Intermediate Spectra Research Articles

Raman activities of nitrogen reduction and ammonia oxidation intermediates on the high-entropy alloy CoCuFeMoNi catalytic surface.

We developed a computational framework to extract the Raman spectra of nitrogen reduction and ammonia oxidation intermediates on high-entropy alloy (HEA) surfaces, integrating density functional theory with microstructural representations to account for the inherent lattice randomness in these materials. As a case study, we computed the Raman activities of intermediates (N2*, NNH*, N*, NH*, and NH3*) and H* adsorption on CoCuFeMoNi HEA surfaces. A comprehensive map of Raman peaks was generated and assigned to specific vibrational modes. The method highlighted the effects of lattice randomness on the Raman spectra compared to those of adsorbates on single-element catalysts. For instance, our results showed that the adsorbed N2 exhibits Raman modes that are dependent on whether the adsorption is vertical or horizontal. These peak differences could serve as unique fingerprints to identify nitrogen reduction reaction pathways. Moreover, it is also possible to detect surface poisoning by hydrogen, a common issue in reductive environments, due to the high-frequency peaks of H* compared to the typical N-metal stretching and bending frequencies. These results provide valuable references for identifying intermediates in nitrogen reduction and ammonia oxidation reactions, offering insights into reaction mechanisms and potential surface poisoning. This approach is generalizable to other reactions and surfaces in catalysis, provided that the relevant intermediates can be identified.

Reactions of Aluminum Oxide Cluster Cations with Ethane: A Mass-Spectrometric and Vibrational Spectroscopy Study.

The pathways for the reactions of aluminum oxide cluster ions with ethane have been measured. For selected ions (Al2O+, Al3O2 +, Al3O4 +, Al4O7 +) the structure of the collisionally-stabilized reaction intermediates were explored by measuring the photodissociation vibrational spectra from 2600 cm-1-3100 cm-1. Density functional theory was used to calculate features of the potential energy surfaces for the reactions and the vibrational spectra of intermediates. Generally, more than one isomer contributes to the observed spectrum. The oxygen-deficient clusters Al2O+ and Al3O2 + have large C-H activation barriers, so only the entrance channel complexes in which intact C2H6 binds to aluminum are observed. This interaction leads to a substantial (~200 cm-1) red shift of the C-H symmetric stretch in ethane, indicating significant weakening of the proximal C-H bonds. In Al3O4 +, the complex formed by interactions with three C2H6 is investigated and, in addition to entrance channel complexes, the C-H activation intermediate Al3O4H+(C2H5)(C2H6)2 is observed. For oxygen-rich Al4O7 +, the C2H6 is favored to bind at an aluminum site far from the reactive superoxide group, reducing the reactivity. As expected, oxygen-rich species and open-shell cluster ions have smaller barriers for C-H bond activation, except for Al3O4 + which is predicted and observed to be reactive.

Uncertainty Quantification of 237Np, 241Am, and 243Am Reaction Rates in Highly Enriched Uranium Fuel Cores at Kyoto University Critical Assembly

Experimental analyses of 237Np, 241Am, and 243Am fission, as well as 237Np capture reaction rates, are conducted with the Serpent 2 code together with ENDF/B-VIII.0 and JENDL-5 using experimental data for the neutron spectra of thermal and intermediate regions obtained in the solid-moderated and solid-reflected cores with highly enriched uranium fuel at the Kyoto University Critical Assembly. Also, uncertainty quantification of the fission and capture reaction rate ratios of the test samples of 237Np, 241Am, and 243Am with reference samples of 235U and 197Au are evaluated by the MARBLE code system. In terms of the fission reaction rate ratios of 237Np/235U, 241Am/235U, and 243Am/235U, a comparison between experiments and Serpent 2 calculations shows an accuracy of about 5%, 15%, and 10%, respectively, together with ENDF/B-VIII.0 and JENDL-5. For the capture reaction rate ratios of 237Np/197Au, Serpent 2 calculations reveal a fairly good accuracy at the thermal neutron spectrum. The total uncertainties of the 237Np/235U, 241Am/235U, and 243Am/235U fission reaction rate ratios by MARBLE with the covariance data of ENDF/B-VIII.0 and JENDL-5 are found to be about 4% at most in all cores, except for about 8% for 243Am/235U with ENDF/B-VIII.0 at the intermediate neutron spectrum.

