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2019


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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]


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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]


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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]


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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


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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.

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link (url) DOI [BibTex]

2015


link (url) DOI [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.

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DOI [BibTex]

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.

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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.

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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.

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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.

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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.

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DOI [BibTex]

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.

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link (url) DOI [BibTex]

link (url) DOI [BibTex]

2009


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Full phase and amplitude control in computer-generated holography

Fratz, M., Fischer, P., Giel, D. M.

OPTICS LETTERS, 34(23):3659-3661, 2009 (article)

Abstract
We report what we believe to be the first realization of a computer-generated complex-valued hologram recorded in a single film of photoactive polymer. Complex-valued holograms give rise to a diffracted optical field with control over its amplitude and phase. The holograms are generated by a one-step direct laser writing process in which a spatial light modulator (SLM) is imaged onto a polymer film. Temporal modulation of the SLM during exposure controls both the strength of the induced birefringence and the orientation of the fast axis. We demonstrate that complex holograms can be used to impart arbitrary amplitude and phase profiles onto a beam and thereby open new possibilities in the control of optical beams. (C) 2009 Optical Society of America

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2009


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Digital polarization holograms with defined magnitude and orientation of each pixel’s birefringence

Fratz, M., Giel, D. M., Fischer, P.

OPTICS LETTERS, 34(8):1270-1272, 2009 (article)

Abstract
A new form of digital polarization holography is demonstrated that permits both the amplitude and the phase of a diffracted beam to be independently controlled. This permits two independent intensity images to be stored in the same hologram. To fabricate the holograms, a birefringence with defined retardance and orientation of the fast axis is recorded into a photopolymer film. The holograms are selectively read out by choosing the polarization state of the read beam. Polarization holograms of this kind increase the data density in holographic data storage and allow higher quality diffractive optical elements to be written. (C) 2009 Optical Society of America

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[BibTex]


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Controlled Propulsion of Artificial Magnetic Nanostructured Propellers

Ghosh, A., Fischer, P.

NANO LETTERS, 9(6):2243-2245, 2009, Featured highlight ‘Nanotechnology: The helix that delivers’ Nature 459, 13 (2009). (article)

Abstract
For biomedical applications, such as targeted drug delivery and microsurgery, it is essential to develop a system of swimmers that can be propelled wirelessly in fluidic environments with good control. Here, we report the construction and operation of chiral colloidal propellers that can be navigated in water with micrometer-level precision using homogeneous magnetic fields. The propellers are made via nanostructured surfaces and can be produced in large numbers. The nanopropellers can carry chemicals, push loads, and act as local probes in rheological measurements.

Featured highlight ‘Nanotechnology: The helix that delivers’ Nature 459, 13 (2009).

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Video - Nanospropellers DOI [BibTex]

Video - Nanospropellers DOI [BibTex]


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Absolute Asymmetric Reduction Based on the Relative Orientation of Achiral Reactants

Kuhn, A., Fischer, P.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 48(37):6857-6860, 2009 (article)

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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.

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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.

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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.

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DOI [BibTex]

DOI [BibTex]