Energy Transfer Research Articles

Diverse pathways in GPCR-mediated activation of Ca2+ mobilization in HEK293 cells

G protein-coupled receptors (GPCRs) transduce extracellular stimuli into intracellular signaling. Ca2+ is a well-known second messenger that can be induced by GPCR activation through the primary canonical pathways involving Gαq- and Gβγ-mediated activation of phospholipase C-β (PLCβ). While some Gs-coupled receptors are shown to trigger Ca2+ mobilization, underlying mechanisms remain elusive. Here we evaluated whether Gs-coupled receptors including the β2-adrenergic receptor (β2AR) and the prostaglandin EP2 and EP4 receptors (EP2R and EP4R) that are endogenously expressed in HEK293 cells utilize common pathways for mediating Ca2+ mobilization. For the β2AR, we found an essential role for Gq in agonist-promoted Ca2+ mobilization while genetic or pharmacological inhibition of Gs or Gi had minimal effect. β-agonist-promoted Ca2+ mobilization was effectively blocked by the Gq-selective inhibitor YM-254890 and was not observed in ΔGαq/11 or ΔPLCβ cells. Bioluminescence resonance energy transfer analysis also suggests agonist-dependent association of the β2AR with Gq. For the EP2R, which couples to Gs, agonist treatment induced Ca2+ mobilization in a pertussis toxin (PTX)-sensitive but YM-254890-insensitive manner. In contrast, EP4R, which couples to Gs and Gi, exhibited Ca2+ mobilization that was sensitive to both PTX and YM-254890. Interestingly, both EP2R and EP4R were largely unable to induce Ca2+ mobilization in ΔGαs or ΔPLCβ cells, supporting a strong dependency on Gs signaling in HEK293 cells. Taken together, we identify differences in the signaling pathways that are utilized to mediate Ca2+ mobilization in HEK293 cells where the β2AR primarily utilizes Gq, EP2R uses Gs and Gi, and EP4R utilizes Gs, Gi and Gq.

Potential-resolved ratiometric electrochemiluminescence detection for prostate-specific antigen based on CdS nanocrystals modified on carbon nanotubes and luminol functionalized nanocomposites.

A ratiometric electrochemiluminescence (ECL) aptamer-based sensing platform was fabricated for prostate-specific antigen (PSA) determination. Activated CdS nanocrystals/multi-walled carbon nanotubes (CdS/MCNTs) and luminol-Pt/PAMAM nanocomposites (L-Pt/PAMAM NCs) were synthesized and used as cathodic and anodic ECL emitters, respectively. Amino group-modified aptamers were assembled on carboxylated magnetic beads, followed by hybridization with probe DNA functionalized L-Pt/PAMAM NCs. In the presence of PSA, the aptamer would bind specifically to the target PSA, thereby releasing L-Pt/PAMAM NCs. After magnetic separation, the separated L-Pt/PAMAM NCs would hybridize with capture DNA on CdS/MCNTs coated on glassy carbon electrode. This binding would lead to a decrease in cathodic ECL signal of CdS/MCNTs, due to the efficient energy transfer from CdS/MCNTs to L-Pt/PAMAM NCs. Meanwhile, L-Pt/PAMAM brought the anodic ECL signal from luminol. With the increase of PSA concentration, the ECL emission from luminol increased and the ECL emission from CdS/MCNTs decreased. The ratio of ECL intensity of luminol at 0.55V and CdS/MCNTs at - 1.25V could be used to quantify the concentration of PSA. This method enables sensitive and reliable detection of PSA over a wide range from 0.05 to 200ngmL-1, and the detection limit is 0.02ngmL-1.

Carbon Dots and Their Films with Narrow Full Width at Half Maximum Orange Emission.

