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2019


Soft-magnetic coatings as possible sensors for magnetic imaging of superconductors
Soft-magnetic coatings as possible sensors for magnetic imaging of superconductors

Ionescu, A., Simmendinger, J., Bihler, M., Miksch, C., Fischer, P., Soltan, S., Schütz, G., Albrecht, J.

Supercond. Sci. and Tech., 33, pages: 015002, IOP, December 2019 (article)

Abstract
Magnetic imaging of superconductors typically requires a soft-magnetic material placed on top of the superconductor to probe local magnetic fields. For reasonable results the influence of the magnet onto the superconductor has to be small. Thin YBCO films with soft-magnetic coatings are investigated using SQUID magnetometry. Detailed measurements of the magnetic moment as a function of temperature, magnetic field and time have been performed for different heterostructures. It is found that the modification of the superconducting transport in these heterostructures strongly depends on the magnetic and structural properties of the soft-magnetic material. This effect is especially pronounced for an inhomogeneous coating consisting of ferromagnetic nanoparticles.

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link (url) DOI [BibTex]

2019


link (url) DOI [BibTex]


Acoustic hologram enhanced phased arrays for ultrasonic particle manipulation
Acoustic hologram enhanced phased arrays for ultrasonic particle manipulation

Cox, L., Melde, K., Croxford, A., Fischer, P., Drinkwater, B.

Phys. Rev. Applied, 12, pages: 064055, November 2019 (article)

Abstract
The ability to shape ultrasound fields is important for particle manipulation, medical therapeutics and imaging applications. If the amplitude and/or phase is spatially varied across the wavefront then it is possible to project ‘acoustic images’. When attempting to form an arbitrary desired static sound field, acoustic holograms are superior to phased arrays due to their significantly higher phase fidelity. However, they lack the dynamic flexibility of phased arrays. Here, we demonstrate how to combine the high-fidelity advantages of acoustic holograms with the dynamic control of phased arrays in the ultrasonic frequency range. Holograms are used with a 64-element phased array, driven with continuous excitation. Moving the position of the projected hologram via phase delays which steer the output beam is demonstrated experimentally. This allows the creation of a much more tightly focused point than with the phased array alone, whilst still being reconfigurable. It also allows the complex movement at a water-air interface of a “phase surfer” along a phase track or the manipulation of a more arbitrarily shaped particle via amplitude traps. Furthermore, a particle manipulation device with two emitters and a single split hologram is demonstrated that allows the positioning of a “phase surfer” along a 1D axis. This paper opens the door for new applications with complex manipulation of ultrasound whilst minimising the complexity and cost of the apparatus.

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link (url) DOI [BibTex]

link (url) DOI [BibTex]


A Helical Microrobot with an Optimized Propeller-Shape for Propulsion in Viscoelastic Biological Media
A Helical Microrobot with an Optimized Propeller-Shape for Propulsion in Viscoelastic Biological Media

Li., D., Jeong, M., Oren, E., Yu, T., Qiu, T.

Robotics, 8, pages: 87, MDPI, October 2019 (article)

Abstract
One major challenge for microrobots is to penetrate and effectively move through viscoelastic biological tissues. Most existing microrobots can only propel in viscous liquids. Recent advances demonstrate that sub-micron robots can actively penetrate nanoporous biological tissue, such as the vitreous of the eye. However, it is still difficult to propel a micron-sized device through dense biological tissue. Here, we report that a special twisted helical shape together with a high aspect ratio in cross-section permit a microrobot with a diameter of hundreds-of-micrometers to move through mouse liver tissue. The helical microrobot is driven by a rotating magnetic field and localized by ultrasound imaging inside the tissue. The twisted ribbon is made of molybdenum and a sharp tip is chemically etched to generate a higher pressure at the edge of the propeller to break the biopolymeric network of the dense tissue.

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link (url) DOI [BibTex]


Acoustic Holographic Cell Patterning in a Biocompatible Hydrogel
Acoustic Holographic Cell Patterning in a Biocompatible Hydrogel

Ma, Z., Holle, A., Melde, K., Qiu, T., Poeppel, K., Kadiri, V., Fischer, P.

