Time-resolved Spectroscopic Techniques Research Articles

Unraveling the Nanosheet Zeolite-Catalyzed Combustion of Aluminum Nanoparticles-Doped exo-Tetrahydrodicyclopentadiene (JP-10) Energetic Fuel.

Nanosheet MFI zeolites (Zeolite Socony Mobil, five) have grown in popularity in cracking catalysis considering their tunability in porous topologies, acidic sites, and sheet thickness, thus allowing them to selectively adsorb molecules of specific sizes, shapes, and polarities, resulting in improved cracking performance for a specific fuel. Five different MFI zeolites in the form of a mesoporous nanosheet structure with a controlled concentration of acidic sites denoted as NSMFI(y), where y is Si/Al ratio, have been synthesized. The effects of the relative acidity content of these NSMFI(y) samples on the zeolite-catalyzed combustion of aluminum nanoparticles (AlNPs)-aided exo-tetrahydrodicyclopentadiene (JP-10) mixed energetic fuel droplets levitated in an oxygen-argon atmosphere were investigated using time-resolved imaging (optical and thermal infrared) and spectroscopic techniques (UV-vis and FTIR). The addition of 1.0 wt % of NSMFI(y) zeolites to AlNPs-JP-10 fluid fuel results in critically reduced ignition delays (9 ± 2 ms), elevated ignition temperatures (2800 ± 170 K), and prolonged burning times (60 ± 10 ms) with an enhanced combustion efficiency. The NSMFI(y) zeolites, which possess high acidity and significant mesoporosity, play a crucial role in improving the combustion efficiency by effectively catalyzing the chemical activation of JP-10 and prolonging the burning of the igniting droplet. The NSMFI (60) variant with the highest acidic site content achieved a maximum combustion efficiency of 80 ± 6%. A comprehensive catalytic combustion mechanism has been elucidated based on the detected reactive intermediates such as hydroxyl radical (OH) and aluminum monoxide (AlO). These findings will help to critically advance the development of next-generation, sustainable, and innovative mixed nanofluid fuels.

Application of Steady-State and Time-Resolved Fluorescence Spectroscopy in Identification of Bee Products

In this study, steady-state and time-resolved fluorescence spectroscopy techniques have been applied to determine fluorescence characteristics and fluorescence decay kinetics parameters (fluorescence lifetimes and their amplitudes) of available on the Polish market bee products, including several nectar honeys, royal jelly, bee bread in honey and in liquid artificial honey. The fluorescence properties of the tested bee products arise from the presence of a unique composition of aromatic amino acids, vitamins, phenolic compounds and Maillard reaction products. In the 300–550 nm region of the emission spectra (excited at 280 nm), each of the tested bee products exhibited (showed) a specific and distinctive vibronic structure, which was not observed in the spectrum of artificial honey. Quantitative and qualitative composition as well as specific interactions between fluorescent constituents determine the specific fluorescence characteristics of a given bee product providing a unique fingerprint that can be used in the identification of bee products of different botanical origin. Combination of stationary and time-resolved fluorescence techniques seems to be a promising approach in the identification, authentication and quality control of bee products to verify their health-beneficial properties.

High Spatial Resolution Detector System Based on Reconfigurable Dual-FPGA Approach for Coincidence Measurements.

Time-resolved spectroscopic and electron-ion coincidence techniques are essential to study dynamic processes in materials or chemical compounds. For this type of analysis, it is necessary to have detectors capable of providing, in addition to image-related information, the time of arrival for each individual detected particle ("x, y, time"). The electronics capable of handling such sensors must meet requirements achievable only with time-to-digital converters (TDC) with a resolution on the order of tens of picoseconds and the use of a field-programmable gate array (FPGA) to manage data acquisition and transmission. This study introduces the design and implementation of an innovative TDC based on two FPGAs working symbiotically with different tasks: the first (AMD/Xilinx Artix® 7) directly implements a TDC, aiming for a temporal precision of 12 picoseconds, while the second (Intel Cyclone® 10) manages the acquisition and connectivity with the external world. The TDC has been optimized to operate on eight channels (+ sync) simultaneously but is potentially extendable to a greater number of channels, making it particularly suitable for coincidence measurements where it is necessary to temporally correlate multiple pieces of information from various measurement systems.

