ultrafast-time-resolved-near-ir-stimulated-raman-measurements

Ultrafast Time-resolved Near-IR Stimulated Raman Measurements of Functional &#960;-conjugate Systems

Femtosecond time-resolved stimulated Raman spectroscopy is a promising method of observing the structural dynamics of short-lived transients with near ...

Gakushuin University

gakushuin university

Viscosity inside the lipid bilayer of egg-PC (egg yolk phosphatidylcholine) liposome with a diameter of 100 nm is examined with picosecond time-resolved fluorescence spectroscopy. The viscosity is estimated independently from the photoisomerization rate and from the rotational relaxation time of the first excited singlet state of trans-stilbene solubilized within the lipid bilayer. The presence of two solvation environments within the bilayer is suggested from both of the methods. One environment is 50 to 100 times more viscous than the other. The use of trans-stilbene as a probe provides valuable information on the solvation environments inside the lipid bilayer of liposome, which serves as a field for a number of biochemical reactions.

Lipid bilayer membrane of egg-PC liposome evaluated as chemical reaction field with picosecond time-resolved fluorescence spectroscopy.

Carotenoids have two major low-lying excited states, the second lowest (S2 (1Bu(+))) and the lowest (S1 (2Ag(-))) excited singlet states, both of which are suggested to be involved in the energy transfer processes in light-harvesting complexes. Studying vibrational dynamics of S2 carotenoids requires ultrafast time-resolved near-IR Raman spectroscopy, although it has much less sensitivity than visible Raman spectroscopy. In this study, the relaxation mechanism of β-carotene from the S2 state to the S1 state is investigated by femtosecond time-resolved multiplex near-IR absorption and stimulated Raman spectroscopy. The energy gap between the S2 and S1 states is estimated to be 6780 cm(-1) from near-IR transient absorption spectra. The near-IR stimulated Raman spectrum of S2 β-carotene show three bands at 1580, 1240, and 1050 cm(-1). When excess energy of 4000 cm(-1) is added, the S1 C═C stretch band shows a large upshift with a time constant of 0.2 ps. The fast upshift is explained by a model that excess energy generated by internal conversion from the S2 state to the S1 state is selectively accepted by one of the vibronic levels of the S1 state and is redistributed among all the vibrational modes. 

Relaxation mechanism of β-carotene from S2 (1Bu(+)) state to S1 (2Ag(-)) state: femtosecond time-resolved near-IR absorption and stimulated resonance Raman studies in 900-1550 nm region.

A number of biochemical reactions proceed inside biomembranes. Because the rate of a chemical reaction is influenced by chemical properties of the reaction field, it is important to examine the chemical properties inside the biomembranes, or lipid bilayer membranes, for understanding biochemical reactions. In this study, we estimate viscosity inside the lipid bilayers of liposomes with picosecond time-resolved fluorescence spectroscopy. trans-Stilbene is solubilized in the lipid bilayers formed by phosphatidylcholines, DSPC, DOPC, DPPC, DMPC, and DLPC, with 18, 18, 16, 14, and 12 carbon atoms in their alkyl chains, respectively, and egg-PC. Viscosity inside the lipid bilayer is estimated from the photoisomerization rate constant and from the rotational relaxation time of the first excited singlet state of trans-stilbene. The effect of the hydrocarbon chain length and temperature on viscosity is examined. The presence of two solvation environments within the lipid bilayer is indicated from the two independent estimations. One environment is 30 to 290 times more viscous than the other. Even single-component lipid bilayers are likely to have heterogeneous structures. 

Viscosity heterogeneity inside lipid bilayers of single-component phosphatidylcholine liposomes observed with picosecond time-resolved fluorescence spectroscopy.

