Time-resolved Spectroscopic Techniques Research Articles

Solvation Dynamics of Wet Ethaline: Water is the Magic Component.

The past two decades witnessed the development of a new type of solvent system, named deep eutectic solvents, which have become increasingly investigated because they offer new and potentially favorable properties, such as wide tunability in electrochemical, mechanical, and transport properties. Deep eutectic solvent (DES) systems are composed of at least one main solvent and an additional component that is meant to interrupt the original solvent/solvent interactions, thereby introducing lower melting points relative to each individual component. Ethaline (a 1:2 mol % mixture of choline chloride and ethylene glycol) is one of the most promising DES systems. However, it is also known to be very hygroscopic, which is a constant concern because water absorption during the use of ethaline alters its properties. Within this work, we demonstrate that modest amounts of water addition (1-10%) to ethaline are of little concern for practical use and can even lead to performance improvements, such as accelerated relaxation and solvation. In contrast, very small amounts of <1% of water lead to additional slowing of the solvent response. Thus, we suggest that the attempt to dry ethaline below 1% moisture is rather counterproductive if one attempts to achieve effective solvation and charge transport properties from DESs. This study investigates the effect of water content on the diffusional relaxation dynamics of ethaline. A set of independent spectroscopic experiments and computational simulations are aimed to provide insight into the solvent response of the DES system using femtosecond time-resolved absorption spectroscopy (fs-TA), broadband dielectric spectroscopy (BDS), nuclear magnetic resonance (NMR) diffusometry and broadband relaxometry, and molecular dynamics simulations (MDS) on ethaline with 0, 0.1, 1, 10, and 28.5 wt % added water. For dry ethaline, we identify choline chloride as the rate-limiting solvation component in ethaline. However, the role of the solvent components changes gradually as water is added. We provide quantitative solvent relaxation rates using the different presented time-resolved spectroscopic techniques and find remarkable agreement between them. Based on the solvent relaxation rates and combined with MDS, we develop a molecular understanding of the individual solvent components and their interactions in dry and wet ethaline with varying amounts of water content.

Electron Transfer Quenching of Rhodamine 6G by N-Methylpyrrole Is an Unproductive Process in the Photocatalytic Heterobiaryl Cross-Coupling Reaction.

In the heterobiaryl cross-coupling reaction between aryl halides (Ar-X) and N-methylpyrrole (N-MP) catalyzed by rhodamine 6G (Rh6G+) under irradiation with visible light, a highly active and long-lived (millisecond time range) rhodamine 6G radical (Rh6G•) is formed upon electron transfer from N,N-diisopropylethylamine (DIPEA) to Rh6G+. In this study, we utilized steady-state and time-resolved spectroscopy techniques to demonstrate the existence of another electron-transfer process occurring from the relatively electron-rich N-MP to photoexcited Rh6G+ that was neglected in the previous reports. In this case, the radical Rh6G• formed is short-lived and undergoes rapid recombination (nanosecond time-range), rendering it ineffective in reducing Ar-X to aryl radicals Ar• that can subsequently be trapped by N-MP. This is further demonstrated via two model reactions involving 4'-bromoacetophenone and 1,3,5-tribromobenzene with insignificant product yields after visible-light irradiation in the absence of DIPEA. The unproductive quenching of photoexcited Rh6G+ by N-MP leads to a lower concentration of photocatalyst available for competitive charge transfer with DIPEA and hence decreases the efficiency of the cross-coupling reaction.

Spontaneous-reduction and photoluminescence tuning in singly-doped Ba5-Ca (PO4)3Cl:Eu2+/Eu3+ phosphors