To obtain carbon dots (CDs) with narrow full width at half maximum (FWHM) and long-wavelength emission, carbon sources with high conjugate sizes and abundant functional groups can be employed to synthesize CDs. In this study, orange-emissive carbon dots (OCDs) were synthesized with phloroglucinol and rhodamine B as precursors. When the molar ratio of them was 30:1, and ethanol was served as the solvent, OCDs with optimized emission wavelength at approximately 580 nm, an FWHM of 30 nm, and a quantum yield (QY) of 27.31% were obtained. Subsequently, the OCDs were incorporated into polyvinyl alcohol (PVA) to fabricate solid-state OCD/PVA fluorescent films, which exhibited an FWHM of 47 nm. The PVA matrix facilitated the dispersion of OCDs, thereby suppressing non-radiative energy transfer among the OCDs and enhancing luminescence efficiency. Consequently, compared with OCDs, the OCD/PVA film exhibited significant luminescent enhancement, and the QY of the composite film was increased to 84.74%. Moreover, OCD/PVA film showed good transmittance and thermal stability. This research offers a solid theoretical and experimental foundation for the potential applications of CDs in the field of solid-state lighting.

Design principles for energy transfer in the photosystem II supercomplex from kinetic transition networks

Photosystem II (PSII) has the unique ability to perform water-splitting. With light-harvesting complexes, it forms the PSII supercomplex (PSII-SC) which is a functional unit that can perform efficient energy conversion, as well as photoprotection, allowing photosynthetic organisms to adapt to the naturally fluctuating sunlight intensity. Achieving these functions requires a collaborative energy transfer network between all subunits of the PSII-SC. In this work, we perform kinetic analyses and characterise the energy landscape of the PSII-SC with a structure-based energy transfer model. With first passage time analyses and kinetic Monte Carlo simulations, we are able to map out the overall energy transfer network. We also investigate how energy transfer pathways are affected when individual protein complexes are removed from the network, revealing the functional roles of the subunits of the PSII-SC. In addition, we provide a quantitative description of the flat energy landscape of the PSII-SC. We show that it is a unique landscape that produces multiple kinetically relevant pathways, corresponding to a high pathway entropy. These design principles are crucial for balancing efficient energy conversion and photoprotection.

Three-dimensional radiation dosimetry of carbon ion beams using surfactant hydrogels: Fundamental investigation.

In carbon ion radiotherapy, accurate measurement of the three-dimensional (3D) absorbed dose distribution is critical for effectively targeting tumors. Although micellar gel dosimeters exhibit considerable potential for measuring 3D absorbed dose distributions, few studies have focused on radiotherapy using carbon ion beams. This study investigated the applicability of the surfactant hydrogel dosimeter (SHD), a micellar gel dosimeter, to measuring a 3D dose absorbed through carbon ion beam irradiation. A cubic target region of 34mm per side was established at a depth of 46mm below the upper surface of an SHD specimen. Scanning irradiation was performed using a pencil beam of carbon ions at the Ion-beam Radiation Oncology Center in Kanagawa ("i-ROCK"), Japan, under irradiation conditions set by the treatment planning system ("Monaco for Carbon", Ver. 5.20, Elekta AB, Sweden) to create a spread-out Bragg peak within the target. The physical dose was set to 10Gy at the isocenter, situated at the center of the target. The SHD responsiveness was measured twice using optical computed tomography (CT) ("Vista 15", Modus Medical Devices, Canada) for three irradiated specimens, and six types of measured optical attenuation coefficient (OAC) were obtained. To assess whether the OAC represented the absorbed dose expected in the treatment plan, we compared the relative distribution of the OAC and that of the absorbed dose. Relative fraction (RF) was used to measure the difference between the relative value of the OAC and that of the absorbed dose. Moreover, the distribution of OH radical (•OH) concentration obtained by Monte Carlo simulation ("PHITS" ver. 3.24 JAEA, Japan) and that of the OAC were compared. In the direction of beam travel, the relative distribution of the OAC was lower than that of the absorbed dose. This discrepancy could be attributed to a decrease in the concentration of •OH produced by irradiation owing to the recombination reaction, which does not accurately reflect the absorbed dose. By contrast, the distributions in the plane perpendicular to the beam travel were consistent. The RF increased from±3% to±13% along the beam travel direction. The small RF in the plane perpendicular to the beam travel could be attributed to the constant distribution of linear energy transfer, regardless of the irradiation position, and the generation of radicals proportionally to the absorbed dose. The increase in RF along the beam travel direction was ascribed to ring artifacts in the irradiated region. The measurement of the absorbed dose distribution in the beam travel direction should be improved. The observed discrepancy is attributed to the reduced reactivity of the SHD due to a high liner energy transfer near the Bragg peak. However, the absorbed dose distribution can be effectively evaluated in the plane perpendicular to the direction of beam travel.

