Picosecond Lifetime Research Articles

Membrane matters: The impact of a nanodisc-bilayer or a detergent microenvironment on the properties of two eubacterial rhodopsins

Multi-spanning membrane proteins usually require solubilization to allow proper purification and characterization, which generally impairs their structural and functional integrity. We have tested the efficacy of several commonly used detergents and membrane-mimicking nanodiscs with respect to solubilization, spectral properties, thermal stability and oligomeric profile of two membrane proteins from the eubacterial rhodopsin family, green proteorhodopsin (PR) and Gloeobacter violaceus rhodopsin (GR). Good solubilization was observed for the detergents TritonX-100 and dodecylphosphocholine (DPC), but DPC in particular strongly affected the thermal stability of PR and especially GR. The least deleterious effects were obtained with n-dodecyl-β-D-maltopyranoside (DDM) and octyl glucose neopentyl glycol (OGNG), which adequately stabilized the native oligomeric and monomeric state of PR and GR, respectively. The transition from the oligomeric to the monomeric state is accompanied by a small red-shift. Both GR and PR were rather unstable in SMA-nanodiscs, but the highest thermal stability was realized by the MSP-nanodisc environment. The size of the MSP-nanodisc was too small to fit the PR hexamer, but large enough to contain the PR monomer and GR trimer. This permitted the comparison of the photocycle of trimeric GR in a membrane-mimicking (MSP-nanodisc) and a detergent (DDM) environment. The ultrarapid early phase of the photocycle (femto- to picosecond lifetimes) showed very similar kinetics in either environment, but the slower part, initiated with proton transfer and generation of the M intermediate, proceeded faster in the nanodisc environment. The implications of our results for the biophysical characterization of PR and GR are discussed.

State-Selective Dynamics of TiO2 Charge-Carrier Trapping and Recombination.

Time-resolved pump-probe photoemission spectroscopy has been used to study the dynamics of charge-carrier recombination and trapping on hydroxylated rutile TiO2(110). Two types of pump excitation were employed, one in the infrared (IR) (0.95 eV) and the other in the ultraviolet (UV) (3.5 eV) region. With IR excitation, electrons associated with defects are excited into the bottom of the conduction band from the polaronic states within the band gap, which are retrapped within 45 ± 10 fs. Under UV excitation, the electrons in these band-gap states (BGSs) and valence-band electrons are excited into the conduction band. In addition to the fast polaron trapping observed with IR excitation, we also observe a long lifetime (∼1 ps) component for both the depletion of hot electrons at the bottom of the conduction band and the refilling of the BGS. This points to a BGS-mediated recombination process with a picosecond lifetime.

Comparative studies on picosecond-resolved fluorescence of d-amino acid oxidases from human with one from porcine kidney. Photoinduced electron transfer from aromatic amino acids to the excited flavin

Fluorescence dynamics of human d-amino acid oxidase (hDAAO) and its five inhibitors have been studied in the picoseconds time domain, and compared with one in d-amino acid oxidase from porcine kidney (pkDAAO) reported. The fluorescence lifetimes were identified as 47 ps in the dimer, 235 ps in the monomer, which are compared with those of pkDAAO (45 ps–185 ps). The fluorescence lifetimes of the hDAAO did not change upon the inhibitor bindings despite of modifications in the absorption spectra. This indicates that the lifetimes of the complexes are too short to detect with the picosecond lifetime instrument. Numbers of the aromatic amino acids are similar between the both DAAOs. The fluorescence lifetimes of hDAAO were analysed with an ET theory using the crystal structure. The difference in the lifetimes of the dimer and monomer was well described in terms of difference in the electron affinity of the excited isoalloxazine (Iso*) between the two forms of the protein, though it is not known whether the structure of the monomer is different from the dimer. Three fastest ET donors were Tyr314, Trp52 and Tyr224 in the dimer, while Tyr314, Tyr224 and Tyr55 in the monomer, which are compared to those in pkDAAO, Tyr314, Tyr224 and Tyr228 in the dimer, and Tyr224, Tyr314 and Tyr228 in the monomer. The ET rate from Trp55 in hDAAO dimer was much faster compared to the rate in pkDAAO dimer. A rise component with negative pre-exponential factor was not observed in hDAAO, which are found in pkDAAO.

