Impact of the spectral and spatial properties of natural light on indoor gas-phase chemistry: Experimental and modeling study.

The characteristics of indoor light (intensity, spectral, spatial distribution) originating from outdoors have been studied using experimental and modeling tools. They are influenced by many parameters such as building location, meteorological conditions, and the type of window. They have a direct impact on indoor air quality through a change in chemical processes by varying the photolysis rates of indoor pollutants. Transmittances of different windows have been measured and exhibit different wavelength cutoffs, thus influencing the potential of different species to be photolysed. The spectral distribution of light entering indoors through the windows was measured under different conditions and was found to be weakly dependent on the time of day for indirect cloudy, direct sunshine, partly cloudy conditions contrary to the light intensity, in agreement with calculations of the transmittance as a function of the zenithal angle and the calculated outdoor spectral distribution. The same conclusion can be drawn concerning the position within the room. The impact of these light characteristics on the indoor chemistry has been studied using the INCA-Indoor model by considering the variation in the photolysis rates of key indoor species. Depending on the conditions, photolysis processes can lead to a significant production of radicals and secondary species.

Communication: On the first ionization threshold of the C2H radical.

The slow photoelectron spectrum of the ethynyl radical has been recorded for the first time by using the DESIRS beamline of the SOLEIL synchrotron facility. Ethynyl was generated using a microwave discharge flow tube. The observation of the X+Π3←XΣ+2 transition allowed the first direct measurement of the adiabatic ionization threshold of this radical (EI = 11.641(5) eV). The experimental results are supported by ab initio calculations. Our preliminary investigation of the cationic ground state potential energy surfaces predicts a non-negligible Renner-Teller effect which has not been discussed previously.

Identification of the major HOx radical pathways in an indoor air environment.

OH and HO2 profiles measured in a real environment have been compared to the results of the INCA-Indoor model to improve our understanding of indoor chemistry. Significant levels of both radicals have been measured and their profiles display similar diurnal behavior, reaching peak concentrations during direct sunlight (up to 1.6×106 and 4.0×107  cm-3 for OH and HO2 , respectively). Concentrations of O3 , NOx , volatile organic compounds (VOCs), HONO, and photolysis frequencies were constrained to the observed values. The HOx profiles are well simulated in terms of variation for both species (Pearson's coefficients: pOH =0.55, pHO2 =0.76) and concentration for OH (mean normalized bias error: MNBEOH =-30%), HO2 concentration being always underestimated (MNBEHO2 =-62%). Production and loss pathways analysis confirmed HONO photolysis role as an OH precursor (here up to 50% of the production rate). HO2 formation is linked to OH-initiated VOC oxidation. A sensitivity analysis was conducted by varying HONO, VOCs, and NO concentrations. OH, HO2 , and formaldehyde concentrations increase with HONO concentrations; OH and formaldehyde concentrations are weakly dependent on NO, whereas HO2 concentrations are strongly reduced with increasing NO. Increasing VOC concentrations decreases OH by consumption and enhances HO2 and formaldehyde.

Assessment of indoor HONO formation mechanisms based on in situ measurements and modeling.

The photolysis of HONO has been found to be the oxidation driver through OH formation in the indoor air measurement campaign SURFin, an extensive campaign carried out in July 2012 in a classroom in Marseille. In this study, the INCA-Indoor model is used to evaluate different HONO formation mechanisms that have been used previously in indoor air quality models. In order to avoid biases in the results due to the uncertainty in rate constants, those parameters were adjusted to fit one representative day of the SURFin campaign. Then, the mechanisms have been tested with the optimized parameters against other experiments carried out during the SURFin campaign. Based on the observations and these findings, we propose a new mechanism incorporating sorption of NO2 onto surfaces with possible saturation of these surfaces. This mechanism is able to better reproduce the experimental profiles over a large range of conditions.

Synchrotron-based valence shell photoionization of CH radical.

