Radical Emission Research Articles

Fiber Optic-Mediated Type I Photodynamic Therapy of Brain Glioblastoma Based on an Aggregation-Induced Emission Photosensitizer.

Glioblastoma (GBM) is one of the most lethal human malignancies. The current standard-of-care is highly invasive with strong toxic side effects, leading to poor prognosis and high mortality. As a safe and effective clinical approach, photodynamic therapy (PDT) has emerged as a suitable option for GBM. Nevertheless, its implementation is significantly impeded by the limits of light penetration depth and the firm reliance on oxygen. To overcome these challenges, herein, a promising strategy that harnesses a modified optical fiber and less oxygen-dependent Type I aggregation-induced emission (AIE) photosensitizer (PS) is developed for the first time to realize in vivo GBM treatments. The proposed AIE PS, namely TTTMN, characterized by a highly twisted molecular architecture and a bulky spacer, exhibits enhanced near-infrared emission and strong production of hydroxyl and superoxide radicals at the aggregated state, thus affording efficient fluorescence imaging-guided PDT once formulated into nanoparticles. The inhibition of orthotopic and subcutaneous GBM xenografts provides compelling evidence of the treatment efficacy of Type I PDT irradiated through a tumor-inserted optical fiber. These findings highlight the substantially improved therapeutic outcomes achieved through fiber optic-mediated Type I PDT, positioning it as a promising therapeutic modality for GBM.

Exploring the Charge-Transport and Optical Characteristics of Organic Doublet Radicals: A Theoretical and Experimental Study with Photovoltaic Applications.

Herein, we present a series of stable radicals containing a trityl carbon-centered radical moiety exhibiting interesting properties. The radicals demonstrate the most blue-shifted anti-Kasha doublet emission reported so far with high color purity (full width at half-maximum of 46 nm) and relatively high photoluminescence quantum yields of deoxygenated toluene solutions reaching 31%. The stable radicals demonstrate equilibrated bipolar charge transport with charge mobility values reaching 10-4 cm2/V·s at high electric fields. The experimental results in combination with the results of TD-DFT calculations confirm that the blue emission of radicals violates the Kasha rule and originates from higher excited states, whereas the bipolar charge transport properties are found to stem from the particularity of radicals to involve the same molecular orbital(s) in electron and hole transport. The radicals act as the efficient materials for interlayers, passivating interfacial defects and enhancing charge extraction in PSCs. Consequently, this leads to outstanding performance of PSC, with power conversion efficiency surpassing 21%, accompanied by a remarkable increase in open-circuit voltage and exceptional stability.

A novel swiss-roll counterflow micro-combustor: Experimental investigation of methane-oxygen flame behavior over time

This study introduces a novel Swiss-roll micro-combustor design that employs a non-premixed counterflow flame for efficient and stable micro-combustion. This design addresses practical system challenges by (1) stabilizing the flame, (2) enhancing heat recovery and gas preheating, (3) aligning gas momentum with the exhaust, and (4) minimizing disruptive fluid motion within the channels. This research investigates the dynamic behavior and combustion characteristics of a methane-oxygen flame within the combustor across a range of equivalence ratios (1.50–3.38). A synergistic approach combining flame dynamics analysis, spectroscopy, and RGB image processing explores the interplay between flame temperature, strain rate, and equivalence ratio. The results demonstrate the effectiveness of the RGB method as a cost-efficient tool for predicting variations in C2∗ and CH∗ radicals and light-intensity radiations. While flame thickness and length exhibit complex dependencies on the fuel-to-oxygen ratio and wall temperature, specific radical emissions vary dynamically with the equivalence ratio. Notably, equivalence ratios of 1.94 and 2.26 exhibit minimal temporal variations in flame properties, suggesting optimal stability and predictability for practical applications. The investigated flame is classified as a “cool flame,” and efficiency declines with richer mixtures due to increased exhaust heat loss and incomplete combustion. This work paves the way for further micro-combustor design optimization and unlocks the potential of non-premixed counterflow flames in diverse micro-scale applications.