Direct observation of an intramolecular charge transfer state in epigenetic nucleobase N6-methyladenine.

N6-Methyladenine (6MeAde), the most abundant internal modification in mRNA, has proved to be an important epigenetic biomarker for gene regulation just like 5-methylcytosine in DNA. Recently, a unique UV-induced response of 6MeAde was reported, which makes it instructive and intriguing to reveal the excited state relaxation mechanism in this methylated adenine and its derivatives. In this work, we investigated 6MeAde and its ribose species N6-methyladenosine (6MeAdo) by using femtosecond time-resolved fluorescence up-conversion (FUC) and broadband transient absorption (TA) spectroscopy. Both 6MeAde and 6MeAdo exhibit a hundreds of femtoseconds lifetime, which originates from the efficient depletion of the ππ* (La) state. A several picoseconds lifetime is also observed and it should be attributed to the ππ* (Lb) state. Surprisingly, dual peak fluorescence emission is observed in 6MeAde and the long wavelength emission is ascribed to an intramolecular charge transfer (ICT) state. The lifetime of this ICT state is determined to be 107 ps. The kinetic isotope effect shows that the ICT state is closely associated with the solute-solvent H-bonding in aqueous solution. In 6MeAdo, the ICT state is apparently quenched and adenine-like excited state dynamics suggests that DNA/RNA containing such modification could still possess excellent photostability under UV irradiation. Our results contain an important insight for understanding excited state properties in epigenetic modified DNA/RNA.

Interplay between Morphology and Electronic Structure in α-Sexithiophene Films on Au(111)

The properties of organic films are strongly influenced by their growth and structure. In this work, we link the results from three different techniques to elucidate the interplay between the morphology and the electronic structure of α-sexithiophene films grown on Au(111) surfaces. Photoelectron emission microscopy and thermal desorption spectroscopy reveal the growth of a two-layer thick wetting layer at room temperature. On top of the wetting layer, the molecules start to form μm-sized crystallites, which are statistically distributed over the surface. This transition in the growth mode is reflected in the electronic structure of the system, studied by two-photon photoemission spectroscopy. While in the wetting layer, exciton formation is suppressed by the interaction with the metal substrate, Frenkel excitons with picosecond lifetimes are observed in the three-dimensional crystallites.

IR Spectroscopy of Fullerene Ions in a Cryogenic Quadrupole Trap

Abstract This paper reports gas-phase IR spectra of (n = 1–3) ions in the range from 1100 to 1600 cm−1. The spectra were recorded with a temperature-variable radio frequency ion trap instrument. The experiments work with mass-selected ions confined in a linear wire quadrupole, where they form helium-tagged complexes following exposure to low-temperature (as low as 2.3 K) and high-density helium buffer gas. All measured lines are homogeneously broadened owing to a strong coupling between the vibrational states of the fullerene cage. The short lifetimes of picoseconds or below rule out measurements of high-resolution IR spectra. Reproducible sidebands with distances between 5 and 20 cm−1 enrich the spectra. Tentative explanations are based on nonlinear and symmetry-breaking interactions or may be due to the influence of the attached He atom. Comparison of the spectrum with that of reveals shifts up to 6 cm−1, while the IR spectra of and are very similar. With the harmonic potential of the trap the ions are squeezed into the rather narrow laser beam, increasing the sensitivity and simplifying the determination of absolute photoabsorption cross sections. Disregarding shifts of several cm−1, the gas-phase results for and are in agreement with previous matrix results and with theoretical predictions. The astrophysical relevance of our results is briefly mentioned.

