Spectral Calculations Research Articles

Prominent Nonlinear Optical Absorption in SnS2‐Based Hybrid Inorganic–Organic Superlattice

AbstractNonlinear optical materials hold great promise for applications in advanced opto‐/opto‐electronic devices. However, achieving a substantial nonlinear absorption coefficient and modulation depth concurrently remains challenging. This study proposes an effective strategy for enhancing the nonlinear optical response of materials through the construction of hybrid inorganic–organic superlattices via convenient organic intercalation. Synthesizing SnS2 intercalated with various tetra‐alkylammonium cations, it is revealed that the optimized sample (SnS2/CTA: SnS2 intercalated with cetyltrimethylammonium, CTA+) exhibits a substantial enhancement of nonlinear absorption across a broad wavelength range (from 515 to 1550 nm) and for diverse nonlinear optical processes (saturable absorption, two‐photon absorption, and three‐photon absorption). Specifically, the SnS2/CTA demonstrates a third‐order nonlinear absorption coefficient of (9.847 ± 0.084) × 103 cm GW−1 and a 69% modulation depth under laser excitation at 800 nm. Under 1550 nm excitation, it displays a fifth‐order nonlinear absorption coefficient of (45.3 ± 1.2) cm3 GW−2 and a 62% modulation depth. Notably, these values surpass those of the majority of non‐exfoliated materials. Structural, spectral, and density functional theory calculations indicate no induced structure defects post‐organic intercalation. The observed bandgap reduction is attributed to the electron injection associated with the organic molecule intercalation. The calculated performance enhancement, based on dielectric enhancement and bandgap reduction, qualitatively aligns with experimental findings.

Rains and Showers in OTREC; Weak Temperature Gradient Modeling

AbstractRainfall in the tropics has been shown to be produced either by isolated but intense convective systems (showers regime) or widespread but weaker systems (rains regime). We examine significant rainfall systems observed in the OTREC project (Organization of Tropical East Pacific Convection) in order to tease out the physical mechanisms differentiating these two regimes. We find that rains occur in very moist environments, typically with weak conditional instability. In contrast, showers develop in drier environments with larger instability. Spectral weak temperature gradient numerical calculations show that showers are associated with episodic rainfall separated by significant quiescent periods, whereas rains produce continuous simulated rainfall after a spinup period. Mass flux profiles of showers and rains are very different, resulting in different effects on the large scale environment.

Temperature and density dependence of Kr L-shell spectrum in hot dense plasmas

Kr L-shell spectroscopy modeling results are discussed in this paper, focusing on the n = 4 to n = 2 line transitions of Be- and Li-like Kr ions. Collisional radiative atomic kinetic and Stark-broadened spectral line shape calculations show electron temperature Te and density ne sensitivity in the spectrum. The combination of the Te dependence due to the relative intensity of Be-like to Li-like line emissions in the range from 1.5 to 3 keV and the ne sensitivity from the Stark broadening effect on the line shapes in the range from 5×1023 to 2×1024/ cc results in a spectrum that can be employed to diagnose Te and ne. Two different collisional radiative atomic kinetic models i.e., Prismspect [J. J. MacFarlane, et al., Int. Fusion Sci. Appl. Conf. Proc. 457 (2003)] and ABAKO [Florido, et al., PRE, 80, 056402 (2009)] produce similar results in level populations and spectra. In x-ray spectroscopy of implosion cores, this Kr L-shell spectrum may prove useful in an intermediate Te range in which Ar is too ionized for its K-shell to be of diagnostic value and Kr is not ionized enough for its K-shell emission to be useful.

On-Off Ratiometric Fluorescence Europium(III) Metal-Organic Framework for Quantitative Detection of the Inflammatory Marker Neopterin.

