Polarization Spectra Research Articles

Insights into the Identification of iPSC- and Monocyte-Derived Macrophage-Polarizing Compounds by AI-Fueled Cell Painting Analysis Tools.

Macrophage polarization critically contributes to a multitude of human pathologies. Hence, modulating macrophage polarization is a promising approach with enormous therapeutic potential. Macrophages are characterized by a remarkable functional and phenotypic plasticity, with pro-inflammatory (M1) and anti-inflammatory (M2) states at the extremes of a multidimensional polarization spectrum. Cell morphology is a major indicator for macrophage activation, describing M1(-like) (rounded) and M2(-like) (elongated) states by different cell shapes. Here, we introduced cell painting of macrophages to better reflect their multifaceted plasticity and associated phenotypes beyond the rigid dichotomous M1/M2 classification. Using high-content imaging, we established deep learning- and feature-based cell painting image analysis tools to elucidate cellular fingerprints that inform about subtle phenotypes of human blood monocyte-derived and iPSC-derived macrophages that are characterized as screening surrogate. Moreover, we show that cell painting feature profiling is suitable for identifying inter-donor variance to describe the relevance of the morphology feature 'cell roundness' and dissect distinct macrophage polarization signatures after stimulation with known biological or small-molecule modulators of macrophage (re-)polarization. Our novel established AI-fueled cell painting analysis tools provide a resource for high-content-based drug screening and candidate profiling, which set the stage for identifying novel modulators for macrophage (re-)polarization in health and disease.

Preparation of ortho-hydroxyl/carboxyl dual-functionalized hypercrosslinked polymers for highly efficient enrichment of nitrosamines with broad polarity prior to gas chromatography-mass spectrometry analysis

N-nitrosamines (NAs) are highly carcinogenic substances commonly detected in food. They demonstrate a broad spectrum of polarity, posing a challenge in finding a suitable adsorbent capable of simultaneously adsorbing and enriching both polar and nonpolar NAs with high extraction recoveries. The present study involves the synthesis of a series of carboxyl functionalized hypercrosslinked polymers, followed by a comparative evaluation of their adsorption performance towards NAs. The results demonstrated that the ortho-hydroxyl/carboxyl dual-functionalized hypercrosslinked polymer (SA-FDA-HCP), synthesized using salicylic acid as the monomer and formaldehyde dimethyl acetal as the crosslinking agent, exhibited significantly enhanced adsorption performance on NAs. The maximum adsorption capacities of SA-FDA-HCP for N-nitrosodimethylamine, N-nitrosodiethylamine, N-nitrosopyrrolidine, and N-nitrosodiphenylamine were determined to be 1.40, 4.18, 2.84, and 52.4 mg g−1, respectively. These values surpass those reported in the literature for other adsorbents. Furthermore, the polymer exhibited extraction recoveries exceeding 80 % for all four NAs, and it exhibits exceptional selectivity towards NAs. The high adsorption performance can be attributed to the synergistic effects of multiple interactions, including electrostatic, hydrogen bonding and hydrophobic interactions. Based on the synthesized hypercrosslinked polymers, a method for analyzing these NAs was developed using dispersed solid-phase extraction combined with gas chromatography-mass spectrometry. The method demonstrates good accuracy and precision within the linear range of 1 - 80 ng mL−1, while providing relative recoveries for the four NAs range from 91.1 % to 111.5 %. The intra-day and inter-day relative standard deviations are between 4.4 % and 9.8 %, as well as 5.6 % and 10.9 %, respectively. Moreover, the limits of detection fall within a range of 0.11 to 0.73 ng mL−1. These results indicate that the developed material holds great potential for the separation, enrichment and analysis of N-nitrosamines across diverse applications.

Harnessing complexity: Nonlinear optical phenomena in L-shapes, nanocrescents, and split-ring resonators.

