Shift Of Spectrum Research Articles

Enhancement strategy of thermal stability and photoluminescent intensity of Cr3+ doped Li3+xZn2–2xGaxSbO6 phosphor in a strong crystal field

Near-infrared phosphor-converted light-emitting diodes (pc-LEDs) have shown enormous influence in various applications such as night vision, non-destructive detection，especially in the realm of plant cultivation. However, the role of phosphors presently employed in plant cultivation is typically limited, serving primarily for the purpose of illumination. In this work, a series of near-infrared phosphors Li3+xZn2–2xGaxSbO6: 0.02Cr3+(LZGS: 0.02Cr3+) under 450 nm excitation was successfully synthesized by high-temperature solid-state method. Through precise modulation of Ga3+ ions, a blue shift in the emission spectrum was observed, demonstrating excellent overlap with the absorption spectrum of Phytochrome. To explain two phenomena of spectral blue shift and the enhancement in luminescence intensity, density functional theory calculations have been performed. Additionally, a crystal field strength Dq/B of 3.48 was achieved, which represents the highest value currently reported for Cr3+-doped phosphors. The results offer potential applications of LZGS: 0.02Cr3+ in temperature sensing, enabling precise detection of the environmental temperature for plant growth. Finally, pc-LED devices were made by combining LZGS: 0.02Cr3+ with 450 nm blue light chips and applied to plant lighting, temperature measurement, and anti-counterfeiting, demonstrating the potential of LZGS: 0.02Cr3+ in multifaceted applications.

Mechanisms of rapid plant community change from the Miocene Succor Creek flora, Oregon and Idaho (USA).

The fossil record of the U.S. Pacific Northwest preserves many Middle Miocene floras with potential for revealing long-term climate-vegetation dynamics during the Miocene Climatic Optimum. However, the possibility of strong, eccentricity-paced climate oscillations and concurrent, intense volcanism may obscure the signature of prevailing, long-term Miocene climate change. To test the hypothesis that volcanic disturbance drove Middle Miocene vegetation dynamics, high-resolution, stratigraphic pollen records and other paleobotanical data from nine localities of the Sucker Creek Formation were combined with sedimentological and geochemical evidence of disturbance within an updated chronostratigraphic framework based on new U-Pb zircon ages from tuffs. The new ages establish a refined, minimum temporal extent of the Sucker Creek Formation, ~15.8 to ~14.8 Ma, and greatly revise the local and regional chronostratigraphic correlations of its dispersed outcrop belt. Our paleoecological analysis at one ~15.52 Ma locality reveals two abrupt shifts in pollen spectra coinciding with the deposition of thick ash-flow tuffs, wherein vegetation dominated by Cupressaceae/Taxaceae, probably representing a Glyptostrobus oregonensis swamp, and upland conifers was supplanted by early-successional forests with abundant Alnus and Betula. Another ephemeral shift from Cupressaceae/Taxaceae swamp taxa in favor of upland conifers Pinus and Tsuga correlates with a shift from low-Ti shale to high-Ti claystone, suggesting a link between altered surface hydrology and vegetation. In total, three rapid vegetation shifts coincide with ash-flow tuffs and are attributed to volcanic disturbance. Longer-term variability between localities, spanning ~1 Myr of the Miocene Climatic Optimum, is chiefly attributed to eccentricity-paced climate change. Overall, Succor Creek plant associations changed frequently over ≤105 years timespans, reminiscent of Quaternary vegetation records. Succor Creek stratigraphic palynology suggests that numerous and extensive collection of stratigraphically controlled samples is necessary to understand broader vegetation trends through time.

Photovoltaic response promoted via intramolecular charge transfer in triphenylpyridine core with small acceptors: A DFT/TD-DFT study

Currently, A−π−A configured molecules (TTP1-TTP6) were designed from the reference compound (TPPR) by modifying the terminal acceptors for photovoltaic materials. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) using the M06/6-311G(d,p) functional were employed to analyze the photonic and electronic properties of the newly designed derivatives. Various analyses; frontier molecular orbitals (FMOs), density of states (DOS), absorption spectra (λmax), transition density matrix (TDM), binding energy (Eb), hole-electron and open circuit voltage (Voc) were performed to explore the photovoltaic properties of triphenylpyridine based compounds. The structural modulation with acceptor moieties significantly tuned their HOMO and LUMO levels, resulting in reduced band gaps (2.833–3.037 eV). They also exhibited broader absorption spectra (λmax) ranging from 482.560 to 514.756 nm as compared to the reference compound (486.289 nm). Notably, TPP3 showed the good photovoltaic response as it displayed the least energy gap (2.833 eV) with lower binding energy (0.415 eV) and bathochromic shift (512.798 nm) in absorption spectra as compared to all other derivatives. Beside this, a comparative study with spiro-OMeTAD and P3HT standard hole transport materials illustrated that these materials can also be utilized as effective photovoltaic materials.

