Spectroscopy Modeling Research Articles

SN 2022oqm: A Bright and Multipeaked Calcium-rich Transient

We present the photometric and spectroscopic evolution of SN 2022oqm, a nearby multipeaked hydrogen- and helium-weak calcium-rich transient (CaRT). SN 2022oqm was detected 13.1 kpc from its host galaxy, the face-on spiral galaxy NGC 5875. Extensive spectroscopic coverage reveals an early hot (T ≥ 40,000 K) continuum and carbon features observed ∼1 day after discovery, SN Ic-like photospheric-phase spectra, and strong forbidden calcium emission starting 38 days after discovery. SN 2022oqm has a relatively high peak luminosity (M B = −17 mag) for CaRTs, making it an outlier in the population. We determine that three power sources are necessary to explain the light curve (LC), with each corresponding to a distinct peak. The first peak is powered by an expanding blackbody with a power-law luminosity, suggesting shock cooling by circumstellar material (CSM). Subsequent LC evolution is powered by a double radioactive decay model, consistent with two sources of photons diffusing through optically thick ejecta. From the LC, we derive an ejecta mass and 56Ni mass of ∼0.6 M ⊙ and ∼0.09 M ⊙. Spectroscopic modeling ∼0.6 M ⊙ of ejecta, and with well-mixed Fe-peak elements throughout. We discuss several physical origins for SN 2022oqm and find either a surprisingly massive white dwarf progenitor or a peculiar stripped envelope model could explain SN 2022oqm. A stripped envelope explosion inside a dense, hydrogen- and helium-poor CSM, akin to SNe Icn, but with a large 56Ni mass and small CSM mass could explain SN 2022oqm. Alternatively, helium detonation on an unexpectedly massive white dwarf could also explain SN 2022oqm.

Development of soil spectroscopy models for the Western Highveld region, South Africa: Why do we need local data?

AbstractThe increasing global demand for sustainable agriculture requires accurate and efficient soil analysis methods. Conventional laboratory techniques are often time‐consuming, costly and environmentally damaging. To address this challenge, we developed and validated locally calibrated mid‐infrared (MIR) spectroscopy models for predicting key soil properties pH, phosphorus (P) and exchangeable cations in soil samples from South Africa's Western Highveld region, using a dataset of 979 soil samples and machine learning algorithms Cubist, partial least squares regression (PLSR) and random forest (RF). A subset of spectra was also submitted to the newly developed Open Soil Spectral Library's (OSSL) prediction models to determine whether global prediction models could be used for local soil property prediction. Accurate predictions for pH, calcium (Ca) and magnesium (Mg), with coefficient of determination (R2) values exceeding 0.76 were obtained with the local calibration algorithms. The predictions for P, potassium (K) and sodium (Na) did not meet the requirements for reliability. Soil spectroscopic prediction models calibrated with local soils outperformed the corresponding global prediction models considered. The OSSL prediction results were inaccurate, with a RPIQ <1, and consistently underpredicted all soil properties. Furthermore, the OSSL collection of prediction models does not include a pH (KCl) model, the routinely used pH measurement method in South Africa. These findings highlight the importance of local calibration for accurate soil property prediction and underscore the need for regional representation in global spectral libraries. This research serves as the first local calibration of MIR spectroscopy models for the Western Highveld region of South Africa and provides a foundation for future local soil property inference model development. It also serves as a potential starting point for a comprehensive South African soil spectral library that can be contributed to global spectral libraries.

Dynamic spectroscopic and optical characterization and modeling of bovine serum albumin corona during interaction with N-hydroxysulfo-succinimide-covalently functionalized gold nanourchins.