We conduct systematic studies of the optical characteristics of plasmonic nanoparticles that exhibit C2v symmetry. In particular, we analyze three distinct geometric configurations: an L-type shape, a crescent, and a split-ring resonator shaped like the Greek letter π. Optical properties are examined using the finite-difference time-domain method. It is demonstrated that all three shapes exhibit two prominent plasmon modes associated with the two axes of symmetry. This is in addition to a wide range of resonances observed at high frequencies corresponding to quadrupole modes and peaks due to sharp corners. Next, to facilitate nonlinear analysis, we employ a semiclassical hydrodynamic model, where the electron pressure term is explicitly accounted for. This model goes beyond the standard Drude description and enables capturing nonlocal and nonlinear effects. Employing this model enables us to rigorously examine the second-order angular resolved nonlinear optical response of these nanoparticles in each of the three configurations. Two pumping regimes are considered, namely, continuous wave (CW) and pulsed excitations. For CW pumping, we explore the properties of the second harmonic generation (SHG). Polarization and angle-resolved SHG spectra are obtained, revealing strong dependence on the nanoparticle geometry and incident wave polarization. The C2v symmetry is shown to play a key role in determining the polarization states and selection rules of the SHG signal. For pulsed excitations, we discuss the phenomenon of broadband terahertz (THz) generation induced by the difference-frequency generation . It is shown that the THz emission spectra exhibit unique features attributed to the plasmonic resonances and symmetry of the nanoparticles. The polarization of the generated THz waves is also examined, revealing interesting patterns tied to the nanoparticle geometry. To gain deeper insight, we propose an analytical theory that agrees very well with the numerical experiments. The theory shows that the physical origin of the THz radiation is the mixing of various frequency components of the fundamental pulse by the second-order nonlinear susceptibility. An expression for the far-field THz intensity is derived in terms of the incident pulse parameters and the nonlinear response tensor of the nanoparticle. The results presented in this work offer new insights into the linear and nonlinear optical properties of nanoparticles with C2v symmetry. The demonstrated strong SHG response and efficient broadband THz generation hold great promise for applications in nonlinear spectroscopy, nanophotonics, and optoelectronics. The proposed theoretical framework also provides a valuable tool for understanding and predicting the nonlinear behavior of other related nanostructures.

Narrow peaks in excitation spectrum of alkali spin polarization: non-adiabatic case of spin dynamics

We theoretically describe the phenomenon of non-adiabatic spin dynamics, which occurs in a gas cell filled by alkali vapor in the presence of a strong alternating magnetic field and pump light. Steep increase of the spin polarization occurs if the frequency of the magnetic field is equal to the certain value. The observable effect relies on the periodic field that consists of two perpendicular components defined by harmonics with the same amplitudes and different frequencies. The considered effect of the coherent spin motion cannot be explained by a resonance, because the Larmor precession is absent without a constant component of magnetic field. Moreover, there are some clearly visible peaks in the excitation spectrum of spin polarization, which are narrow in comparison to the relaxation rate. Detailed analysis according to proposed quantum model results in the reasoning of the effect via qualitative properties of non-adiabatic dynamics of atomic spin.

Characterizing strong-field tunneling ionization with a phase-dependent THz polarization spectrum.

The terahertz radiation emitted by asymmetrically ionized wavepackets in two-color strong-field tunneling ionization is essential for detecting the system's associated electron dynamics and structural properties. We propose to characterize and control tunneling ionization using a phase-dependent terahertz polarization (PTP) spectrum, analyzed through a combination of the classical trajectory Monte Carlo method, an analytical model based on the virial theorem, and the rigorous solution of the time-dependent Schrödinger equation as a benchmark. Our results demonstrate that the PTP spectrum offers a high-precision measure of the Coulomb effect through the relative phase of the two-color laser. Comparisons of PTP results calculated using different methods suggest how the electron can be manipulated by controlling the relative phase and laser intensity. In particular, the PTP spectrum can be used to calibrate the relative phase and provides a convenient and robust reconstruction of the time-averaging of tunneling positions with high precision using the analytical model. These insights reveal that the PTP spectrum as a whole can be a new and useful tool for the all-optical characterization of ultrafast atomic and molecular ionization.

