Quantification of Carboxylic and Carbonyl Functional Groups in Organic Aerosol Infrared Absorbance Spectra

Atmospheric aerosols are one of the least understood components of the climate system and incur adverse health effects on susceptible populations. Organic aerosols can make up as much as 80% of atmospheric aerosols (Lim and Turpin 2002 Lim, H. J. and Turpin, B. J. 2002. Origins of Primary and Secondary Organic Aerosol in Atlanta: Results’ of Time-Resolved Measurements During the Atlanta supersite experiment. Environ. Sci. Technol., 36: 4489–4496. 10.1021/es0206487[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]), and so its quantification and characterization plays an important role in reducing our uncertainty with regards to aerosol impacts on health and climate. As the number of organic molecules in the atmosphere are diverse in number (Hamilton et al. 2004 Hamilton, J. F., Webb, P. J., Lewis, A. C., Hopkins, J. R., Smith, S. and Davy, P. 2004. Partially Oxidised Organic Components in Urban Aerosol using GCXGC-TOF/MS. Atmos. Chem. Phys., 4: 1279–1290. [Crossref], [Web of Science ®] , [Google Scholar]), we advance a functional group representation of organic molecules as measured by Fourier transform infrared spectroscopy (FTIR) to characterize the chemical composition of particle samples. This study describes and evaluates the algorithm introduced by Russell et al. (2009 Russell, L. M., Takahama, S., Liu, S., Hawkins, L. N., Covert, D. S.Quinn, P. K. 2009. Oxygenated Fraction and Mass of Organic Aerosol from Direct Emission and Atmospheric Processing Measured on the R/V Ronald Brown During TEXAQS/GoMACCS 2006. J. Geophys. Res.-Atmos., 114: D00F05 10.1029/2008JD011275[Crossref], [Web of Science ®] , [Google Scholar]) for apportionment and quantification of oxygenated (carbonyl and hydroxyl) functional groups from infrared absorption spectra. Molar absorptivities for carbonyl and hydroxyl bonds in carboxylic groups are obtained for several dicarboxylic compounds, and applied to a multifunctional compound and mixture to demonstrate the applicability of this method for more complex samples. Furthermore, functional group abundances of two aldehydic compounds, 2-deoxy-d-ribose and glyceraldehyde, atomized from aqueous solution are in quantitative agreement with number of bonds predicted after transformation of these compounds into diols. The procedure for spectra interpretation and quantitative analysis is described through the context of an algorithm in which contributions of background and analyte absorption to the infrared spectrum are apportioned by the superposition of lineshapes constrained by laboratory measurements.

Copyright 2013 American Association for Aerosol Research     

Field Validation of the New Miniature Versatile Aerosol Concentration Enrichment System (mVACES)

Recently a new compact aerosol concentration enrichment system was developed at the University of Southern California, specifically intended to provide particle-laden air at flow rates and pressures suitable for interfacing with on-line continuous aerosol instrumentation for chemical analysis such as mass spectrometers. The re-design and engineering of the miniature Versatile Aerosol Concentration Enrichment System (mVACES) and primarily laboratory-based validation of the individual components and overall system has been previously reported (Geller et al. 2005 Geller, M. D., Biswas, S., Fine, P. M. and Sioutas, C. 2005. A New Compact Aerosol Concentrator for Use in Conjunction with Low Flow-Rate Continuous Aerosol Instrumentation. J. Aerosol Sci., 36: 1006–1022. [CSA][CROSSREF][Crossref], [Web of Science ®] , [Google Scholar]). From September to December 2005, a field performance validation study of the mVACES was conducted in Los Angeles, California at a mixed urban site influenced by both freeway traffic and construction. A variety of continuous and semi-continuous physical and chemical composition measurements were performed to assess the performance of the mVACES compared to accepted methods for validation. Near-ideal performance for aerosol concentration enhancement by the mVACES was observed for mass and number distribution with minimal evidence for distortion of the size distribution. Similarly, near-ideal concentration enhancement factors were observed for both inorganic and organic species suggesting that the mVACES works equally well across the range of externally mixed urban aerosol. The data suggest that aerosol concentration enhancements up to an ideal factor of 20 in a delivered flow on the order of 1.5 liters min^–1 are readily achievable in an urban environment for the ambient conditions studied.     

Theory of Multi-Nozzle Impactor Stages and the Interpretation of Stage Mensuration Data

We describe a general theory of multi-nozzle cascade impactor stages and show how testers of inhaled drug products, such as metered-dose or dry-powder inhalers, can decide, solely from the stage nozzle dimensions, whether any used impactor is satisfactorily operating within its expected aerodynamic performance range. We first account for the realistic shape of particle collection efficiency curves and show that the effective diameter, described by Roberts and Romay (2005) Roberts D. L.Romay F. J.Relationship of Stage Mensuration Data to the Performance of New and Used Cascade ImpactorsJ. Aerosol Med2005184396–413[Crossref], [PubMed] , [Google Scholar], is sufficiently accurate as the primary indication of the aerodynamic performance.

