Electronic Relaxation Research Articles

Thieno[3,4-d]pyrimidin-4(3H)-thione: an effective, oxygenation independent, heavy-atom-free photosensitizer for cancer cells.

All-organic, heavy-atom-free photosensitizers based on thionation of nucleobases are receiving increased attention because they are easy to make, noncytotoxic, work both in the presence and absence of molecular oxygen, and can be readily incorporated into DNA and RNA. In this contribution, the DNA and RNA fluorescent probe, thieno[3,4-d]pyrimidin-4(1H)-one, has been thionated to develop thieno[3,4-d]pyrimidin-4(3H)-thione, which is nonfluorescent and absorbs near-visible radiation with about 60% higher efficiency. Steady-state absorption and emission spectra are combined with transient absorption spectroscopy and CASPT2 calculations to delineate the electronic relaxation mechanisms of both pyrimidine derivatives in aqueous and acetonitrile solutions. It is demonstrated that thieno[3,4-d]pyrimidin-4(3H)-thione efficiently populates the long-lived and reactive triplet state generating singlet oxygen with a quantum yield of about 80% independent of solvent. It is further shown that thieno[3,4-d]pyrimidin-4(3H)-thione exhibits high photodynamic efficacy against monolayer melanoma cells and cervical cancer cells both under normoxic and hypoxic conditions. Our combined spectroscopic, computational, and in vitro data demonstrate the excellent potential of thieno[3,4-d]pyrimidin-4(1H)-thione as a heavy-atom-free PDT agent and paves the way for further development of photosensitizers based on the thionation of thieno[3,4-d]pyrimidine derivatives. Collectively, the experimental and computational results demonstrate that thieno[3,4-d]pyrimidine-4(3H)-thione stands out as the most promising thiobase photosensitizer developed to this date.

Strong anharmonicity and high thermoelectric performance of cubic thallium-based fluoride perovskites TlXF3 (X = Hg, Sn, Pb).

State-of-the-art first-principles calculations are performed to investigate the thermoelectric transport properties in thallium-based fluoride perovskites TlXF3 (X = Hg, Sn, Pb) by considering anharmonic renormalization of the phonon energy and capturing reasonable electron relaxation times. The lattice thermal conductivity, κL, of the three compounds is very low, among which TlPbF3 is only 0.42 W m-1 K-1 at 300 K, which is less than half of that of quartz glass. The low acoustic mode group velocity and strong three-phonon scattering caused by the strong anharmonicity of the Tl atom are the origin of the ultralow κL. Meanwhile, the strong ionic bonds between X (X = Hg, Sn, Pb) and F atoms provide good electrical transport properties. The results show that the ZT value of TlHgF3 at 900 K is 1.58, which is higher than the 1.5 value of FeNbSb at 1200 K. TlSnF3 and TlPbF3 also exceed 1, which is close to the classical thermoelectric material PbTe:Na. Furthermore, we present the methods and expected effects of improving the ZT value through nanostructures.

Reduced electron relaxation time of perovskite films via g-C3N4 quantum dot doping for high-performance perovskite solar cells.

Perovskite film-quality is a crucial factor to improve the photovoltaic properties of perovskite solar cells, which is closely related to the morphology of crystallization grain size of the perovskite layer. However, defects and trap sites are inevitably generated on the surface and at the grain boundaries of the perovskite layer. Here, we report a convenient method for preparing dense and uniform perovskite films, employing g-C3N4 quantum dots doped into the perovskite layer by regulating proper proportions. This process produces perovskite films with dense microstructures and flat surfaces. As a result, the higher fill factor (0.78) and a power conversion efficiency of 20.02% are obtained by the defect passivation of g-C3N4QDs.