Advancing polarity-transcendent design: Development of a photoelectrochemical sensor with extended detection range

In photoelectrochemical (PEC) sensors, traditional detection modes such as "signal-on", "signal-off", and "polarity-switchable" limit target signals to a single polarity range, necessitating novel design strategies to enhance the operational scope. To overcome this limitation, we propose, for the first time, a "polarity-transcendent" design concept that enables a continuous response across the polarity spectrum, significantly broadening the sensor's concentration detection range. This concept is exemplified in our new "background-enhanced signal-off polarity-switchable" (BESOPS) mode, where the model analyte let-7a activates a cascade shearing reaction of a DNAzyme walker in conjunction with CRISPR/Cas12a, quantitatively peeling off Cu2O-H2 strands at the Cu2O/TiO2 electrode interface to expose the TiO2 surface. This exposure generates an anodic photocurrent at the expense of the cathodic photocurrent from Cu2O/TiO2, facilitating a seamless transition of the target signal from cathodic to anodic. Through systematic experiments and comparative analyses, the BESOPS sensor demonstrates highly sensitive and precise quantification of let-7a, with a detection limit of 2.5 aM and a broad operating range of 10 aM to 10 nM. Its performance exceeds most reported sensor platforms, highlighting the significant potential of our polarity-transcendent design in expanding the operational range of PEC sensors. This innovative approach paves the way for developing next-generation PEC sensors with enhanced applicability and heightened sensitivity in various critical fields.

Understanding the multi-wavelength thermal dust polarisation from the Orion molecular cloud in light of the radiative torque paradigm

Dust grains play a key role in various astrophysical processes and serve as indicators of interstellar medium structures, density, and mass. Understanding their physical properties and chemical composition is a crucial goal in astrophysics. Dust polarisation is a valuable tool for studying these properties. The radiative torque (RAT) paradigm, which includes radiative torque alignment (RAT-A) and radiative torque disruption (RAT-D), is essential to interpreting the dust polarisation data and constraining the fundamental properties of dust grains. However, it has been used primarily to interpret observations at a single wavelength. In this study, we analyse the thermal dust polarisation spectrum obtained from observations with SOFIA/HAWC+ and JCMT/POL-2 in the Orion molecular cloud 1 (OMC-1) region and compare the observational data with our numerical results using the RAT paradigm. In general, we show that the dense gas exhibits a positive spectral slope, whereas the warm regions show a negative one. We demonstrate that a one-layer dust (one-phase) model can only reproduce the observed spectra at certain locations and cannot match those with prominent V-shaped spectra (for which the degree of polarisation initially decreases with wavelength from 54 to ~300µm and then increases at longer wavelengths). To address this, we improved our model by incorporating two dust components (warm and cold) along the line of sight, resulting in a two-phase model. This improved model successfully reproduces the V-shaped spectra. The best model corresponds to a mixture composition of silicate and carbonaceous grains in the cold medium. Finally, by assuming the plausible model of grain alignment, we were able to infer the inclination angle of the magnetic fields in OMC-1. This approach is an important step towards a better understanding the physics of grain alignment and constraining 3D magnetic fields using dust polarisation spectra.

Optical spectroscopy and energy transfer in Tm3+ - Ho3+ ions system in LiY0.3Lu0.7F4 mixed crystals

Here we present the study of spectral and kinetic characteristics of Tm3+ and Ho3+ ions system in LiY0.3Lu0.7F4 mixed crystal. Polarized spectra of absorption and luminescence transitions between 3F4 – 3H6 and 5I7 – 5I8 states of Tm3+ and Ho3+ ions respectively as well as energy transfer efficiency were investigated. It was shown that LiY0.3Lu0.7F4 mixed crystal provides some broadening of Tm3+ and Ho3+ spectral lines for 4f-4f intermultiplet transitions. The evaluated Förster energy transfer critical radius for LiY0.3Lu0.7F4: Tm3++Ho3+ (10 at. % + 2 at. %) crystal was 22 Å. The backtransfer efficiency from Ho3+ to Tm3+ in the described energy transfer process CHo-Tm results in value of 0.83 × 10−40 cm6/s and relation of froward and back-transfer coefficients CTm-Ho/CHo-Tm appears to be 6.8 calculated from our spectroscopic data, which make it prospective active medium for sensitized laser oscillation in IR spectral region.