To ensure that a used impactor is performing in the same aerodynamic range allowed for new impactors, one must also satisfy the other, more secondary factors of cascade impaction aerodynamics, most notably the distance to the collection surface relative to the nozzle diameter. We show what this constraint means in practice for used Next Generation Impactors (NGIs; Marple et al. 2003a Marple V. A.Roberts D. L.Romay F. J.Miller N. C.Truman K. G.Van Oort M.Olsson B.Holroyd M. J.Mitchell J. P.Hochrainer D.Next Generation Pharmaceutical Impactor, Part I: DesignJ. Aerosol Med2003a16283–299[Crossref], [PubMed] , [Google Scholar], b Marple V. A.Olson B. A.Santhanakrishnan K.Mitchell J. P.Murray S. C.Hudson-Curtis B. L.Next Generation Pharmaceutical Impactor—Part II: Archival CalibrationJ. Aerosol Med2003b16[Crossref], [PubMed] , [Google Scholar]; 2004 Marple V. A.Olson B. A.Santhanakrishnan K.Roberts D. L.Mitchell J. P.Hudson-Curtis B. L.Next Generation Pharmaceutical Impactor: A New Impactor for Pharmaceutical Inhaler Testing. Part III. Extension of Archival Calibration to 15 L/minJ. Aerosol Med200417335–343[Crossref], [PubMed] , [Google Scholar]), and show that partially occluded nozzles are the most likely nozzles to fail this test.

Applying this principle that used impactors should perform in the same aerodynamic range as new impactors, we derive constraints on the nozzle diameters of any used NGI (Table 6, main text). We can partially apply this principle to other common impactors used for inhaler testing, such as the Andersen and the Marple-Miller, but are hindered by the absence of a published acceptable range for the distance to the impaction collection surface and by the limited published information on the shape of their stage collection efficiency curves.     

2-Aminothiophenol as building blocks for novel heterocycles

Herein, the chemistry of 2-aminothiophenol has been utilized in the synthesis of several interesting products such as oxidation and reaction with π-deficient compounds. On oxidizing 2-aminothiophenol by sodium hypochlorite furnishes 2-[(2-aminophenyl)-dithio]aniline. Treatment of the obtained product with acetyl chloride affords N-(2-[2-(acetylamino)-phenyl-disulphanyl)-phenyl]acetamide. Reaction of the former acetamide with POCl₃ yields 2-methyl-1,3-benzothiazole. Moreover, (3,4,8,9)-dibenzo-2,7-dithia-5,10-diaza4 Field, L. and Lawson, J. E. 1958. J. Am. Chem. Soc., 80: 838[Crossref], [Web of Science ®] , [Google Scholar] 4 Field, L. and Lawson, J. E. 1958. J. Am. Chem. Soc., 80: 838[Crossref], [Web of Science ®] , [Google Scholar] 4 Field, L. and Lawson, J. E. 1958. J. Am. Chem. Soc., 80: 838[Crossref], [Web of Science ®] , [Google Scholar]propellane is formed on reacting the target 2-aminothiophenol with cyclohexane-1,2-dione, whereas its reactions with electron π-acceptors such as 2,3-dichloro-1,4-naphthoquinone (DCHNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetra-cyanoethylene (TCNE), and 1-(dicyanomethylen)acenaphthen-2-one yield various heterocycles.     

Development of an Aerosol Dynamics Model for Dry Deposition Process Using the Moment Method

An aerosol dynamics model for dry deposition process is developed based on the moment method. Since it is hard to fully apply the moment method to the widely used dry deposition velocity expressions based on the resistance theory, the dry deposition velocity expression by Raupach et al. (2001) Raupach, M. R., Briggs, P. R., Ahmad, N. and Edge, V. E. 2001. Endosulfan Tansport: II. Modeling airborne Dispersal and Deposition by Spray and Vapor. J. Environ. Qual., 30: 729–740. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar] is used. Detailed deposition mechanisms such as Brownian diffusion, gravitational settling, and impaction are considered in the expression. To verify the validity of the derived dynamic equation, aerosol dynamics for the dry deposition process is estimated with the expressions of Raupach et al. (2001) Raupach, M. R., Briggs, P. R., Ahmad, N. and Edge, V. E. 2001. Endosulfan Tansport: II. Modeling airborne Dispersal and Deposition by Spray and Vapor. J. Environ. Qual., 30: 729–740. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar], of Wesely (1989) Wesely, M. L. 1989. Parameterizations of Surface Resistance to Gaseous Dry Deposition in Regional-Scale, Numerical Models. Atmos. Environ., 23: 1293–1304. [Crossref], [Web of Science ®] , [Google Scholar] modified for particles (Seinfeld and Pandis 1998 Seinfeld, J. H. and Pandis, S. N. 1998. Atmospheric Chemistry and Physics, 958–996. New York, , USA: Wiley.  [Google Scholar]), in CMAQ, and with constant value used in RAINS-ASIA. Those expressions give different dynamics. Generally, the result for this study is between the result of modified Wesely's expression and CMAQ. When using the modified Wesely's expression with the number of sections being equal or smaller than 10, the resultant size distribution does not give the peak shape accurately.     