Developing a feasible scheme for solid-state lighting with high-quality white light remains a significant challenge. Particularly, tunable luminescence with single-component white emission have been widely studied to improve the luminescence performance of phosphor-converted white light-emitting diodes (pc-WLEDs) phosphors. In this work, a novel spontaneous reduction phenomenon was first found in Eu-activated apatite-type Ba5(PO4)3Cl phosphors prepared by a solid-phase reaction in air. Under 362 nm excitation, the luminescence results showed that a broad blue Eu2+ emission band with a peak at 437 nm appears unexpectedly in addition to the usual sharp orange-red emission of Eu3+. The mixed-valence fact of Eu2+/Eu3+ was further confirmed by X-ray photoelectron spectra and time-resolved spectroscopy techniques. The underlying mechanism could be explained by a charge compensation model. Accordingly, the local crystal-site engineering control of the luminescence in Ba5-yCay(PO4)3Cl:Eu2+/Eu3+ had been studied in detail by the introduction of Ca2+. It is found that the Ca2+ substitution of Ba2+ will lead to new splitting peaks of Eu3+ emission and a red-shift followed by a blue-shift of Eu2+ emission respectively, which could eventually adjust the luminescence of phosphors to the proper white light region. These phenomena are mainly ascribed to the introduction of Ca2+ to the structure modification of activator coordination environment. Finally, based on the thermal quenching results indicate that the potential application of the single-doped mixed-valence phosphor system in pc-WLEDs.

Real-time interfacial electron dynamics revealed through temporal correlations in x-ray photoelectron spectroscopy.

We present a novel technique to monitor dynamics in interfacial systems through temporal correlations in x-ray photoelectron spectroscopy (XPS) signals. To date, the vast majority of time-resolved x-ray spectroscopy techniques rely on pump–probe schemes, in which the sample is excited out of equilibrium by a pump pulse, and the subsequent dynamics are monitored by probe pulses arriving at a series of well-defined delays relative to the excitation. By definition, this approach is restricted to processes that can either directly or indirectly be initiated by light. It cannot access spontaneous dynamics or the microscopic fluctuations of ensembles in chemical or thermal equilibrium. Enabling this capability requires measurements to be performed in real (laboratory) time with high temporal resolution and, ultimately, without the need for a well-defined trigger event. The time-correlation XPS technique presented here is a first step toward this goal. The correlation-based technique is implemented by extending an existing optical-laser pump/multiple x-ray probe setup by the capability to record the kinetic energy and absolute time of arrival of every detected photoelectron. The method is benchmarked by monitoring energy-dependent, periodic signal modulations in a prototypical time-resolved XPS experiment on photoinduced surface-photovoltage dynamics in silicon, using both conventional pump–probe data acquisition, and the new technique based on laboratory time. The two measurements lead to the same result. The findings provide a critical milestone toward the overarching goal of studying equilibrium dynamics at surfaces and interfaces through time correlation-based XPS measurements.

Nature of Linear Spectral Properties and Fast Electronic Relaxations in Green Fluorescent Pyrrolo[3,4-c]Pyridine Derivative.

The electronic nature of 4-hydroxy-1H-pyrrolo[3,4-c]pyridine-1,3,6(2H,5H)-trione (HPPT) was comprehensively investigated in liquid media at room temperature using steady-state and time-resolved femtosecond transient absorption spectroscopic techniques. The analysis of the linear photophysical and photochemical parameters of HPPT, including steady-state absorption, fluorescence and excitation anisotropy spectra, along with the lifetimes of fluorescence emission and photodecomposition quantum yields, revealed the nature of its large Stokes shift, specific changes in the permanent dipole moments under electronic excitation, weak dipole transitions with partially anisotropic character, and high photostability. Transient absorption spectra of HPPT were obtained with femtosecond resolution and no characteristic solvate relaxation processes in protic (methanol) solvent were revealed. Efficient light amplification (gain) was observed in the fluorescence spectral range of HPPT, but no super-luminescence and lasing phenomena were detected. The electronic structure of HPPT was also analyzed with quantum-chemical calculations using a DFT/B3LYP method and good agreement with experimental data was shown. The development and investigation of new pyrrolo[3,4-c]pyridine derivatives are important due to their promising fluorescent properties and potential for use in physiological applications.

Dependent excited state absorption and dynamic of β-BF2 substituted metalloporphyrins: The metal ion effect

Absorption and relaxation dynamics of electronic states of free-base, Co(II), Cu(II) and Zn(II) porphyrins bearing a β-(2,2-difluoro-1,3,2-dioxaborinin-5-yl) group were investigated in dimethyl sulfoxide by using distinct time-resolved spectroscopic techniques. Furthermore, excited state absorption cross-section spectra were determined by combining white light continuum Z-Scan and transient absorption techniques. In the case of the free-base (2H) and Zn(II) porphyrins, we were able to quantify singlet–triplet conversion by analyzing the evolution of time-resolved fluorescence. Relaxation lifetimes from the excited to the ground state were observed in both porphyrins at nanosecond time scale. However, for Co(II) and Cu(II) metalloporphyrins it was observed in the picosecond time scale through femtosecond transient absorption, indicating that both compounds relax back to the ground state only by internal conversion processes. Co(II) and Cu(II) heavy atoms seem to prohibit the radiative and intersystem crossing processes.

