Impact of the particle mixing state on the hygroscopicity of internally mixed sodium chloride-ammonium sulfate single droplets: a theoretical and experimental study.

Sodium chloride (NaCl) is the main constituent of sea-salt aerosols. During atmospheric transport, sea-salt aerosols can interact with gases and other particles including secondary aerosols containing ammonium sulfate ((NH4)2SO4). This paper reports on the deliquescence relative humidity (DRH) of internally mixed sodium chloride-ammonium sulfate (NaCl/(NH4)2SO4) coarse particles by means of an acoustic levitation system fitted with a confocal Raman microscope (CRM). The chemical composition and physical state of individual levitated particles of different initial NaCl mole fractions were monitored during the deliquescence cycle by CRM. Experimental results were compared to the data predicted by the thermodynamic model E-AIM (Extended-Aerosol Inorganics Model). We demonstrated that NH4Cl, Na2SO4 and NH4NaSO4·2H2O are formed in recrystallized particles and coexist with NaCl and (NH4)2SO4. All these products are randomly distributed within the particles. Deliquescence curves described two or three-stage phase transitions depending on the initial composition of the droplet. Significant discrepancies between the model and the laboratory experiments were observed for NaCl mole fractions varying between 0.40 and 0.77 due to a divergence between the predicted and the truly present products in the particles' solid fraction during the humidification cycle.

Enhancing Double-Beam Laser Tweezers Raman Spectroscopy (LTRS) for the Photochemical Study of Individual Airborne Microdroplets.

A new device and methodology for vertically coupling confocal Raman microscopy with optical tweezers for the in situ physico- and photochemical studies of individual microdroplets (Ø ≤ 10 µm) levitated in air is presented. The coupling expands the spectrum of studies performed with individual particles using laser tweezers Raman spectroscopy (LTRS) to photochemical processes and spatially resolved Raman microspectroscopy on airborne aerosols. This is the first study to demonstrate photochemical studies and Raman mapping on optically levitated droplets. By using this configuration, photochemical reactions in aerosols of atmospheric interest can be studied on a laboratory scale under realistic conditions of gas-phase composition and relative humidity. Likewise, the distribution of photoproducts within the drop can also be observed with this setup. The applicability of the coupling system was tested by studying the photochemical behavior of microdroplets (5 µm < Ø < 8 µm) containing an aqueous solution of sodium nitrate levitated in air and exposed to narrowed UV radiation (254 ± 25 nm). Photolysis of the levitated NaNO3 microdroplets presented photochemical kinetic differences in comparison with larger NaNO3 droplets (40 µm < Ø < 80 µm), previously photolyzed using acoustic traps, and heterogeneity in the distribution of the photoproducts within the drop.

Photodegradation of methyl thioglycolate particles as a proxy for organosulphur containing droplets.

Understanding the formation and transformation of sulphur-rich particles is of prime importance since they contribute to the global atmospheric sulphur budget. In this work, we performed a series of experiments on a photoactive organosulphur compound namely, methyl thioglycolate, as a model of an organosulphur species of marine origin. By investigating the photoproducts within levitated droplets, we showed that elemental sulphur (α-S8) and sulphate (SO42-) can be photochemically generated at the gas-liquid interface by heterogeneous interaction with gaseous O2 and H2O. These results demonstrate that the surface of levitated droplets facilitate the oxidation of methyl thioglycolate in the dark, while illumination is necessary to produce the oxidation in bulk experiments.

Bonding, Luminescence, Metallophilicity in Linear Au3 and Au2Ag Chains Stabilized by Rigid Diphosphanyl NHC Ligands.

