Characteristic Spectral Patterns Research Articles

Discrimination of double-click synthetic echoes by bottlenose dolphins: Effects of inter-highlight interval and phasea).

Two bottlenose dolphins (Tursiops truncatus) were trained to discriminate double-click synthetic "echoes" differing in inter-highlight interval (IHI). In the first experimental task, dolphins passively listened to background (S-) stimuli with constant IHI and responded on discriminating a change to target (S+) stimuli with a slightly increased IHI. The second task was similar, but the highlights were assigned random, frequency-independent phase angles. This phase randomization was designed to interfere with potential auditory cues from characteristic spectral interference patterns linked to IHI changes. Discrimination thresholds were higher with randomized phase when the S- stimuli had IHIs of 50-250 μs. Thresholds were highest and comparable at the longest S- IHIs of 375 and 500 μs and were independent of phase condition. Although dolphin detection of changes in highlight envelope timing can explain threshold patterns at 375 and 500 μs, this cue did not explain performance at IHIs less than the dolphin auditory temporal window of ∼250 μs. Modeling results suggested that phase manipulations eliminated the availability of a simple difference in spectral magnitudes at the shortest IHIs, but the perception of a time separation pitch cue may still explain the dolphins' observed threshold patterns.

Ultrasound wavelet spectra enable direct tissue recognition and full-color visualization

Traditional brightness-mode ultrasound imaging is primarily constrained by the low specificity among tissues and the inconsistency among sonographers. The major cause is the imaging method that represents the amplitude of echoes as brightness and ignores other detailed information, leaving sonographers to interpret based on organ contours that depend highly on specific imaging planes. Other ultrasound imaging modalities, color Doppler imaging or shear wave elastography, overlay motion or stiffness information to brightness-mode images. However, tissue-specific scattering properties and spectral patterns remain unknown in ultrasound imaging. Here we demonstrate that the distribution (size and average distance) of scattering particles leads to characteristic wavelet spectral patterns, which enables tissue recognition and high-contrast ultrasound imaging. Ultrasonic wavelet spectra from similar particle distributions tend to cluster in the eigenspace according to principal component analysis, whereas those with different distributions tend to be distinguishable from one another. For each distribution, a few wavelet spectra are unique and act as a fingerprint to recognize the corresponding tissue. Illumination of specific tissues and organs with designated colors according to the recognition results yields high-contrast ultrasound imaging. The fully-colorized tissue-specific ultrasound imaging potentially simplifies the interpretation and promotes consistency among sonographers, or even enables the applicability for non-professionals.

Facile synthesis, novel structure, and tunable luminescence properties of K6Bi13(PO4)15:Dy3+,Eu3+ phosphors for ultraviolet converted white light-emitting diodes

A variety of novel Dy3+/Eu3+ mono- and co-doped K6Bi13(PO4)15 (KBPO) luminescent materials have been fabricated by a simple solid-state method for the first time. Both experimental studies and theoretical calculations verify that the K6Bi13(PO4)15 crystals are suitable to be utilized as host materials for the lanthanide activator ions. The XRD, EDS, and XPS results reveal that the Dy3+ and Eu3+ have been effectively incorporated into the KBPO host matrix and do not damage the structure of KBPO. The Dy3+ or Eu3+ mono-doped phosphors display the characteristic spectral patterns of the activator ions upon UV excitation whereas an energy transfer between Dy3+ and Eu3+ occurs which helps to obtain the tunable luminescence of the KBPO:Dy3+,Eu3+ phosphors. The emission colors of the KBPO:Dy3+,Eu3+ regularly shift from green-blue, through white, and finally toward yellow and orange-red by varying the activator doping concentrations under a fixed excitation wavelength. Interestingly, the single-phase white light emitting phosphors with CIE chromaticity coordinates of (0.3122, 0.3106) and (0.3602, 0.3246) are obtained by doping appropriate concentrations of Dy3+ and Eu3+, which match well with the standard white light illuminate of (0.333, 0.333). Moreover, the annealing conditions are optimized and the luminescent mechanisms and temperature-dependent luminescence performance are systematically investigated. Finally, the WLEDs device prepared by KBPO:Dy3+,Eu3+ phosphor and UV chip displays a dazzling white light with favorable CIE (Commission Internationale de I'Eclairage 1931 chromaticity) coordinates, color rendering index (Ra), correlated color temperature (CCT), and thermal stability, which provides direct evidence that the as-prepared inorganic luminescent materials may have prospects as an eminent single-phase white light emitting materials for white light-emitting diodes (WLEDs) and optoelectronic devices.