Enhancing stability and luminescence quantum yield of CsPbBr3 quantum dots by embedded in borosilicate glass

Halide perovskite quantum dots have attracted considerable research interest as excellent candidate for photonic and optoelectronic applications due to their unique optoelectronic properties. Stability is prerequisite and therefore is of critical importance. Here we demonstrate highly stable luminescent CsPbBr3 quantum dots (QDs) can be achieved in different glass matrices via the high temperature melting process and melt-quench method. The microstructure of CsPbBr3 QDs glass as well as their optical properties are systematically characterized by microscopic techniques and time-resolved spectroscopic techniques. We conclude the surface passivation is the key aspect for the high stability and high luminescence by embedding the quantum dots in the glass matrix. This study provides technical method to form highly stable luminescent solid devices and detailed physical understanding which is critical for the practical applications.

Surfactant tail length dependence of the photophysics and dynamics of a chemotherapeutic drug within anionic micellar aggregates

The present work reports a photophysical study of norfloxacin (NOF), an efficient chemotherapeutic antibacterial drug, in well-characterized biomimetic micellar aggregates of anionic surfactants. The major focus of the present investigation lies in deciphering the effect of the surfactant chain length on the structural dynamics of the drug within a micelle-encapsulated state through steady-state and time-resolved fluorescence spectroscopic techniques. The anionic surfactants employed for the purpose are decyl sodium sulfate (S10S), dodecyl sodium sulfate (S12S) and tetradecyl sodium sulfate (S14S). Our experimental results evince that increasing hydrophobic surfactant tail length exerts a profound influence on promoting a specific prototropic form of NOF within the micellar aggregates; an apparently enigmatic observation is that increasing hydrophobicity of the micellar microheterogeneous system indeed favors the cationic species of the drug. This is interpreted on the basis of electrostatic stabilization between the drug (cationic form) and anionic surface charge of the as-employed micellar assemblies, while the micellar hydration model fails to rationalize the experimental findings. Particular emphasis is also given on delineating the probable location and the modulated rotational-relaxation dynamics of the drug molecule within the micellar aggregates. The interaction thermodynamics and dynamics of norfloxacin within anionic micelles is critically dependent on the tail length of the surfactant such that the micellar hydration model is found to be inadequate to explain the photophysics of the drug whereas electrostatic interaction appears to play the governing role.

Fusogenic Effect of Cholesterol Prevails over the Inhibitory Effect of a Peptide-Based Membrane Fusion Inhibitor.

Membrane fusion is the primary step in the entry of enveloped viruses into the host cell. Membrane composition modulates the membrane fusion by changing the organization dynamics of the fusion proteins, peptides, and membranes. The asymmetric lipid compositions of the viral envelope and the host cell influence the membrane fusion. Cholesterol is an important constituent of mammalian cells and plays a vital role in the entry of several viruses. In our pursuit of developing peptide-based general fusion inhibitors, we have previously shown that a coronin 1-derived peptide, TG-23, inhibited polyethylene glycol-induced fusion between symmetric membranes without cholesterol. In this work, we have studied the effect of TG-23 on the polyethylene glycol-mediated fusion between 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE), and 1,2-dioleoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (DOPG) (60/30/10 mol %) and DOPC/DOPE/DOPG/CH (50/30/10/10 mol %) membranes and between DOPC/DOPE/DOPG (60/30/10 mol %) and DOPC/DOPE/DOPG/CH (40/30/10/20 mol %) membranes. Our results demonstrate that the TG-23 peptide inhibited the fusion between membranes containing 0 and 10 mol % cholesterol though the efficacy is less than that of symmetric fusion between membranes devoid of cholesterol, and the inhibitory efficacy becomes negligible in the fusion between membranes containing 0 and 20 mol % cholesterol. Several steady-state and time-resolved fluorescence spectroscopic techniques have been successfully utilized to evaluate the organization, dynamics, and membrane penetration of the TG-23 peptide. Taken together, our results demonstrate that the reduction of the inhibitory effect of TG-23 in asymmetric membrane fusion containing cholesterol of varying concentrations is not due to the altered peptide structure, organization, and dynamics, rather owing to the intrinsic negative curvature-inducing property of cholesterol. Therefore, the membrane composition is an added complexity in the journey of developing peptide-based membrane fusion inhibitors.