In this study, bovine serum albumin (BSA) is used as a globular protein model to examine the conformational changes that occur during the interaction of BSA with N-hydroxysulfo-succinimide (sodium salt)-functionalized gold nanourchins (GNUs), for which dynamic spectroscopic techniques are employed. The results showed that the absorbance of phosphate-buffered saline-BSA at 278 nm decreased when a GNU was added to the solution due to adsorption, and it decreased further when the GNU was increased. The intensity and width of the peak of local surface plasmon resonance increased, indicating the effect of corona formation. Dynamic UV-vis spectroscopy and scattering revealed a nonlinear behavior of BSA-GNU interaction. The bioplasmonic solution resulted in higher transmission and scattering than the BSA solution. Fourier transform-near-infrared spectra exhibited several bands due to overtones and combinations of the amide group and different proportions of α-helix and β-sheet components in BSA before and after the addition of the GNU. Time-resolved fluorescence spectroscopy demonstrated an initial increase in blueshifted emission, followed by a redshifted quenching of two major peaks of Tyr and tryptophan (Trp). The binding and dissociation constants were determined as Kb = 2.17 × 1010 M-1 and Kd = 4.6 × 10-11, respectively, using the Stern-Volmer relation. Both the dynamic CMOS-based imaging and the cadmium sulfide sensors demonstrated a nonlinear response of bioplasmonic solution. By increasing the GNU, the resistance of the solution decreased in the order of A > S1 > S3, where S3 exhibited the highest initial transmission with a longer desorption time. MATLAB modeling showed 80% surface coverage by the protein in 15 s at 0.05M, equivalent to a thickness of 1.7 nm, which was in agreement with the value determined by using the Stokes-Einstein relation.

Investigation on concentration detection of turbid solution based on hemisphere sample cell and multidimensional spectroscopy

The study developed a hemisphere sample cell and constructed a multidimensional spectroscopy acquisition system to enhance the accuracy of detecting turbid solution with scattering properties. The system simultaneously captures absorption and scattering information from the tested samples. Monte Carlo simulation was employed to model the transmission light intensity distribution data from sample cells of various shapes. It was found that the hemisphere sample cell increases the dimensionality of transmission light intensity information and enables the acquisition of more scattering-related data. Furthermore, 46 samples of intralipid-20% solution with varying concentrations were examined. Models were constructed using partial least squares (PLS) regression with one-dimensional and two-dimensional light intensity distribution data. The results indicate that the model using two-dimensional light intensity distribution data significantly outperforms the model using one-dimensional data, reducing the root mean square error by 39.96% and increasing the correlation coefficient by 0.332%. Experimental results demonstrate that the multidimensional spectroscopic modeling method employing the hemisphere sample cell can significantly enhance the accuracy and speed of detecting chemical composition concentrations in turbid solution.

Green Syngas Production from Natural Lignin, Sunlight, and Water over Pt‐Decorated InGaN Nanowires

AbstractTransformation of lignin to syngas can turn waste into treasure yet remains a tremendous challenge because of its naturally evolved stubborn structure. In this work, light‐driven reforming of natural lignin in water for green syngas production is explored using Pt‐decorated InGaN nanowires. The spectroscopic characterizations, isotope, and model compound experiments, as well as density function theory calculation, disclose that among a variety of groups including aromatic ring, −OH, −OCH3, −C3H7 with complex chemical bonds of O−H, C−H, C−C, C−O, etc., InGaN nanowires are cooperative with Pt for preferably breaking the C−O bond of the rich O−CH3 group in lignin to liberating ⋅CH3 by photogenerated holes with a minimum dissociation energy of 2.33 eV. Syngas are subsequently yielded from the continuous evolution of ⋅CH3 and ⋅OH from photocatalytic reforming of lignin in water. Together with the superior optoelectronic attributes of Pt‐decorated InGaN nanowires, the evolution rate of syngas approaches 43.4 mol ⋅ g−1 ⋅ h−1 with tunable H2/CO ratios and a remarkable turnover number (TON) of 150, 543 mol syngas per mol Pt. Notably, the architecture demonstrates a high light efficiency of 12.1 % for syngas generation under focused light without any extra thermal input. Outdoor test ascertains the viability of producing syngas with the only inputs of natural lignin, water, and sunlight, thus presenting a low‐carbon route for synthesizing transportation fuels and value‐added chemicals.

