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We study the accuracy of excited state (ES) geometries using optimally tuned LC-PBE functionals with tuning based on GW quasiparticle energies. We compare the results obtained with the PBE, PBE0, non-tuned, and tuned LC-PBE functionals with available high-level CC reference values as well as experimental data. First, we compare ES geometrical parameters obtained for three different types of systems: molecules composed of a few atoms, 4-(dimethylamino)benzonitrile (DMABN), and conjugated dyes. To this end, we used wave-function results as benchmarks. Next, we evaluate the accuracy of the theoretically simulated spectra as compared to the experimental ones for five large dyes. Our results show that, besides small compact molecules for which tuning LC-PBE does not allow obtaining geometries more accurate than those computed with standard functionals, tuned range-separated functionals are clearly to be favored, not only for ES geometries but also for 0–0 energies, band shapes, and intensities for absorption and emission spectra. In particular, the results indicate that GW-tuned LC-PBE functionals provide improved matching with experimental spectra as compared to conventionally tuned functionals. It is an open question whether TD-DFT with GW-tuned functionals can qualitatively mimic the actual many-body Bethe–Salpeter (BSE/GW) formalism for which analytic ionic gradients remain to be developed. [ABSTRACT FROM AUTHOR]

In this study, we used the non-hydrolytic sol–gel methodology to synthesize gadolinium vanadate particles doped with different Er3+ and Yb3+ molar ratios. Er3+ and Yb3+ chlorides and vanadium alkoxide were used as precursors during the sol–gel synthesis. The resulting powders were treated at 800 °C and characterized by x-ray diffraction and photoluminescence. The x-ray diffractogram displayed peaks attributed to the gadolinium vanadate matrix. Photoluminescence helped to evaluate the Fluorescence Intensity Ratio (FIR), which is important for understanding the nanothermometer property. The FIR of the GdVO4:Er3+/Yb3+ samples containing different Er3+ and Yb3+ molar ratios increased as a function of the laser power, which indicated that the local temperature increased. The excitation spectra obtained at fixed wavelengths of 525 and 555 nm displayed bands at 322, 379, and 489 nm, ascribed to the charge transfer band and Er3+ levels. Upon excitation at 321 nm, the emission spectra in the visible region presented intense bands at 525 and 555 nm, due to Er3+ emission, and excitation at 321 nm led to emission in the infrared region, 980 and 1550 nm. In conclusion, the synthesized system can be employed as a temperature sensor. [ABSTRACT FROM AUTHOR]

Wave packet interferometry with vacuum ultraviolet light has been used to probe a complex region of the electronic spectrum of molecular nitrogen, N2. Wave packets of Rydberg and valence states were excited by using double pulses of vacuum ultraviolet (VUV), free-electron-laser (FEL) light. These wave packets were composed of contributions from multiple electronic states with a moderate principal quantum number (n ∼ 4–9) and a range of vibrational and rotational quantum numbers. The phase relationship of the two FEL pulses varied in time, but as demonstrated previously, a shot-by-shot analysis allows the spectra to be sorted according to the phase between the two pulses. The wave packets were probed by angle-resolved photoionization using an infrared pulse with a variable delay after the pair of excitation pulses. The photoelectron branching fractions and angular distributions display oscillations that depend on both the time delays and the relative phases of the VUV pulses. The combination of frequency, time delay, and phase selection provides significant control over the ionization process and ultimately improves the ability to analyze and assign complex molecular spectra. [ABSTRACT FROM AUTHOR]

We calculate electron impact partial and total ionization cross sections of R-carvone (C10H14O), 2-butanol (C4H10O), imidazole (C3H4N2), and 2-nitroimidazole (C3H3N3O2). We have used the Binary Encounter Bethe (BEB) model to obtain total electron impact ionization cross sections (TICSs). The modified BEB method in combination with mass spectrum data of the molecules is used to calculate the partial ionization cross section (PICS) of the cationic fragments dissociating from the parent molecule. Our PICS data for R-carvone and 2-butanol are in good agreement with the experimental data for all the cation fragments along with the TICS data. For imidazole and 2-nitroimidazole, the estimates of the PICS are reported for the first time in the present study. We have found that both the modified BEB method and the mass spectrum dependence method work effectively to estimate PICS if we have information about the appearance energies and relative abundance data of the target under investigation. [ABSTRACT FROM AUTHOR]

While carrying out Beyond Born–Oppenheimer theory based diabatization, the solutions of adiabatic-to-diabatic transformation equations depend on the paths of integration over two-dimensional cross-sections of multi-dimensional space of nuclear degrees of freedom. It is shown that such path-dependent solutions leading to diabatic potential energy surface matrices computed along any two different paths are related through an orthogonal matrix, and thereby, those surface matrices should provide unique observables. While exploring the numerical validity of the theoretical framework, we construct diabatic Hamiltonians for the five low-lying electronic states ( X ̃ 2 E 1 g , B ̃ 2 E 2 g , and C ̃ 2 A 2 u ) of benzene radical cation ( C 6 H 6 + ) along three different approaches of contour integration over two dimensional nuclear planes constituted by seven non-adiabatically active normal modes. Three different diabatic surface matrices are further employed to generate the photoelectron spectra of the benzene molecule (C6H6). It is interesting to note that the spectral peak positions and intensity patterns for all three cases are almost close to each other and also exhibit very good agreement with the experimental results. [ABSTRACT FROM AUTHOR]

We model near-field thermal emission from metasurfaces structured as two-dimensional arrays of ellipsoidal SiC particles. The modeling approach is developed from fluctuational electrodynamics and is applicable to systems of ellipsoidal particles within the dipole limit. In all simulations, the radial lengths of particles are restricted to the range of 10–100 nm, and interparticle spacing is constrained to at least three times the particle characteristic length. The orientation and dimensions of constituent ellipsoidal particles are varied to tune localized surface phonon resonances and control the near-field energy density above metasurfaces. Results show that particle orientation can be used to regulate the relative magnitude of resonances in the energy density, and particle dimensions may be changed to adjust the frequency of these resonances within the Reststrahlen band. Metasurfaces constructed from particles with randomized dimensions display comparatively broadband thermal emission rather than the three distinct resonances seen in metasurfaces made with ellipsoidal particles of equivalent dimensions. When the interparticle spacing in a metasurface exceeds about three times the particle characteristic length, the spectral energy density above the metasurface is dominated by individual particle self-interaction and can be approximated as a linear combination of single-particle spectra. When interparticle spacing is at the lower limit of three times the characteristic length, however, multiparticle interaction effects increase and the spectral energy density above a metasurface deviates from that of single particles. This work provides guidance for designing all-dielectric, particle-based metasurfaces with desired near-field thermal emission spectra, such as thermal switches. [ABSTRACT FROM AUTHOR]