Solvation-induced switching of the conformational state of alkoxy- and crown-substituted trisphthalocyaninates studied by UV-Vis and 1H-NMR spectroscopy

Solvation-induced switching between staggered and gauche conformers of europium(III) triple-decker complexes with [Formula: see text]-butoxy- and crown-substituted phthalocyanine ligands [(BuO)8Pc][Formula: see text]and [(15C5)4Pc][Formula: see text]was studied by UV-Vis and 1H-NMR in toluene and chloroform media. The crown-substituted complex Eu2[(15C5)4Pc]3 was conformationally invariant, adopting the staggered arrangement of adjacent ligands in both solvents. In contrast, in the case of butoxy-substituted complex Eu2[(BuO)8Pc]3, the staggered and gauche forms were stabilized in toluene and chloroform, respectively. These conclusions could easily be drawn from the UV-Vis data. In contrast, a comparison of the 1H-NMR spectra of the complexes in both solvents showed that the spectral manifestation of conformational switching was obscured by media effects, although some characteristic spectral patterns of each conformation could still be identified on the example of the complex with hexa-[Formula: see text]-butoxy-15-crown-5-phthalocyanine ligands Eu2[(BuO)6(15C5)Pc]3.

Profiling of Tumor Cell-Delivered Exosome by Surface Enhanced Raman Spectroscopy-Based Biosensor for Evaluation of Nasopharyngeal Cancer Radioresistance.

Although the advancement of radiotherapy significantly improves the survival of nasopharyngeal cancer (NPC), radioresistance associated with recurrence and poor outcomes still remains a daunting challenge in the clinical scenario. Currently, effective biomarkers and convenient detection methods for predicting radioresistance have not been well established. Here, the surface-enhanced Raman spectroscopy combined with proteomics is used to firstly profile the characteristic spectral patterns of exosomes secreted from self-established NPC radioresistance cells, and reveals specific variations of proteins expression during radioresistance formation, including collagen alpha-2 (I) chain (COL1A2) that is associated with a favorable prognosis in NPC and is negatively associated with DNA repair scores and DNA repair-related genes via bioinformatic analysis. Furthermore, deep learning model-based diagnostic model is generated to accurately identify the exosomes from radioresistance group. This work demonstrates the promising potential of exosomes as a novel biomarker for predicting the radioresistance and develops a rapid and sensitive liquid biopsy method that will provide a personalized and precise strategy for clinical NPC treatment.

Comprehensive characterization of polycyclic aromatic hydrocarbon emissions from heavy-duty diesel vehicles utilizing GC × GC-ToF-MS

Comprehensive characterization of diesel vehicle emitted polycyclic aromatic hydrocarbon (PAH) emissions is yet to achieve due to the limitation of analytical methods. Therefore, we herein developed a two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-ToF-MS) method and quantified the total PAHs from diesel vehicles based on their characteristic fragments and mass spectral patterns. Overall, the emission factors (EFs) of total PAHs (gas + particle) are observed to range from 4.1 ± 2.5 mg km−1 to 51.4 ± 22.2 mg km−1 under cold-start and hot-start conditions for one China IV and two China VI heavy-duty diesel vehicles (HDDVs), of which the un-speciated PAHs account for more than 97%. Gaseous PAHs (g-PAHs) are dominated by three-ring PAHs, whereas particulate PAHs (p-PAHs) are dominated by two-ring PAHs. The total PAHs partition significantly into the gas phase for whole fleets and cycles, except that five-ring PAHs partition almost completely into the particle phase. The aftertreatment technologies (e.g., diesel particulate filter, DPF) significantly reduce the total PAH emissions by 49.8 ± 33.2%. The minimum toxic equivalency factors (TEFs) are deployed to estimate the toxicity of the total PAHs. Much higher toxicity is obtained than those in previous studies, indicating that the PAH toxicity of diesel vehicle emissions might be largely underestimated.