Machine tool systems structural characterization, energy transfer, and evolution analysis of milling Ti6Al4V considering cutting vibration

Machine tool systems structural characterization, energy transfer, and evolution analysis of milling Ti6Al4V considering cutting vibration

Multifunctional visible light photocatalytic carbon dots synergize with reactive oxygen species for anti-quorum sensing and anti-bacteria for salmon preservation

Quorum sensing (QS)-induced spoilage causes approximately 15–20% of annual food wastage. However, traditional natural QS inhibitors exhibit poor water solubility and no catalytic activity. Therefore, this study aimed to synthesize novel anti-QS carbon dots (RR-CDs) with good water solubility, visible light photocatalytic activity, and high biocompatibility. The RR-CDs (<200 μg mL−1) exhibited considerable broad-spectrum antibacterial activity by generating reactive oxygen species (ROS) to disrupt the cell membrane wall structure. Owing to the appropriate bandgap of RR-CDs, a high ROS content, including ·O2−, 1O2, and ·OH, was generated via energy transfer under visible light irradiation. Furthermore, the combined effect of RR-CDs and ROS reduced the biofilm formation, swarming, swimming, and extracellular protease production of Pseudomonas fluorescens by 48.45%, 25.51%, 52.79%, and 38.67%, respectively, by inhibiting LuxI/R expression, which further decreased pgaC, tyrB, motB, and aprE expression by >50 %. Notably, RR-CDs exhibited no obvious cytotoxicity; furthermore, they could extend the shelf life of salmon by 3 d. Altogether, these results present and validate the strong ability of photocatalytic RR-CDs for QS inhibition and show their potential in aquatic product preservation.

Achieving Bright Up‐Conversion Luminescence of Eu3⁺ and Tb3⁺ Ions within Coordination Polymers

AbstractAchieving the up‐conversion luminescence (UCL) centered around trivalent lanthanide (Ln3+) ions in coordination polymers (CPs) is extremely challenging. Herein, Yb3⁺‐doped Ln‐CPs of [Eu1‐xYbx(pfbz)2(phen)Cl] (x = 0.3, namely 3; x = 0.5, namely 4; x = 0.7; namely 5), and [Tb1‐xYbx(pfbz)2(phen)Cl] (x = 0.2, namely 6; x = 0.5, namely 7; x = 0.6, namely 8) are reported by doping Yb3⁺ into Ln‐CPs of [Ln(pfbz)2(phen)Cl] (Ln = Eu, 1; Ln = Tb, 2). Both 5 and 8 visually exhibit excellent cooperative sensitization UCL of Eu3⁺ and Tb3⁺ ions, while 5 represents the first instance of an Ln‐CP where the UCL of Eu3⁺ ion is visually observable. Investigations into the UCL of these CPs reveal that the energy transfer is achieved through direct energy transfer from two individual Yb3⁺ ions, marking the first time such a mechanism has been employed in UCL in Eu/Tb‐CPs.

Differentiating Reactive Oxygen Species with DNA Framework Monitors.

The lifespan, oxidizing properties, bonding behaviors, and reactivity of reactive oxygen species (ROS) produced during photocatalytic activation can vary significantly due to the differences in electron configurations of ROS, which are dependent on their generation mechanisms: energy transfer or charge transfer. Hence, identifying and differentiating ROS of different mechanisms can improve our understanding of redox reactions and related diseases, providing a basis for the prevention and treatment of related diseases. Here, we have developed a DNA framework monitor (DFM) based on dynamic DNA structural changes to effectively distinguish the two types of ROS produced in photocatalytic activation of O2. This DFM provides a visualization tool for observing the reaction kinetics of ROS with DNA, not only distinguishing two types of ROS with different mechanisms but also serving as a universal system for evaluating the efficacy and performance of nanomaterials for ROS regulation.