We report the first experimental observations of X(+) (1)Σ(+)←X (2)Π and a(+) (3)Π←X (2)Π single-photon ionization transitions of the CH radical performed on the DESIRS beamline at the SOLEIL synchrotron facility. The radical was produced by successive hydrogen-atom abstractions on methane by fluorine atoms in a continuous microwave discharge flow tube. Mass-selected ion yields and photoelectron spectra were recorded as a function of photon energy using a double imaging photoelectron/photoion coincidence spectrometer. The ion yield appears to be strongly affected by vibrational and electronic autoionizations, which allow the observation of high Rydberg states of the neutral species. The photoelectron spectra enable the first direct determinations of the adiabatic ionization potential and the energy of the first triplet state of the cation with respect to its singlet ground state. This work also brings valuable information on the complex electronic structure of the CH radical and its cation and adds new observations to complement our understanding of Rydberg states and autoionization processes.

Critical evaluation of the potential energy surface of the CH3 + HO2 reaction system.

The CH3 + HO2 reaction system was studied theoretically by a newly developed, HEAT345-(Q) method based CHEAT1 protocol and includes the combined singlet and triplet potential energy surfaces. The main simplification is based on the CCSDT(Q)/cc-pVDZ calculation which is computationally inexpensive. Despite the economic and black-box treatment of higher excitations, the results are within 0.6 kcal/mol of the highly accurate literature values. Furthermore, the CHEAT1 surpassed the popular standard composite methods such as CBS-4M, CBS-QB3, CBS-APNO, G2, G3, G3MP2B3, G4, W1U, and W1BD mainly due to their poor performance in characterizing transition states (TS). For TS structures, various standard DFT and MP2 method have also been tested against the resulting CCSD/cc-pVTZ geometry of our protocol. A fairly good agreement was only found in the cases of the B2PLYP and BHandHLYP functionals, which were able to reproduce the structures of all TS studied within a maximum absolute deviation of 7%. The complex reaction mechanism was extended by three new low lying reaction channels. These are indirect water elimination from CH3OOH resulted formaldehyde, H2 elimination yielded methylene peroxide, and methanol and reactive triplet oxygen were formed via H-shift in the third channel. CHEAT1 protocol based on HEAT345-(Q) method is a robust, general, and cheap alternative for high accurate kinetic calculations.

Photolysis of CF3CH2CHO in the presence of O2 at 248 and 266 nm: quantum yields, products, and mechanism.

Three different detection techniques, coupled to pulsed laser photolysis (PLP), have been employed to determine the quantum yields of CF3CH2CHO at 248 and 266 nm: CF3CH2CHO + hν → CF3CH2 + HCO (R1a), CF3CH2CHO + hν → CF3CH3 + CO (R1b), and CF3CH2CHO + hν → CF3CH2O + H (R1c). (a) In the presence of air, Fourier transform infrared (FTIR) spectroscopy was employed at a total pressure of 760 Torr to monitor and quantify the loss of CF3CH2CHO at both wavelengths as well as the build-up of formed products (CO, CF3CH3, CF3CHO, and CF3CH2OH) after various laser pulses. Cyclohexane was added as OH-scavenger in most experiments. CF3CH3 was observed and quantified at both wavelengths, confirming that channel R1b is occurring. Small amounts of HCOOH and COF2 were also detected. (b) Time-resolved cw-cavity ring down spectroscopy (cw-CRDS) at 40 Torr He coupled to photolysis at 248 nm was employed for the detection of HO2 radicals. Varying the O2 concentration allows distinguishing the origin of the HO2 radicals from either R1a or R1c. OH radicals were simultaneously detected by laser-induced fluorescence. (c) Time-resolved tunable diode laser absorption spectroscopy (TDLAS) at 30 Torr N2 coupled to photolysis at 266 nm was employed for the determination of the quantum yields of CO. By varying the O2 concentration, a distinction can be achieved between the yields of prompt CO R1b or decomposition of highly excited CF3CH2CO from R1c and HCO radicals R1a. Channel R1a has been identified as the major reaction path. The overall quantum yield, Φλ(CF3CH2CHO), at 248 nm was found as Φ248nm = (0.76 ± 0.14) and (0.73 ± 0.20) from cw-CRDS and FTIR experiments, respectively. At 266 nm, the overall quantum yield was found as Φ266nm = (0.55 ± 0.10) and (0.47 ± 0.10) from TDLAS and FTIR experiments, respectively.