Hyperspectral Image Super-Resolution via Recurrent Feedback Embedding and Spatial–Spectral Consistency Regularization

Hyperspectral images with tens to hundreds of spectral bands usually suffer from low spatial resolution due to the limitation of the amount of incident energy. Without auxiliary images, the single hyperspectral image super-resolution (SR) method is still a challenging problem because of the high-dimensionality characteristic and special spectral patterns of hyperspectral images. Failing to thoroughly explore the coherence among hyperspectral bands and preserve the spatial–spectral structure of the scene, the performance of existing methods is still limited. In this article, we propose a novel single hyperspectral image SR method termed RFSR, which models the spectrum correlations from a sequence perspective. Specifically, we introduce a recurrent feedback network to fully exploit the complementary and consecutive information among the spectra of the hyperspectral data. With the group strategy, each grouping band is first super-resolved by exploring the consecutive information among groups via feedback embedding. For better preservation of the spatial–spectral structure among hyperspectral data, a regularization network is subsequently appended to enforce spatial–spectral correlations over the intermediate estimation. Experimental results on both natural and remote sensing hyperspectral images demonstrate the advantage of our approach over the state-of-the-art methods.

Multivariate Curve Resolution (MCR) of real-time infrared spectra for analyzing the curing behavior of solid MF thermosetting resin

The isothermal curing of melamine resin is investigated by in-line infrared spectroscopy at different temperatures. The infrared spectra are decomposed into time courses of characteristic spectral patterns using Multivariate Curve Resolution (MCR). It was found that depending on the applied curing temperature, melamine films with different spectral fingerprints and correspondingly different chemical network structures are formed. The network structures of fully cured resin films are specific for the applied curing temperatures used and cannot simply be compensated by changes in the curing time. For industrial curing processes, this means that cure temperature is the main system determining factor at constant M:F ratio. However, different MF resin networks can be specifically obtained from one and the same melamine resin by suitable selection of the curing time and temperatures profiles to design resin functionality. The spectral fingerprints after short curing time as well as after long curing time reflect the fundamental differences in the thermoset networks that can be obtained with industrial short-cycle and multi-daylight presses.

Ultraviolet A irradiation induces ultraweak photon emission with characteristic spectral patterns from biomolecules present in human skin

Oxidative stress is associated with photoaging of the skin as well as with skin cancer, and is therefore, critical to monitor. Ultraweak photon emission (UPE) is extremely weak light generated during the oxidative process in the living body and has been used as a non-invasive and label-free marker for the evaluation of oxidative stress. However, the mechanism of UPE generation is not clear. Therefore, we aimed to elucidate the molecular mechanism underlying UPE generation by analyzing the spectra of UPE generated from biomolecules in the skin during ultraviolet A (UVA) exposure. The spectra of UVA-induced UPE generated from linoleic acid, linolenic acid, elastin, phospholipids, and 5,6-dihydroxyindole-2-carboxylic acid were measured, and the spectrum of human skin tissue was also obtained. The spectral patterns varied for the different biomolecules and the peaks were distinct from those of the skin tissue. These results suggested that the UPE generated from skin tissue is a collection of light emitted by biomolecules. Moreover, we proposed that UPE is generated through a photosensitization reaction and energy transfer. The identified characteristic spectral patterns of UPE can be useful to elucidate UVA-induced oxidative stress in the skin, with implications for prevention and treatment of photoaging and skin diseases.

Unravelling the Phases of Melamine Formaldehyde Resin Cure by Infrared Spectroscopy (FTIR) and Multivariate Curve Resolution (MCR).