Fibrous Filter Efficiency and Pressure Drop in the Viscous-Inertial Transition Flow Regime

Fibrous filter pressure drop and aerosol collection efficiency were measured at low air pressures (0.2–0.8 atm) and high face velocities (5–19 m/s) to give fiber Reynolds numbers lying in the viscous-inertial transition flow regime (1–15). In this regime, contemporary filtration theory based on Kuwabara's viscous flow through an ensemble of fibers underpredicts single fiber impaction by several orders of magnitude. Streamline curvature increases substantially as air stream inertial forces become significant. Dimensionless pressure drop measurements followed the viscous-inertial theory of Robinson and Franklin (1972 Robinson, M. and Franklin, H. 1972. The Pressure Drop of a Fibrous Filter at Reduced Ambient Pressures. J. Aerosol Sci., 3: 413–427. [Crossref] , [Google Scholar]) rather than Darcy's linear pressure–velocity relationship. Sodium chloride and iron nano-agglomerate aerosols were tested to provide a comparison between particles of dissimilar densities and shape factors. Total filter efficiency collapsed when plotted against the particle Stokes number and fiber Reynolds number. Efficiencies were then modeled with an impactor type equation where the cutpoint Stokes number and a steepness parameter described data well in the sharply increasing portion of the curve (20%–80% efficiency). A minimum in collection efficiency was observed at small Stokes numbers and attributed to interception and diffusive effects. The cutpoint Stokes number was a linearly decreasing function of fiber Reynolds number. Single fiber efficiencies were calculated from total filter efficiencies and compared to contemporary viscous flow impaction theory (Stechkina et al. 1969 Stechkina, I. B., Kirsch, A. A. and Fuchs, N. A. 1969. Studies on Fibrous Aerosol Filters—IV. Calculation of Aerosol Deposition in Model Filters in the Range of Maximum Penetration. Ann. Occup. Hyg., 12: 1–8. [Crossref], [PubMed] , [Google Scholar]), and numerical simulations of single fiber efficiencies from the literature. Existing theories underpredicted measured single fiber efficiencies, although comparison is problematic. The assumption of uniform flow conditions for each successive layer of fibers is questionable; thus, the common exponential relationship between single fiber efficiency and total filter efficiency may not be appropriate in this regime.

Copyright 2012 American Association for Aerosol Research     

Numerical Modeling of Nanoparticle Collection Efficiency of Single-Stage Wire-in-Plate Electrostatic Precipitators

The numerical models for predicting the collection efficiency of particles in the size range of 0.3 ～ 10.0 μm in electrostatic precipitators (ESPs) have been well developed. However, for nanoparticles, or particles with the diameter below 100 nm, the existing models can't predict the collection efficiency very well because the electric field and ion concentration distribution were not simulated, or charging models were not adopted appropriately to calculate particle charges. In this study, a 2-D numerical model was developed to predict the nanoparticle collection efficiency in single-stage wire-in-plate ESPs. Laminar flow field was solved by using the Semi-Implicit Method for Pressure-Linked Equation (SIMPLER Method), while electric field strength and ion concentration distribution were solved based on Poisson and diffusion-convection equations, respectively. The charged particle concentration distribution and the particle collection efficiency were then calculated based on the convection-diffusion equation with particle charging calculated by Fuchs diffusion charging theory. The simulated collection efficiencies of 6–100 nm nanoparticles were compared with the experimental data of Huang and Chen (2002 Huang, S. H. and Chen, C. C. 2002. Ultrafine Aerosol Penetration through Electrostatic Precipitators.. Environ. Sci. Technol., 36: 4625–4632. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar]) for a wire-in-plate dry ESP (aerosol flow rate: 100 L/min, applied voltage: ?15.5 ～ –21.5 kV). Good agreement was obtained. The simulated particle collection efficiencies were further shown to agree with the experimental data obtained in the study for a wire-in-plate wet ESP (Lin et al. 2010 Lin, G. Y., Tsai, C. J., Chen, S. C., Tzu, M. C. and Li, S. N. 2010. An Efficient Single-Stage Wet Electrostatic Precipitator for Fine and Nanosized Particle Control.. Aerosol Sci. Technol, 44: 38–45. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]) (aerosol flow rate: 5 L/min, applied voltage: +3.6 ～+4.3 kV) using monodisperse NaCl particles of 10 and 50 nm in diameter. It is expected that the present model can be used to facilitate the design of ESPs for nanoparticle control and electrostatic nanoparticle samplers.     