Benefiting from the unique photoluminescence behavior of the lanthanide(III) ions and organic ligands, a lanthanide(III) metal-organic framework (Ln-MOF) material can simultaneously demonstrate photoluminescence of lanthanide(III) cations and organic molecules and endow its superior applications of fluorescence sensing behaviors. Herein, we present a europium(III) MOF material {[Eu2(BPTA)·(CH3COO)2·3DMA]·0.5DMA·3H2O}n (1) (where H4BPTA is 3,3',5,5'-biphenyltetracarboxylic acid) for photoluminescence performance of quantitatively sensing the inflammatory marker neopterin (Neo). The obtained 1 comprises Eu2(COO)4 paddlewheel secondary building units, which could be bridged by BPTA4- ligands to extend a 2D framework. The fluorescence titration indicates 1 can achieve simultaneous fluorescence behavior of Eu3+ ions and Neo via on-off ratiometric effects and thus could be exploited as the ratiometric fluorescence sensor matrix. Such a fluorescence phenomenon of 1 as a ratiometric sensor for quantitative detection of Neo via an on-off ratiometric effect is never observed in MOF chemistry. Moreover, naked-eye visible color variations of the fluorescence for 1 could be observed from red to blue with increasing concentrations of Neo, confirmed by fluorescent test strips as well as portable fluorescent hydrogels. And 1 also shows a low detection limit of 15.11 nM. A synergetic contribution of the competitive absorption, fluorescence resonance energy-transfer, and photoinduced electron-transfer mechanisms between Neo and the framework of 1 realizes the on-off ratiometric fluorescence behavior for Neo detection, supported by the UV-vis spectral overlap experiment and DFT calculations.

Investigating the antimicrobial and anti-inflammatory activities of novel thiophene derivatives by in-vitro studies, molecular docking, spectral analysis, and quantum chemical calculations

The rise of antibiotic-resistant pathogens and the widespread occurrence of inflammatory diseases have raised considerable global health concerns. Consequently, there is a critical need to formulate novel and potent drug candidates to counteract these pressing global threats effectively. Hence, this study presents a comprehensive investigation involving spectral (FT-IR, and 1H NMR) analysis, experimental, molecular docking, and quantum chemical calculations employing density functional theory (DFT) to fully characterize and identify the synthesized compounds (Thiosemicarbazide Schiff base (TSB), 4‑methoxy aniline Schiff base (ASB), Phenyl urea Schiff base (PSB) at the ωB97XD/6-311++G(2d,2p) level of theory. Noteworthy observations from the antimicrobial investigations against four different microorganisms: Staphylococcus aureus, Escherichia coli, Candida albicans, and Aspergillus niger, TSB and ASB displayed varying degrees of antimicrobial activity. Notably, they exhibited the most significant effect against Candida albicans and A. niger, showing promise in combatting fungal infections. In contrast, PSB demonstrated moderate to high antimicrobial activity against E. coli, ranging from 15 mm to 24 mm. Molecular docking studies further confirmed TSB's strong binding affinity against Candida albicans with -6.4 kcal/mol, indicating robust interaction with the target protein. TSB also exhibited reasonably good binding affinities of -5.5 kcal/mol and -5.1 kcal/mol against Aspergillus niger and E. coli, respectively. ASB and PSB displayed particularly strong binding affinities against specific microorganisms, making them potential candidates for further investigation as antimicrobial agents. Furthermore, investigation into anti-inflammatory activity revealed that PSB demonstrated the highest free radical scavenging activity, with a percentage of 62.39 % and an IC50 value of 41.83. ASB followed with a free radical scavenging activity of 58.71 % and an IC50 value of 67.62, while TSB exhibited a free radical scavenging activity of 57.79 % with an IC50 value of 72. These findings were consistent with molecular docking analysis, suggesting that TSB effectively interacts with the active sites of the target proteins, potentially modulating the inflammatory response. Interestingly, PSB showed superior free radical scavenging activity compared to ASB and TSB, indicating its potential as an effective anti-inflammatory agent.