Detection of moisture content of edamame based on the fusion of reflectance and transmittance spectra of hyperspectral imaging

AbstractEdamame is a nutritious and economically valuable soybean. The moisture content is an important indicator of the quality of the edamame. The traditional methods in the detection of moisture content of edamame have the disadvantage of large detection errors. In this research, the fusion of transmittance and reflectance spectra of hyperspectral imaging combined with chemometrics was proposed to predict the moisture content of edamame. Also, the effect of different preprocessing of the spectra on the predictive performance was analyzed. Single spectra, primary fusion spectra, and intermediate fusion spectra were established as the prediction models for partial least squares regression (PLSR) and partial least squares support vector regression (LSSVR), respectively. The results of the prediction models showed that the spectral transform absorption (STA) combined with PLSR has the best prediction performance for a single spectrum with predictive correlation (RP) of 0.7749 and ratio of prediction to deviation (RPD) of 1.7. Standard normal variate (SNV) combined with LSSVR has the best prediction performance for primary fusion spectra with RP of 0.8821 and RPD of 1.9. SNV combined with LSSVR has the best prediction performance for intermediate fusion spectra with RP of 0.9149 and RPD of 2.4. The Rp and RPD of prediction models of the moisture content of edamame based on fusion spectra were significantly improved compared with single spectra. Compared with primary fusion, intermediate fusion is a more suitable fusion strategy. This research provides experimental basis for the prediction of moisture content of edamame using spectral fusion combined with chemometrics.

Transient spectroscopic insights into nitroindole’s T1 state: Elucidating its intermediates and unique photochemical properties

Indoles are notable for their distinct photophysical and photochemical properties, making them useful indicators in biological systems and promising candidates for a variety of pharmaceutical applications. While some indoles exhibit room temperature phosphorescence, such a phenomenon has not been observed in nitroindoles. Typically, adding of a nitro group into aromatic compounds promotes ultrafast intersystem crossing and increases the formation quantum yield of the lowest excited triplet (T1). Therefore, understanding the reactivity of nitroindoles′ T1 states is imperative. This study investigated the physical properties and chemical reactivities of the T1 state of 6-nitroindole (3HN-6NO2) in both polar aprotic and protic solvents, using transient absorption spectroscopy. Our results demonstrate the basicity and acidity of 3HN-6NO2, emphasizing its potential for protonation and dissociation in mildly acidic and basic conditions, respectively. Furthermore, 3HN-6NO2 has a high oxidizing capacity, participating in electron transfer reactions and proton-coupled electron transfer to produce radicals. Interestingly, in protic solvents like alcohols, 3HN-6NO2 dissociates at the –NH group and forms N-H…O hydrogen-bonded complexes with the nitro group. By identifying transient absorption spectra of intermediates and quantifying kinetic reaction rate constants, we illuminate the unique properties of the T1 state nitroindoles, enriching our understanding of their photophysical and photochemical behaviors. The results of this study have significant implications for their potential application in both biological systems and materials science.

Understanding and Managing Pineal Parenchymal Tumors of Intermediate Differentiation: An In-Depth Exploration from Pathology to Adjuvant Therapies.

Pineal parenchymal cell tumors constitute a rare group of primary central nervous system neoplasms (less than 1%). Their classification, especially the intermediate subtype (PPTIDs), remains challenging. A literature review was conducted, navigating through anatomo-pathological, radiotherapy, and neurosurgical dimensions, aiming for a holistic understanding of these tumors. PPTIDs, occupying an intermediate spectrum of malignancy, reveal diverse histological patterns, mitotic activity, and distinct methylation profiles. Surgical treatment is the gold standard, but when limited to partial removal, radiotherapy becomes crucial. While surgical approaches are standardized, due to the low prevalence of the pathology and absence of randomized prospective studies, there are no shared guidelines about radiation treatment modalities. Surgical removal remains pivotal, demanding a personalized approach based on the tumor extension. This review underscores the considerable variability in treatment approaches and reported survival rates within the existing literature, emphasizing the need for ongoing research to better define optimal therapeutic strategies and prognostic factors for PPTIDs, aiming for further and more detailed stratification among them.