The heterofunctional and rigid ligand N,N'-diphosphanyl-imidazol-2-ylidene (PCNHCP; P = P(t-Bu)2), through its phosphorus and two N-heterocyclic carbene (NHC) donors, stabilizes trinuclear chain complexes, with either Au3 or AgAu2 cores, and dinuclear Au2 complexes. The two oppositely situated PCNHCP (L) ligands that "sandwich" the metal chain can support linear and rigid structures, as found in the known tricationic Au(I) complex [Au3(µ3-PCNHCP,κP,κCNHC,κP)2](OTf)3 (OTf = CF3SO3; [Au3L2](OTf)3; Chem. Commun. 2014, 50, 103-105) now also obtained by transmetalation from [Ag3(µ3-PCNHCP,κP,κCNHC,κP)2](OTf)3 ([Ag3L2](OTf)3), or in the mixed-metal tricationic [Au2Ag(µ3-PCNHCP,κP,κCNHC,κP)2](OTf)3 ([Au2AgL2](OTf)3). The latter was obtained stepwise by the addition of AgOTf to the digold(I) complex [Au2(µ2-PCNHCP,κP,κCNHC)2](OTf)2 ([Au2L2](OTf)2). The latter contains two dangling P donors and displays fluxional behavior in solution, and the Au···Au separation of 2.8320(6) Å in the solid state is consistent with metallophilic interactions. In the solvento complex [Au3Cl2(tht)(µ3-PCNHCP,κP,κCNHC,κP)](OTf)·MeCN ([Au3Cl2(tht)L](OTf)·MeCN), which contains only one L and one tht ligand (tht = tetrahydrothiophene), the metal chain is bent (148.94(2)°), and the longer Au···Au separation (2.9710(4) Å) is in line with relaxation of the rigidity due to a more "open" structure. Similar features were observed in [Au3Cl2(SMe2)L](OTf)·2MeCN. A detailed study of the emission properties of [Au3L2](OTf)3, [Au3Cl2(tht)L](OTf)·MeCN, [Au2L2](OTf)2, and [Au2AgL2](OTf)3 was performed by means of steady state and time-resolved photophysical techniques. The complex [Au3L2](OTf)3 displays a bright (photoluminescence quantum yield = 80%) and narrow emission band centered at 446 nm with a relatively small Stokes' shift and long-lived excited-state lifetime on the microsecond timescale, both in solution and in the solid state. In line with the very narrow emission profile centered in the violet-blue region, fabrication of organic light-emitting devices (OLEDs) comprising the [Au3L2](OTf)3 complex demonstrated its usefulness as a deep-blue emitter in solution-processed OLEDs. Electrochemical and Raman spectroscopic studies were also performed on [Au3L2](OTf)3. Experimental results were rationalized by means of Wave-Function Theory (WFT) and Density Functional Theory (DFT). MP2 calculations gave a satisfactory description of the structures of the cationic complexes [Au3L2](3+) and [Au2L2](2+) and pointed to Au···Au interactions having an electrostatic component owing to the dissimilar charge distribution in the chain caused by the heterofunctional ligand. The nature of the emitting states and their geometric distortions relative to the ground states in [Au3L2](3+) and [Au2L2](2+) was studied by DFT, revealing contraction of the Au···Au distances and coordination geometry changes by association of the dangling P donor, respectively.

Au-Au chemical bonding induced by UV irradiation of dinuclear gold(I) complexes: a computational study with experimental evidence.

Two luminescent dinuclear gold(I) species, namely diselenophosphinate [Au2{µ-Se2P((CH2)2Ph)2}2] and dithiophosphinate [Au2{µ-S2P((CH2)2Ph)2}2], exhibiting interesting structural, absorption and emission properties have been studied. In the solid state, both complexes exist in a dinuclear monomeric form, exhibiting no aurophilic interaction, and display similar photophysical properties. It is shown, using DFT computations, that Au-Au chemical bonding appears in the first excited state of these complexes, whereas such bonding does not exist in their ground state; Raman spectroscopy experiments, which bring to light the stretching of this new bond, confirm the theoretical results. Moreover, TDDFT computations permitted us to assign the observed absorption bands of the UV-visible spectra of the two species to LMCT transitions and to describe the emission.

Direct photodegradation of internally mixed sodium chloride and malonic acid single aerosols: Impact of the photoproducts on the hygroscopic properties of the particles.

Sea-salt aerosols (SSA) are one of the key natural aerosols in our atmosphere, consisting predominantly of sodium chloride (NaCl). Throughout their atmospheric transport, these aerosols undergo complex internal mixing, giving rise to a rich variety of inorganic and organic species, including dicarboxylic acids. This study investigates firstly the composition and deliquescence properties of coarse particles containing pure malonic acid (MA2, CH2(COOH)2) and internally mixed NaCl and MA2, by means of an acoustic levitation system coupled with a Raman microspectrometer. Secondly, we report here the first experimental observation and characterization of the products arising from photochemical reactions under UV-Visible irradiation (338 ≤ λ ≤ 414 nm) in the absence of an oxidant under acoustic levitation conditions in MA2 and NaCl/MA2 aerosols. Furthermore, the impact of photodegradation on the hygroscopic properties of these particles is examined. We confirmed the irreversible formation of monosodium malonate (NaMA, HOOCCH2COONa), which coexists with NaCl or MA2 on non-irradiated particles. We also demonstrated the formation of oxalic acid (OA2, HOOC-COOH) within irradiated MA2 droplets and the appearance of glyoxylic acid (GlyA, HCOCOOH) in NaCl containing droplets. The photolysis process exerts a marked effect on the hygroscopic properties of the particles, resulting in a shift in deliquescence transitions toward higher relative humidity (RH) values. This study contributes to the understanding of the intricate physicochemical processes involved in SSA during their atmospheric transport. Likewise, this work sheds light on the impacts of these types of aerosols on cloud formation and climate change.