Mechanistic Insights into Curvature Formation in Synthetic Vesicles.

The mimicking of natural lipid bilayers with synthetic amphiphilic systems is of great interest to researchers, as insights could lead to better understanding of the complexities of cell membranes, as well as new materials and healthcare technologies. Recapitulating natural lipid asymmetry across bilayer membranes has important implications for curvature in cell, vesicle, and organelle morphologies, but has been challenging to achieve with synthetic lipid combinations or standard amphiphilic block copolymers. In a recent article, Elizebath et al. report the synthesis of a new type of synthetic amphiphile able to dynamically induce asymmetry in an artificially bilayer membrane. The molecules were designed around an extended π-conjugated hydrophobic core with tertiary amine terminated oxyalkylene side chains. Protonation of the tertiary amines on the bilayer exterior leads to curvature induction, bilayer fission, and vesicle formation as monitored by time resolved spectroscopy techniques and microscopy. The results were further validated with density functional theory (DFT) calculations. The delicate balance between different molecular scale interactions in the supramolecular structures led to the dynamic transformation of the bilayer membranes. Insights described could be used to advance the assembly of hierarchical life-like materials.

Raman Vibrational Signatures of Excited States of Echinenone in the Orange Carotenoid Protein (OCP) and Implications for its Photoactivation Mechanism

In this study, the vibrational characteristics of optically excited echinenone in various solvents and the Orange Carotenoid Protein (OCP) in red and orange states are systematically investigated through steady-state and time-resolved spectroscopy techniques. Time-resolved experiments, employing both Transient Absorption (TA) and Femtosecond Stimulated Raman Spectroscopy (FSRS), reveal different states in the OCP photoactivation process. The time-resolved studies indicate vibrational signatures of exited states positioned above the S1 state during the initial 140 fs of carotenoid evolution in OCP, an absence of a vibrational signature for the relaxed S1 state of echinenone in OCP, and more robust signatures of a highly excited ground state (GS) in OCP. Differences in S1 state vibration population signatures between OCP and solvents are attributed to distinct conformations of echinenone in OCP and hydrogen bonds at the keto group forming a short-lived intramolecular charge transfer (ICT) state. The vibrational dynamics of the hot GS in OCP show a more pronounced red shift of ground state CC vibration compared to echinenone in solvents, thus suggesting an unusually hot form of GS. The study proposes a hypothesis for the photoactivation mechanism of OCP, emphasizing the high level of vibrational excitation in longitudinal stretching modes as a driving force. In conclusion, the comparison of vibrational signatures reveals unique dynamics of energy dissipation in OCP, providing insights into the photoactivation mechanism and highlighting the impact of the protein environment on carotenoid behavior. The study underscores the importance of vibrational analysis in understanding the intricate processes involved in early phase OCP photoactivation.

Practical Method for Achieving Single-Photon Femtosecond Time-Resolved Spectroscopy: Transient Stimulated Emission.

Recent advances in single-photon femtosecond spectroscopy have highlighted the power of entangled photons in probing the properties of materials, previously inaccessible through semiclassical spectroscopic approaches. In this study, we theoretically propose a new single-photon-based femtosecond time-resolved spectroscopy technique termed single-photon transient stimulated emission (SP-TSE). SP-TSE not only enables the selective investigation of singly excited superposition states but also harnesses the quantum mechanical nature of photons for the efficient data acquisition of transient responses, thereby supporting the feasibility of experimental realization of SP-TSE. The key aspect of SP-TSE is the selective detection of two-photon states produced through stimulated emission using coincidence counting techniques. Our theoretical framework, supported by numerical simulations, demonstrates the efficacy in capturing the pure decoherence dynamics of a model molecular cavity, highlighting its potential to reveal quantum mechanical properties that are difficult to observe with semiclassical femtosecond time-resolved experiments.