Ion-pairing effects by organic anions on the supramolecular assembling kinetics of sulfonated porphyrins

Camphorsulfonic (CSA) and p-toluenesulfonic (p-TsOH) acids promote the self-assembling process of the diacid meso-tetrakis(4-sulfonatophenyl)porphyrin (H2TPPS4) into J-aggregates. A general decrease of the rate constants on increasing the acid concentration has been observed for these organic acids. For camphorsulfonic acid the formation of chiral J-aggregates, whose handedness is related to that of the acid, has been revealed by circular dichroism spectra. Changes in the aggregation rates, kinetic profiles and g-factors but no chiral discrimination have been observed for the two different enantiomers, when using different mixing protocols. Moreover, at high acid concentration, aggregation is inhibited and the formation of a new porphyrin species has been detected for both acids. This species has been characterized by steady-state and time-resolved spectroscopic techniques and has been ascribed to an ion pair between the diacid porphyrin and the organic counter-anion. Its role in the aggregation of the initial diacid species has been discussed.

Exploiting a Neutral BODIPY Copolymer as an Effective Agent for Photodynamic Antimicrobial Inactivation.

We report the synthesis and photophysical properties of a neutral BODIPY photosensitizing copolymer (poly-8-(4-hydroxymethylphenyl)-4,4-difluoro-2,6-diethynyl-4-bora-3a,4a-diaza-s-indacene) containing ethynylbenzene links between the BODIPY units. The copolymer absorbs further towards the red in the UV-vis spectrum compared to the BODIPY precursor. Photolysis of the polymer produces a singlet excited state which crosses to the triplet surface in less than 300 ps. This triplet state was used to form singlet oxygen with a quantum yield of 0.34. The steps leading to population of the triplet state were studied using time-resolved spectroscopic techniques spanning the pico- to nanosecond timescales. The ability of the BODIPY polymer to generate a biocidal species for bactericidal activity in both solution- and coating-based studies was assessed. When the BODIPY copolymer was dropcast onto a surface, 4 log and 6 log reductions in colony forming units/ml representative of Gram-positive and Gram-negative bacteria, respectively, under illumination at 525 nm were observed. The potent broad-spectrum antimicrobial activity of a neutral metal-free copolymer when exposed to visible light conditions may have potential clinical applications in infection management.

Light-adapted charge-separated state of photosystem II: structural and functional dynamics of the closed reaction center.

Photosystem II (PSII) uses solar energy to oxidize water and delivers electrons for life on Earth. The photochemical reaction center of PSII is known to possess two stationary states. In the open state (PSIIO), the absorption of a single photon triggers electron-transfer steps, which convert PSII into the charge-separated closed state (PSIIC). Here, by using steady-state and time-resolved spectroscopic techniques on Spinacia oleracea and Thermosynechococcus vulcanus preparations, we show that additional illumination gradually transforms PSIIC into a light-adapted charge-separated state (PSIIL). The PSIIC-to-PSIIL transition, observed at all temperatures between 80 and 308 K, is responsible for a large part of the variable chlorophyll-a fluorescence (Fv) and is associated with subtle, dark-reversible reorganizations in the core complexes, protein conformational changes at noncryogenic temperatures, and marked variations in the rates of photochemical and photophysical reactions. The build-up of PSIIL requires a series of light-induced events generating rapidly recombining primary radical pairs, spaced by sufficient waiting times between these events-pointing to the roles of local electric-field transients and dielectric relaxation processes. We show that the maximum fluorescence level, Fm, is associated with PSIIL rather than with PSIIC, and thus the Fv/Fm parameter cannot be equated with the quantum efficiency of PSII photochemistry. Our findings resolve the controversies and explain the peculiar features of chlorophyll-a fluorescence kinetics, a tool to monitor the functional activity and the structural-functional plasticity of PSII in different wild-types and mutant organisms and under stress conditions.