Methodology for Performance Evaluation of Dust Control Systems with an Application to Electrostatic Precipitators

A general methodology is presented that enables rigorous estimation of the total collection efficiency and the size distribution of particles penetrating dust control systems. This methodology assumes lognormal inlet particle-size distributions and can be used with fractional efficiency formulations that predict, under such conditions, lognormal outlet particle-size distributions. Multimodal inlet particle distributions can be accommodated additively. This methodology is applied to Electrostatic Precipitator Systems (ESPs), with the Nobrega et al. (2004) Nobrega, S. W., Falaguasta, M. C. R. and Coury, J. R. 2004. A Study of a Wire-Plate Electrostatic Precipitator Operating in the Removal of Polydispersed Particles. Braz. J. Chem. Eng., 21(2): 275–284. [Crossref], [Web of Science ®] , [Google Scholar] model selected for predicting their fractional efficiencies. For ease of use, a graphical solution has been developed for the Nobrega et al. fractional efficiency relations, but its availability is not a prerequisite for the application of the general methodology. For the latter, the fractional efficiencies corresponding to three particle diameters need to be estimated and this can be done either graphically or numerically using the model of Nobrega et al. or any other fractional efficiency formulation of interest.

Fine particles emerge as the most important pollutant worldwide in terms of human health, creating thus the need for credible particle size-specific inventories. In line with the above, a generic and rigorous method, capable of producing size-specific emission estimates from uncontrolled and controlled sources, has been developed (Economopoulou and Economopoulos 2001 Economopoulou, A. A. and Economopoulos, A. P. 2001. Method for Estimating Size-Specific Particulate Emission Inventories. J. Environ. Eng., ASCE, 127: 1139–1148. [Crossref], [Web of Science ®] , [Google Scholar]). For controlled sources, this method relies on the development of easy to use models that predict the total efficiency and the lognormal size distribution of particles penetrating the control systems used. Such models have already been developed for dry cyclone separators (Economopoulou and Economopoulos 2002a Economopoulou, A. A. and Economopoulos, A. P. 2002a. Rapid Performance Evaluation and Optimal Sizing of Dry Cyclone Separators. J. Environ. Eng., ASCE, 128: 275–285. [Crossref], [Web of Science ®] , [Google Scholar], 2002b Economopoulou, A. A. and Economopoulos, A. P. 2002b. Size Distribution of Particles Penetrating Dry Cyclone Separators. J. Environ. Eng., ASCE, 128: 919–928. [Crossref], [Web of Science ®] , [Google Scholar]) and venturi scrubbers (Economopoulou and Harrison 2007a Economopoulou, A. A. and Harrison, R. M. 2007a. Graphical Analysis of the Performance of Venturi Scrubbers for Particle Abatement. Part I: Rapid Collection Efficiency Evaluation. Aerosol Sci. Technol., 41: 51–62. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar], 2007b Economopoulou, A. A. and Harrison, R. M. 2007b. Graphical Analysis of the Performance of Venturi Scrubbers for Particle Abatement. Part II: Size Distribution of Penetrating Particles. Aerosol Sci. Technol., 41: 63–74. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]). The present methodology extends the use of the inventory methodology to ESP-controlled sources and, in addition, it provides a generalized basis for covering other types of control systems with any fractional efficiency formulation considered appropriate.     