Photon Upconversion through a Cascade Process of Two-Photon Absorption in CsPbBr3 and Triplet–Triplet Annihilation in Porphyrin/Diphenylanthracene

Photon upconversion constitutes an exceptionally rich area of research in photonics and electronics, where low-energy light is converted to high-energy light through nonlinear processes represented by two-photon absorption (TPA) and triplet–triplet annihilation (TTA). Here, we report a cascade process of TPA in inorganic perovskite quantum dots (PQDs) of CsPbBr3 and TTA in an organic molecule (9,10-diphenylanthracene) mediated by an octaethylporphyrinatoplatinum(II) (PtOEP) sensitizer. This sequential energy transfer enables upconversion from four photons from a near-infrared femtosecond laser at 800 nm to one photon at 430 nm with a large anti-Stokes shift of ∼1.3 eV. We characterize the energy transfer from PQDs to PtOEP by picosecond lifetime spectroscopy and a Stern–Volmer plot of the steady-state photoluminescence while considering dynamic and static quenching as well as trivial absorption and Forster (fluorescence) resonance energy transfer. The serial connection of TPA and TTA achieved in a simple ...

SiGeC Waveguide for All-Optical Data Switching

The SiGeC waveguide based ultrafast all-optical switching by using the cross-absorption modulation (XAM) effect is demonstrated to perform the wavelength conversion and format inversion of a pulsed return-to-zero on–off keying (PRZ-OOK) data stream. Under the intensively optical data-bit illumination as the pump, the two-photon absorption (TPA) effect is observed to induce free carriers in the SiGeC for absorbing the power of the probe beam. This free-carrier absorption (FCA) procedure inversely modulates the probe beam to cause the XAM switching via the intensively pumping data-bit-induced TPA/FCA process. With employing the Ge content into the SiC matrix, the picosecond free-carrier lifetime of the SiGeC can be obtained by further degrading the injected pumping energy under all-optical switching operation. With reducing the pumping energy from 0.5 nJ to 22 pJ, the effective response time of the all-optical XAM switching successfully shortens from 120 to 2 ps. Experiments declare that even a relatively l...

Diastereomerically Differentiated Excited State Behavior in Ruthenium(II) Hexafluoroacetylacetonate Complexes of Diphenyl Thioindigo Diimine.

Mono- and diruthenium hexafluoroacetylacetonate (hfac) complexes of the thioindigo-N,N'-diphenyldiimine chelating ligand 3 have been prepared. The thioindigo diimine ligand binds to ruthenium in a bidentate fashion in the mononuclear compound 2 and serves as a bidentate chelating bridging ligand in the diruthenium complexes 1a and 1b. Compound 2 was isolated as a racemic mixture while the diruthenium complexes were isolated as the meso (ΔΛ) 1a and rac (ΔΔ and ΛΛ) 1b diastereomers. In-depth structural characterization of the compounds was performed, including X-ray crystallography, 1H, 13C, and 19F nuclear magnetic resonance (NMR) spectroscopy, and 2D NMR correlation experiments. Electrochemical properties were evaluated utilizing cyclic voltammetry. Ground state optical properties of the complexes were examined using UV-visible spectroscopy and spectroelectrochemistry. The excited state dynamics of the series were investigated by ultrafast transient absorption spectroscopy. Variable temperature NMR experiments demonstrated that the rac diruthenium compound 1b undergoes conformational exchange with a rate constant of 8700 s-1 at 298 K, a behavior that is not observed in the meso diastereomer 1a. The series of complexes possess metal-to-ligand charge transfer (MLCT) absorption bands in the near-infrared (λmax 689-783 nm). The compounds do not display photoluminescence in room temperature solution-phase experiments or in experiments at 77 K. Transient absorption spectroscopy measurements revealed excited states with picosecond lifetimes for 1a, 1b, and 2, and spectroelectrochemical experiments confirmed assignment of the transient species as arising from MLCT transitions. Unexpectedly, the transient absorption measurements revealed disparate time constants for the excited state decay of diastereomers 1a and 1b.

Ultrafast Relaxation Dynamics in Zinc Tetraphenylporphyrin Surface-Mounted Metal Organic Framework

Ordered porphyrin-based metal organic frameworks (MOFs) may serve as a model for mimicking the natural photosynthesis with highly ordered chlorophylls, i.e., porphyrin-like chromophores. Study of light harvesting and energy transfer as the primary event of photosynthesis is of great importance leading to improvement of photovoltaics overall performance. Detailed characterization of ultrafast dynamics of zinc tetraphenylporphyrin (ZnTPP) surface mounted metal organic framework (SURMOF) is reported by using various steady-state and time-resolved laser spectroscopic techniques, i.e., time-correlated single photon counting, fluorescence up-conversion and transient absorption pump–probe with 20 fs resolution. Obtained results in these nanoporous materials were compared with corresponding results for ZnTPP in ethanol measured under the same conditions. Dramatic quenching of both upper excited singlet state S2 and first excited state S1 was observed. Subpicosecond and picosecond lifetimes were detected in transi...