Interface analysis of oxide free MoS2 films fabricated by solution process.

We report a solution-based approach for the synthesis of oxidation-free MoS2 films, focusing on interface analysis. Through a sulfurization-free solution process and single-step annealing, the oxidation-free MoS2 film is successfully prepared on Si3N4 surfaces, showing improved uniformity with a surface roughness below 0.5nm and a thickness of 4nm at a precursor solution concentration of 30 mM, annealed between 700 and 800ºC. The MoS2 films exhibit a hexagonal lattice structure with crystallographic orientations of (1 1 0 0) and (1 2 1 0) with lattice spacings of 0.27nm and 0.16nm respectively. Interfacial analysis by X-ray photoelectron spectroscopy (XPS) on SiO2 reveals migration of oxygen species as evidenced by a shift in the Si 2p spectrum at binding energies between 102.6eV and 102.8eV. MoS2 films on Si3N4 show a complex Si 2p peak evolution at binding energies between 100.9 and 101.8eV, providing valuable insights into the synthesis of oxide-free MoS2 films for potential applications in advanced electronic devices.

Novel isocyanobenzene carbazole-based thermally activated delayed fluorophors towards solution-processed blue emitting OLED devices with high efficiency

Achieving efficient blue emission is an exigent challenge for the application of thermally activated delayed fluorescent organic light-emitting diodes (TADF-OLEDs). Carbazole benzonitrile-based TADF molecules exhibit promising performance in achieving the goal. Here, by replacing the cyano group in the sensitizer with the isocyano group, a 9 nm hypochromatic shift in photoluminescence spectra of the sensitizer and an enhanced efficiency of the Förster energy transfer (FET) in TADF-sensitized fluorescence (TSF) is found. By using the isocyano-based compounds as sensitizers, a maximum external quantum efficiency of 24.5% is obtained in solution-processed OLEDs, surpassing the cyano-based counterparts with similar structures. Moreover, the full width at half maximum (FWHM) of the emitter in the electroluminescence spectrum is also decreased from 47 nm to 38 nm, indicating a more complete energy transfer.

Breaking New Grounds: solid-state synthesis of TiO2 – La2O3 – CuO Nanocomposites for degrading Brilliant Green dye under Visible Light

Environmental pollution, particularly from industrial dyes and chemicals, poses a significant threat to ecosystems and human health. Traditional pollution mitigation methods are often inefficient and costly. Photocatalysis has emerged as a promising solution for degrading pollutants using light energy. Titanium dioxide (TiO2) is a widely studied photocatalyst due to its stability, non-toxicity, and strong oxidative power. However, its efficiency is limited by a wide bandgap, restricting absorption to the UV region, and rapid electron-hole recombination. To address these limitations, doping TiO2 with materials like La2O3 and CuO has been explored to enhance its photocatalytic activity under visible light. This study investigates the enhancement of TiO2 nanocomposites by incorporating La2O3 and CuO. X-ray diffraction (XRD) revealed that the nanocomposites retained TiO2's anatase and rutile phases with improved crystallinity. Scanning electron microscopy (SEM) displayed spherical nanoparticles forming agglomerates, typically due to high surface energy. Energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of La and Cu in the TiO2 matrix. Fourier-transform infrared (FTIR) spectroscopy identified characteristic vibrational modes of Ti–O, La–O, and Cu–O bonds, suggesting strong chemical interactions between dopants and TiO2 lattice. Ultraviolet-visible (UV-Vis) spectroscopy showed a red shift in absorption spectra with La2O3 and CuO addition, reducing the bandgap energy from 3.23 eV (pure TiO2) to 2.27 eV for the TiO2–0.1La2O3–0.2CuO composite. Photoluminescence (PL) spectroscopy indicated improved charge separation and reduced electron-hole recombination rates in the synthesized nanocomposites. Photocatalytic performance was evaluated by degrading Brilliant Green (BG) dye under visible light. The TiO2–0.1La2O3–0.2CuO (TLC0.2) nanocomposite achieved a maximum dye degradation of over 95% after 204 minutes under optimal conditions (C0 = 17 mg/L and a S/L ratio of 1 g/L). Adding the inorganic agent Na2SO4 to this process significantly enhanced photocatalytic activity, increasing degradation from 56% to 95% after 180 min of visible light irradiation under C0 = 20 mg/L and S/L = 0.5 g/L conditions, as it shows a high stability after six reuse cycles. In conclusion, La2O3 and CuO doping significantly enhance TiO2 nanocomposites' crystalline structure, morphology, optical properties, and photocatalytic efficiency, demonstrating their potential for environmental remediation and solar energy conversion.