Optical Spectroscopy and Photoionization Model of Planetary Nebula NGC 6572

We investigated NGC 6572 through optical spectroscopy to determine its kinematical and chemical properties. Two intermediate dispersion spectra (R~5000) centered around Hα and Hβ were used to derive the nebular expansion velocity from emission lines associated with Hα, Hβ, [OIII], [NII], and [SII] ions. A low dispersion spectrum (R~1000) was used to determine the nebular electron temperature, density, and chemical composition. We performed photoionization modeling to construct a self-consistent nebular model, whileintermediate-resolution spectral images showed the global elliptical structure of the nebula. The expansion velocity deduced from most of the emission lines is consistent with the typical expansion velocity of planetary nebulae, i.e., around 15-20 kms-1. The nebular physical properties align well with those determined by other studies. The nebular abundances were found to be lower than the solar abundances (except for oxygen) but still comparable with the abundances derived by other researchers. The photoionization model generated spectral lines that are consistent with the lines found in the observations. Further spectroscopic observations with higher resolution and wider range at various position angles will be very useful to reveal a more complete and detailed structure of the nebula and to improve the determination of the nebular physical properties.

Threshold photoelectron spectroscopy of organosulfur radicals.

We report vibrationally resolved threshold photoelectron spectra of several sulfur-containing reactive intermediates. This includes the organosulfur radicals CH2S, CH3S, CH2SH, CH3S2, and S2H, which are relevant in atmospheric chemistry and in astrochemical settings. Due to the high reactivity, the radicals were prepared in situ via pyrolysis of (CH3)2S2. The organosulfur species were characterized by photoion mass-selected threshold photoelectron spectroscopy, employing the photoelectron-photoion coincidence setup (PEPICO) and synchrotron radiation from the Swiss Light Source. We report improved ionization energies and characterize ionic ground and excited states, both singlet and triplet. The vibrational structure was simulated based on computed geometries and vibrational frequencies, giving insight into the geometry change upon ionization.

Efficient Harmonic Neural Networks With Compound Discrete Cosine Transform Filters and Shared Reconstruction Filters.

The harmonic neural network (HNN) learns a combination of discrete cosine transform (DCT) filters to obtain an integrated feature from all spectra in the frequency domain. HNN, however, faces two challenges in learning and inference processes. First, the spectrum feature learned by HNN is insufficient and limited because the number of DCT filters is much smaller than that of feature maps. In addition, the number of parameters and the computation costs of HNN are significantly high because the intermediate spectrum layers are expanded multiple times. These two challenges will severely harm the performance and efficiency of HNN. To solve these problems, we first propose the compound DCT (C-DCT) filters integrating the nearest DCT filters to retrieve rich spectrum features to improve the performance. To significantly reduce the model size and computation complexity for improving the efficiency, the shared reconstruction filter is then proposed to share and dynamically drop the meta-filters in every frequency branch. Integrating the C-DCT filters with the shared reconstruction filters, the efficient harmonic network (EH-Net) is introduced. Extensive experiments on different datasets demonstrate that the proposed EH-Nets can effectively reduce the model size and computation complexity while maintaining the model performance. The code has been released at https://github.com/zhangle408/EH-Nets.

Super-resolution Localization Problem Based on the Mobile Scenario

Target positioning has always been a hot research topic in the field of sensors. In recent years, radar detection technology has become increasingly mature, resulting in a large number of radar sensors have begun to be used in traffic, security, medical and other fields for target detection. This paper mainly studies the super-resolution localization problem of FMCW FMCW in moving scenes. It analyzes the echo data by mathematical modeling to obtain the distance and angle information of the object to find the place of the object. To restore the motion trajectory of objects more realistically and achieve super-resolution positioning, a super-resolution radar positioning model based on Kriging interpolation based on the Fourier spectrum is established. By constructing a frame of intermediate frequency data Fourier spectrum tensor space, Fourier spectrum analysis is used to obtain the spectral characteristics of spatiotemporal changes when objects move. The Fourier spectrum surface is reasonably predicted through the statistical method - kriging interpolation. More Fourier spectrum information of objects in the time dimension can be obtained, and then more object points can be restored to achieve super-resolution positioning. This is widely used in the automotive field, which develops autonomous driving systems to help drivers better control the vehicle and reduce the probability of car accidents.

