Dibenzo[hi,st]ovalene as Highly Luminescent Nanographene: Efficient Synthesis via Photochemical Cyclodehydroiodination, Optoelectronic Properties, and Single-Molecule Spectroscopy

Dibenzo[hi,st]ovalene (DBOV), as a new nanographene, has demonstrated promising optical properties, such as red emission with a high fluorescence quantum yield of 79% and stimulated emission, as well as high thermal stability and photostability, which indicated its promise as a light-emitting and optical gain material. However, the previous synthetic routes required at least 12 steps. This obstructed access to different derivatives, e.g., to obtain crystals suitable for X-ray diffraction analysis and to tune the optoelectronic properties. Here, we report an efficient synthetic pathway to DBOV based on a sequential iodination-benzannulation of bi(naphthylphenyl)diyne, followed by photochemic…

Synthesis, Characterization, and Spectroscopy of Type-II Core/Shell Semiconductor Nanocrystals with ZnTe Cores

CdSe/ZnS Nanocrystals with Dye-Functionalized Polymer Ligands Containing Many Anchor Groups

Cytotoxicity of Metal and Semiconductor Nanoparticles Indicated by Cellular Micromotility

In the growing field of nanotechnology, there is an urgent need to sensitively determine the toxicity of nanoparticles since many technical and medical applications are based on controlled exposure to particles, that is, as contrast agents or for drug delivery. Before the in vivo implementation, in vitro cell experiments are required to achieve a detailed knowledge of toxicity and biodegradation as a function of the nanoparticles' physical and chemical properties. In this study, we show that the micromotility of animal cells as monitored by electrical cell-substrate impedance analysis (ECIS) is highly suitable to quantify in vitro cytotoxicity of semiconductor quantum dots and gold nanorods…

Origin of the Red Sites and Energy Transfer Rates in Single MEH-PPV Chains at Low Temperature

Single poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) molecules dispersed in thin poly(methylmethacrylate) films have been investigated by fluorescence emission, excitation and time-resolved spectroscopy at 1.2 K. For the molecular weight studied (∼200 kDa) a bimodal distribution of emission maxima is observed. Based on a comparison of the spectroscopic properties of blue and red sites and on polarisation-resolved measurements, we argue in agreement with recent quantum-chemical calculations that the red subpopulation most probably does not arise from interchromophoric excitation delocalisation but is to be attributed to longer chromophoric units originating from orde…

Strong enhancement of the Breit-Wigner-Fano Raman line in carbon nanotube bundles caused by plasmon band formation

We investigate the origin of the Breit-Wigner-Fano line in the Raman spectra of individual single-walled carbon nanotubes and their bundles. Using confocal Raman microscopy and atomic-force microscopy we found that the Breit-Wigner-Fano line intensity increases strongly with the bundle thickness. We confirmed this result by Raman investigations of partially decomposed bundles, which were additionally investigated by transmission electron microscopy. Our random-phase approximation based theory, which identifies the Breit-Wigner-Fano line as an excited band of plasmon-phonon modes, is fully consistent with the experimental results.

Observation of Very Narrow Linewidths in the Fluorescence Excitation Spectra of Single Conjugated Polymer Chains at 1.2 K

Fluorescence emission and excitation spectra of single poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] polymer molecules embedded in poly(methylmethacrylate) have been recorded at 1.2 K. The ubiquitous spectral diffusion causes large variations in the spectral shape and apparent linewidth in the emission spectra. Nevertheless, we find very narrow (approximately 0.1 cm(-1)) purely electronic zero-phonon lines in the excitation spectra, which are 2 orders of magnitude smaller than previous estimates of the homogeneous linewidth. These results complement the molecular description of the low energy transitions in conjugated polymers.

Coherent Electronic Coupling versus Localization in Individual Molecular Dimers

International audience; The electronic excitation transfer and coherent electronic coupling strength were investigated in molecular dimers by spectrally resolved confocal fluorescence spectroscopy. The direct probe of electronic coupling strength distribution was possible due to static disorder in polymer host by single molecule measurements. The dimers with delocalized excitation were also found in comparison to emission originated from localized states. The delocalized and localized state transitions were observed for dimers which were attributed to structural fluctuations of guest-host system.

Single Molecule Studies of a Ladder Type Conjugated Polymer: Vibronic Spectra, Line Widths, and Energy Transfer

Confocal fluorescence microscopy and spectroscopy are employed to investigate single poly(ladder-type pentaphenylene) (LPPentP) molecules dispersed in thin poly(methyl methacrylate) (PMMA) films at 1.2 K. Emission spectra of single chains show single as well as multi-chromophore emission indicating variegated communication along the chains. The vibronic structure in the emission spectra resembles the one found for other ladder-type polymers. Purely electronic zero-phonon lines in emission are substantially broadened, most probably due to fast spectral diffusion. By surmounting the limitations of emission spectroscopy, nonemitting donor chromophores, which transfer their excitation energy in…

Control of the electronic energy transfer pathway between two single fluorophores by dual pulse excitation.

We report on the control of the energy transfer pathway in individual donor-acceptor dyads by proper timing of light pulses matching the donor and acceptor transition frequencies, respectively. Excitation of both chromophores at virtually the same time induces efficient singlet-singlet annihilation, whereby excitation energy effectively flows from the acceptor to the donor. The dual pulse excitation scheme implemented here allows for all-optical switching of the fluorescence intensity at the single-molecule level. The population of higher excited states at the donor site was found to significantly increase the photobleaching probability.

Investigations of the emission properties of single CdS-nanocrystallites

Semiconductor nanocrystallites (NCs) with a radius in the range of the bulk exciton radius exhibit a strong quantum size effect. We investigated CdS-NCs, that were spin coated on a glass cover slip, with a low temperature confocal microscope. At low coverage we could image the fluorescence light from single NCs. The typical emission spectra of single NCs show four peaks. Besides the main peak related to near bandgap recombination, up to two LO-phonon satellites and one blue shifted peak were observed. It could be shown that the absorption can be polarization dependent. From the images as well as from the intensity autocorrelation function it could be concluded that the fluorescence emission…

Design and synthesis of colloidal nanocrystal heterostructures with tetrapod morphology.

