Chemiluminescence Emission Research Articles

Tunable Chemiluminescence Kinetics with Hierarchically Structured HKUST-1 and Its Sensing Application for Concanavalin A Analysis.

Introducing novel catalysts is essential for developing chemiluminescence (CL) systems that exhibit sustained and robust emission. Traditional Luminol-H2O2 systems typically feature flash-type CL emission. In this study, we discovered that the porous material HKUST-1 can induce a long-lasting and intense CL emission when combined with Luminol-H2O2. This long-term emission signal can be directly detected by the smartphone. By changing the calcination temperature, a series of microporous and hierarchically porous HKUST-1 materials were prepared as catalysts to adjust the kinetic characteristics of the CL signal of Luminol-H2O2 system from flash-type to glow-type. A systematic investigation into the influence of the central metal and ligand, aperture, and particle size of HKUST-1 on the CL kinetic properties revealed that the pore structure has the most pronounced impact on the dynamics of the Luminol-H2O2 CL reaction. Capitalizing on the intense emission of the HKUST-1-catalyzed Luminol-H2O2 system, we established a CL sandwich immunoassay strategy for concanavalin A (ConA), demonstrating good linearity and low detection limit. This research presents a significant endeavor in modulating the dynamics of CL signal emissions.

Label-free differential chemiluminescent immunosensor based on magnetic nanoparticles CuFe2O4@ABEI-GNPs with dual catalytic sites

BackgroundCancer has become one of the main causes of death globally. The level of tumor markers in serum is correlated with the occurrence of cancer. Carcinoembryonic antigen (CEA) is the most commonly utilized tumor marker for cancer detection. Recently, various analytical technologies have been reported to detect biomarkers. However, developing a simple, sensitive, and noninvasive approach for CEA detection remains challenging in cancer diagnosis. Consequently, there is an urgent need for researchers to carry out innovative approaches for CEA detection. ResultIn this work, copper ferrite nanoparticles (CuFe2O4 NPs) with excellent dispersity and fascinating magnetism have been successfully synthesized. To get CuFe2O4@ABEI-GNPs, ABEI-gold NPs (ABEI-GNPs) were generated on the surface of CuFe2O4 NPs by using N-(4-Aminobutyl)-N-ethylisoluminol (ABEI) as a mild reduction reagent to reduce chloroauric acid tetrahydrate (HAuCl4·4H2O). The CuFe2O4@ABEI-GNPs exhibited a superior chemiluminescence (CL) performance compared with CuFe2O4@ABEI NPs, which was attributed to the synergistic catalysis effects of CuFe2O4 NPs and GNPs. Interestingly, two unique CL emission peaks were observed in the kinetic curve of CuFe2O4@ABEI-GNPs. Furthermore, it was found that the kinetic curve could be regulated by the pH of hydrogen peroxide (H2O2) and a possible CL mechanism was proposed. Owing to the favorable CL properties of CuFe2O4@ABEI-GNPs, a label-free differential immunosensor was fabricated for CEA monitoring using the intensity difference between CL-1 and CL-2. The developed immunosensor exhibited a wide linear range from 0.1 to 5000 pg/mL, and a low detection limit of 0.05 pg/mL. Significance and noveltyThe immunosensor was capable of determining CEA in real samples with simple operation, high accuracy, and good sensitivity. This study introduces a novel approach for developing CL functionalized materials, which have broad application potential in bioassays. The proposed differential method could serve as a novel tool for determining CEA in the diagnosis of clinical cancer.

Long-Lasting Chemiluminescence Based on Functionalized Multicolor Protein Capsules for Multiple Visualization Detection of Avian Influenza Virus Biomarkers.