Effect of Broadness of Wave Spectrum on Significant Wave Height and Wave Power for Open Ocean Conditions of the Peru Basin

Abstract When estimating significant wave height and wave power, it is regularly assumed 4 for the spectral estimate factor. It means considering a narrowband wave spectrum. That approach is accurate enough when the spectral broadness parameter is near zero. Since the Peru Basin is an open ocean: swells and local wind waves can overlap; therefore, its wave spectrum should be considered broadband. This work aims to demonstrate that the wave spectrum in the Peru Basin has waves in a broad band of frequencies and also discuss how this characteristic affects estimating the significant wave height and wave power. The methodology comprises numerical methods, inferential statistics, and spectral analysis applied to ocean data. The paper's conclusions declare the Peru Basin wave spectrum as broadband. The estimated significant wave height for broadband wave spectrum is 7% lower than if the wave spectrum was considered narrowband. We propose 3.7 as the spectral estimate factor for calculating the significant wave height in the Peru Basin instead of the commonly used 4. The significant wave height error when assuming a narrowband wave spectrum slightly affects the spectral parametric wave power calculation, causing a maximum overestimation of 5%. Nevertheless, accurately estimating significant wave height is critical for diverse marine technologies.

Comprehensive Similarity Algorithm and Molecular Dynamics Simulation-Assisted Terahertz Spectroscopy for Intelligent Matching Identification of Quorum Signal Molecules (N-Acyl-Homoserine Lactones).

To investigate the mechanism of aquatic pathogens in quorum sensing (QS) and decode the signal transmission of aquatic Gram-negative pathogens, this paper proposes a novel method for the intelligent matching identification of eight quorum signaling molecules (N-acyl-homoserine lactones, AHLs) with similar molecular structures, using terahertz (THz) spectroscopy combined with molecular dynamics simulation and spectral similarity calculation. The THz fingerprint absorption spectral peaks of the eight AHLs were identified, attributed, and resolved using the density functional theory (DFT) for molecular dynamics simulation. To reduce the computational complexity of matching recognition, spectra with high peak matching values with the target were preliminarily selected, based on the peak position features of AHL samples. A comprehensive similarity calculation (CSC) method using a weighted improved Jaccard similarity algorithm (IJS) and discrete Fréchet distance algorithm (DFD) is proposed to calculate the similarity between the selected spectra and the targets, as well as to return the matching result with the highest accuracy. The results show that all AHL molecular types can be correctly identified, and the average quantization accuracy of CSC is 98.48%. This study provides a theoretical and data-supported foundation for the identification of AHLs, based on THz spectroscopy, and offers a new method for the high-throughput and automatic identification of AHLs.

Note for Higher Reliability of Structural Analysis by Spectral Calculations

Note for Higher Reliability of Structural Analysis by Spectral Calculations

An optical immunosensor employing a composite sensitive membrane and nanobody as a sensing probe for detecting carcinoembryonic antigen

We present an S-tapered fiber (STF) immunosensor featuring a gold nanoparticle/graphene oxide (GNP/GO) composite membrane for specific and label-free detection of carcinoembryonic antigen (CEA). Through spectral monitoring and calculation, we have developed a highly specific and sensitive immunosensor with a sensitivity of 27.9 nm/nM (R2 = 0.996) and a detection limit of 0.01 nM. Moreover, this biosensor demonstrates label-free operation and rapid detection of low concentrations of CEA. The proposed optical biosensor holds significant potential as a biophotonic platform for applications in clinical diagnostics, medical settings, and biomedical research.

Spectral Tuning and Excitation-Energy Transfer by Unique Carotenoids in Diatom Light-Harvesting Antenna.