Enhanced optical, dielectric and transport properties in PVDF based (La0.5Bi0.5FeO3)0.5-(BaTiO3)0.5 composites

In this comprehensive study, we investigated PVDF composites incorporating LaBiFeO3-BaTiO3 (LaBiFO-BaTO) perovskite fillers, focusing on their structural, optical, dielectric, impedance, modulus and DC-conductivity properties. The fabrication involved precise preparation of LaBiFO-BaTO perovskite via solid-state reaction, ensuring phase purity conducive to composite integration. Using a solution casting method, PVDF films with varying LaBiFO-BaTO concentrations (5 %, 10 %, and 15 % wt) were successfully synthesized. XRD confirmed the synthesis of single-phase LaBiFO-BaTO and revealed structural modifications in PVDF composites, highlighting improved filler-matrix interactions at higher concentrations. Scanning electron microscopy and atomic force microscopy depicted the morphological evolution and surface roughness changes with increasing filler content. Optical studies indicated a red shift in absorption spectra with higher LaBiFO-BaTO concentrations, correlating with a decrease in the direct band gap energy of the composites. Electrical characterization demonstrated enhanced dielectric properties and impedance behaviour in PVDF/LaBiFO-BaTO composites, suggesting their suitability for applications in capacitors and optoelectronic devices. This systematic investigation provides valuable insights into optimizing PVDF-based composites for advanced functional materials. The composites exhibit enhanced dielectric permittivity at room temperature, attributed to space charge polarization and the high dielectric constant of LaBiFO-BaTO. Dielectric loss (tanδ) remains minimal (<0.1), decreasing with frequency, indicative of low energy dissipation suitable for high-frequency applications. Further the dielectric relaxation have been examined using Havrilak-Negami model. Impedance and modulus analyses reveal temperature-dependent behaviours, with reduced impedance and enhanced charge transfer kinetics in higher concentration composites. DC conductivity measurements demonstrate increased charge transport properties with temperature, influenced by thermally activated charge hopping mechanisms. Overall, PVDF/LaBiFO-BaTO composites show promising characteristics for capacitors, sensors, and optoelectronic devices, suggesting avenues for further optimization and broader application in advanced technologies.

Doping effects on boron carbide quantum dots for solar cells application: DFT study

The DFT method was used to explore the photovoltaic properties of nitrogen- and phosphorus-doped boron carbide quantum dots (BC3QDs). Results showed chemical activity values of -5.512 eV for nitrogen-doped and -3.971 eV for phosphorus-doped BC3QDs, with nitrogen-doped samples exhibiting higher chemical activity. Doping introduced mid-gap states, causing a red shift in the absorption spectra of 106 nm for nitrogen and 118 nm for phosphorus doping. Nitrogen doping (N-doping) enhanced charge transfer capabilities compared to phosphorus doping (P-doping). The nitrogen-doped BC3QDs also displayed HOMO and LUMO energy levels (-5.373 eV and -2.103 eV, respectively) that are closer to TiO2 and I−/I3−, making them more compatible for solar cell applications by increasing electron injection, fill factor, light collection efficiency, and open-circuit voltage. Despite an improved energy conversion potential, the N-doped BC3QDs’ efficiency (72.34%) was impacted by rapid non-radiative recombination. These insights can guide the design of BC3QDs in solar energy applications, photocatalytic devices, and QD nano-composites for energy harvesting.