Computational optimal transport is used to analyze the difference between pairs of continuous molecular spectra. It is demonstrated that transport distances which are derived from this approach may be a more appropriate measure of the difference between two continuous spectra than more familiar measures of distance under many common circumstances. Associated with the transport distances is the transport map which provides a detailed analysis of the difference between two molecular spectra and is a key component of our study of quantitative differences between two continuous spectra. The use of optimal transport for comparing molecular spectra is developed in detail here with a set of model spectra, so that the discussion is self-contained. The difference between the transport distance and more common definitions of distance is elucidated for some well-chosen examples and it is shown where transport distances may be very useful alternatives to standard definitions of distance. The transport distance between a theoretical and experimental electronic absorption spectrum for SO2 is studied and it is shown how the theoretical spectrum can be modified to fit the experimental spectrum better adjusting the theoretical band origin and the resolution of the theoretical spectrum. This analysis includes the calculation of transport maps between the theoretical and experimental spectra suggesting future applications of the methodology. [ABSTRACT FROM AUTHOR]

We investigate the temporal correlation between very-high-frequency (VHF, at frequencies of the order of 10–100 MHz), ultrahigh-frequency (UHF, at frequencies within 1–6 GHz), and x-ray (with photon energies more than 10 keV) emissions, which accompany the development of a high-voltage discharge initiated in a long gap at voltages up to 1 MV. The x-ray and UHF emissions are found to emerge starting approximately from the prepulse current onset observed before the discharge gap breakdown and both gradually decay coming to this instant. The UHF emission spectrum is represented with frequencies up to 6 GHz, with the highest spectral power being achieved within 1–2 GHz. The radio emission power drops sharply at frequencies below 1 GHz and increases closer to 150 MHz with the highest spectral power of VHF radiation being reached within 60–90 MHz. The VHF emission can appear before the discharge current and UHF emission onsets in the form of 100-ns-long prepulses, and its intensity significantly increases as the UHF emission starts. The analysis of the temporal correlation between x rays, VHF, and UHF radiations, discharge current, and voltage waveforms indicates that the generation mechanisms of the discharge electromagnetic radiations are difficult to be interpreted in terms of the developing or colliding streamer concepts. [ABSTRACT FROM AUTHOR]

The electronic and vibrational spectra of the meso-tetrakis(4-sulfonatophenyl)-porphyrins (TSPP) have been studied computationally using the PFD-3B functional with time-dependent density functional theory for the excited states. The calculated UV-vis absorption and emission spectra in aqueous solution are in excellent agreement with the experimental measurements of both H2TSPP−4 (monomer) at high pH and H4TSPP−2 (forming J-aggregate) at low pH. Moreover, our calculations reveal an infrared absorption at 1900 cm−1 in the singlet and triplet excited states that is absent in the ground state, which is chosen as a probe for transient IR absorption spectroscopy to investigate the vibrational dynamics of the excited state. Specifically, the S2 to S1 excited state internal conversion process time, the S1 state vibrational relaxation time, and the lifetime of the S1 excited electronic state are all quantitatively deduced. [ABSTRACT FROM AUTHOR]

Here, we analyzed the effect of a donor molecule (Rh6G) on the random laser emission of an acceptor molecule (Rh640 perchlorate) coated on the surface of a polymer optical fiber. Due to the energy transfer mechanism, the random lasing threshold of Rh640 perchlorate was found to be reduced in the presence of Rh6G. Also, the emission spectrum of Rh640 perchlorate was blue-shifted with the addition of Rh6G. Meanwhile, there is an enhancement in the lasing threshold of Rh6G in the presence of Rh640 perchlorate. The present study demonstrates that by properly adjusting the concentrations of both donor and acceptor molecules, we can obtain a dual-color random laser emission from polymer optical fiber. [ABSTRACT FROM AUTHOR]

Quantum-chemistry methods in the time domain with Gaussian basis sets are increasingly used to compute high-harmonic generation (HHG) spectra of atomic and molecular systems. The quality of these approaches is limited by the accuracy of Gaussian basis sets to describe continuum energy states. In the literature, optimal-continuum Gaussian basis sets have been proposed: Kaufmann et al. [J. Phys. B: At., Mol. Opt. Phys. 22, 2223 (1989)], Woźniak et al. [J. Chem. Phys. 154, 094111 (2021)], Nestmann and Peyerimhoff [J. Phys. B: At., Mol. Opt. Phys. 23, L773 (1990)], Faure et al. [Comput. Phys. Commun. 144, 224 (2002)], and Krause et al. [J. Chem. Phys. 140, 174113 (2014)]. In this work, we have compared the performances of these basis sets to simulate HHG spectra of H atom at different laser intensities. We have also investigated different strategies to balance basis sets with these continuum functions, together with the role of angular momentum. To quantify the performance of the different basis sets, we introduce local and global HHG descriptors. Comparisons with the grid and exact calculations are also provided. [ABSTRACT FROM AUTHOR]

The rotational spectrum of the molecular ion HCNH+ is revisited using double-resonance spectroscopy in an ion trap apparatus, with six transitions measured between 74 and 445 GHz. Due to the cryogenic temperature of the trap, the hyperfine splittings caused by the 14N quadrupolar nucleus were resolved for transitions up to J = 4 ← 3, allowing for a refinement of the spectroscopic parameters previously reported, especially the quadrupole coupling constant eQq. [ABSTRACT FROM AUTHOR]

First-principles calculations for electrochemistry require accurate treatment of both electronic structure and solvation. The perturbative GW approximation starting from density functional theory (DFT) calculations accurately models materials systems with varying dimensionality. Continuum solvation models enable efficient treatment of solvation effects in DFT calculations, but their applications with beyond-DFT electronic structure methods such as GW have been limited. Here, we introduce the frequency-dependent liquid polarizability from a nonlocal continuum solvation model in the screened Coulomb interaction of full-frequency GW calculations with a solvated DFT starting point. We show that the liquid screening contributions substantially reduce the HOMO–LUMO gap of molecules by 3–5 eV, while solvent effects on the DFT starting point negligibly impact the GW gap. The resulting framework facilitates the simultaneous electronic and solvation accuracy needed for first-principles electrochemistry. [ABSTRACT FROM AUTHOR]

The vibrational self-consistent field (VSCF) method yields anharmonic states and spectra for molecular vibrations, and it serves as the starting point for more sophisticated correlated-vibration methods. Convergence of the iterative, non-linear optimization in VSCF calculations can be erratic or altogether unsuccessful, particularly for chemical systems involving low-frequency motions. In this work, a vibrational formulation of the Direct Inversion of the Iterative Subspace method of Pulay is presented and investigated. This formulation accounts for distinct attributes of the vibrational and electronic cases, including the expansion of each single-mode vibrational wavefunction in its own basis set. The resulting Direct Inversion of the Iterative Subspace method is shown to substantially accelerate VSCF convergence in all convergent cases as well as rectify many cases where Roothaan-based methods fail. Performance across systems ranging from small, rigid molecules to weakly bound molecular clusters is investigated in this analysis. [ABSTRACT FROM AUTHOR]