Photophysics of Zinc Porphyrin Aggregates in Dilute Water-Ethanol Solutions.

Dimeric and multimeric aggregates of a model metalloporphyrin, zinc tetraphenylporphyrin (ZnTPP), have been produced in a controlled manner by incrementally increasing the water content of dilute aqueous ethanol solutions. Steady state absorption, fluorescence emission, and fluorescence excitation spectra have been measured to identify the aggregates present as a function of solvent composition. The dynamics of the excited states of the aggregates produced initially by excitation in the Soret region have been measured by ultrafast fluorescence upconversion techniques. Only the monomer produces measurable emission from S2 with a picosecond lifetime; all Soret-excited aggregates, including the dimer, decay radiationlessly on a femtosecond time scale. The S1 state is the only significant product of the radiationless decay of the S2 state of the excited monomer, and the aggregates also produce substantial quantum yields of S1 fluorescence when initially excited in the Soret region. The resulting fluorescent aggregates all decay on a subnanosecond time scale, likely by a mechanism that involves dissociation of the excited monomer from the excitonic multimer. The ZnTPP dimers excited at their ground state geometries in the Soret region exhibit a dynamic behavior that is quite different from those produced following noncoherent triplet-triplet annihilation under the same conditions. The important implications of these observations in determining the aggregation conditions promoting efficient photon upconversion by excitonic annihilation in a variety of media are thoroughly discussed.

Ultrafast Excited-State Dynamics of Cytosine Aza-Derivative and Analogues.

Excited state dynamics of 5-azacytosine (5-AC), 2,4-diamino-1,3,5-triazine (2,4-DT), and 2-amino-1,3,5-triazine (2-AT) were comprehensively investigated by steady state absorption, fluorescence, and femtosecond transient absorption measurements. Time-dependent density functional theory (TDDFT) calculations were performed to help assign the absorption bands and understand the excited state decay mechanisms. The experimental results of excited singlet state dynamics for 5-AC, 2,4-DT, and 2-AT with femtosecond time resolution were reported for the first time. Two distinct decay pathways, with ∼1 ps and tens of picosecond lifetimes, were observed in 5-AC. Only one decay pathway with 17 ps lifetime was observed in 2,4-DT while an emissive state was found in 2-AT. TDDFT calculations suggest that 5-AC has a dark nπ* (S1) state below the first allowed ππ* (S2) state, which leads to the ultrafast decay of the ππ* state. In 2,4-DT, there is no dark nπ* state below the bright ππ* (S1) state and the 17 ps lifetime is assigned to the relaxation from the ππ* (S1) state to ground state. Two dark nπ* states (S1 and S2) were found in 2-AT, which exhibits much more complex excited state dynamics compared with the other two. Photoluminescence in 2-AT has been confirmed to be fluorescence emission from its bright ππ* (S3) state. Our results strongly suggest that electronic structures are very sensitive to the substitution on the triazine ring and that the photophysical properties of nucleic acid analogues depend highly on their molecular structures.

Ultrafast Elemental and Oxidation-State Mapping of Hematite by 4D Electron Microscopy.

We describe a new methodology that sheds light on the fundamental electronic processes that occur at the subsurface regions of inorganic solid photocatalysts. Three distinct kinds of microscopic imaging are used that yield spatial, temporal, and energy-resolved information. We also carefully consider the effect of photon-induced near-field electron microscopy (PINEM), first reported by Zewail et al. in 2009. The value of this methodology is illustrated by studying afresh a popular and viable photocatalyst, hematite, α-Fe2O3 that exhibits most of the properties required in a practical application. By employing high-energy electron-loss signals (of several hundred eV), coupled to femtosecond temporal resolution as well as ultrafast energy-filtered transmission electron microscopy in 4D, we have, inter alia, identified Fe4+ ions that have a lifetime of a few picoseconds, as well as associated photoinduced electronic transitions and charge transfer processes.

