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2020


Chiroptical spectroscopy of a freely diffusing single nanoparticle
Chiroptical spectroscopy of a freely diffusing single nanoparticle

Sachs, J., Günther, J., Mark, A. G., Fischer, P.

Nature Communications, 11(4513), September 2020 (article)

Abstract
Chiral plasmonic nanoparticles can exhibit strong chiroptical signals compared to the corresponding molecular response. Observations are, however, generally restricted to measurements on stationary single particles with a fixed orientation, which complicates the spectral analysis. Here, we report the spectroscopic observation of a freely diffusing single chiral nanoparticle in solution. By acquiring time-resolved circular differential scattering signals we show that the spectral interpretation is significantly simplified. We experimentally demonstrate the equivalence between time-averaged chiral spectra observed for an individual nanostructure and the corresponding ensemble spectra, and thereby demonstrate the ergodic principle for chiroptical spectroscopy. We also show how it is possible for an achiral particle to yield an instantaneous chiroptical response, whereas the time-averaged signals are an unequivocal measure of chirality. Time-resolved chiroptical spectroscopy on a freely moving chiral nanoparticle advances the field of single-particle spectroscopy, and is a means to obtain the true signature of the nanoparticle’s chirality.

link (url) DOI [BibTex]


Microchannels with Self-Pumping Walls
Microchannels with Self-Pumping Walls

Yu, T., Athanassiadis, A., Popescu, M., Chikkadi, V., Güth, A., Singh, D., Qiu, T., Fischer, P.

ACS Nano, September 2020 (article)

Abstract
When asymmetric Janus micromotors are immobilized on a surface, they act as chemically powered micropumps, turning chemical energy from the fluid into a bulk flow. However, such pumps have previously produced only localized recirculating flows, which cannot be used to pump fluid in one direction. Here, we demonstrate that an array of three-dimensional, photochemically active Au/TiO2 Janus pillars can pump water. Upon UV illumination, a water-splitting reaction rapidly creates a directional bulk flow above the active surface. By lining a 2D microchannel with such active surfaces, various flow profiles are created within the channels. Analytical and numerical models of a channel with active surfaces predict flow profiles that agree very well with the experimental results. The light-driven active surfaces provide a way to wirelessly pump fluids at small scales and could be used for real-time, localized flow control in complex microfluidic networks.

link (url) DOI [BibTex]


Scalable Fabrication of Molybdenum Disulfide Nanostructures and their Assembly
Scalable Fabrication of Molybdenum Disulfide Nanostructures and their Assembly

Huang, Y., Yu, K., Li, H., Liang, Z., Walker, D., Ferreira, P., Fischer, P., Fan, D.

Adv. Mat., (2003439), September 2020 (article)

Abstract
Molybdenum disulfide (MoS2) is a multifunctional material that can be used for various applications. In the single‐crystalline form, MoS2 shows superior electronic properties. It is also an exceptionally useful nanomaterial in its polycrystalline form with applications in catalysis, energy storage, water treatment, and gas sensing. Here, the scalable fabrication of longitudinal MoS2 nanostructures, i.e., nanoribbons, and their oxide hybrids with tunable dimensions in a rational and well‐reproducible fashion, is reported. The nanoribbons, obtained at different reaction stages, that is, MoO3, MoS2/MoO2 hybrid, and MoS2, are fully characterized. The growth method presented herein has a high yield and is particularly robust. The MoS2 nanoribbons can readily be removed from its substrate and dispersed in solution. It is shown that functionalized MoS2 nanoribbons can be manipulated in solution and assembled in controlled patterns and directly on microelectrodes with UV‐click‐chemistry. Owing to the high chemical purity and polycrystalline nature, the MoS2 nanostructures demonstrate rapid optoelectronic response to wavelengths from 450 to 750 nm, and successfully remove mercury contaminants from water. The scalable fabrication and manipulation followed by light‐directed assembly of MoS2 nanoribbons, and their unique properties, will be inspiring for device fabrication and applications of the transition metal dichalcogenides.

link (url) [BibTex]

link (url) [BibTex]


Spatial ultrasound modulation by digitally controlling microbubble arrays
Spatial ultrasound modulation by digitally controlling microbubble arrays

Ma, Z., Melde, K., Athanassiadis, A. G., Schau, M., Richter, H., Qiu, T., Fischer, P.

