Progresses on the Use of Two-Photon Absorption Laser Induced Fluorescence (TALIF) Diagnostics for Measuring Absolute Atomic Densities in Plasmas and Flames

Recent developments in plasma science and technology have opened new areas of research both for fundamental purposes (e.g., description of key physical phenomena involved in laboratory plasmas) and novel applications (material synthesis, microelectronics, thin film deposition, biomedicine, environment, flow control, to name a few). With the increasing availability of advanced optical diagnostics (fast framing imaging, gas flow visualization, emission/absorption spectroscopy, etc.), a better understanding of the physicochemical processes taking place in different electrical discharges has been achieved. In this direction, the implementation of fast (ns) and ultrafast (ps and fs) lasers has been essential for the precise determination of the electron density and temperature, the axial and radial gradients of electric fields, the gas temperature, and the absolute density of ground-state reactive atoms and molecules in non-equilibrium plasmas. For those species, the use of laser-based spectroscopy has led to their in situ quantification with high temporal and spatial resolution, with excellent sensitivity. The present review is dedicated to the advances of two-photon absorption laser induced fluorescence (TALIF) techniques for the measurement of reactive species densities (particularly atoms such as N, H and O) in a wide range of pressures in plasmas and flames. The requirements for the appropriate implementation of TALIF techniques as well as their fundamental principles are presented based on representative published works. The limitations on the density determination imposed by different factors are also discussed. These may refer to the increasing pressure of the probed medium (leading to a significant collisional quenching of excited states), and other issues originating in the high instantaneous power density of the lasers used (such as photodissociation, amplified stimulated emission, and photoionization, resulting to the saturation of the optical transition of interest).

Interrogation of O-ATRP Activation Conducted by Singlet and Triplet Excited States of Phenoxazine Photocatalysts

Organocatalyzed ATRP (O-ATRP) is a growing field exploiting organic chromophores as photoredox catalysts (PCs) that engage in dissociative electron transfer (DET) activation of alkyl halide initiators following absorption of light. Characterizing DET rate coefficients (<i>k_act</i>) and photochemical yields across various reaction conditions and PC photophysical properties will inform catalyst design and efficient use during polymerization. The studies described herein consider a class of phenoxazine PCs where synthetic handles of core-substitution and <i>N</i>-aryl substitution enable tunability of the electronic and spin character of the catalyst excited state as well as DET reaction driving force ( ). Using Stern-Volmer quenching experiments through variation of diethyl 2-bromo-2-methylmalonate (DBMM) initiator concentration, collisional quenching is observed. Eight independent measurements of <i>k_act</i>are reported as a function of for four PCs: four triplet reactants and four singlets with <i>k_act</i> values ranging from 1.1´10⁸ M^-1s^-1 where DET itself controls the rate to 4.8´10⁹ M^-1s^-1 where diffusion is rate limiting. This overall data set, as well as a second one inclusive of five literature values from related systems, is readily modeled with only a single parameter of reorganization energy under the frameworks of adiabatic Marcus electron transfer theory and Marcus-Savéant theory of DET. The results provide a predictive map where <i>k_act</i> can be estimated if is known and highlight that DET in these systems appears insensitive to PC reactant electronic and spin properties outside of their impact on driving force. Next, on the basis of measured <i>k_act</i> values in selected PC systems and knowledge of their photophysics, we also consider activation yields specific to the reactant spin states as the DBMM initiator concentration is varied. In <i>N</i>-naphthyl-containing PCs characterized by near-unity intersystem crossing, the T₁ is certainly an important driver for efficient DET. However, at DBMM concentrations common to polymer synthesis, the S₁ is also active and drives 33% of DET reaction events. Even in systems with low yields of ISC, such as in <i>N</i>-phenyl-containing PCs, reaction yields can be driven to useful values by exploiting the S₁ under high DBMM concentration conditions. Finally, we have quantified photochemical reaction quantum yields, which take into account potential product loss processes after electron-transfer quenching events. Both S₁ and T₁ reactant states produce the PC^·+ radical cation with a common yield of 71%, thus offering no evidence for spin selectivity in deleterious back electron transfer. The sub-unity PC^·+ yields suggest that some combination of solvent (DMAc) oxidation and energy-wasting back electron transfer is likely at play and these pathways should be factored in subsequent mechanistic considerations.

