Ultraviolet Absorption Spectra Research Articles

Covalent interaction of ovalbumin with proanthocyanidins improves its thermal stability and antioxidant and emulsifying activity.

The structure of proanthocyanidins (PC) contains a large number of active phenolic hydroxyl groups, which makes it have strong antioxidant capacity. This study investigated the structural and functional properties of ovalbumin (OVA) modified by its interaction with PC. It was found that on increasing the concentration ratio of PC to OVA from 10:1 to 40:1, the free amino and total sulfhydryl contents of OVA decreased from 470.59 ± 38.77 and 29.81 ± 0.31 nmol mg-1 to 96.61 ± 4.55 and 21.22 ± 0.78 nmol mg-1, respectively, and the free sulfhydryl content increased from 7.65 ± 0.41 to 9.48 ± 0.58 nmol mg-1. These results indicated that CN and CS bonds were formed and PC was covalently linked with OVA. The PC content in the OVA-PC conjugates increased from 281.93 ± 12.92 to 828.81 ± 46.09 nmol mg-1 on increasing the concentration ratio of PC to OVA from 10:1 to 40:1. The contents of α-helix and β-turn of OVA decreased, and the contents of β-sheet and random coil increased, confirmed by circular dichroism. The tertiary structure of OVA was also altered according to the results of fluorescence and ultraviolet absorption spectra. The surface hydrophobicity of OVA-PC conjugates decreased with increasing bound polyphenol content. The conjugation of OVA to PC significantly improved its emulsification and antioxidant activity and denaturation temperature. This study may provide valuable information for improving OVA's functional properties and its PC conjugates for applications in the food industry. © 2024 Society of Chemical Industry.

An ultrafast optical sensor for simultaneous detection of NH3 temperature and concentration based on ultraviolet absorption spectral redshift combined with spectral reconstruction

As a renewable and carbon-free fuel with high energy density, ammonia (NH3) is a promising alternative to fossil fuels. Real-time detection of its temperature and concentration is significant in improving NH3 combustion efficiency. In this paper, we report an optical sensor, which enables simultaneous measurement of temperature and concentration of NH3. The key idea is to acquire the temperature of NH3 through absorption spectral redshift, and determine its concentration by building three-dimensional field map combined with spectral reconstruction. Firstly, we explain the generation mechanism of temperature-induced redshift in ultraviolet differential absorption spectrum based on energy level distribution theory. The relationship between spectral redshift and temperature is then established using spectral autocorrelation algorithm. Secondly, a spectral reconstruction method based on absorbed intensity mapping wavelength is proposed to ensure real-time detection of NH3. Finally, a three-dimensional field map between temperature, reconstruction slope, and concentration is constructed to achieve the detection. Results indicated that the mean relative error in temperature measurement was 1.04 % and the mean absolute error in concentration detection was 0.26 mg/m3 in air. Additionally, the NH3 sensor enabled long-term detection with a detection limit of 15.50 μg/m2, demonstrating its potential to broaden the application of NH3 as a fuel.

A Dual Emission Fluorescence Probe Based on Silicon Nanoparticles and Rhodamine B for Ratiometric Detection of Kaempferol.

In this paper, blue fluorescent silicon nanoparticles (SiNPs) with outstanding optical properties and robust stability were synthesized by a simple one-step hydrothermal method. By introducing red emissive rhodamine B (RhB) into SiNPs solution, a dual emission nanoprobe (SiNPs@RhB) was constructed, which showed excellent pH stability, salt resistance and photobleaching resistance. The SiNPs@RhB probe could emit two peaks at 444nm and 583nm under 365nm excitation. It was found that the fluorescence intensity of the two emission peaks decreased in different degrees with the addition of different concentrations of kaempferol (Kae). According to this phenomenon, a novel ratiometric fluorescence method was established for the detection of Kae via utilizing SiNPs@RhB as nanoprobe. The detection range and limit of detection (LOD) were 0.5 ~ 150 µM and 0.24 µM, respectively. The ratiometric fluorescence method exhibited the superiority of rapid detection, excellent stability, wide linear range and high sensitivity. The detection mechanism was studied by ultraviolet visible absorption spectra, fluorescence spectra and fluorescence lifetime. Furthermore, the method was applied to the detection of Kae in real samples (kaempferia powder, sea buckthorn granules and sea buckthorn dry emulsion).