Missing levels in intermediate spectra

We derive an expression for the nearest-neighbor spacing distribution P(s) of the energy levels of quantum systems with intermediate dynamics between regularity and chaos and missing levels due to random experimental errors. The expression is based on the Brody distribution, the most widely used for fitting mixed spectra as a function of one parameter. By using Monte Carlo simulations of intermediate spectra based on the β-Hermite ensemble of random matrix theory (RMT), we evaluate the quality of the formula and its suitability for fitting purposes. Estimations of the Brody parameter and the fraction of missing levels can be obtained by a least-square two-parameter fitting of the experimental P(s). The results should be important to distinguish the origins of deviations from RMT in experimental spectra.

HEXOKINASE1 and glucose-6-phosphate fuel plant growth and development.

As photoautotrophic organisms, plants produce an incredible spectrum of pigments, anti-herbivory compounds, structural materials and energic intermediates. These biosynthetic routes help plants grow, reproduce and mitigate stress. HEXOKINASE1 (HXK1), a metabolic enzyme and glucose sensor, catalyzes the phosphorylation of hexoses, a key introductory step for many of these pathways. However, previous studies have largely focused on the glucose sensing and signaling functions of HXK1, and the importance of the enzyme's catalytic function is only recently being connected to plant development. In this brief Spotlight, we describe the developmental significance of plant HXK1 and its role in plant metabolic pathways, specifically in glucose-6-phosphate production. Furthermore, we describe the emerging connections between metabolism and development and suggest that HXK1 signaling and catalytic activity regulate discrete areas of plant development.

TRU oxide sample reactivity worths measured in the FCA-IX assemblies with systematically changed neutron energy spectra

ABSTRACT A series of integral experiments was conducted to evaluate the fission and the capture cross-sections of transuranic (TRU) nuclides at the fast critical facility FCA of the Japan Atomic Energy Agency (JAEA). The experiments were carried out using seven uranium-fueled assemblies of the FCA. The neutron energy spectra of the core regions were adjusted so as to change from an intermediate neutron spectrum to a fast neutron spectrum on an assembly-by-assembly basis. The integral data measured with these experimental configurations provide some neutron energy characteristics: 1) fission rate ratios (FRRs) of 237Np, 238Pu, 242Pu, 241Am, 243Am, and 244Cm relative to 239Pu by using absolutely calibrated fission chambers, 2) small sample reactivity worths (SRWs) of 237Np, 238Pu, 240Pu, 241Am, and 243Am where oxide powders of around 15 to 20 grams were used, 3) criticalities, and 4) spectral indices such as fission rate ratios of 238U relative to 235U. In this paper, details of the SRW measurements are reported, and the latest Japanese Evaluated Nuclear Data Library JENDL-5 is tested by using the integral data obtained in systematically varied neutron energy spectra.

Grid-based Atmospheric Retrievals for Reflected-light Spectra of Exoplanets Using PSGnest

Techniques to retrieve the atmospheric properties of exoplanets via direct observation of their reflected light have often been limited in scope owing to computational constraints imposed by the forward-model calculations. We have developed a new set of techniques that significantly decrease the time required to perform a retrieval while maintaining accurate results. We constructed a grid of 1.4 million precomputed geometric albedo spectra valued at discrete sets of parameter points. Spectra from this grid are used to produce models for a fast and efficient nested sampling routine called PSGnest. Beyond the upfront time to construct a spectral grid, the amount of time to complete a full retrieval using PSGnest is on the order of seconds to minutes using a personal computer. An extensive evaluation of the error induced from interpolating intermediate spectra from the grid indicates that this bias is insignificant compared to other retrieval error sources, with an average coefficient of determination between interpolated and true spectra of 0.998. We apply these new retrieval techniques to help constrain the optimal bandpass centers for retrieving various atmospheric and bulk parameters from a LuvEx-type mission observing several planetary archetypes. We show that spectral observations made using a 20% bandpass centered at 0.73 μm can be used alongside our new techniques to make detections of H2O and O2 without the need to increase observing time beyond what is necessary for a signal-to-noise ratio of 10. The methods introduced here will enable robust studies of the capabilities of future observatories to characterize exoplanets.