Here, we study resin cure and network formation of solid melamine formaldehyde pre-polymer over a large temperature range via dynamic temperature curing profiles. Real-time infrared spectroscopy is used to analyze the chemical changes during network formation and network hardening. By applying chemometrics (multivariate curve resolution, MCR), the essential chemical functionalities that constitute the network at a given stage of curing are mathematically extracted and tracked over time. The three spectral components identified by MCR were methylol-rich, ether linkages-rich and methylene linkages-rich resin entities. Based on dynamic changes of their characteristic spectral patterns in dependence of temperature, curing is divided into five phases: (I) stationary phase with free methylols as main chemical feature, (II) formation of flexible network cross-linked by ether linkages, (III) formation of rigid, ether-cross-linked network, (IV) further hardening via transformation of methylols and ethers into methylene-cross-linkages, and (V) network consolidation via transformation of ether into methylene bridges. The presented spectroscopic/chemometric approach can be used as methodological basis for the functionality design of MF-based surface films at the stage of laminate pressing, i.e., for tailoring the technological property profile of cured MF films using a causal understanding of the underlying chemistry based on molecular markers and spectroscopic fingerprints.

Screening of Gunshot Residue in Skin Using Attenuated Total Reflection Fourier Transform Infrared (ATR FT-IR) Hyperspectral Microscopy.

The detection of gunshot residues (GSR) in skin is important in criminal forensic investigations related with firearms. Conventionally, the procedure is based on the detection of metallic or inorganic residues (IGSR). In this work, we propose attenuated total reflectance Fourier transform infrared (ATR FT-IR) hyperspectral microscopy as a complementary and nondestructive technique for detection of organic GSR (OGSR). The spectra were acquired from GSR of three ammunition manufacturers, which were collected from shooter's hands by the tape-lifting method. Before spectroscopic analysis, a Na-Ca bleach solution was added to all GSR samples on the tape for destroying skin debris. Positive detection of OGSR spectra were achieved by ATR FT-IR hyperspectral microscopy. Spectra show characteristic patterns of nitrate ester compounds which agrees with the propellant chemical composition. Characteristic ATR FT-IR spectral patterns of OGSR were measured from visualized GSR particles demonstrating the potential of ATR FT-IR hyperspectral microscopy.

Subterranean Acoustic Activity Patterns of Vitacea polistiformis (Lepidoptera: Sesiidae) in Relation to Abiotic and Biotic Factors.

Grape root borer (GRB), Vitacea polistiformis, is a root-feeding pest of grapevines in the US southeast that causes underground damage well before vines show visible symptoms. A 269-d study was conducted at 31 sites in a Florida vineyard to record short bursts of insect movement and feeding vibrations in grapevine root systems and provide information that can improve timing and targeting of GRB management efforts. Characteristic spectral and temporal patterns in the subterranean vibrations facilitated discrimination of GRB from background noise and non-targeted arthropods. Infestation likelihood of GRB at each site was estimated from previous studies relating infestation to burst rate. In all, 39% of recordings indicated low infestation likelihood. Sites with medium or high infestation likelihood were confined to a small region of the vineyard where a vine with larval feeding damage was confirmed. The restricted area suggests that the biological control or chemical treatments could be reduced elsewhere. Acoustic activity was significantly greater in fall and winter than in spring, and greater in evening than afternoon; fall evenings seemed best for GRB acoustic surveys. The GRB seasonal and circadian acoustic variation reflected phenological variation in grape root growth and nutrients and was not significantly correlated with temperature.

Front-face and right-angle fluorescence spectroscopy for monitoring extra virgin olive oil spectrum evolution

Fluorescence spectroscopic techniques were applied in a study in order to monitor the evolution of the spectral pattern of extra virgin olive oil (EVOO) samples exposed to indirect light at room temperature. Detailed information was extracted from three-dimensional front-face (FF) fluorescence spectra with excitation wavelengths ranging from 230 to 646 nm and emission wavelengths ranging from 250 to 698.5 nm. Relevant emission regions were revealed in FF experiments that were useful to study the variability of the characteristic spectral patterns and to develop fast inspection procedures. Such procedures include simultaneous excitation at wavelengths lower than 400 nm, which was proposed and implemented in a rightangle prototype in order to monitor the evolution of EVOO samples exposed to indirect light. Emission signals at local maxima around 400, 434, 464, 513 and 674 nm were found to be relevant. Ongoing research highlights that hyperspectral images provide spectral patterns of the olives, allowing more precise sorting into categories, which would enable the classification into lots of oils with more homogeneous characteristics for subsequent modelling.

Chiroptical and vibrational spectroscopic study of genuine and counterfeit medicines containing tadalafil.

