Header logo is


2013


Hybrid nanocolloids with programmed three-dimensional shape and material composition
Hybrid nanocolloids with programmed three-dimensional shape and material composition

Mark, A. G., Gibbs, J. G., Lee, T., Fischer, P.

NATURE MATERIALS, 12(9):802-807, 2013, Max Planck Press Release. (article)

Abstract
Tuning the optical(1,2), electromagnetic(3,4) and mechanical properties of a material requires simultaneous control over its composition and shape(5). This is particularly challenging for complex structures at the nanoscale because surface-energy minimization generally causes small structures to be highly symmetric(5). Here we combine low-temperature shadow deposition with nanoscale patterning to realize nanocolloids with anisotropic three-dimensional shapes, feature sizes down to 20 nm and a wide choice of materials. We demonstrate the versatility of the fabrication scheme by growing three-dimensional hybrid nanostructures that contain several functional materials with the lowest possible symmetry, and by fabricating hundreds of billions of plasmonic nanohelices, which we use as chiral metafluids with record circular dichroism and tunable chiroptical properties.

Max Planck Press Release.

pf

Video - Fabrication of Designer Nanostructures DOI [BibTex]


Chiral Colloidal Molecules And Observation of The Propeller Effect
Chiral Colloidal Molecules And Observation of The Propeller Effect

Schamel, D., Pfeifer, M., Gibbs, J. G., Miksch, B., Mark, A. G., Fischer, P.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 135(33):12353-12359, 2013 (article)

Abstract
Chiral molecules play an important role in biological and chemical processes, but physical effects due to their symmetry-breaking are generally weak. Several physical chiral separation schemes which could potentially be useful, including the propeller effect, have therefore not yet been demonstrated at the molecular scale. However, it has been proposed that complex nonspherical colloidal particles could act as ``colloidal molecules{''} in mesoscopic model systems to permit the visualization of molecular phenomena that are otherwise difficult to observe. Unfortunately, it is difficult to synthesize such colloids because surface minimization generally favors the growth of symmetric particles. Here we demonstrate the production of large numbers of complex colloids with glancing angle physical vapor deposition. We use chiral colloids to demonstrate the Baranova and Zel'dovich (Baranova, N. B.; Zel'dovich, B. Y. Chem. Phys. Lett. 1978, 57, 435) propeller effect: the separation of a racemic mixture by application of a rotating field that couples to the dipole moment of the enantiomers and screw propels them in opposite directions. The handedness of the colloidal suspensions is monitored with circular differential light scattering. An exact solution for the colloid's propulsion is derived, and comparisons between the colloidal system and the corresponding effect at the molecular scale are made.

pf

Video - Nanospropellers DOI [BibTex]

Video - Nanospropellers DOI [BibTex]


Indirect absorption spectroscopy using quantum cascade lasers: mid-infrared refractometry and photothermal spectroscopy
Indirect absorption spectroscopy using quantum cascade lasers: mid-infrared refractometry and photothermal spectroscopy

Pfeifer, M., Ruf, A., Fischer, P.

OPTICS EXPRESS, 21(22):25643-25654, 2013 (article)

Abstract
We record vibrational spectra with two indirect schemes that depend on the real part of the index of refraction: mid-infrared refractometry and photothermal spectroscopy. In the former, a quantum cascade laser (QCL) spot is imaged to determine the angles of total internal reflection, which yields the absorption line via a beam profile analysis. In the photothermal measurements, a tunable QCL excites vibrational resonances of a molecular monolayer, which heats the surrounding medium and changes its refractive index. This is observed with a probe laser in the visible. Sub-monolayer sensitivities are demonstrated. (C) 2013 Optical Society of America

pf

DOI [BibTex]


Plasmonic nanohelix metamaterials with tailorable giant circular dichroism
Plasmonic nanohelix metamaterials with tailorable giant circular dichroism

Gibbs, J. G., Mark, A. G., Eslami, S., Fischer, P.

APPLIED PHYSICS LETTERS, 103(21), 2013, Featured cover article. (article)

Abstract
Plasmonic nanohelix arrays are shown to interact with electromagnetic fields in ways not typically seen with ordinary matter. Chiral metamaterials (CMMs) with feature sizes small with respect to the wavelength of visible light are a promising route to experimentally achieve such phenomena as negative refraction without the need for simultaneously negative e and mu. Here we not only show that giant circular dichroism in the visible is achievable with hexagonally arranged plasmonic nanohelix arrays, but that we can precisely tune the optical activity via morphology and lattice spacing. The discrete dipole approximation is implemented to support experimental data. (C) 2013 AIP Publishing LLC.

