Biomedical subjects

K Müllen

Publications and source records attributed to K Müllen.

At least 19 recordsLinked to original sources

PubMed2006

Solvent-free MALDI-MS: developmental improvements in the reliability and the potential of MALDI in the analysis of synthetic polymers and giant organic molecules.

A dry sample preparation strategy was previously established as a new method for matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS), so-called solvent-free MALDI-MS. In this contribution, we examine systems that have been shown problematic with conventional solvent-based MALDI approaches. Problems frequently encountered are solubility, miscibility, and segregation effects during crystallization as a result of unfavorable analyte and matrix polarities. In all cases studied, solvent-free MALDI-MS simplified the measurement and improved the analysis. Solvent-free MALDI-MS enables more reliable results in well-known problematic systems such as polydimethylsiloxane with its segregation effects. However, even in highly compatible analyte/matrix systems such as polystyrene and dithranol, there were undesirable suppression effects when employing THF as solvent. Generally, the solvent-free method allows for more homogeneous analyte/matrix mixtures as well as higher shot-to-shot and sample-to-sample reproducibility. As a result, less laser power has to be applied, which yields milder MALDI conditions, reduced background signals, and provides better resolution of the analyte signals. Solvent-free MALDI-MS proved valuable for the characterization of nanosized material, e.g., fullereno-based structures, which indicated having an increased fragmentation-susceptibility. New analyte/matrix combinations (e.g., polyvinylpyrrolidone/dithranol) are accessible independent of solubility and compatibility in common solvents. An improved quantitation potential is recognized (e.g., insoluble polycyclic aromatic hydrocarbon against soluble dendrite precursor). The rapid and easy measurement of industrial products demonstrates the solvent-free method capable for improved throughput analysis of a variety of compounds (e.g., poly(butylmethacrylate) diol) in routine industrial analysis. Hence, this new MALDI method leads to qualitative and quantitative improvements, making it a powerful tool for analytical purposes, which may also prove to be valuable in future automation attempts.

Organic Chemicals↗

PubMed2005

Time-resolved measurements of intramolecular energy transfer in single donor/acceptor dyads.

We have investigated electronic excitation energy transfer in a specifically designed bichromophoric donor/acceptor dyad in which the donor (perylenediimide) and acceptor (terrylenediimide) are linked by a rigid heptaphenyl-spacer. Because of the choice of the bridge, which defines the distance and orientation of the two chromophores, donor as well as acceptor emission is observed. The significantly smaller photostability of the donor allows for time-resolved measurements of the acceptor emission at the single-molecule level with and without energy transfer from the donor. By analyzing the differences of the rise/decay profiles for both pathways, we could determine time constants of energy transfer with high accuracy for single dyads. The results show that the experimental approach presented here works even for situations in which the energy transfer times are smaller than the temporal resolution of the detection system.

Journal Article↗

PubMed2005

Energy dissipation in multichromophoric single dendrimers.

Single-molecule spectroscopy of well-chosen dendritic multichromophoric systems allows investigation of fundamental photophysical processes such as energy or electron transfer in much greater detail than the respective ensemble measurements. In dendrimers with multiple chromophores, energy hopping and transfer to the chromophore with the energetically lowest S(1) state was observed. If more than one chromophore is in an excited state in one molecule, annihilation, either singlet-triplet or singlet-singlet, can occur. In the latter case, a higher singlet state is populated opening new deactivation pathways. In the presence of an electron donor, reversible electron transfer could be observed, and the rate constants of forward and backward electron transfer were established. The value of these rate constants fluctuates time-correlated with the rotational motion of the dendrimer arms and the mobility of the embedding matrix.

Dendrimers↗

PubMed2005

Soft deposition of organic macromolecules with fast atom bombardment mass spectrometry.

In order to investigate the requirements for soft deposition of intact positively charged organic macromolecules, an homogenous series of modal compounds such as polyphenylene dendronized perylenes (PDPs), C(80)H(52), C(200)H(132) and C(320)H(212) and a series of derivatives involving perylene derivative, C(98)H(104)N(8)O(4), terrylene derivative, C(78)H(82)N(6)O(4) and quaterrylene derivative, C(140)H(138)N(10)O(8), were used for soft-landing experiments on a metallic or matrix coated surface using fast atom bombardment mass spectrometry. Soft-landing can be achieved at impact energies below 180 eV with no production of fragments. The deposition rate shows strong energy dependence with similar behavior of the different organic compounds. A single isotope of the molecule was selected and soft-landed at increased resolution.

Journal Article↗

PubMed2004

Toward nanoamphiphiles: efficient synthesis of desymmetrized polyphenylene dendrimers.