The production and distribution of counterfeit pharmaceuticals present a serious problem worldwide. This is true especially in case of phosphodiesterase type 5 inhibitors for treating erectile dysfunction, where consumers often prefer buying them anonymously from unverified sources. In this study, genuine and counterfeit Cialis® 20mg tablets were analyzed by electronic circular dichroism, vibrational circular dichroism, and infrared spectroscopy. The characteristic spectral patterns were identified by comparison with the spectra of tadalafil standard as an active pharmaceutical ingredient, and its presence was confirmed in all samples. The amount of tadalafil, however, was markedly lower in the case of counterfeit tablet as the observed band intensities were considerably lower. No other significant differences between the genuine and counterfeit tablets were revealed. Ab initio density functional theory calculations provided a detailed description of the stable conformers of tadalafil in a solution and enabled thorough interpretation of the experimental spectra.

Establishment of a spectral database for classification of edible oils using matrix-assisted laser desorption/ionization mass spectrometry

In this study, we aim to establish a comprehensive spectral database for analysis of edible oils using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). More than 900 edible oil samples, including 30 types of edible oils, were analyzed and compared, and the characteristic peaks and spectral features of each edible oil were obtained. Edible oils were divided into eight groups based on their characteristic spectral patterns and principal component analysis results. An overall correct rate of 97.2% (98.1% for testing set) was obtained for classification of 435 edible oil products using partial least square-discriminant analysis, with nearly 100% correct rate for commonly used edible oils. Differentiation of counterfeit edible oils, repeatedly cooked edible oils and gutter oils from normal edible oils could also be achieved based on the MALDI-MS spectra. The establishment of this spectral database provides reference spectra for spectral comparison and allows rapid classification of edible oils by MALDI-MS.

Transition metal(II) complexes of histidine-containing tripeptides: Structures, and infrared spectroscopy by IRMPD

Complexes of divalent metal ions (Cu2+ and Ni2+) with histidine tripeptide complexes (HAA, AHA and AAH) are interesting gas-phase models for some of the most widely observed patterns of metal ion binding to peptides and proteins. Gas-phase structures were characterized using infrared multiple photon dissociation (IRMPD) spectroscopy in ion-trapping mass spectrometers, along with density functional theory (DFT) computations. Ground states are square-planar with two deprotonated amide nitrogens bound to the metal ion via a double iminol rearrangement (IM binding mode), but contrary to expectations based on solution behavior, the histidine imidazole group is not bound to the metal, but instead is hydrogen bonded remote from the metal ion. The alternative “charge-solvated” (CS) binding mode (amide carbonyl oxygens binding the metal ion) lies higher in energy, but in many cases was observed to be present as conformationally unrelaxed ions with an abundance (relative to the IM conformation) that was dependent on instrument configuration and source and trap conditions. Taking advantage of the ability to form and trap both IM and CS conformations for a few of the complexes, the infrared spectroscopy of both conformations was explored in the fingerprint (1000–1800 cm−1) and hydrogen-stretching (3200–3800 cm−1) regions. For the fingerprint region, agreement is very good between the observed IRMPD spectra and the spectra predicted by DFT calculations at the B3LYP/6–311 + +g(d,p) level. Agreement in the H-stretching region is not perfect, but the characteristic IM and CS spectral patterns are evident.

Caracterización espectral de Quillaja saponaria (Mol.)

<p align="justify">This paper presents a spectral reflectance characterization of the specie Quillaja saponaria (Mol.), endemic tree of Chile and valued by society due to its provision of several ecosystem services that gives to society and also for its high concentration of saponins in cortex widely used in the pharmacological industry. For spectral characterization a foliar spectral signatures protocol was designed which included standardized instrumental and environmental parameters. The spectral response of different individuals was measured to evaluate the spectral behaviour and degree of variability within species in the visible and near infrared ranges (VNIR; 400-990 nm) with two hyperspectral sensors (ASD HH and camera PDF-65-V10E). The resulting spectral signatures obtained with ASD HH showed a variation less than 5% of reflectance in VNIR and lesser than that in the transition zone from red to near infrared (red-edge; 680-730 nm). Additionally, two distinctive spectral features were detected for the specie, the first is related to a fast increase of reflectance in bands 450-480 nm and the second, to a marked decrease in the 920-970 nm range associated with water absorption features. At branch level, these distinctive features are maintained but with a smaller magnitude of reflectance, which could indicate that they are useful characteristic spectral patterns that can eventually be used for monitoring the physical health state of the specie using remote sensing. On the other hand, we used a PDF-65 camera for study the plant vigour from different health states (healthy, ill, died) with spectral vegetation index. The Plant Senescence Reflectance Index detected stress on leaves, and Triangular Vegetation Index allows for a gradually characterization of every state. This work provides the first spectral reference for one of the most important sclerophyll species of Chile.</p>