Vienna-Type DMA of High Resolution and High Flow Rate

A variant of the Vienna DMA (Winklmayr et al. 1991 Winklmayr, W., Reischl, G. P., Lindner, A. O. and Berner, A. 1991. A New Electromobility Spectrometer for the Measurement of Aerosol Size Distributions in the Size Range From 1 to 1000 nm. J. Aerosol Sci., 22: 289–296. [CROSSREF][CSA][Crossref], [Web of Science ®] , [Google Scholar]; Reischl et al. 1997 Reischl, G. P., Makela, J. M. and Necid, J. 1997. Performance of Vienna Type Differential Mobility Analyzer at 1.2–20 Nanometer. Aerosol Sci. Technol., 27: 651–672. [CSA][Taylor & Francis Online], [Web of Science ®] , [Google Scholar]) with inner and outer electrode radii of 25 and 33 mm, and a conventional trumpet inlet diameter of 97 mm has been tested. It incorporates a reduced pressure drop sheath gas exhaust system that enables reaching flow rates approaching 4000 L/min. Several new additional flow features are included to delay the transition to turbulent conditions. A cylindrical geometry with a DMA length L of 97 mm (distance between the aerosol inlet and outlet slits) is seen to keep the flow laminar up to the highest Reynolds number achieved, though showing slight signs of flow quality deterioration at about Re = 20,000. An equally long DMA with an inner electrode shaped as a 5° cone caped by a spherical dome remains stable up to the highest Reynolds number achieved. It is expected to continue this trend to considerably higher flow rates. Both these long configurations exhibit line widths close to the ideal Brownian diffusion limit, reaching FWHH of 4% for a particle mass diameter of 1 nm. A short DMA with an axial length L of 18 mm and an inner electrode shaped as a 5° cone caped by an ellipse of 3/2 aspect ratio remains also laminar at the highest speeds attained, and exhibits FWHH as small as 2.4%. It departs moderately from ideal behaviour at small flow rates, presumably due to its non-cylindrical geometry. More serious departures observed at high Reynolds numbers may perhaps be due to flow unsteadiness radiated into the working section by sound waves from the turbulent exhaust region. This is the first report of a DMA capable of excellent resolution at 1 nm, yet with a sufficiently wide and long working section to enable (in principle) covering the size range up to 100 nm.     

Design,synthesis, and preliminary evaluation as antimicrobial activity of novel spiro-1, 3-thiazolidine C-acyclic nucleoside analogs

Synthesis of a new class of 1, 3-thiazolidine nucleoside analogs is described. Reaction of 2-amino-2-deoxy-D-glucopyranose hydrochloride 2 with carbon disulfide yielded 5-hydroxy-4-(D-arabino-1, 2, 3, 4-tetrahydroxybutyl)-thiazolidin-2-thione 3, which on acetylation yielded 5-acetoxy-4-(D-arabino-1, 2, 3, 4-tetraacetoxy-butyl)-thiazolidin-2-thione 4. The acetylated sugar 4 reacted with hydrazonoyl chlorides 1a–f, affording the 5-acetoxy-4-(D-arabino-1, 2, 3, 4-tetraacetoxybutyl)-spiro-1 Chen, H., Fan, Y-H., Natarajan, A., Guo, Y., Iyasere, J., Harbinski, F., Luus, L., Christ, W., Aktas, H. and Halperin, J. A. 2004. Bioorg. Med. Chem. Lett., 14: 5401–5405. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar] 3 Nasr, M. N., Gineinah, M. M. and El-Bendary, E. R. 2003. Arch. Pharm., 336: 560–566. [Crossref] , [Google Scholar]thiazolidine-2,2′ -1 Chen, H., Fan, Y-H., Natarajan, A., Guo, Y., Iyasere, J., Harbinski, F., Luus, L., Christ, W., Aktas, H. and Halperin, J. A. 2004. Bioorg. Med. Chem. Lett., 14: 5401–5405. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar] 3 Nasr, M. N., Gineinah, M. M. and El-Bendary, E. R. 2003. Arch. Pharm., 336: 560–566. [Crossref] , [Google Scholar] 4 Belleau, B., Brasilli, L., Chan, L. and Zacheri, B. 1993. Cameron J. Bioorg. Med. Chem. Lett., 3: 1723–1928. [Crossref], [Web of Science ®] , [Google Scholar]thiadiazole derivatives 8a–f. The antibacterial activity of the novel 1, 3-thiazolidine-2,2′ -spiro- 1 Chen, H., Fan, Y-H., Natarajan, A., Guo, Y., Iyasere, J., Harbinski, F., Luus, L., Christ, W., Aktas, H. and Halperin, J. A. 2004. Bioorg. Med. Chem. Lett., 14: 5401–5405. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar] 3 Nasr, M. N., Gineinah, M. M. and El-Bendary, E. R. 2003. Arch. Pharm., 336: 560–566. [Crossref] , [Google Scholar] 4 Belleau, B., Brasilli, L., Chan, L. and Zacheri, B. 1993. Cameron J. Bioorg. Med. Chem. Lett., 3: 1723–1928. [Crossref], [Web of Science ®] , [Google Scholar]thiadiazole nucleoside analogs is highlighted. All compounds with free NH group in the thiazolidine series 8a–f showed significant biological activity against all the standard strains.     