Spectrum of the Hole Excitation in Spin-Orbit Mott Insulator Na2IrO3

We study the motion of a hole with internal degrees of freedom, introduced to the zigzag magnetic ground state of Na2IrO3, by using the self-consistent Born approximation. We find that the low-, intermediate-, and high-energy spectra are primarily attributed to the singlet, triplet, and quintet hole contributions, respectively. The spectral functions exhibit distinct features such as the electron-like dispersion of low-energy states near the Γ point, the maximum M-point intensity of mid-energy states, and the hole-like dispersion of high-energy states. These features are robust and almost insensitive to the exchange model and Hund’s coupling, and are in qualitative agreement with the angular-resolved photoemission spectra observed in Na2IrO3. Our results reveal that the interference between internal degrees of freedom in different sublattices plays an important role in inducing the complex dispersions.

Early events in amyloid-β self-assembly probed by time-resolved solid state NMR and light scattering

Self-assembly of amyloid-β peptides leads to oligomers, protofibrils, and fibrils that are likely instigators of neurodegeneration in Alzheimer’s disease. We report results of time-resolved solid state nuclear magnetic resonance (ssNMR) and light scattering experiments on 40-residue amyloid-β (Aβ40) that provide structural information for oligomers that form on time scales from 0.7 ms to 1.0 h after initiation of self-assembly by a rapid pH drop. Low-temperature ssNMR spectra of freeze-trapped intermediates indicate that β-strand conformations within and contacts between the two main hydrophobic segments of Aβ40 develop within 1 ms, while light scattering data imply a primarily monomeric state up to 5 ms. Intermolecular contacts involving residues 18 and 33 develop within 0.5 s, at which time Aβ40 is approximately octameric. These contacts argue against β-sheet organizations resembling those found previously in protofibrils and fibrils. Only minor changes in the Aβ40 conformational distribution are detected as larger assemblies develop.

Morphological, Phytochemical, and Photosynthetic Performance of Grafted Tomato Seedlings in Response to Different LED Light Qualities under Protected Cultivation

Healing and acclimatization are critical in vegetable grafting under controlled environments. Here, we investigated the impacts of LED light qualities on the morphological traits and photosynthetic performance of grafted tomato seedlings. Seeds of the tomatoes “DRW 7806 F1” and “Maxifort” (Solanum lycopersicum × Solanum habrochaites) used as scion and rootstock were planted in 104-cell plug trays into a mixture of cocopeat and perlite (volume ratio: 3 to 1). Survival ratio, above- and underground growth, photosynthetic performance, soluble carbohydrate content, pigmentation, and antioxidant enzymes activity were evaluated following 20 days of exposure to different light qualities, including white (35% B, 49% intermediate spectra, 16% R) light as control, blue, red, and a combination of red (68%) and blue with the same light intensity of 75 ± 5 µmol m−2 s−1. The lowest scion diameter, leaf area, root and shoot dry weight, SPAD value, and the highest scion length and amount of soluble carbohydrate were detected in R-exposed seedlings. Moreover, R-exposed seedlings showed leaf epinasty and reduced photosynthetic performance. On the other hand, RB-exposed seedlings showed the highest leaf area, shoot and root dry weight, plant fresh and dry weight, scion stem diameter and photosystem II efficiency. In addition, superoxide dismutase activity was increased in R-exposed seedlings, while guaiacol peroxidase activity was enhanced in seedlings grown in RB. In conclusion, a combination of R and B is suggested as the suitable light spectrum to promote plant growth and photosynthetic performance in grafted tomato seedlings.

Steering the product spectrum in high-pressure anaerobic processes: CO2 partial pressure as a novel tool in biorefinery concepts