Studying RNA Using Single Molecule Fluorescence Resonance Energy Transfer

Single-molecule spectroscopy of molecular aggregates at low temperature

We have conducted single-molecule spectroscopy of a fluorescent polyphenylene dendrimer consisting of four peripheral perylenemonoimides which serve as energy donors and a central terrylenediimide which is the energy acceptor. After selective excitation of the donors the low-temperature emission spectra of single dendrimers show the purely electronic zero-phonon line as the most prominent feature of the acceptor. These sharp emission lines are subjected to appreciable spectral shifts. Fluorescence excitation spectroscopy of individual dendrimers in the spectral region of the donor absorption allows to extract energy transfer rates for single donors within the dendrimer. Although the energy …

Superexchange-mediated electronic energy transfer in a model dyad

On the basis of time-dependent density functional theory (TD-DFT) calculations coupled to the polarizable continuum model (PCM) and single molecule spectroscopic studies, we provide a detailed investigation of excitation energy transfer within a model bi-chromophoric system where a perylene monoimide (PMI) donor is bridged to a terrylene diimide (TDI) acceptor through a ladder-type pentaphenylene (pPh) spacer. We find that the electronic excitation on the PMI donor significantly extends over the bridge giving rise to a partial charge transfer character and inducing a approximately 3-fold increase in the electronic interaction between the chromophores, which explains the failure of the Först…

Comparative evaluation of the impact on endothelial cells induced by different nanoparticle structures and functionalization

In the research field of nanoparticles, many studies demonstrated a high impact of the shape, size and surface charge, which is determined by the functionalization, of nanoparticles on cell viability and internalization into cells. This work focused on the comparison of three different nanoparticle types to give a better insight into general rules determining the biocompatibility of gold, Janus and semiconductor (quantum dot) nanoparticles. Endothelial cells were subject of this study, since blood is the first barrier after intravenous nanoparticle application. In particular, stronger effects on the viability of endothelial cells were found for nanoparticles with an elongated shape in compa…

Structure and luminescence properties of supramolecular polymers of amphiphilic aromatic thioether–peptide conjugates in water

We present the preparation of luminophore–peptide conjugates that self-assemble into supramolecular polymers in neutral buffer. To this end, we have prepared a small library of six conjugates with varying substitution patterns of the aromatic thioethers, as well as varying amino acid sequences. The latter have allowed us to tune the thermodynamic driving force for self-assembly and probe their photoluminescent properties either in the monomeric or polymeric state, while fully avoiding selective solvent techniques or organic solvent mixtures. All of the supramolecular structures were characterised with transmission electron microscopy, circular dichroism measurements, as well as steady-state…

Bio serves nano: biological light-harvesting complex as energy donor for semiconductor quantum dots.

Light-harvesting complex (LHCII) of the photosynthetic apparatus in plants is attached to type-II core-shell CdTe/CdSe/ZnS nanocrystals (quantum dots, QD) exhibiting an absorption band at 710 nm and carrying a dihydrolipoic acid coating for water solubility. LHCII stays functional upon binding to the QD surface and enhances the light utilization of the QDs significantly, similar to its light-harvesting function in photosynthesis. Electronic excitation energy transfer of about 50% efficiency is shown by donor (LHCII) fluorescence quenching as well as sensitized acceptor (QD) emission and corroborated by time-resolved fluorescence measurements. The energy transfer efficiency is commensurable …

Single Semiconductor Nanocrystals under Compressive Stress: Reversible Tuning of the Emission Energy

The photoluminescence of individual CdSe/CdS/ZnS core/shell nanocrystals has been investigated under external forces. After mutual alignment of a correlative atomic force and confocal microscope, individual particles were colocalized and exposed to a series of force cycles by using the tip of the AFM cantilever as a nanoscale piston. Thus, force-dependent changes of photophysical properties could be tracked on a single particle level. Remarkably, individual nanocrystals either shifted to higher or to lower emission energies with no indications of multiple emission lines under applied force. The direction and magnitude of these reversible spectral shifts depend on the orientation of nanocrys…

A Simple and Versatile Route to Stable Quantum Dot−Dye Hybrids in Nonaqueous and Aqueous Solutions

Hybrid systems consisting of core/shell semiconductor quantum dots (QDs) and organic rylene dyes have been prepared and characterized. Complex formation is mediated by bidentate carboxylate moieties covalently linked to the dye molecules. The complexes were very stable with respect to time (at least months), dilution (sub nM), and precipitation. After preparation in organic solvent, complexes could be easily transferred into water. The strong quenching of QD emission by the dye molecules (transfer efficiencies up to 95%) was satisfactorily modeled by an FRET process. Single complexes immobilized in thin polymer films were imaged by confocal fluorescence microscopy.

Flexibility of phenylene oligomers revealed by single molecule spectroscopy

The rigidity of a p-phenylene oligomer (p-terphenyl) has been investigated by single molecule confocal fluorescence microscopy. Two different rylene diimide dyes attached to the terminal positions of the oligomer allowed for wavelength selective excitation of the two chromophores. In combination with polarization modulation the spatial orientation of the transition dipoles of both end groups could be determined independently. We have analyzed 597 single molecules in two different polymer hosts, polymethylmethacrylate and Zeonex. On average we find a 22 degrees deviation from the linear gas phase geometry (T = 0 K), indicating a rather high flexibility of the p-phenylene oligomer independent…

Toward oxygen binding curves of single respiratory proteins

Oxygen binding curves of single molecules promise to discriminate between different models describing cooperativity because load distributions are accessible. Individual tarantula hemocyanins could be detected by fluorescence correlation spectroscopy using intrinsic tryptophan fluorescence as sensor of bound oxygen. However, imaging of immobilized proteins was not possible due to fast photo-bleaching. It is shown that tetra-methyl-carboxy-rhodamine (TAMRA), commonly used as a fluorescence label in single-molecule spectroscopy, can also be applied to monitor bound oxygen. The dye's fluorescence is quenched due to Förster energy transfer to the oxygenated active sites of hemocyanin.