Time- and Temperature-Dependent Luminescence of Manganese Ions in Ceramic Magnesium Aluminum Spinels.

Samples of magnesium aluminum spinel ceramics doped with manganese ions were prepared by a high-temperature solid-state reaction method; their potential as red-emitting phosphors was analyzed using a time-resolved luminescence spectroscopy technique, from room temperature to 10 K. It was found that in the red spectral range, the luminescence spectra of manganese ions in the MgAl2O4 spinel showed a narrow band peaking at 651 nm due to the emission of Mn4+ and a broader emission band in the region of 675 ÷ 720 nm; the ratio of intensities for these bands depends on the synthesis conditions. By applying a special multi-step annealing procedure, the MgAl2O4:Mn4+ phosphor containing only tetravalent manganese ions, Mn4+, was synthesized. Broad-band far-red emission observed from MgAl2O4:Mn and Mg1.25Al1.75O3.75F0.25:Mn phosphors, prepared by a conventional method of a solid-state reaction, was interpreted as coming from Mn3+ ions.

Optical encoding of luminescent carbon nanodots in confined spaces.

Stable emissive carbon nanodots were generated in zeolite crystals using near infrared photon irradiation gradually converting the occluded organic template, originally used to synthesize the zeolite crystals, into discrete luminescent species consisting of nano-sized carbogenic fluorophores, as ascertained using Raman microscopy, and steady-state and time-resolved spectroscopic techniques. Photoactivation in a confocal laser fluorescence microscope allows 3D resolved writing of luminescent carbon nanodot patterns inside zeolites providing a cost-effective and non-toxic alternative to previously reported metal-based nanoclusters confined in zeolites, and opens up opportunities in bio-labelling and sensing applications.

Bell correlations between light and vibration at ambient conditions.

Time-resolved Raman spectroscopy techniques offer various ways to study the dynamics of molecular vibrations in liquids or gases and optical phonons in crystals. While these techniques give access to the coherence time of the vibrational modes, they are not able to reveal the fragile quantum correlations that are spontaneously created between light and vibration during the Raman interaction. Here, we present a scheme leveraging universal properties of spontaneous Raman scattering to demonstrate Bell correlations between light and a collective molecular vibration. We measure the decay of these hybrid photon-phonon Bell correlations with sub-picosecond time resolution and find that they survive over several hundred oscillations at ambient conditions. Our method offers a universal approach to generate entanglement between light and molecular vibrations. Moreover, our results pave the way for the study of quantum correlations in more complex solid-state and molecular systems in their natural state.

Role of Spin-Orbit Coupling in Long Range Energy Transfer in Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are emerging as a promising platform for solar energy conversion applications. Their potential utilization as efficient chromophores in artificial photosynthesis is closely related to the understanding of light-harvesting and energy transfer processes that occur within these molecular scaffolds. Herein, we present the photophysical investigation of Ru(II), Ir(III), and Os(II) polypyridyl complexes incorporated into the backbone of UiO-67. In this work, we systematically study the effect of spin-orbit coupling on dipole-dipole energy transfer in MOFs using steady-state and time-resolved spectroscopic techniques. The results of our work indicate successful triplet-to-singlet energy transfer and a sizable increase in the transfer kinetics and critical distance, as direct consequences of strong spin-orbit couplings. Remarkably, the reported R0 value for OsDCBPY (R0 = 88 ± 10 Å) represents one of the largest Förster distances observed in an MOF. Collectively, this work contributes to the general knowledge of energy transfer in materials and provides groundwork for efficient utilization in artificial photosynthetic assemblies.

Morphological Evolution of Strongly Fluorescent Water Soluble AIEEgen-Triblock Copolymer Mixed Aggregates with Shape-Dependent Cell Permeability.