SYNTHESES OF ADDUCTS OF ACTIVE METABOLITES OF CARCINOGENIC POLYCYCLIC AROMATIC HYDROCARBONS WITH 2′-DEOXYRIBONUCLEOSIDES

Syntheses are reported for: (1 Harvey, R. G. 1991. Polycyclic Aromatic Hydrocarbons: Chemistry and Carcinogenicity, Cambridge, , U.K.: Cambridge University Press.  [Google Scholar]) adducts of the quinone metabolites of benzo[a]pyrene (BPQ) and benz[a]anthracene (BAQ) with 2′-deoxyadenosine and 2′-deoxyguanosine; (2 Conney, A. H. 1982. Induction of Microsomal Enzymes by Foreign Chemicals and Carcinogenesis by Polycyclic Aromatic Hydrocarbons. Cancer Res., 42: 4875–4917. [PUBMED][INFOTRIEVE][CSA][PubMed], [Web of Science ®] , [Google Scholar]) ¹⁵ N-labelled analogs of these adducts (four or five nitrogen atoms ¹⁵ N-labelled); (3 Dipple, A. 1994. “Reactions of Polycyclic Aromatic Hydrocarbons with DNA”. In DNA Adducts: Identification and Biological Significance, Edited by: Hemminki, K., Dipple, A., Segerbäck, D., Kadulbar, F. F., Shuker, D. and Bartsch, H. pp. 107–129. IARC Scientific Publication No. 125.  [Google Scholar]) depurinated adducts of BPQ and BAQ with adenine or guanine covalently linked to the N7 or N9 positions of the purine bases; (4 Jeffrey, A. M., Weinstein, I. B., Jennette, K., Grzeskowiak, K., Nakanishi, K., Harvey, R. G., Autrup, H. and Harris, C. 1977. Structures of Benzo[a]pyrene-Nucleic Acid Adducts Formed in Human and Bovine Bronchial Explants. Nature (London)., 269: 348–350. [CSA][CROSSREF][Crossref], [PubMed], [Web of Science ®] , [Google Scholar]) ¹³ C-labelled derivatives of benzo[a]pyrene, BPQ, benzo[a]pyrene trans-7,8-dihydrodiol, and the benzo[a]pyrene anti-diol epoxide (with ¹³ C-atoms at the 5- and 11-positions); and (5 Jennette, K., Jeffrey, A. M., Blobstein, S. H., Beland, F. A., Harvey, R. G. and Weinstein, I. B. 1977. Characterization of Nucleoside Adducts from the in Vitro Reaction of Benzo[a]pyrene-7,8-dihydrodiol-9,10-oxide or Benzo[a]pyrene-4,5-oxide with Nucleic Acids. Biochemistry, 16: 932–938. [PUBMED][INFOTRIEVE][CSA][CROSSREF][Crossref], [PubMed], [Web of Science ®] , [Google Scholar]) depurinated adducts formed by reactions of the benzo[a]pyrene radical-cation at the C ⁸ -, N ⁷ -, and N ⁹ -positions of adenine and guanine.     

Numerical Evaluation of the Transfer Function of a Low Pressure DMA by Using the Langevin Dynamic Equation

The effect of Brownian diffusive particle trajectory of nanoparticles on the transfer function of the low pressure Differential Mobility Analyzer (LPDMA) was evaluated by a numerical simulation of the Langevin dynamic equation. The results of the simulation were compared with previously reported experimental results (Seto et al. 1997 Seto, T., Nakamoto, T., Okuyama, K., Adachi, M., Kuga, Y. and Takeuchi, K. 1997. Size Distribution Measurement of Nanometer-Sized Aerosol Particles using DMA under Low-Pressure Conditions. J. Aerosol Sci., 28: 193–206. [CROSSREF][Crossref] , [Google Scholar]; Seol et al. 2000 Seol, K. S., Tsutatani, Y., Camata, R. P., Yabumoto, J., Isomura, S., Okada, Y., Okuyama, K. and Takeuchi, K. 2000. A Differential Mobility Analyzer and A Faraday Cup Electrometer for Operation at 200-930 Pa Pressure. J. Aerosol Sci., 31: 1389–1395. [CSA][CROSSREF][Crossref] , [Google Scholar]) and Stolzenburg's transfer function (1988). As the operational pressure decreased, the peak and FWHM (full width of the transfer function at half of its maximum) values of transfer function, as calculated by numerical simulation, were increased, which was not evident from Stolzenburg's transfer function. In comparison with the experiments of Seto et al., discrepancies in the higher electrical mobility regime than from central mobility were found, which could be caused by the incomplete flow control of their LPDMA. However, the transfer function, as calculated by numerical simulation was in good agreement with experimental results reported by Seol et al., performed with the improved LPDMA at well-controlled operation conditions.     