DFT based analysis of pressure driven mechanical, opto-electronic, and thermoelectric properties in lead-free InGeX3 (X = Cl, Br) perovskites for solar energy applications

Lead halide perovskites have distinct physiochemical properties and demonstrate remarkable power conversion efficiency. We used density functional theory to investigate the electrical, optical, structural, and elastic features of non-toxic InGeCl3 and InGeBr3 halide perovskite compounds at different hydrostatic pressures, from 0 to 8 GPa. InGeCl3 and InGeBr3 halide perovskite exhibit noteworthy changes in their electronic and optical properties under different pressure conditions. When the pressure is 0 GPa, the direct bandgap for InGeCl3 is 0.886 eV, and for InGeBr3 it is 0.536 eV. This gap decreases as the pressure rises. Specifically, InGeBr3 exhibits conducting properties at 3 GPa due to its larger bromine atoms, whereas InGeCl3 requires a higher pressure of 6 GPa to achieve similar conductivity. This type of nature suggests that larger halogen atoms reduce the bandgap more effectively under pressure. As the pressure increases, the behavior of the lattice constant and unit cell volume decreases constantly, from 5.257 and 145.267 Å3 for InGeCl3 to 5.509 and 167.168 Å3 for InGeBr3 at 0 GPa for both compounds. When subjected to pressure, the bonds between In-X and Ge-X atoms experience compression, leading to a decrease in surface area and an enhancement in mechanical strength. Overall, the compounds exhibit characteristics of semiconductors, as evidenced by evaluations of their electrical properties. As pressure increases, the bandgap decreases linearly, narrowing until it aligns with the Fermi level, leading to a transition toward a metallic state. In addition, the pressure induces a rise in the electrical density of states around the Fermi level by displacing valence band electrons in an upward direction. As pressure increases, the electron density peak shifts to lower photon energy values. Notably, InGeCl3 exhibits a more pronounced shift in this peak compared to InGeBr3, indicating greater sensitivity to pressure. In terms of optical properties, both compounds demonstrate significant absorption coefficients in the visible region, suggesting their potential suitability for photovoltaic applications. The dielectric constant, absorption, and reflectivity values all increase gradually as pressure increases. The absorption spectra shift toward longer wavelengths. Furthermore, the mechanical properties analysis reveals that all InGeX3 compounds are mechanically stable up to 8 GPa pressure.

New Horizons for Temperature Sensing and Bioimaging Using Er3+‐Doped Core@Shell Nanoparticles and Effects of H2O and D2O Solvents on Their Spectroscopic Properties

AbstractLanthanide‐doped nanoparticles (NPs) exhibit temperature‐dependent luminescence, enabling the design of luminescent nanothermometers for industrial and medical applications. This research demonstrates the temperature‐sensing properties of NaYF4:7.5%Er3+@NaYF4 and NaErF4@NaYF4 NPs, which have a hexagonal shape and average size of 17 nm. Their core@shell structure is confirmed using high‐resolution transmission electron microscopy, and they exhibit intense upconversion (UC) emission under 1532 nm excitation in H2O and D2O colloids. The recorded spectra show Er3+ emission bands with varying intensity ratios depending on the Er3+ concentration, chosen solvent, and temperature. The spectroscopic properties of the studied NPs allow for their excitation and observation of emission within biological windows, which makes them useful for bio‐related applications. The emission of prepared NPs is analyzed as a function of temperature from 298 up to 358/363 K in H2O and D2O. The ratios for thermally‐coupled levels and non‐TCLs and their relative sensitivities are studied. For the high dopant concentration sample in water, the O─H vibrations and blue shift in the absorption spectrum lead to a record relative sensitivity of 2.50% K−1 (at 363 K) for the 2H11/2/4I11/2 ratio. The use of synthesized NPs for bioimaging under 1550 nm excitation is also demonstrated to observe their accumulation in the guts of Daphnia magna.

Tetrafunctionalized Azocalix[4]resorcinarene Dye: A Chromogenic Supramolecule Used for the Selective Liquid-Liquid Extraction and Spectrophotometric Determination of Cu(II)