Regioisomerism vs Conformation: Impact of Molecular Design on the Emission Pathway in Organic Light-Emitting Device Emitters.

Despite the design and proposal of several new structural motifs as thermally activated delayed fluorescent (TADF) emitters for organic light-emitting device (OLED) applications, the nature of their interaction with the host matrix in the emissive layer of the device and their influence on observed photophysical outputs remain unclear. To address this issue, we present, for the first time, the use of up to four regioisomers bearing a donor-acceptor-donor electronic structure based on the desymmetrized naphthalene benzimidazole scaffold, equipped with various electron-donating units and possessing distinguished conformational lability. Quantum chemical calculations allow us to identify the most favorable conformations adopted by the electron-rich groups across the entire pool of regioisomers. These conformations were then compared with conformational changes caused by the interaction of the emitter with the Zeonex and 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP) matrices, and the correlation with observed photophysics was monitored by UV-vis absorption and steady-state photoluminescence spectra, combined with time-resolved spectroscopic techniques. Importantly, a CBP matrix was found to have a significant impact on the conformational change of regioisomers, leading to unique TADF emission mechanisms that encompass dual emission and inversion of the singlet-triplet excited-state energies and result in the enhancement of TADF efficiency. As a proof of concept, regioisomers with optimal donor positions were utilized to fabricate an OLED, revealing, with the best-performing dye, an external quantum emission of 11.6%, accompanied by remarkable luminance (28,000 cd/m2). These observations lay the groundwork for a better understanding of the role of the host matrix. In the long term, this new knowledge can lead to predicting the influence of the host matrix and adopting the structure of the emitter in a way that allows the development of highly efficient and efficient OLEDs.

Critical Assessment of Micellar Surface Charge-Dependent Disaggregation and Reaggregation of a Bis-Indole Self-Aggregate: What Should Be Our Case-Dependent Choice?

"Aggregation-caused quenching" is a deep-seated mechanism and has been widely used by the researchers as the possible basis for new sensor development. Contrast to aggregation, its turn around process, disaggregation, has gained much less consideration so far. Unfortunately, study of the further scope for reaggregation of the disaggregated probe assembly in the same solution, as and when required, is still under the rare category. The central theme of the current study is focused on this aspect. For this purpose, the effects of headgroup charge (cationic, anionic, and nonionic) and polarity of the micelles on the degree of disaggregation and subsequent emission amelioration of a synthesized bis-indole derivative, 3,3'-bisindolyl(phenyl)methane (BIPM), are studied using steady-state and time-resolved spectroscopic techniques. The relative emission yield of BIPM (φf = 0.01) is significantly enhanced in the presence of cetyltrimethylammonium bromide (φf = 0.21) and polyoxyethylene (20) sorbitan monolaurate (φf = 0.24), whereas comparatively less emission enhancement is recorded within the sodium dodecyl sulfate system (φf = 0.07). In contrast, addition of an external biophilic agent, uric acid, causes requenching of the enhanced emission because of the reaggregation of the disaggregated probes. Detailed microscopic and calorimetric studies are also adopted to investigate the disaggregation-reaggregation mechanism of BIPM associations. The study will provide prior insights about the use of suitable micellar systems for the required degree of disaggregation as well as for the modulation of emission efficiency by controlled tuning of the disaggregation-reaggregation equilibrium for similar probe associations in pure aqueous medium avoiding any chemical transformation.

Investigation of the Excited-State Electron Transfer and Cage Escape Yields Between Halides and a Fe(III) Photosensitizer.