Adv. Mat., October 2019 (article)

Abstract
Acoustophoresis is promising as a rapid, biocompatible, non-contact cell manipulation method, where cells are arranged along the nodes or antinodes of the acoustic field. Typically, the acoustic field is formed in a resonator, which results in highly symmetric regular patterns. However, arbitrary, non-symmetrically shaped cell assemblies are necessary to obtain the irregular cellular arrangements found in biological tissues. We show that arbitrarily shaped cell patterns can be obtained from the complex acoustic field distribution defined by an acoustic hologram. Attenuation of the sound field induces localized acoustic streaming and the resultant convection flow gently delivers the suspended cells to the image plane where they form the designed pattern. We show that the process can be implemented in a biocompatible collagen solution, which can then undergo gelation to immobilize the cell pattern inside the viscoelastic matrix. The patterned cells exhibit F-actin-based protrusions, which indicates that the cells grow and thrive within the matrix. Cell viability assays and brightfield imaging after one week confirm cell survival and that the patterns persist. Acoustophoretic cell manipulation by holographic fields thus holds promise for non-contact, long-range, long-term cellular pattern formation, with a wide variety of potential applications in tissue engineering and mechanobiology.

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link (url) DOI [BibTex]


Arrays of plasmonic nanoparticle dimers with defined nanogap spacers
Arrays of plasmonic nanoparticle dimers with defined nanogap spacers

Jeong, H., Adams, M. C., Guenther, J., Alarcon-Correa, M., Kim, I., Choi, E., Miksch, C., Mark, A. F. M., Mark, A. G., Fischer, P.

ACS Nano, September 2019 (article)

Abstract
Plasmonic molecules are building blocks of metallic nanostructures that give rise to intriguing optical phenomena with similarities to those seen in molecular systems. The ability to design plasmonic hybrid structures and molecules with nanometric resolution would enable applications in optical metamaterials and sensing that presently cannot be demonstrated, because of a lack of suitable fabrication methods allowing the structural control of the plasmonic atoms on a large scale. Here we demonstrate a wafer-scale “lithography-free” parallel fabrication scheme to realize nanogap plasmonic meta-molecules with precise control over their size, shape, material, and orientation. We demonstrate how we can tune the corresponding coupled resonances through the entire visible spectrum. Our fabrication method, based on glancing angle physical vapor deposition with gradient shadowing, permits critical parameters to be varied across the wafer and thus is ideally suited to screen potential structures. We obtain billions of aligned dimer structures with controlled variation of the spectral properties across the wafer. We spectroscopically map the plasmonic resonances of gold dimer structures and show that they not only are in good agreement with numerically modeled spectra, but also remain functional, at least for a year, in ambient conditions.

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link (url) DOI [BibTex]


Genetically modified M13 bacteriophage nanonets for enzyme catalysis and recovery
Genetically modified M13 bacteriophage nanonets for enzyme catalysis and recovery

Kadiri, V. M., Alarcon-Correa, M., Guenther, J. P., Ruppert, J., Bill, J., Rothenstein, D., Fischer, P.

Catalysts, 9, pages: 723, August 2019 (article)

Abstract
Enzyme-based biocatalysis exhibits multiple advantages over inorganic catalysts, including the biocompatibility and the unchallenged specificity of enzymes towards their substrate. The recovery and repeated use of enzymes is essential for any realistic application in biotechnology, but is not easily achieved with current strategies. For this purpose, enzymes are often immobilized on inorganic scaffolds, which could entail a reduction of the enzymes’ activity. Here, we show that immobilization to a nano-scaled biological scaffold, a nanonetwork of end-to-end cross-linked M13 bacteriophages, ensures high enzymatic activity and at the same time allows for the simple recovery of the enzymes. The bacteriophages have been genetically engineered to express AviTags at their ends, which permit biotinylation and their specific end-to-end self-assembly while allowing space on the major coat protein for enzyme coupling. We demonstrate that the phages form nanonetwork structures and that these so-called nanonets remain highly active even after re-using the nanonets multiple times in a flow-through reactor.

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link (url) DOI [BibTex]

link (url) DOI [BibTex]


Light-controlled micromotors and soft microrobots
Light-controlled micromotors and soft microrobots

Palagi, S., Singh, D. P., Fischer, P.