Bio-inspired fabrication of thin films via surface amidation of TEMPO-oxidized cellulose nanocrystals for improved UV-shielding properties

Ultraviolet (UV) radiation impacts various aspects of human beings, and there has been significant interest in membrane materials with UV shielding. However, conventional ultraviolet shielding materials are typically petroleum-based polymers like polyethylene, which pose challenges in terms of degradation and reusability, leading to environmental pollution and other issues. The development of environmentally friendly bio-based UV shielding film materials from wood fiber raw materials holds immense importance for sustainable development. In this study, TEMPO-oxidized cellulose nanocellulose crystals (TOCNC) were utilized as the starting material to obtain modified nanocellulose suspension through amination with aniline and acetamide. Subsequently, nanocellulose films were prepared and characterized for their morphology and structure analysis. With the presence of carboxyl groups on TOCNC along with the incorporation of functional groups such as benzene rings, the absorption rate of the TOCNC composite film reaches 93.2 % across the entire ultraviolet absorption spectrum, significantly enhancing its UV shielding performance. The proposed film exhibits great potential for applications in UV-sensitive food packaging, electronic product packaging materials, plastic films, etc.

Enhancing the stability of O/W emulsions by the interactions of casein/carboxymethyl chitosan and its application in whole nutrient emulsions

The influence of Carboxymethyl chitosan (CMCS) on the emulsification stability mechanism of casein (CN) and its effects on the stability of whole nutrient emulsions were investigated. The complex solutions of CN and CMCS were prepared and the turbidity, ultraviolet (UV) absorption spectrum, fluorescence spectrum, circular dichroism (CD) spectrum, Fourier transform infrared (FTIR) spectrum, interfacial tension and microstructural observations were used to study the inter-molecular interaction of CMCS and CN. The effects of CMCS on the emulsion stability of CN were further analyzed by particle size, ζ-potential, instability index and rheological properties. Moreover, the accelerated stability of whole nutrient emulsions prepared by CMCS and CN was evaluated. The results revealed that CN-CMCS complexes were mainly formed by hydrogen bonding. The stability of the CN-CMCS composite emulsions were improved, as evidenced by the interfacial tension decreasing from 165.96 mN/m to 158.49 mN/m, the particle size decreasing from 45.85 μm to 12.98 μm, and the absolute value of the potential increasing from 29.8 mV to 33.5 mV. The stability of whole nutrient emulsion was also significantly enhanced by the addition of CN-CMCS complexes. Therefore, CN-CMCS complex could be served as a novel emulsifier to improve the stability of O/W emulsions.

Core Hole Effect to Valence Excitations: Tracking and Visualizing the Same Excitation in XPS Shake-Up Satellites and UV Absorption Spectra.

Introducing a core hole significantly alters the electronic structure of a molecule, and various X-ray spectroscopy techniques are available for probing the valence electronic structure in the presence of a core hole. In this study, we visually demonstrate the influence of a core hole on valence excitations by computing the ultraviolet absorption spectra and the shake-up satellites in X-ray photoelectron spectra for pyrrole, furan, and thiophene, as complemented by the natural transition orbital (NTO) analysis over transitions with and without a core hole. Employing equivalent core hole time-dependent density functional theory (ECH-TDDFT) and TDDFT methods, we achieved balanced accuracy in both spectra for reliable comparative analysis. We tracked the same involved valence transition in both spectra, offering a vivid illustration of the core hole effect via the change in corresponding particle NTOs introduced by a 1s core hole on a Cα, Cβ, or O atom. Our analysis deepens the understanding of the core hole effect on valence transitions, a phenomenon ubiquitously observed in general X-ray spectroscopic analyses.

Ultraviolet Photodissociation Dynamics of the 1-Methylallyl Radical.