Interrogation of O-ATRP Activation Conducted by Singlet and Triplet Excited States of Phenoxazine Photocatalysts

Organocatalyzed ATRP (O-ATRP) is a growing field exploiting organic chromophores as photoredox catalysts (PCs) that engage in dissociative electron transfer (DET) activation of alkyl halide initiators following absorption of light. Characterizing DET rate coefficients (<i>k_act</i>) and photochemical yields across various reaction conditions and PC photophysical properties will inform catalyst design and efficient use during polymerization. The studies described herein consider a class of phenoxazine PCs where synthetic handles of core-substitution and <i>N</i>-aryl substitution enable tunability of the electronic and spin character of the catalyst excited state as well as DET reaction driving force ( ). Using Stern-Volmer quenching experiments through variation of diethyl 2-bromo-2-methylmalonate (DBMM) initiator concentration, collisional quenching is observed. Eight independent measurements of <i>k_act</i>are reported as a function of for four PCs: four triplet reactants and four singlets with <i>k_act</i> values ranging from 1.1´10⁸ M^-1s^-1 where DET itself controls the rate to 4.8´10⁹ M^-1s^-1 where diffusion is rate limiting. This overall data set, as well as a second one inclusive of five literature values from related systems, is readily modeled with only a single parameter of reorganization energy under the frameworks of adiabatic Marcus electron transfer theory and Marcus-Savéant theory of DET. The results provide a predictive map where <i>k_act</i> can be estimated if is known and highlight that DET in these systems appears insensitive to PC reactant electronic and spin properties outside of their impact on driving force. Next, on the basis of measured <i>k_act</i> values in selected PC systems and knowledge of their photophysics, we also consider activation yields specific to the reactant spin states as the DBMM initiator concentration is varied. In <i>N</i>-naphthyl-containing PCs characterized by near-unity intersystem crossing, the T₁ is certainly an important driver for efficient DET. However, at DBMM concentrations common to polymer synthesis, the S₁ is also active and drives 33% of DET reaction events. Even in systems with low yields of ISC, such as in <i>N</i>-phenyl-containing PCs, reaction yields can be driven to useful values by exploiting the S₁ under high DBMM concentration conditions. Finally, we have quantified photochemical reaction quantum yields, which take into account potential product loss processes after electron-transfer quenching events. Both S₁ and T₁ reactant states produce the PC^·+ radical cation with a common yield of 71%, thus offering no evidence for spin selectivity in deleterious back electron transfer. The sub-unity PC^·+ yields suggest that some combination of solvent (DMAc) oxidation and energy-wasting back electron transfer is likely at play and these pathways should be factored in subsequent mechanistic considerations.

Time-resolved observations of vibrationally excited NO X 2Π (v′) formed from collisional quenching of NO A 2Σ+ (v = 0) by NO X 2Π: evidence for the participation of the NO a 4Π state

Time resolved observations of the products of NO A 2Σ+ collisional quenching show fast and slow components, consistent with the involvement of a reservoir state (a 4Π) through which a portion of the quenching occurs.

Direct Measure of the Local Concentration of Pyrenyl Groups in Pyrene-Labeled Dendrons Derived from the Rate of Fluorescence Collisional Quenching

The model-free analysis (MFA) was applied to measure the average rate constant (<k>) for pyrene excimer formation (PEF) in a series of pyrene-labeled dendrons referred to as Pyx-G(N), where x (= 2N) is the number of pyrenyl labels born by a dendron of generation N ranging from 1 to 6. <k> was measured in four different solvents, namely tetrahydrofuran (THF), toluene, N,N-dimethylformamide (DMF), and dimethylsulfoxide (DMSO). <k> was found to increase linearly with increasing local pyrene concentration ([Py]loc), where [Py]loc had been determined mathematically for the Pyx-G(N) dendrons. The slope of each straight line changed with the nature of the solvent and represented kdiff, the bimolecular rate constant for PEF. kdiff depended on the solvent viscosity (η) and the probability (p) for PEF upon encounter between an excited and a ground-state pyrene. In a same solvent, kdiff for the Pyx-G(N) dendrons was about 360 ± 30 times smaller than kdiff obtained for ethyl 4-(1-pyrene)butyrate (PyBE), a pyrene model compound similar to the pyrene derivative used to label the dendrons. The massive decrease in kdiff observed for the Pyx-G(N) samples reflected the massive loss in mobility experienced by the pyrenyl labels after being covalently attached onto a macromolecule compared to freely diffusing PyBE. Interestingly, the kdiff values obtained for the Pyx-G(N) dendrons and the PyBE model compound followed similar trends as a function of solvent, indicating that the difference in behavior between the kdiff values obtained in different solvents were merely due to the changes in the η and p values between the solvents. Normalizing the <k> values obtained with the Pyx-G(N) dendrons by the kdiff values obtained for PyBE in the same solvents accounted for changes in η and p, resulting in a master curve upon plotting <k>/(fdiff × kdiff) as a function of [Py]loc, where fdiff was introduced to account for some pyrene aggregation in the higher generation dendron (Py64-G(6)). This result demonstrates that <k> represents a direct measure of [Py]loc in pyrene-labeled macromolecules.