The light-harvesting antennae of diatoms and spinach are composed of similar chromophores; however, they exhibit different absorption wavelengths. Recent advances in cryoelectron microscopy have revealed that the diatom light-harvesting antenna fucoxanthin chlorophyll a/c-binding protein (FCPII) forms a tetramer and differs from the spinach antenna in terms of the number of protomers; however, the detailed molecular mechanism remains elusive. Herein, we report the physicochemical factors contributing to the characteristic light absorption of the diatom light-harvesting antenna based on spectral calculations using an exciton model. Spectral analysis reveals the significant contribution of unique fucoxanthin molecules (fucoxanthin-S) in FCPII to the diatom-specific spectrum, and further analysis determines their essential role in excitation-energy transfer to chlorophyll. It was revealed that the specificity of these fucoxanthin-S molecules is caused by the proximity between protomers associated with the tetramerization of FCPII. The findings of this study demonstrate that diatoms employ fucoxanthin-S to harvest energy under the ocean in the absence of long-wavelength sunlight and can provide significant information about the survival strategies of photosynthetic organisms to adjust to their living environment.

Isolation and Structure Elucidation of New Metabolites from the Mariana-Trench-Associated Fungus Aspergillus sp. SY2601.

Fungi are important resource for the discovery of novel bioactive natural products. This study investigated the metabolites produced by Mariana-Trench-associated fungus Aspergillus sp. SY2601 in EY liquid and rice solid media, resulting in the isolation and structure determination of 28 metabolites, including five new compounds, asperindopiperazines A-C (1-3), 5-methoxy-8,9-dihydroxy-8,9-deoxyaspyrone (21), and 12S-aspertetranone D (26). Structures of the new compounds were elucidated based on extensive NMR spectral analyses, HRESIMS data, optical rotation, ECD, and 13C NMR calculations. The new compound 12S-aspertetranone D (26) exhibited antibacterial activity against both methicillin-resistant Staphylococcus aureus and Escherichia coli with MIC values of 3.75 and 5 μg/mL, respectively.

Comprehensive quantum chemical study of the associative complex of para-aminobenzoic acid and 7-diethylamino 4-methyl coumarin by adsorption and aromatic bridges.

The present study accounts for the quantum chemical and nonlinear optical properties of the combination of para-aminobenzoic acid and 7-diethylamino 4-methyl coumarin. Three different complexes were designed, surface interaction (adsorption) and two by connecting both molecules with π-bridge benzene and biphenyl. The amino and carboxyl groups were observed to behave as strong donor and acceptor sites in all the complexes. The band gap of the adsorbed complex was found more suitable. The absorption wavelength and intensity both were seen to increase with the increase in the number of benzene rings in the π-bridge. The values of first- and second-order hyperpolarizability suggest the improved nonlinear optical responses of the introduced complexes. Additionally, the negative value of second-order hyperpolarizability suggests the possibility of the occurrence of reverse saturable absorption in these combinations. The reported work gives theoretical insights into the nonlinear optical properties of the combination of para-aminobenzoic acid and 7-diethylamino 4-methyl coumarin. The molecular modeling and the quantum chemical studies were performed with Gaussian software packages. The standard B3LYP-6-311++G(d,p) basis functionals were used for energy minimization and other spectral calculations. All the surface analyses reported here are obtained by employing Multiwfn software. The chemical reactivity was established by the global reactivity descriptors. The intramolecular interactions and charge localization were stated using inter-fragment charge transfer analysis.

Research on potato (Solanum tuberosum L.) nitrogen nutrition diagnosis based on hyperspectral data

AbstractReducing the overapplication of nitrogen fertilizers to potatoes (Solanum tuberosum L.) can reduce production costs and their impact on the environment. One approach to produce these impacts is to reduce overapplications of fertilizers by using the nitrogen nutrition index (NNI = plant nitrogen concentration/critical nitrogen concentration) as a basis for in‐season nitrogen recommendations. The objective of this study was to create a remote sensing–based algorithm to estimate NNI. This study collected hyperspectral data (350–1830 nm) during the potato tuber formation period in 2022 and 2023. The climate regime for the study area was a mid‐temperate semiarid continental monsoon; in our study, three different spectral parameter calculation methods were employed. First, the empirical vegetation index, determined through a fixed two‐band calculation. Second, the optimal vegetation index, computed on a band‐by‐band basis. Lastly, the trilateral spectral approach, wherein the indicators are typically associated with the red edge, blue edge, and green edge. The optimum vegetation index had the highest correlation with NNI. The support vector machine, random forest (RF), and back propagation neural network models were used to create NNI prediction models. All machine learning models effectively estimated NNI, and during validation, the R2 (coefficient of determination) was >0.700. In general, the RF model outperformed the other models and during validation had an R2 of 0.869, a root mean square error of 0.052, and a relative error of 5.504%. This study demonstrates the scalability, simplicity, and cost‐effectiveness of combining hyperspectral technology and machine learning for rapid potato NNI estimation.