The ultraviolet (UV) photodissociation dynamics of the 1-methylallyl (1-MA) radical were studied using the high-n Rydberg atom time-of-flight (HRTOF) technique in the wavelength region of 226-244 nm. The 1-MA radicals were produced by 193 nm photodissociation of the 3-chloro-1-butene and 1-chloro-2-butene precursor. The 1 + 1 REMPI spectrum of 1-MA agrees with the previous UV absorption spectrum in this wavelength region. Quantum chemistry calculations show that the UV absorption is mainly attributed to the 3pz Rydberg state (perpendicular to the allyl plane). The H atom photofragment yield (PFY) spectrum of 1-MA from 3-chloro-1-butene displays a broad peak around 230 nm, while that from 1-chloro-2-butene peaks at ∼236 nm. The translational energy distributions of the H atom loss product channel, P (ET)'s, show a bimodal distribution indicating two dissociation pathways in 1-MA. The major pathway is isotropic in product angular distribution with β ∼ 0 and has a low fraction of average translational energy in the total excess energy, ⟨fT⟩, in the range of 0.13-0.17; this pathway corresponds to unimolecular dissociation of 1-MA after internal conversion to form 1,3-butadiene + H. The minor pathway is anisotropic with β ∼ -0.23 and has a large ⟨fT⟩ of ∼0.62-0.72. This fast pathway suggests a direct dissociation of the methyl H atom on a repulsive excited state surface or the repulsive part of the ground state surface to form 1,3-butadiene + H. The fast/slow pathway branching ratio is in the range of 0.03-0.08.

Prediction of Vacuum Ultraviolet/Ultraviolet Gas-Phase Absorption Spectra Using Molecular Feature Representations and Machine Learning.

Ultraviolet (UV) absorption spectroscopy is a widely used tool for quantitative and qualitative analyses of chemical compounds. In the gas phase, vacuum UV (VUV) and UV absorption spectra are specific and diagnostic for many small molecules. An accurate prediction of VUV/UV absorption spectra can aid the characterization of new or unknown molecules in areas such as fuels, forensics, and pharmaceutical research. An alternative to quantum chemical spectral prediction is the use of artificial intelligence. Here, different molecular feature representation techniques were used and developed to encode chemical structures for testing three machine learning models to predict gas-phase VUV/UV absorption spectra. Structure data files (.sdf) and VUV/UV absorption spectra for 1397 volatile and semivolatile chemical compounds were used to train and test the models. New molecular features (termed ABOCH) were introduced to better capture pi-bonding, aromaticity, and halogenation. The incorporation of these new features benefited spectral prediction and demonstrated superior performance compared to computationally intensive molecular-based deep learning methods. Of the machine learning methods, the use of a Random Forest regressor returned the best accuracy score with the shortest training time. The developed machine learning prediction model also outperformed spectral predictions based on the time-dependent density functional theory.

Insight into the mechanism of the aggregation behavior of wheat protein modulated by l-lysine under microwave irradiation.

This study explored the mechanism of l-lysine intervention in wheat gluten protein (WG) gel formation under a microwave (MW) field. The results showed that the MW treatment had higher ζ-potential values at the same heating rate. After adding l-lysine, the solution conductivity and dielectric loss were significantly increased. Moreover, the WG gel strength enhanced 4.40% under the MW treatment. The Fourier spectra showed that the α-helix content was decreased 13.78% with the addition of lysine. The ultraviolet absorption spectra and fluorescence spectra indicated that MW irradiation impacted the interactions between WG molecules more effectively than the water bath heating, promoting the denaturation and unfolding of the protein structure. In addition, scanning electron microscopy analysis showed that the incorporation of lysine promoted an ordered network structure formation of the protein, which enhanced the gel properties. This indicated that the zwitterion of l-lysine played a regulatory role in the aggregation of proteins in the MW field.

Spin-orbit coupling in excited electronic states of AgH

Potential energy curves have been calculated for the low-lying electronic states of AgH, correlating to the 4d10 5s1 (2S), 4d10 5p1 (2Po), 4d9 5s2 (2D), and 4d10 6s1 (2S) states of atomic silver, using the MRCI method with scalar relativistic and spin–orbit corrections. Spectroscopic constants were obtained for 24 individual Ω states, and several excited states of AgH observed in the ultraviolet absorption spectra, i.e., the C1Π, B1Σ+, b3Δ1, and D1Π states, were relabeled based on the new ab initio data. The calculated Einstein A coefficients indicated that almost all electronic transitions with ΔΩ = 0, ±1 are allowed.