Tuned quantum cutting efficiency by Li+/Na+ molar content in LixNa1-xGd(MoO4)2:Er3+/Yb3+ phosphors

Quantum cutting materials have garnered significant interest due to their potential applications in enhancing photoelectric conversion efficiency in devices such as solar cells. The host matrices that accommodate rare earth ions play a pivotal role in determining the optical transition properties, which are crucial for quantum cutting. In this study, both Er3+ single-doped and Er3+/Yb3+ co-doped LixNa1-xGd(MoO4)2 (x = 0, 0.01, 0.1, 0.3, 0.5, 0.7, 0.9, 0.99 and 1.0) were synthesized via a high-temperature solid-state reaction to tune the optical transitions properties and enhance quantum cutting efficiency. Optical transition intensity parameters (Judd-Ofelt parameters) of Er3+ were calculated and shown to vary significantly with the Li+/Na+ molar content, demonstrating that these optical properties can be effectively tuned by adjusting the sample composition. The reliability of these calculations was confirmed by comparing the radiative transition rate ratios between two green emissions of Er3 obtained through both theoretical and experimental methods. A two-step energy transfer mechanism was identified as the basis for quantum cutting process, and the relevant energy transfer and nonradiative relaxation rates were determined. Notably, the quantum cutting efficiency reached a peak value of 155.65 % in Li0.5Na0.5Gd(MoO4)2 sample, indicating that successful tuning of the sample's optical transition properties effectively enhanced its quantum cutting efficiency. These findings underscore the viability of tuning the optical properties of rare earth-doped materials to design highly efficient quantum cutting materials.

Electronic Confinement-Restrained Anti-Site Defects in Sodium-Rich Phosphates Toward Multi-Electron Transfer and High Energy Efficiency.

Sodium (Na) super-ionic conductor structured Na3MnTi(PO4)3 (NMTP) cathodes have garnered interest owing to their cost-effectiveness and high operating voltages. However, the voltage hysteresis phenomenon triggered by anti-site defects ( -ASD), namely, the occupation of Mn2+ in the Na2 vacancies in NMTP, leads to sluggish diffusion kinetics and low energy efficiency. This study employs an innovative electronic confinement-restrained strategy to achieve the regulation of -ASD. Partial replacement of titanium (Ti) with electron-rich vanadium (V) favors strong electronic interactions with Mn2+, restraining Mn2+ migration. The results suggest that this strategy can significantly increase the vacancy formation energy and migration energy barrier of manganese (Mn), thus inhibiting -ASD formation. As proof of this concept, an Na-rich Na3.5MnTi0.5V0.5(PO4)3 (NMTVP) material is designed, wherein the electronic interaction enhanced the redox activity and achieved more Na+ storage under high-voltage. The NMTVP cathode delivered a reversible specific capacity of up to 182.7 mAh g-1 and output an excellent specific energy of 513.8Wh kg-1, corresponding to ≈3.2 electron transfer processes, wherein the energy efficiency increased by 35.5% at 30C. Through the confinement effect of electron interactions, this strategy provides novel perspectives for the exploitation and breakthrough of high-energy-density cathode materials in Na-ion batteries.

Effect of Na2CO3 content on thermophysical properties, corrosion behaviors of KNO3-NaNO2 molten salt

Molten salt is popularly used as high temperature heat transfer and thermal energy storage medium. In order to decrease the melting point and increase decomposition temperature of molten salt, phase diagrams for KNO3-NaNO2 binary nitrates were calculated. And the binary salt with the lowest eutectic point was prepared. Furthermore, the effect of Na2CO3 addition on optimal selected KNO3-NaNO2 binary molten salt thermophysical properties and corrosion behavior are experimentally investigated. The results show that the addition of 7 wt% Na2CO3 to KNO3-NaNO2 binary molten salt can lower the melting point by 5.8 %. The addition of 9 wt% Na2CO3 to KNO3-NaNO2 binary molten salt can increase the decomposition temperature by 20.6 %, enhance the specific heat capacity by 4.8 % and increase the thermal conductivity by 7.5 %, but at the same time viscosity increased about 70 % at 300 °C. Meanwhile, the density increases with the increase of Na2CO3 content addition. The average corrosion rate of 316 stainless steel increases with the increasing of Na2CO3 content, which is consistent with the cross-section SEM results.