Coherent Inverse Compton Scattering in Fast Radio Bursts Revisited

Growing observations of temporal, spectral, and polarization properties of fast radio bursts (FRBs) indicate that the radio emission of the majority of bursts is likely produced inside the magnetosphere of its central engine, likely a magnetar. We revisit the idea that FRBs are generated via coherent inverse Compton scattering (ICS) off low-frequency X-mode electromagnetic waves (fast magnetosonic waves) by bunches at a distance of a few hundred times the magnetar radius. The following findings are revealed: (1) Crustal oscillations during a flaring event would excite kHz Alfvén waves. Fast magnetosonic waves with essentially the same frequency can be generated directly or be converted from Alfvén waves at a large radius, with an amplitude large enough to power FRBs via the ICS process. (2) The cross section increases rapidly with radius and significant ICS can occur at r ≳ 100R ⋆ with emission power much greater than the curvature radiation power but still in the linear scattering regime. (3) The low-frequency fast magnetosonic waves naturally redistribute a fluctuating relativistic plasma in the charge-depleted region to form bunches with the right size to power FRBs. (4) The required bunch net charge density can be sub-Goldreich–Julian, which allows a strong parallel electric field to accelerate the charges, maintain the bunches, and continuously power FRB emission. (5) This model can account for a wide range of observed properties of repeating FRB bursts, including high degrees of linear and circular polarization and narrow spectra as observed in many bursts from repeating FRB sources.

Modeling the Far-infrared Polarization Spectrum of a High-mass Star-forming Cloud

The polarization spectrum, or wavelength dependence of the polarization fraction, of interstellar dust emission provides important insights into the grain alignment mechanism of interstellar dust grains. We investigate the far-infrared polarization spectrum of a realistic simulated high-mass star-forming cloud under various models of grain alignment and emission. We find that neither a homogeneous grain alignment model nor a grain alignment model that includes collisional dealignment is able to produce the falling spectrum seen in observations. On the other hand, we find that a grain alignment model with grain alignment efficiency dependent on local temperature is capable of producing a falling spectrum that is in qualitative agreement with observations of OMC-1. For the model most in agreement with OMC-1, we find no correlation between the temperature and the slope of the polarization spectrum. However, we do find a positive correlation between the column density and the slope of the polarization spectrum. We suggest this latter correlation to be the result of wavelength-dependent polarization by absorption.

Structural Fine‐Tuning to Achieve Highly Fluorescent Organic and Water‐Soluble Thiazolo[5,4‐d]thiazole Chromophores

AbstractFluorescent molecular systems are important for various applications such as sensing of analytes, probes for biologically relevant processes and as optoelectronic materials. Achieving high fluorescence quantum yield across the spectrum of solvent polarity and in solid‐state is challenging in molecular materials. Herein, we present a strategy to achieve strongly fluorescent molecular materials based on weak intramolecular charge‐transfer (ICT) in a family of unsymmetrical donor‐thiazolo[5,4‐d]thiazole‐acceptor systems (both neutral and cationic). Detailed photophysical studies reveal that the delicate balance between the donor and acceptor result in high solution‐state fluorescence quantum yield (>80 %) in both polar protic and apolar solvents. Quantum chemical computations uncover a hitherto unappreciated insight that the extent of ICT is aptly represented by the change in Mulliken charges between the ground and excited state for different fragments rather than the classical approach of monitoring the change in dipole moment for the entire molecule. This insight rationalizes the observed photophysical properties and can have implications in the design of tuneable donor‐π‐acceptor systems.

Structural Fine-Tuning to Achieve Highly Fluorescent Organic and Water-Soluble Thiazolo[5,4-d]thiazole Chromophores.

Fluorescent molecular systems are important for various applications such as sensing of analytes, probes for biologically relevant processes and as optoelectronic materials. Achieving high fluorescence quantum yield across the spectrum of solvent polarity and in solid-state is challenging in molecular materials. Herein, we present a strategy to achieve strongly fluorescent molecular materials based on weak intramolecular charge-transfer (ICT) in a family of unsymmetrical donor-thiazolo[5,4-d]thiazole-acceptor systems (both neutral and cationic). Detailed photophysical studies reveal that the delicate balance between the donor and acceptor result in high solution-state fluorescence quantum yield (>80 %) in both polar protic and apolar solvents. Quantum chemical computations uncover a hitherto unappreciated insight that the extent of ICT is aptly represented by the change in Mulliken charges between the ground and excited state for different fragments rather than the classical approach of monitoring the change in dipole moment for the entire molecule. This insight rationalizes the observed photophysical properties and can have implications in the design of tuneable donor-π-acceptor systems.