Design and synthesis of multi-coloured electrochromic and electrofluorochromic asymmetric materials by adjusting the central potential of the compounds

Carbazole and triphenylamine derivatives have become popular research topics in the field of electrochromism and electrofluorochromic due to their excellent reversible oxidative activity, reversible colour change and reversible fluorescence change during electrochemical processes. Four asymmetric carbazole-triphenylamine derivatives 6a-d were designed and synthesized. Both ultraviolet absorption (UV) spectra and fluorescence emission (PL) spectra changed with the change in voltage applied to all compounds. These compounds were fabricated into electrochromic and electrofluorochromic devices, and these devices exhibited excellent cycling stability (cycling stability remains above 95% after 11000 s), short switching time (1.1 s ∼ 1.6 s), high PL contrast (146 ∼ 172), and high colour contrast (47.2% ∼ 50.6%). All the samples fluoresced off in the oxidised state and exhibited alternating yellow-green characteristics, and fluoresced on in the reduced state while exhibiting a highly transparent and colourless state. The experimental results indicated that these materials are expected to be used for the preparation of wearable devices and transparent displays. The research demonstrated that rich color changes can be achieved by adjusting the electrochemical properties of dual redox centered materials.

Application of bi-directional long short-term memory in separating NO and SO2 ultraviolet differential absorption spectrum signals

To safeguard the environment, it is crucial to monitor the emissions of nitrogen oxide (NO) and sulfur dioxide (SO2), harmful pollutants generated during fossil fuel combustion in industries. However, accurately measuring ultra-low concentrations of SO2 and NO remains a challenge. In this study, we developed an optical measurement system based on ultraviolet differential optical absorption spectroscopy (UV-DOAS) to address this issue. The 200–230 nm cross-sensitivity band was chosen for SO2 and NO. Experimental data with a mixed gas concentration range of 1–25 ppm for SO2 and NO was utilized. We proposed a fast algorithm based on Bi-directional Long Short-Term Memory (Bi-LSTM) to extract the differential optical density, overcoming the mutual interference between SO2 and NO. A nonlinear calibration model was employed to invert the separated differential absorption spectra and determine the gas concentrations. The results demonstrated a detection limit (DL) of 0.27 ppm and a full-scale error of 3.15 % for SO2, while for NO, the DL was 0.32 ppm and the full-scale error was 2.81 %. The uncertainties in SO2 and NO detection were calculated as 1.73 % and 1.96 %, respectively.

Introducing hafnium to atomically small- and medium-sized tin clusters (HfSnn0/-/2- (n = 4–17)): A computational investigation of geometrical and growth behavior, spectral properties, electronic configuration and thermochemistry

The global and local minimum configurations of single Hf atom doped Sn clusters are conducted via density function theory (DFT) combined with artificial bee colony algorithm (ABCluster). Furthermore, DFT method is also used to systematically investigate on their structural growth evolution, spectral and electronic information, thermochemical properties following the size of tin clusters doped Hf atom. Structurally, the ground-state geometries of neutral, anion and di-anion are discovered that, from n = 4, the number of Sn atoms in cluster, HfSnn0/-/2- adsorb additional Sn atom on the prior architecture one by one until forming n = 17 for HfSnn-10/-, as well as forming n = 16 for HfSnn-12-. And for the HfSn110/- and HfSn102- as beginning the species veritably develop sealed architectures. The strongest vibrational modes of sealed nanoclusters are stretching modes of Hf atom with infrared actives and breathing modes of the Sn cage framework with Raman actives, respectively. The natural population analysis (NPA) elucidates the stronger relationship between the Hf atoms and the tin frameworks in sealed clusters than that in unsealed clusters. The results of thermochemical properties, molecular orbital shell (MOs), adaptive natural density partitioning (AdNDP) and ultraviolet visible absorption spectrum (UV–Vis) indicate that, the HfSn16 with high symmetry of Td exhibits thermochemical stability and optoelectronic properties, which is utilized potentially as zero-dimensional unit of self-assembling fluorescent nanomaterials.