Long-lasting chemiluminescence (CL) emissions are necessary for improving the detection accuracy and expanding the application scope. Here, we have synthesized three oil-in-water (O/W) multicolor protein capsules (LCBA, F/LCBA, and RB/F/LCBA) using a simple ultrasound method and have engineered specific target-triggered catalytic hairpin assembly on their surface and chemiluminescence resonance energy transfer inside. Consequently, three multicolor capsules exhibit excellent structural stability, generate blue-, green-, and red-colored emissions when reacting with H2O2, have long-lasting CL emission over 1 h, and successfully achieve the accurate multiple visualization detection of avian influenza virus subtype targets. Without the need for complex instruments and analysis procedures, the CL imaging assays can be carried out and recorded with a common smartphone. The detection limits for visualizing H1N1, H7N9, and H5N1 are 5.5, 7.6, and 9.0 pM, respectively. There is a linear range between 20.0 and 625 pM and excellent selectivity against interfering DNA. Furthermore, visualization detection has been successfully applied for the detection of H1N1, H7N9, and H5N1 in healthy human serum samples. With these merits, this facile, ultrasensitive, and multiple visualization sensor has potential applications in point-of-care testing and early diagnosis.

Polyoxometalate-induced hydrogel with in situ nano/bioenzyme cascade reaction generating intensive and long-lasting glow-type chemiluminescence

In this study, we introduce a straightforward one-step, in-situ strategy for the generation of long-lasting and intensive glow-type chemiluminescence (CL) for glucose sensing in biological samples. The approach involves the utilization of polyoxometalate (POM)-induced alginate hydrogel, which effectively encapsulates both the catalysts (POM and glucose oxidase (GOx)) and the CL reagent (luminol) in solution. Leveraging the peroxidase-like nanozyme properties of POM and the bioenzyme GOx, embedded within the nano-sized pores of the hydrogel, we achieve intensive and persistent CL emission lasting over 16 h. The POM-hydrogel-based CL system demonstrates remarkable storage stability and reproducibility, and it can be applied to quantitatively determine serum glucose with high accuracy. Our study indicates that the POM-hydrogel platform, supporting and confining nano/bioenzyme cascade reactions, holds great promise for the establishment of glow-type CL systems, which could be of great value in various fields of CL biosensing and imaging.

Amino-rich silicon quantum dots as efficient activator with intrinsic chemiluminescence for the detection of peroxydisulfate

The specific detection of peroxydisulfate (S2O82−, PDS) is significant and challenging due to the rapid development of PDS-related technologies and their widespread application in multiple fields. However, traditional analytical methods are mainly based on their strong oxidizing properties, making it difficult to simultaneously achieve specific identification and high sensitivity for PDS detection in complex water environments. Here, we purposely prepared amino-rich SiQDs (N-SiQDs) as an effective catalyst and introduced H2O2 acts as a co-reactant for PDS activation and determination with strong intrinsic chemiluminescence (CL) emission. High yield of reactive active oxygen (mainly O2˙− and ˙OH) were generated during CL process, which trigger electron-hole annihilation between the N-SiQDs˙+ and N-SiQDs˙− accounted for extraordinary CL emission. On this basis, a new CL assay for PDS detection was fabricated with broad linear range of 5 × 10−7M-5 × 10−5 M and low detection limit (3.2 × 10−7 M). Due to the absence of SO4˙− involvement during CL emission, the sensing platform is sensitive enough, satisfactory selectivity and does not respond to transition-metal ions and inorganic anions that have interferences in the PDS CL sensors reported before. This work not only deepens insight into the mechanisms of nanomaterials assisted PDS activation but also provides a new perspective on the modified metal-free QDs CL probe for chemical species detection.

An ingenious chemiluminescence sensing strategy for recalcitrant triphenyl phosphate based on oxidant-free UV-activated MIL-100(Fe) gel system