Note: a laser-flash photolysis and laser-induced fluorescence detection technique for measuring total HO2 reactivity in ambient air.

A novel instrument for measuring total HO2 reactivity in the troposphere was successfully developed using a laser-flash photolysis and laser-induced fluorescence detection technique. Validation and testing were conducted through kinetic measurements of the reaction of HO2 radicals with NO2, and the results were found to be in good agreement with recent recommended values. The limit of detection (LOD) for HO2 loss rate measurement is achieved to be 0.024 s(-1) (3σ) with 60 times decay integrations. An observation of ambient air was carried out in a suburb of Tokyo to test the practical use of the developed instrument and un-expected rapid HO2 loss rate has been observed.

Atmospheric and kinetic studies of OH and HO2 by the FAGE technique.

A new FAGE setup has recently been built at the University of Lille, France. It permits the quantification of OH and HO2 in the atmosphere with a detection limit of 3 x 105 molecules/(cm3 x min) for OH and 1 x 10(6) molecules/(cm3 x min) for HO2. Its coupling to a photolysis cell enables the measurement of the total reactivity of the hydroxyl radical in ambient air and kinetic studies in laboratory. Two configurations have been considered: one with the photolysis cell at 90 degrees to the FAGE nozzle, the other on line with the FAGE nozzle. The two configurations have been tested and validated by measuring the well known rate constants of OH with CH4, C3H8 and CO. The advantages and drawbacks of each configuration have been evaluated. The "on line" configuration limits losses and permits measurements over a larger reactivity range but is affected by OH formation from the laser beam striking the FAGE nozzle, thus limiting the ability to carry out energy dependence studies which can, in contrast, be successfully performed in the 90 degrees configuration.

First direct detection of HONO in the reaction of methylnitrite (CH3ONO) with OH radicals.

We report on the development of a new environmental simulation chamber coupled with an in situ continuous wave cavity ring-down spectrometer operating in the near IR (∼1.5 µm). The first application reported in this paper dealt with the chemical mechanism of UV photolysis of methyl nitrite (CH(3)ONO) in air. HONO has been detected for the first time and shown to be formed in the OH + CH(3)ONO reaction. A dense spectrum of cis-HONO absorption lines has been observed near 1.5 µm, in agreement with a previous study (Guilmot et al.). CH(2)O has been measured as primary product with good sensitivity and time resolution. In contrast to Zhao et al., we did not detect any NO(2) absorption features in this wavelength range. Calibration experiments provided very low NO(2) absorption cross sections in this region (∼10(-25) cm(2)), leading to conclude that NO(2) cannot be observed in this wavelength range in the presence of equal amounts of CH(2)O.

In vivo therapy of malignant melanoma by means of antagonists of alphav integrins.

Integrin alphavbeta3 (vitronectin receptor) has been implicated in human malignant melanoma progression and angiogenesis as a receptor that provides survival signals. However, little is known about the therapeutic potential of antagonists of alphavbeta3. In this report, we characterize the activities of 2 antagonists of alphavbeta3 integrins: a human specific monoclonal antibody (MAb), 17E6, and a cyclic RGD peptide that blocked cell adhesion and induced detachment of previously substrate-attached cells in vitro. In vivo, alphavbeta3 antagonists behaved as anti-tumor drugs in a dose- and time-dependent manner. Moreover, different therapeutic treatments proved to be effective even in the therapy of established macroscopic tumor masses, thus supporting the use of these antagonists in clinical therapy. Using a panel of 6 human melanomas and 5 carcinomas, MAb 17E6 efficiently blocked the in vivo tumor growth of melanomas expressing alphavbeta3 as xenografts but did not affect the alphavbeta3-negative (although alphav integrin-positive) tumors. This demonstrated that alphavbeta3 is a pivotal integrin for the growth of human melanomas. Furthermore, since MAb 17E6 does not recognize murine alphavbeta3, the effect is due only to the direct anti-tumor activity and not to the well-known anti-angiogenic activity of alphav-integrin antagonists. Taken together, our results confirm the essential role of alphavbeta3 integrin in the growth of human malignant melanoma in vivo and provide strong evidence of the therapeutic potential of alphav-integrin antagonists for the treatment of such tumors.