Influence of Cerium Oxide Abrasive Particle Morphologies on Polishing Performance

AbstractIn this study, two morphologies of cerium oxide (CeO2) abrasive particles, octahedral and spheroidal, are synthesized by solvothermal method using cerium nitrate hexahydrate (Ce(NO3)3‐6H2O) as raw material. Fourier infrared spectroscopy, X‐ray diffractometer (XRD) and scanning electron microscopy (SEM) are used to characterize the composition and morphology of CeO2 abrasive particles. The synthesized CeO2 is used for chemical mechanical polishing (CMP) of the Si surface of 6H‐SiC wafers, and the surface morphology of the polished wafers are observed using atomic force microscopy (AFM). After polishing with octahedral and spheroidal abrasive particles, the surface roughness of the wafers are 0.327 and 0.287 nm, and the material removal rates (MRR) are 870 and 742 nm h−1, respectively. Calculations comparing the ultraviolet absorption spectra and bandgap energies of the two types of abrasive particles as well as molecular dynamics (MD) simulations reveal that the synthesized octahedral CeO2 particles possessed stronger surface chemical activity and material removal performance.

Analysis of Spectral Characteristics of Certain Polyene Antibiotics in the Presence of Dmso and Cholesterol

This work presents ultraviolet (UV) spectra of various concentrations of polyene antibiotics. The spectra of Levorin and Amphotericin B differ in three main absorption maxima. The maximum absorption spectra of antibiotics vary in the range of 370–430 nm. UV absorption spectra reflect the characteristic spectrum of polyenes belonging to this class. Amphotericin B and Levorin in combination with cholesterol lower the maximum of the UV absorption spectra. Analysis of the obtained results shows that cholesterol molecules, combining with double-bond systems of Amphotericin B and Levorin, gradually reduce the maximum absorption of UV spectra, which creates opportunities for their more active use in various fields of biomedicine.

Photoabsorption spectra of solid O2 in ultraviolet and far-vacuum ultraviolet region at 9–30 K

Abstract We report ultraviolet and far-vacuum ultraviolet (FUV) absorption spectra of solid molecular oxygen recorded over the wavelength region 110–365 nm for temperatures between 9 and 30 K, in which the light source was dispersed from a synchrotron. The UV/FUV spectra of solids O2 deposited at various temperatures appeared distinctly different profiles due to variation of compositions of α-O2, β-O2, and the imperfect crystal structure at the specific temperature; in addition, the icy sample exhibited its own scattering curve deposited at specific temperature. Resolved from the thermal ramping technique, the absorption spectra of solids α-O2 and β-O2 were established in the wavelength region 110–250 nm at 9 and 30 K, respectively, for the first time.

Amorphous 1-propanol interstellar ice beyond its melting point

ABSTRACT The recent discovery of 1-propanol (CH3CH2CH2OH) in the interstellar medium (ISM) is of tremendous interest since fatty alcohols have been proposed as constituents of proto-cell membranes. Motivated by this discovery, we present the laboratory mid-infrared (MIR) and vacuum ultraviolet (VUV) absorption spectra of 1-propanol ice under astrochemical conditions, mimicking an icy mantle on cold dust in the ISM. Both MIR and VUV spectra were recorded at ultrahigh vacuum of ∼10-9 mbar and at temperatures ranging from 10 K to sublimation. The morphology of the 1-propanol ice deposited at 10 K was amorphous. By warming the ice to temperatures of 140 K and above, with subsequent recording of IR spectra, we observe complete sublimation of 1-propanol molecules from the substrate around 170 K. No amorphous-to-crystalline phase change was observed upon warming to higher temperatures. Additionally, we observe the IR and VUV signatures of 1-propanol ice on the substrate well beyond its melting point (147 K). To the best of our knowledge, this is the first reported observation of a molecular ice staying well beyond its melting point under such conditions. This result shows that the morphology of icy mantles on ISM cold dust grains is more complex than previously thought. Our atomistic molecular dynamics simulations capture the experimental trends and shed light on the microscopic origin of this unusual phase behaviour of 1-propanol.

Treatment of Coking Wastewater Using Hydrodynamic Cavitation Coupled with Fenton Oxidation Process.