Synthesis of Heterotelechelic α,ω Dye-Functionalized Polymer by the RAFT Process and Energy Transfer between the End Groups

The synthesis of a vinyl polymer with two different fluorescent dye end groups using reversible addition-fragmentation chain transfer (RAFT) polymerization is described. Use of a pentafluorophenyl (PFP) activated ester chain transfer agent (CTA) provided a polymer with an R end group that was reactive toward amines and a dithioester ω end group. The R PFP ester was amidated with Oregon Green Cadaverin. This did not harm the ω dithioester, which was subsequently aminolyzed with an excess of n-propylamine in the presence of Texas Red-2-sulfonamidoethyl methanethiosulfonate, resulting in a disulfide bond connecting the second dye to the polymer chain. Excess dyes and side products were removed…

Two-photon excitation microscopy of tryptophan-containing proteins.

We have examined the feasibility of observing single protein molecules by means of their intrinsic tryptophan emission after two-photon excitation. A respiratory protein from spiders, the 24-meric hemocyanin, containing 148 tryptophans, was studied in its native state under almost in vivo conditions. In this specific case, the intensity of the tryptophan emission signals the oxygen load, allowing one to investigate molecular cooperativity. As a system with even higher tryptophan content, we also investigated latex spheres covered with the protein avidin, resulting in 340 tryptophans per sphere. The ratio of the fluorescence quantum efficiency to the bleaching efficiency was found to vary b…

Imaging and force transduction in correlative scanning force and confocal fluorescence microscopy

Correlative scanning force and confocal fluorescence microscopy has been used to study individual molecules, nanoparticles and nanoparticle oligomers. By applying a compressive force via the AFM cantilever, spectral blue and red shifts in the range of several meV/GPa have been observed for single dye molecules and semiconductor quantum dots. Moreover, individual Au nanoparticle dimers linked by a chlorophyll binding protein have been imaged in both modes and plasmonic fluorescence enhancement of the chlorophyll emission of up to a factor of 15 has been found.

Steady light from quantum dots, at last. But how?

Assemblies of semiconductor quantum dots and light-harvesting-complex II

Abstract A novel hybrid system composed of fluorescent core/shell semiconductor quantum dots and the light harvesting complex II (LHCIIb), a membrane protein of higher plants, has been assembled. Experiments with different mutants show that hybrid formation can be mediated by a C-terminal His 6 tag attached to the protein as well as by positive charges of the first N-terminal amino acids of LHCIIb. Quenching of the quantum dot fluorescence upon binding of LHCIIb was partially attributed to energy transfer from the quantum dots to LHCIIb.

Oligomeric Sensor Kinase DcuS in the Membrane of Escherichia coli and in Proteoliposomes: Chemical Cross-linking and FRET Spectroscopy

The DcuSR (dicarboxylate uptake sensor and regulator) system of Escherichia coli is a typical two-component system consisting of a membranous sensor kinase (DcuS) and a cytoplasmic response regulator (DcuR) (11, 26, 48). DcuS responds to C4-dicarboxylates like fumarate, malate, or succinate (19). In the presence of the C4-dicarboxlates, the expression of the genes of anaerobic fumarate respiration (dcuB, fumB, and frdABCD) and of aerobic C4-dicarboxylate uptake (dctA) is activated. DcuS is a histidine protein kinase composed of two transmembrane helices with an intermittent sensory PAS domain in the periplasm (PASP) that was also termed the PDC domain (for PhoQ/DcuS/DctB/CitA domain or fold…

CitA/CitB Two-Component System Regulating Citrate Fermentation in Escherichia coli and Its Relation to the DcuS/DcuR System In Vivo

ABSTRACT Citrate fermentation by Escherichia coli requires the function of the citrate/succinate antiporter CitT ( citT gene) and of citrate lyase ( citCDEFXG genes). Earlier experiments suggested that the two-component system CitA/CitB, consisting of the membrane-bound sensor kinase CitA and the response regulator CitB, stimulates the expression of the genes in the presence of citrate, similarly to CitA/CitB of Klebsiella pneumoniae . In this study, the expression of a chromosomal citC-lacZ gene fusion was shown to depend on CitA/CitB and citrate. CitA/CitB is related to the DcuS/DcuR two-component system which induces the expression of genes for fumarate respiration in response to C 4 -di…

Accidental Contamination of Substrates and Polymer Films by Organic Quantum Emitters.

[Image: see text] We report the observation of ubiquitous contamination of dielectric substrates and poly(methyl methacrylate) matrices by organic molecules with optical transitions in the visible spectral range. Contamination sites of individual solvent-related fluorophores in thin films of poly(methyl methacrylate) constitute fluorescence hotspots with quantum emission statistics and quantum yields approaching 30% at cryogenic temperatures. Our findings not only resolve prevalent puzzles in the assignment of spectral features to various nanoemitters on bare dielectric substrates or in polymer matrices but also identify the means for the simple and cost-efficient realization of single-phot…

Synthesis and Spectroscopic Properties of Silica−Dye−Semiconductor Nanocrystal Hybrid Particles

We prepared silica-dye-nanocrystal hybrid particles and studied the energy transfer from semiconductor nanocrystals (= donor) to organic dye molecules (= acceptor). Multishell CdSe/CdS/ZnS semiconductor nanocrystals were adsorbed onto monodisperse Stöber silica particles with an outer silica shell of thickness 2-23 nm containing organic dye molecules (Texas Red). The thickness of this dye layer has a strong effect on the energy transfer efficiency, which is explained by the increase in the number of dye molecules homogeneously distributed within the silica shell, in combination with an enhanced surface adsorption of nanocrystals with increasing dye amount. Our conclusions were underlined by…

Photon antibunching and collective effects in the fluorescence of single bichromophoric molecules.

The fluorescence of individual pairs of perylenemonoimide chromophores coupled via a short rigid linker is investigated. Photon antibunching is reported, indicating collective effects in the fluorescence, which are further substantiated by the observation of collective triplet off times and triplet lifetime shortening. The experimental findings are analyzed in terms of singlet-singlet and singlet-triplet annihilation based on Forster type energy transfer. The results reported here demonstrate that the statistical properties of the emission light of isolated single quantum systems can serve as a hallmark of intermolecular interactions.

Detection of Single Oxygen Molecules with Fluorescence-Labeled Hemocyanins

This study introduces a method to detect individual oxygen molecules by fluorescence microscopy of single hemocyanins. These respiratory proteins from a tarantula bind oxygen with high affinity. A spectrometric signature of the oxygenated protein is transferred to an attached fluorescence label, which can be detected at the single-molecule level. This technique opens new perspectives for the development of small and sensitive oxygen sensors as well as for the investigation of cooperative oxygen binding in respiratory proteins.