Featured cover article.

pf

DOI [BibTex]

DOI [BibTex]

2011


Quantum-Cascade Laser-Based Vibrational Circular Dichroism
Quantum-Cascade Laser-Based Vibrational Circular Dichroism

Luedeke, S., Pfeifer, M., Fischer, P.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 133(15):5704-5707, 2011 (article)

Abstract
Vibrational circular dichroism (VCD) spectra were recorded with a tunable external-cavity quantum-cascade laser (QCL). In comparison with standard thermal light sources in the IR, QCLs provide orders of magnitude more power and are therefore promising for VCD studies in strongly absorbing solvents. The brightness of this novel light source is demonstrated with VCD and IR absorption measurements of a number of compounds, including proline in water.

pf

DOI [BibTex]

2011


DOI [BibTex]


Actively coupled cavity ringdown spectroscopy with low-power broadband sources
Actively coupled cavity ringdown spectroscopy with low-power broadband sources

Petermann, C., Fischer, P.

OPTICS EXPRESS, 19(11):10164-10173, 2011 (article)

Abstract
We demonstrate a coupling scheme for cavity enhanced absorption spectroscopy that 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 nonlaser light sources with spectral power densities of less than 30 mu W/nm. Although the acousto-optical element reduces the ultimate detection limit by introducing additional losses, it permits absorptivities to be measured with a high dynamic range, especially in lossy environments. Absorption measurements for the forbidden transition of gaseous oxygen in air at similar to 760nm are presented using a low-coherence cw-superluminescent diode. The same setup was electronically configured to cover absorption losses from 1.8 x 10(-8)cm(-1) to 7.5\% per roundtrip. This could be of interest in process analytical applications. (C) 2011 Optical Society of America

pf

DOI [BibTex]

DOI [BibTex]


Magnetically actuated propulsion at low Reynolds numbers: towards nanoscale control
Magnetically actuated propulsion at low Reynolds numbers: towards nanoscale control

Fischer, P., Ghosh, A.

NANOSCALE, 3(2):557-563, 2011 (article)

Abstract
Significant progress has been made in the fabrication of micron and sub-micron structures whose motion can be controlled in liquids under ambient conditions. The aim of many of these engineering endeavors is to be able to build and propel an artificial micro-structure that rivals the versatility of biological swimmers of similar size, e. g. motile bacterial cells. Applications for such artificial ``micro-bots'' are envisioned to range from microrheology to targeted drug delivery and microsurgery, and require full motion-control under ambient conditions. In this Mini-Review we discuss the construction, actuation, and operation of several devices that have recently been reported, especially systems that can be controlled by and propelled with homogenous magnetic fields. We describe the fabrication and associated experimental challenges and discuss potential applications.

pf

Video - Nanospropellers DOI [BibTex]


no image
Aerial righting reflexes in flightless animals

Jusufi, A., Zeng, Y., Full, R., Dudley, R.

Integ. Comp. Biol. , 2011 (article)

bio

[BibTex]

[BibTex]


Weak value amplified optical activity measurements
Weak value amplified optical activity measurements

Pfeifer, M., Fischer, P.

Opt. Express, 19(17):16508-16517, OSA, 2011 (article)

Abstract
We present a new form of optical activity measurement based on a modified weak value amplification scheme. It has recently been shown experimentally that the left- and right-circular polarization components refract with slightly different angles of refraction at a chiral interface causing a linearly polarized light beam to split into two. By introducing a polarization modulation that does not give rise to a change in the optical rotation it is possible to differentiate between the two circular polarization components even after post-selection with a linear polarizer. We show that such a modified weak value amplification measurement permits the sign of the splitting and thus the handedness of the optically active medium to be determined. Angular beam separations of Δθ ∼ 1 nanoradian, which corresponds to a circular birefringence of Δn ∼ 1 × 10−9, could be measured with a relative error of less than 1%.

pf

link (url) DOI [BibTex]

link (url) DOI [BibTex]

2006


Chiral molecules split light: Reflection and refraction in a chiral liquid
Chiral molecules split light: Reflection and refraction in a chiral liquid

Ghosh, A., Fischer, P.