Linkage of azurophil granule secretion in neutrophils to chloride ion transport and endosomal transcytosis.

Neutrophils contain at least two types of secretory granules. The present work links the secretion of the (lysosomal type) azurophil granules, but not that of specific granules, to endosomal transport mechanisms. (a) Selective stimulation of azurophil granule secretion by the Na-ionophore Monensin, or nonselective stimulation by FMLP after cytochalasin B pretreatment elicited marked pinocytic activity in parallel with azurophil granule release, whereas FMLP alone, selective for specific granules, elicited little fluid pinocytosis. (b) Pinosomes thus formed fused with azurophil granules, suggesting that exocytosis of azurophil granules might occur via endosomal organelles. This hypothesis was tested by determining the effect on the endosomal pathway(s) of two treatments that selectively prevent the release of azurophil granule contents without interfering with specific granule secretion, namely replacement of Cl- with gluconate- or the addition of zinc. Replacement of Cl- was found to impair the pinocytosis process itself, whereas ZnSO4 appeared to prevent the fusion between endosomes and azurophil granules. These data support the concept that the (lysosomal type) azurophil granules, but not the specific granules, are secreted through the endosomal pathway.

Selective secretion of azurophil granule contents induced by monovalent cation ionophores in human neutrophils: evidence for direct ionophore effects on the granule membrane.

The study of factors contributing to secretion of neutrophil azurophil granules has previously been complicated by the inability to induce their release without concomitant exocytosis of specific granules. This publication describes the action of the first two agents, the Na-ionophore monensin and the K-ionophore nigericin which elicited only secretion of azurophil granules. Secretion depended on H+/alkali ion antiport by the ionophores since it was abolished in Na(+)- and K(+)-poor choline buffer. The secretagogue effects of both ionophores did not correlate with changes either in cytoplasmic pH or in transmembrane potential and were not associated with Ca-transients, but were closely associated with azurophil granule alkalinization suggesting that the secretory event resulted from alkali ion/H+ antiport at the granule membrane. Addition of zinc inhibited azurophil (but not specific) granule secretion in response to monensin, CB/FMLP, and zymosan, indicating that secretion induced by these agents shares a common step(s).

Bacterial lipopolysaccharide enhances chemoattractant-induced elastase secretion by human neutrophils.

Bacterial lipopolysaccharide (LPS) has previously been shown to enhance a number of chemoattractant-induced responses by human neutrophils. The possible role of elastase, a neutral protease with broad substrate specificity, in neutrophil-mediated vascular injury of a variety of diseases prompted us to examine a) whether or not LPS enhances the direct chemoattractant-induced secretion of elastase, b) the quantitative requirements of LPS and chemotactic factors, and c) some structural requirements of LPS for this effect. Our results show that LPS at 10 ng/ml and above, enhanced formyl-methionyl-leucyl-phenylalanine-induced neutrophil secretion of elastase, as well as secretion of myeloperoxidase and vitamin B12-binding protein. This effect was independent of cytochalasins or surface stimulation, and thus may occur during chemotactic factor stimulation in vivo. LPS also enhanced neutrophil secretory responses to the complement fragments C5a, C5a des arg, and, to a lesser degree, to leukotriene B4 and platelet-activating factor. This enhancement effect appeared to require the presence of the lipid A moiety and/or parts of the core polysaccharide but not the O-antigen portion of the LPS molecule. Our findings identify a possible LPS-dependent mechanism of neutrophil elastase-mediated tissue injury in Gram-negative infections.