The MACE architecture represents the state of the art in the field of machine learning force fields for a variety of in-domain, extrapolation, and low-data regime tasks. In this paper, we further evaluate MACE by fitting models for published benchmark datasets. We show that MACE generally outperforms alternatives for a wide range of systems, from amorphous carbon, universal materials modeling, and general small molecule organic chemistry to large molecules and liquid water. We demonstrate the capabilities of the model on tasks ranging from constrained geometry optimization to molecular dynamics simulations and find excellent performance across all tested domains. We show that MACE is very data efficient and can reproduce experimental molecular vibrational spectra when trained on as few as 50 randomly selected reference configurations. We further demonstrate that the strictly local atom-centered model is sufficient for such tasks even in the case of large molecules and weakly interacting molecular assemblies. [ABSTRACT FROM AUTHOR]

We calculated the one- (OPA) and two-photon absorption (TPA) spectra of two large water-soluble stilbene derivatives presenting TPA cross sections of about 400 GM. However, the reported experimental TPA spectra present a spectral gap region, and a theoretical study of these promising molecules seems now timely and relevant. These molecules are composed of 200 or more atoms, becoming a challenge to obtain the TPA spectra even using density functional theory at the time-dependent quadratic response formalism. Thus, both OPA and TPA were also calculated using the INDO-S semi-empirical method. We used explicit solvent molecules using the sequential-quantum mechanics/molecular mechanics to include the solvent effects. Our results show that different transitions are participating in the OPA and TPA processes and that exchange–correlation functionals, including larger Hartree–Fock contributions, provide a better description of the OPA spectra; however, the opposite trend is observed on the TPA spectra. Alternatively, INDO-S/CISD, including contributions from single and double excitations, systematically describes both OPA and TPA bands with similar shifts and better reproduces the relative intensities of the two TPA bands compared to the experimental ones. The OPA spectra are characterized by a Highest Occupied Molecular Orbital-Lowest Unoccupied Molecular Orbital (HOMO–LUMO) excitation, while the low-energy TPA band is ascribed to a single transition encompassing the (HOMO-1)–LUMO and HOMO–(LUMO+1) excitations and the high-energy one is a combination of several transitions. Thus, although more studies are required to better assess the capability of the INDO-S/CISD method in describing the TPA spectra of large molecules, our results corroborate that it is a promising alternative. [ABSTRACT FROM AUTHOR]

Intensities of 14 lines in the sixth overtone (7–0) band of carbon monoxide (12C16O) are measured in the visible range between 14 300 and 14 500 cm−1 using a frequency-stabilized cavity ring-down spectrometer. This is the first observation of such a high and weak overtone spectrum of the CO molecule. A theoretical model is constructed and tested based on the use of a high accuracy ab initio dipole moment curve and a semi-empirical potential energy curve. Accurate studies of high overtone transitions provide a challenge to both experiment and theory as the lines are very weak: below 2 × 10−29 cm molecule−1 at 296 K. Agreement between theory and experiment within the experimental uncertainty of a few percent is obtained. However, this agreement is only achieved after issues with the stability of the Davidson correction to the multi-reference configuration interaction calculations are addressed. [ABSTRACT FROM AUTHOR]

The rotational spectrum of the molecular ion HCNH+ is revisited using double-resonance spectroscopy in an ion trap apparatus, with six transitions measured between 74 and 445 GHz. Due to the cryogenic temperature of the trap, the hyperfine splittings caused by the 14N quadrupolar nucleus were resolved for transitions up to J = 4 ← 3, allowing for a refinement of the spectroscopic parameters previously reported, especially the quadrupole coupling constant eQq. [ABSTRACT FROM AUTHOR]

By employing the doorway-window (DW) on-the-fly simulation protocol, we performed ab initio simulations of peak evolutions and beating maps of electronic two-dimensional (2D) spectra of a polyatomic molecule in the gas phase. As the system under study, we chose pyrazine, which is a paradigmatic example of photodynamics dominated by conical intersections (CIs). From the technical perspective, we demonstrate that the DW protocol is a numerically efficient methodology suitable for simulations of 2D spectra for a wide range of excitation/detection frequencies and population times. From the information content perspective, we show that peak evolutions and beating maps not only reveal timescales of transitions through CIs but also pinpoint the most relevant coupling and tuning modes active at these CIs. [ABSTRACT FROM AUTHOR]

We present a new collocation method for computing the vibrational spectrum of a polyatomic molecule. Some form of quadrature or collocation is necessary when the potential energy surface does not have a simple form that simplifies the calculation of the potential matrix elements required to do a variational calculation. With quadrature, better accuracy is obtained by using more points than basis functions. To achieve the same advantage with collocation, we introduce a collocation method with more points than basis functions. Critically important, the method can be used with a large basis because it is incorporated into an iterative eigensolver. Previous collocation methods with more points than functions were incompatible with iterative eigensolvers. We test the new ideas by computing energy levels of molecules with as many as six atoms. We use pruned bases but expect the new method to be advantageous whenever one uses a basis for which it is not possible to find an accurate quadrature with about as many points as there are basis functions. For our test molecules, accurate energy levels are obtained even using non-optimal, simple, equally spaced points. [ABSTRACT FROM AUTHOR]

Real time modeling of fluorescence with vibronic resolution entails the representation of the light–matter interaction coupled to a quantum-mechanical description of the phonons and is therefore a challenging problem. In this work, taking advantage of the difference in timescales characterizing internal conversion and radiative relaxation—which allows us to decouple these two phenomena by sequentially modeling one after the other—we simulate the electron dynamics of fluorescence through a master equation derived from the Redfield formalism. Moreover, we explore the use of a recent semiclassical dissipative equation of motion [C. M. Bustamante et al., Phys. Rev. Lett. 126, 087401 (2021)], termed coherent electron electric-field dynamics (CEED), to describe the radiative stage. By comparing the results with those from the full quantum-electrodynamics treatment, we find that the semiclassical model does not reproduce the right amplitudes in the emission spectra when the radiative process involves the de-excitation to a manifold of closely lying states. We argue that this flaw is inherent to any mean-field approach and is the case with CEED. This effect is critical for the study of light–matter interaction, and this work is, to our knowledge, the first one to report this problem. We note that CEED reproduces the correct frequencies in agreement with quantum electrodynamics. This is a major asset of the semiclassical model, since the emission peak positions will be predicted correctly without any prior assumption about the nature of the molecular Hamiltonian. This is not so for the quantum electrodynamics approach, where access to the spectral information relies on knowledge of the Hamiltonian eigenvalues. [ABSTRACT FROM AUTHOR]

The light output of quantum cascade lasers is strongly affected by electric field-domain oscillations if the laser shows electrical instabilities. This can result in a substantial broadening of the emission spectrum, which is investigated here by detailed simulations for a terahertz device. We explain how the light pulsation is affected by electrical injection conditions and external capacitances. Experimental data confirm that the oscillation frequencies are not essentially affected by circuit conditions, while a large external capacitance produces almost non-observable oscillations due to stabilization of the circuit. [ABSTRACT FROM AUTHOR]