A new synthetic approach for the desymmetrization of polyphenylene dendrimers (PPDs) is described. Tetrakis(4-ethynylphenyl)methane undergoes facile Diels-Alder cycloaddition with substoichiometric quantities of tetraphenylcyclopentadienones bearing one polar functional group. A single ethynyl group is thereby converted to a rigid, selectively functionalized polyphenylene moiety, which serves as a focal point for further transformations or interfacial anchoring. This is the key feature for the design of desymmetrized monodisperse macromolecules with a spherical shape. The remaining unreacted ethynyl groups provide a trifold core for the stepwise elaboration of first- and second-generation polyphenylene dendrons, which may, in turn, bear specific numbers of different peripheral functional groups at their terminae. Moreover, the resulting macromolecules exhibit the characteristic shape-persistence and monodispersity of PPDs. This approach is an important achievement in nanosciences, especially for tailoring new nanoamphiphiles. It is also of synthetic importance, as it enables the separation of two regioisomeric polyphenylene dendrimers for the first time.

Journal Article↗

PubMed2004

Prototypical single-molecule chemical-field-effect transistor with nanometer-sized gates.

A prototypical single-molecule chemical-field-effect transistor is presented, in which the current through a hybrid-molecular diode is modified by nanometer-sized charge transfer complexes covalently linked to a molecule in an STM junction. The effect is attributed to an interface dipole which shifts the substrate work function by approximately 120 meV. It is induced by the complexes from electron acceptors covalently bound to the molecule in the gap and electron donors coming from the ambient fluid. This proof of principle is regarded as a major step towards monomolecular electronic devices.

Journal Article↗

PubMed2004

Single-molecule conformations probe free volume in polymers.

In this communication, we showed that the conformational dynamics of the tetraphenoxy-perylenetetracarboxy diimide single dye molecule embedded in different polymer matrixes allows a direct visualization of the local free volume. By monitoring the fluorescence lifetime of the dye molecule in time and at different locations in the matrix, different lifetimes were observed. Attributed to two distinct stable conformations of the dye molecule, the lifetime variations permitted characterization of the spatial distribution and temporal dynamics of free volume.

Journal Article↗

PubMed2003

Direct proof of electron transfer in a rigid first generation triphenyl amine core dendrimer substituted with a peryleneimide acceptor.

The combination of nanosecond transient absorption experiments and single photon timing experiments proved the occurrence of an electron transfer process in the triphenyl amine core dendrimer, N1P1, by demonstrating the presence of an ion-pair absorption for N1P1 in solvents of medium polarity. By means of femtosecond transient absorption measurements the rise time of this ion-pair absorption dominated by the radical anion absorption could be determined, resulting in a value of 180 ps in MeTHF and 138 ps in THF. Furthermore, in femtosecond fluorescence upconversion as well as in monochromatic femtosecond transient absorption, a few ps component was resolved which was assigned to a vibrational and solvent relaxation process of the locally excited singlet state of the peryleneimide.

Journal Article↗

PubMed2002

Characterization of an insoluble poly(9,9-diphenyl-2,7-fluorene) by solvent-free sample preparation for MALDI-TOF mass spectrometry.

The application of solvent-free sample preparation for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) allowed the characterization of an insoluble fraction of poly(9,9-diphenylfluorene) that was previously hindered by the lack of suitable characterization methods. The MALDI mass spectrometric analysis gives valuable mechanistic information about the heterogeneous polymerization process of the insoluble high molecular weight fraction of the polymer. The fragmentation appearing even under moderate desorption and ionization conditions of this rigid backbone analyte is identified as a multiple loss of the bulky phenyl side groups and can be avoided by applying the new MALDI matrix 7,7,8,8-tetracyanoquinodimethane. A specialized fragmentation study by postsource decay MALDI-TOF MS reveals a molecular weight dependent change in fragmentation mechanism from an exclusive cleavage of side groups from long polymer chains to an additional cleavage of the polymer backbone of short polymer chains.

Journal Article↗

PubMed2001

Recalcitrance of poly(vinylpyrrolidone): evidence through matrix-assisted laser desorption-ionization time-of-flight mass spectrometry.

The aerobic biodegradability of an extensively used synthetic polymer was monitored the first time on a laboratory-scale fixed-bed bioreactor (FBBR) applying matrix-assisted laser desorption-ionization time-of-flight mass spectrometry (MALDI-TOF MS). Polymeric poly(vinylpyrrolidone) (PVP) was spiked at concentrations of 10 mg l(-1) onto the FBBR run with river water and the biodegradation monitored after lyophilization of aliquots of the test liquor applying MALDI-TOF-MS. The latter proved to be a powerful tool for qualitative screening purposes of PVP in a molecular mass range <20 kDa in particularly yielding a high sensitivity and shot-to-shot reproducibility. The sample-to-sample reproducibility was enhanced applying the anchor target device. Post-source decay-MALDI-TOF-MS fragmentation investigations determined the unknown end groups of PVP unambiguously. Poor biodegradability of PVP can be assumed, since even after 30 days, no oxidation of the terminal groups and no difference in the repeating units was observed. A decrease in the molecular mass distribution can be drawn back rather to adsorption of PVP in the FBBR other than to biodegradation. This was further investigated performing an adsorption experiment with sewage sludge as solid matrix and analyses of the aqueous phase and sludge samples. Extrapolating these results to the situation in wastewater treatment plants, it is highly likely that PVP is eliminated from the dissolved phase by adsorption onto sludge particles.