Experimental Study on the Influence of Different Loading Rates on Fatigue Mechanical Properties of Sandstone

Underground rock engineering often encounters long-term cyclic loading and unloading. Under the influence of this effect, the mechanical characteristics of rocks will inevitably change, which will affect the stability and safety of underground engineering. Therefore, it is necessary to study the fatigue characteristics of rocks under a certain period of action. With an RDL series electronic creep relaxation testing machine, fatigue loading and unloading tests of sandstone at different loading rates were carried out, followed by uniaxial compression on the samples. The study shows that the stress–strain curves of the uniaxial compression specimens have three stages: a compaction pore fracture stage, an elastic deformation stage, and an unstable fracture developing to failure stage. The stress–strain curves of the samples with a certain number of cycles of loading and unloading give the thinning and dense phenomenon, and the axial upper limit strain and axial cumulative residual strain gradually decrease as the loading rate increases. With the increase, the uniaxial compressive strength of the reloaded samples increases gradually, which is higher than the ordinary uniaxial compressive strength. In the process of cyclic loading and unloading, the internal particles of the sample present fracture and reorganization of the fragile structure and, at the same time, compaction stability.

Competitive sensitization effect towards Luminescence-tuned Lanthanide-doped TiO2/SiO2 Core-shell nanoparticles for enhanced responsivity oxygen detection

The luminescence of TiO2 doped with Sm3+ can be excited through TiO2 band-to-band absorption, which exhibits oxygen sensitivity. However, its carrier behaviors and oxygen sensing mechanism have not yet been clarified, which inhibits the further improvement of sensitivity. In this study, using Eu3+ ions as an “energy level probe,” we demonstrated a novel strategy using a C@SiO2:2%Sm3+@TiO2 hollow double-shell nanostructure containing surface oxygen vacancies, designated a competitive sensitization effect for the first time. Density-functional theory combined with the experimental results revealed the carrier behaviors and oxygen sensing mechanism. Further, we demonstrated that the charge state of oxygen vacancies is controlled by the adsorption and desorption of dioxygen molecules, which affects electron relaxation and indirectly affects the luminescent behaviors. The effective exploitation of the competitive sensitization effect and revelation of the oxygen sensing mechanism ensured that the excitation of Sm3+ in C@SiO2:2%Sm3+@TiO2 can be controlled by the ambient oxygen concentration. Therefore, compared to the widely reported Sm3+-doped TiO2, C@SiO2:2%Sm3+@TiO2 demonstrated increased oxygen sensitivity (by over three folds) with a detection minimum of sub-100 ppm. Moreover, as ambient oxygen concentration changes, the luminescence color of the films prepared by using C@SiO2:2%Sm3+@TiO2 and commercial blue phosphors changes significantly (from pink to blue).

THz Surface Plasmons in Wide and Freestanding Graphene Nanoribbon Arrays

Graphene is a thin-film carbon material that has immense potential as a key ingredient in new nanoelectronic and nanophotonic devices due to its unique characteristics. In particular, plasmons in graphene appear as a practical tool for the manipulation of light with potential applications from cancer treatment to solar cells. A motivating tunability of graphene properties has been observed in graphene nanoribbons (GNRs) due to their geometrically controllable bandgaps that, in turn, influence the plasmonic properties. The formidable effort made over recent years in developing GNR-based technologies is, however, weakened by a lack of predictive approaches that draw upon available semi-analytical electromagnetic models. An example of such a framework is used here, focusing on experimentally realized GNRs from 155 to 480 nm wide and organized as two-dimensional (2D) GNR arrays. The results show that the plasmon frequency behavior is highly affected by the experimental setup or geometrical factors. In particular, the bandgap of the analyzed systems is of the order of a few meV with a density of states opening around zero energy (Fermi level) in contrast to what is observed in graphene. From the plasmonic part, it is observed in all 2D GNR arrays that the frequency–momentum trend follows a q-like plasmon dispersion whose plasmon frequency can be increased substantially by increasing the ribbon width or charge density concentration. Forbidden plasmon regions are observed for high values of plasmon excitation angle or electron relaxation rate. From a sensing point of view, the important finding is the fact that 2D GNR arrays of 155 nm wide with high values of electron relaxation rate have plasmon responses similar to those observed for α−thrombin in water. Our predictions are projected to be of fast support for detecting plasmons in more complex designs of ribbon nanodevices with potential applications in molecular sensing of aqueous molecules.

Four-Photon Absorption Iron Complex for Magnetic Resonance/Photoacoustic Dual-Model Imaging and an Enhanced Ferroptosis Process.