Raman imaging is one of the very informative methods for the characterization of chemically and structurally heterogeneous materials without employing specific molecular labels. Multifocus Raman imaging is one of the fast-imaging alternatives to the conventional single point mapping technique. Since multiple focal points probe the sample simultaneously, this imaging methodology is faster compared to single point mapping. We have further demonstrated the efficiency of this methodology by investigating the morphological features of a porous PMMA film. A Raman image of a 50 × 50 μm(2) area was obtained in less than 4 minutes (with a 10 × 10 multifocus configuration). Importantly, a 100 × 100 μm(2) area could now be analyzed in minutes while a similar Raman image by single point mapping would take hours to days. Optical sectioning using multifocus Raman imaging reveals unique hierarchical features of the porous polymer thin film. Larger pores are limited to the surface and the inner bulk exhibits characteristic small-pores and an interconnected highly porous morphology. The fast multifocal Raman imaging would be advantageous to the diverse field of scientific disciplines where the speed of image acquisition remains a challenge despite the unparalleled specificity and sensitivity of Raman spectroscopy. 

Rapid microstructure characterization of polymer thin films with 2D-array multifocus Raman microspectroscopy.

Charge transfer and charge delocalisation processes play key roles in the functions of large biomolecular systems and organic/inorganic devices. Many of the short-lived transients involved in these processes can be sensitively detected by monitoring their low-energy electronic transitions in the near-IR region. Ultrafast time-resolved near-IR Raman spectroscopy is a promising tool for investigating the structural dynamics of the short-lived transients as well as their electronic dynamics. In this study, we have developed a femtosecond time-resolved near-IR multiplex stimulated Raman spectrometer using the Raman pump pulse at 1190 nm and a broadband probe pulse covering the 900-1550 nm region. Spectral and temporal instrument responses of the spectrometer are estimated to be 5 cm(-1) and 120 fs, respectively. Time-resolved near-IR stimulated Raman spectra of poly(3-dodecylthiophene) (P3DDT) are recorded in toluene solution for investigating its structural changes following the photoexcitation. The spectra strongly indicate conformational changes of P3DDT in excited states associated with the elongation of its effective conjugation length. The results on P3DDT fully demonstrate the effectiveness of the newly developed femtosecond time-resolved near-IR stimulated Raman spectrometer. 

Development of a femtosecond time-resolved near-IR multiplex stimulated Raman spectrometer in resonance with transitions in the 900-1550 nm region.

Solvent-free, nonvolatile, room-temperature alkylated-π functional molecular liquids (FMLs) are rapidly emerging as a new generation of fluid matter. However, precision design to tune their physicochemical properties remains a serious challenge because the properties are governed by subtle π-π interactions among functional π-units, which are very hard to control and characterize. Herein, we address the issue by probing π-π interactions with highly sensitive pyrene-fluorescence. A series of alkylated pyrene FMLs were synthesized. The photophysical properties were artfully engineered with rational modulation of the number, length, and substituent motif of alkyl chains attached to the pyrene unit. The different emission from the excimer to uncommon intermediate to the monomer scaled the pyrene-pyrene interactions in a clear trend, from stronger to weaker to negligible. Synchronously, the physical nature of these FMLs was regulated from inhomogeneous to isotropic. The inhomogeneity, unexplored before, was thoroughly investigated by ultrafast time-resolved spectroscopy techniques. The result provides a clearer image of liquid matter. Our methodology demonstrates a potential to unambiguously determine local molecular organizations of amorphous materials, which cannot be achieved by conventional structural analysis. Therefore this study provides a guide to design alkylated-π FMLs with tailorable physicochemical properties.

A Guide to Design Functional Molecular Liquids with Tailorable Properties using Pyrene-Fluorescence as a Probe.