Nature Communications, 11(4537), September 2020 (article)

Abstract
Acoustic waves, capable of transmitting through optically opaque objects, have been widely used in biomedical imaging, industrial sensing and particle manipulation. High-fidelity wavefront shaping is essential to further improve performance in these applications. An acoustic analog to the successful spatial light modulator (SLM) in optics would be highly desirable. To date there have been no techniques shown that provide effective and dynamic modulation of a sound wave and which also support scale-up to a high number of individually addressable pixels. In the present study, we introduce a dynamic spatial ultrasound modulator (SUM),which dynamically reshapes incident plane waves into complex acoustic images. Its trans-mission function is set with a digitally generated pattern of microbubbles controlled by a complementary metal–oxide–semiconductor (CMOS) chip, which results in a binary amplitude acoustic hologram. We employ this device to project sequentially changing acoustic images and demonstrate the first dynamic parallel assembly of microparticles using a SUM.

link (url) DOI [BibTex]


Characterization of active matter in dense suspensions with heterodyne laser Doppler velocimetry
Characterization of active matter in dense suspensions with heterodyne laser Doppler velocimetry

Sachs, J., Kottapalli, S. N., Fischer, P., Botin, D., Palberg, T.

Colloid and Polymer Science, August 2020 (article)

Abstract
We present a novel approach for characterizing the properties and performance of active matter in dilute suspension as well as in crowded environments. We use Super-Heterodyne Laser-Doppler-Velocimetry (SH-LDV) to study large ensembles of catalytically active Janus particles moving under UV illumination. SH-LDV facilitates a model-free determination of the swimming speed and direction, with excellent ensemble averaging. In addition, we obtain information on the distribution of the catalytic activity. Moreover, SH-LDV operates away from walls and permits a facile correction for multiple scattering contributions. It thus allows for studies of concentrated suspensions of swimmers or of systems where swimmers propel actively in an environment crowded by passive particles. We demonstrate the versatility and the scope of the method with a few selected examples. We anticipate that SH-LDV complements established methods and paves the way for systematic measurements at previously inaccessible boundary conditions.

link (url) DOI [BibTex]

link (url) DOI [BibTex]


Biocompatible magnetic micro‐ and nanodevices: Fabrication of FePt nanopropellers and cell transfection
Biocompatible magnetic micro‐ and nanodevices: Fabrication of FePt nanopropellers and cell transfection

Kadiri, V. M., Bussi, C., Holle, A. W., Son, K., Kwon, H., Schütz, G., Gutierrez, M. G., Fischer, P.

Adv. Mat., 32(2001114), May 2020 (article)

Abstract
The application of nanoparticles for drug or gene delivery promises benefits in the form of single‐cell‐specific therapeutic and diagnostic capabilities. Many methods of cell transfection rely on unspecific means to increase the transport of genetic material into cells. Targeted transport is in principle possible with magnetically propelled micromotors, which allow responsive nanoscale actuation and delivery. However, many commonly used magnetic materials (e.g., Ni and Co) are not biocompatible, possess weak magnetic remanence (Fe3O4), or cannot be implemented in nanofabrication schemes (NdFeB). Here, it is demonstrated that co‐depositing iron (Fe) and platinum (Pt) followed by one single annealing step, without the need for solution processing, yields ferromagnetic FePt nanomotors that are noncytotoxic, biocompatible, and possess a remanence and magnetization that rival those of permanent NdFeB micromagnets. Active cell targeting and magnetic transfection of lung carcinoma cells are demonstrated using gradient‐free rotating millitesla fields to drive the FePt nanopropellers. The carcinoma cells express enhanced green fluorescent protein after internalization and cell viability is unaffected by the presence of the FePt nanopropellers. The results establish FePt, prepared in the L10 phase, as a promising magnetic material for biomedical applications with superior magnetic performance, especially for micro‐ and nanodevices.

link (url) DOI [BibTex]


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.

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.

link (url) DOI [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.

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.

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.

link (url) 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.

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.

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.

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.

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.

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.

DOI [BibTex]

DOI [BibTex]