Efficient electrocatalytic reduction of nitric oxide (NO) to ammonia (NH3) on metal-free B4@g-C3N4 nanosheet

The combustion of fossil fuels releases substantial amounts of nitric oxide (NO), posing serious environmental and health risks. Addressing NO pollution effectively is, therefore, a pressing need. Conversion of NO into valuable chemicals is an appealing strategy with dual benefits, including waste utilization and sustainable energy transformation. In this study, we investigate the metal-free electrocatalytic reduction of NO (NORR) to NH3 on a B4 atomic cluster supported by a g-C3N4 nanosheet (B4@g-C3N4) using density functional theory (DFT). Our findings reveal that NO is efficiently activated on the B4@g-C3N4 catalyst, favoring side-on and N end-on adsorption configurations. Significant electron transfer and strong adsorption energies confirm the chemisorption of NO. The NORR exhibits an impressively low limiting potential (UL) of −0.29 V in the gas phase, which decreases further under solvent effects and varying charge states (−2e-, −1e-, +1e-, +2e-). Additionally, the high negative UL values for competing side reactions such as H2 (−0.42 V), N2 (−0.29 V), and N2O (−0.72 V) underscore the selectivity of B4@g-C3N4 for ammonia synthesis. These results highlight the promising potential of B4@g-C3N4 nanosheets for eco-friendly ammonia production from NO, providing a theoretical basis for future experimental efforts to combat NO pollution.

Real-time measurement of two-dimensional LET distributions of proton beams using scintillators.

&#xD;The linear energy transfer (LET) of proton therapy beams increases rapidly from the Bragg peak to the end of the beam. Although the LET can be determined using analytical or computational methods, a technique for efficiently measuring its spatial distribution has not yet been established. Thus, the purpose of this study is to develop a technique to measure the two-dimensional LET distribution in proton therapy in real time using a combination of multiple scintillators with different quenching. Inorganic and organic scintillator sheets were layered and irradiated with proton beams. Two-color signals of the CMOS sensor were obtained from the scintillation light and calibration curves were generated using LET. LET was calculated using Monte Carlo simulations as LETt and LETd weighted by fluence and dose, respectively. The accuracy of the calibration curve was evaluated by comparing the calculated and measured LET values for the 200 MeV monoenergetic and spread-out Bragg peak (SOBP) beams. LET distributions were obtained from the calibration curves.&#xD;Main results:&#xD;The deviation between the calculated and measured LET values was evaluated. For both LETt and LETd, the deviation in the plateau region of the monoenergetic and SOBP beams tended to be larger than those in the peak region. The deviation was smaller for LETd. In the obtained LETd distribution, the deviation between the calculated and measured values agreed within 3% in the peak region, while the deviation was larger in other regions. The LET distribution can be measured with a single irradiation using two scintillator sheets. This method may be effective for verifying LET in daily clinical practice and for quality control.&#xD.

Double detection of mycotoxins based on aptamer induced Fe3O4@TiO2@Ag Core − Shell nanoparticles “turn on” fluorescence resonance energy transfer

Multiple and sensitive mycotoxin detection is an essential early-warning mechanism for safeguarding human health, and preserving the environment. We synthesized a turn-on Fluorescence Resonance Energy Transfer (FRET) aptamer sensor based on the unique fluorescence quenching and substrate recognition characteristics of Ag NTs (energy receptors) and aptamer modified Fe3O4@TiO2 NP (energy donor) to detect multiple toxins using a single diagnostic approach. The addition of aflatoxin B1 (AFB1) and ochratoxin A (OTA) resulted in a change in fluorescence intensity at 510 and 650 nm, which can be employed for simultaneous recognition with detection limits of 0.94 ng·mL−1 (R2 = 0.997) and 0.54 ng·mL−1 (R2 = 0.995). The aptasensors have been successfully applied for the determination of AFB1 and OTA in grain and oil samples with high recovery rates. The approach provides novel possibilities for the development of sensitive and selective aptasensors with potential applications in aptamer-recognized multifunctional biosensing.