Four-photon absorption (4PA) multimodal therapeutic agent applied to tumor ferroptosis process tracking is rarely reported. In this paper, two functionalized terpyridine iron complexes (TD-FeCl3, TD-Fe-TD) with four-photon absorption properties were designed and synthesized. The four-photon absorption cross sections of TD-FeCl3 reached 6.87 × 10-74cm8·s3·photon-3. Due to its strong near-infrared absorption, TD-FeCl3 has excellent photoacoustic imaging (PAI) capability for accurate PA imaging. TD-FeCl3 has an efficient longitudinal electron relaxation rate (r1 = 2.26 mM-1 s-1) and high spatial resolution, which can be applied as T1-weighted magnetic resonance imaging (MRI) contrast agent for tumor imaging in vivo. In addition, Fe3+ as a natural ferroptosis tracer, TD-FeCl3, is able to deplete glutathione (GSH) effectively, which can further enhance the ferroptosis process. We found that the series of cheap transition metal complexes has four-photon absorption activity and can be used as multimodal (MRI/PAI) diagnostic agents for tumor tracing processes.

Quantum efficiency, photoemission energy spectra, and mean transverse energy of ultrananocrystalline diamond photocathode

The quantum efficiency and mean transverse energy of electrons emitted from a cathode determine the quality of beams generated from photoinjectors. The nitrogen-incorporated ultrananocrystalline diamond, (N)UNCD, is a new class of robust semiconductor photocathodes, which has been considered in photoinjectors for high peak current extraction. In this work, we measure the spectral response in quantum efficiency, photoemission energy spectra, and mean transverse energy of the (N)UNCD photocathode using a photoemission electron microscope. The observed quantum efficiency was comparable to that of copper photocathodes. Photoemission spectra showed the evidence of scattering of electrons before emission. This relaxation of electrons due to scattering is also observed in the spectral response of the mean transverse energy. The mean transverse energy is limited to ∼70 meV at the threshold. We attribute this to the physical and chemical roughness of the (N)UNCD photocathode and, hence, smoother films will be required to further reduce the mean transverse energy obtained from the (N)UNCD photocathode.

Photo-Responded Antibacterial Therapy of Reinfection in Percutaneous Implants by Nanostructured Bio-Heterojunction.

Percutaneous implants may experience infection for several times during their servicing periods. They need antibacterial activity and durability to reduce recurrent infection and cytocompatibility to reconstruct biosealing. A novel photoresponse bio-heterojunction (PCT) is developed herein. It consists of TiO2 nanotubes loaded with CuS nanoparticles and wrapped with polydopamine (PDA) layer. In PCT, a built-in electric field directing from TiO2 to CuS and then to PDA is formed, and with near-infrared (NIR) irradiation, it drives photoexcited electrons to transfer in opposite direction, resulting in the separation of electron-hole pairs and formation of reactive oxygen species (ROS). Simultaneously, PCT shows photothermal effect due to nonradiative relaxation of photoexcited electrons and thermal vibration of lattices. The synergic effect of photogenerated ROS and hyperthermia increases bacterial membrane permeability and leakage of cellular components, endowing PCT with outstanding antibacterial performance. More importantly, PCT has good antibacterial durability and cytocompatibility due to the inhibited leaching of CuS by PDA layer. In reinfected models, with NIR irradiation, PCT sterilizes bacteria, reduces inflammatory response and enhances re-integration of soft tissue efficiently. This work provides an outstanding bio-heterojunction for percutaneous implants in treating reinfection by NIR irradiation and rebuilding biosealing.

Efficient Hot Electron Transfer and Extended Separation of Charge Carriers at the 1P Hot State in Sb2Se3/CdSe p-n Heterojunction.