Ultrastructural cytochemistry of complex carbohydrates in developing feline neutrophils.

The feline species provides animal models for at least six congenital lysosomal disorders. Since knowledge of normal feline neutrophils is a prerequisite for studies of their abnormalities, the present report describes the morphology and cytochemistry of normal feline neutrophils and compares the subcellular distribution of sulfate- and vicinal-glycol-containing complex carbohydrates to that of peroxidase and acid phosphatase. Immature feline primary granules, formed in promyelocytes, were stained for peroxidase, acid phosphatase, sulfate, and vicinal glycols. During maturation, primary granules retained strong staining for peroxidase, but staining for vicinal glycols decreased, and acid phosphatase and sulfate reactivity was lost. Secondary granules formed in myelocytes lacked peroxidase, acid phosphatase, and sulfate staining, but stained intensely for vicinal-glycol-containing complex carbohydrates. No analogues of tertiary granules previously described in rabbits and humans were demonstrated in feline neutrophils. However, a new sequential staining technique for peroxidase and vicinal glycols has suggested the formation in myelocytes and late neutrophils of a third granule type that contained peroxidase, acid phosphatase, and vicinal glycols but lacked sulfate staining. Thus, the staining characteristics of primary and secondary granules in cats closely resembled those in humans and rabbits. The third (late-forming) type of granule has not previously been described in other species.

Morphometry of feline neutrophil granule genesis.

During neutrophil granule genesis, the formation of primary granules is generally thought to be limited to the promyelocyte stage; whereas synthesis of secondary granules is thought to occur only at the myelocyte stage. This hypothesis was tested morphometrically in feline neutrophils that are known to contain both granule types. Marrow specimens obtained from six cats were stained with peroxidase for identification of neutrophil primary granules and counterstained with periodic acid-thiocarbohydrazide-silver proteinate (PA-TCH-SP) for identification of secondary granules. By regression analysis using arithmetic models, numbers of cytoplasmic granules in 311 cells were correlated with the degree of nuclear chromatin condensation, which was shown to be an adequate parameter for cell maturation. Promyelocytes and myelocytes had similar mean numbers of peroxidase-positive granules per unit area. A significant increase (p less than or equal to 0.0001) in the numbers of peroxidase-positive granules was noted between the metamyelocyte and the mature neutrophil stage, despite the lack of peroxidase activity in endoplasmic reticulum and Golgi lamellae. By contrast, a significant increase of peroxidase-negative granules between the metamyelocyte and the mature neutrophil stage was not clearly established with these methods. The increase in peroxidase-positive granules may indicate continued production of peroxidase-containing granules and/or redistribution of peroxidase among lysosomal organelles in late feline neutrophils.

Ultrastructural morphology and cytochemistry of iron-deficient polymorphonuclear leukocytes.

Previous studies have documented decreased activities of certain enzymes and altered function in polymorphonuclear leukocytes (PMN) during iron deficiency. The present study was undertaken to determine if the enzymatic abnormalities could be correlated with morphologic or quantitative change in PMN granules. Ultrastructural examination of primary and secondary granules and assessment of the secondary granule components alkaline phosphatase and vicinal glycol-containing glycoconjugates was performed in rabbit bone marrow, peripheral blood, and peritoneal heterophils. In addition, biochemical quantifications of the secondary granule component alkaline phosphatase and the primary granule marker beta-glucuronidase were performed. The results confirmed that a marked, significant decrease in alkaline phosphatase occurs in iron-deficient animals; however, no biochemical decrease in beta-glucuronidase activity was observed. Ultrastructurally, PMN secondary granules of iron-deficient rabbits tended to be more numerous than in controls when examined with morphometric and glycoconjugate staining methods, but lacked staining in alkaline phosphatase preparations. These results demonstrate that iron-deficient rabbits produce normal to increased quantities of primary and secondary granules, despite a uniform deficiency of alkaline phosphatase, a secondary granule marker.