Expanded Application of Piper nigrum: Guided Isolation of Alkaloids with Inhibitory Activities of AChE/BuChE and Aβ Aggregation.

Piper nigrum is a popular crop that can be used as seasoning or as an additive but its active ingredients also have an effect on the nervous system. Nineteen new amide alkaloids (1a/1b, 2-5, 6a/6b, 7, 8a/8b, 9, 10a/10b, 11a-11b, 12-14) were isolated from P. nigrum, guided by inhibitory activity of AChE and LC-MS/MS based on GNPS. The configurations were determined by extensive spectral analysis, Bulkiness rule, and NMR calculations. The inhibitory activities of AChE/BuChE and Aβ aggregation were tested, and the results showed compounds 2, 7, and 12 had significant inhibitory activities. These components were identified in the crude fraction and their relative quantities were tested, which suggested that compound 2 was the index component in the active site from P. nigrum.

Formyl phloroglucinol meroterpenoids from the leaves of Eucalyptus globulus subsp. maidenii and their ATP-citrate lyase inhibitory activities

Three new formyl phloroglucinol meroterpenoids, eumaidials A-C (1–3), were isolated from the leaves of Eucalyptus globulus subsp. maidenii, along with ten known analogues (4–13). Their chemical structures were determined by various spectral data and electronic circular dichroism calculations. Eumaidial A (1) is the first β-caryophyllene-based formyl phloroglucinol meroterpenoids from the genus Eucalyptus. Compounds 1–4 and 10 exhibited ATP-citrate lyase inhibitory activities, and compounds 2 and 3 suppressed the hepatocyte lipogenesis.

Flux and estimated spectra from a low-intensity laser-driven X-ray source

Abstract Laser-driven X-rays as probes for high-energy-density physics spans an extremely large parameter space with laser intensities varying by 8 orders of magnitude. We have built and characterized a soft X-ray source driven by a modest intensity laser of 4 × 1013 W/cm2. Emitted X-rays were measured by diamond radiation detectors and a filtered soft X-ray camera. A material-dependence study on Al, Ti, stainless steel alloy 304, Fe, Cu and Sn targets indicated 5-μm-thick Cu foils produced the highest X-ray yield. X-ray emission in the laser direction and emission in the reverse direction depend strongly on the foil material and the thickness due to the opacity and hydrodynamic disassembly time. The time-varying X-ray signals are used to measure the material thinning rate and is found to be ∼1.5 μm/ns for the materials tested implying thermal temperature around 0.6 eV. The X-ray spectra from Cu targets peaks at ∼2 keV with no emission >4 keV and was estimated using images with eight different foil filters. One-dimensional hydrodynamic and spectral calculations using HELIOS-CR provide qualitative agreement with experimental results. Modest intensity lasers can be an excellent source for nanosecond bursts of soft X-rays.

Colorimetric differentiation of arsenite and arsenate anions using a bithiophene sensor with two binding sites: DFT studies and application in food and water samples.

Chemosensor N7R1 with two acidic binding sites was synthesized, and the ability of the sensor to differentiate arsenite and arsenate in the organo-aqueous medium was evaluated using colorimetric sensing methods. N7R1 distinguished arsenite with a peacock blue color and arsenate with a pale green color in a DMSO/H2O (9 : 1, v/v) solvent mixture. The specific selectivity for arsenite was achieved in DMSO/H2O (7 : 3, v/v). The sensor demonstrated stability over a pH range of 5 to 12. The computed high binding constant of 9.3176 × 1011 M-2 and a lower detection limit of 11.48 ppb for arsenite exposed the chemosensor's higher potential for arsenite detection. The binding mechanism with a 1 : 2 binding process is confirmed using UV-Vis and 1H NMR titrations, electrochemical studies, mass spectral analysis and DFT calculations. Practical applications were demonstrated by utilizing test strips and molecular logic gates. Chemosensor N7R1 successfully detected arsenite in real water samples, as well as honey and milk samples.