Experimental Measurement and Numerical Study of Particle Deposition in Highly Idealized Mouth-Throat Models

Particle deposition in the human mouth-throat is an important factor in evaluating efficiency of drug delivered by inhalation devices, such as pMDIs or DPIs. Current USP standard impactor induction ports (which serve as an in vitro representative of the adult mouth-throat) underpredict in vivo mouth-throat deposition. However, preliminary experimental data in the prototype geometry of a highly idealized mouth-throat has indicated that it is a promising replacement for the USP mouth-throat (Zhang et al. 2004 Zhang, Y., Finlay, W. H. and Matida, E. A. 2004. Particle Deposition Measurements and Numerical Simulation in a Highly Idealized Mouth-Throat. J. Aerosol Sci., 35: 789–803. [CROSSREF][CSA][Crossref] , [Google Scholar]).

In this study, partial optimization design of the highly idealized mouth-throat was performed using computational fluid dynamics (CFD) simulations. The performance of six candidate highly idealized mouth-throat geometries, each with a straight tube inlet of inner diameter 17.3 mm, was evaluated experimentally by measuring monodisperse particle deposition efficiency. Gravimetry was used to determine particle deposition in these geometries. Monodisperse particles of di-2-ethylhexyl-sebecate (DEHS) oil with mass median diameters of 2.1–7.5 μm (GSD < 1.1) were used at two steady inhalation flow rates of 30 and 90 l/min. The results showed that, at the higher flow rate of 90 l/min, a mouth-throat with a bend region 8.5 mm in diameter and a curvature radius of 50 mm follows the in vivo average summarized by Stahlhofen et al. (1989) Stahlhofen, W., Rudolf, G. and James, A. C. 1989. Intercomparison of Experimental Regional Aerosol Deposition Data. J. Aerosol Med., 2(3): 285–308. [CSA][Crossref] , [Google Scholar] most closely. In contrast, at the lower flow rate of 30 l/min, the mouth-throat with a bend region 7.5 mm in diameter mimics the above in vivo curve but the in vivo-in vitro match is worse than for 90 l/min case. Enhanced particle deposition caused by a Reynolds number effect was observed in all geometries studied. Overall, an adequately designed highly idealized mouth-throat can largely reproduce in vivo mouth-throat deposition. For different flow rates, different key dimensions are required with the present highly idealized mouth-throats in order to adequately reproduce the in vivo average curve.     

Bipolar Diffusion Charging of Soot Aggregates

Experimental measurements of bipolar diffusion charging efficiency over the range of 15–400 nm are compared for oil droplets, flame generated soot aggregates, and diesel engine exhaust particulate matter to explore possible effects of particle morphology. Charging efficiency is recorded using a tandem differential mobility analyzer (DMA) approach; the first DMA selects a monodisperse aerosol and the second compares the flux of these particles through a neutralizer versus an identical blank housing. Electrostatic precipitation of mobility selected soot particles onto TEM grids provides comparative data on changes in soot particle morphology with mobility diameter. The measurements yield soot charging efficiencies that slightly, but systematically, differ from those of equal mobility diameter oil droplets. Single positive charging of soot climbs to ～ 10% higher than oil droplets at 50 nm and then decreases to 15% lower by 400 nm as the soot develops a progressively more fractal-like structure. Negative charging exhibits the same pattern, except the variations are +15% and –10%, respectively. These trends, as well as those for double and triple charging, fall intermediate between Fuchs predictions and the model of Wen et al. (1984a) Wen, H. Y., Reischl, G. P. and Kasper, G. 1984a. Bipolar Diffusion Charging of Fibrous Aerosol Particles—I. Charging Theory. J. Aerosol Sci., 15: 89–101. [Crossref], [Web of Science ®] , [Google Scholar] for charging of fibrous particles.     

Pyrido[2,3-d]pyrimidine-2,7-dithiol in heterocyclic synthesis: Synthesis and characterization of several new fused pyridopyrimidine heterocycles