BackgroundOrganophosphate flame retardants (OPFRs) are notorious emerging contaminants threatening the environment and human health. Triphenyl phosphate (TPHP), which has an extremely serious biotoxicity, is a typical harmful OPFR. Due to its wide use, TPHP has been discovered in various environmental mediums. Moreover, it is pretty recalcitrant to the removal process, resulting in the need for a technique to understand it better. Hence, accurate and quick discrimination of TPHP in the environment is critical to further evaluate its potential effect on ecosystems and human health. ResultsAn ingenious oxidant-free chemiluminescence (CL) sensor based on the oxidant-free UV/MIL-100(Fe) gel system was established for TPHP detection. The oxidation of luminol in the UV-activated MIL-100(Fe) gel has resulted in remarkable CL emission, which is contributed by reactive oxygen species (ROS) generated by it. Notably, the CL intensity was inhibited significantly after introducing TPHP. An investigation into the mechanism underlying the effect of CL suppression demonstrated that TPHP competed with luminol to consume ROS from UV-activated MIL-100(Fe) gel, contributing to CL inhibition. The subsequent sensing performance experiments demonstrated the advantages of environmentally friendly, economic efficiency, user-friendly operation, rapid determination, potential for compact size, high selectivity, and sensitivity. Additionally, these investigations confirmed the low limit of detection (210 ng L−1) and wide linear range (10–1000 μg L−1). SignificanceIn this paper, a green, economical, and oxidant-free CL sensing strategy for TPHP has been established. It has the advantage of being rapid, having the potential for compact size, high selectivity, and sensitivity. This ingenious method has promising applications in real-time and online environmental monitoring, and it paves the way for the rapid and environmentally friendly identification of emerging contaminants that are structurally stable and recalcitrant to remove.

Chemiluminescence during the high-temperature pyrolysis and oxidation of ammonia

Chemiluminescent emissions from NH2*, NH*, NO*, and OH* during the pyrolysis and oxidation of ammonia (NH3) are quantitatively characterized to gain insight into their reaction mechanisms. Time profiles of light emitted from high-temperature reactions of NH3/Ar and NH3/O2/Ar mixtures have been measured behind reflected shock waves at temperatures of 2300–2600 K and pressures of 1.6–1.9 bar in a high-repetition-rate shock tube. The emission intensities have been calibrated based on the well-characterized OH* chemiluminescence in a hydrogen-oxygen system and converted to photon emission rates for quantitative comparison with kinetic simulations. A kinetic model describing the pyrolysis and oxidation of ammonia and reactions of excited species has been constructed by combining the reaction mechanisms proposed in recent modeling studies. With only modest updates of the thermodynamic functions and the rate constants for the formation and quenching of excited species, the observed chemiluminescence profiles could be reasonably reproduced, with a few exceptions. The rate of production analysis indicates that NH2* is produced by the reaction of NH3 with H as well as thermal excitation of NH2, that the energy transfer reactions from 3N2 to NH and NO are responsible for the formation of NH* and NO*, respectively, and that the formation of OH* is competitively contributed by the reactions of H with N2O, 3N2 with OH, and NH with NO. Remaining discrepancies between the experiment and modeling are noted, and potential directions for further model improvement are discussed.

Intermittency transition to azimuthal instability in a turbulent annular combustor

We experimentally study the transition from a state of combustion noise to azimuthal thermoacoustic instability in a laboratory-scale turbulent annular combustor. This combustor has sixteen swirl-stabilized burners to facilitate continuous and spatially distributed combustion along the annular region. Our approach involves simultaneous measurement of CH* chemiluminescence emission of the flame using two high-speed cameras and the acoustic pressure fluctuations using eight piezoelectric pressure transducers mounted on the backplane of combustor. We observe that the transition from combustion noise to azimuthal instability occurs through mode shifting, where the system switches from a longitudinal mode to an azimuthal mode as the equivalence ratio is decreased. Throughout this progression, the combustor exhibits various dynamical behaviors, including intermittency, dual-mode instability, standing azimuthal instability, and beating azimuthal instability. These dynamical states are determined from the acquired pressure signals by decomposing the acoustic pressure fluctuations into clockwise (CW) and counterclockwise (CCW) waves, enabling a reconstruction of the amplitude of acoustic pressure fluctuations, nature angle, (anti-)nodal line location, and spin ratio. The global heat release response is then examined during various dynamical states, contrasting their behavior at different non-dimensional time steps by phase-averaging the fluctuations of the heat release rate over the acoustic pressure cycle. Distinctive flame behaviors were observed based on the direction of pressure wave propagation, showcasing characteristic CCW spinning, standing, and CW spinning heat release patterns. Moreover, our examination of relative phase distributions during various dynamical states, computed by analyzing the phase of heat release rate fluctuations across all burners with respect to one burner, reveals the emergence of diverse patterns in the interaction of neighboring flames influenced by acoustic field.