Developing near ultraviolet (NUV) excited yellow-emitting phosphors with emission spectrum encompassing cyan light is an inevitable requirement for pursuing full-spectrum high-quality lighting. In this study, a yellow-emitting phosphor, LuMgGaO 4 :Bi3+, was successfully synthesized through the selection of gallate with facile synthesis, chemical stability, and favorable cationic sites. Under excitation by NUV light, LuMgGaO 4 :Bi3+ emits yellow light with a significant Stokes shift, low emission energy, and a large full width at half maximum (FWHM), which originates from d -state emission. The origin of excitation and d -state emission is elaborated through crystal structure and spectral data analysis, as well as theoretical calculations grounded on semi-empirical models. The results suggest that the excitation spectrum of LuMgGaO 4 :Bi3+ is composed of Bi3+ pairs, MMCT, and 1S 0 →3P 1 electron transitions, and the d -state emission of LuMgGaO 4 :Bi3+ originates from Bi3+ pairs. The packaged WLED lamp can emit warm white light without any cyan or yellow light traps present. The results indicate that LuMgGaO 4 :Bi3+ phosphor holds immense potential for employment in full-spectrum WLED lighting. [ABSTRACT FROM AUTHOR]

Förster Resonance Energy transfer (FRET) is a nonradiative process that may occur from an electronically excited donor to an acceptor when the emission spectrum of the donor overlaps with the absorption spectrum of the acceptor. FRET experiments have been done in the gas phase based on specially designed mass‐spectroscopy setups with the goal to obtain structural information on biomolecular ions labeled with a FRET pair (i.e., donor and acceptor dyes) and to shed light on the energy‐transfer process itself. Ions are accumulated in a radio‐frequency ion trap or a Penning trap where mass selection of those of interest takes place, followed by photoexcitation. Gas‐phase FRET is identified from detection of emitted light either from the donor, the acceptor, or both, or from a fragmentation channel that is specific to the acceptor when electronically excited. The challenge associated with the first approach is the collection and detection of photons emitted from a thin ion cloud that is not easily accessible while the second approach relies both on the photophysical and chemical behavior of the acceptor. In this review, we present the different instrumentation used for gas‐phase FRET, including a discussion of advantages and disadvantages, and examples on how the technique has provided important structural information that is not easily obtainable otherwise. Furthermore, we describe how the spectroscopic properties of the dyes are affected by nearby electric fields, which is readily discernable from experiments on simple model systems with alkyl or π‐conjugated bridges. Such spectral changes can have a significant effect on the FRET efficiency. Ideas for new directions are presented at the end with special focus on cold‐ion spectroscopy. [ABSTRACT FROM AUTHOR]

During the last decades, various strategies have been optimized to enhance clearance of a variable spectrum of retained molecules to ensure hemodynamic tolerance to fluid removal and improve long-term survival in patients affected by kidney failure. Treatment effects are the result of the interaction of individual patient characteristics with device characteristics and treatment prescription. Historically, the nephrology community aimed to provide adequate treatment, along with the best possible quality of life and outcomes. In this article, we analyzed blood purification techniques that have been developed with their different characteristics. [ABSTRACT FROM AUTHOR]

The transfer of nuclear spent fuel from the reactor storage pool to dry storage or for reprocessing or final disposition requires information about its isotopic composition, decay heat, and other thermomechanical properties. The spent nuclear fuel assembly of a typical advanced pressurized water reactor, AP-1000, was characterized using the Monte Carlo MCNPX code and SCALE/ORIGEN code. The simulation of operational history started from the operation of the first fresh core for an average fuel assembly with certain physical isotopic parameters until 25 GWd/tonne U discharge burnup. The analysis considered the calculations of the radionuclide inventories, activity, neutron emission spectrum, gamma-ray emission spectrum, and decay power after 700 effective full power days and for post different time ranges until a 1 million–year cooling period. The comparison of some results of the two codes showed small differences due to the consideration of the continuous-energy variation for neutrons in the MCNPX code and the discrete energy assumption in the SCALE/ORIGEN code. [ABSTRACT FROM AUTHOR]

A rare earth oxyborate crystal K2Nd2O(BO3)2 has been grown by means of high temperature solution method for the first time. It crystallizes in monoclinic P21/c (No. 14) space group, and the lattice parameters are a=11.318(6) Å, b=6.575(4) Å, c=10.689(6) Å, β=117.062(12)°, and Z=4. The absorption spectrum, emission spectrum, and fluorescence lifetime of K2Nd2O(BO3)2 have been evaluated, and the foundational spectral parameters have been analysed according to the Judd‐Ofelt theory. The high concentration of activated ions (1.13×1022 ions/cm3), large absorption coefficient (87.63 cm−1), long fluorescence lifetime (91.2 μs), and large emission cross section (2.03×10−20 cm2) of K2Nd2O(BO3)2 suggest its potential applications of microchip lasers. [ABSTRACT FROM AUTHOR]

4U 1702−429, an atoll-type neutron star low-mass X-ray binary, was observed twice by the AstroSat /Soft X-ray Telescope (SXT) and Large Area X-ray Proportional Counters (LAXPC-20) on 2018 April 27 and 2019 August 8. Persistent emission spectra of the source were well fitted with the model combination - constant × tbabs (thcomp × diskbb+powerlaw). The parameters obtained from the spectral analysis revealed the source to be in a hard spectral state during the observations. Time-resolved spectral analyses were performed on the three type I X-ray bursts detected from the source. Burst analysis showed that the source underwent a photospheric radius expansion. Consequently, the radius of the neutron star and distance to the source (with isotropic and anisotropic burst emission) were obtained as 12.65 |$\substack{+0.90\\-0.86}$| km and 6.92 |$\substack{+0.16\\-0.09}$| and 8.43 |$\substack{+0.20\\-0.10}$| kpc, respectively. [ABSTRACT FROM AUTHOR]

We report the synthesis, structures, and magnetic and luminescence properties of a series of new monoand dinuclear Er3+ complexes derived from sterically demanding aryloxide and fluorinated alkoxide ligands: [4-tBu-2,6-(Ph2CH)2C6H2O]3Er(THF) (1), [(C6F5)3CO]3Er(Me3SiOH) (2), [(C6F5)3CO]3Er[(Me3Si)2NH] (3), [(C6F5)3CO]3Er(C6H5CH3) (4), [(C6F5)3CO]3Er(o-Me2NC6H4CH3) (5) and {[Ph(CF3)2CO]2Er(μ²-OC (CF3)2Ph)}2 (6). In compounds 1, 2, and 4, the Er3+ ion is four-coordinated and adopts a distorted trigonal pyramidal geometry, while in 3, 5, and 6, the coordination geometry of Er3+ is impacted by the presence of several relatively short Er...F distances, making them rather 6-coordinated. All compounds behave as field-induced Single Molecule Magnets (SMMs) and exhibit an Er3+ characteristic near infrared (NIR) emission associated with the 4I13/2 → 4I15/2 transition with a remarkably long lifetime going up to 73 µs, which makes them multifunctional luminescent SMMs. The deconvolution of the NIR emission spectra allowed us to provide a direct probe of the crystal field splitting in these compounds, which was correlated with magnetic data. [ABSTRACT FROM AUTHOR]