Probing the electronic state of a single coronene molecule by the emission from proximate fluorophores.

We measured electronic transitions of the 2D graphene-type molecule hexa-peri-hexabenzocoronene (HBC) at the single-molecule level. The large intersystem crossing rate and long triplet state lifetime in the range of seconds are prohibitive for direct single-molecule observation. By covalently coupling fluorescent acceptor molecules (perylenecarboximide, PMI) to HBC, efficient singlet energy transfer gives rise to strong PMI fluorescence. Confocal single-molecule fluorescence microscopy with two excitation colours matching the HBC and PMI transition frequencies, respectively, was conducted. Single HBC-6PMI molecules were readily observed via the PMI emission. It was found that after selectiv…

Assembly and Separation of Semiconductor Quantum Dot Dimers and Trimers

Repeated precipitation of colloidal semiconductor quantum dots (QD) from a good solvent by adding a poor solvent leads to an increasing number of QD oligomers after redispersion in the good solvent. By using density gradient ultracentrifugation we have been able to separate QD monomer, dimer, and trimer fractions from higher oligomers in such solutions. In the corresponding fractions QD dimers and trimers have been enriched up to 90% and 64%, respectively. Besides directly coupled oligomers, QD dimers and trimers were also assembled by linkage with a rigid terrylene diimide dye (TDI) and separated again by ultracentrifugation. High-resolution transmission electron micrographs show that the …

Fluorescence intensity fluctuations of single atoms, molecules and nanoparticles

In many experiments on single molecules or nanocrystals it has been observed that the stream of emitted photons is interrupted by dark intervals. This phenomenon is a true single-particle effect because in an ensemble the various members emit independently and uncorrelated which generally leads to some constant average intensity of the fluorescence. Several instances are presented where single emitters pass through cycles of full, intermediate or no emission. While the phenomenon appears to be quite universal, the physical mechanisms causing the intensity fluctuations are very diverse and widespread. They include quantum jumps between states of different multiplicity, spectral shifts due to…

A Bichromophore Based on Perylene and Terrylene for Energy Transfer Studies at the Single-Molecule Level

A functionalized dialkylperylene and a modified terrylenetetracarboxdiimide (TTCDI) were joined by a hexanediyl spacer. The resulting bichromophoric molecule 1 (R = 4-tert-butylphenoxy) is a suitable model system for donor–acceptor energy transfer studies at the single-molecule level.

Cover Feature: Alkali Blues: Blue‐Emissive Alkali Metal Pyrrolates (Chem. Eur. J. 26/2019)

Physikalische Chemie 2004

Die Einzelmolekulspektroskopie hat sich in den letzten Jahren methodisch stetig weiterentwickelt und damit zu neuen Erkenntnissen uber die elektronische Struktur von Halbleiternanokristallen und die elektronische Kopplung zwischen Molekulen gefuhrt. Magnetisch kontrollierbare Flussigkeiten eroffnen Einsatzmoglichkeiten in der Dampfungstechnik sowie in der lokalen Tumortherapie. Mikrochips fur die Manipulation kleinster Flussigkeitsmengen halten Einzug in Analytik und Reaktionstechnik.

Raman Imaging of Single Carbon Nanotubes

[19] The single crystals of the Bu4NBr0.6I1.4Cl salt, were obtained by addition of IBr to a solution of Bu4NCl in ethanol at a reagent ratio of 1:0.5. Stoichiometry of the anion has been found by EDX. Based on a Raman study the anion consists of the I2Br ‐ (band at 140 cm ‐1 ), IBr2 ‐ (band at 150‐ 176 cm ‐1 ), BrICl ‐ (band at 225 cm ‐1 ), and ICl2 ‐ (band at 250‐263 cm ‐1 ) trihalide anions. [20] The X-ray diffraction data from single crystals for both trihalide salts were measured using an Enraf Nonius CAD4 diffractometer with graphite monochromatic Mo Ka radiation (k = 0.71073 a) at room temperature. Unit cell parameters of the new a¢¢¢- crystal were determined from a leastsquares analy…

Photothermisches Kontrastverfahren erreicht Einzelmolekülempfindlichkeit

Three-dimensional orientational colocalization of individual donor--acceptor pairs.

We report on the determination of the three-dimensional orientation of the donor and acceptor transition dipoles in individual fluorescence resonance energy transfer (FRET) pairs by means of scanning optical microscopy with annular illumination. Knowledge of the mutual orientation of the donor and acceptor dipole is mandatory for reliable distance determination based on FRET efficiency measurements. In our model system perylenediimide as the donor and terryelenediimide as the acceptor are coupled via a stiff p-terphenyl linker. The absorption dipoles of the donor and acceptor are selectively addressed by the 488 nm and 647 line of an Ar/Kr mixed gas laser, respectively. A clear deviation fr…

Alkali Blues: Blue‐Emissive Alkali Metal Pyrrolates

2-Iminopyrroles [HtBu L, 4-tert-butyl phenyl(pyrrol-2-ylmethylene)amine] are non-fluorescent π systems. However, they display blue fluorescence after deprotonation with alkali metal bases in the solid state and in solution at room temperature. In the solid state, the alkali metal 2-imino pyrrolates, M(tBu L), aggregate to dimers, [M(tBu L)(NCR)]2 (M=Li, R=CH3 , CH(CH3 )CNH2 ), or polymers, [M(tBu L)]n (M=Na, K). In solution (solv=CH3 CN, DMSO, THF, and toluene), solvated, uncharged monomeric species M(tBu L)(solv)m with N,N'-chelated alkali metal ions are present. Due to the electron-rich pyrrolate and the electron-poor arylimino moiety, the M(tBu L) chromophore possesses a low-energy intra…

Fluorescence excitation and emission spectroscopy on single MEH-PPV chains at low temperature.