Flowerlike Co-MOFs catalyzed chemiluminescence for sensitive detection of tetrachlorophenquinone in environmental waters

Tetrachlorobenzoquinone (TCBQ) as one of the most toxic quinones has potential risk of causing canceration, and the monitoring of TCBQ in the environment is of significant importance. In this study, a flowerlike Co-PTA-400(Ar) metal organic frameworks (MOF) catalyzed TCBQ-H2O2 chemiluminescence (CL) system was established for sensitive determination of trace TCBQ in environmental waters. The reaction between TCBQ and H2O2 can result in weak CL emission, and the CL signal was enhanced about 10-fold using flowerlike Co-PTA-400(Ar) as catalyst. The luminescence mechanism was investigated through kinetic studies and free radical scavenging experiments. The strong CL emission of TCBQ mainly relied on the generation of abundant •OH by the catalysis of Co-PTA-400(Ar). This strategy allows to develop a highly sensitive method for the determination of TCBQ in the linear range of 1 ∼ 50 μM, with a detection limit of 0.56 μM (3σ). The proposed method was applied for analysis of three spiked water samples with recoveries ranging from 95.7% to 100.5%. This method offering the advantages of rapid analysis, low costs, and high sensitivity, is appealing for detection of TCBQ in environmental waters.

Effects of a 3D-Printed Atomizer Component on Fuel-Spray and Flame Characteristics of a Jet-Stabilized Compact Gas Turbine Combustor Fed With Liquid Fuels

Abstract In this work, the effects of replacing an atomizer component of a confined jet-stabilized gas turbine combustor with a 3D-printed part have been studied. The part is called airblast, and it serves as a wall that collects and flows liquid droplets for a secondary atomization. Therefore, the liquid-surface interaction on the rough surface of the 3D-printed part was of interest. The combustor was operated under various conditions with either a conventionally machined airblast or the 3D-printed airblast. Flames with two liquid fuels were studied for fuel flexibility, and the position of a primary fuel injection was varied to study the influence of the liquid-surface interaction length. Load flexibility was investigated with air jet velocity settings, and flame equivalence ratios of ϕ = 0.8 and 1.0 were tested. Shadowgraphy-based particle tracking analyses presented a reduced atomization performance with the 3D-printed airblast, showing large droplet size distributions. However, no significant change in the combustor performance was observed from OH* chemiluminescence images and emission data, which confirms the versatility of the combustor and assures the compatibility of 3D-printed components with the combustor of this study.

Influence of AM Generated Burner Surface Roughness on NOx Emissions and Operability of Hydrogen-Rich Fuels

ABSTRACT The additive manufacturing (AM) technique enables the fabrication of advanced burner components to enhance the hydrogen capability of the existing gas turbines (GTs) and reduce the carbon footprints of the power generation sector. This technique produces rough surfaces that may require post-processing to maintain the desired functionality of a burner, particularly for hydrogen fuel with unique thermo-physical properties. This study, therefore, compared the stability of three swirlers of variable surface roughness manufactured using AM and traditional machining methods, with one of the AM swirler post-processed by grit-blasting. The comparison included a conventional benchmark (100% CH4), low carbon (23%volCH4/77%volH2) and zero carbon (100% H2) fuels across a range of equivalence ratios. Additionally, the study quantified the flame topology and emissions performance of the fuel blends for each swirler using high-speed OH* chemiluminescence and exhaust gas emissions measurements, respectively. The experimental investigation concluded that the AM-generated surface roughness within the considered range does not detrimentally impact NOX emissions and the stability of the fuel mix. However, the flame location was observed to be influenced by surface roughness and shifted more toward the vertical centerline of the burner with increased roughness. From the practical perspective, the results showed that post-manufacturing surface finishing offers negligible performance advantages, indicating potential cost reductions. It is recommended that further studies should investigate the influence of increased surface roughness on burner performance, as well as numerical modeling techniques which could provide an insight into when AM surfaces are likely to be more influential.

