Gold-silica-gold nanosandwiches: tunable bimodal plasmonic resonators.
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Crystallization↗
Biomedical subjects
Mikael Käll
Publications and source records attributed to Mikael Käll.
Raman spectroscopic studies of terthiophenes for molecular electronics.
The effect of thiol and selenol functionalization on the vibrational spectra and photochemical stability of terthiophene based molecular wires was investigated using surface-enhanced Raman scattering (SERS). The molecules were found to exhibit markedly different properties at the silver surface of the SERS substrate, despite having almost identical Raman spectra in solution and in the solid state. In contrast to terthiophene (3T), the bisthiolterthiophene (T3) and biselenol-terthiophene (Se3) molecules were stable against photoinduced structural changes when adsorbed to the metal surface at low concentrations. This indicates that the strong bonds to the silver surface, via S or Se terminal atoms, leads to a rapid decay of photoexcited states. Comparison with ab initio calculations shows that both T3 and Se3 bind with only one of the functional groups to the Ag surface.
Journal Article↗
Photo-induced transformations in 2,2':5',2''-terthiophene thin films on silver.
We report on transient photo-induced structural changes of 2,2':5',2''-terthiophene (3T) adsorbed on silver nanoparticles. Surface-enhanced Raman scattering (SERS) data show that the film thickness predetermines the eventual course of these changes. In particular, for high molecular concentrations (thick adsorbate layers), illumination leads to a photoinduced polymerization of the 3T film. For thin layers ( approximately monolayer coverage), the photoinduced spectral evolution is qualitatively different. We interpret the latter process as a cleavage of the terthiophene molecule, resulting in isolated thiophene units. Calculations of excitation energies for 3T + 3Ag+ and 1T + Ag+ revealed visible transitions, while calculated Raman frequencies indicated 1T as a possible photoproduct. As no photoinduced transformations are observed for 3T in the solid or solution phases, it is likely that the processes reported here originate in surface-enhanced charge-transfer between the Ag-surface and the organic adsorbate.
Adsorption↗
Creating hot nanoparticle pairs for surface-enhanced Raman spectroscopy through optical manipulation.
We use optical tweezers to move single silver nanoparticles into near-field contact with immobilized particles, forming isolated surface-enhanced Raman spectroscopy (SERS) active Ag particle dimers. The surface-averaged SERS intensity increases by a factor approximately 20 upon dimerization. Electrodynamics calculations indicate that the final approach between the particles is due to "optical binding". The described methodology may facilitate controlled single molecule SERS analysis.
Metal Nanoparticles↗
On the importance of optical forces in surface-enhanced Raman scattering (SERS).
This contribution reports on the combination of optical tweezers with SERS spectroscopy of colloidal silver nanoparticles covered by thiophenol. The experimental design is based on two different laser beams, one used for Raman excitation (lamda = 514.5 nm) and one for optical tweezing (lamda=830 nm). For a fixed Raman excitation power, the SERS signal from thiophenol is found to increase dramatically when the trapping laser is activated. This result is interpreted as a combination of two effects, an accumulation of nanoparticles in the optical trap and an optically induced aggregation of these nanoparticles.
Journal Article↗
Localized surface plasmon resonance sensing of lipid-membrane-mediated biorecognition events.
Supported phospholipid bilayers (SPBs) have emerged as important model systems for studies of the natural cell membrane and its components, which are essential for the integrity and function of cells in all living organisms, and also constitute common targets for therapeutic drugs and in disease diagnosis. However, the preferential occurrence of spontaneous SPB formation on silicon-based substrates, but not on bare noble-metal surfaces, has so far excluded the use of the localized surface plasmon resonance (LSPR) sensing principle for studies of lipid-membrane-mediated biorecognition reactions. This is because the LSPR phenomenon is associated with, and strongly confined to, the interfacial region of nanometric noble-metal particles. This problem has been overcome in this study by a self-assembly process utilizing localized rupture of phospholipid vesicles on silicon dioxide in the bottom of nanometric holes in a thin gold film. The hole-induced localization of the LSPR field to the voids of the holes is demonstrated to provide an extension of the LSPR sensing concept to studies of reactions confined exclusively to SPB-patches supported on SiO2. In particular, we emphasize the possibility of performing label-free studies of lipid-membrane-mediated reaction kinetics, including the compatibility of the assay with array-based reading (approximately 7 x 7 microm2) and detection of signals originating from bound protein in the zeptomole regime.
Adsorption↗
A microfluidic system enabling Raman measurements of the oxygenation cycle in single optically trapped red blood cells.
Using a lab-on-a-chip approach we demonstrate the possibility of selecting a single cell with certain properties and following its dynamics after an environmental stimulation in real time using Raman spectroscopy. This is accomplished by combining a micro Raman set-up with optical tweezers and a microfluidic system. The latter gives full control over the media surrounding the cell, and it consists of a pattern of channels and reservoirs defined by electron beam lithography that is moulded into rubber silicon (PDMS). Different buffers can be transported through the channels using electro-osmotic flow, while the resonance Raman response of an optically trapped red blood cell (RBC) is simultaneously registered. This makes it possible to monitor the oxygenation cycle of the cell in real time and to investigate effects like photo-induced chemistry caused by the illumination. The experimental set-up has high potential for in vivo monitoring of cellular drug response using a variety of spectroscopic probes.
Adult↗
Confined plasmons in nanofabricated single silver particle pairs: experimental observations of strong interparticle interactions.