Effective and economical processes for the advanced treatment of coking wastewater were urgently needed to reduce the persistent organic pollutants of external drainage. In the present work, we investigated the degradation of organic pollutants in coking wastewater through IHC/FO (imping stream hydrodynamic cavitation (IHC) coupled with the Fenton oxidation (FO) process) and IHC alone for their feasibility in the advanced treatment of coking wastewater. To select the optimum parameters, attention was paid to the effects of main operation conditions including inlet fluid pressure, medium temperature, initial pH, reaction time, and initial Fe(II) and initial H2O2 concentrations. The results showed that the effects of conditions that need energy to be maintained (such as initial pH and inlet pressure) on the organic pollutant removal efficiency through IHC/FO were less pronounced than those through IHC alone. Moreover, the application of IHC/FO could remove more organic pollutants from coking wastewater than IHC even at an energy-efficient condition. For example, the highest COD removal efficiency of 12.5% was achieved in the IHC treatment at 0.4 MPa, pH 3, and 60 min for the reaction time. In the case of IHC/FO, the maximum COD removal of 33.2% was obtained at pH 7, 0.1 MPa, 12 mmol/L H2O2, and 3 mmol/L Fe2+ after reacting for 15 min. The ultraviolet and visible spectrophotometry (UV-Vis) absorption spectra and gas chromatography and mass spectrometry (GC-MS) analysis further revealed that the kinds and amounts of pollutants (especially those that had benzenes) remaining in water treated through IHC/FO were much fewer and smaller than in water treated through IHC alone. The better performances of IHC/FO than IHC alone were likely related to the more hydroxyl radicals produced through IHC/FO. Taken together, our findings indicate that IHC/FO has great application potential in the advanced treatment of coking wastewater.

The ultraviolet and vacuum ultraviolet absorption spectrum of gamma-pyrone; the singlet states studied by configuration interaction and density functional calculations

A synchrotron based vacuum ultraviolet absorption spectrum for γ-pyrone has been interpreted in terms of singlet excited electronic states using a variety of coupled cluster, configuration interaction, and density functional calculations. The extremely weak spectral onset at 3.557 eV shows eight vibrational peaks, which following previous analyses, are attributed to a forbidden 1A2 state. A contrasting broad peak with a maximum at 5.381 eV has a relatively high cross-section of 30 Mb; this arises from three overlapping states, where a 1A1 state dominates over progressively weaker 1B2 and 1B1 states. After fitting the second band to a polynomial Gaussian function and plotting the regular residuals over 20 vibrational peaks, we have had limited success in analyzing this fine structure. However, the small separation between these three states clearly shows that their vibrational satellites must overlap. Singlet valence and Rydberg state vibrational profiles were determined by configuration interaction using the CAM-B3LYP density functional. Vibrational analysis using both the Franck–Condon and Herzberg–Teller procedures showed that both procedures contributed to the profiles. Theoretical Rydberg states were evaluated by a highly focused CI procedure. The superposition of the lowest photoelectron spectral band on the vacuum ultraviolet spectrum near 6.4 eV shows that the 3s and 3p Rydberg states based on the 2B2 ionic state are present; those based on the other low-lying ionic state (X2B1) are destroyed by broadening; this is a dramatic extension of the broadening previously witnessed in our studies of halogenobenzenes.

Analysis of the 3.2–3.3 μm Interstellar Absorption Feature on Three Milky Way Sightlines

We report new analyses of spectra of the 3.2–3.3 μm absorption feature observed in the diffuse interstellar medium toward three Milky Way sources: 2MASS J17470898 − 2829561 (2M1747) and the Quintuplet Cluster, both located in the Galactic center, and Cygnus OB2-12. The 3.2–3.3 μm interval coincides with the CH-stretching region for compact polycyclic aromatic hydrocarbons (PAHs). We focus on the 2M1747 spectrum. Its published optical depth spectrum contains residual telluric transmission features, which arise from the 0.06 difference in mean airmasses between the observations of the source and its telluric standard star. We corrected the published spectrum by adding the airmass residual optical depth spectrum. The corrected spectrum is well fit by a superposition of four Gaussians. The absorption spectra of the other two sources were also fit by four Gaussians, with similar central wavelengths, widths, and relative peak opacities. We associate the three longer wavelength Gaussians covering the 3.23–3.31 μm interval with compact PAHs in positive, neutral, and negative charge states. We identify the shortest-wavelength Gaussian, near 3.21 μm, with irregularly shaped PAHs. Constraints imposed by spectral smoothness on the corrected 2M1747 spectrum, augmented by a PAH cluster formation model for post-asymptotic giant branch stars, suggests that >99% of the PAHs in the diffuse interstellar medium reside in small clusters. This study supports the PAH hypothesis, and it suggests that a family of primarily compact PAHs with a C66H20 (circumvalene) parent is consistent with the observed mid-infrared and ultraviolet interstellar absorption spectrum.