A new classification method for MALDI imaging mass spectrometry data acquired on formalin-fixed paraffin-embedded tissue samples

Matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI IMS) shows a high potential for applications in histopathological diagnosis, and in particular for supporting tumor typing and subtyping. The development of such applications requires the extraction of spectral fingerprints that are relevant for the given tissue and the identification of biomarkers associated with these spectral patterns. We propose a novel data analysis method based on the extraction of characteristic spectral patterns (CSPs) that allow automated generation of classification models for spectral data.Formalin-fixed paraffin embedded (FFPE) tissue samples from N=445 patients assembled on 12 tissue microarrays were analyzed. The method was applied to discriminate primary lung and pancreatic cancer, as well as adenocarcinoma and squamous cell carcinoma of the lung.A classification accuracy of 100% and 82.8%, resp., could be achieved on core level, assessed by cross-validation. The method outperformed the more conventional classification method based on the extraction of individual m/z values in the first application, while achieving a comparable accuracy in the second. LC–MS/MS peptide identification demonstrated that the spectral features present in selected CSPs correspond to peptides relevant for the respective classification. This article is part of a Special Issue entitled: MALDI Imaging, edited by Dr. Corinna Henkel and Prof. Peter Hoffmann.

Identification of polybrominated diphenyl ether metabolites based on calculated boiling points from COSMO-RS, experimental retention times, and mass spectral fragmentation patterns.

The COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS) was used to predict the boiling points of several polybrominated diphenyl ethers (PBDEs) and methylated derivatives (MeO-BDEs) of monohydroxylated BDE (OH-BDE) metabolites. The linear correlation obtained by plotting theoretical boiling points calculated by COSMO-RS against experimentally determined retention times from gas chromatography-mass spectrometry facilitated the identification of PBDEs and OH-BDEs. This paper demonstrates the applicability of COSMO-RS in identifying unknown PBDE metabolites of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) and 2,2',4,4',6-pentabromodiphenyl ether (BDE-100). Metabolites of BDE-47 and BDE-100 were formed through individual incubations of each PBDE with recombinant cytochrome P450 2B6. Using calculated boiling points and characteristic mass spectral fragmentation patterns of the MeO-BDE positional isomers, the identities of the unknown monohydroxylated metabolites were proposed to be 2'-hydroxy-2,3',4,4'-tetrabromodiphenyl ether (2'-OH-BDE-66) from BDE-47, and 2'-hydroxy-2,3',4,4',6-pentabromodiphenyl ether (2'-OH-BDE-119) and 4-hydroxy-2,2',3,4',6-pentabromodiphenyl ether (4-OH-BDE-91) from BDE-100. The collective use of boiling points predicted with COSMO-RS, and characteristic mass spectral fragmentation patterns provided a valuable tool toward the identification of isobaric compounds.

The correlation of odors in the environment with ion mobility spectra patterns

Ion mobility spectrometry was applied for the detection of environmental odors. The ion mobility spectra were taken at different sampling sites where odors were detectable and emitted from industrial, municipal, and agricultural sources. After ionization with a tritium ion source, the negative spectra in particular showed characteristic spectral patterns that were dependent upon the emission source. These patterns are reproducible over a long period of time and are comparable for different sampling sites with similar emission sources. The signal intensity detected excellently correlates with the odor intensity measured by a trained assessor. The IMS signal intensity and the mass spectral data also show good agreement. A decreasing intensity of single compounds leads also to a reduced IMS signal intensity. However, meteorological parameters—especially a high humidity—must be considered during the measurement.