Spin crossover complexes [Fe(NH2trz)3](X)2·nH2O investigated by means of polarized Raman scattering and DFT calculations.

Vibrational spectra of the spin crossover (SCO) polymers [Fe(NH2trz)3](X)2·nH2O where NH2trz = 4-NH2-1,2,4-triazole and X = Cl, Br, BF4, and NO3 have been analyzed. Our results show that the anions and water molecules have no significant influence on the vibrational properties of the Fe(NH2-trz)3 polymer chains. A detailed study of the nitrate derivative, based on the DFT analysis of the polarized spectra of single crystals, has been undertaken to propose the normal mode assignment of the Raman peaks in the low spin state of the compound. Changes in the Raman spectra in the high spin state could therefore be analyzed and interpreted by several Raman bands identified as molecular probes of the SCO phenomenon. Various factors (laser power, humidity, pressure) that influence the transition temperatures and the hysteresis loops have been identified and adjusted for obtaining reliable measurements. We demonstrate in particular that all the techniques used to probe the phase transition process give comparable results providing that the sample environment is well controlled.

Uptake of ozone by allergenic pollen grains.

Ozone exacerbates allergy symptoms to certain pollens. The molecular mechanisms by which ozone affects pollen grains (PGs) and allergies are not fully understood, especially as the effects of pollutants may vary depending on the type of pollen. In this work, pollens of 22 different taxa were exposed under laboratory conditions to ozone (100 ppb) to quantify the ozone uptake by the PGs. The ozone uptake was highly variable among the 22 taxa tested. The highest ozone uptake per PG was measured on Acer negundo PGs (2.5 ± 0.2 pg∙PG-1). On average, tree pollens captured significantly more ozone than herbaceous pollens (average values of 0.5 and 0.02 pg∙PG-1, respectively). No single parameter (such as the number of apertures, pollen season, pollen size, or lipid fraction) could predict a pollen's ability to take up ozone. Lipids seem to act as a barrier to ozone uptake and play a protective role for some taxa. After inhalation of PGs, pollen-transported ozone could be transferred to mucous membranes and exacerbate symptoms through oxidative stress and local inflammation. Although the amount of ozone transported is small in absolute terms, it is significant compared to the antioxidant capacity of nasal mucus at a microscale. This mechanism of pollen-induced oxidative stress could explain the aggravation of allergic symptoms during ozone pollution episodes.

Diurnal variation and potential sources of indoor formaldehyde at elementary school, high school and university in the Centre Val de Loire region of France.

Formaldehyde (HCHO) is one of the abundant indoor pollutants and has been classified as a human carcinogen by the International Agency for Research on Cancer (IARC). Indoor HCHO at schools is particularly important due to the high occupancy density and the health effects on children. In this study, high time resolved measurement of formaldehyde concentration was conducted in the classrooms at elementary school, high school and university under normal students' activities in three different locations in the Region Centre Val de Loire-France. Indoor average formaldehyde concentrations at those three educational institutions were observed to be in the range 10.96-17.95 µg/m3, not exceeding the World Health Organization (WHO) guideline value of 100 µg/m3. As expected, ventilation was found playing an important role in the control of indoor formaldehyde concentration. After opening windows for 30 min, formaldehyde level decreased by ~25% and 38% in the classroom at the elementary school and the high school, respectively. In addition to the primary sources, the objective of this study was also to determine potential secondary sources of indoor formaldehyde in these schools by measuring the other volatile organic compounds (VOCs) present in the classrooms by a Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS). The measurements suggest that the release of residue from tobacco smokers is one of the major sources of indoor HCHO at the high school, which increases HCHO by ~55% averagely within 1 h. Moreover, the control experiments conducted in the university suggests that VOCs such as that released from cleaning products like terpenes, can contribute to the increase of indoor formaldehyde levels through chemical reactions with ozone. This study confirms simple recommendations to reduce the indoors HCHO concentration in schools: use ventilation systems, limit the emissions like cigarette smoke or cleaning products. It also points out that the secondary sources of formaldehyde must be also considered in the classroom.

Vibrational and valence photoelectron spectroscopies, matrix photochemistry, and conformational studies of ClC(O)SSCl.