Synthesis of SCD3-containing bicyclo[1.1.1]pentanes enabled by photocatalyzed difunctionalization of [1.1.1]propellane

Bicyclo[1.1.1]pentanes (BCPs) have emerged as appealing bioisosteres for para-substituted benzene rings in drug design. In this study, we report an intermolecular photocatalytic addition of [1.1.1]propellane and S-(methyl-d3) arylsulfonothioates to synthesize novel deuterium-containing BCPs derivatives via energy transfer processes (EnT). This efficient and green protocol provides an access to introduce deuterium into BCP scaffolds and enriches the present library of BCPs compounds for drug design.

UAV-mounted IRS assisted wireless powered mobile edge computing systems: Joint beamforming design, resource allocation and position optimization

Intelligent reflecting surface (IRS) and unmanned aerial vehicle (UAV) have been recently used in wireless-powered mobile edge computing (MEC) systems to enhance the computation bits and energy harvesting performance. However, in the conventional IRS- and UAV-aided MEC systems, the IRS is installed at fixed locations on a building, which restricts the computation performance. UAV-mounted IRS (UAV-IRS), as a promising technology, combines the advantages of UAV and IRS. Hence, in this work, we study a UAV-IRS wireless-powered MEC system, where multiple UAV-IRSs are considered between Internet of Things (IoT) devices and the base station to improve the computation bits and energy harvesting. The multi-antenna base station first charges the IoT devices via radio frequency signals, and then IoT devices offload their computation tasks to the base station via UAV-IRSs. We formulate a computation bits maximization problem for all IoT devices by jointly determining detection beamforming at IoT devices, active energy beamforming at the base station, power allocation, time slot assignment, CPU frequency, the phase shifts design in the wireless energy transfer (WET) and task offloading, and UAV-IRSs positions. A block coordinate descent (BCD) algorithm by decomposing the introduced problem into four blocks is proposed, while the detection beamforming, active energy beamforming, transmit power, time slot assignment, CPU frequency, and the phase shifts design in the task offloading are derived in closed-form results. Also, the successive convex approximation and semidefinite relaxation (SDR) are adopted to obtain the UAV-IRS positions and the phase shifts in the WET, respectively. The simulation results verify the effectiveness of the presented BCD method compared with the different benchmark schemes.

Transpiration and plant hydraulics of Abies veitchii under fluctuating environmental conditions in cool montane forest

AbstractIn subalpine fir wave forests, strips of dead and weakened trees occur perpendicular to the slope next to strips of healthy trees. To reveal the transpiration by weakened Abies veitchii trees exposed to increased atmospheric evaporative demand, we investigated the ecophysiological traits closely related to the growth and transpiration, comparing them with those of the healthy trees and saplings in the fir wave of Mt. Shimagare in central Japan. The transpiration rate (E) was investigated using sap flux sensors to measure heat pulse velocity and compared with the surrogate for the needle water demand, which was computed using a multilayered gas and energy transfer model (modeled E, Emod). Weakened trees exhibited smaller diameter growth and narrower sapwood than healthy trees, as well as lower heat pulse velocity compared with healthy saplings. However, needle‐level traits did not differ significantly between weakened and healthy trees. Needle water potential at midday was as negative as the needle turgor loss point, and the measured heat pulse velocity increased linearly with Emod but leveled off above a certain Emod value in weakened trees and healthy saplings, suggesting that trees restricted E to balance the needle water budget. Heat pulse velocity of weakened trees leveled off at Emod lower than that of healthy saplings, probably due to lower capacity for water supply to the needles. Restriction of E would occur less frequently but be necessary for both weakened and healthy A. veitchii on Mt. Shimagare to avoid hydraulic failure, sacrificing photosynthetic carbon assimilation.