Field deployable laser sensor for calibration-free and real-time measurement of NOx from stationary sources

Nitrogen oxides (NOx) are common pollutants emitted from stationary sources, such as industrial boilers and power plants, with significant adverse impacts on the environment and biosphere. The abatement of NOx from anthropic industrial processes requires reliable and sensitive monitoring systems. To address this challenge, we report a sensitive, robust, and compact quantum cascade laser (QCL)-based sensor to measure NO and NO2 emissions from industrial exhausts. This sensor uses two quantum cascade lasers, which take advantage of the intense absorption spectra of NO at 1929 cm−1 and NO2 at 1599 cm−1. A high-temperature multipass cell is designed to withstand harsh environments, which increases the light path length. The NOx concentrations are directly determined from the wavelength modulation spectroscopic model without the need for calibration. We conducted several laboratory experiments to evaluate the sensor's performance, with a focus on accuracy, sensitivity and selectivity. In the end, we showcased the field deployment of our sensor by continuously measuring NOx concentrations in a 2.8-MW gas-fired industrial boiler.

On-line measurement of COD and nitrate in water against stochastic background interference based on ultraviolet–visible spectroscopy and physics-informed multi-task learning

Traditional ultraviolet–visible spectroscopic quantitative analytical methods face challenges in simultaneous and long-term accurate measurement of chemical oxygen demand (COD) and nitrate due to spectral overlap and the interference from stochastic background caused by turbidity and chromaticity in water. Addressing these limitations, a compact dual optical path spectrum detection sensor is introduced, and a novel ultraviolet–visible spectroscopic quantitative analysis model based on physics-informed multi-task learning (PI-MTL) is designed. Incorporating a physics-informed block, the PI-MTL model integrates pre-existing physical knowledge for enhanced feature extraction specific to each task. A multi-task loss wrapper strategy is also employed, facilitating comprehensive loss evaluation and adaptation to stochastic backgrounds. This novel approach significantly outperforms conventional models in COD and nitrate measurement under stochastic background interference, achieving impressive prediction R2 values of 0.941 for COD and 0.9575 for nitrate, while reducing root mean squared error (RMSE) by 60.89 % for COD and 77.3 % for nitrate in comparison to the conventional chemometric model partial least squares regression (PLSR), and by 30.59 % and 65.96 %, respectively, in comparison to a benchmark convolutional neural network (CNN) model. The promising results emphasize its potential as a spectroscopic instrument designed for online multi-parameter water quality monitoring against stochastic background interference, enabling long-term accurate measurement of COD and nitrate levels.

Automated workflow for analyzing thermodynamic stability in polymorphic perovskite alloys

In this first-principles investigation, we explore the polymorphic features of pseudo-cubic alloys, focusing on the impact of mixing organic and inorganic cations on their structural and electronic properties, configurational disorder, and thermodynamic stability. Employing an automated cluster expansion within the generalized quasichemical approximation (GQCA), our results reveal how the effective radius of the organic cation (rMA = 2.15 Å, rFA = 2.53 Å) and its dipole moment (μMA = 2.15 D, μFA = 0.25 D), influences Glazer’s rotations in the A1−xCsxPbI3 (A = MA, FA) sublattice, with MA-based alloy presenting a higher critical temperature (527 K) and being stable for x > 0.60 above 200 K, while its FA analog has a lower critical temperature (427.7 K) and is stable for x < 0.15 above 100 K. Additionally, polymorphic motifs magnify relativistic effects, impacting the thermodynamic behavior of the systems. Our methodology leverages the SimStack framework, an automated scientific workflow that enables the nuanced modeling of polymorphic alloys. This structured approach allows for comprehensive calculations of thermodynamic properties, phase diagrams, optoelectronic insights, and power conversion efficiencies while meticulously incorporating crucial relativistic effects like spin-orbit coupling (SOC) and quasi-particle corrections. Our findings advocate for the rational design of thermodynamically stable compositions in solar cell applications by calculating power conversion efficiencies using a spectroscopic limited maximum efficiency model, from which we obtained high efficiencies of about 28% (31–32%) for MA1−xCsxPbI3 with 0.50 < x < 1.00 (FA1−xCsxPbI3 with 0.0 < x < 0.20) as thermodynamically stable compositions at room temperature. The workflow’s significance is highlighted by a Colab-based notebook, which facilitates the analysis of raw data output, allowing users to delve into the physics of these complex systems. Our work underscores the pivotal role of composition and polymorphic degrees in determining the stability and optoelectronic properties of MHP alloys. It demonstrates the effectiveness of the SimStack workflow in advancing our understanding of these materials.