Fluorescence emission and excitation spectra of single MEH-PPV polymer molecules dispersed in thin PMMA films have been recorded at 1.2 and 20 K. We observe single as well as multichromophore emission in single chain emission spectra, whereby the relative fractions depend on the two different molecular weights (50 and 350 kDa) studied. The molecular weight also affects the distribution of peak emission maxima, which is monomodal (bimodal) for the low (high) molecular weight. The appearance of an additional "red" subpopulation for the high molecular weight sample is attributed to interactions of multiple chromophores from a sufficiently flexible single chain. The comparison of emission spect…

Optical Properties of Assemblies of Molecules and Nanoparticles

Organic dye molecules, colloidal semiconductor quantum dots, and light-harvesting complexes have been employed as optically active building blocks to create complex molecular assemblies via covalent and non-covalent interactions. Taking advantage of the chemical flexibility of the dye and quantum dot components, as well as recombinant protein expression and the ordering capability of cholesteric phases, specific optical function could be implemented. Photophysical phenomena that have been addressed include light-harvesting, electronic excitation energy transfer (EET), and lasing. Optical single-molecule experiments allow control of energy transfer processes in individual molecular dyads and…

Electronic Excitation Energy Transfer between Two Single Molecules Embedded in a Polymer Host

Unidirectional electronic excitation energy transfer from a photoexcited donor chromophore to a ground state acceptor chromophore - both linked by a rigid bridge - has been investigated by low temperature high-resolution single molecule spectroscopy. Our approach allows for accurately accessing static disorder in the donor and acceptor electronic transitions and to calculate the spectral overlap for each couple. By plotting the experimentally determined transfer rates against the spectral overlap, we can distinguish and quantify Förster- and non-Förster-type contributions to the energy transfer.

Photoblinking and photobleaching of rylene diimide dyes.

We investigate photoblinking and photobleaching of perylene diimide (PDI) and its higher homologue terrylene diimide (TDI). Single molecule fluorescence trajectories of the dye molecules embedded in PMMA under ambient conditions exhibit "on"-"off" blinking in the time range from ms to s. Due to the limited statistics of individual trajectories we construct ensemble distributions of "on" and "off" times which follow power laws with similar power law coefficients (m(on) ≈ 1.18, m(off) ≈ 1.31). The blinking is attributed to reversible formation of radical cations which are presumably created by electron transfer from higher excited triplet states T(n) of the molecules to acceptor levels in the…

Energy transfer rates and pathways of single donor chromophores in a multichromophoric dendrimer built around a central acceptor core.

An artificial light-harvesting dendrimer showing highly efficient electronic excitation energy transfer from four peripheral donors to one central acceptor has been investigated by single-molecule spectroscopy at low temperatures. Confocal imaging in combination with frequency selective excitation spectroscopy gives direct access to energy transfer rates of individual donors and allows the determination of energy transfer pathways within a single multichromophoric aggregate.

Correlative atomic force and confocal fluorescence microscopy: single molecule imaging and force induced spectral shifts (Conference Presentation)

A grand challenge in nanoscience is to correlate structure or morphology of individual nano-sized objects with their photo-physical properties. An early example have been measurements of the emission spectra and polarization of single semiconductor quantum dots as well as their crystallographic structure by a combination of confocal fluorescence microscopy and transmission electron microscopy.[1] Recently, the simultaneous use of confocal fluorescence and atomic force microscopy (AFM) has allowed for correlating the morphology/conformation of individual nanoparticle oligomers or molecules with their photo-physics.[2, 3] In particular, we have employed the tip of an AFM cantilever to apply c…

Ultrafast Charge Separation at the CdSe/CdS Core/Shell Quantum Dot/Methylviologen Interface: Implications for Nanocrystal Solar Cells

Exciton separation dynamics in the electron transfer system containing highly photostable CdSe/CdS core/shell nanocrystal quantum dots and adsorbed methylviologen was investigated by means of femtosecond absorption spectroscopy. The experiments revealed that electron extraction from the photoexcited core is possible, and the rate of the ET reaction strongly depends on the CdS shell thickness. A CdS associated exponential decay constant β of 0.33 A−1 was obtained reflecting the electronic barrier effect of the shell. These findings show that core/shell structures are well suited for the design of optimized QD-based solar cells.

CdSe/ZnS-Nanokristalle mit farbstoffmarkierten Polymerliganden mit mehrfachen Ankergruppen

Water-soluble, cyclodextrin-functionalized semiconductor nanocrystals: Preparation and pH-dependent aggregation and emission properties

Abstract Using peramino-functionalized β-cyclodextrin molecules for phase.transfer of hydrophobic CdSe multishell nanocrystals into water, we obtained hydrophilic nanoparticles with high quantum yield (up to 50%). At pH > 9, the aqueous solution of these nanocrystals remained stable for several months. The nanoparticles showed a strong influence of the pH of the aqueous solution on the emission of the nanocrystals: the quantum yield varied reversible from ∼10% at pH=6 to ∼50% at pH=14, an effect which according to particle size characterization by dynamic light-scattering and asymmetric flow field-flow fractionation has mainly been attributed to reversible partial aggregation of the hydroph…

Quantification of the singlet-singlet annihilation times of individual bichromophoric molecules by photon coincidence measurements.

Singlet−singlet annihilation (SSA) times in individual bichromophoric molecules have been quantified by time-resolved photon coincidence measurements. An analytical expression has been derived to obtain the SSA times from the coincidence histograms. The results have been confirmed by Monte Carlo simulations. SSA was found to be about three times faster than the fluorescence lifetime of the chromophores. Considering the spectral overlap for SSA and for energy transfer from an excited to a ground state chromophore, we conclude that in the weak coupling limit for any arrangement of the two chromophores both processes occur on similar time scales.

Lateral Size Dependence in FRET between Semiconductor Nanoplatelets and Conjugated Fluorophores

Sensitization of organic molecules by semiconductor nanocrystals is a promising way to boost the absorption of the former, important for applications in fluorescence labeling and photocatalysis. Se...