Developing a single-phase white emitting nanophosphor with high quantum efficiency has become a hotspot for scientific world. Herein, single-phase white-light emitting Zn1-x O:xDy3+ nanophosphors have been synthesized via a sonochemical method. X-ray diffraction analysis and Raman spectroscopy-based investigations confirmed the hexagonal wurtzite phase for Zn1-xO:xDy3+ nanophosphors with preferential growth along the (101) plane. Scanning electron microscopy images showed the formation of a ribbonshaped morphology with a diameter of ~25 nm. The emission spectra of the Dy3+-activated ZnO nanophosphors exhibited three distinct peaks, namely blue (480 nm), yellow (572 nm), and red (635 nm) emissions, under near-UV excitations related to the 4F9/2 → 6HJ (J = 15/2, 13/2, and 11/2) transitions of Dy3+ ions. The values of CIE chromaticity coordinates for the optimized phosphor (x = 0.329, y = 0.334) with correlated color temperature (CCT) of 5657 K indicated cool white-light emission from the phosphor. The thermal stability of ZnO:Dy3+ nanophosphors was probed by temperature-dependent luminescence. Quantitative evaluation of Judd-Ofelt intensity parameters, radiative parameters, luminescence decay, and quantum efficiency of Zn1-xO:xDy3+ using the J-O theory suggests that these nanophosphors are promising luminescent media for commercial white LEDs and other display devices. [ABSTRACT FROM AUTHOR]

Much of the information gleaned from observations of star-forming regions comes from the analysis of their molecular emission spectra, particularly in the radio regime. The time-consuming nature of fitting synthetic spectra to observations interactively for such line-rich sources, however, often results in such analysis being limited to data extracted from a single-dish observation or a handful of pixels from an interferometric observation. Yet, star-forming regions display a wide variety of physical conditions that are difficult, if not impossible, to accurately characterize with such a limited number of spectra. We have developed an automated fitting routine that visits every pixel in the field of view of an Atacama Large Millimeter/submillimeter Array (ALMA) data cube and determines the best-fit physical parameters, including excitation temperature and column densities, for a given list of molecules. In this proof-of-concept work, we provide an overview of the fitting routine and apply it to 0.″26, 1.1 km s−1 resolution ALMA observations of two sites of massive star formation in NGC 6334I. Parameters were found for 21 distinct molecules by generating synthetic spectra across 7.48 GHz of spectral bandwidth between 280 and 351 GHz. Spatial images of the derived parameters for each of the >8000 pixels are presented with special attention paid to the C2H4O2 isomers and their relative variations. We highlight the greater scientific utility of the column density and velocity images of individual molecules compared to traditional moment maps of single transitions. [ABSTRACT FROM AUTHOR]

Achieving tunable emissions spanning the spectrum, from blue to near‐infrared (NIR) light, within a single component is a formidable challenge with significant implication, particularly in tailoring multicolor luminescence for anti‐counterfeiting purposes. In this study, we demonstrate a broad spectrum of emissions, covering blue to red and extending into NIR light in [BPy]2CdX4 : xSb3+ (BPy=Butylpyridinium; X=Cl, Br; x=0 to 0.08) through precise multisite structural fine‐tuning. Notably, the multicolor emissions from [BPy]2CdBr4 : Sb3+ manifest a distinctive pattern, transitioning from blue to yellow in tandem with the host [BPy]2CdBr4 and further extending from yellow to NIR with its homologous [BPy]2CdCl4 : Sb3+, resulting in the simultaneous presence of intersecting and independent emission colors. Detailed modulation of chemical composition enables partial luminescence switching, facilitating the creation of diverse patterns with multicolor luminescence by employing [BPy]2CdX4 : xSb3+ as phosphors. This study for the first time successfully implements several groups of tunable emission colors in a single matrix via multisite fine‐tuning. Such an effective strategy not only develops the specific relationships between tunable emissions and adjustable compositions, but also introduces a cost‐effective and straightforward approach to achieving unique, high‐level, plentiful‐color and multiple‐information‐storage labels for advanced anti‐counterfeiting applications. [ABSTRACT FROM AUTHOR]

Silicon carbide quantum dots ( QDs) were prepared by simple chemical etching method using a mixture of hydrofluoric acid, nitric acid, and analytically pure sulfuric acid as etchants. Ultrasonic cavitation fragmentation was performed on the corrosive mixture, and then it was subjected to high-speed tomographic cutting in a concentration gradient solvent to obtain silicon carbide QDs with excellent optical properties and controllable particle size. The evolution process of microstructure of SiC QDs during corrosion process, the microstructure and emission spectra of SiC QDs were detected and analyzed, and then correlation mechanism at quantum dots size, spectrum, and color was established by emission spectra as a link. The results show that under the conditions of a =1 000 hypergravity coefficient and a centrifugation time of 120 min, the average diameter of QDs at 0, 30, and 60 mm displacement from the liquid surface is about 2, 5, and 7 nm. Under single wavelength excitation, as the diameter of SiC QDs changes from 2→5→7 nm, the relative intensity peak of photoluminescence shows a red shift from 417→435→445 nm, and the luminescence color also show a corresponding change pattern of blue green →green→yellow green; further research had found that the full width at half maximum of the emission spectra of QDs of three sizes show an increase of 81→97→106 nm with increasing liquid depth. Preliminary analysis suggests that it was due to the higher uniformity of particle size distribution of quantum dots near the upper liquid surface compared to those far away from the upper liquid surface after high-speed centrifugal chromatography cutting. [ABSTRACT FROM AUTHOR]

The radiation hardness of ultrabroadband spintronic terahertz emitters against γ and proton irradiation is investigated. We find that irradiation doses equivalent to those experienced by a space instrument en-route to and operated on Mars have a minor effect on the performance of the emitters. In particular, the ultrawide emission spectrum ranging from 0.1–30 THz, which covers a large part of the vibrational fingerprint region, remains unchanged. These results make this emitter type highly interesting as an essential building block for broadband gas sensors based on terahertz time-domain spectroscopy for future space missions. [ABSTRACT FROM AUTHOR]

We explore the application of artificial neural networks (ANNs) for predicting plasma temperatures in Laser-Induced Breakdown Spectroscopy (LIBS) analysis. Estimating plasma temperature from emission spectra is often challenging due to spectral interference and matrix effects. Traditional methods like the Boltzmann plot technique have limitations, both in applicability due to various matrix effects and in accuracy owing to the uncertainty of the underlying spectroscopic constants. Consequently, ANNs have already been successfully demonstrated as a viable alternative for plasma temperature prediction. We leverage synthetic data to isolate temperature effects from other factors and study the relationship between the LIBS spectra and temperature learnt by the ANN. We employ various post-hoc model interpretation techniques, including gradient-based methods, to verify that ANNs learn meaningful spectroscopic features for temperature prediction. Our findings demonstrate the potential of ANNs to learn complex relationships in LIBS spectra, offering a promising avenue for improved plasma temperature estimation and enhancing the overall accuracy of LIBS analysis. [ABSTRACT FROM AUTHOR]