PHYSICAL REVIEW LETTERS, 97(17), 2006, Featured highlight ‘Fundamental optical physics: Refraction’ Nature Photonics, Nov. 2006. (article)

Abstract
A light beam changes direction as it enters a liquid at an angle from another medium, such as air. Should the liquid contain molecules that lack mirror symmetry, then it has been predicted by Fresnel that the light beam will not only change direction, but will actually split into two separate beams with a small difference in the respective angles of refraction. Here we report the observation of this phenomenon. We also demonstrate that the angle of reflection does not equal the angle of incidence in a chiral medium. Unlike conventional optical rotation, which depends on the path-length through the sample, the reported reflection and refraction phenomena arise within a few wavelengths at the interface and thereby suggest a new approach to polarimetry that can be used in microfluidic volumes.

Featured highlight ‘Fundamental optical physics: Refraction’ Nature Photonics, Nov. 2006.

pf

DOI [BibTex]

2006


DOI [BibTex]


Direct chiral discrimination in NMR spectroscopy
Direct chiral discrimination in NMR spectroscopy

Buckingham, A., Fischer, P.

CHEMICAL PHYSICS, 324(1):111-116, 2006 (article)

Abstract
Conventional nuclear magnetic resonance spectroscopy is unable to distinguish between the two mirror-image forms (enantiomers) of a chiral molecule. This is because the NMR spectrum is determined by the chemical shifts and spin-spin coupling constants which - in the absence of a chiral solvent - are identical for the two enantiomers. We discuss how chirality may nevertheless be directly detected in liquid-state NMR spectroscopy: In a chiral molecule, the rotating nuclear magnetic moment induces an electric dipole moment in the direction perpendicular to itself and to the permanent magnetic field of the spectrometer. We present computations of the precessing electric polarization following a pi/2 pulse. Our estimates indicate that the electric polarization should be detectable in favourable cases. We also predict that application of an electrostatic field induces a chirally sensitive magnetization oscillating in the direction of the permanent magnetic field. We show that the electric-field-perturbed chemical shift tensor, the nuclear magnetic shielding polarizability, underlies these chiral NMR effects. (c) 2005 Elsevier B.V. All rights reserved.

pf

DOI [BibTex]

DOI [BibTex]


Ring-resonator-based frequency-domain optical activity measurements of a chiral liquid
Ring-resonator-based frequency-domain optical activity measurements of a chiral liquid

Vollmer, F., Fischer, P.

OPTICS LETTERS, 31(4):453-455, 2006 (article)

Abstract
Chiral liquids rotate the plane of polarization of linearly polarized light and are therefore optically active. Here we show that optical rotation can be observed in the frequency domain. A chiral liquid introduced in a fiber-loop ring resonator that supports left and right circularly polarized modes gives rise to relative frequency shifts that are a direct measure of the liquid's circular birefringence and hence of its optical activity. The effect is in principle not diminished if the circumference of the ring is reduced. The technique is similarly applicable to refractive index and linear birefringence measurements. (c) 2006 Optical Society of America.

pf

DOI [BibTex]


Sign of the refractive index in a gain medium with negative permittivity and permeability
Sign of the refractive index in a gain medium with negative permittivity and permeability

Chen, Y., Fischer, P., Wise, F.

JOURNAL OF THE OPTICAL SOCIETY OF AMERICA B-OPTICAL PHYSICS, 23(1):45-50, 2006 (article)

Abstract
We show how the sign of the refractive index in any medium may be derived using a rigorous analysis based on Einstein causality. In particular, we consider left-handed materials, i.e., media that have negative permittivities and permeabilities at the frequency of interest. We find that the consideration of gain in such media can give rise to a positive refractive index. (c) 2006 Optical Society of America.

pf

DOI [BibTex]

DOI [BibTex]

2001


Isotropic second-order nonlinear optical susceptibilities
Isotropic second-order nonlinear optical susceptibilities

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

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

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

pf

DOI [BibTex]

2001


DOI [BibTex]


Reply to ``Comment on `Phenomenological damping in optical response tensors'{''}
Reply to “Comment on ‘Phenomenological damping in optical response tensors’”

Buckingham, A., Fischer, P.

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

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

pf

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.

pf

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.

pf

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.

pf

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.

pf

DOI [BibTex]

DOI [BibTex]