The colliding-wind binary HD 168112

Context. Radio surveys of early-type stars have revealed a number of non-thermal emitters. Most of these have been shown to be binaries, where the collision between the two stellar winds is responsible for the non-thermal emission. Aims. HD 168112 is a non-thermal radio emitter, whose binary nature has only recently been confirmed spectroscopically. We obtained independent spectroscopic observations to determine its orbit, in addition to radio observations to see if the thermal or non-thermal nature of the emission changes during the periastron passage. Methods. We monitored HD 168112 spectroscopically for a 13 yr time span. From these data, we determined the orbital parameters, which we compared to the previous results in the literature. The stellar parameters of both components were determined by comparing the spectra to TLUSTY models. From the spectral index of the radio observations, we found how the nature of the emission changes as the system goes through periastron. Combining our results with other literature data allowed us to further constrain the orbital and stellar parameters. Results. We find HD 168112 to have an orbital period of P = 512.17−0.11+0.41 days, an eccentricity of e = 0.7533−0.0124+0.0053, and a mass ratio close to one. From our spectroscopic modelling, we derived the stellar parameters, but we had difficulty arriving at a spectroscopic mass ratio of one. The radio observations around periastron show only thermal emission, suggesting that most of the synchrotron photons are absorbed in the two stellar winds at that phase. Combining our data with the optical interferometry detection, we could constrain the inclination angle to i ~ 63°, and the mass of each component to ~26 M⊙. Conclusions. We have provided an independent spectroscopic confirmation of the binary nature of HD 168112. Although detected as a non-thermal radio emitter, near periastron the radio emission of this highly eccentric system is thermal and is mainly formed in the colliding-wind region. This effect will also occur in other colliding-wind binaries.

Rotational spectroscopy of CH3OD with a reanalysis of CH3OD toward IRAS 16293–2422

We have started a measurement campaign of numerous methanol isotopologs in low-lying torsional states in order to provide extensive line lists for radio astronomical observations from an adequate spectroscopic model and to investigate how the intricate vibrationtorsion-rotation interactions manifest themselves in the spectra of different isotopic species. After CD3OH and CD3OD, we turn our focus to CH3OD, which is an important species for studying deuteration in prestellar cores and envelopes that enshroud protostars. Notably, deuteration is frequently viewed as a diagnostic tool for star formation. The measurements used in this study were obtained in two spectroscopic laboratories and cover large fractions of the 34 GHz-1.35 THz range. As done in previous studies, we employed a torsion-rotation Hamiltonian model for our analysis that is based on the rho-axis method. The resulting model describes the ground and first excited torsional states of CH3OD well up to quantum numbers J ⩽ 51 and Ka ⩽ 18. We derived a line list for radio astronomical observations from this model that is accurate up to at least 1.35 THz and should be sufficient for all types of radio astronomical searches for this methanol isotopolog in these two lowest torsional states. This line list was applied to a reinvestigation of CH3OD in data from the Protostellar Interferometric Line Survey of IRAS 16293–2422 obtained with the Atacama Large Millimeter/submillimeter Array. The new accurately determined value for the column density of CH3OD implies that the deuteration in methanol differs in its two functional groups by a factor of ~7.5.

Terminal Hydride Complex of High-Spin Mn.

The iron-molybdenum cofactor of nitrogenase (FeMoco) catalyzes fixation of N2 via Fe hydride intermediates. Our understanding of these species has relied heavily on the characterization of well-defined 3d metal hydride complexes, which serve as putative spectroscopic models. Although the Fe ions in FeMoco, a weak-field cluster, are expected to adopt locally high-spin Fe2+/3+ configurations, synthetically accessible hydride complexes featuring d5 or d6 electron counts are almost exclusively low-spin. We report herein the isolation of a terminal hydride complex of four-coordinate, high-spin (d5; S = 5/2) Mn2+. Electron paramagnetic resonance and electron-nuclear double resonance studies reveal an unusually large degree of spin density on the hydrido ligand. In light of the isoelectronic relationship between Mn2+ and Fe3+, our results are expected to inform our understanding of the valence electronic structures of reactive hydride intermediates derived from FeMoco.