Financing green industrial transitions: A Swedish case study

Achieving global climate targets requires massive reductions in greenhouse gas emissions from energy-intensive industrial sectors. We investigate whether financing is an important obstacle for radical emission reduction in industry. We study Sweden as a case of a country that is comparatively advanced in its planning for transitions to low-carbon industrial production. We find that the size of capital investments or the availability of financing for these investments is not perceived as a significant obstacle. There are a number of factors explaining this, such as the fact that the companies involved in this study are well-established, large corporates, and hence well placed to finance their transition plans through conventional corporate finance channels, that conditions for market demand are good in the EU, and that many of the firms are in early stages of developing new technologies, when capital need is smaller compared to later stages. We also find that many financial actors express a strong appetite for sustainable investments. Finally, we observe that despite financing not being perceived as an obstacle, there is still a large and important role to play for public actors for reducing the risk of investments and accelerating the pace of change going forward.

Studies on the propagation dynamics and source mechanism of quasi-monochromatic gravity waves observed over São Martinho da Serra (29° S, 53° W), Brazil

Abstract. A total of 209 events of quasi-monochromatic atmospheric gravity waves (QMGWs) were acquired over 5 years of gravity waves (GWs) observation in southern Brazil. The observations were made by measuring the OH (hydroxyl radical) emission using an all-sky imager hosted by the Southern Space Observatory (SSO) coordinated by the National Institute for Space Research at São Martinho da Serra (RS) (29.44° S, 53.82° W). Using a two-dimensional fast-Fourier-Transform-based spectral analysis, it has been shown that the QMGWs have horizontal wavelengths of 10–55 km, periods of 5–74 min, and phase speeds up to 100 m s−1. The waves exhibited clear seasonal dependence on the propagation direction with anisotropic behavior, propagating mainly toward the southeast during the summer and autumn seasons and mainly toward the northwest during the winter. On the other hand, the propagation directions in the spring season exhibited a wide range from northwest to south. A complementary backward ray-tracing result revealed that the significant factors contributing to the propagation direction of the QMGWs are their source locations and the dynamics of the background winds per season. Three case studies in winter were selected to investigate further the propagation dynamics of the waves and determine their possible source location. We found that the jet stream associated with the cold front and their interaction generated these three GW events.

Photoactivated Circularly Polarized Luminescent Organic Radicals in Doped Amorphous Polymer

AbstractLuminescent organic radicals, especially those with photoactivated circularly polarized luminescence (CPL) features, hold great significance for cutting‐edge optoelectronic applications, but their development still remains a challenge. In this study, we propose a novel strategy to achieve photoactivated CPL radicals by bonding two phosphine centers within an axial chiral system, yielding a compound of R/S‐5,5‐bis(diphenylphosphino)‐4,4′‐bibenzo[d][1,3]dioxole (R/S‐BDP). The photoactivated R/S‐BDP molecules in polymer matrix display a robust quantum yield of 19.8 % and a dissymmetry factor (glum) of 1.2×10−4, marking this work as the first example of photoactivated CPL radicals. Furthermore, the glum is improved to 1.0×10−2 by using a liquid crystal as host. Experimental and theoretical analyses reveal that R/S‐BDP molecules, endowed with double phosphine cores in axial chirality, offer a direct way for intramolecular electron transfer upon photoirradiation. This leads to the generation of radical ionic pairs, which subsequently trigger the donor‐acceptor arrangement through intermolecular electron transfer, thereby resulting in stable radical emission. The extended photoactivated BDP‐F exhibits a remarkably high quantum efficiency of 57.8%. Ultimately, the distinctive photo‐responsive CPL radical luminescence has been successfully used for information displays and anti‐counterfeiting.

Photoactivated Circularly Polarized Luminescent Organic Radicals in Doped Amorphous Polymer.