ClC(O)SSCl was prepared by an improved method by the reaction of [(CH(3))(2)CHOC(S)](2)S with SO(2)Cl(2) in hexane. The photoelectron spectra in the gas phase present four distinct regions, corresponding to ionizations from electrons formally located at the S, O, and Cl atoms and at the C═O bond. The vibrational IR and Raman spectra of the liquid were interpreted in terms of the most stable syn-gauche conformer (the O═C double bond syn with respect to the S-S single bond and the C-S single bond gauche with respect to the S-Cl single bond) in equilibrium with the less stable anti-gauche form, both occurring in two enantiomeric forms. The randomization process between the conformers was induced by broad-band UV-visible irradiation in matrix conditions, and several photoproducts were identified by FTIR spectroscopy. The experimental results were complemented by theoretical calculations.

Crystal structure, spectroscopic characterization and Hirshfeld surface analysis of aqua-dichlorido-{N-[(pyridin-2-yl)methyl-idene]aniline}copper(II) monohydrate.

The reaction of N-phenyl-1-(pyridin-2-yl)methanimine with copper chloride dihydrate produced the title neutral complex, [CuCl2(C12H10N2)(H2O)]·H2O. The CuII ion is five-coordinated in a distorted square-pyramidal geometry, in which the two N atoms of the bidentate Schiff base, as well as one chloro and a water mol-ecule, form the irregular base of the pyramidal structure. Meanwhile, the apical chloride ligand inter-acts through a strong hydrogen bond with a water mol-ecule of crystallization. In the crystal, mol-ecules are arranged in pairs, forming a stacking of symmetrical cyclic dimers that inter-act in turn through strong hydrogen bonds between the chloride ligands and both the coordinated and the crystallization water mol-ecules. The mol-ecular and electronic structures of the complex were also studied in detail using EPR (continuous and pulsed), FT-IR and Raman spectroscopy, as well as magnetization measurements. Likewise, Hirshfeld surface analysis was used to investigate the inter-molecular inter-actions in the crystal packing.

Formation of new halogenothiocarbonylsulfenyl halides, XC(S)SY, through photochemical matrix reactions starting from CS2 and a dihalogen molecule XY (XY=Cl2, Br2, or BrCl).

Isolation of a dihalogen molecule XY (XY=Cl2, Br2, or BrCl) with CS2 in a solid Ar matrix at about 15 K leads, by broad-band UV-vis photolysis (200

Photochemical reaction channels of OCS with Cl2, ICl, or IBr isolated together in an argon matrix: isolation of syn-iodocarbonylsulfenyl bromide.

The photolytically induced reactions of a dihalogen XY (= Cl2, ICl, or IBr) with OCS isolated together in an Ar matrix at about 15 K lead to different photoproducts depending on the natures of X and Y. In addition to the known species ClCO*, OCCl2, syn-ClC(O)SCl, syn-ClC(O)SSCl, IC(O)Cl, IC(O)Br, and syn-BrC(O)SBr, syn-iodocarbonylsulfenyl bromide, syn-IC(O)SBr, has thus been identified for the first time as a photoproduct of the reactions involving IBr. The first product to be formed in the reactions with Cl2 or ICl is the ClCO* radical which reacts subsequently with halogen or sulfur atoms or other matrix guests to give the corresponding carbonyl dihalide (OCCl2 and IC(O)Cl), syn-ClC(O)SCl or syn-ClC(O)SSCl. The analogous reaction with IBr affords syn-BrC(O)SBr, IC(O)Br, and syn-IC(O)SBr. The changes have been followed, the products characterized experimentally by IR measurements, and the spectra analyzed in the light of the results of appropriate theoretical calculations.

New members of an old family: isolation of IC(O)Cl and IC(O)Br and evidence for the formation of weakly bound Br*...CO.

The photochemically induced reactions of a dihalogen, XY, with CO isolated together in an Ar matrix at about 15 K lead to the formation of carbonyl dihalide molecules XC(O)Y, where X and Y may be the same or different halogen atoms, Cl, Br, or I. In addition to the known compounds OCCl2, OCBr2, and BrC(O)Cl, the carbonyl iodide chloride, IC(O)Cl, and carbonyl iodide bromide, IC(O)Br, compounds have thus been identified for the first time as products of the reactions involving ICl and IBr, respectively. The first product to be formed in reactions with Cl2, BrCl, or ICl is the ClCO* radical, which reacts subsequently with a second halogen atom to give the corresponding carbonyl dihalide [OCCl2, BrC(O)Cl, or IC(O)Cl]. The analogous reaction with Br2 affords, in low yield, the unusually weakly bound BrCO* radical, better described as a van der Waals complex, Br*...CO. The changes have been followed and the products characterized experimentally by their infrared spectra, and the spectra have been analyzed in light of the results afforded by ab initio (Hartree-Fock and Moeller-Plesset second-order) and density functional theory calculations.