based on a loop-gap resonator. For this original device, the basic principle and numerical studies as well as fabrication and measurements of the frequency dependence of the scattering parameter are reported. By simulating the NMER spin dynamics for our device and taking the F-19 NMER signal of enantiomer-pure 1,1,1-trifluoropropan-2-ol, we predict a chirality induced NMER signal that accounts for 1%-5% of the standard achiral NMR signal. Published by AIP Publishing.

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DOI [BibTex]

DOI [BibTex]


Active Nanorheology with Plasmonics
Active Nanorheology with Plasmonics

Jeong, H. H., Mark, A. G., Lee, T., Alarcon-Correa, M., Eslami, S., Qiu, T., Gibbs, J. G., Fischer, P.

Nano Letters, 16(8):4887-4894, July 2016 (article)

Abstract
Nanoplasmonic systems are valued for their strong optical response and their small size. Most plasmonic sensors and systems to date have been rigid and passive. However, rendering these structures dynamic opens new possibilities for applications. Here we demonstrate that dynamic plasmonic nanoparticles can be used as mechanical sensors to selectively probe the rheological properties of a fluid in situ at the nanoscale and in microscopic volumes. We fabricate chiral magneto-plasmonic nanocolloids that can be actuated by an external magnetic field, which in turn allows for the direct and fast modulation of their distinct optical response. The method is robust and allows nanorheological measurements with a mechanical sensitivity of similar to 0.1 cP, even in strongly absorbing fluids with an optical density of up to OD similar to 3 (similar to 0.1% light transmittance) and in the presence of scatterers (e.g., 50% v/v red blood cells).

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DOI [BibTex]

DOI [BibTex]


Dispersion and shape engineered plasmonic nanosensors
Dispersion and shape engineered plasmonic nanosensors

Jeong, H. H., Mark, A. G., Alarcon-Correa, M., Kim, I., Oswald, P., Lee, T. C., Fischer, P.

Nature Communications, 7, pages: 11331, March 2016 (article)

Abstract
Biosensors based on the localized surface plasmon resonance (LSPR) of individual metallic nanoparticles promise to deliver modular, low-cost sensing with high-detection thresholds. However, they continue to suffer from relatively low sensitivity and figures of merit (FOMs). Herein we introduce the idea of sensitivity enhancement of LSPR sensors through engineering of the material dispersion function. Employing dispersion and shape engineering of chiral nanoparticles leads to remarkable refractive index sensitivities (1,091 nmRIU(-1) at lambda = 921 nm) and FOMs (>2,800 RIU-1). A key feature is that the polarization-dependent extinction of the nanoparticles is now characterized by rich spectral features, including bipolar peaks and nulls, suitable for tracking refractive index changes. This sensing modality offers strong optical contrast even in the presence of highly absorbing media, an important consideration for use in complex biological media with limited transmission. The technique is sensitive to surface-specific binding events which we demonstrate through biotin-avidin surface coupling.

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link (url) DOI [BibTex]


Magnetic Propulsion of Microswimmers with DNA-Based Flagellar Bundles
Magnetic Propulsion of Microswimmers with DNA-Based Flagellar Bundles

Maier, A. M., Weig, C., Oswald, P., Frey, E., Fischer, P., Liedl, T.

Nano Letters, 16(2):906-910, January 2016 (article)

Abstract
We show that DNA-based self-assembly can serve as a general and flexible tool to construct artificial flagella of several micrometers in length and only tens of nanometers in diameter. By attaching the DNA flagella to biocompatible magnetic microparticles, we provide a proof of concept demonstration of hybrid structures that, when rotated in an external magnetic field, propel by means of a flagellar bundle, similar to self-propelling peritrichous bacteria. Our theoretical analysis predicts that flagellar bundles that possess a length-dependent bending stiffness should exhibit a superior swimming speed compared to swimmers with a single appendage. The DNA self-assembly method permits the realization of these improved flagellar bundles in good agreement with our quantitative model. DNA flagella with well-controlled shape could fundamentally increase the functionality of fully biocompatible nanorobots and extend the scope and complexity of active materials.

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DOI [BibTex]

DOI [BibTex]

2012


Fourier-transform photocurrent spectroscopy using a supercontinuum light source
Fourier-transform photocurrent spectroscopy using a supercontinuum light source

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

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

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

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DOI [BibTex]

2012


DOI [BibTex]


Eine neue Form von Cavity Enhanced Absorption Spectroscopy
Eine neue Form von Cavity Enhanced Absorption Spectroscopy

Petermann, C., Fischer, P.

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

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

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

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link (url) [BibTex]

link (url) [BibTex]


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Variants of guided self-organization for robot control

Martius, G., Herrmann, J.

Theory in Biosci., 131(3):129-137, Springer Berlin / Heidelberg, 2012 (article)

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link (url) DOI [BibTex]

link (url) 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.

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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.

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DOI [BibTex]

DOI [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.

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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.

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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.

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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.

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DOI [BibTex]

DOI [BibTex]