Luminescent organic radicals, especially those with photoactivated circularly polarized luminescence (CPL) features, hold great significance for cutting-edge optoelectronic applications, but their development still remains a challenge. In this study, we propose a novel strategy to achieve photoactivated CPL radicals by bonding two phosphine centers within an axial chiral system, yielding a compound of R/S-5,5-bis(diphenylphosphino)-4,4'-bibenzo[d][1,3]dioxole (R/S-BDP). The photoactivated R/S-BDP molecules in polymer matrix display a robust quantum yield of 19.8 % and a dissymmetry factor (glum) of 1.2×10-4, marking this work as the first example of photoactivated CPL radicals. Furthermore, the glum is improved to 1.0×10-2 by using a liquid crystal as host. Experimental and theoretical analyses reveal that R/S-BDP molecules, endowed with double phosphine cores in axial chirality, offer a direct way for intramolecular electron transfer upon photoirradiation. This leads to the generation of radical ionic pairs, which subsequently trigger the donor-acceptor arrangement through intermolecular electron transfer, thereby resulting in stable radical emission. The extended photoactivated BDP-F exhibits a remarkably high quantum efficiency of 57.8%. Ultimately, the distinctive photo-responsive CPL radical luminescence has been successfully used for information displays and anti-counterfeiting.

Effects of halogen atom substitution on luminescent radicals: a case study on tris(2,4,6-trichlorophenyl)methyl radical-carbazole dyads.

A series of halogen-substitute carbazole TTM radicals was synthesized. The effect of halogen substituents on radical luminescence was systematically evaluated. It was found that the well-known heavy atom effect does not work in the emission of radicals and that halogen substitution of the donor carbazole can change the HOMO and alter the absorption and emission wavelengths. In addition, the photostability was found to be improved with respect to TTM but not significantly different from that of closed-shell fluorescent molecules.

Comparing the decarbonization benefit provided by waste-based hydrogen routes to green steel production process: an analytical model

In the present context of global decarbonization, the steelmaking sector plays a key role. It is indeed one of the so-called hard-to-abate sectors. The high emissions from steelmaking depend on the use of the Blast Furnace-Basic Oxygen Furnace (BF-BOF) route, which generates 1.8 tCO2eq per ton of Liquid Steel (LS). The production of direct reduced iron (DRI) to power an electric arc furnace is currently the most adopted solution to achieve the decarbonization goals. This alternative, based on the use of natural gas, offers a decarbonization potential of about 34% compared to the BF-BOF route. The most promising alternative, however, consists of using electrolysis-based hydrogen (H2) to produce DRI. This solution would drastically reduce direct and indirect process emissions but requires a radical energy transition. In the current transition phase, waste-based H2 production routes could be attractive, but their potential need to be evaluated with respect to the steelmaking process. To this concern, the objective of the present work is to assess the decarbonization potential of three waste-based H2 production routes (i.e., gasification, incineration and anaerobic digestion-based) with respect to the electrolysis-based steelmaking route. An environmental analytical model was therefore developed to evaluate the total (i.e., direct, indirect, and avoided) greenhouse gases emissions associated with the production of 1 ton of LS by employing the different routes. A sensitivity analysis was also carried out to understand the benefit provided by each waste-based H2 alternative in the current energy transition phase. The results obtained confirmed the need for radical emission reductions from electricity generation to make electrolysis-based H2 production environmentally favorable and revealed a high decarbonization potential for waste-based routes in the current energy transition phase.

Photoinduced Carbonyl Radical Luminescence in Host-Guest Systems.

Developing a free radical emission system in different states, especially in water, is highly challenging and desired. Herein, a host-guest coassembly strategy was used to protect the in situ photoactivated radical emission of carbonyl compounds in solid and aqueous solutions by doping them into a series of small molecules with hydroxyl groups. The intermolecular interactions between host and guest and the electron-donating ability of the hydroxyl group can significantly promote the formation and stabilization of luminescence by carbonyl radicals. Accordingly, the stimuli-responsive property of the free radical system was investigated in detail, and the self-assembled aggregates showed photoactive and thermoresponsive behaviors. In addition, an advanced ammonia compound identification system can be built based on a radical emission system. Our design strategy sheds light on developing free radical systems that can emit in various states, which will greatly broaden the application range of free radicals.