Molecular dynamics simulations of 18-crown-6 aqueous solutions

Physicochemical, thermodynamic and structural properties of 18-crown-6 aqueous solutions were investigated by molecular dynamics simulations. Force fields for flexible solute and solvent molecules were used. The calculated values of the density, hydration enthalpy, self-diffusion coefficients and their concentration dependences were found to be close to experimental data. The structure of hydration shells of crown ether molecules and the structure of water in the solutions were determined. A residence lifetime distribution of water molecules from the first hydration shell of a crown ether molecule shows a presence of long-lived states with typical lifetimes of hundreds picoseconds.

How the hydrophobic factor drives protein folding

How hydrophobicity (HY) drives protein folding is studied. The 1971 Nozaki-Tanford method of measuring HY is modified to use gases as solutes, not crystals, and this makes the method easy to use. Alkanes are found to be much more hydrophobic than rare gases, and the two different kinds of HY are termed intrinsic (rare gases) and extrinsic (alkanes). The HY values of rare gases are proportional to solvent-accessible surface area (ASA), whereas the HY values of alkanes depend on special hydration shells. Earlier work showed that hydration shells produce the hydration energetics of alkanes. Evidence is given here that the transfer energetics of alkanes to cyclohexane [Wolfenden R, Lewis CA, Jr, Yuan Y, Carter CW, Jr (2015) Proc Natl Acad Sci USA 112(24):7484-7488] measure the release of these shells. Alkane shells are stabilized importantly by van der Waals interactions between alkane carbon and water oxygen atoms. Thus, rare gases cannot form this type of shell. The very short (approximately picoseconds) lifetime of the van der Waals interaction probably explains why NMR efforts to detect alkane hydration shells have failed. The close similarity between the sizes of the opposing energetics for forming or releasing alkane shells confirms the presence of these shells on alkanes and supports Kauzmann's 1959 mechanism of protein folding. A space-filling model is given for the hydration shells on linear alkanes. The model reproduces the n values of Jorgensen et al. [Jorgensen WL, Gao J, Ravimohan C (1985) J Phys Chem 89:3470-3473] for the number of waters in alkane hydration shells.

Measurement of picosecond lifetimes in neutron-rich Xe isotopes

Background: Lifetimes of nuclear excited states in fission fragments have been studied in the past following isotope separation, thus giving access mainly to the fragments’ daughters and only to long-lived isomeric states in the primary fragments. For the first time now, short-lived excited states in the primary fragments, produced in neutron-induced prompt fission of 235U and 241Pu, were studied within the EXILL&FATIMA campaign at the intense neutron-beam facility of the Institute Laue-Langevin in Grenoble. Purpose: We aim to investigate the quadrupole collective properties of neutron-rich even-even 138,140,142Xe isotopes lying between the double shell closure N = 82 and Z = 50 and a deformed region with octupole collectivity. Method: The γ rays emitted from the excited fragments were detected with a mixed array consisting of 8 HPGe EXOGAM Clover detectors (EXILL) and 16 LaBr3(Ce) fast scintillators (FATIMA). The detector system has the unique ability to select the interesting fragment making use of the high resolution of the HPGe detectors and determine subnanosecond lifetimes using the fast scintillators. For the analysis the generalized centroid difference method was used. Results: We show that quadrupole collectivity increases smoothly with increasing neutron number above the closed N = 82 neutron shell. Our measurements are complemented by state-of-the-art theory calculations based on shell-model descriptions. Conclusions: The observed smooth increase in quadrupole collectivity is similar to the evolution seen in the measured masses of the xenon isotopic chain and is well reproduced by theory. This behavior is in contrast to higher Z even-even nuclei where abrupt change in deformation occurs around N = 90.

Rotationally Resolved Vacuum Ultraviolet Resonance-Enhanced Multiphoton Ionization (VUV REMPI) of Acetylene via the G̃ Rydberg State.