Why Do Ionic Surfactants Significantly Alter the Chemiluminogenic Properties of Acridinium Salt?

Acridinium esters, due to their capability for chemiluminescence (CL), are employed as indicators and labels in biomedical diagnostics and other fields. In this work, the influence of ionic surfactants, hexadecyltrimethylammonium chloride and bromide (CTAC and CTAB, cationic) and sodium dodecyl sulphate (SDS, anionic) on the CL parameters and mechanism of representative emitter, 10-methyl-9-[(2-methylphenoxy)carbonyl]acridinium trifluoromethanesulphonate (2MeX) in a H2O2/NaOH environment, is studied. Our investigations revealed that the type of surfactant and its form in solution have an impact on the CL kinetic constants and integral efficiencies, while changes in those emission properties resulting from the type of ion (Cl- vs. Br-) are negligible. The major changes were recorded for systems containing surfactants at concentrations higher than the critical micelle concentration. The cationic surfactants (CTAC, CTAB) cause a substantial increase in CL emission kinetics and a moderate increase in its integral efficiency. At the same time, the opposite effect is observed in the case of SDS. Molecular dynamics simulations suggest that changes in emission parameters are likely due to differences in the binding strength of 2MeX substrate with surfactant molecules, which is higher for SDS than for CTAC. The results can help in rational designing of optimal acridinium CL systems and demonstrate their usefulness in distinguishing the pre- and post-micellar environment and the charge of surfactants.

Internal light-driven efficient chemiluminescence of graphitic carbon nitride quantum dots for improved carboxin sensing

Developing a new chemiluminescence (CL) sensor platform to achieve the identification of pollutants in the water environment is a significant and currently hot topic for researchers. Building on the effective development of a CL internal light source, this paper designed a direct, simple, and rapid pesticide identification strategy. Specifically, graphite carbon nitride quantum dots (CNQDs) with excellent optical properties were synthesized using a solvent heat treatment strategy. Acting as an energy acceptor, CNQDs triggered CL emission in the presence of singlet oxygen (1O2). The newly developed CNQDs/1O2 CL sensor exhibited a specific response toward carboxin (CBX) with high sensitivity. Based on this discovery, we have developed a highly selective, ultra-sensitive, and fast CL sensing platform for detecting CBX in water environments. Through numerous experiments, we attributed the CL emission of the CNQDs/1O2 system to the specific chemiluminescent resonance energy transfer (CRET) process between CNQDs and 1O2. Interestingly, the CL light of the CNQDs/1O2 system could serve as an internal light source to excite CBX generating a large amount of 1O2 through photosensitization, which was crucial for further enhancing the CL efficiency of the CNQDs/1O2/CBX system and also enabled the CL sensing of CBX. This study is the first to successfully identify CBX in water using CL sensors, showcasing the potential of CL internal light sources in regulating CL efficiency and offering new perspectives on detecting pollutants in complex environments.

Hybrid Mn Atomic Clusters/Single-Dispersed Atoms with Dual Antioxidant Activities for a Chemiluminescent Immunoassay.

Single-dispersed atoms (SDAs) as catalysts have drawn extensive attention due to their ultimate atom utilization efficiency and desirable catalytic capability. Atomic clusters (ACs) with potential multiple enzyme-like activities also display great practicability in catalysis-based biosensing. In this work, hybrid Mn ACs/SDAs were implanted in the frameworks of defect-engineered MIL 101(Cr) modulated by excess acetic acid, with a high loading capability of 13.9 wt %. Distinctively, Mn SDAs display weak superoxide dismutase (SOD)-like activity for specifically eliminating superoxide anion (O2•-), while Mn ACs/SDAs display both catalase-like and SOD-like activities for remarkable elimination of total reactive oxygen species (ROS) due to the cooperative effect of the two atom-scale catalytic sites. Thus, Mn ACs/SDAs can efficiently inhibit the chemiluminescent (CL) emission of multiple ROS-mediated luminol systems with a superior quenching rate of 85.5%. To validate the practicability of Mn ACs/SDAs for a sensitive CL assay, an immunoassay method was established to detect acetamiprid by using Mn ACs/SDAs as signal quenchers, which displayed a quantification range of 10 pg mL-1-25 ng mL-1 and a detection limit of 3.3 pg mL-1. This study paves an avenue for developing ACs/SDAs with multiple antioxidant activities that are suitable for application in biosensing.