Background: Neurofibromatosis type 1 (NF1) is a highly heterogeneous autosomal genetic disorder characterized by a broad spectrum of clinical and molecular manifestations. The correlations between genotype and phenotype in NF1 remain elusive. This study aimed to elucidate genotype–phenotype associations in a large Chinese cohort of NF1 patients. Methods: We included NF1 patients from our center who underwent genetic testing for NF1 variants and systemic examination. Genotype–phenotype correlation analyses were performed, focusing on variation types and involved neurofibromin domains. Results: A total of 195 patients were enrolled, comprising 105 males and 90 females, with a median age of 18 years. Truncating variants, single amino acid variations, and splicing variants accounted for 139/195 (71.3%), 23/195 (11.8%), and 33/195 (16.9%), respectively. Patients with splicing variants exhibited a significantly higher prevalence of spinal plexiform neurofibromas (spinal PNF) than those with truncating variants (76.4% vs. 51.8%; p = 0.022). Variations affecting the PKC domain were associated with higher rates of cutaneous neurofibromas (CNF) (100% vs. 64.9%, p < 0.001), Lisch nodules (100% vs. 61.2%, p < 0.001), plexiform neurofibromas (PNF) (100% vs. 95.7%, p = 0.009), and psychiatric disorders (11.8% vs. 1.6%, p = 0.042). Patients with mutations in the CSRD had an elevated risk of secondary primary malignancies (11.6% vs. 2.8%, p = 0.015). GRD involvement might enhance the risk of Lisch nodules (76.9% vs. 53.7%, p = 0.044). Variations in the Sec14-PH domain were correlated with a higher rate of CNF (76.8% vs. 58.6%, p = 0.014). Additionally, we found that the p.R1748* variants carry a high risk of malignancy. Conclusion: Our study suggested some novel genotype–phenotype correlations within a Chinese cohort, providing innovative insights into this complex field that may contribute to genetic counseling, risk stratification, and clinical management for the NF1 population. [ABSTRACT FROM AUTHOR]

Mixing multicolor phosphors for simulating the full spectrum of sunlight illumination is a popular solution to obtain high-quality white light. However, there is still a need to overcome the cyan gap in the emission spectrum. In this work, a series of garnet Ca2Y0.94-xLuxZr2-yHfyAl3O12:6%Ce3+ (abbreviated as CY0.94-xLuxZr2-yHfyA:Ce3+) cyan phosphors are designed and prepared by substituting Y3+ and Zr4+ in Ca2YZr2Al3O12:6%Ce3+ with Lu3+ and Hf4+ with smaller ionic radius and larger mass. Under 405 nm violet light excitation, the optimized Ca2Y0.88Lu0.06Hf2Al3O12:6%Ce3+ (CY0.88Lu0.06Hf2A:Ce3+) shows a bright cyan emission band in the range of 430-750 nm with the peak at 477 nm. Importantly, the emission intensity and thermal stability properties of CY0.88Lu0.06Hf2A:Ce3+ were significantly improved by 58% and 47% compared to those of pure Ca2YZr2Al3O12:Ce3+. Small and heavy cation substitution could induce highly stable rigid structure, thus enhancing emission intensity and stability. The color rendering index increases from 84.5 to 92.0 after supplementing CY0.88Lu0.06Hf2A:Ce3+ phosphor in white light-emitting diode devices combining commercial red, green, and blue phosphors with a violet chip, indicating its practical application in full-spectrum lighting. The present study provides promising strategies for the design and development of efficient cyan materials for high-quality full visible spectrum light-emitting diode lighting. [ABSTRACT FROM AUTHOR]

Transparent glass-ceramics containing CaF 2 single-phase or CaF 2 /Ca 5 (PO 4) 3 F two-phase were obtained by heat-treating the precursor glass. Compared with the precursor glass, the glass-ceramics containing CaF 2 crystal with low phonon energy greatly enhance the emission intensity. Further research was conducted on the influence of various crystallization procedures on the luminescent properties of the glass-ceramic, and the procedure crystallized at 660 °C for 4 h was determined to be the optimal heat treatment. The SEM results indicate that the crystal size of the glass-ceramics is in the nanometer scale, which guarantees the possibility of its optical application. The three-photon absorption process of the Tb3+/Yb3+ co-doped glass-ceramics containing CaF 2 single-phase was confirmed based on the up-conversion emission spectra excited at different power of 980 nm laser. The chromaticity coordinates of the Tb3+/Yb3+ co-doped glass-ceramic are located in the green region, indicating its potential applications in green lighting and other optical display devices. [ABSTRACT FROM AUTHOR]

The transparent [Li 0.04 (K 0.5 Na 0.5) 0.96 ]NbO 3 +0.5mol% Er 2 O 3 (KNNLN-Er) lead-free piezoelectric ceramics were prepared by stereolithography technique. The influence of different sintering holding time (4h∼8h) on the micromorphology, relative density, shrinkage, electric properties, and photoluminescence properties were systematically investigated. The KNNLN-Er ceramics show the coexistence of orthorhombic and tetragonal structures. The grain size increases obviously and then decreases slightly with the holding time increasing. The KNNLN-Er ceramics exhibit good piezoelectric performance (piezoelectric constant d 33 ∼97 pC/N, electromechanical couple coefficient k t ∼0.36) and the moderate transparency of 34% when the holding time is 6h during sintering at 1120°C. Besides, the intensity of the photoluminescence emission spectra increases with the holding time increasing. Furthermore, in order to estimate the properties of the KNNLN-Er transparent ceramics, an ultrasonic transducer with a center frequency of 10.5 MHz was fabricated, which can be used for photoacoustic and fluorescence imaging. The results indicate that the KNNLN-Er ceramics have potential for multimode imaging applications. [ABSTRACT FROM AUTHOR]