We present a 1 + 1' resonance-enhanced multiphoton ionization (REMPI) scheme for acetylene via the linear G̃ 4sσ (1)Πu Rydberg state, offering partial rotational resolution and the possibility to detect excitation in both the cis- and trans-bending modes. The resonant transition to the G̃ state is driven by a vacuum ultraviolet (VUV) photon, generated by resonant four-wave mixing (FWM) in krypton. Ionization from the short-lived G̃ state then occurs quickly, driven by the high intensity of the residual light from the FWM process. We have observed nine bands in the region between 79 200 cm(-1) and 80 500 cm(-1) in C2H2 and C2D2. We compare our results with published spectra in this region and suggest alternative assignments for some of the Renner-Teller split bands. Similar REMPI schemes should be applicable to other small molecules with picosecond lifetime Rydberg states.

Picosecond Lifetimes with High Quantum Yields from Single-Photon-Emitting Colloidal Nanostructures at Room Temperature.

Minimizing the luminescence lifetime while maintaining a high emission quantum yield is paramount in optimizing the excitation cross-section, radiative decay rate, and brightness of quantum solid-state light sources, particularly at room temperature, where nonradiative processes can dominate. We demonstrate here that DNA-templated 60 and 80 nm diameter gold nanoparticle dimers, featuring one fluorescent molecule, provide single-photon emission with lifetimes that can fall below 10 ps and typical quantum yields in a 45-70% range. Since these colloidal nanostructures are obtained as a purified aqueous suspension, fluorescence spectroscopy can be performed on both fixed and freely diffusing nanostructures to quantitatively estimate the distributions of decay rate and fluorescence intensity enhancements. These data are in excellent agreement with theoretical calculations and demonstrate that millions of bright fluorescent nanostructures, with radiative lifetimes below 100 ps, can be produced in parallel.

Carbon nanotubes dispersed in aqueous solution by ruthenium(ii) polypyridyl complexes.

Cationic ruthenium(ii) polypyridyl complexes with appended pyrene groups have been synthesized and used to disperse single-walled carbon nanotubes (SWCNT) in aqueous solutions. To this end, planar pyrene groups enable association by means of π-stacking onto carbon nanotubes and, in turn, the attachment of the cationic ruthenium complexes. Importantly, the ionic nature of the ruthenium complexes allows the formation of stable dispersions featuring individualized SWCNTs in water as confirmed in a number of spectroscopic and microscopic assays. In addition, steady-state photoluminescence spectroscopy was used to probe the excited state interactions between the ruthenium complexes and SWCNTs. These studies show that the photoluminescence of both, that is, of the ruthenium complexes and of SWCNTs, are quenched when they interact with each other. Pump-probe transient absorption experiments were performed to shed light onto the nature of the photoluminescence quenching, showing carbon nanotube-based bands with picosecond lifetimes, but no new bands which could be unambigously assigned to photoinduced charge transfer process. Thus, from the spectroscopic data, we conclude that quenching of the photoluminescence of the ruthenium complexes is due to energy transfer to proximal SWCNTs.

Energy dissipation pathways in Photosystem 2 of the diatom, Phaeodactylum tricornutum, under high-light conditions.

To prevent photooxidative damage under supraoptimal light, photosynthetic organisms evolved mechanisms to thermally dissipate excess absorbed energy, known as non-photochemical quenching (NPQ). Here we quantify NPQ-induced alterations in light-harvesting processes and photochemical reactions in Photosystem 2 (PS2) in the pennate diatom Phaeodactylum tricornutum. Using a combination of picosecond lifetime analysis and variable fluorescence technique, we examined the dynamics of NPQ activation upon transition from dark to high light. Our analysis revealed that NPQ activation starts with a 2-3-fold increase in the rate constant of non-radiative charge recombination in the reaction center (RC); however, this increase is compensated with a proportional increase in the rate constant of back reactions. The resulting alterations in photochemical processes in PS2 RC do not contribute directly to quenching of antenna excitons by the RC, but favor non-radiative dissipation pathways within the RC, reducing the yields of spin conversion of the RC chlorophyll to the triplet state. The NPQ-induced changes in the RC are followed by a gradual ~ 2.5-fold increase in the yields of thermal dissipation in light-harvesting complexes. Our data suggest that thermal dissipation in light-harvesting complexes is the major sink for NPQ; RCs are not directly involved in the NPQ process, but could contribute to photoprotection via reduction in the probability of (3)Chl formation.