Adv. Opt. Mat., 7, pages: 1900370, August 2019 (article)

Abstract
Mobile microscale devices and microrobots can be powered by catalytic reactions (chemical micromotors) or by external fields. This report is focused on the role of light as a versatile means for wirelessly powering and controlling such microdevices. Recent advances in the development of autonomous micromotors are discussed, where light permits their actuation with unprecedented control and thereby enables advances in the field of active matter. In addition, structuring the light field is a new means to drive soft microrobots that are based on (photo‐) responsive polymers. The behavior of the two main classes of thermo‐ and photoresponsive polymers adopted in microrobotics (poly(N‐isopropylacrylamide) and liquid‐crystal elastomers) is analyzed, and recent applications are reported. The advantages and limitations of controlling micromotors and microrobots by light are reviewed, and some of the remaining challenges in the development of novel photo‐active materials for micromotors and microrobots are discussed.

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link (url) DOI [BibTex]


Self-Assembled Phage-Based Colloids for High Localized Enzymatic Activity
Self-Assembled Phage-Based Colloids for High Localized Enzymatic Activity

Alarcon-Correa, M., Guenther, J., Troll, J., Kadiri, V. M., Bill, J., Fischer, P., Rothenstein, D.

ACS Nano, March 2019 (article)

Abstract
Catalytically active colloids are model systems for chemical motors and active matter. It is desirable to replace the inorganic catalysts and the toxic fuels that are often used, with biocompatible enzymatic reactions. However, compared to inorganic catalysts, enzyme-coated colloids tend to exhibit less activity. Here, we show that the self-assembly of genetically engineered M13 bacteriophages that bind enzymes to magnetic beads ensures high and localized enzymatic activity. These phage-decorated colloids provide a proteinaceous environment for directed enzyme immobilization. The magnetic properties of the colloidal carrier particle permit repeated enzyme recovery from a reaction solution, while the enzymatic activity is retained. Moreover, localizing the phage-based construct with a magnetic field in a microcontainer allows the enzyme-phage-colloids to function as an enzymatic micropump, where the enzymatic reaction generates a fluid flow. This system shows the fastest fluid flow reported to date by a biocompatible enzymatic micropump. In addition, it is functional in complex media including blood where the enzyme driven micropump can be powered at the physiological blood-urea concentration.

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link (url) DOI [BibTex]

link (url) DOI [BibTex]


Absolute diffusion measurements of active enzyme solutions by NMR
Absolute diffusion measurements of active enzyme solutions by NMR

Guenther, J., Majer, G., Fischer, P.

J. Chem. Phys., 150(124201), March 2019 (article)

Abstract
The diffusion of enzymes is of fundamental importance for many biochemical processes. Enhanced or directed enzyme diffusion can alter the accessibility of substrates and the organization of enzymes within cells. Several studies based on fluorescence correlation spectroscopy (FCS) report enhanced diffusion of enzymes upon interaction with their substrate or inhibitor. In this context, major importance is given to the enzyme fructose-bisphosphate aldolase, for which enhanced diffusion has been reported even though the catalysed reaction is endothermic. Additionally, enhanced diffusion of tracer particles surrounding the active aldolase enzymes has been reported. These studies suggest that active enzymes can act as chemical motors that self-propel and give rise to enhanced diffusion. However, fluorescence studies of enzymes can, despite several advantages, suffer from artefacts. Here we show that the absolute diffusion coefficients of active enzyme solutions can be determined with Pulsed Field Gradient Nuclear Magnetic Resonance (PFG-NMR). The advantage of PFG-NMR is that the motion of the molecule of interest is directly observed in its native state without the need for any labelling. Further, PFG-NMR is model-free and thus yields absolute diffusion constants. Our PFG-NMR experiments of solutions containing active fructose-bisphosphate aldolase from rabbit muscle do not show any diffusion enhancement for the active enzymes nor the surrounding molecules. Additionally, we do not observe any diffusion enhancement of aldolase in the presence of its inhibitor pyrophosphate.

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link (url) DOI [BibTex]

link (url) DOI [BibTex]


Chemical Nanomotors at the Gram Scale Form a Dense Active Optorheological Medium
Chemical Nanomotors at the Gram Scale Form a Dense Active Optorheological Medium

Choudhury, U., Singh, D. P., Qiu, T., Fischer, P.