Exploring the ON/OFF nonlinear optical (NLO) response in tetracene-based chromophores: A DFT study on solvent and frequency-dependent NLO properties for switching applications

Tetracene-based nonlinear optical (NLO) materials are an ambient field of interest in optoelectronic technology. Inspired by this material, we theoretically designed D-D-A framework molecules (ZO and ZO-1 to ZO-16) with auxiliary donor and acceptor screening of solo tetracene linear surface and investigated their reactivity, electrical properties, solvent-dependent optical and ON/OFF NLO properties utilizing DFT simulations. The CPCM and IEFPCM model is used to examine how entire spectrum of medium polarity, ranging from less polar to more polar solvents (chloroform (ε = 4.71) < tetrahydrofuran (ε = 7.43) < DMSO (ε = 46.83 < water (ε = 78.36)) affect the optical absorption and NLO characteristics (βtot, αtot, and μtot) of suggested compounds (ZO and ZO-1 to ZO-16). Furthermore, natural bond orbital analysis (NBO) and topological analysis (MEP, ELF, and LOL) were used to explain the NLO results. Regarding the charge transfer robustness, ZO-9, a promising tetracene derivative, is identified as an appealing second-order NLO candidate, with the lowest energy gap (1.642 eV) and largest λmax (546.692 nm) among all investigated derivatives. Moreover, the solvent-dependent optical absorption spectrum shows that polar solvent (THF) alleviates the λmax from 273.081 nm to 707.511 nm in ZO-11. Similarly, solvent also influences the NLO properties in all designed compounds, especially in ZO-9, which displayed giant βtotal = 7.244 × 105 in chloroform, 8.640 × 105 in THF, 1.153 × 106 in DMSO, and 1.180 × 106 in water as well as in gas (1.993 × 105). Additionally, the results of the second harmonic generation (SHG) β(−2ω, ω, ω) and the electro-optical Pockels effect (EOPE) β(−ω,ω,0) computed at the frequencies of ω = 1064 nm (0.0428 au) and ω = 532 nm (0.0856 au) validates that all tetracene based derivatives are excellent NLO candidates for laser working condition and switching applications.

Adiponectin and Adiponectin Receptors in Atherosclerosis.

Adiponectin is an abundantly secreted hormone that communicates information between the adipose tissue, and the immune and cardiovascular systems. In metabolically healthy individuals, adiponectin is usually found at high levels and helps improve insulin responsiveness of peripheral tissues, glucose tolerance, and fatty acid oxidation. Beyond its metabolic functions in insulin-sensitive tissues, adiponectin plays a prominent role in attenuating the development of atherosclerotic plaques, partially through regulating macrophage-mediated responses. In this context, adiponectin binds to its receptors, adiponectin receptor 1 (AdipoR1) and AdipoR2 on the cell surface of macrophages to activate a downstream signaling cascade and induce specific atheroprotective functions. Notably, macrophages modulate the stability of the plaque through their ability to switch between pro-inflammatory responders, and anti-inflammatory pro-resolving mediators. Traditionally, the extremes of the macrophage polarization spectrum span from M1 pro-inflammatory and M2 anti-inflammatory phenotypes. Previous evidence has demonstrated that the adiponectin-AdipoR pathway influences M1-M2 macrophage polarization; adiponectin promotes a shift towards an M2-like state, whereas AdipoR1- and AdipoR2-specific contributions are more nuanced. To explore these concepts in depth, we discuss in this review the impact of adiponectin and AdipoR1/R2 on 1) metabolic and immune responses, and 2) M1-M2 macrophage polarization, including their ability to attenuate atherosclerotic plaque inflammation, and their potential as therapeutic targets for clinical applications.

Menadione sodium bisulfite as an efficient anti-corrosion additive for mild steel in acid corrosion: Electrochemical, surface morphological and theoretical studies