Context. Space-based mid-infrared (IR) spectroscopy is a powerful tool for the characterization of important star formation tracers of warm gas which are unobservable from the ground. The previous mid-IR spectra of bright high-mass protostars with the Infrared Space Observatory (ISO) in the hot-core phase typically show strong absorption features from molecules such as CO2, C2H2, and HCN. However, little is known about their fainter counterparts at earlier stages. Aims. We aim to characterize the gas-phase molecular features in James Webb Space Telescope Mid-Infrared Instrument Medium Resolution Spectrometer (MIRI/MRS) spectra of the young and clustered high-mass star-forming region IRAS 23385+6053. Methods. Spectra were extracted from several locations in the MIRI/MRS field of view, targeting two mid-IR sources tracing embedded massive protostars as well as three H2 bright outflow knots at distances of >8000 au from the multiple. Molecular features in the spectra were fit with local thermodynamic equilibrium (LTE) slab models, with their caveats discussed in detail. Results. Rich molecular spectra with emission from CO, H2, HD, H2O, C2H2, HCN, CO2, and OH are detected towards the two mid-IR sources. However, only CO and OH are seen towards the brightest H2 knot positions, suggesting that the majority of the observed species are associated with disks or hot core regions rather than outflows or shocks. The LTE model fits to 12CO2, C2H2, HCN emission suggest warm 120–200 K emission arising from a disk surface around one or both protostars. The abundances of CO2 and C2H2 of ~10−7 are consistent with previous observations of high-mass protostars. Weak ~500 K H2O emission at ~6–7 µm is detected towards one mid-IR source, whereas 250–1050 K H2O absorption is found in the other. The H2O absorption may occur in the disk atmosphere due to strong accretion-heating of the midplane, or in a disk wind viewed at an ideal angle for absorption. CO emission may originate in the hot inner disk or outflow shocks, but NIRSpec data covering the 4.6 µm band head are required to determine the physical conditions of the CO gas, as the high temperatures seen in the MIRI data may be due to optical depth. OH emission is detected towards both mid-IR source positions and one of the shocks, and is likely excited by water photodissociation or chemical formation pumping in a highly non-LTE manner. Conclusions. The observed molecular spectra are consistent with disks having already formed around two protostars in the young IRAS 23385+6054 system. Molecular features mostly appear in emission from a variety of species, in contrast to the more evolved hot core phase protostars which typically show only absorption; however, further observations of young high-mass protostars are needed to disentangle geometry and viewing angle effects from evolution. [ABSTRACT FROM AUTHOR]

This article describes the synthesis and crystal structure of ten new Tc(V) complexes with pyrazine containing homologous alkoxy ligands. We carried out an analysis of the Hirshfeld surfaces for the described compounds and found out that with increasing length of the hydrocarbon substituent from CH3 to C10H21 the percentage of H⋯H interactions in crystals increases from 28% to 59%. The purpose of this article was to show the pattern of increase in interplanar distances in crystals depending on the length of the hydrocarbon substituent, and also to study the thermochemical properties of Tc(V) complexes. The mechanism of thermolysis does not depend on the length of the hydrocarbon substituent and differs only in the temperature range of the reactions. The absorption bands of the obtained complexes in IR and UV-vis spectra do not depend on the length of the hydrocarbon substituent. Using a complex with a propyl substituent as an example, the UV-vis spectral data of the mother solution are presented. Based on DFT calculations of spectra and molecular models, an indirect identification of the reaction intermediate is provided. Using a complex with a methyl substituent as an example, data on MALDI spectrometry are presented. [ABSTRACT FROM AUTHOR]

The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on Envisat provided infrared limb emission spectra, which were used to infer global distributions of CFC-11, CFC-12, and HCFC-22. Spectra were analysed using constrained non-linear least-squares fitting. Changes with respect to earlier data versions refer to the use of version 8 spectra, the altitude range where the background continuum is considered, details of the regularization and microwindow selection, and the occasional joint fitting of interfering species, the use of new spectroscopic data, the joint fit of a tangent-height-dependent spectral offset, and the use of 2D temperature fields. In the lower stratosphere the error budget is dominated by uncertainties in spectroscopic data, while above this measurement noise is the leading error source. The vertical resolution of CFC-11 and CFC-12 is 2–3 km near the tropopause, about 4 km at 30 km altitude, and 6–10 km at 50 km. The vertical resolution of HCFC-22 is somewhat coarser, 3–4 km at the tropopause and 10–12 km at 35 km altitude. In the altitude range of interest, the horizontal resolution is typically limited by the horizontal sampling of the measurements, not by the smearing of the retrievals. Horizontal information displacement does not exceed 150 km , which can become an issue only for comparisons with model simulations with high horizontal resolution or localized in situ observations. Along with the regular data product, an alternative representation of the data on a coarser vertical grid is offered. These data can be used without consideration of the averaging kernels. The new data version provides improvement with respect to reduction of biases and improved consistency between the full- and reduced-resolution mission period of MIPAS. [ABSTRACT FROM AUTHOR]

New approach to the interpretation of the multiplet structure in the Shpol'skii spectra based on the symmetry consideration of the impurity molecule and crystal matrix is proposed. The reasons and peculiarities of doublet structure formation in the spectra of molecules without inversion center and highly symmetric molecules are considered. It is shown that the structure of electron density distribution in the naphthalene molecule causes a doubly degenerate of the electronic level of its ground state. The calculated data are compared with the experimental results. The main research stages and directions in the field of narrow-line spectroscopy of organic molecules are marked. [ABSTRACT FROM AUTHOR]

Fluorescent polymeric materials have been exploited in the fields of aesthetical purposes, biomedical engineering, and three‐dimensional printing applications. While the fluorescent materials are prepared by the polymerization of fluorescent monomer or the blending a fluorescent dye with common polymer, the covalent immobilization of fluorescent dye onto common polymers is not the practical technique. In this paper, dansylated nitrile N‐oxide (Dansyl‐NO) has been designed and synthesized to be a stable nitrile N‐oxide as the derivative of 2‐hydroxy‐1‐naphthaldehyde. While Dansyl‐NO shows good reactivity to an alkene and an alkyne to give fluorescent Dansyl‐Ene and Dansyl‐Yne, respectively, it hardly reacts to a nitrile. The results indicate that Dansyl‐NO serves as a fluorescent dye clickable to alkenes and alkynes. To know the effects of solvent on the fluorescent properties, the UV‐vis and fluorescence spectra of Dansyl‐Ene are measured in three solvents. Dansyl‐Ene shows fluorescent solvatochromism, which appears to be red‐shifted along with the increase in solvent polarity. Poly(styrene‐co‐butadiene) directly reacts with Dansyl‐NO to give fluorescent modified SB. The emission spectrum of modified SB is blue‐shifted compared with that of Dansyl‐Ene. The blue‐shift could be possibly attributed to the presence of less polar polymer skeleton around the dansyl moieties of modified SB. [ABSTRACT FROM AUTHOR]

Cyan phosphors are urgently needed to fill the cyan gap and improve the spectral continuity of white light-emitting diodes (LEDs) to cater to the high demand for high-quality lighting. Here, a series of new Eu2+-activated La3Si6.5Al1.5N9.5O5.5 (LSANO) cyan phosphors were prepared, and their luminescence properties and color centers were analyzed through fluorescence spectral measurements from 7 K to 475 K. At 300 K, the photoluminescence excitation (PLE) spectrum monitored at 483 nm presents a broadband of 200–460 nm with a peak at 398 nm, matching well with commercial violet LED chips. When excited by 398 nm violet light, the photoluminescence emission (PL) spectrum of LSANO:0.01Eu2+ exhibits a cyan emission band at about 483 nm. At 7 K, the emission spectrum clearly shows an asymmetric emission band and the emission peak wavelength changes from 483 nm (300 K) to 500 nm (7 K), indicating that there are two possible color centers in the LSANO:Eu2+ phosphor. Moreover, the maximum emission value can be adjusted from 480 to 499 nm by adjusting the doping content of Eu2+. Finally, a violet-chip-based white LED with the optimized color quality of Ra = 91.4, Rf = 90.1, and Rg = 93.6 was fabricated by adding the prepared cyan phosphor, verifying the potential application of the prepared cyan phosphor LSANO:Eu2+ in high-quality white LEDs. [ABSTRACT FROM AUTHOR]