Structural and functional impacts of neonicotinoids analogues on Apis mellifera's chemosensory protein: Insights from spectroscopic and molecular modeling investigations

In the intricate web of ecological relationships, pollinators such as the Italian honeybee (Apis mellifera) play a crucial role in maintaining biodiversity and agricultural productivity. This study focuses on the interactions between three neonicotinoid compounds and the honeybee's chemosensory protein 3 (CSP3), a key player in their olfactory system. Employing advanced spectroscopic techniques and molecular modeling, we explore the binding dynamics and conformational changes in CSP3 upon exposure to these pesticides. The research reveals that all three neonicotinoids considerably quench CSP3's fluorescence through a dynamic and static mixing mechanism, indicating a strong binding affinity, predominantly driven by hydrophobic interactions. UV–visible absorption, synchronous fluorescence, and 3D fluorescence spectra support slight changes in the microenvironment around the aromatic amino acids of CSP3. Circular dichroism spectra indicate a reduction in CSP3's α-helix content, suggesting structural alterations. Molecular docking and dynamics simulations further elucidate the binding modes and stability of these interactions, highlighting the role of specific amino acids in CSP3's binding cavity. Findings provide critical insights into molecular mechanisms by which neonicotinoids may impair honeybee chemosensory function, offering implications for designing safer pesticides and understanding the broader ecological impact of these chemicals on pollinator health.

Barium stars as tracers of s -process nucleosynthesis in AGB stars III. Systematic deviations from the AGB models

Barium (Ba) stars help to verify asymptotic giant branch (AGB) star nucleosynthesis models since they experienced pollution from an AGB binary companion and thus their spectra carry the signatures of the slow neutron capture process ($s$ process). For a large number (180) of Ba stars, we searched for AGB stellar models that match the observed abundance patterns. We aim to uncover any systematic deviations of the sample abundances from the predictions of the nucleosynthesis models. We employed three machine learning algorithms as classifiers: a Random Forest method, developed for this work, and the two classifiers used in our previous study. Compared to that work, we also expanded our observational sample with 11 Ba stars available in the supersolar metallicity range. We studied the statistical behaviour of the different $s$-process elements in the observational sample to investigate if the AGB models systematically under- or overpredict the abundances observed in the Ba stars and show the results in the form of violin plots of the residuals between spectroscopic abundances and model predictions. We inspected the correlations between the observed Fe/H the $s$-process elemental abundances, and the residuals. We employed the Zr/Fe and Nb/Fe abundances as a thermometer to constrain the operational temperature that rules the production of these elements in the sample stars, assuming a steady-state $s$ process. We also investigated the mass distribution of the identified polluter AGB stars and the behaviour of the delta parameter, which describes the fraction of accreted AGB material relative to the Ba star envelope. We find a significant trend in the residuals that implies an underproduction of the elements just after the first $s$-process peak (Nb, Mo, and Ru) in the models relative to the observations. This may originate from a neutron-capture process (e.g. the intermediate neutron-capture process, $i$ process) not yet included in the AGB models of metallicity from solar to roughly 1/5 solar, corresponding to the range of the Ba stars. Correlations are found between the residuals of these peculiar elements, suggesting a common origin for the deviations from the models. In addition, there is a weak metallicity dependence of the residuals of these elements. The $s$-process temperatures derived with the Zr/Fe Nb/Fe thermometer have an unrealistic value for the majority of our stars. The most likely explanation is that at least a fraction of these elements are not produced in a steady-state $s$ process, and instead may be due to processes not included in the AGB models. The mass distribution of the identified models confirms that our sample of Ba stars was polluted by low-mass AGB stars (&lt; 4 Most of the matching AGB models require low accreted mass, but a few systems with high accreted mass are needed to explain the observations.