Utilization of hot carriers is very crucial in improving the efficiency of solar energy devices. In this work, we have fabricated an Sb2Se3/CdSe p-n heterojunction via a cation exchange method and investigated the possibility of hot electron transfer and relaxation pathways through ultrafast spectroscopy. The enhanced intensity of the CdSe hot excitonic (1P) bleach in the heterostructure system confirmed the hot electron transfer from Sb2Se3 to CdSe. Both the 1S and 1P signals are dynamically very slow in the heterosystem, validating this charge migration phenomenon. Interestingly, recovery of the 1P signal is much slower than that of 1S. This is very unusual as 1S is the lowest-energy state. This observation indicates the strength of hot electron transfer in this unique heterojunction, which helps in increasing the carrier lifetime in the hot state. Extended separation of charge carriers and enhanced hot carrier lifetime would be extremely helpful in extracting carriers and boost the performance of optoelectronic devices.

Spectral and kinetic properties of silver sulfide quantum dots in an external electric field

The effect of an external electric field on the luminescence characteristics of silver sulfide nanoparticles embedded in a film based on an optically passive dielectric matrix has been studied. The luminescence characteristics were studied using methods of optical and time-resolved spectroscopy involving the time-correlated single-photon counting technique. The morphology of the nanoparticles was studied using transmission electron microscopy. It was shown that in an external electric field, an increase in the intensity of the recombination luminescence band is observed for silver sulfide nanoparticles, together with an increase in the electronic relaxation rate. This effect is explained by the fact that the electric field enhances the transport of free holes to electron traps which are radiative recombination centers. The observed effects indicate that silver sulfide nanoparticles can be effectively used as active layers of organic light-emitting diodes, where an external field of the order of 500 kV/cm will not lead to a deterioration in their operating luminescence characteristics.

Observation of a transient intermediate in the ultrafast relaxation dynamics of the excess electron in strong-field-ionized liquid water

A unified picture of the electronic relaxation dynamics of ionized liquid water has remained elusive despite decades of study. Here, we employ sub-two-cycle visible to short-wave infrared pump-probe spectroscopy and ab initio nonadiabatic molecular dynamics simulations to reveal that the excess electron injected into the conduction band (CB) of ionized liquid water undergoes sequential relaxation to the hydrated electron s ground state via an intermediate state, identified as the elusive p excited state. The measured CB and p-electron lifetimes are 0.26 ± 0.02 ps and 62 ± 10 fs, respectively. Ab initio quantum dynamics yield similar lifetimes and furthermore reveal vibrational modes that participate in the different stages of electronic relaxation, with initial relaxation within the dense CB manifold coupled to hindered translational motions whereas subsequent p-to-s relaxation facilitated by librational and even intramolecular bending modes of water. Finally, energetic considerations suggest that a hitherto unobserved trap state resides ~0.3-eV below the CB edge of liquid water. Our results provide a detailed atomistic picture of the electronic relaxation dynamics of ionized liquid water with unprecedented time resolution.

Design Principles of Responsive Relaxometric 19F Contrast Agents: Evaluation from the Point of View of Relaxation Theory and Experimental Data.

19F magnetic resonance imaging (MRI) is a promising tool in medical diagnostics. An important class of 19F MRI contrast agents is based on paramagnetic resonance enhancement. This effect allows an improvement in sensitivity by increasing the number of scans per unit of time or facilitates the development of responsive contrast agents that are based on changes in relaxation rates as a detection principle. In this work, Bloch-Redfield-Wangsness relaxation theory was used to predict the relaxation properties of existing lanthanoid and transition metal complexes of fluoroorganic ligands and to evaluate several design strategies for responsive contrast agents. Electron-nucleus dipole-dipole, Curie relaxation, and contact interactions were included in the model. Potential significance of chemical shift anisotropy-anisotropic dipolar shielding cross-correlation was discussed. The calculated and experimental results were well aligned. The presented model, along with the optimized field-dependent values of electronic relaxation times, could be used for the preliminary selection of the optimal metal ion for applications in 19F MRI. The results indicate potential advantages of other metal ions in addition to Gd3+ particularly Cu2+, Mn2+, Ni2+, Fe3+, and other lanthanoids as a part of 19F contrast agents.