Excited-state quenching and reduction of [Fe(phtmeimb)2]+, where phtmeimb is phenyl[tris(3-methyl-imidazolin-2-ylidene)]borate, with iodide, bromide, and chloride were studied in dichloromethane, acetonitrile, and acetonitrile/water 1:1 mixture by means of steady-state and time-resolved spectroscopic techniques. Quenching rate constants were almost diffusion-limited in dichloromethane and acetonitrile and followed the expected periodic trend, i.e., I- > Br- > Cl-. Confirmation of excited-state reductive electron transfer was only unambiguously obtained when iodide was used as a quencher. The cage escape yields, i.e., the separation of the geminate radical pair formed upon bimolecular excited-state electron transfer, were determined. These yields were larger in dichloromethane (0.079) than in acetonitrile (0.017), and no photoproduct could be observed in acetonitrile/water 1:1. This study further emphasizes that solvents with low dielectric constant are more suited for productive excited-state electron transfer using Fe(III) photosensitizers with 2LMCT excited state.

Shell thickness influence on the carrier dynamics of InP/ZnS QDs

InP/ZnS core/shell quantum dots (QDs) have been widely applied in many fields due to their excellent luminescence performance. In this study, the correlation between the ZnS shell thickness and the ultrafast carrier dynamics in InP/ZnS QDs was investigated by using femtosecond time-resolved transient absorption spectroscopy and time-resolved photoluminescence techniques. We found that a thicker ZnS shell could confine more carriers to the InP core, thus effectively weakening the interactions between the carriers in the core and the interfacial defect states; this further enhanced the quantum yields and photoluminescence properties in InP/ZnS QDs.

Charge Trapping in Semiconductor Photocatalysts: A Time- and Space-Domain Perspective.

Harnessing solar energy to produce value-added fuels and chemicals through photocatalysis techniques holds promise for establishing a sustainable and environmentally friendly energy economy. The intricate dynamics of photogenerated charge carriers lies at the core of the photocatalysis. The balance between charge trapping and band-edge recombination has a crucial influence on the activity of semiconductor photocatalysts. Consequently, the regulation of traps in photocatalysts becomes the key to optimizing their activities. Nevertheless, our comprehension of charge trapping, compared to that of well-studied charge recombination, remains somewhat limited. This limitation stems from the inherently heterogeneous nature of traps at both temporal and spatial scales, which renders the characterization of charge trapping a formidable challenge. Fortunately, recent advancements in both time-resolved spectroscopy and space-resolved microscopy have paved the way for considerable progress in the investigation and manipulation of charge trapping. In this Perspective, we focus on charge trapping in photocatalysts with the aim of establishing a direct link to their photocatalytic activities. To achieve this, we begin by elucidating the principles of advanced time-resolved spectroscopic techniques such as femtosecond time-resolved transient absorption spectroscopy and space-resolved microscopic methods, such as single-molecule fluorescence microscopy and surface photovoltage microscopy. Additionally, we provide an overview of noteworthy research endeavors dedicated to probing charge trapping using time- and space-resolved techniques. Our attention is then directed toward recent achievements in the manipulation of charge trapping in photocatalysts through defect engineering. Finally, we summarize this Perspective and discuss the future challenges and opportunities that lie ahead in the field.

DFT, real sample and smartphone studies of fluorescent probe, N-doped carbon quantum dots for sensitive and selective detection of bilirubin

