Search Results (15)

Background: The present work is devoted to the biological effects of sol–gel-derived silica (Si)–copper (Cu) nanomaterials. Methods and Results: Tetraethyl orthosilane (TEOS) was used as a silica precursor; copper was introduced as a solution in ethanol with Cu(OH)₂. The obtained samples were denoted as Si/Cu (gel) and Si/Cu/500 (500 °C heat-treated). Their phase formation and morphology were studied by XRD and SEM. The antibacterial activity was tested by two Gram-positive bacteria, three Gram-negative bacteria, and two types of eukaryotic species. Most bacteria were more sensitive to Si/Cu/500 materials than to Si/Cu (gel). The yeasts were more sensitive to Si/Cu (gel). The new nanomaterials were tested for oxidant activity at pH 7.4 (physiological) and pH 8.5 (optimal) in three model systems by the chemiluminescent method. They significantly inhibited the generation of free radicals and ROS. This result underlines their potential as regulators of the free radical processes in living systems. The epithelial tumor cell lines appeared more sensitive than the non-transformed fibroblasts, likely due to their metabolic activity and proliferation rates, leading to greater accumulation of the substances. Using Daphnia magna, the ecotoxicity study showed that the LC₅₀ was reached at 1 mg/L of Si/Cu/500. Si/Cu (gel) was more toxic. Conclusions: Our results reveal the potential of these nanohybrids to be applied in living, eukaryotic systems. The cytotoxicity evaluation showed higher tolerance of normal, non-transformed cells, in concurrence with the oxidation tests. Full article

The fundamental investigation on the chemiluminescence characteristics of NH₃-based flames is essential for the development of low-cost, real-time optical diagnostic sensor technologies. In this study, we have experimentally examined the chemiluminescence properties of non-premixed ammonia-methane laminar jet flames under various initial NH₃ blending ratios (X_NH3 from 0.2 to 1.0 in volume) by conducting the emission spectrum analysis within the 200–800 nm band and capturing the distribution images of key excited radicals. The results revealed that the emission spectra of OH*, CH*, CN*, NH*, and NH₂* were clearly identifiable. As anticipated, the chemiluminescence characteristics of NH₃-CH₄ non-premixed flames were significantly influenced by X_NH3; i.e., the overall signal intensity decreased monotonically within the 200–400 nm band but increased within the 400–800 nm band as X_NH3 increased. The signal intensity characteristics of OH*, CH*, NH*, and NH₂*, indicated by radical images, were consistent with the spectrometer measurements. Particularly, it was found that the intensity ratio of CH*/NH₂* was an ideal marker of initial X_NH3 in present flames, given their sensitivity with X_NH3 and relative ease of measurement with the cost-effective sensors designed for invisible wavelengths. Moreover, in the flame front, CH* was located in the oxidant side, while NH₂* was in the fuel side with a broader distribution zone. An increase of X_NH3 led to greater flame thickness and shifted the peak position of excited radicals far away from the fuel side. Full article

In this study, the soot formation and oxidation processes in different turbulent, pre-evaporated and partially premixed diesel surrogate flames are experimentally investigated. For this purpose, a piloted jet flame surrounded by an air co-flow is used. Starting from a defined diesel surrogate mixture, different fuel blends with increasing blending ratios of poly(oxymethylene) dimethyl ether (OME) are studied. The Reynolds number, equivalence ratio, and vaporization temperature are kept constant to ensure the comparability of the different fuel mixtures. The effects of OME addition on flame structures, soot precursors, and soot are investigated, showing soot reduction when OME is added to the diesel surrogate. Using chemiluminescence images of C₂ radicals (line of sight) and subsequent Abel-inversion, flame lengths and global flame structure are analyzed. The flame structure is visualized by means of planar laser-induced fluorescence (PLIF) of hydroxyl radicals (OH). The spatial distribution of soot precursors, such as polycyclic aromatic hydrocarbons (PAHs), is simultaneously measured by PLIF using the same excitation wavelength. In particular, aromatic compounds with several benzene rings (e.g., naphthalene or pyrene), which are known to be actively involved in soot formation and growth, have been visualized. Spatially distributed soot particles are detected by using laser-induced incandescence (LII), which allows us to study the onset of soot clouds and its structures qualitatively. Evident soot formation is observed in the pure diesel surrogate flame, whereas a significant soot reduction with changing PAH and soot structures can be identified with increasing OME addition. Full article

