Phase-modulated two-photon photoluminescence identifies the nature of emissive states of quasi tw... more Phase-modulated two-photon photoluminescence identifies the nature of emissive states of quasi two-dimensional q-MPB and q-CPB perovskites.
Physical chemistry chemical physics : PCCP, Jan 8, 2017
Probing the vibrational dynamics of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide... more Probing the vibrational dynamics of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (CnmimNTf2) ionic liquids (ILs) using femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) has indicated the ultrafast vibrational energy transfer between counter ions which is governed by interionic interactions and facilitated by hydrogen bonds. In this study, fs-CARS is used to investigate the ultrafast dynamics of the vibrational modes of the CnmimNTf2 ILs with n = 6, 8, 10, and 12 in a spectral region, which involves the imidazolium ring and the alkyl side-chain vibrations. The vibrational Raman modes with wavenumbers around 1418 cm(-1) are excited through the CARS process and the ultrafast time evolution of the consequently excited vibrational modes is monitored. The investigation of the life times of the fs-CARS transient signals indicates that the time scale of the dynamics becomes much faster when the alkyl side-chain length of the CnmimNTf2 is longer than ...
Journal of Photochemistry and Photobiology a Chemistry, Jun 1, 2006
Femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) gives access to ultrafa... more Femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) gives access to ultrafast molecular dynamics. Due to the spectrally broad laser pulses, usually poorly resolved spectra result from this spectroscopy. However, it can be demonstrated that by shaping the femtosecond pulses a selective excitation of specific vibrational modes is possible. We demonstrate that using a feedback-controlled optimization technique, molecule-specific CARS spectra can
Journal of the American Chemical Society, Jul 1, 2002
The coupling of specific nuclear and electronic degrees of freedom of a molecular system during n... more The coupling of specific nuclear and electronic degrees of freedom of a molecular system during non-radiative electronic transitions plays a central role in photochemistry and photobiology. This breakdown of the Born-Oppenheimer approximation during processes such as internal conversion determines the mechanism and product distribution of photochemical reactions and is responsible for the high efficiency of photobiological processes. In order to explore this phenomena in beta-carotene, a molecule that plays a primary role as an auxiliary light-harvesting pigment in photosynthesis, a spectroscopic method was employed that allows for the individual vibrational modes to be monitored selectively within the dynamics of an internal conversion process. This spectroscopic technique employs an initial pump laser to excite the molecule into an excited electronic state and resolves the subsequent relaxation process by interrogating the system with a time-delayed, coherent anti-Stokes Raman process (CARS), which acts as a mode-selective filter for observing the population flow within specific vibrational modes with a time resolution in the femtosecond regime.
ABSTRACT We analyze the results of recent femtosecond CARS-experiments on the iodine molecule wit... more ABSTRACT We analyze the results of recent femtosecond CARS-experiments on the iodine molecule within time-dependent quantum calculations. Dependent on the delay-time between three ultrashort pulses, the third-order polarization shows oscillations which are characteristic for the wave packet motion in the electronic ground or B excited state. For the overall dependence of the CARS-signal on the pulse delay the treatment of the vibrational degree of freedom is sufficient. The specific decay and long time behaviour of the recorded signals however, can only be understood if the rotational degree of freedom is taken into account.
Cells are complex chemical systems, where the molecular composition at different cellular locatio... more Cells are complex chemical systems, where the molecular composition at different cellular locations and specific intracellular chemical interactions determine the biological function. An in-situ nondestructive characterization of the complicated chemical processes (like e.g. apoptosis) is the goal of our study. Here, we present the results of simultaneous and three-dimensional imaging of double organelles (nucleus and membrane) in single HeLa cells by means of either labelled or label-free surface-enhanced Raman spectroscopy (SERS). This combination of imaging with and without labels is not possible when using fluorescence microscopy. The SERS technique is used for a stereoscopic description of the intrinsic chemical nature of nuclei and the precise localization of folate (FA) and luteinizing hormone-releasing hormone (LHRH) on the membrane under highly confocal conditions. We also report on the time-dependent changes of cell nuclei as well as membrane receptor proteins during apopt...