Computational study of added H2 impacts on mixture formation, OH radical and unregulated emissions of spark-ignition methanol engine under various boundary parameters

Numerical simulations of hydrogen (H2) impacts on mixture formation, OH radical generation, and formaldehyde (HCHO) and unburned methanol (CH3OH) emissions of spark-ignition (SI) methanol engine based methanol late-injection strategy under different methanol injection timings (MIT), ignition timings (IT), excess air ratios (λ) and added H2 ratios (RH2) boundary parameters were conducted. The simulation results show that the ideal methanol concentration distribution is obtained at the MIT = 85°CA BTDC. The OH radical plays a dominant role in methanol oxidation. The OHPMF (peak OH radical mass fraction) of RH2 = 9 % ≫ OHPMF of RH2 = 6 % > OHPMF of RH2 = 3 % > OHPMF of RH2 = 0 % at MIT = 85°CA BTDC. Compared with IT and λ, the RH2 is more decisive for the generation of OH radical. The HCHO is a major intermediate and an important unregulated emission of methanol engine. In the initial stage of methanol reaction, added H2 can accelerate the generation of OH radical, further promote the oxidation of methanol, and greatly raise the generation of HCHO. The peak HCHO mass fraction increases with the increase of RH2. At MIT = 85°CA BTDC and exhaust valve opening, the HCHO emission of RH2 = 3 %, 6 %, and 9 % is approximately 51 %, 76.5 % and 89.4 % lower than that of RH2 = 0 %, respectively. The generation and post-oxidation of HCHO mainly depended on average in-cylinder temperature. There is a lowest CH3OH emission at MIT = 85°CA BTDC, IT = 28°CA BTDC, λ = 1.4 and pure methanol. At MIT = 85°CA BTDC, λ = 1.4 and exhaust valve opening, the CH3OH emission of RH2 = 3 %, 6 %, and 9 % is approximately 52.8 %, 75.5 % and 92.5 % lower than that of RH2 = 0 %, respectively.

An Experimental and Detailed Kinetics Modeling Study of Norbornadiene in Hydrogen and Methane Mixtures: Ignition Delay Time and Spectroscopic CO Measurements

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.

Study on the Combustion Characteristics of Ethanol Nanofuel

This study investigates the thermophysical and combustion characteristics of ethanol-based nanofuels incorporating aluminum (Al) and nickel-coated aluminum (Ni-Al). The nanofuels are prepared with varying concentrations of Al and Ni-Al nanoparticles. The results reveal that, despite the non-uniform deposition of nickel on Al particles, a sintering reaction occurs between the two materials. Nanofuels containing Al exhibit unburned Al residues after combustion, while nanofuels containing Ni-Al show intense AlO radical emission during combustion termination, indicating enhanced combustion. However, nanofuels containing Ni-Al demonstrate a lower burning rate compared to Al nanofuels, attributed to the lower thermal conductivity of nickel. Overall, the findings suggest that nanofuels containing Ni-Al possess higher energy potential but extended combustion duration.

Correlation between chemical composition, wettability and carbon anode performance: Exploration of high quality carbon anode preparation for aluminum electrolysis

The chemical composition of coal tar pitch has a significant effect on its wettability and the performance of carbon anode for aluminum electrolysis. This study aimed to reveal the correlation among chemical composition, wettability, and carbon anode performance, as well as provide strategies for reducing energy consumption, greenhouse gases, and hazardous waste emissions during aluminum electrolysis processes. First, the chemical composition of modified coal tar pitch was regulated by adding low-temperature coal tar pitch. The effects of low-temperature coal tar pitch mixing amount on the chemical composition, basic properties, contact angle, static wettability, functional groups, and coke microstructure were studied. In particular, electron paramagnetic resonance (EPR) and atomic force microscopy (AFM) were performed to qualitatively and quantitatively analyze radical emissions and surface structure of coal tar pitch at the microscopic scale. Subsequently, the correlation of chemical composition, wettability, and performance was discussed according to the effect of low-temperature coal tar pitch on the performance of carbon anode. Results showed that the incorporation of low-temperature coal tar pitch reduced the softening point and viscosity, and the increase in fluidity improved the contact angle and static wettability. Meanwhile, the increase in volatile content and the decrease in coking value, surface roughness, nanoscale adhesion, and free radical release concentration jointly weakened the bonding strength between coal tar pitch and calcined petroleum coke. The performance of the carbon anode prepared by blending low-temperature coal tar pitch weakened, except for the ash content. Consequently, the balance between the wettability and bonding strength of coal tar pitch is essential for the preparation of high-quality anode for aluminum electrolysis.