Full spectroscopic model and trihybrid experimental-perturbative-variational line list for NH

ABSTRACT Imidogen (NH) is a reactive molecule whose presence in astrochemical environments is of interest due to its role in the formation of nitrogen-containing molecules and as a potential probe of nitrogen abundance. Spectroscopic NH monitoring is useful for Earth-based combustion and photolysis processes of ammonia and other nitrogen-containing species. NH is also relevant to ultracold molecular physics and plasma studies. To enable these diverse applications, high-quality molecular spectroscopic data are required. Here, a new line list with significant advantages over existing data is presented. Most notably, this line list models isotopologue spectroscopy and forbidden transitions (important for NH visible absorption), alongside some overall improvements to accuracy and completeness. This approach takes advantage of existing experimental data (from a previous MARVEL compilation) and perturbative line lists together with new MRCI ab initio electronic data. These are used to produce a novel variational spectroscopic model and trihybrid line list for the main 14N1H isotopologue, as well as isotopologue-extrapolated hybrid line lists for the 14N2H, 15N1H, and 15N2H isotopologues. The new 14N1H ExoMol-style trihybrid line list, kNigHt, comprises 4076 energy levels (1078 experimental) and 327 014 transitions up to 47 500 cm−1 (211 nm) between five low-lying electronic states (X 3Σ−, a 1Δ, b 1Σ+, A 3Π, and c 1Π). For most anticipated applications aside from far-infrared studies, this line list will be of sufficient quality; any improvements should focus on the b 1Σ+ energies, and the a 1Δ – A 3Π and b 1Σ+ – A 3Π spin–orbit couplings.

Rapid quality assessment and traceability of ginger powder from Northeast India and Indian market based on near infrared spectroscopic fingerprinting.

Ginger (Zingiber officinale Rosc.) varies widely due to varying concentrations of phytochemicals and geographical origin. Rapid non-invasive quality and traceability assessment techniques ensure a sustainable value chain. The objective of this study is the development of suitable machine learning models to estimate the concentration of 6-gingerol and check traceability based on the spectral fingerprints of dried ginger samples collected from Northeast India and the Indian market using near-infrared spectrometry. Samples from the market and Northeast India underwent High Performance Liquid Chromatographic analysis for 6-gingerol content estimation. Near infrared (NIR) Spectrometer acquired spectral data. Quality prediction utilized partial least square regression (PLSR), while fingerprint-based traceability identification employed principal component analysis and t-distributed stochastic neighbor embedding (t-SNE). Model performance was assessed using RMSE and R2 values across selective wavelengths and spectral fingerprints. The standard normal variate pretreated spectral data over the wavelength region of 1,100-1,250 nm and 1,325-1,550 nm showed the optimal calibration model with root mean square error of calibration and R2 C (coefficient of determination for calibration) values of 0.87 and 0.897 respectively. A lower value (0.24) of root mean square error of prediction and a higher value (0.973) of R2 P (coefficient of determination for prediction) indicated the effectiveness of the developed model. t-SNE performed better clustering of samples based on geographical location, which was independent of gingerol content. The developed NIR spectroscopic model for Indian ginger samples predicts the 6-gingerol content and provides geographical traceability-based identification to ensure a sustainable value chain, which can promote efficiency, cost-effectiveness, consumer confidence, sustainable sourcing, traceability, and data-driven decision-making.

Retraction: Spectroscopic and molecular modeling studies of binding interaction between the new complex of yttrium and 1,10-phenanthroline derivatives with DNA and BSA.

[This retracts the article DOI: 10.3389/fchem.2023.1231504.].

The High-Energy X-ray Probe (HEX-P): the circum-nuclear environment of growing supermassive black holes

Ever since the discovery of the first active galactic nuclei (AGN), substantial observational and theoretical effort has been invested into understanding how massive black holes have evolved across cosmic time. Circum-nuclear obscuration is now established as a crucial component, with almost every AGN observed known to display signatures of some level of obscuration in their X-ray spectra. However, despite more than six decades of effort, substantial open questions remain: how does the accretion power impact the structure of the circum-nuclear obscurer? What are the dynamical properties of the obscurer? Can dense circum-nuclear obscuration exist around intrinsically weak AGN? How many intermediate mass black holes occupy the centers of dwarf galaxies? In this paper, we showcase a number of next-generation prospects attainable with the High-Energy X-ray Probe (HEX-P1) to contribute toward solving these questions in the 2030s. The uniquely broad (0.2–80 keV) and strictly simultaneous X-ray passband of HEX-P makes it ideally suited for studying the temporal co-evolution between the central engine and circum-nuclear obscurer. Improved sensitivities and reduced background will enable the development of spectroscopic models complemented by current and future multi-wavelength observations. We show that the angular resolution of HEX-P both below and above 10 keV will enable the discovery and confirmation of accreting massive black holes at both low accretion power and low black hole masses even when concealed by thick obscuration. In combination with other next-generation observations of the dusty hearts of nearby galaxies, HEX-P will be pivotal in paving the way toward a complete picture of black hole growth and galaxy co-evolution.