VS4 Nanodendrites with Narrow Bandgaps in Activating Dissolved Oxygen for Boosted Chemiluminescence and Hemin Detection by Unexpected Quenching.

Chemiluminescence (CL)-based analytical methods utilize luminophores that need to be activated with an oxidizing agent to trigger CL emission. Despite its susceptibility to decomposition when exposed to external light or trace metals, hydrogen peroxide (H2O2) has been widely used to develop chemiluminescent methods due to the limited number of suitable alternatives for activating chemiluminescent luminophores. Also, analytical methods based on the well-known luminol/H2O2 CL system have low sensitivity. Dissolved oxygen (DO) is a naturally abundant and environmentally benign alternative oxidant for luminol and other CL luminophores. However, DO alone is inactive and needs an efficient catalyst or a coreaction accelerator for its activation. Because of the narrow bandgap of VS4 (ca. 1.12 eV), it can facilitate fast electron-transfer kinetics with an acceptor molecule such as DO. Here, we introduce vanadium tetrasulfide (VS4) to boost CL for the first time. Under the optimized conditions, VS4 nanodendrite catalyzes the generation of reactive oxygen species by activating DO which subsequently reacts with luminol to generate intense CL. It enhances the CL intensity of luminol/DO by about 10,000 times. Surprisingly, hemin remarkably quenches the generated CL of luminol/DO/VS4 nanodendrites, which is completely opposite to its typical enhancement of luminol CL. Based on the remarkable concentration-dependent quenching of the luminol/DO/VS4 nanodendrite CL by hemin, we have developed a sensitive CL method that can selectively detect hemin in the linear concentration range of 1-250 nM and achieved a limit of detection of 0.11 nM. The practical utility of the developed method was demonstrated by the determination of hemin in a pharmaceutical drug for the treatment of acute intermittent porphyria and in human serum. This study demonstrates that VS4 holds great promise in analytical method development.

Hydrogen peroxide enhanced glow-type chemiluminescence of hydrazine hydrate modified carbon quantum dots-potassium persulfate system

Most known chemiluminescence (CL) systems are flash-type that generate weak luminescence and decline quickly after dozens of seconds, while the glow-type CL systems have stable emission for an extended period to achieve accurate quantitation. In this work, a long-term CL system based on hydrazine-hydrate (N2H4·H2O) modified carbon quantum dots (N-CQDs) as a luminescent probe, with K2S2O8 and H2O2 as co-reactants, was proposed. The CL emission enhanced by H2O2 increased 18-fold more than that of N-CQDs and K2S2O8 direct reaction, and decayed by 5% of the maximum intensity over 700 s. In the reaction system, K2S2O8 and H2O2 co-reactants can promote each other to continuously generate corresponding radicals (•OH, O2•−, 1O2), which in turn trigger the CL emission of N-CQDs. This phenomenon was identified as the primary cause for the production of persistent CL. In addition, a stable and selective CL sensor based on the N-CQDs-K2S2O8-H2O2 CL enhancing system was developed for ascorbic acid quantitation in the linear range from 0.1 to 10.0 mM with a detection limit of 0.036 mM. The method has been applied to the analysis of tablet samples and holds potential in pharmaceutical analysis field.

ClinOleic Impairs ROS Production and Phagocytosis in M1 Macrophages Without Affecting M1 Differentiation.