The need for new antimicrobial agents (AntAg) is driven by the persistent antibiotic resistance in microorganisms, as well as the increasing frequency of pandemics. Due to the deficiency of AntAg, research aimed at developing speedy approaches to find new drug candidates is relevant. This study aims to conduct an in silico study of the biological activity spectrum as well as the molecular binding mechanisms of four structurally different forms of levofloxacin (Lvf) with bacterial topoisomerases targets of type IIA (DNA gyrase and topoisomerase IV) to enable the development of drugs with an improved characterization of the safety profile. To achieve this goal, a number of software products were used, such as ChemicPen v. 2.6, PyMol 2.5, Avogadro 1.2.0, PASS, AutoDockTools 1.5.7 with the new generation software Autodock Vina. These software products are the first to be made available for visualization of clusters with determination of ligand-receptor pair binding affinity, as well as clustering coordinates and proposed mechanisms of action. One of the real structures of Lvf, a decarboxylated derivative, was obtained with tribochemical (TrbCh) exposure. The action spectrum of molecular ligands is described based on a Bayesian probability activity prediction model (PASS software Version 2.0). Predicted and real (PMS and RMS) molecular structures of Lvf, with decreasing levels of structural complexity, were translated into descriptors via Wiener (W), Balaban (Vs), Detour (Ip), and Electropy € indices. The 2D «structure-activity» diagrams were used to differentiate closely related structures of levofloxacin. PMS and RMS were visualized as 3D models of the ligand-receptor complexes. The contact regions of RMS and PMS with key amino acid residues—SER-79, DT-15, DG-1, DA-1—were demonstrated. The intra- and inter-molecular binding sites, data on free energy (affinity values, kcal/mol), the binding constant Kb (M−1), and the number of clusters are presented. The research results obtained from the presented in silico approach to explore the spectrum of action find quantitative "structure-activity" correlations, and predict molecular mechanisms may be of applied interest for directed drug discovery. [ABSTRACT FROM AUTHOR]

The study of large biomolecules, in particular DNA, is of practical interest. Marker bands of the Raman spectrum of DNA provide information about the conformational state and structure of the macromolecule. At the same time, when dealing with biological experiments, a small amount of DNA is available, which is why it is important to enhance the signal from DNA and find the proper substrate. However, it is difficult to enhance Raman spectra for large molecules as DNA without functionalization that could introduce changes in the DNA structure. In this work, a conventional substrate as CaF2 and a photonic crystal as a substrate with enhancer signal property and without DNA functionalization were applied. The factor of enhancement for DNA from salmon testes was reached up to 10 without Raman spectra distortion. The Raman spectral bands on different types of substrates are analyzed and compared. [ABSTRACT FROM AUTHOR]

Changes in vibrational spectra are among the most important manifestations of the interaction between transition metal dichalcogenides and nucleic acid bases (NAB). Infrared and Raman spectra were calculated using the DFT/M06-2X method for the most stable stacked and covalently bonded complexes of pyrimidine bases with MoS2. Obtained spectra were analyzed to determine the spectral markers of the interactions between the pyrimidine bases and MoS2. We found that interaction with MoS2 leads to significant changes in both frequencies and intensities of NAB vibrations. The correlation between the changes and interaction energies of the NAB molecules with MoS2 was demonstrated. In general, changes in the vibrational frequencies in complexes with covalent bonds are significantly greater than ones in stacked ones. For the bonded complexes, the most significant changes are observed for those fragments of the NAB molecules that are directly involved in the formation of the covalent bonds. Calculations predict the decrease of the IR intensity and Raman activities of the NAB molecules in the spectra of stacked complexes and their increase in the spectra of covalently bonded complexes. [ABSTRACT FROM AUTHOR]

Ardisia crenata Sims, an important ethnic medicine, is recorded in the Chinese Pharmacopoeia for treating laryngeal diseases and upper respiratory tract infections. This study aimed to evaluate the antimicrobial effect of extracts and potential antimicrobial compounds of A. crenata Sims. It was found that the roots of A. crenata Sims have a potential inhibitory effect on Candida albicans and Aspergillus flavus, with MICs of 1.56 mg/mL and 0.39 mg/mL, and the leaves of A. crenata Sims have a potential inhibitory effect on Pseudomonas aeruginosa and Staphylococcus aureus, with MICs of 3.12 mg/mL and 6.77 mg/mL, respectively. Meanwhile, five compounds including one catechin and four bergenins were obtained from roots. These components were identified on the fingerprint spectrum, representing chromatographic peaks 16, 21, 22, 23, and 25, respectively. Among these, 11-β-d-glucopyranosyl-bergenin and (−)-gallocatechin showed potential inhibition for Staphylococcus aureus and Pseudomonas aeruginosa with MIC of 0.26 and 0.33 mg/mL, respectively. The roots, stems, and leaves of A. crenata Sims are very similar in chemical composition, with large differences in content. Principal component analysis (PCA) and Hierarchical cluster analysis (HCA) showed that 16 batches of A. crenata Sims could be divided into four main production areas: Guizhou, Jiangsu, Guangxi, and Jiangxi. Furthermore, molecular docking results showed that 11-β-d-glucopyranosyl-bergenin had a better affinity for Casein lytic proteinase P (ClpP), and (−)-gallocatechin possessed a strong affinity for LasA hydrolysis protease and LasB elastase. These findings suggest catechin and bergenins from A. crenata Sims can be used as antimicrobial activity molecules. [ABSTRACT FROM AUTHOR]

Fluorescence pH sensing has proven to be efficient but with the drawback that molecules photobleach, requiring frequent calibrations. Double-emission peak molecules allow ratiometric measurements and theoretically avoid calibration. However, they are often expensive and fragile and usually have very low quantum yields. Single emission peaks such as fluorescein and derivatives are inexpensive and have very high quantum yields. Because they are single emission peaks, the pH is assumed to be derived from the ratio of emitted intensities at measured pH and at high pH values, i.e., they require frequent calibration. However, the shape of their single emitted peak evolves slightly with pH. In this paper, we first demonstrate a simple method to calculate the emission spectrum shape of each prototropic form of fluorescein (and derivatives) as well as the values of the pKas. A complete model of the evolution of the emission spectrum shape with pH is then constructed. Second, we evaluate the potential of these molecules for pH sensing by fitting the experimental spectra with the complete emission model. The method is applied to fluorescein, FITC and FAM. Depending on the molecule, pH can be measured from pH 1.9 to pH 7.3 with standard deviations between 0.06 and 0.08 pH units. Estimating pH and pKas from shape instead of intensity allows calibration-free measurements even with single-emission peak molecules. [ABSTRACT FROM AUTHOR]