In this investigation, nitrogen-doped carbon quantum dots (NCQDs) were successfully synthesized, showcasing robust fluorescence characteristics and photostability. These NCQDs demonstrated biocompatibility and were utilized as effective sensing agents for bilirubin (BR) detection. Their remarkable Stern-Volmer constant, attributed to exceptional molar absorptivity and photoluminescence quantum yield, rendered them highly proficient in BR sensing. Various analytical techniques such as X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) were employed to characterize the synthesized NCQDs, providing comprehensive insights into their structural, elemental, chemical composition, particle size, morphology, and optical properties. For sensing purposes, UV–Vis, steady-state, and time-resolved fluorescence spectroscopic techniques were utilized. The average particle size of the NCQDs was determined to be approximately 4.5 ± 0.3 nm. Notably, the Stern-Volmer constant (Ksv) for BR sensing from these quantum dots surpassed previously reported values in the literature. A linear relationship between emission intensity ratio and BR concentration within a range of 1.35–14.20 μM was observed. Accurate quantification of BR was achieved with a high Stern-Volmer constant (Ksv) S11 of approximately 7.48 × 105 M-1 and a limit of detection (LOD) of 4.86 μM. Leveraging the NCQDs as fluorescent probes, a highly sensitive and selective BR detection method based on the Förster resonance energy transfer (FRET) mechanism was established, with emission occurring at 360 nm. Density functional theory (DFT) studies supported FRET as the primary mechanism for fluorescence quenching, indicating electron transfer from NCQDs to BR, as evidenced by the energies of the lowest unoccupied molecular orbitals (LUMOs) of both NCQDs and BR. Real sample analyses of BR levels in human serum yielded a recovery range of 94.8 % to 104.21 %, validating the practical applicability of the method. Furthermore, smartphone-based BR detection using NCQDs achieved an LOD of 11.74 µM.

In-situ and operando Grazing Incidence XAS: a novel set-up and its application to model Pd electrodes for alcohols oxidation

Abstract In this article, we present an in-situ and operando time-resolved X-ray Absorption Spectroscopy (XAS) technique which exploits a combination of Grazing Incidence XAS (GIXAS) and Fixed Energy X-ray Absorption Voltammetry (FEXRAV), the Grazing Incidence FEXRAV (GI-FEXRAV). A case-study is also outlined. Palladium ultra-low loadings were deposited above Au polycrystalline iso-oriented substrates adopting three different deposition methods: surface-controlled electrochemical methods, direct electrodeposition, and physical vapour deposition (PVD). These catalytical surfaces were prepared for the investigation by GI-FEXRAV of the Pd oxidation/dissolution phenomenon that could occur when the metal is used in the anodic compartment of Direct Alcohol Fuel Cells (DAFCs) or in electrochemical reformers. Moreover, we report a robust, low cost and versatile procedure to obtain wide and flat iso-oriented gold substrates that can mimic monocrystalline gold (1 1 1) in the electrochemical response. The use of GI-FEXRAV for the operando characterization of the catalysts, in conjunction with the designed experimental cell and our flexible Au-based electrochemical substrates show an invaluable potential in the operando study of fundamental phenomena in heterogeneous electrocatalysis model systems and, due to its versatility, paves the way to further studies on a wide selection of electrochemical systems.

Spatially and Temporally Resolved Dynamic Response of Co-Based Composite Interface during the Oxygen Evolution Reaction.

Interfacial interaction dictates the overall catalytic performance and catalytic behavior rules of the composite catalyst. However, understanding of interfacial active sites at the microscopic scale is still limited. Importantly, identifying the dynamic action mechanism of the "real" active site at the interface necessitates nanoscale, high spatial-time-resolved complementary-operando techniques. In this work, a Co3O4 homojunction with a well-defined interface effect is developed as a model system to explore the spatial-correlation dynamic response of the interface toward oxygen evolution reaction. Quasi in situ scanning transmission electron microscopy-electron energy-loss spectroscopy with high spatial resolution visually confirms the size characteristics of the interface effect in the spatial dimension, showing that the activation of active sites originates from strong interfacial electron interactions at a scale of 3 nm. Multiple time-resolved operando spectroscopy techniques explicitly capture dynamic changes in the adsorption behavior for key reaction intermediates. Combined with density functional theory calculations, we reveal that the dynamic adjustment of multiple adsorption configurations of intermediates by highly activated active sites at the interface facilitates the O-O coupling and *OOH deprotonation processes. The dual dynamic regulation mechanism accelerates the kinetics of oxygen evolution and serves as a pivotal factor in promoting the oxygen evolution activity of the composite structure. The resulting composite catalyst (Co-B@Co3O4/Co3O4 NSs) exhibits an approximately 70-fold turnover frequency and 20-fold mass activity than the monomer structure (Co3O4 NSs) and leads to significant activity (η10 ∼257 mV). The visual complementary analysis of multimodal operando/in situ techniques provides us with a powerful platform to advance our fundamental understanding of interfacial structure-activity relationships in composite structured catalysts.