Calibration↗

PubMed2001

Supramolecular staircase via self-assembly of disklike molecules at the solid-liquid interface.

A series of soluble hexabenzocoronene (HBC) derivatives with pendant optically active (S)-3,7-dimethyloctanyl and (R,S)-3,7-dimethyloctanyl (mixture of stereoisomers) hydrocarbon side chains with and without a phenylene spacer were assembled into differently ordered arrays at the interface between a solution and the basal plane of highly oriented pyrolytic graphite (HOPG). Molecularly resolved scanning tunneling microscopy (STM) images revealed that all derivatives self-assemble into oriented crystals in quasi-two dimensions. However, while for the alkyl-substituted HBCs (1,4) all of the single aromatic cores within a monolayer exhibit the same contrast in the STM, the single aromatic cores with a phenylene group between the alkyl side chains and the aromatic core (2a,2b,3) exhibit different contrasts within a monolayer. For the disks carrying racemic branched or n-alkyl side chains (2b,3) a random distribution of the two different contrasts within the 2D-crystal is observed, while the optically active phenylene-alkyl-substituted HBC (2a) exhibits a periodical distribution of three contrasts within the monolayer. We attribute the different contrasts of the aromatic cores in the presence of the phenylene groups to a loss of the planarity of the whole molecule and different conformations, which allow the conjugated disks to attain different equilibrium positions above the surface of HOPG. In the case of the optically active side chains a regular superstructure with three distinctly different positions such as in a staircase is attained. The self-assembly processes are governed by the interplay of intramolecular as well as intermolecular and interfacial interactions. In the present case, the interactions may induce both the molecules to acquire well distinct positions along the z axis and to adopt different conformations. The reported results open new avenues of exploration. For instance, the different couplings of conjugated molecules with the substrate at different separations can be investigated by means of scanning tunneling spectroscopy (STS). Furthermore, experiments on the STM tip-induced switching of single molecules embedded in a monolayer appear feasible.

Journal Article↗

PubMed2001

Polyphenylene dendrimers with perylene diimide as a luminescent core.

A novel synthesis is presented of a fourfold ethynyl-substituted perylene diimide dye 4, which acts as a core molecule for the buildup of polyphenylene dendrimers. Around the luminescent core 4, a first-generation (5), a second-generation (6), and a third-generation (7) polyphenylene dendritic environment consisting of pentaphenylbenzene building blocks are constructed. The dendrimers 5 and 6 are synthesized by an exclusively divergent route, whereas for 7, a combination of a divergent and convergent approaches is applied. Absorption and emission spectra of 5-7 in different solvents and in a film have been measured and compared to a nondendronized model compound 13. In solution, the internal chromophore is scarcely influenced by the dendritic scaffold; however, in the solid state, aggregation of the perylene diimide is prevented very effectively by the four rigid dendrons. Additionally, fluorescence quantum yields in solution have been determined for 5-7 and 13; they decrease as the number of generation increases.

Journal Article↗

PubMed2001

Single-molecule spectroscopy of a dendrimer-based host-guest system.

We report on a single-molecule study of a host-guest system that consists of a second-generation polyphenylene dendrimer and the cyanine dye Pinacyanol. The use of single-molecule spectroscopy enables us to obtain more detailed information on the properties of the host-guest system and can be used to confirm solution data. At low dye to dendrimer ratios the system is present as a one-to-one complex, while for higher ratios an ion-pair system is formed. Changes in the spectral properties of the single molecules are explained by differences in local polarisability. The difference of the triplet lifetimes of single free dye molecules and of associated ones is interpreted as deriving from a larger free volume for the dye molecules in the dendritic host relative to the rigid polymer matrix.

Journal Article↗

PubMed2001

Triplet states as non-radiative traps in multichromophoric entities: single molecule spectroscopy of an artificial and natural antenna system.