Background: The detection and extraction of trace metal ions, particularly copper(II), are critical for environmental monitoring and industrial processes. Calixresorcinarene, with its unique cavity structure, offers excellent platforms for designing selective chemosensors and extractants. Functionalization of calixresorcinarene with azo groups can enhance their chromogenic properties, enabling both extraction and detection in a single step. Objective: This study aimed to evaluate its (Azocalix[4]resorcinaren) efficacy as a selective chemosensor for the liquid-liquid extraction and spectrophotometric determination of Cu(II) ions. Methods: Application in Extraction and Detection: The ability of the dye to selectively extract Cu(II) ions from aqueous solutions was investigated via liquid-liquid extraction experiments. The dye-Cu(II) complex formation was monitored by UV-Vis spectrophotometry, with systematic optimization of experimental conditions, including pH, solvent system, and extraction duration. Results: The synthesized azocalix[4]resorcinarene dye exhibited a pronounced selectivity towards Cu(II) ions, forming a stable, colored complex. The complexation induced a distinct bathochromic shift in the absorption spectrum, allowing for precise spectrophotometric detection. Optimal extraction was achieved at a specific pH and solvent combination, with the method demonstrating a low detection limit and high sensitivity. The dye showed minimal interference from other metal ions, confirming its selectivity for Cu(II). Conclusion: The tetrafunctionalized azocalix[4]resorcinarene dye is a highly effective chromogenic agent for the selective extraction and detection of Cu(II) ions. Its robust performance in both extraction efficiency and spectrophotometric detection underscores its potential utility in environmental analysis and industrial applications where trace metal detection is crucial.

Enhanced Singlet Oxygen Generation in Aggregates of Naphthalene-Fused BODIPY and Its Application in Photodynamic Therapy.

Several reports are available on aggregation-induced emission and its applications in biomedical imaging and other material sciences. However, enhancement of singlet oxygen generation in nanoaggregates is rarely reported. Here, we report the synthesis of Naph-BODIPY Br2, which absorbs at 661 nm (monomer) with a high molar absorption coefficient. The presence of bromine promotes intersystem crossing, thereby enhancing the singlet oxygen quantum yield (ΦΔ ∼ 0.50 in methanol). In order to increase hydrophilicity, we developed Naph-BODIPY Br2 nanoaggregates (∼100 nm), which demonstrated aggregation-induced properties and exhibited a bathochromic shift with an absorption maximum at 757 nm. The bathochromic shift in the UV-vis spectra due to aggregation is corroborated by TD-DFT analysis. The computational data also confirm the presence of a low-lying triplet state, which enhances the generation of singlet oxygen, making it effective for photodynamic therapy. These aggregates showed excellent singlet oxygen generation in aqueous media, compared to their monomeric form and standard methylene blue. Their hydrophilic nature and high singlet oxygen generation enabled significant phototoxicity against human carcinoma cells with IC50 values of 4.06 ± 0.01 and 4.09 ± 0.1 μM, respectively, for MCF-7 and A549 cells upon 5 min exposure to light. Moreover, their phototoxicity further increases with an increasing exposure time of light for both cell lines. Notably, Naph-BODIPY Br2 nanoaggregates exhibited nearly zero dark cell toxicity and effectively induced apoptosis in cancer cells upon light activation, highlighting their potential as powerful photosensitizers for photodynamic cancer therapy.

Prediction and visualization of 3D wake field of a rectangular high-rise building in tropical island cities based on UAV measurements

It is especially crucial to utilize measured data as samples to increase the accuracy of wind field prediction. However, scarce wake field measured data of high-rise buildings leads to the deviation between prediction results and the actual wake distribution. In this study, a six-rotor unmanned aerial vehicle wind measurement system (UAVWMS) equipped with an anemometer is used to measure the wake field of a rectangular high-rise building in a tropical island city, and the characteristics of fluctuating wind velocity spectra and distribution patterns of the wind velocity and turbulence intensity in the wake region are analyzed; the Kriging method is adopted to predict and visualize the three-dimensional (3D) wake field based on the measured data from UAVWMS. The results show that the exponential law is better than the logarithmic law in fitting the incoming wind velocity profile in the tropical island city. The measured points in the wake region, located near the central axis of the building, exhibit a pronounced reduction in wind velocity and an increase in turbulence intensity compared to those in the incoming region. Compared to the incoming wind velocity spectra and empirical spectra, the peak frequencies of wake wind velocity spectra shift to the high-frequency band. In addition, the wake wind velocity spectra are lower in the low-frequency band and higher in the high-frequency band. When designing a measured scheme based on UAVWMS, it's crucial to place measured points surrounding the target spatial wake field as much as possible. It helps enhance the accuracy of predicting wind parameters within the 3D spatial wake field. The research results provide a theoretical reference for the measurement, prediction and visualization of the wake field of high-rise buildings in dense urban buildings.