Hsp70 is biologically relevant for its chaperon functions. The CX(-) and CX(+) sublines, which de... more Hsp70 is biologically relevant for its chaperon functions. The CX(-) and CX(+) sublines, which derive from the parental colon carcinoma CX2 cell line, are accordingly very similar. They have been reported to be specifically different only in Hsp70 membrane expression, which is associated with immunostimulatory effects. CX(-) /CX(+) have been phenotypically characterized by immunofluorescence studies and Raman spectroscopy combined with robust clustering and multivariate analysis. With the latter we address the potential of overall characterization for CX(-) /CX(+) discrimination and gain molecular insights into Hsp70 differential expression. Due to their strong resemblance, CX(-) and CX(+) show similar mean Raman spectra, which look indiscernible at first. Interestingly, their rather protein-dominated Raman spectra reveal, besides changes in protein and amino acids, very specific changes in DNA/RNA nucleotides involving pyrimidine ring Raman hypochromic effects. Therefore, discriminating CX(-) from CX(+) is ultimately achieved based on principal component scores. Because CX(-) /CX(+) are associated with the same lipid marker, changes in proteins support lipid interactions with regulatory proteins. More importantly, changes observed in nucleobases, which are indicative of DNA/RNA-protein binding interactions, suggest transcription deregulations as participating precursor onsets of different transport mechanisms that lead to Hsp70 differential expression and associated phenotypic variation. Besides immunofluorescence, we have used Raman spectroscopy combined with multivariate analysis within an autologous tumor system for label-free nondestructive cell-subline discrimination, and demonstrate, to our knowledge, the first overall phenotypic monitoring with insights into Hsp70 differential expression. This might well prove to be useful for Raman label-free cell-sorting of the CX(-) /CX(+) sublines.
Phase-modulated two-photon photoluminescence identifies the nature of emissive states of quasi tw... more Phase-modulated two-photon photoluminescence identifies the nature of emissive states of quasi two-dimensional q-MPB and q-CPB perovskites.
Physical chemistry chemical physics : PCCP, Jan 8, 2017
Probing the vibrational dynamics of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide... more Probing the vibrational dynamics of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (CnmimNTf2) ionic liquids (ILs) using femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) has indicated the ultrafast vibrational energy transfer between counter ions which is governed by interionic interactions and facilitated by hydrogen bonds. In this study, fs-CARS is used to investigate the ultrafast dynamics of the vibrational modes of the CnmimNTf2 ILs with n = 6, 8, 10, and 12 in a spectral region, which involves the imidazolium ring and the alkyl side-chain vibrations. The vibrational Raman modes with wavenumbers around 1418 cm(-1) are excited through the CARS process and the ultrafast time evolution of the consequently excited vibrational modes is monitored. The investigation of the life times of the fs-CARS transient signals indicates that the time scale of the dynamics becomes much faster when the alkyl side-chain length of the CnmimNTf2 is longer than ...
Journal of Photochemistry and Photobiology a Chemistry, Jun 1, 2006
Femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) gives access to ultrafa... more Femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) gives access to ultrafast molecular dynamics. Due to the spectrally broad laser pulses, usually poorly resolved spectra result from this spectroscopy. However, it can be demonstrated that by shaping the femtosecond pulses a selective excitation of specific vibrational modes is possible. We demonstrate that using a feedback-controlled optimization technique, molecule-specific CARS spectra can
Journal of the American Chemical Society, Jul 1, 2002
The coupling of specific nuclear and electronic degrees of freedom of a molecular system during n... more The coupling of specific nuclear and electronic degrees of freedom of a molecular system during non-radiative electronic transitions plays a central role in photochemistry and photobiology. This breakdown of the Born-Oppenheimer approximation during processes such as internal conversion determines the mechanism and product distribution of photochemical reactions and is responsible for the high efficiency of photobiological processes. In order to explore this phenomena in beta-carotene, a molecule that plays a primary role as an auxiliary light-harvesting pigment in photosynthesis, a spectroscopic method was employed that allows for the individual vibrational modes to be monitored selectively within the dynamics of an internal conversion process. This spectroscopic technique employs an initial pump laser to excite the molecule into an excited electronic state and resolves the subsequent relaxation process by interrogating the system with a time-delayed, coherent anti-Stokes Raman process (CARS), which acts as a mode-selective filter for observing the population flow within specific vibrational modes with a time resolution in the femtosecond regime.