A Simple Molecular Design Strategy for Luminescent Radicals to Achieve Near-Infrared Emission.

The spin-allowed doublet emission of luminescent radicals has recently attracted significant attention. However, the spectral range of most reported luminescent radical emitters and their corresponding organic light-emitting diodes (OLEDs) is confined to the red and deep red regions, with only a few extending to the near-infrared region, specifically in the context of an emission peak exceeding 800 nm. Herein, a luminescent radical, 2-(4-(bis(2,4,6-trichlorophenyl)methyl radical)-3,5-dichlorophenyl)-4-phenyl-4H-thieno[3,2-b]indole (TTM-2PTI), with NIR emission peaking at 830 nm in toluene, was obtained through attaching a 4-phenyl-4H-thieno[3,2-b]indole group to the TTM radical core. An organic light-emitting diode (OLED) utilizing TTM-2PTI as the emitter exhibits electroluminescence (EL) emission peaking at 870 nm, which is the longest EL wavelength among the doublet-emissive near-infrared (NIR) OLEDs. This work provides a simple molecular design strategy to achieve NIR emission of radicals by leveraging the lower steric hindrance and electron-donating ability of thiophene.

Achieving short-wavelength free radical emission by combining small conjugated structure and anti-Kasha emission

Since the natural narrow bandgaps of free radicals usually lead to emission in the long-wavelength region, it is still of great challenge to design radical luminescent materials with stable and short-wavelength emission in the ambient environment. In this work, a series of dicarbonyl-substituted organic molecules with small conjugated structures were used to form free radicals with short-wavelength radical emission. These low-conjugated molecules with only one benzene ring showed stable photoinduced free radical emission after doping with polymethyl methacrylate (PMMA) because the rigid polymer environment could help stabilize the free radicals and limit the non-radiative energy transfer. Moreover, PMMA with electron-withdrawing groups could promote the generation of carbonyl radical cations. The theoretical calculation suggests that the free radical with anti-Kasha emission derived from high energy excited state (D4 or D5) would directly relax to the ground state, combining with the small spin delocalization of the low conjugation free radical, leading to short-wavelength emission. More importantly, such free radical emissions could also respond to external stimulation such as light irradiation or heat treatment. These materials show great potential in lithography information recording and information encryption. This design strategy provides new insights into molecular and functional diversity of free radical materials.

Isotope Detection in Microwave-Assisted Laser-Induced Plasma

Isotope detection and identification is paramount in many fields of science and industry, such as in the fusion and fission energy sector, in medicine and material science, and in archeology. Isotopic information provides fundamental insight into the research questions related to these fields, as well as insight into product quality and operational safety. However, isotope identification with established mass-spectrometric methods is laborious and requires laboratory conditions. In this work, microwave-assisted laser-induced breakdown spectroscopy (MW-LIBS) is introduced for isotope detection and identification utilizing radical and molecular emission. The approach is demonstrated with stable B and Cl isotopes in solids and H isotopes in liquid using emissions from BO and BO2, CaCl, and OH molecules, respectively. MW-LIBS utilizes the extended emissive plasma lifetime and molecular-emission signal-integration times up to 900 μs to enable the use of low (~4 mJ) ablation energy without compromising signal intensity and, consequently, sensitivity. On the other hand, long plasma lifetime gives time for molecular formation. Increase in signal intensity towards the late microwave-assisted plasma was prominent in BO2 and OH emission intensities. As MW-LIBS is online-capable and requires minimal sample preparation, it is an interesting option for isotope detection in various applications.