BackgroundElevated CO2 partial pressure (pCO2) has been proposed as a potential steering parameter for selective carboxylate production in mixed culture fermentation. It is anticipated that intermediate product spectrum and production rates, as well as changes in the microbial community, are (in)directly influenced by elevated pCO2. However, it remains unclear how pCO2 interacts with other operational conditions, namely substrate specificity, substrate-to-biomass (S/X) ratio and the presence of an additional electron donor, and what effect pCO2 has on the exact composition of fermentation products. Here, we investigated possible steering effects of elevated pCO2 combined with (1) mixed substrate (glycerol/glucose) provision; (2) subsequent increments in substrate concentration to increase the S/X ratio; and (3) formate as an additional electron donor.ResultsMetabolite predominance, e.g., propionate vs. butyrate/acetate, and cell density, depended on interaction effects between pCO2–S/X ratio and pCO2–formate. Individual substrate consumption rates were negatively impacted by the interaction effect between pCO2–S/X ratio and were not re-established after lowering the S/X ratio and adding formate. The product spectrum was influenced by the microbial community composition, which in turn, was modified by substrate type and the interaction effect between pCO2–formate. High propionate and butyrate levels strongly correlated with Negativicutes and Clostridia predominance, respectively. After subsequent pressurized fermentation phases, the interaction effect between pCO2–formate enabled a shift from propionate towards succinate production when mixed substrate was provided.ConclusionsOverall, interaction effects between elevated pCO2, substrate specificity, high S/X ratio and availability of reducing equivalents from formate, rather than an isolated pCO2 effect, modified the proportionality of propionate, butyrate and acetate in pressurized mixed substrate fermentations at the expense of reduced consumption rates and increased lag-phases. The interaction effect between elevated pCO2 and formate was beneficial for succinate production and biomass growth with a glycerol/glucose mixture as the substrate. The positive effect may be attributed to the availability of extra reducing equivalents, likely enhanced carbon fixating activity and hindered propionate conversion due to increased concentration of undissociated carboxylic acids.

Mechanism study on pyrolysis interaction between cellulose, hemicellulose, and lignin based on photoionization time-of-flight mass spectrometer (PI-TOF-MS) analysis

It is critical to accurately reveal the interactions between biomass components for the selective preparation and directional exploitation of pyrolysis products. The rapid, simultaneous capture of the full mass spectrum of intermediates is advantageous for elucidating the interaction mechanism. To depict the real complicated pyrolysis reactions, a simplified coupled cross-pyrolysis process among the biomass components is examined. The interaction was studied by the examination of offline product distribution, bio-oil, and bio-gas composition, as well as the evolution of pyrolysis intermediates using an online photoionization time-of-flight mass spectrometer (PI-TOF-MS). Results indicate that the interaction only affects product distribution, rather than creating a new pyrolysis reaction pathway. The cracking of glycosidic bonds during low-temperature cellulose depolymerization provides hydrogen donor (H∙) and hydroxyl donor (OH∙) for the primary cleavage of hemicellulose and lignin. It increases the ring opening of C5 of hemicellulose and the cleavage of lignin's phenylpropane side chains, promoting the production of aliphatic compounds, guaiac-based phenols, and syringe-based phenols. CO cracking on the side chain of phenylpropane provides donors for the ring opening of cellulose’s secondary pyrolysis products, further promoting the production of aliphatic chains. High temperatures hasten the fragmentation of partial aliphatic chains and the demethylation of phenols, providing donors and molecular fragments (methyl and methoxy, etc.) for the aromatization of linear molecules and encouraging the generation of aromatic compounds. The study's findings will help to improve knowledge of the biomass pyrolysis interaction and be used as a reference for targeted biomass utilization and the optimization of catalytic pyrolysis strategies.

Wave Packet Calculation of Absolute UV Cross Section of Criegee Intermediates.

Criegee intermediates, R1R2COO, are reactive species formed in the atmosphere through the ozonolysis of alkenes. They have an intense ultraviolet (UV) adsorption between 300 to 400 nm. However, experimentally determining the absolute cross sections is not easy. We used wave packet propagation on an one-dimensional adiabatic potential energy curve (PEC) along the OO bond to simulate the UV spectra for various Criegee intermediates. Our results showed a very fast, ∼20 fs, decay out of the Franck-Condon region. This gives justification for using the semiclassical approach which was utilized in previous studies. From the comparison of various quantum chemistry methods, we found that multireference methods can give spectra with a width and cross section reproducing the experimental results, while single reference methods tend to give narrower skewed peaks with a larger cross section. From the test using wave packet propagation on various approximated PECs and transition moment functions, we show that the Gaussian approximation within the reflection method is valid. In addition, we found that we can obtain peak positions that reproduce the experimental results by shifting those obtained by MRCI+Q, CASSCF, EOMCCSD, and TDCAMB3LYP by -0.2, -1.0, -0.3, and -0.5 eV, respectively. The Gaussian approximation using peak position, oscillator strength, and peak width from MRCI+Q is a cost-effective way to simulate the UV spectra of Crigee intermediates for which experimental determination may be hard.