The effect of surface charge on nonspecific uptake and cytotoxicity of CdSe/ZnS core/shell quantum dots

In this work, cytotoxicity and cellular impedance response was compared for CdSe/ZnS core/shell quantum dots (QDs) with positively charged cysteamine–QDs, negatively charged dihydrolipoic acid–QDs and zwitterionic D-penicillamine–QDs exposed to canine kidney MDCKII cells. Pretreatment of cells with pharmacological inhibitors suggested that the uptake of nanoparticles was largely due to receptor-independent pathways or spontaneous entry for carboxylated and zwitterionic QDs, while for amine-functionalized particles involvement of cholesterol-enriched membrane domains is conceivable. Cysteamine–QDs were found to be the least cytotoxic, while D-penicillamine–QDs reduced the mitochondrial activ…

Emergence of Coherence through Variation of Intermolecular Distances in a Series of Molecular Dimers

Quantum coherences between electronically excited molecules are a signature of entanglement and play an important role for energy transport in molecular assemblies. Here we monitor and analyze for a homologous series of molecular dimers embedded in a solid host the emergence of coherence with decreasing intermolecular distance by single-molecule spectroscopy and quantum chemistry. Coherent signatures appear as an enhancement of the purely electronic transitions in the dimers which is reflected by changes of fluorescence spectra and lifetimes. Effects that destroy the coherence are the coupling to the surroundings and to vibrational excitations. Complementary information is provided by excit…

Watching the photo-oxidation of a single aromatic hydrocarbon molecule

International audience; The photooxidation of single dye molecules (see scheme) can be followed by confocal fluorescence microscopy. The self-sensitized reaction with singlet oxygen leads to a suite of products, which may be differentiated spectrally. Tentative structures for certain photoproducts have been obtained from quantum-chemical calculations.

Faltung einzelner konjugierter Polymerketten während des Annealing-Prozesses

State transition identification in multivariate time series (STIMTS) applied to rotational jump trajectories from single molecules

Time resolved data from single molecule experiments often suffer from contamination with noise due to a low signal level. Identifying a proper model to describe the data thus requires an approach with sufficient model parameters without misinterpreting the noise as relevant data. Here, we report on a generalized data evaluation process to extract states with piecewise constant signal level from simultaneously recorded multivariate data, typical for multichannel single molecule experiments. The method employs the minimum description length principle to avoid overfitting the data by using an objective function, which is based on a tradeoff between fitting accuracy and model complexity. We val…

Semiconductor Nanocrystals with Multifunctional Polymer Ligands

In this letter, we describe the preparation of a versatile polymer ligand, which can be attached to CdSe/ZnS semiconductor nanocrystals via a phase transfer reaction. The ligand is based on a chain of reactive esters, which can, in principle, be substituted by any compound containing amino-functionalities. The polymer/nanocrystal complexes are characterized in terms of structure and photostability.

Light-harvesting chlorophyll protein (LHCII) drives electron transfer in semiconductor nanocrystals

Type-II quantum dots (QDs) are capable of light-driven charge separation between their core and the shell structures; however, their light absorption is limited in the longer-wavelength range. Biological light-harvesting complex II (LHCII) efficiently absorbs in the blue and red spectral domains. Therefore, hybrid complexes of these two structures may be promising candidates for photovoltaic applications. Previous measurements had shown that LHCII bound to QD can transfer its excitation energy to the latter, as indicated by the fluorescence emissions of LHCII and QD being quenched and sensitized, respectively. In the presence of methyl viologen (MV), both fluorescence emissions are quenched…

Statistical analysis of time resolved single molecule fluorescence data without time binning

We depict two algorithms to calculate correlation functions from two different time resolved single molecule fluorescence experiments without the need of time binning. Our first procedure allows to calculate the reduced linear dichroism from polarization resolved fluorescence data. Since we process single photon counts instead of time binned data, considerably faster fluctuations of the dichroism can be analyzed than with conventional methods. With our second procedure time resolved fluorescence obtained with a time correlated single photon counting setup can be analyzed with respect to fluorescence lifetime fluctuations. Again this new algorithm processes single photon events making time b…

Photodynamics at the CdSe Quantum Dot–Perylene Diimide Interface: Unraveling the Excitation Energy and Electron Transfer Pathways

Excitation energy and charge transfer processes in perylene diimide dye–CdSe quantum dot complexes have been studied by femtosecond transient absorption spectroscopy. After excitation of the quantu...

Single-Molecule Optical Switching: A Mechanistic Study of Nonphotochemical Hole-Burning

Persistent spectral hole-burning of dopant chromophores embedded in solid matrices has proven to be a sensitive high-resolution spectroscopic tool to investigate structural and dynamic properties of amorphous and crystalline hosts at low temperature [1]. A commonly encountered mechanism of holeformation is the nonphotochemical process, for which it is assumed that the frequency selective laser excitation and the subsequent relaxation of guest and host eventually leads to a change of configurational degrees of freedom in the nearby environment of the photo-excited centers or in the impurities themselves (or both) [2]. However, detailed knowledge about the microscopic mechanism of the nonphot…

The folding of individual conjugated polymer chains during annealing.

Impact of local compressive stress on the optical transitions of single organic dye molecules

The ability to mechanically control the optical properties of individual molecules is a grand challenge in nanoscience and could enable the manipulation of chemical reactivity at the single-molecule level. In the past, light has been used to alter the emission wavelength of individual molecules or modulate the energy transfer quantum yield between them. Furthermore, tensile stress has been applied to study the force dependence of protein folding/unfolding and of the chemistry and photochemistry of single molecules, although in these mechanical experiments the strength of the weakest bond limits the amount of applicable force. Here, we show that compressive stress modifies the photophysical …

Single molecule probing of dynamics in supercooled polymers

6 pages; International audience; Fluorescence experiments with single BODIPY molecules embedded in a poly(methyl acrylate) matrix have been performed at various temperatures in the supercooled regime. By using pulsed excitation, fluorescence lifetime and linear dichroism time trajectories were accessible at the same time. Both observables have been analyzed without data binning. While the linear dichroism solely reflects single particle dynamics, the fluorescence lifetime observable depends on the molecular environment, so that the dynamics from the polymer host surrounding a chromophore contributes to this quantity. We observe that the lifetime correlation decays slightly faster than polar…

Single Molecule Spectroscopy: Methodological Developments and Experiments at Low Temperature

Probing the self-assembly and stability of oligohistidine based rod-like micelles by aggregation induced luminescence.

OA hybrid The synthesis and self-assembly of a new C2-symmetric oligohistidine amphiphile equipped with an aggregation induced emission luminophore is reported. We observe the formation of highly stable and ordered rod-like micelles in phosphate buffered saline, with a critical aggregation concentration below 200 nM. Aggregation induced emission of the luminophore confirms the high stability of the anisotropic assemblies in serum.