Bright Free‐Radical Emission in Ionic Liquids

AbstractIt is challenging to achieve stable and efficient radical emissions under ambient conditions. Herein, we present a rational design strategy to protect photoinduced carbonyl free radical emission through electrostatic interaction and spin delocalization effects. The host‐guest system is constructed from tricarbonyl‐substituted benzene molecules and a series of imidazolium ionic liquids as the guest and host, respectively, whereby the carbonyl anion radical emission can be in situ generated under the light irradiation and further stabilized by electrostatic interaction. More importantly, the anion species and the alkyl chain length of imidazolium ionic liquids show a noticeable effect on luminescence efficiency, with the highest radical emission efficiency is as high as 53.3 % after optimizing the imidazole ionic liquid's structure, which is about four times higher than the polymer‐protected radical system. Theoretical calculations confirm the synergistic effect of strong electrostatic interactions and that the spin delocalization effect significantly stabilizes the radical emission. Moreover, such a radical emission system also could be integrated with a fluorescent dye to induce multi‐color or even white light emission with reversible temperature‐responsive characteristics. The radical emission system can also be used to detect different amine compounds on the basis of the emission changes and photoactivation time.

Bright Free-Radical Emission in Ionic Liquids.

It is challenging to achieve stable and efficient radical emissions under ambient conditions. Herein, we present a rational design strategy to protect photoinduced carbonyl free radical emission through electrostatic interaction and spin delocalization effects. The host-guest system is constructed from tricarbonyl-substituted benzene molecules and a series of imidazolium ionic liquids as the guest and host, respectively, whereby the carbonyl anion radical emission can be in situ generated under the light irradiation and further stabilized by electrostatic interaction. More importantly, the anion species and the alkyl chain length of imidazolium ionic liquids show a noticeable effect on luminescence efficiency, with the highest radical emission efficiency is as high as 53.3 % after optimizing the imidazole ionic liquid's structure, which is about four times higher than the polymer-protected radical system. Theoretical calculations confirm the synergistic effect of strong electrostatic interactions and that the spin delocalization effect significantly stabilizes the radical emission. Moreover, such a radical emission system also could be integrated with a fluorescent dye to induce multi-color or even white light emission with reversible temperature-responsive characteristics. The radical emission system can also be used to detect different amine compounds on the basis of the emission changes and photoactivation time.

Analysis of CN emission as a marker of organic compounds in meteoroids using laboratory simulated meteors

Fragments of small solar system bodies entering Earth’s atmosphere have possibly been important contributors of organic compounds to the early Earth. The cyano radical (CN) emission from meteors is considered as potentially one of the most suitable markers of organic compounds in meteoroids, however, its detection in meteor spectra has been thus far unsuccessful. With the aim to improve our abilities to identify CN emission in meteor observations and use its spectral features to characterize the composition of incoming asteroidal meteoroids, we present a detailed analysis of CN emission from high-resolution spectra of 22 laboratory simulated meteors including ordinary, carbonaceous, and enstatite chondrites, as well as a large diversity of achondrites (i.e., ureilite, aubrite, lunar, martian, howardite, eucrite, and diogenite), mesosiderite, and iron meteorites. We describe the variations of CN emission from different classes of asteroidal meteor analogues, its correlation and time evolution relative to other major meteoroid components. We demonstrate that CN can be used as a diagnostic spectral feature of carbonaceous and carbon-rich meteoroids, while most ordinary chondrites show no signs of CN. Our results point out strong correlation between CN and H emission and suggest both volatile features are suitable to trace contents of organic matter and water molecules present within meteoroids. For the application in lower resolution meteor observations, we demonstrate that CN can be best recognized in the early stages of ablation and for carbon-rich materials by measuring relative intensity ratio of CN band peak to the nearby Fe I-4 lines.