Fast electron and slow hole spin relaxation in CsPbI3 nanocrystals

Spin-dependent properties of lead halide perovskites (LHPs) have recently gained significant attention paving their way toward spin-optoelectronic applications. However, separate measurements of the electron and hole spin relaxation rates are so far missing in LHPs. The knowledge of the electron and hole spin relaxation timescales is necessary to understand the spin-dependent properties of LHPs. Here, we report on the spin polarization dynamics in CsPbI3 nanocrystals (NCs). We employ polarization dependent ultrafast differential transmission spectroscopy (DTS) at room temperature to study the spin polarization dynamics in this system. In the case of pure CsPbI3 NCs, it is not possible to measure separately electron and hole spin relaxation rates from the polarization dependent DTS. Here, we introduce the soluble fullerene derivative PC60BM as an electron acceptor along with CsPbI3 to create an imbalance between the photoexcited electrons and holes in the NCs and, thus, affecting their spin-dependent carrier distribution. CsPbI3:PC60BM blend sample shows a distinct difference in the spin dependent kinetics of the DTS spectra as compared to the NCs-only sample. With the help of a kinetic model for the spin-dependent charge carrier distributions, we separately determine the electron and hole spin relaxation times in CsPbI3 NCs. We find that the room temperature hole spin lifetime (τh ∼ 5 ps) is ∼13 times longer than the electron spin lifetime (τe ∼ 0.4 ps). We ascribe the fast electron spin relaxation to the presence of strong spin–orbit coupling in the conduction band, which is ineffective for holes in the s-type valence band.

Multilayer atomic cluster expansion for semilocal interactions

Traditionally, interatomic potentials assume local bond formation supplemented by long-range electrostatic interactions when necessary. This ignores intermediate range multi-atom interactions that arise from the relaxation of the electronic structure. Here, we present the multilayer atomic cluster expansion (ml-ACE) that includes collective, semi-local multi-atom interactions naturally within its remit. We demonstrate that ml-ACE significantly improves fit accuracy compared to a local expansion on selected examples and provide physical intuition to understand this improvement.

Electron temperature relaxation in the clusterized ultracold plasmas

Ultracold plasmas are a promising candidate for the creation of strongly coupled Coulomb systems. Unfortunately, the values of the coupling parameter Γe actually achieved after photoionization of the neutral atoms remain relatively small because of the considerable intrinsic heating of the electrons. A conceivable way to get around this obstacle might be to utilize a spontaneous ionization of the ultracold Rydberg gas, where the initial kinetic energies could be much less. However, the spontaneous avalanche ionization will result in a very inhomogeneous distribution (clusterization) of the ions, which can change the efficiency of the electron relaxation in the vicinity of such clusters substantially. In the present work, this hypothesis is tested by an extensive set of numerical simulations. As a result, it is found that despite a less initial kinetic energy, the subsequent relaxation of the electron velocities in the clusterized plasmas proceeds much more violently than in the case of the statistically uniform ionic distribution. The electron temperature, first, experiences a sharp initial jump (presumably, caused by the “virialization” of energies of the charged particles) and, second, exhibits a gradual subsequent increase (presumably, associated with a multi-particle recombination of the electrons at the ionic clusters). As a possible tool to reduce the anomalous temperature increase, we also considered a two-step plasma formation, involving the blockaded Rydberg states. This leads to a suppression of the clusterization due to a quasi-regular distribution of ions. In such a case, according to the numerical simulations, the subsequent evolution of the electron temperature proceeds more gently, approximately with the same rate as in the statistically uniform ionic distribution.

The photoprotection mechanism in the black–brown pigment eumelanin

The natural black-brown pigment eumelanin protects humans from high-energy UV photons by absorbing and rapidly dissipating their energy before proteins and DNA are damaged. The extremely weak fluorescence of eumelanin points toward nonradiative relaxation on the timescale of picoseconds or shorter. However, the extreme chemical and physical complexity of eumelanin masks its photoprotection mechanism. We sought to determine the electronic and structural relaxation pathways in eumelanin using three complementary ultrafast optical spectroscopy methods: fluorescence, transient absorption, and stimulated Raman spectroscopies. We show that photoexcitation of chromophores across the UV-visible spectrum rapidly generates a distribution of visible excitation energies via ultrafast internal conversion among neighboring coupled chromophores, and then all these excitations relax on a timescale of ∼4 ps without transferring their energy to other chromophores. Moreover, these picosecond dynamics are shared by the monomeric building block, 5,6-dihydroxyindole-2-carboxylic acid. Through a series of solvent and pH-dependent measurements complemented by quantum chemical modeling, we show that these ultrafast dynamics are consistent with the partial excited-state proton transfer from the catechol hydroxy groups to the solvent. The use of this multispectroscopic approach allows the minimal functional unit in eumelanin and the role of exciton coupling and excited-state proton transfer to be determined, and ultimately reveals the mechanism of photoprotection in eumelanin. This knowledge has potential for use in the design of new soft optical components and organic sunscreens.