Novel methodologies utilizing pulsed or intense CW irradiation obtained from lasers have a major impact on biological sciences. In this article, recent development in biophysical researches fully utilizing the laser irradiation is described for three topics, time-resolved fluorescence spectroscopy, time-resolved thermodynamics, and manipulation of the biological assemblies by intense laser irradiation. First, experimental techniques for time-resolved fluorescence spectroscopy are concisely explained in Section 2. As an example of the recent application of time-resolved fluorescence spectroscopy to biological systems, evaluation of the viscosity of lipid bilayer membranes is described. The results of the spectroscopic experiments strongly suggest the presence of heterogeneous membrane structure with two different viscosity values in liposomes formed by a single phospholipid. Section 3 covers the time-resolved thermodynamics. Thermodynamical properties are important to characterize biomolecules. However, measurement of these quantities for short-lived intermediate species has been impossible by traditional thermodynamical techniques. Recently, development of a spectroscopic method based on the transient grating method enables us to measure these quantities and also to elucidate reaction kinetics which cannot be detected by other spectroscopic methods. The principle of the measurements and applications to some protein reactions are reviewed. Manipulation and fabrication of supramolecues, amino acids, proteins, and living cells by intense laser irradiation are described in Section 4. Unconventional assembly, crystallization and growth, amyloid fibril formation, and living cell manipulation are achieved by CW laser trapping and femtosecond laser-induced cavitation bubbling. Their spatio-temporal controllability is opening a new avenue in the relevant molecular and bioscience research fields. This article is part of a Special Issue entitled "Biophysical Exploration of Dynamical Ordering of Biomolecular Systems" edited by Dr. Koichi Kato.

Novel physical chemistry approaches in biophysical researches with advanced application of lasers: Detection and manipulation.

The electronic and vibrational relaxation of carotenoids is one of the key processes in the protection of living cells as well as in the functions of proteins involved in photosynthesis. In this study, the electronic and vibrational relaxation dynamics of β-carotene and its derivatives with substituents on the terminal rings is investigated using femtosecond time-resolved absorption and stimulated Raman spectroscopy in the near-IR region. The carbonyl substituent induces low-frequency shifts of the steady-state and transient absorption bands, decreases of the excited-state lifetimes and the acceleration of vibrational relaxation of the conjugated main chain, whereas the hydroxyl substituent only slightly affects them. The effects of the carbonyl group in the electronic relaxation dynamics are explained well by the lengthening of effective conjugation by the carbonyl group through a partial conjugation between the main chain and the terminal ring. Time-resolved near-IR stimulated Raman spectroscopy demonstrates the significance of the peripheral substitution with the carbonyl group for the vibrational energy relaxation of β-carotene derivatives in the lowest excited singlet state.

Vibrational relaxation dynamics of β-carotene and its derivatives with substituents on terminal rings in electronically excited states as studied by femtosecond time-resolved stimulated Raman spectroscopy in the near-IR region.

Conjugated polymers incorporated with cycloplatinated complexes (P1-Pt and P2-Pt) were used as dispersants for single-walled carbon nanotubes (SWCNTs). Significant changes in the UV-vis absorption spectra were observed after the formation of the polymer/SWCNT hybrids. Molecular dynamics (MD) simulations revealed the presence of a strong interaction between the cycloplatinated complex moieties and the SWCNT surface. The photoinduced electron transfer processes in these hybrids were strongly dependent on the type of the comonomer unit. Upon photoexcitation, the excited P1-Pt donates electrons to the SWCNT, while P2-Pt accepts electrons from the photoexcited SWCNT. These observations were supported by results from Raman and femtosecond time-resolved transient absorption spectroscopy experiments. The strong electronic interaction between the Pt complexes and the SWCNT gives rise to a new hybrid system that has a controllable photoinduced electron transfer flow, which are important in regulating the charge transport processes in SWCNT-based optoelectronic devices.

Control of Electron Flow Direction in Photoexcited Cycloplatinated Complex Containing Conjugated Polymer-Single-Walled Carbon Nanotube Hybrids.

In this study, the effect of alcohol on polyiodide formation in room-temperature ionic liquid (RTIL) was examined by time evolutions of Raman spectra in the low-frequency region and by color changes of the sample. The RTIL was 1-methyl-3-propylimidazolium iodide, [Cmim][I]. Polyiodides develop in [Cmim][I]‑lithium salt-ethanol solutions (Abe et al., Chem. Phys. 502 (2018) 72.). Without the external addition of iodine or without an external electric field, the irreversible transformation from I to I indicates that charge unbalancing was promoted by lithium ion. Polyiodide formations were not induced by sodium or potassium ions. Strong alcohol effects were observed directly by the time-dependent Raman bands in the low-frequency region.