Dimethyl-2,5-bis(4-methoxyphenylamino)terephthalate (DBMPT) is a water-insoluble fluorogenic molecule, which has been rendered water-soluble in physiological conditions, by the addition of triblock copolymers (TBPs), P123 (PEO19PPO69PEO19), and F127 (PEO100PPO65PEO100). DBMPT-TBP mixed aggregates, formed in the process, exhibit significant aggregation-induced enhancement of emission, with nanosecond fluorescence lifetimes. Dynamics involved in suppression of nonradiative pathways and consequent enhancement of fluorescence are followed by femtosecond transient absorption and time-resolved fluorescence spectroscopic techniques. Interestingly, shapes of the aggregates formed with the two TBPs are found to be very different, even though they differ only in the length of hydrophilic blocks. DBMPT-P123 aggregates are micrometer-sized and spherical, while DBMPT-F127 aggregates form nanorods. Evolution of their morphologies, as a function of TBP concentration, is monitored using cryo-TEM, FESEM, and fluorescence lifetime imaging microscopy. Fluorescence lifetime distribution provides useful insight into microheterogeneity in these mixed aggregates. Excellent cell permeability is observed for DBMPT-F127 nanorods, in contrast to DBMPT-P123 microspheres. These fluorescent nanorods exhibit the ability to mark lipid droplets within the cell and hence bear the promise for application in intracellular imaging.

NO Dynamics in Microbial Denitrification System

Abstract Nitric oxide (NO) is generated in some biological systems. Due to its radical character, it exhibits high reactivity, but biological system can manage NO without sustaining any damage to bio-compounds in the cell. As a model system to understand how the NO dynamics is controlled in the cell, we have been studying denitrification of microbial respiration, in which NO is generated as an intermediate product. In denitrification, it was found that NO produced by the NO-generating enzyme (NiR: nitrite reductase) can be smoothly transferred to the NO-decomposing enzyme (NOR: nitric oxide reductase) by making a complex of the two enzymes. The chemical mechanism of the NO decomposition by NOR was also revealed by the time-resolved spectroscopic techniques.

Exciton Dynamics in Pyrene and Perylene Nanoaggregates

Photophysical and diffusion properties of excitons generated in perylene and pyrene nanoaggregates have been investigated using steady state as well as time-resolved absorption and emission spectroscopic techniques. The average sizes and heights of the nanoaggregates prepared by the reprecipitation method have been estimated as 120 ± 20 and 60 ± 10 nm, respectively. X-ray diffraction spectra reveal that molecular packing in these nanoaggregates is very similar to that in the α-form (face-to-face pair or dimeric structure) of the crystals, but with possibilities of a large number of disordered regions consisting of monomer molecules. Therefore, following photoexcitation of nanoaggregates, both monomeric and dimeric exciton states are populated. This work, for the first time, could reveal the dynamics of interactions between these two kinds of exciton states, because of which the photophysical and diffusion properties of the excitons are significantly different from those in single crystals. Population yield of the dimeric self-trapped exciton or E state, which is the lowest energy exciton state, is negligibly small via self-trapping of dimeric excitons (dimeric channel) in the <200 ps time domain because of efficient energy transfer from dimeric excitons to monomers. However, the monomeric excitons, which are populated either independently through direct photoexcitation or by energy transfer from the dimeric excitons, contribute to an additional (monomeric) channel populating the E state via energy transfer processes occurring in the nanosecond (ns) time domain. Diffusion coefficients and diffusion lengths of the monomeric excitons estimated in both these nanoaggregates are comparable to those in the β-form of the crystals but much larger than those values reported for the α-form and hence ensure a better or comparable efficiency of energy migration in nanoaggregates as compared to that of single crystals.

A Time-Resolved Spectroscopic Investigation of a Novel BODIPY Copolymer and Its Potential Use as a Photosensitiser for Hydrogen Evolution.

A novel 4,4-difuoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) copolymer with diethynylbenzene has been synthesised, and its ability to act as a photosensitiser for the photocatalytic generation of hydrogen was investigated by time-resolved spectroscopic techniques spanning the ps- to ns-timescales. Both transient absorption and time-resolved infrared spectroscopy were used to probe the excited state dynamics of this photosensitising unit in a variety of solvents. These studies indicated how environmental factors can influence the photophysics of the BODIPY polymer. A homogeneous photocatalytic hydrogen evolution system has been developed using the BODIPY copolymer and cobaloxime which provides hydrogen evolution rates of 319 μmol h−1 g−1 after 24 h of visible irradiation.