Di-Pyridine-Containing Macrocyclic Triamide Fe(II) and Ni(II) Complexes as ParaCEST Agents.

Fe(II) and Ni(II) paraCEST contrast agents containing the di-pyridine macrocyclic ligand 2,2',2″-(3,7,10-triaza-1,5(2,6)-dipyridinacycloundecaphane-3,7,10-triyl)triacetamide (DETA) are reported here. Both [Fe(DETA)]2+ and [Ni(DETA)]2+ complexes were structurally characterized. Crystallographic data revealed the seven-coordinated distorted pentagonal bipyramidal geometry of the [Fe(DETA)]·(BF4)2·MeCN complex with five coordinated nitrogen atoms from the macrocyclic ring and two coordinated oxygen atoms from two amide pendant arms. The [Ni(DETA)]·Cl2·2H2O complex was six-coordinated in nature with a distorted octahedral geometry. Four coordinated nitrogen atoms were from the macrocyclic ring, and two coordinated oxygen atoms were from two amide pendant arms. [Fe(DETA)]2+ exhibited well-resolved sharp proton resonances, whereas very broad proton resonances were observed in the case of [Ni(DETA)]2+ due to the long electronic relaxation times. The CEST peaks for the [Fe(DETA)]2+ complex showed one highly downfield-shifted and intense peak at 84 ppm with another shifted but less intense peak at 28 ppm with good CEST contrast efficiency at body temperature, whereas [Ni(DETA)]2+ showed only one highly shifted intense peak at 78 ppm from the bulk water protons. Potentiometric titrations were performed to determine the protonation constants of the ligand and the thermodynamic stability constant of the [M(DETA)]2+ (M = Fe, Co, Ni, Cu, Zn) species at 25.0 °C and I = 0.15 mol·L-1 NaClO4. Metal exchange studies confirmed the stability of the complexes in acidic medium in the presence of physiologically relevant anions and an equimolar concentration of Zn(II) ions.

Electroplated waveguides to enhance DNP and EPR spectra of silicon and diamond particles.

Electroplating the waveguide of a 7 T polarizer in a simple innovative way increased microwave power delivered to the sample by 3.1 dB. Silicon particles, while interesting for hyperpolarized MRI applications, are challenging to polarize due to inefficient microwave multipliers at the electron Larmor frequency at high magnetic fields and fast electronic relaxation times. Improving microwave transmission directly translates to more efficient EPR excitation at high-field, low-temperature conditions and promises faster and higher Si polarization buildup through dynamic nuclear polarization (DNP).

Fermi energy dependence of ultrafast photoluminescence from graphene

The application of graphene in new light-emitting devices has been extensively studied since the demonstration of the ultrafast luminescence from single-layer graphene. The control of luminescence using doping techniques is crucial for these applications. In particular, for the application of graphene in flexible and wearable devices, electrochemical doping is a promising approach, and its influence on luminescence properties of the resulting material needs to be examined. In this study, we demonstrate the effect of the electrochemical doping of graphene using an ion gel on the photoluminescence (PL) of graphene at the emission energy ℏω of 0.9 eV. The Fermi energy EF of graphene was controlled from +40 to −560meV, and femtosecond PL was observed. The PL intensity was maximum when EF was −440meV (|EF|≈ℏω/2). This trend of the PL intensity is due to (i) an increase in the PL emission rate owing to the doping-induced empty states in the valence band acting as the final states of the radiative relaxation of hot electrons and (ii) an increase in the non-radiative relaxation rate owing to the acceleration of carrier–carrier scattering by the doping-induced increase in the density of states around the EF.