Energy transfer in antenna systems, ordered arrays of chromophores, is one of the key steps in the photosynthetic process. The photophysical processes taking place in such multichromophoric systems, even at the single molecule level, are complicated and not yet fully understood. Instead of directly studying individual antenna systems, we have chosen to focus first on systems for which the amount of chromophores and the interactions among the chromophores can be varied in a systematic way. Dendrimers with a controlled number of chromophores at the rim fulfill those requirements perfectly. A detailed photophysical study of a second-generation dendrimer, containing eight peryleneimide chromophores at the rim, was performed 'J. Am. Chem. Soc., 122 (2000) 9278'. One of the most intriguing findings was the presence of collective on/off jumps in the fluorescence intensity traces of the dendrimers. This phenomenon can be explained by assuming a simultaneous presence of both a radiative trap (energetically lowest chromophoric site) and a non-radiative trap (triplet state of one chromophore) within one individual dendrimer. It was shown that an analogue scheme could explain the collective on/off jumps in the fluorescence intensity traces of the photosynthetic pigment B-phycoerythrin (B-PE) (Porphyridium cruentum). The different values of the triplet lifetime that could be recovered for a fluorescence intensity trace of B-PE were correlated with different intensity levels in the trace, suggesting different chromophores acting as a trap as function of time.

Bile Pigments↗

PubMed2001

Polyphenylene dendrimers with different fluorescent chromophores asymmetrically distributed at the periphery.

A new synthetic approach leading to asymmetrically substituted polyphenylene dendrimers is presented. Following this method, polyphenylene dendrimers decorated with an increasing number of chromophores at the periphery have been obtained up to the second generation. Especially the synthesis of a polyphenylene dendrimer bearing three donor chromophores and one acceptor chromophore has been realized. Intramolecular energy transfer within this molecule is demonstrated by applying absorption and fluorescence measurements.

Journal Article↗

PubMed2001

Self-organized discotic liquid crystals for high-efficiency organic photovoltaics.

Self-organization of liquid crystalline and crystalline-conjugated materials has been used to create, directly from solution, thin films with structures optimized for use in photodiodes. The discotic liquid crystal hexa-peri-hexabenzocoronene was used in combination with a perylene dye to produce thin films with vertically segregated perylene and hexabenzocoronene, with large interfacial surface area. When incorporated into diode structures, these films show photovoltaic response with external quantum efficiencies of more than 34 percent near 490 nanometers. These efficiencies result from efficient photoinduced charge transfer between the hexabenzocoronene and perylene, as well as from effective transport of charges through vertically segregated perylene and hexabenzocoronene pi systems. This development demonstrates that complex structures can be engineered from novel materials by means of simple solution-processing steps and may enable inexpensive, high-performance, thin-film photovoltaic technology.

Journal Article↗

PubMed2001

Intramolecular energy hopping and energy trapping in polyphenylene dendrimers with multiple peryleneimide donor chromophores and a terryleneimide acceptor trap chromophore.

Intramolecular Förster-type excitation energy transfer (FRET) processes in a series of first-generation polyphenylene dendrimers substituted with spatially well-separated peryleneimide chromophores and a terryleneimide energy-trapping chromophore at the rim were investigated by steady-state and time-resolved fluorescence spectroscopy. Energy-hopping processes among the peryleneimide chromophores are revealed by anisotropy decay times of 50--80 ps consistent with a FRET rate constant of k(hopp) = 4.6 ns(-1). If a terryleneimide chromophore is present at the rim of the dendrimer together with three peryleneimide chromophores, more than 95% of the energy harvested by the peryleneimide chromophores is transferred and trapped in the terryleneimide. The two decay times (tau(1) = 52 ps and tau(2) = 175 ps) found for the peryleneimide emission band are recovered as rise times at the terryleneimide emission band proving that the energy trapping of peryleneimide excitation energy by the terryleneimide acceptor occurs via two different, efficient pathways. Molecular- modeling-based structures tentatively indicate that the rotation of the terryleneimide acceptor group can lead to a much smaller distance to a single donor chromophore, which could explain the occurrence of two energy-trapping rate constants. All energy-transfer processes are quantitatively describable with Förster energy transfer theory, and the influence of the dipole orientation factor in the Förster equation is discussed.

Journal Article↗

PubMed2001

Novel perylene chromophores obtained by a facile oxidative cyclodehydrogenation route.

New perylene chromophores, phenyl-substituted diindeno[1,2,3-cd:1',2',3'-lm]perylenes 5a,b and 4,4',7,7'-tetraphenyldiacenaphtho[1,2-k:1',2',k']diindeno[1,2,3-cd:1',2',3'-me]perylenes 22a,b, have been synthesized from substituted fluoranthene derivatives 3a,b and 4a,b by means of a surprisingly simple oxidative cyclodehydrogenation reaction. The resulting chromophores, when substituted with alkyl chains at the periphery, show good solubility in organic solvents, and a full characterization of the novel red, green, and blue dyes by field-desorption mass spectrometry, UV/Vis and 1H and 13C NMR spectroscopy becomes possible.

Journal Article↗