Controlling Excited State Localization in Bichromophoric Photosensitizers via the Bridging Group.

A series of photosensitizers comprised of both an inorganic and an organic chromophore are investigated in a joint synthetic, spectroscopic, and theoretical study. This bichromophoric design strategy provides a means by which to significantly increase the excited state lifetime by isolating the excited state away from the metal center following intersystem crossing. A variable bridging group is incorporated between the donor and acceptor units of the organic chromophore, and its influence on the excited state properties is explored. The Franck-Condon (FC) photophysics and subsequent excited state relaxation pathways are investigated with a suite of steady-state and time-resolved spectroscopic techniques in combination with scalar-relativistic quantum chemical calculations. It is demonstrated that the presence of an electronically conducting bridge that facilitates donor-acceptor communication is vital to generate long-lived (32 to 45 μs), charge-separated states with organic character. In contrast, when an insulating 1,2,3-triazole bridge is used, the excited state properties are dominated by the inorganic chromophore, with a notably shorter lifetime of 60 ns. This method of extending the lifetime of a molecular photosensitizer is, therefore, of interest for a range of molecular electronic devices and photophysical applications.

Evidence of Excited-State Vibrational Mode Governing the Photorelaxation of a Charge-Transfer Complex.

Modern, nonlinear, time-resolved spectroscopic techniques have opened new doors for investigating the intriguing but complex world of photoinduced ultrafast out-of-equilibrium phenomena and charge dynamics. The interaction between light and matter introduces an additional dimension, where the complex interplay between electronic and vibrational dynamics needs the most advanced theoretical-computational protocols to be fully understood on the molecular scale. In this study, we showcase the capabilities of ab initio molecular dynamics simulation integrated with a multiresolution wavelet protocol to carefully investigate the excited-state relaxation dynamics in a noncovalent complex involving tetramethylbenzene (TMB) and tetracyanoquinodimethane (TCNQ) undergoing charge transfer (CT) upon photoexcitation. Our protocol provides an accurate description that facilitates a direct comparison between transient vibrational analysis and time-resolved spectroscopic signals. This molecular level perspective enhances our understanding of photorelaxation processes confined in the adiabatic regime and offers an improved interpretation of vibrational spectra. Furthermore, it enables the quantification of anharmonic vibrational couplings between high- and low-frequency modes, specifically the TCNQ "rocking" and "bending" modes. Additionally, it identifies the primary vibrational mode that governs the adiabaticity between the ground state and the CT state. This comprehensive understanding of photorelaxation processes holds significant importance in the rational design and precise control of more efficient photovoltaic and sensor devices.

C3-Symmetric Indole-Based Truxenes: Design, Synthesis, and Photophysical Studies.

In recent years, truxenes and related polyaromatic hydrocarbons (PAHs) have engrossed ample interest of the scientific community because of their ease of synthesis, functionalizations, and use as building blocks for the synthesis of fullerene fragments, liquid crystals, larger polyarenes, and C3-tripod materials. In the present work, we have disclosed an ingenious method for the construction of various indolo-truxene hybrid molecules in good yields (52-90%), by means of the acid-catalyzed cotrimerization, Friedel-Crafts acylation, and Fischer indole synthesis, and fully characterized them through the standard spectroscopic techniques. The photophysical properties of the thus-prepared compounds have also been investigated using steady-state absorption and fluorescence and time-resolved fluorescence spectroscopy techniques. Moreover, the density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations have been studied to correlate them with the measured photophysical properties of the synthesized indolo-truxene derivatives.