Theoretical investigation of electronic excitation energy transfer in bichromophoric assemblies.

Electronic excitation energy transfer (EET) rates in rylene diimide dyads are calculated using second-order approximate coupled-cluster theory and time-dependent density functional theory. We investigate the dependence of the EET rates on the interchromophoric distance and the relative orientation and show that Forster theory works quantitatively only for donor-acceptor separations larger than roughly 5 nm. For smaller distances the EET rates are over- or underestimated by Forster theory depending on the respective orientation of the transition dipole moments of the chromophores. In addition to the direct transfer rates we consider bridge-mediated transfer originating from oligophenylene un…

Electronic Excitation Energy Transfer in Multichromophoric Assemblies: A Single Molecule Insight

In recent years, single molecule spectroscopy has provided novel insights into the fundamentals of electronic excitation energy transfer in molecular aggregates. In order of increasing structural complexity, we have studied simple molecular dimers and multichromophoric dendrimers. It will be shown that the combination of frequency-selective single molecule spectroscopy and confocal fluorescence microscopy at 1.4 K is a unique tool to study energy transfer processes in these systems. In particular, from the line widths of single molecule excitation spectra, rate constants of energy transfer can be deduced directly. A detailed analysis shows that, for several cases, the mechanism of energy tr…

Energy Transfer at the Single-Molecule Level: Synthesis of a Donor-Acceptor Dyad from Perylene and Terrylene Diimides

In 2004, we reported single-pair fluorescence resonance energy transfer (spFRET), based on a perylene diimide (PDI) and terrylene diimide (TDI) dyad (1) that was bridged by a rigid substituted para-terphenyl spacer. Since then, several further single-molecule-level investigations on this specific compound have been performed. Herein, we focus on the synthesis of this dyad and the different approaches that can be employed. An optimized reaction pathway was chosen, considering the solubilities, reactivities, and accessibilities of the building blocks for each individual reaction whilst still using established synthetic techniques, including imidization, Suzuki coupling, and cyclization reacti…

Conformational Dynamics of the Dengue Virus Protease Revealed by Fluorescence Correlation and Single-Molecule FRET Studies.

The dengue virus protease (DENV-PR) represents an attractive target for counteracting DENV infections. It is generally assumed that DENV-PR can exist in an open and a closed conformation and that active site directed ligands stabilize the closed state. While crystal structures of both the open and the closed conformation were successfully resolved, information about the prevalence of these conformations in solution remains elusive. Herein, we address the question of whether there is an equilibrium between different conformations in solution which can be influenced by addition of a competitive inhibitor. To this end, DENV-PR was statistically labeled by two dye molecules constituting a FRET …

Oxygen-Induced Blinking of Single CdSe Nanocrystals

Fluorescence labels as sensors for oxygen binding of arthropod hemocyanins

The molecular basis of high cooperativity in multi-subunit proteins is still unknown in most cases. Oxygen binding by multi-subunit hemocyanins produces two intrinsic spectroscopic signals which are, however, either limited to the UV or are very weak. Here we demonstrate that fluorescence labels emitting in the visible can be used as sensors for cooperative oxygen binding of hemocyanins. Fluorescence resonance energy transfer to the oxygenated active sites quenches the emission of the labels by roughly 50% upon oxygenation of the protein. The labels give strong and photo-stable emission, allowing imaging of single hemocyanin molecules. Therefore, this study opens up a new perspective for in…

Energy and charge transfer in nanoscale hybrid materials.

Hybrid materials composed of colloidal semiconductor quantum dots and π-conjugated organic molecules and polymers have attracted continuous interest in recent years, because they may find applications in bio-sensing, photodetection, and photovoltaics. Fundamental processes occurring in these nanohybrids are light absorption and emission as well as energy and/or charge transfer between the components. For future applications it is mandatory to understand, control, and optimize the wide parameter space with respect to chemical assembly and the desired photophysical properties. Accordingly, different approaches to tackle this issue are described here. Simple organic dye molecules (Dye)/quantum…

Synthesis and Characterization of Highly Luminescent CdSe—Core CdS/Zn0.5Cd0.5S/ZnS Multishell Nanocrystals.

We report on the preparation and structural characterization of CdSe nanocrystals, which are covered by a multishell structure from CdS and ZnS. By using the newly developed successive ion layer adhesion and reaction (SILAR) technique, we could gradually change the shell composition from CdS to ZnS in the radial direction. Because of the stepwise adjustment of the lattice parameters in the radial direction, the resulting nanocrystals show a high crystallinity and are almost perfectly spherical, as was investigated by X-ray diffraction and electron microscopy. Also, due to the radial increase of the respective valence- and conduction-band offsets, the nanocrystals are well electronically pas…

Comparison of quantum dot-binding protein tags: Affinity determination by ultracentrifugation and FRET

Abstract Background Hybrid complexes of proteins and colloidal semiconductor nanocrystals (quantum dots, QDs) are of increasing interest in various fields of biochemistry and biomedicine, for instance for biolabeling or drug transport. The usefulness of protein–QD complexes for such applications is dependent on the binding specificity and strength of the components. Often the binding properties of these components are difficult and time consuming to assess. Methods In this work we characterized the interaction between recombinant light harvesting chlorophyll a / b complex (LHCII) and CdTe/CdSe/ZnS QDs by using ultracentrifugation and fluorescence resonance energy transfer (FRET) assay exper…

Probing the spectral dynamics of single terrylenediimide molecules in low-temperature solids

Abstract Fluorescence excitation lines of single terrylenediimide (TDI) molecules were recorded in the matrices polyethylene (PE) and hexadecane (HD) in the temperature range between 1.4 and 13 K. From line width distributions at 2.5 K in both matrices it was concluded that the disorder, theoretically modeled by a distribution of two-level systems (TLSs), is about three times stronger in PE. Temperature-dependent measurements of the line shape of single chromophores showed a reversible broadening and shift of the zero-phonon lines. We attributed this behavior to dephasing caused by pseudolocal phonons and to spectral diffusion caused by fluctuating TLSs of the disordered host. Following the…

Single-Molecule Spectroscopy of MEH-PPV Polymer Molecules in Different Host Matrices