The corrosion inhibition behavior of Menadione Sodium Bisulfite (MSB) in 1.0 M HCl medium was evaluated using weight loss, electrochemical techniques (Tafel polarisation and Electrochemical impedance spectra), surface analysis (SEM and EDX), Density Functional Theory (DFT), Noncovalent interaction- Reduced Density Gradient (NCI-RDG) and Monte Carlo (MC) simulation techniques. Weight loss measurement showed that as inhibitor concentration increased, the corrosion rate decreased which means that a protective film formed on the metal surface. At 300 ppm, the inhibitor showed a maximum inhibition efficiency of 89.7 %. Tafel polarisation studies indicate that the inhibitor is mixed-type in nature. The inhibitor adsorption on the mild steel is the best fit for the Langmuir isotherm model. As the weak interaction of sodium and oxygen in the inhibitor molecules, the inhibitor exhibits two distinct equilibrium behaviors. (i) inhibitor with sodium (solid-state) and inhibitor without sodium (in liquid-state). These two behaviors were theoretically investigated using DFT and MD simulation studies. The inhibitor and metal interaction is further supported using these theoretical studies. The electron population of the inhibitor was analyzed using molecular electrostatic potential, NCI-RDG, Fukui function, and natural bond orbital analysis. These studies further give an understating of the inhibitor and metal interactions.

LiteBIRD science goals and forecasts: primordial magnetic fields

We present detailed forecasts for the constraints on the characteristics of primordial magnetic fields (PMFs) generated prior to recombination that will be obtained with the LiteBIRD satellite. The constraints are driven by some of the main physical effects of PMFs on the CMB anisotropies: the gravitational effects of magnetically-induced perturbations; the effects on the thermal and ionization history of the Universe; the Faraday rotation imprint on the CMB polarization spectra; and the non-Gaussianities induced in polarization anisotropies. LiteBIRD represents a sensitive probe for PMFs.We explore different levels of complexity, for LiteBIRD data and PMF configurations, accounting for possible degeneracies with primordial gravitational waves from inflation. By exploiting all the physical effects, LiteBIRD will be able to improve the current limit on PMFs at intermediate and large scales coming from Planck. In particular, thanks to its accurate B-mode polarization measurement, LiteBIRD will improve the constraints on infrared configurations for the gravitational effect, giving B n B=-2.9 1 Mpc< 0.8 nG at 95% C.L., potentially opening the possibility to detect nanogauss fields with high significance. We also observe a significant improvement in the limits when marginalized over the spectral index, B n Bmarg 1 Mpc< 2.2 nG at 95 % C.L. From the thermal history effect, which relies mainly on E-mode polarization data, we obtain a significant improvement for all PMF configurations, with the marginalized case, √⟨B 2⟩marg<0.50 nG at 95 % C.L. Faraday rotation constraints will take advantage of the wide frequency coverage of LiteBIRD and the high sensitivity in B modes, improving the limits by orders of magnitude with respect to current results, B n B=-2.9 1 Mpc < 3.2 nG at 95 % C.L. Finally, non-Gaussianities of the B-mode polarization can probe PMFs at the level of 1 nG, again significantly improving the current bounds from Planck. Altogether our forecasts represent a broad collection of complementary probes based on widely tested methodologies, providing conservative limits on PMF characteristics that will be achieved with the LiteBIRD satellite.

Effect of the external electric fields on the polarization and vibrational spectrum of 1-ethyl-3-methylimidazolium bis(trifluormethylsulfonyl)imide on graphene surface

Ionic liquids, emerging as innovative solvents for energy harvesting, necessitate a comprehensive understanding of their structural characteristics at the graphene-ionic liquid interface. This work delves into the effects of external electric fields (EEFs) on the polarization and vibrational spectrum of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][NTf2]) on a graphene surface, employing density functional theory calculations. The analysis reveals that the geometrical configuration and stability of functional groups within the graphene-[Emim][NTf2] system are influenced by both the direction and intensity of the applied EEF. Notably, the threshold EEF strength required for dissociation varies based on the structural configuration of the anion. The electronic energy, dipole moment, and polarization rate under varying EEF conditions have been quantitatively assessed, providing insights into their EEF-dependent behaviors. Utilizing the independent gradient model approach, the inter-ion interactions, such as hydrogen bonding and van der Waals forces, under the influence of EEFs were analyzed, and how these interactions evolve with changes in the direction and intensity of the EEFs were also explored. Furthermore, the vibrational spectrum of [Emim][NTf2] on the graphene surface, spanning a range of 10–3500 cm−1, was meticulously calculated to systematically investigate the impact of the EEF on the vibrational spectra of the graphene-[Emim][NTf2] system. A key finding of this work is the distinct shifts in the vibrational peaks of the cis and trans isomers of [NTf2]− on the graphene surface, which can be attributed to differences in their exchange energies. Specifically, the exchange energy for the cis isomer of [NTf2]− is measured at 107.43 kJ∙mol−1, in contrast to 98.51 kJ∙mol−1 for the trans isomer.