Silicon photonics foundry fabricated, slow-light enhanced, low power thermal phase shifter

In this research, we developed a low-power silicon photonics foundry-fabricated slow-light thermal phase shifter (SLTPS) where the slow-light (SL) effect is achieved using an integrated Bragg grating (BG) waveguide. Heating the grating induces a red shift in the transmission spectrum, leading to an increased group index ng during operation, which facilitates a further reduction in the voltage needed for a π phase shift, i.e., Vπ. Additionally, we investigated a compact Mach–Zehnder Interferometer (MZI) that incorporates the SLTPS in both arms with a phase shifter length of 50 μm. A detailed theoretical analysis was conducted to address the non-idealities of the SL-MZI due to uneven optical power splitting and unbalanced loss in the two MZI arms. Vπ and power consumption for a π phase shift (Pπ) of the SL-MZI were quantified for operation in the slow-light regime, demonstrating a Vπ of 1.1 V and a Pπ of 3.63 mW at an operational wavelength near the photonic band edge. The figure of merit Pπ×τ is commonly used to assess the performance of thermal optical switches. The SL-MZI in this work has achieved a low Pπ×τ of 5.1 mW μs with an insertion loss of 4.4 dB, indicating a trade-off with the Vπ reduction.

Technical note: Altitude scaling of 36Cl production from Fe

Abstract. Cosmogenic nuclide production rates depend on the excitation functions of the underlying nuclear reactions and the intensity and energy spectrum of the cosmic-ray flux. The cosmic-ray energy spectrum shifts towards lower average energies with decreasing altitude (increasing atmospheric depth), so production rate scaling will differ for production reactions that have different energy sensitivities. Here, we assess the possibility of the unique scaling of 36Cl production from Fe by modeling changes in the 36ClFe/36ClK and 36ClFe/10Beqtz production ratios with altitude. We evaluate model predictions against measured 36Cl concentrations in magnetite and K-feldspar and 10Be concentrations in quartz from granitic rocks exposed across an elevation transect (ca. 1700–4300 ma.s.l.) in western North America. The data are broadly consistent with model predictions. The null hypothesis that 36ClFe/10Beqtz and 36ClFe/36ClK production ratios are invariant with altitude can be rejected at the 90 % confidence level. Thus, reaction-specific scaling factors will likely yield more accurate results than non-reaction-specific scaling factors when scaling 36Cl production in Fe-rich rocks and minerals.

Structural Modeling of Fluorinated Quinoxaline Core–Based Chromophores for Efficient Photovoltaic Materials: A DFT Study

ABSTRACTHerein, a series of fluorinated quinoxaline core–based chromophores (MTH1‐MTH6) with A1–π–A2–π–A1 configuration was designed by structural modulation of end‐capped acceptors in MTHR. The quantum chemical calculations were accomplished at MPW1PW91/6‐311G(d,p) functional to explore optoelectronic and photovoltaic properties of these designed compounds. The findings revealed that all the derivatives exhibited narrow band gap (Egap = 2.163–2.666 eV) with red shift spectra (610.24–766.944 eV in chloroform) as compared with MTHR. The designed compounds exhibited comparable open‐circuit voltage (Voc) and higher power conversion efficiencies (PCEs) as compared with the MTHR. Among the entitled chromophores, MTH1 was found to be a promising chromophore for organic solar cells (OSCs) owning to its lowest Egap (2.163 eV) with highest absorption peak (766.944 nm in chloroform and 717.709 nm in gaseous phase). The aforementioned findings indicate that molecular engineering of chromophores with extended acceptors enhances photovoltaic response, and this motivates researchers to develop highly effective photovoltaic devices.

Roles of ESIPT and TICT in the Photophysical Process of a Ratiometric Fluorescence Sensor for Al3.

Precise detection of Al3+ with the aid of a fluorescence sensor is of fundamental importance in the fields of water pollution control and food safety. A comprehensive understanding of the photophysical process of the sensor as well as its underlying detection mechanism is a precondition for the design of highly efficient sensors. This contribution performs a thorough investigation of the ratiometric fluorescence sensing mechanism of an Al3+ sensor with the aid of density functional theory and time-dependent density functional theory. Two excited-state intramolecular proton transfer (ESIPT) processes are observed on the S1 state potential energy surface, which leads to emission around 565 nm. A twisted intramolecular charge transfer state is observed after one of the ESIPT processes via cis-trans isomerization of the C═N bond. However, the large energy barrier hinders its occurrence, which is quite unusual. Al3+ is found to form three strong coordination bonds with the sensor, which eliminates ESIPT processes and induces a significant blue shift of the emission spectrum to 480 nm. The origination of the sensor's selectivity is also uncovered by investigating the interaction between the sensor and interfering metal ions.