Prednisone-induced morphologic and chemical changes in the liver of dogs.

Glucocorticoid treatment in dogs is known to cause hepatocellular swelling due to accumulation of cytoplasmic compounds which variably have been identified histochemically as fat, glycogen, or water. In the present study changes in dog liver, after treatment for 15 days with two different doses of oral or intramuscular prednisone, were examined using histological, histochemical, and ultrastructural techniques as well as quantitative chemical analysis. Thirty mongrel dogs were divided into two control groups and three treatment groups of six dogs each. Dogs which received prednisone orally at 1.2 mg/kg body weight/day, or 4 mg/kg body weight/day, respectively, or received intramuscular prednisone injections of 4 mg/kg body weight/day had hepatomegaly due primarily to hepatocellular accumulation of glycogen. Compared to controls, no changes in the hepatic water concentration were observed, whereas the relative amounts of liver fat were decreased slightly and those of protein were decreased markedly. Hepatocellular glycogen could be demonstrated histochemically in tissues fixed in absolute alcohol, but not in tissues treated with aqueous fixative, such as 10% buffered formalin or Bouin's solution. Glycogen deposition occurred predominantly in the midzone of hepatic acini. Affected hepatocytes varied in size and shape. The most severely affected cells were enlarged five to ten fold with glycogen occupying most of the cytoplasmic space restricting the mitochondria, endoplasmic reticulum, and other organelles to a narrow zone around the cell periphery and the nucleus. It was concluded that treatment with prednisone causes hepatomegaly due to glycogenosis in the dog.

Prednisone treatment alters the serum amylase and lipase activities in normal dogs without causing pancreatitis.

In order to test the hypothesis that treatment with glucocorticoids causes pancreatitis in dogs, 18 mongrel dogs were divided into three groups of six individuals, each group receiving prednisone at different doses orally or intramuscularly for two weeks. Two groups consisting of six dogs each served as controls. Treatment for two weeks with oral prednisone at 1.2 mg/kg body weight or at 4 mg/kg body weight daily decreased the serum amylase activities, but increased the serum lipase activities. Postmortem examinations revealed microscopic evidence of mild pancreatitis in only one dog given prednisone, that clinically appeared normal. It was concluded that daily doses of 4 mg prednisone/kg body weight or less given orally or intramuscularly for two weeks do not cause pancreatitis in dogs.

Vicinal glycol-staining identifies secondary granules in human normal and Chédiak-Higashi neutrophils.

Neutrophil secondary granules contain large amounts of glycoprotein. We evaluated periodate-thiocarbohydrazide-silver proteinate (PA-TCH-SP) staining of these granules after alpha-amylase digestion to assess their content of vicinal glycol-containing glycoconjugates and the usefulness of this stain as a positive stain for secondary granules. Using this method, early stages of secondary granule genesis were observed prior to completion of primary granule genesis in myelocytes. Immature secondary granules appeared round to ovoid, but irregular in outline and demonstrated strong staining of the limiting membrane and matrix material. In mature granules, matrix staining was unaltered; however, membrane staining was decreased. Some immature primary granules in promyelocytes demonstrated strong PA-TCH-SP reactivity which was masked in mature primary granules of band and segmented neutrophils. The Golgi apparatus showed progressively increasing PA-TCH-SP reactivity toward its mature surface which was often convex in promyelocytes and myelocytes and concave in segmented neutrophils. The Chédiak-Higashi secondary granules were cytochemically and morphologically similar to those of normal individuals and were not statistically decreased in number when compared to controls. They were only rarely observed contacting or fusing with giant granules which had consumed all primary granules leaving an easily detected population of secondary granules. Thus the alpha-amylase-PA-TCH-SP method demonstrates a large amount of unmasked vicinal glycol-containing glycoconjugates in neutrophil secondary granules, which allows their differentiation from primary granules.