Finding Value in Wastewaters from the Cork Industry: Carbon Dots Synthesis and Fluorescence for Hemeprotein Detection

Valorisation of industrial low-value waste residues was preconized. Hence, carbon dots (C-dots) were synthesized from wastewaters of the cork industry—an abundant and affordable, but environmentally-problematic industrial effluent. The carbon nanomaterials were structurally and morphologically characterised, and their photophysical properties were analysed by an ensemble of spectroscopy techniques. Afterwards, they were successfully applied as highly-sensitive fluorescence probes for the direct detection of haemproteins. Haemoglobin, cytochrome c and myoglobin were selected as specific targets owing to their relevant roles in living organisms, wherein their deficiencies or surpluses are associated with several medical conditions. For all of them, remarkable responses were achieved, allowing their detection at nanomolar levels. Steady-state and time-resolved fluorescence, ground-state UV–Vis absorption and electronic circular dichroism techniques were used to investigate the probable mechanisms behind the fluorescence turn-off of C-dots. Extensive experimental evidence points to a static quenching mechanism. Likewise, resonance energy transfer and collisional quenching have been discarded as excited-state deactivating mechanisms. It was additionally found that an oxidative, photoinduced electron transfer occurs for cytochrome c, the most electron-deficient protein. Besides, C-dots prepared from citric acid/ethylenediamine were comparatively assayed for protein detection and the differences between the two types of nanomaterials highlighted.

Forbidden atomic carbon, nitrogen, and oxygen emission lines in the water-poor comet C/2016 R2 (Pan-STARRS)

Context. The N2 and CO-rich and water-depleted comet C/2016 R2 (Pan-STARRS) – hereafter “C/2016 R2” – is a unique comet for detailed spectroscopic analysis. Aims. We aim to explore the associated photochemistry of parent species, which produces different metastable states and forbidden emissions, in this cometary coma of peculiar composition. Methods. We reanalyzed the high-resolution spectra of comet C/2016 R2 obtained in February 2018 using the UVES spectrograph of the European Southern Observatory Very Large Telescope. Various forbidden atomic emission lines of [CI], [NI], and [OI] were observed in the optical spectrum of this comet when it was at 2.8 au from the Sun. The observed forbidden emission intensity ratios are studied in the framework of a couple-chemistry emission model. Results. The model calculations show that CO2 is the major source of both atomic oxygen green and red doublet emissions in the coma of C/2016 R2 (while for most comets it is generally H2O), whereas, CO and N2 govern the atomic carbon and nitrogen emissions, respectively. Our modeled oxygen green-to-red-doublet and carbon-to-nitrogen emission ratios are higher by a factor of three than what is found from observations. These discrepancies could be due to uncertainties associated with photon cross sections or unknown production and/or loss sources. Our modeled oxygen green-to-red-doublet emission ratio is close to what is seen in observations when we consider an O2 abundance with a production rate of 30% relative to the CO production rate. We constrained the mean photodissociation yield of CO, producing C(1S) at about 1%, a quantity which has not been measured in the laboratory. The collisional quenching is not a significant loss process for N(2D) though its radiative lifetime is significant (~10 h). Hence, the observed [NI] doublet-emission ratio ([NI] 5198/5200) of 1.22, which is smaller than the terrestrial measurement by a factor 1.4, is mainly due to the characteristic radiative decay of N(2D).

Synthesis of new fluorescent pyrylium dyes and study of their interaction with N-protected amino acids

Six new fluorescent styrylpyrylium dyes have been synthesized and the collisional quenching taking place upon their interaction with Z-protected amino acids has been studied.

On the nonadiabatic collisional quenching of OH(A) by H2: a four coupled quasi-diabatic state description

12A, 22A, and 32A electronic states of OH(A) + H2 where conical intersections facilitate the quenching of OH(A) by H2.