Structural Rigidification Strategy Based on Self-Assembly Enabled Reversible Excited-State Conversion of Iridium(III) Complexes for Multiple-Stimulus-Responsive Data Encryption.

Stimulus-responsive chromic materials exhibit color-switching properties under specific external stimuli and have been widely used in various fields. Transition-metal complexes show great potential applications as promising candidates for stimulus-responsive chromic materials, as their excited states not only depend on the chemical composition but are also affected by the intermolecular stacking modes. Owing to the intrinsic difficulty in the ordered stacking of the octahedral configuration, changing the stacking modes of iridium(III) complexes for multiple-stimulus responsiveness remains a significant challenge. In this work, we propose a structural rigidification strategy based on self-assembly to reversibly regulate the excited states of iridium(III) complexes, therefore achieving color switch under different stimulus conditions. We prepare cationic iridium(III) complexes by using tetrakis(perfluorophenyl)-borate ([B(PhF5)4]-) as the counterion, whose matching tetrahedral configuration and electron-deficient aromaticity enables polar-π interaction with the octahedral iridium(III) cations, inducing self-assembly to form structural rigidification. The structural rigidity restricts the large conformational changes of the metal-to-ligand charge transfer (3MLCT) excited state, and facilitates the conversion from the 3MLCT to the ligand-center (3LC) excited state in aggregated states. The excited-state conversion results in a 54 nm blue shift (from yellow to sky blue) in the photoluminescence spectra. As a result, we report a series of cationic iridium(III) complexes with different responses to low temperature, vapor fuming, and mechanical force, therefore achieving multiple-stimulus-responsive data encryption. Our work provides a novel strategy to achieve ordered stacking of octahedral complexes, shows a deeper understanding of the photophysical processes of transition-metal complexes, and offers a new perspective to develop multiple-stimulus-responsive chromic materials.

Enhancing Spectrometer Performance with Unsupervised Machine Learning.

Solid-state NMR spectroscopy (SSNMR) is a powerful technique to probe structural and dynamic properties of biomolecules at an atomic level. Modern SSNMR methods employ multidimensional pulse sequences requiring data collection over a period of days to weeks. Variations in signal intensity or frequency due to environmental fluctuation introduce artifacts into the spectra. Therefore, it is critical to actively monitor instrumentation subject to fluctuations. Here, we demonstrate a method rooted in the unsupervised machine learning algorithm principal component analysis (PCA) to evaluate the impact of environmental parameters that affect sensitivity, resolution and peak positions (chemical shifts) in multidimensional SSNMR protein spectra. PCA loading spectra illustrate the unique features associated with each drifting parameter, while the PCA scores quantify the magnitude of parameter drift. This is demonstrated both for double (HC) and triple resonance (HCN) experiments. Furthermore, we apply this methodology to identify magnetic field B0 drift, and leverage PCA to "denoise" multidimensional SSNMR spectra of the membrane protein, EmrE, using several spectra collected over several days. Finally, we utilize PCA to identify changes in B1 (CP and decoupling) and B0 fields in a manner that we envision could be automated in the future. Overall, these approaches enable improved objectivity in monitoring NMR spectrometers, and are also applicable to other forms of spectroscopy.

Spectral line broadening of the Raman scattered waves in laser plasmas

Parametric instabilities are of a great concern especially in the context of laser fusion. Electromagnetic waves scattered by these instabilities can reach high amplitudes, thereby diverting a significant portion of the energy from the incident laser beam, which is essential for compressing and heating the fuel capsule. In addition, the emerging electrostatic wave can trap and accelerate electrons, which, upon impact, can preheat the target and thus prevent its effective compression. Here, we focus on the stimulated Raman scattering and the associated processes. Spectral broadening of the backward Raman scattering daughter wave is theoretically described process, which is caused by so-called trapped particle instability. The existence of trapped and freely moving electrons in plasma influenced by high amplitude electron plasma wave leads also to the anomalous dispersion of this wave. It is reflected in the shifts in the electrostatic spectrum which, on the other hand, must be visible also in the electromagnetic spectrum via the feed-back loop of the instability. In the present paper, we discuss scattered wave modes spectral broadening using results of numerical simulations.