Influence of the substitution position on spin communication in photoexcited perylene-nitroxide dyads.

By virtue of the modularity of their structures, their tunable optical and magnetic properties, and versatile applications, photogenerated triplet-radical systems provide an ideal platform for the study of the factors controlling spin communication in molecular frameworks. Typically, these compounds consist of an organic chromophore covalently attached to a stable radical. After formation of the chromophore triplet state by photoexcitation, two spin centres are present in the molecule that will interact. The nature of their interaction is governed by the magnitude of the exchange interaction between them and can be studied by making use of transient electron paramagnetic resonance (EPR) techniques. Here, we investigate three perylene-nitroxide dyads that only differ with respect to the position where the nitroxide radical is attached to the perylene core. The comparison of the results from transient UV-vis and EPR experiments reveals major differences in the excited state properties of the three dyads, notably their triplet state formation yield, excited state deactivation kinetics, and spin coherence times. Spectral simulations and quantum chemical calculations are used to rationalise these findings and demonstrate the importance of considering the structural flexibility and the contribution of rotational conformers for an accurate interpretation of the data.

Vibrational circular dichroism spectra of proline in water at different pH values.

Recording VCD spectra of aqueous solution poses a particular challenge as water is a strong infrared absorber. Likewise, the computational analysis of VCD spectra by means of DFT-based spectral calculations requires the consideration of explicit solvent molecules, thus posing an even greater challenge. Several studies suggested that by modeling the solvent environment with a few water molecules in a micro-solvation approach would be sufficient to describe experimental spectra. For example, using proline at different pH values, we herein show that a change in the relative spatial orientation of a single water molecule in five-fold solvated structures strongly affects the computed VCD spectral signatures and that Boltzmann-weighted spectra do not correctly reproduce the experiment. We thus explored an approach based on molecular dynamics and subsequent DFT-calculations, in which we considered 30 water molecules (about 1.5 solvation shells). Once again, it was found that the Boltzmann-weighted spectra obtained on the basis of several hundred structures did not correctly reproduce experimental signatures, and a simple averaging scheme resulted in well-matching spectra with comparable bandwidths. The rationale behind the procedure was that sampling the configurational space of the solvent molecules is as equally important as the conformational sampling of the solute. For conformationally more flexible molecules, it is assumed that a much larger set of structures will have to be computed in order to properly sample the conformational space of both solute and solvent.

Density functional theory/time-dependent density functional theory investigations on the color-structure relationship of biopigment molecules

The study of molecular derivatives of biological dyes is of great importance for the green transformation of the printing, dyeing, and textile industries. In this study, B3LYP density functional methods are used to optimize the geometric configuration of the selected molecules and to explore the relationship between the structure and color of biological dye molecules and their color mechanism. This study focuses on the analysis of polyenes, quinones, indoles, and azide biological dyes in colors commonly used in the textile industry: blue, yellow, purple, red, green, and so on. Quantum chemical investigations show that the conjugate structure of a biological dye is directly related to its color and that the group or structure affecting the conjugate structure will in many cases cause a change in color. In addition, time-dependent density functional theory spectral calculations with the CAM-B3LYP functional for UV-Vis spectra show that in the visible band, the color of the remaining band after subtracting the absorption wavelengths was exactly the same as the color of the pigment. These results indicate that the color of the pigment is exactly complementary to the light absorption color of the material. Our study provides theoretical guidance for the design of molecular derivatives of biological dyes and is expected to promote the green transformation of the textile, printing, and dyeing industries to a certain extent.