ABSTRACT We analyze the results of recent femtosecond CARS-experiments on the iodine molecule wit... more ABSTRACT We analyze the results of recent femtosecond CARS-experiments on the iodine molecule within time-dependent quantum calculations. Dependent on the delay-time between three ultrashort pulses, the third-order polarization shows oscillations which are characteristic for the wave packet motion in the electronic ground or B excited state. For the overall dependence of the CARS-signal on the pulse delay the treatment of the vibrational degree of freedom is sufficient. The specific decay and long time behaviour of the recorded signals however, can only be understood if the rotational degree of freedom is taken into account.
Cells are complex chemical systems, where the molecular composition at different cellular locatio... more Cells are complex chemical systems, where the molecular composition at different cellular locations and specific intracellular chemical interactions determine the biological function. An in-situ nondestructive characterization of the complicated chemical processes (like e.g. apoptosis) is the goal of our study. Here, we present the results of simultaneous and three-dimensional imaging of double organelles (nucleus and membrane) in single HeLa cells by means of either labelled or label-free surface-enhanced Raman spectroscopy (SERS). This combination of imaging with and without labels is not possible when using fluorescence microscopy. The SERS technique is used for a stereoscopic description of the intrinsic chemical nature of nuclei and the precise localization of folate (FA) and luteinizing hormone-releasing hormone (LHRH) on the membrane under highly confocal conditions. We also report on the time-dependent changes of cell nuclei as well as membrane receptor proteins during apopt...
Hsp70 is biologically relevant for its chaperon functions. The CX(-) and CX(+) sublines, which de... more Hsp70 is biologically relevant for its chaperon functions. The CX(-) and CX(+) sublines, which derive from the parental colon carcinoma CX2 cell line, are accordingly very similar. They have been reported to be specifically different only in Hsp70 membrane expression, which is associated with immunostimulatory effects. CX(-) /CX(+) have been phenotypically characterized by immunofluorescence studies and Raman spectroscopy combined with robust clustering and multivariate analysis. With the latter we address the potential of overall characterization for CX(-) /CX(+) discrimination and gain molecular insights into Hsp70 differential expression. Due to their strong resemblance, CX(-) and CX(+) show similar mean Raman spectra, which look indiscernible at first. Interestingly, their rather protein-dominated Raman spectra reveal, besides changes in protein and amino acids, very specific changes in DNA/RNA nucleotides involving pyrimidine ring Raman hypochromic effects. Therefore, discriminating CX(-) from CX(+) is ultimately achieved based on principal component scores. Because CX(-) /CX(+) are associated with the same lipid marker, changes in proteins support lipid interactions with regulatory proteins. More importantly, changes observed in nucleobases, which are indicative of DNA/RNA-protein binding interactions, suggest transcription deregulations as participating precursor onsets of different transport mechanisms that lead to Hsp70 differential expression and associated phenotypic variation. Besides immunofluorescence, we have used Raman spectroscopy combined with multivariate analysis within an autologous tumor system for label-free nondestructive cell-subline discrimination, and demonstrate, to our knowledge, the first overall phenotypic monitoring with insights into Hsp70 differential expression. This might well prove to be useful for Raman label-free cell-sorting of the CX(-) /CX(+) sublines.
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Papers by Arnulf Materny