A Fe²⁺-EGTA(ethylene glycol-bis (β-aminoethyl ether)-N,N,N′,N′-tetraacetic acid)-H₂O₂ system emits photons, and quenching this chemiluminescence can be used for determination of anti-hydroxyl radical (•OH) activity of various compounds. The generation of •OH and light emission due to oxidative damage to EGTA may depend on the buffer and pH of the reaction milieu. In this study, we evaluated the effect of pH from 6.0 to 7.4 (that may occur in human cells) stabilized with 10 mM phosphate buffer (main intracellular buffer) on a chemiluminescence signal and the ratio of this signal to noise (light emission from medium alone). The highest signal (4698 ± 583 RLU) and signal-to-noise ratio (9.7 ± 1.5) were noted for pH 6.6. Lower and higher pH caused suppression of these variables to 2696 ± 292 RLU, 4.0 ± 0.8 at pH 6.2 and to 3946 ± 558 RLU, 5.0 ± 1.5 at pH 7.4, respectively. The following processes may explain these observations: enhancement and inhibition of •OH production in lower and higher pH; formation of insoluble Fe(OH)₃ at neutral and alkaline environments; augmentation of •OH production by phosphates at weakly acidic and neutral environments; and decreased regeneration of Fe²⁺-EGTA in an acidic environment. Fe²⁺-EGTA-H₂O₂ system in 10 mM phosphate buffer pH 6.6 seems optimal for the determination of anti-•OH activity. Full article

TiO₂ was loaded on the porous nickel foam from the suspended ethanol solution and used for the photocatalytic removal of NO_x. Such prepared material was heat-treated at various temperatures (400–600 °C) to increase the adhesion of TiO₂ with the support. Obtained TiO₂/nickel foam samples were characterized by XRD, UV–Vis/DR, FTIR, XPS, AFM, SEM, and nitrogen adsorption at 77 K. Photocatalytic tests of NO abatement were performed in the rectangular shape quartz reactor, irradiated from the top by UV LED light with an intensity of 10 W/m². For these studies, a laminar flow of NO in the air (1 ppm) was applied under a relative humidity of 50% and a temperature of 28 °C. Concentrations of both NO and NO₂ were monitored by a chemiluminescence NO analyzer. The adsorption of nitrogen species on the TiO₂ surface was determined by FTIR spectroscopy. Performed studies revealed that increased temperature of heat treatment improves adhesion of TiO₂ to the nickel foam substrate, decreases surface porosity, and causes removal of hydroxyl and alcohol groups from the titania surface. The less hydroxylated surface of TiO₂ is more vulnerable to the adsorption of NO₂ species, whereas the presence of OH groups on TiO₂ enhances the adsorption of nitrate ions. Adsorbed nitrate species upon UV irradiation and moisture undergo photolysis to NO₂. As a consequence, NO₂ is released into the atmosphere, and the efficiency of NO_x removal is decreasing. Photocatalytic conversion of NO to NO₂ was higher for the sample heated at 400 °C than for that at 600 °C, although coverage of nickel foam by TiO₂ was lower for the former one. It is stated that the presence of titania defects (Ti³⁺) at low temperatures of its heating enhances the adsorption of hydroxyl groups and the formation of hydroxyl radicals, which take part in NO oxidation. Contrary to that, the presence of titania defects in TiO₂ through the formation of ilmenite structure (NiTiO₃) in TiO₂/nickel foam heated at 600 °C inhibits its photocatalytic activity. No less, the sample obtained at 600 °C indicated the highest abatement of NO_x due to the high and stable adsorption of NO₂ species on its surface. Full article