Hierarchical Equations of Motion for Quantum Chemical Dynamics: Recent Methodology Developments and Applications.

ConspectusQuantum effects are critical to understanding many chemical dynamical processes in condensed phases, where interactions between molecules and their environment are usually strong and non-Markovian. In this Account, we review recent progress from our group in development and application of the hierarchical equations of motion (HEOM) method, highlighting its ability to address some challenging problems in quantum chemical dynamics.In the HEOM method, the bath degrees of freedom are represented using effective modes from exponential decomposition of the bath correlation function. Complex spectral densities and low temperature simulations often require a larger number of modes, making the simulations very expensive. Recent advances, such as the barycentric spectral decomposition (BSD) technique, can significantly reduce the number of effective modes, allowing to handle complex spectral densities and enabling simulations at very low temperatures, including near-zero temperature dynamics.Another key improvement in the computational efficiency is the use of tensor network methods like matrix product states and hierarchical tensor networks. These techniques allow for efficient HEOM propagation with thousands of effective modes, crucial for simulating large molecular systems interacting with multiple baths. This combination enables simulations of excitation energy transfer (EET) in systems like the Fenna-Matthews-Olson (FMO) complex and even larger systems with experimentally determined spectral densities.The versatility of the HEOM method is demonstrated through applications to a wide range of chemical dynamics problems. Simulations of EET and related ultrafast spectroscopy are first briefly covered. Applications of the HEOM to quantum tunneling effects in proton transfer reactions are then presented. Early works have studied the non-Kramers dependence of the rate constant as a function of bath friction due to deep tunneling and revealed vibrationally nonadiabatic dynamics within the so-called nontraditional view of proton transfer reactions. A recent work on the large kinetic isotope effects in soybean lipoxygenase also indicated that many quantum correction approximations to classical transition-state theory may fall short in describing deep tunneling effects.Charge transport and separation dynamics in organic semiconductors are another area where the HEOM method has been instrumental. We first demonstrate that the HEOM provides a unified description of both band-like and thermally assisted charge carrier transport in organic materials. The effect of non-nearest neighbor transitions is then investigated by combining generalized master equations with exact memory kernels. The HEOM method also enables simulation of charge separation in organic photovoltaics (OPVs) and reveals how factors such as external electric fields, entropy, and charge delocalization influence the charge separation barrier and dynamics.Moreover, HEOM has been applied to investigate hydrogen atom scattering on the Au(111) surface and vibrational energy relaxation at molecule-metal interfaces. These studies provide deeper insights into how electron-hole pair excitations and temporary charge transfer states influence the nuclear motion, offering a new framework for simulating nonadiabatic dynamics on metal surfaces.In summary, the HEOM method has developed into a robust tool for simulating quantum effects in condensed phases. Future developments in algorithm efficiency and computational power will likely expand its applicability to even more complex systems.

Precision across temperatures: Eu/Tb luminescent thermometer with exceptionally high and stable sensitivity from 180 to 320 K

Luminescence thermometry, leveraging the temperature-dependent luminescent properties of coordination compounds, offers precise and remote temperature measurement. However, many existing luminescent thermometers exhibit a narrow peak in temperature sensitivity, restricting their effective operating range. In this study, we synthesized new complexes [LnL2(NO3)(TPPO)2], where Ln = Eu (1), Tb (2), Gd (3), Tb0.94Eu0.06 (4), (HL - 4,4,4-trifluoro-1-(furan-2-yl) butan-1,3-dione, TPPO - triphenylphosphine oxide, which demonstrate an exceptionally wide and stable range of maximum temperature sensitivity of 3 %×K−1, spanning from 180 to 320 K. Furthermore, the temperature uncertainty remained low and stable across the same temperature region, ensuring reliable measurements. An unusual behavior was observed in the ion-to-ion energy transfer process rate constant, which exhibited an additional peak between 120 and 180 K. This phenomenon warrants further investigation to fully understand the underlying mechanisms. The obtained results allow for creation of new highly efficient luminescent thermometers tailored for specific complex applications, including cryobiology and microfluidics.