We report on the optical properties of single isolated silver nanodisks and pairs of disks fabricated by electron beam lithography. By systematically varying the disk size and surface separation and recording elastic scattering spectra in different polarization configurations, we found evidence for extremely strong interparticle interactions. The dipolar surface plasmon resonance for polarization parallel to the dimer axis exhibited a red shift as the interdimer separation was decreased; as expected from previous work, an extremely strong shift was observed. The scattering spectra of single particles and pairs separated by more than one particle radius can be well described by the coupled dipole approximation (CDA), where the particles are approximated as point dipoles using a modified dipole polarizability for oblate spheroids. For smaller particle separations (d < 20 nm), the simple dipole model severely underestimates the particle interaction, indicating the importance of multipolar fields and finite-size effects. The discrete dipole approximation (DDA), which is a finite-element method, describes the experimental results well even at d < 20 nm, including particles that have metallic bridges.
Journal Article↗
Controlling plasmon line shapes through diffractive coupling in linear arrays of cylindrical nanoparticles fabricated by electron beam lithography.
The effect of diffractive coupling on the collective plasmon line shape of linear arrays of Ag nanoparticles fabricated by electron beam lithography has been investigated using Rayleigh scattering spectroscopy. The array spectra exhibit an intricate multi-peak structure, including a narrow mode that gains strength for interparticle distances that are close to the single particle resonance wavelength. A version of the discrete dipole approximation method provides an excellent qualitative description of the observed behavior.
Electrons↗
Plasmonic sensing characteristics of single nanometric holes.
The optical response of isolated holes in 20 nm thin gold is probed as a function of alkanethiol CH(3)(CH2)x SH (x epsilon in 1-15) and protein adsorption using dark-field spectroscopy. We establish that the plasmon excitations of single and short-range ordered 60 nm holes exhibit similar E-field decay lengths delta approximately 10-20 nm and that a single hole can be used to resolve the successive adsorption of a protein (biotin-BSA) and its interaction partner (neutravidin). The data confirm the localized character of the hole plasmon and demonstrate that its applicability for bio/chemosensing is similar to that of particle plasmons.
Journal Article↗
Unified treatment of fluorescence and raman scattering processes near metal surfaces.
We present a general model study of surface-enhanced resonant Raman scattering and fluorescence focusing on the interplay between electromagnetic effects and the molecular dynamics. Our model molecule is placed close to two Ag nanoparticles and has two electronic levels. A Franck-Condon mechanism provides electron-vibration coupling. Using realistic parameter values for the molecule we find that an electromagnetic enhancement by 10 orders of magnitude can yield Raman cross sections sigma(R) of the order 10(-14) cm(2). We also discuss the dependence of sigma(R) on incident laser intensity.
Journal Article↗
Polarization-dependent surface-enhanced Raman spectroscopy of isolated silver nanoaggregates.
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Colloids↗
Importance of substrate and photo-induced effects in Raman spectroscopy of single functional erythrocytes.
Hemoglobin (Hb) in single erythrocytes (red blood cells), adsorbed on polylysine-coated glass surfaces, was studied using resonance Raman spectroscopy and global Raman imaging. The erythrocytes were found to be sensitive to both surface adsorption and laser illumination. Substrate-dependent changes of the cell membrane shape were observed immediately after cell adsorption, while a photo-induced increase of fluorescence was observed for visible excitation (lambda=514.5 nm). Concurrent changes in Raman spectra revealed a conversion of oxy-Hb (2+) to the inactive met-Hb state (3+). These effects severely complicate the interpretation of Raman images. However, at a low accumulated photon dose, the preparation method enabled the recording of Raman spectra during the oxygenation cycle of a single erythrocyte in buffer, which illustrates the feasibility of Raman investigations of functional cells in in-vivo environments.
Cell Culture Techniques↗
Surface-plasmon-enhanced optical forces in silver nanoaggregates.
We use extended Mie theory to investigate optical forces induced by and acting on small silver nanoparticle aggregates excited at surface plasmon resonance. It is shown that single molecules can be trapped at junctions between closely spaced nanoparticles, which are simultaneously pulled together by optical forces. These effects could significantly influence surface-enhanced Raman scattering and related spectroscopies under normal experimental conditions and contribute to single-molecule sensitivity.
Journal Article↗
Laser-induced growth of Ag nanoparticles from aqueous solutions.
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Journal Article↗
Resonance Raman spectroscopy of optically trapped functional erythrocytes.
We introduce a novel setup combining a micro-Raman spectrometer with external optical tweezers, suitable for resonance Raman studies of single functional trapped cells. The system differs from earlier setups in that two separate laser beams used for trapping and Raman excitation are combined in a double-microscope configuration. This has the advantage that the wavelength and power of the trapping and probe beam can be adjusted individually to optimize the functionality of the setup and to enable the recording of resonance Raman profiles from a single trapped cell. Trapping is achieved by tightly focusing infrared (IR) diode laser radiation (830 nm) through an inverted oil-immersion objective, and resonance Raman scattering is excited by the lines of an argon:krypton ion laser. The functionality of the system is demonstrated by measurements of trapped single functional erythrocytes using different excitation lines (488.0, 514.5, and 568.2 nm) in resonance with the heme moiety and by studying spectral evolution during illumination. We found that great care has to be taken in order to avoid photodamage caused by the visible Raman excitation, whereas the IR trapping irradiation does not seem to harm the cells or alter the hemoglobin Raman spectra. Stronger photodamage is induced by Raman excitation using 488.0- and 514.5-nm irradiation, compared with excitation with the 568.2-nm line.
Cells, Immobilized↗