High-energy-density compounds such as norbornadiene (NBD) are being considered as potential cost-effective fuel additives, or partial replacements, for high-speed propulsion applications. To assess the ability of NBD to influence basic fuel reactivity enhancement and to build a database for developing future NBD kinetics models, ignition delay times were measured in two shock-tube facilities at Texas A&M University for H₂/O₂, CH₄/O₂, H₂/NBD/O₂, and CH₄/NBD/O₂ mixtures (ϕ = 1) that were highly diluted in argon. The reflected-shock temperatures ranged from 1014 to 2227 K, and the reflected-shock pressures remained near 1 atm for all of the experiments, apart from the hydrogen mixtures, which were also tested near 7 atm, targeting the second-explosion limit. The molar concentrations of NBD were supplemented to the baseline mixtures representing 1–2% of the fuel by volume. A chemiluminescence diagnostic was used to track the time history of excited hydroxyl radical (OH*) emission, which was used to define the ignition delay time at the sidewall location. Spectroscopic CO data were also obtained using a tunable quantum cascade laser to complement both the ignition and the chemiluminescence data. The CH₄/O₂ mixtures containing NBD demonstrated reduced ignition delay times, with a pronounced effect at lower temperatures. Conversely, this additive increased the ignition delay time dramatically in the H₂/O₂ mixture, which was attributed to changes in the fundamental chemistry with the introduction of molecules containing carbon bonds, which require stronger activation energies for ignition. Correlations were developed to predict the ignition delay time, which depends on species concentration, temperature, and pressure. Additionally, one tentative mechanism was tested, combining base chemistry from NUIGMech 1.1 with pyrolysis and oxidation reactions for NBD using the recent efforts from experimental and theoretical literature studies. The numerical predictions show that the rapid decomposition of NBD provides a pool of active H-radicals, significantly increasing the reactivity of methane. This study represents the first set of gas-phase ignition and CO time-history data measured in a shock tube for hydrogen and methane mixtures containing the additive NBD. Full article

Research on combustion characteristics can provide basic information and theoretical support for the design of insensitive propellant. This work aims to investigate the combustion characteristics of insensitive triple-base propellant. All propellants were prepared based on same triple-base propellant, but they were desensitized with the same desensitizer in different ways. The high-speed camera, spontaneous luminescence, NO, NH chemiluminescence, and OH-planar laser induction fluorescence (PLIF) methods were employed to capture the combustion flame and derive the distributions of important intermediates. Results show that ignition delay times of insensitive propellants are obviously longer. This indicated that the application of the desensitizer has a partly hindering effect on the early ignition stage. The combustion time of insensitive propellants is mostly similar, which means that the desensitizer has little influence on the intensity of actual combustion. The change in flame height and area of insensitive propellants over time indicated that the combustion progressivity of some insensitive propellants was more prominent, which means that the desensitizer concentration and desensitizing methods all affect the performance of insensitive propellant. The signal intensities of NO and NH show a negative correlation, indicating that a competitive relationship probably exists between the formation of NO and NH radicals during the reaction process. The high concentration of OH mainly locates outside NO, suggesting that there may be a transformation between NO and OH. The maximum signal intensity of NO and NH of different insensitive propellants confirmed that both the concentration of desensitizers and the desensitizing methods exhibit important effect on the reaction process. Full article

Low Temperature Combustion (LTC) is a relevant process for internal combustion engines (ICE). This combustion mode is based on premixed fuel/air and fuel lean in-cylinder mixture allowing reduction in NOx and PM emissions while maintaining higher thermal efficiency. In order to investigate the effect of engine operating conditions on the behavior of LTC mode, including OH radical evolution, optical measurements and numerical simulations were performed on a transparent CR diesel engine. The homogeneity of the engine charge was obtained by using very early injection timings. In this study, varying injection strategies were investigated for different engine speeds. In parallel to the experimentation, simulations of LTC mode for the same experimental operations were carried out. The model used in this study is based on a stochastic reactor model. This model includes a turbulence (k-ε) model based on a zero-dimensional energy cascade to calculate the turbulent time scale during the cycle. On the other hand, due to the stochastic approach and to reduce initial heterogeneities of the mixture, a confidence parameter was introduced in the global model to consider the real variation ranges of engine. This latter was modeled as a function of the Reynolds number allowing to initiate heterogeneities of temperature and of species mass. OH radicals were estimated with high spatial and temporal resolution using chemiluminescence measurements. Simulated in-cylinder pressure and the OH radical rate were compared to the experimental data. A good agreement was observed in terms of in-cylinder pressure trace and ignition delay times, meaning that the confidence coefficient model is accurate to describe the initial heterogeneities of the mixture. The simulated OH rate profile has the same shape as the measured OH trace and the main ignition occurs at the same time. This study corroborates that the OH radical is an appropriate tool to identify combustion stages. Full article