Lipid emulsions are the primary source of calories and fatty acids that are used to provide essential energy and nutrients to patients suffering from severe intestinal failure and critical illness. However, their use has been linked to adverse effects on patient outcomes, notably affecting immune defenses and inflammatory responses. ClinOleic is a lipid emulsion containing a mixture of olive oil and soybean oil (80:20). The effect of ClinOleic on the differentiation of M1 macrophages remains unclear. In this study, we isolated human monocytes and added ClinOleic to differentiation culture media to investigate whether it affects monocyte polarization into M1 macrophages and macrophage functions, such as reactive oxygen species (ROS) production and phagocytosis. ROS production was stimulated by live S. aureus and detected with L-012, a chemiluminescence emission agent. Phagocytic capacity was assayed using pHrodo™ Green S. aureus Bioparticles® Conjugate. We found that M1 cell morphology, surface markers (CD80 and CD86), and M1-associated cytokines (TNF-α and IL-6) did not significantly change upon incubation with ClinOleic during M1 polarization. However, S. aureus-triggered ROS production was significantly lower in M1 macrophages differentiated with ClinOleic than in those not treated with ClinOleic. The inhibitory effect of ClinOleic on macrophage function also appeared in the phagocytosis assay. Taken together, these findings reveal that ClinOleic has a limited impact on the M1 differentiation phenotype but obviously reduces ROS production and phagocytosis.

The Influence of Gamma Radiation on Different Gelatin Nanofibers and Gelatins.

Gelatin nanofibers are known as wound-healing biomaterials due to their high biocompatible, biodegradable, and non-antigenic properties compared to synthetic-polymer-fabricated nanofibers. The influence of gamma radiation doses on the structure of gelatin nanofiber dressings compared to gelatin of their origin is little known, although it is very important for the production of stable bioactive products. Different-origin gelatins were extracted from bovine and donkey hides, rabbit skins, and fish scales and used for fabrication of nanofibers through electrospinning of gelatin solutions in acetic acid. Nanofibers with sizes ranging from 73.50 nm to 230.46 nm were successfully prepared, thus showing the potential of different-origin gelatin by-products valorization as a lower-cost alternative to native collagen. The gelatin nanofibers together with their origin gelatins were treated with 10, 20, and 25 kGy gamma radiation doses and investigated for their structural stability through chemiluminescence and FTIR spectroscopy. Chemiluminescence analysis showed a stable behavior of gelatin nanofibers and gelatins up to 200 °C and increased chemiluminescent emission intensities for nanofibers treated with gamma radiation, at temperatures above 200 °C, compared to irradiated gelatins and non-irradiated nanofibers and gelatins. The electron paramagnetic (EPR) signals of DMPO adduct allowed for the identification of long-life HO● radicals only for bovine and donkey gelatin nanofibers treated with a 20 kGy gamma radiation dose. Microbial contamination with aerobic microorganisms, yeasts, filamentous fungi, Staphylococcus aureus, Escherichia coli, and Candida albicans of gelatin nanofibers treated with 10 kGy gamma radiation was under the limits required for pharmaceutical and topic formulations. Minor shifts of FTIR bands were observed at irradiation, indicating the preservation of secondary structure and stable properties of different-origin gelatin nanofibers.

A detailed kinetic submechanism for OH[formula omitted] chemiluminescence in hydrogen combustion revisited. Part 2