Fluorescence emission and excitation spectra of single MEH-PPV molecules dispersed in three different host polymers (PMMA, PS, and Zeonex) have been recorded at 1.2 K. We observed only minor effects of the host matrix on the following parameters: the ratios of single-chromophoric to multichromophoric emission, the widths of the distributions of emission maxima, and the (generally very low) fraction of emission spectra with sharp zero-phonon lines. The differences are tentatively attributed to different conformations of MEH-PPV chains, subtle variations in local chromophore−matrix interactions, and/or different distributions of conjugation lengths of emitting chromophores, respectively. Usin…

Intramolecular electronic excitation energy transfer in donor∕acceptor dyads studied by time and frequency resolved single molecule spectroscopy

Electronic excitation energy transfer has been studied by single molecule spectroscopy in donor/acceptor dyads composed of a perylenediimide donor and a terrylenediimide acceptor linked by oligo(phenylene) bridges of two different lengths. For the shorter bridge (three phenylene units) energy is transferred almost quantitatively from the donor to the acceptor, while for the longer bridge (seven phenylene units) energy transfer is less efficient as indicated by the occurrence of donor and acceptor emission. To determine energy transfer rates and efficiencies at the single molecule level, several methods have been employed. These comprise time-correlated single photon counting techniques at r…

<title>Probing the interactions of single CdSe quantum dots with their local environment</title>

The fluorescence blinking of single CdSe/ZnS nanocrystals under different experimental conditions is investigated. We show that the blinking process is very sensitive to the particle environment even if the nanocrystals are covered with a few monolayers of ZnS. Especially the presence of oxygen leads to a shortening of the on-times but leaves the off-times almost unaffected. Therefore, oxygen which is adsorbed to the surface might act as a scavenger for photo generated electrons and leaves the particle in its (positively charged) dark state.

Excitation Energy Transfer in Organic Materials: From Fundamentals to Optoelectronic Devices

In this review, we discuss investigations of electronic excitation energy transfer in conjugated organic materials at the bulk and single molecule level and applications of energy transfer in fluorescent and phosphorescent organic light emitting devices. A brief overview of common descriptions of energy transfer mechanisms is given followed by a discussion of some basic photophysics of conjugated materials including the generation of excited states and their subsequent decay through various channels. In particular, various examples of bimolecular excited state annihilation processes are presented. Energy transfer studies at the single molecule level provide a new tool to study electronic co…

Optical Microscopy and Spectroscopy of Single Molecules

Photothermal contrast reaches single-molecule sensitivity.

Synthesis of an Acceptor–Donor–Acceptor Multichromophore Consisting of Terrylene and Perylene Diimides for Multistep Energy Transfer Studies

Motivated by the results obtained from the investigation of singlet–singlet annihilation in a linear multichromophore comprising terrylene diimides (TDI) and perylene diimide (PDI) in 2010, we report the detailed process toward the successful synthesis of a TDI–PDI–TDI dyad. Ineffective synthetic pathways, which were necessary for the understanding of the step-by-step construction of the complex multichromophore, are described, leading toward a universal synthetic plan for multicomponent systems containing rylene diimides separated by rigid oligophenylene spacers.

Acceptor Concentration Dependence of Förster Resonance Energy Transfer Dynamics in Dye–Quantum Dot Complexes

The dynamics of the photoinduced Forster resonance energy transfer (FRET) in a perylene diimide–quantum dot organic–inorganic hybrid system has been investigated by femtosecond time-resolved absorption spectroscopy. The bidentate binding of the dye acceptor molecules to the surface of CdSe/CdS/ZnS multishell quantum dots provides a well-defined dye-QD geometry for which the efficiency of the energy transfer reaction can be easily tuned by the acceptor concentration. In the experiments, the spectral characteristics of the chosen FRET pair facilitate a selective photoexcitation of the quantum dot donor. Moreover, the acceptor related transient absorption change that occurs solely after energy…

Fluoreszenzmikroskopische Verfolgung des photooxidativen Abbaus eines einzelnen aromatischen Kohlenwasserstoffmoleküls

Polar accumulation of the metabolic sensory histidine kinases DcuS and CitA in Escherichia coli

Signal transduction in prokaryotes is frequently accomplished by two-component regulatory systems in which a histidine protein kinase is the sensory component. Many of these sensory kinases control metabolic processes that do not show an obvious requirement for inhomogeneous distribution within bacterial cells. Here, the sensory kinases DcuS and CitA, two histidine kinases of Escherichia coli, were investigated. Both are membrane-integral and involved in the regulation of carboxylate metabolism. The two-component sensors were fused with yellow fluorescent protein (YFP) and live images of immobilized cells were obtained by confocal laser fluorescence microscopy. The fluorescence of the fusio…

CCDC 1852851: Experimental Crystal Structure Determination

Related Article: Qiang Chen, Stefan Thoms, Sven Stöttinger, Dieter Schollmeyer, Klaus Müllen, Akimitsu Narita, Thomas Basché|2019|J.Am.Chem.Soc.|141|16439|doi:10.1021/jacs.9b08320

CCDC 1855069: Experimental Crystal Structure Determination

Related Article: Oliver Back, Christoph Förster, Thomas Basché, Katja Heinze|2019|Chem.-Eur.J.|25|6542|doi:10.1002/chem.201806103

CCDC 1855071: Experimental Crystal Structure Determination

Related Article: Oliver Back, Christoph Förster, Thomas Basché, Katja Heinze|2019|Chem.-Eur.J.|25|6542|doi:10.1002/chem.201806103

CCDC 1855070: Experimental Crystal Structure Determination

Related Article: Oliver Back, Christoph Förster, Thomas Basché, Katja Heinze|2019|Chem.-Eur.J.|25|6542|doi:10.1002/chem.201806103

CCDC 1855068: Experimental Crystal Structure Determination

Related Article: Oliver Back, Christoph Förster, Thomas Basché, Katja Heinze|2019|Chem.-Eur.J.|25|6542|doi:10.1002/chem.201806103

CCDC 1852850: Experimental Crystal Structure Determination

Related Article: Qiang Chen, Stefan Thoms, Sven Stöttinger, Dieter Schollmeyer, Klaus Müllen, Akimitsu Narita, Thomas Basché|2019|J.Am.Chem.Soc.|141|16439|doi:10.1021/jacs.9b08320