Recent studies have demonstrated that ammonia is an emerging energy vector for the distribution of hydrogen from stranded sources. However, there are still many unknown parameters that need to be understood before ammonia can be a substantial substitute in fuelling current power generation systems. Therefore, current attempts have mainly utilised ammonia as a substitute for natural gas (mainly composed of methane) to mitigate the carbon footprint of the latter. Co-firing of ammonia/methane is likely to occur in the transition of replacing carbonaceous fuels with zero-carbo options. Hence, a better understanding of the combustion performance, flame features, and radical formation of ammonia/methane blends is required to address the challenges that these fuel combinations will bring. This study involves an experimental approach in combination with numerical modelling to elucidate the changes in radical formation across ammonia/methane flames at various concentrations. Radicals such as OH*, CH*, NH*, and NH₂* are characterised via chemiluminescence whilst OH, CH, NH, and NH₂ are described via RANS κ-ω SST complex chemistry modelling. The results show a clear progression of radicals across flames, with higher ammonia fraction blends showing flames with more retreated shape distribution of CH* and NH* radicals in combination with more spread distribution of OH*. Simultaneously, equivalence ratio is a key parameter in defining the flame features, especially for production of NH₂*. Since NH₂* distribution is dependent on the equivalence ratio, CFD modelling was conducted at a constant equivalence ratio to enable the comparison between different blends. The results denote the good qualitative resemblance between models and chemiluminescence experiments, whilst it was recognised that for ammonia/methane blends the combined use of OH, CH, and NH₂ radicals is essential for defining the heat release rate of these flames. Full article

Ascorbic acid (AA) has antioxidant properties. However, in the presence of Fe²⁺/Fe³⁺ ions and H₂O₂, it may behave as a pro-oxidant by accelerating and enhancing the formation of hydroxyl radicals (^•OH). Therefore, in this study we evaluated the effect of AA at concentrations of 1 to 200 µmol/L on ^•OH-induced light emission (at a pH of 7.4 and temperature of 37 °C) from 92.6 µmol/L Fe²⁺—185.2 µmol/L EGTA (ethylene glycol-bis (β-aminoethyl ether)-N,N,N′,N′-tetraacetic acid)—2.6 mmol/L H₂O₂, and 92.6 µmol/L Fe³⁺—185.2 µmol/L EGTA—2.6 mmol/L H₂O₂ systems. Dehydroascorbic acid (DHAA) at the same range of concentrations served as the reference compound. Light emission was measured with multitube luminometer (AutoLumat Plus LB 953) for 120 s after automatic injection of H₂O₂. AA at concentrations of 1 to 50 µmol/L and of 1 to 75 µmol/L completely inhibited light emission from Fe²⁺-EGTA-H₂O₂ and Fe³⁺-EGTA-H₂O₂, respectively. Concentrations of 100 and 200 µmol/L did not affect chemiluminescence of Fe³⁺-EGTA-H₂O₂ but tended to increase light emission from Fe²⁺-EGTA-H₂O₂. DHAA at concentrations of 1 to 100 µmol/L had no effect on chemiluminescence of both systems. These results indicate that AA at physiological concentrations exhibits strong antioxidant activity in the presence of chelated iron and H₂O₂. Full article

Recently we demonstrated the simultaneous detection of the chemiluminescence of the radicals OH* (310 nm) and CH* (430 nm), as well as the thermal radiation of soot in laminar and turbulent methane/air diffusion flames. As expected, a strong spatial and temporal coupling of OH* and CH* in laminar and moderate turbulent flames was observed. Taking advantage of this coupling, multispecies tomography enables us to quantify the reconstruction quality completely independent of any phantom studies by simply utilizing the reconstructed distribution of both species. This is especially important in turbulent flames, where it is difficult to separate measurement noise from turbulent fluctuations. It is shown that reconstruction methods based on Tikhonov regularization should be preferred over the widely used algebraic reconstruction technique (ART) and multiplicative algebraic reconstruction techniques (MART), especially for high-speed imaging or generally in the limit of low signal-to-noise ratio. Full article