Adv. Mat., (1807382), Febuary 2019 (article)

Abstract
The rheological properties of a colloidal suspension are a function of the concentration of the colloids and their interactions. While suspensions of passive colloids are well studied and have been shown to form crystals, gels, and glasses, examples of energy‐consuming “active” colloidal suspensions are still largely unexplored. Active suspensions of biological matter, such as motile bacteria or dense mixtures of active actin–motor–protein mixtures have, respectively, reveals superfluid‐like and gel‐like states. Attractive inanimate systems for active matter are chemically self‐propelled particles. It has so far been challenging to use these swimming particles at high enough densities to affect the bulk material properties of the suspension. Here, it is shown that light‐triggered asymmetric titanium dioxide that self‐propel, can be obtained in large quantities, and self‐organize to make a gram‐scale active medium. The suspension shows an activity‐dependent tenfold reversible change in its bulk viscosity.

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link (url) DOI [BibTex]


First Observation of Optical Activity in Hyper-Rayleigh Scattering
First Observation of Optical Activity in Hyper-Rayleigh Scattering

Collins, J., Rusimova, K., Hooper, D., Jeong, H. H., Ohnoutek, L., Pradaux-Caggiano, F., Verbiest, T., Carbery, D., Fischer, P., Valev, V.

Phys. Rev. X, 9(011024), January 2019 (article)

Abstract
Chiral nano- or metamaterials and surfaces enable striking photonic properties, such as negative refractive index and superchiral light, driving promising applications in novel optical components, nanorobotics, and enhanced chiral molecular interactions with light. In characterizing chirality, although nonlinear chiroptical techniques are typically much more sensitive than their linear optical counterparts, separating true chirality from anisotropy is a major challenge. Here, we report the first observation of optical activity in second-harmonic hyper-Rayleigh scattering (HRS). We demonstrate the effect in a 3D isotropic suspension of Ag nanohelices in water. The effect is 5 orders of magnitude stronger than linear optical activity and is well pronounced above the multiphoton luminescence background. Because of its sensitivity, isotropic environment, and straightforward experimental geometry, HRS optical activity constitutes a fundamental experimental breakthrough in chiral photonics for media including nanomaterials, metamaterials, and chemical molecules.

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link (url) DOI [BibTex]

link (url) DOI [BibTex]

2015


Enzymatically active biomimetic micropropellers for the penetration of mucin gels
Enzymatically active biomimetic micropropellers for the penetration of mucin gels

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

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

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

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link (url) DOI [BibTex]

2015


link (url) DOI [BibTex]


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

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

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

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

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DOI [BibTex]

DOI [BibTex]


Optimal Length of Low Reynolds Number Nanopropellers
Optimal Length of Low Reynolds Number Nanopropellers

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

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

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

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DOI [BibTex]

DOI [BibTex]


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

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

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

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

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DOI [BibTex]

DOI [BibTex]


Dynamic Inclusion Complexes of Metal Nanoparticles Inside Nanocups
Dynamic Inclusion Complexes of Metal Nanoparticles Inside Nanocups

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

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

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

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DOI [BibTex]

DOI [BibTex]


Surface roughness-induced speed increase for active Janus micromotors
Surface roughness-induced speed increase for active Janus micromotors

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

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

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

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DOI [BibTex]

DOI [BibTex]


Active colloidal microdrills
Active colloidal microdrills

Gibbs, J. G., Fischer, P.

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

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

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DOI [BibTex]

DOI [BibTex]


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

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

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

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

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link (url) DOI [BibTex]

link (url) DOI [BibTex]

2007


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

Vollmer, F., Fischer, P.

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

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

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DOI [BibTex]

2007


DOI [BibTex]


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

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

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

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

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DOI [BibTex]


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

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

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

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

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DOI [BibTex]

DOI [BibTex]

2002


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

Fischer, P., Albrecht, A.

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

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

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DOI [BibTex]

2002


DOI [BibTex]


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

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

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

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

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DOI [BibTex]

DOI [BibTex]


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

Fischer, P., Albrecht, A.

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

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

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[BibTex]

[BibTex]

1998


Surface second-order nonlinear optical activity
Surface second-order nonlinear optical activity

Fischer, P., Buckingham, A.

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

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

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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]