Spectroscopic, biochemical and computational studies of bioactive DNA minor groove binders targeting 5′-WGWWCW-3′ motif

Spectroscopic, biochemical, and computational modelling studies have been used to assess the binding capability of a set of minor groove binding (MGB) ligands against the self-complementary DNA sequences 5′-d(CGCACTAGTGCG)-3′ and 5′-d(CGCAGTACTGCG)-3′. The ligands were carefully designed to target the DNA response element, 5′-WGWWCW-3′, the binding site for several nuclear receptors. Basic 1D 1H NMR spectra of the DNA samples prepared with three MGB ligands show subtle variations suggestive of how each ligand associates with the double helical structure of both DNA sequences. The variations among the investigated ligands were reflected in the line shape and intensity of 1D 1H and 31P-{1H} NMR spectra. Rapid visual inspection of these 1D NMR spectra proves to be beneficial in providing valuable insights on MGB binding molecules. The NMR results were consistent with the findings from both UV DNA denaturation and molecular modelling studies. Both the NMR spectroscopic and computational analyses indicate that the investigated ligands bind to the minor grooves as antiparallel side-by-side dimers in a head-to-tail fashion. Moreover, comparisons with results from biochemical studies offered valuable insights into the mechanism of action, and antitumor activity of MGBs in relation to their structures, essential pre-requisites for future optimization of MGBs as therapeutic agents.

Validation of Raman spectroscopic models to verify the origin of Australian beef grown under different production systems

Verification of beef production systems and authentication of origin is becoming increasingly important as consumers base purchase decisions on a greater number of perceived values including the healthiness and environmental impact of products. Previously Raman spectroscopy has been explored as a tool to classify carcases from grass and grain fed cattle. Thus, the aim of the current study was to validate Partial Least Squares Discriminant Analysis (PLS-DA) models created using independent samples from carcases sampled from northern and southern Australian production systems in 2019, 2020 and 2021. Validation of the robustness of discrimination models was undertaken using spectral measures of fat from 585 carcases which were measured in 2022 using a Raman handheld device with a sample excised for fatty acid analysis. PLS-DA models were constructed and then employed to classify samples as either grass or grain fed in a two-class model. Overall, predictions were high with accuracies of up to 95.7% however, variation in the predictive ability was noted with models created for southern cattle yielding an accuracy of 73.2%. While some variation in fatty acids and therefore models can be attributed to differences in genetics, management and diet, the impact of duration of feeding is currently unknown and thus further work is warranted.

Structural, Mechanical, and Optoelectronic Properties of CH3NH3PbI3 as a Photoactive Layer in Perovskite Solar Cell

The structural, electronic, mechanical, and optical properties of pseudo-cubic CH3NH3PbI3 perovskite have been studied within the framework of density functional theory, in line with solar cell applications. The computed values of lattice and elastic constants concurred with the available theoretical and experimental data. This compound has a semi-conducting behavior, with a direct band gap of about 1.49 eV. Note that the solar radiation spectrum has a maximum energy intensity value of approximately 1.50 eV. Thus, semiconductors with such gaps are preferred for photovoltaic applications. Its elastic parameters reveal that it is a ductile material that is mechanically stable. Optical descriptors such as refractive index, reflectivity, extinction, energy loss, and absorption have been explored with the aim of establishing the optical features of the material. Our findings demonstrate that this perovskite is suitable for solar cell applications based on the size and nature of the band gap, as also supported by the obtained upper limit value of simulated power conversion efficiency via the spectroscopic limited maximum efficiency mathematical model.