For industrial applications, we propose a concept of clean and efficient combustion through burning syngas on an impinging burner. We performed experimental measurements of particle image velocimetry, OH radical (OH*) chemiluminescence, flame temperature, and CO emission to examine the fuel mixing and reaction of premixed impinging flames of CH₄/syngas/air with H₂/CO in varied proportions. The velocity distribution of the combustion flow field showed that a deceleration area in the main flow formed through the mutual impingement of two jet flows, which enhanced the mixing of fuel and air because of an increased momentum transfer. The deceleration area expanded with an increased CO proportion, which indicated that the mixing of fuel and air also increased with the increased CO proportion. Our examination of the OH* chemiluminescence demonstrated that its intensity increased with increased CO proportion, which showed that the reaction between fuel and air accordingly increased. CO provided in the syngas hence participated readily in the reaction of the CH₄/syngas/air premixed impinging flames when the syngas contained CO in a large proportion. Although the volume flow rate of the provided CO quadrupled, the CO emission increased by only 12% to 15%. The results of this work are useful to improve the feasibility of fuel-injection systems using syngas as an alternative fuel. Full article

Reaction mechanisms of various kinds of photocatalysts have been reviewed based on the recent reports, in which various spectroscopic techniques including luminol chemiluminescence photometry, fluorescence probe method, electron spin resonance (ESR), and nuclear magnetic resonance (NMR) spectroscopy were applied. The reaction mechanisms elucidated for bare and modified TiO₂ were described individually. The modified visible light responsive TiO₂ photocatalysts, i.e., Fe(III)-deposited metal-doped TiO₂ and platinum complex-deposited TiO₂, were studied by detecting paramagnetic species with ESR, •O₂⁻ (or H₂O₂) with chemiluminescence photometry, and OH radicals with a fluorescence probe method. For bare TiO₂, the difference in the oxidation mechanism for the different crystalline form was investigated by the fluorescence probe method, while the adsorption and decomposition behaviors of several amino acids and peptides were investigated by ¹H-NMR spectroscopy. Full article

This work demonstrates how formation of strongly chemiluminescent 3-hydroxyphthalic hydrazide by hydroxylation of non-chemiluminescent phthalic hydrazide can be applied as a selective reaction probe to obtain information on authentic hydroxyl radical, i.e., ^•OH_aq, formation, in black light illuminated Degussa P25 TiO₂ aerated suspensions in the pH range from 3 to 11. The ^•OH_aq formation was found to be strongly pH dependent. At alkaline pH, the apparent quantum efficiency of ^•OH_aq formation was estimated to be at the ~10⁻² level whereas at acidic pH it was near zero. Addition of phosphate and fluoride ions substantially enhanced the ^•OH_aq production in the acidic pH range. It is suggested that ^•OH_aq-radical formation in TiO₂ photocatalysis can occur by oxidation of hydroxyl ions in the water layer adsorbed on TiO₂ surfaces. Full article

The free-radical-scavenging activities of various solvent extracts of Microcos paniculata were evaluated through in vitro model systems, such as 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulfonate) (ABTS) and Co (II) EDTA-induced luminol chemiluminescence by flow injection. In all three of these systems the ethyl acetate (EtOAc) extract showed the highest free-radical-scavenging activity compared with the other three (n-BuOH, water and petroleum ether) extracts. Free-radical-scavenging assay-guided chromatographic separation of the EtOAc extract, using a normal-phase and reverse-phase silica gel column chromatography yielded five compounds: a new triterpene named methyl 3b-O-p-hydroxy-E-cinnamoyloxy-2a,23-dihydroxyolean-12-en-28-oate (1), whose spectral data are presented for the first time, together with four known compounds, epicatechin (2), 3-trans-feruloyl maslinic acid (3), maslinic acid (4) and sucrose (5). All of the compounds were isolated from Microcos paniculata for the first time. The compounds were identified by spectroscopic methods. Among them, compound 2 displayed significant free-radical-scavenging activity which is similar to that of standard antioxidant ascorbic acid (V_C) and therefore may be a promising natural antioxidant. Full article