In this series of two papers, we present a novel physically sound kinetic submechanism aimed at modeling the formation and decay of chemiluminescent (electronically excited) OH∗ molecules in the ignition and combustion of hydrogen and hydrogen-based mixtures over a wide range of temperatures and pressures. The present Part describes the construction of this detailed reaction submechanism based on the groundwork and findings of the preceding paper. In so doing, we relied both on critical evaluation of known and at times conflicting experimental and theoretical data on the elementary reaction kinetics of OH∗ and on our quantum chemical calculations and rate constant estimates for the key processes. The kinetic model under development was validated against the representative dataset of the observed OH(A2Σ+→X2Π) chemiluminescent emission accompanying the high-temperature (post-shock) oxidation of various H2-containing mixtures. To improve its performance against the collected OH∗ emission data, the rate constants of some reactive and quenching processes, to which the OH∗ kinetics is the most sensitive and for which there is a particular uncertainty, were jointly varied within the limits imposed by theoretical considerations and/or the scatter in the available experimental evidence. Thus, by refining the rate constants of these elementary processes, we obtained a reasonable reaction submechanism for OH∗ that describes the known experimental data better than previous models.Novelty and significance statement Although ultraviolet OH∗ chemiluminescence as an optical signature of the combustion process and the underlying chemistry is known to provide unique capabilities for combustion diagnostics, the development of the detailed reaction mechanisms intended for quantitative interpretation of the OH∗ emission measurements has now almost stagnated. Indeed, existing kinetic models contain a discouragingly small number of elementary processes and, apparently, do not account for the full variety of possible reaction pathways of OH∗ formation and depletion. Therefore, in this serial work, we have intended to revise the current ideas about the kinetics of OH∗ production and consumption during ignition and combustion and focused first on the OH∗ kinetics in a reacting H2/O2/Ar/N2 mixture. The principal outcome of this Part of the series is a new physically based kinetic submechanism aimed at modeling the formation and decay of electronically excited OH∗ molecules in the ignition and combustion of hydrogen and hydrogen-containing mixtures. Its incorporation into any conventional kinetic model of hydrogen oxidation enables quantitative interpretation of the OH(A2Σ+−X2Π) chemiluminescent emission observed experimentally in flames and shock-heated reacting flows with an accuracy higher than that of previous analogous mechanisms. No less importantly, the rate constant approximations for a number of individual elementary processes with OH∗, recommended here based on the critical review of literature data and on our quantum chemical calculations, are also of independent interest for the kinetics of electronically excited OH∗ particles. Finally, the OH∗ reaction subset we suggested for hydrogen flames can form the basis of more complex OH∗ chemiluminescence modeling reaction mechanisms for other fuels and fuel compositions.

A detailed kinetic submechanism for OH[formula omitted] chemiluminescence in hydrogen combustion revisited. Part 1

In this series of two papers, we present a novel physically sound kinetic submechanism aimed at modeling the formation and decay of chemiluminescent (electronically excited) OH∗ molecules in the ignition and combustion of hydrogen and hydrogen-based mixtures over a wide range of thermodynamic parameters and mixture compositions. The present part of this series describes the preparatory stages of the work, such as the aggregation of the data set for the OH∗ chemiluminescent emission (including the OH∗ emission profiles obtained in our shock-tube experiments), the choice of the basic kinetic model of hydrogen oxidation, and, importantly, quantum chemical calculations and theoretical estimates for the rate constant of the nonadiabatic preassociation reaction H + O + M ⇆ OH∗ + M, recognized as a major source of excited OH∗ molecules in hydrogen-air flames. These rate constant estimates are carried out in a wide range of temperatures (200–4000 K) and pressures (10−3−100 bar). It is shown that the rate constant of this key reaction exhibits distinct non-Arrhenius temperature behavior and, moreover, has a complex fall-off pressure dependence, with the transition from a third to a second-order, high-pressure regime occurring at pressures about 10 atm. The obtained dependence on temperature and pressure is in excellent agreement with the known experimental data and can be recommended (as part of the appropriate reaction mechanisms) for further kinetic modeling of OH∗ chemiluminescence accompanying the high-temperature oxidation of hydrogen and other fuels.Novelty and Significance StatementAlthough ultraviolet OH∗ chemiluminescence as an optical signature of the combustion process and the underlying chemistry is known to provide unique capabilities for combustion diagnostics, the development of the detailed reaction mechanisms intended for quantitative interpretation of the OH∗ emission measurements has now almost stagnated. Indeed, existing kinetic models contain a discouragingly small number of elementary processes and, apparently, do not account for the full variety of possible reaction pathways of OH∗ formation and depletion. Therefore, in this serial work, we have revised the current ideas about the kinetics of OH∗ production and consumption during ignition and combustion and focused first on the OH∗ kinetics in a reacting H2/O2/Ar/N2 mixture. The fundamentally significant and novel results of this Part of the present series are (i) the rate constant of the nonadiabatic preassociation reaction H + O + M ⇆ OH∗ + M (the primary source of OH∗ in hydrogen combustion), theoretically obtained for the first time as a function of temperature and pressure, and (ii) the OH∗ emission profiles obtained in our shock-tube experiments. The other aspects described here, such as the aggregation of the literature-based data set for the post-shock OH∗ chemiluminescent emission and the choice of the basic kinetic model of hydrogen oxidation, are also of interest and relevance.