Lithium-triggered spontaneous formation of polyiodides in room-temperature ionic liquid-alcohol solutions.

The initial charge separation process of conjugated polymers is one of the key factors for understanding their conductivity. The structure of photogenerated transients in conjugated polymers can be observed by resonance Raman spectroscopy in the near-IR region because they exhibit characteristic low-energy transitions. Here, we investigate the structure and dynamics of photogenerated transients in a regioregular poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C-butyric acid methyl ester (PCBM) blend film, as well as in a pristine P3HT film, using femtosecond time-resolved resonance inverse Raman spectroscopy in the near-IR region. The transient inverse Raman spectrum of the pristine P3HT film at 50 ps suggests coexistence of neutral and charged excitations, whereas that of the P3HT:PCBM blend film at 50 ps suggests formation of positive polarons with a different structure from those in an FeCl₃-doped P3HT film. Time-resolved near-IR inverse Raman spectra of the blend film clearly show the absence of charge separation between P3HT and PCBM within the instrument response time of our spectrometer, while they indicate two independent pathways of the polaron formation with time constants of 0.3 and 10 ps.

Direct Observation of Structure and Dynamics of Photogenerated Charge Carriers in Poly(3-hexylthiophene) Films by Femtosecond Time-Resolved Near-IR Inverse Raman Spectroscopy.

The Raman spectra of a series of synthesized DC molecules (benzylidene malononitrile derivatives) with different electron donating (EDG) and electron withdrawing (EWG) group have been presented and analyzed with DFT calculated spectra. In particular, different functional groups effect on cyano stretching (∼2200 cm), phenyl ring breathing and alkenic double bond stretch which often appears mixed up (1475-1650 cm) are studied systematically for several aromatic conjugated DC derivatives. Interestingly, symmetric stretching frequency of the DC compounds having two CN groups at geminal position appears at higher wavenumber (by 11-15 cm) compared to their corresponding asymmetric stretch frequency. Angle (between dicyano group) dependent theoretical study indicates that the relative appearance of cyano symmetric/anti-symmetric stretching frequency depends on whether dicyano groups are at the geminal or vicinal position and the angle between them. Complete band assignments of observed Raman frequencies have been performed by potential energy distributions (PEDs) available in GAR2PED software. Our results will help to understand the vibrational feature of this important class of compounds in biological medium when used as probe.

Towards the critical understanding of selected vibrational features in biologically important dicyano aromatic conjugated molecules: Importance of electron donating/withdrawal groups and geometry associated with dicyano group.

Optoelectronically active viscous liquids are ideal for fabricating foldable/stretchable electronics owing to their excellent deformability and predictable π-unit-based optoelectronic functions, which are independent of the device shape and geometry. Here we show, unprecedented 'liquid electret' devices that exhibit mechanoelectrical and electroacoustic functions, as well as stretchability, have been prepared using solvent-free liquid porphyrins. The fluidic nature of the free-base alkylated-tetraphenylporphyrins was controlled by attaching flexible and bulky branched alkyl chains at different positions. Furthermore, a subtle porphyrin ring distortion that originated from the bulkiness of alkyl chains was observed. Its consequences on the electronic perturbation of the porphyrin-unit were precisely elucidated by spectroscopic techniques and theoretical modelling. This molecular design allows shielding of the porphyrin unit by insulating alkyl chains, which facilitates its corona-charged state for a long period under ambient conditions.

Koichi Iwata

Department of Chemistry,
Faculty of Science

Gakushuin University

Ultrafast Time-resolved Near-IR Stimulated Raman Measurements of Functional π-conjugate Systems

Koichi Iwata

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Department of Chemistry,Faculty of Science

Gakushuin University

Ultrafast Time-resolved Near-IR Stimulated Raman Measurements of Functional π-conjugate Systems

Department of Chemistry,
Faculty of Science