Statistical relations between spectropolarimetric observables and the polar strength of the stellar dipolar magnetic field

Global magnetic fields of early-type stars are commonly characterised by the mean longitudinal magnetic field 〈Bz〉 and the mean field modulus 〈B〉, derived from the circular polarisation and intensity spectra, respectively. Observational studies often report a root mean square (rms) of 〈Bz〉 and an average value of 〈B〉. In this work, I used numerical simulations to establish statistical relationships between these cumulative magnetic observables and the polar strength, Bd, of a dipolar magnetic field. I show that in the limit of many measurements randomly distributed in rotational phase, 〈Bz〉rms = 0.179−0.043+0.031 Bd and 〈B〉avg = 0.691−0.023+0.020 Bd. The same values can be recovered with only three measurements, provided that the observations are distributed uniformly in the rotational phase. These conversion factors are suitable for ensemble analyses of large stellar samples, where each target is covered by a small number of magnetic measurements.

Vinyl and methyl-ester groups in the insoluble polymer drug patiromer identified and quantified by solid-state NMR

Patiromer (Veltassa®) is a crosslinked, insoluble co-polymer drug used as a nonabsorbent potassium binder, approved for treatment of hyperkalemia. Quantitative solid-state 13C nuclear magnetic resonance (NMR) analysis with comprehensive peak assignment, component quantification, and calculation of mole and weight fractions of monomer units was performed on three doses of patiromer. The workflow is documented in detail. Spectrally edited solid-state 13C NMR spectra of patiromer show =CHn peaks of matching intensity at 116 and 141 ppm, characteristic of -CH=CH2 vinyl groups. Similar spectral features can be observed in earlier studies but were previously ignored. In this study, the vinyl signals are well-resolved in a 2-s direct polarization (DP) spectrum without and with dipolar dephasing, which confirms that these sp2-hybridized carbons are bonded to hydrogen and partially mobile, consistent with vinyl side groups from incompletely reacted divinyl crosslinkers. The vinyl groups account for 1.6% of all carbon, 3% of the monomer units, and nearly 1/3 of the crosslinkers. Furthermore, an unexpected OCH3 moiety accounting for ∼1.2% of all carbons was identified by spectral editing; its chemical shift of 54 ppm is more consistent with a methyl ester than with a methyl ether. It can originate from incomplete hydrolysis of ∼6% of methyl-2-fluoroacrylate, the main monomer of patiromer. Characteristic cross peaks in two-dimensional 1H–13C heteronuclear correlation NMR confirm the presence of the vinyl and OCH3 groups. Trace amounts of xanthan gum are also detected. The quantitative 13C NMR spectrum of patiromer has been matched in a simulation using a model with five monomer units.

Polarized spectroscopy of Sm3+ ions in monoclinic KGd(WO4)2 crystals for lasers emitting in the red

Single-crystals of potassium gadolinium double tungstate KGd(WO4)2 doped with Sm3+ ions up to 20 at.% were grown from the flux using K2W2O7 as a solvent and a detailed polarization-resolved spectroscopic study of Sm3+ ions was performed with the goal of developing novel materials emitting in the visible spectral range. Polarized absorption spectra were measured and 4f-4f transition intensities of Sm3+ ions were calculated using a modified Judd-Ofelt theory yielding the intensity parameters of Ω2 = 8.027, Ω4 = 7.210 and Ω6 = 2.322 [10−20 cm2] and α = −0.017 [10−4 cm]. Polarized stimulated-emission properties of Sm3+ ions were studied. For the 4G5/2 → 6H9/2 transition in the red, the maximum σSE is 0.55 × 10−20 cm2 at 649.0 nm for light polarization E || Np (luminescence branching ratio: 40.2 %). The radiative lifetime of the 4G5/2 state is 734 μs. The luminescence dynamics from this manifold was analyzed using the Inokuti-Hirayama model. The possible role of 4f – 4f excited-state absorption from the 4G5/2 level in preventing laser operation in the orange and deep red is analyzed. A 0.8 at.% Sm:KGd(WO4)2 laser generated an output power of 37.8 mW at 649 nm, with a laser threshold of 87 mW and a slope efficiency of 17.6 %.