Highly efficient upconversion photodynamic performance of rare-earth-coupled dual-photosensitizers: ultrafast experiments and excited-state calculations

Abstract Upconversion photodynamic therapy (UC-PDT), which integrates upconversion nanoparticles (UCNPs) with photosensitizers (PSs), presents a promising advancement in the field of phototherapy. However, despite the extensive studies focused on the design and synthesis of UCNPs, there is a paucity of systematic research on the mechanisms underlying the synergistic upconversion photodynamic effects. Here we have synthesized upconversion core@dotted-shell nanoparticles (CDSNPs) and covalently tethered them with two distinct PSs, thereby constructing a dual-PS UC-PDT system with high synergistic photodynamic performance. To unravel the mechanism underlying the synergism, we employed a combination of quantum mechanical calculations and ultrafast time-resolved spectroscopy techniques. The results indicate that rare earth oxides play a pivotal role in enhancing the intersystem crossing processes of PSs through modulating their excited electronic states. Additionally, Förster resonance energy transfer between two distinct PSs contributes to the amplification of triplet state populations, thus further enhancing the photodynamic effect. In vitro experiments demonstrate that the prepared CDSNPs based dual-PS system exhibits excellent biocompatibility with normal cells and exceptional synergistic photodynamic efficacy against tumor cells upon near-infrared excitation. This research contributes theoretical insights into the design and application of multi-photosensitizer UC-PDT systems, laying the groundwork for more efficient preclinical implementations in the future.

Tunneling-Driven Marcus-Inverted Triplet Energy Transfer in a Two-Dimensional Perovskite.

Quantum tunneling, a phenomenon that allows particles to pass through potential barriers, can play a critical role in energy transfer processes. Here, we demonstrate that the proper design of organic-inorganic interfaces in two-dimensional (2D) hybrid perovskites allows for efficient triplet energy transfer (TET), where quantum tunneling of the excitons is the key driving force. By employing temperature-dependent and time-resolved photoluminescence and pump-probe spectroscopy techniques, we establish that triplet excitons can transfer from the inorganic lead-iodide sublattices to the pyrene ligands with rapid and weakly temperature-dependent characteristic times of approximately 50 ps. The energy transfer rates obtained based on the Marcus theory and first-principles calculations show good agreement with the experiments, indicating that the efficient tunneling of triplet excitons within the Marcus-inverted regime is facilitated by high-frequency molecular vibrations. These findings offer valuable insights into how one can effectively manipulate the energy landscape in 2D hybrid perovskites for energy transfer and the creation of diverse excitonic states.

Insight into the anti-proliferation activity and photoinduced NO release of four nitrosylruthenium isomeric complexes and their HSA complex adducts.

Four Ru(II)-centered isomeric complexes [RuCl(5cqn)(Val)(NO)] (1-4) were synthesized with 5cqn (5-chloro-8-hydroxyquinoline) and chiral Val (Val=L- or D-valine) as co-ligand, and their structures were confirmed using the X-ray diffraction method. The cytotoxicity and photodynamic activity of the isomeric complexes and their human serum albumin (HSA) complex adducts were evaluated. Both the isomeric complexes and their HSA complex adducts significantly affected HeLa cell proliferation, with an IC50 value in the range of 0.3-0.5μM. The photo-controlled release of nitric oxide (NO) in solution was confirmed using time-resolved Fourier transform infrared and electron paramagnetic resonance spectroscopy techniques. Furthermore, photoinduced NO release in living cells was observed using a selective fluorescent probe for NO. Moreover, the binding constants (Kb) of the complexes with HSA were calculated to be 0.17-1.98×104 M-1 and the average number of binding sites (n) was found to be close to 1, it can serve as a crucial carrier for delivering metal complexes. The crystal structure of the HSA complex adduct revealed that one [RuCl(H2O)(NO)(Val)]+ molecule binds to a pocket in domain I. This study provides insight into possible mechanism of metabolism and potential applications for nitrosylruthenium complexes.