Pyridine-2(1H)-thione 1 reacted with phenyl isothiocyanate to give pyrido[2,3-d]pyrimidine derivative 3. Compound 3 reacted with halogen containing compounds 4a–d and methyl iodide in dimethylformamide/potassium hydroxide solution at room temperature to give 2,7-bisalkylthiopyrido[2,3-b]pyrimidine derivatives 5a–d and 9, respectively. Compounds 5a–d could be cyclized into thienopyrido[2,3-d]pyrimidine derivatives 6a–d by boiling with ethanolic potassium hydroxide solution. Compound 6a reacted with acetic anhydride or formic acid and gave the corresponding pyrimido[4″,5″:4′,5′]thieno[3′,2′:5,6]pyrido[2,3-d]pyrimidine derivatives 8a,b. Compound 9 reacted with hydrazine hydrate to yield pyrazolo[4′,3′:5,6]pyrido[2,3-d]pyrimidine derivative 11 which could be reacted with nitrous acid and dimethylformamide-dimethylacetal (DMF-DMA) and gave the final isolable products corresponding to the pyrazolo[4′,3′:5,6]pyrido[2,3-d]tetrazolo-[5,1-b]pyrimidine and pyrimido[1″,2″:1′,5′]pyrazolo[4′,3′:5,6]pyrido[2,3-d]1 Abbas, A. A., Elneairy, M. A.A. and Mabkhot, Y. N. 2001. J. Chem. Res.(S), 4: 124[Crossref] , [Google Scholar] 2 Riad, B. Y., Negem, A. M., Abdou, S. E. and Daboun, H. A. 1987. Heterocycles, 26: 205[Crossref], [Web of Science ®] , [Google Scholar] 4 Gad-Elkareem, M. A.M. and Abedelhamid, A. O. 2004. Afinidad, 61(513): 427[Web of Science ®] , [Google Scholar]triazolo-[4,3-b] pyrimidine derivatives 13 and 17, respectively. Compound 11 also reacted with some β-dicarbonyl compounds such as acetylacetone (18) and ethyl acetoacetate (20) to yield the corresponding pyrimido[1″,2″:1′,5′]pyrazolo[4′,3′:5,6]pyrido[2,3-d]pyrimidine derivatives 19 and 21, respectively. Finally, compound 11 reacted with chloroacetyl chloride (22) to give the corresponding imidazo[1″′,2″′:1″,5″]pyrazolo[4″,3″:5′,6′]pyrido[3′,2′:5,6]pyrimido[2,1-c]1 Abbas, A. A., Elneairy, M. A.A. and Mabkhot, Y. N. 2001. J. Chem. Res.(S), 4: 124[Crossref] , [Google Scholar] 2 Riad, B. Y., Negem, A. M., Abdou, S. E. and Daboun, H. A. 1987. Heterocycles, 26: 205[Crossref], [Web of Science ®] , [Google Scholar] 4 Gad-Elkareem, M. A.M. and Abedelhamid, A. O. 2004. Afinidad, 61(513): 427[Web of Science ®] , [Google Scholar]triazine derivative 23.     

DYNAMICS OF IMINE AND ACETOPHENONE DERIVATIVES IN SOLUTION STUDIED BY ONE-DIMENSIONAL DIFFUSION-ORDERED NMR SPECTROSCOPY (DOSY)

This paper describes the usefulness of one-dimensional diffusion-ordered NMR spectroscopy (1D-DOSY) in investigating dynamics and interactions of molecules in solution as well as in analyzing the structure of molecules. We synthesized the three imines, N-benzylidene-4-methylbenzene-Sulfonamide (1 Kondo, K., Kazuta, K., Saitoh, A. and Murakami, Y. 2003. Heterocycles, 59: 97–100.  [Google Scholar]), N-(4-chloro-benzylidene)4-methyl-benzene-sulfonamide (2 Horibe, H., Kazuta, K., Kotoku, M., Kondo, K., Okuno, H., Murakami, Y. and Aoyama, T. 2003. Synlett, : 2047–2051. [Web of Science ®] , [Google Scholar]), and N- (4-methoxybenzylidene)-4-methyl-benzene sulfonamide (3 Horibe, H., Fukuda, Y., Kondo, K., Okuno, H., Murakami, Y. and Aoyama, T. 2004. Tetrahedron, 60: 10701–10709. [Crossref], [Web of Science ®] , [Google Scholar]), and acetophenone (4 Sakamoto, Y., Kondo, K., Tokunaga, M., Kazuta, K., Fujita, H., Murakami, Y. and Aoyama, T. 2004. Heterocycles, 63: 1345–1357. [Crossref], [Web of Science ®] , [Google Scholar]) and its three derivatives, 4-chloroacetophenone (5 Sakamoto, Y., Kondo, K., Onozato, M. and Aoyama, T. 2006. Polycycl. Aromat. Comp., 26: 59–68. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]), 4-nitro-acetophenone (6 Kondo, K., Kazuta, K., Fujita, H., Sakamoto, Y. and Murakami, Y. 2002. Tetrahedron, 58: 5209–5214. [Crossref], [Web of Science ®] , [Google Scholar]), and 4-methoxyaceto -phenone (7 Gostam, T., Morean, C., Jutean, A., Guichard, E. and Delsuc, M. A. 2004. Magn. Reson. Chem., 42: 496–499.  [Google Scholar]). 1D-DOSY was applied to a mixture of compounds (1 Kondo, K., Kazuta, K., Saitoh, A. and Murakami, Y. 2003. Heterocycles, 59: 97–100.  [Google Scholar]), (2 Horibe, H., Kazuta, K., Kotoku, M., Kondo, K., Okuno, H., Murakami, Y. and Aoyama, T. 2003. Synlett, : 2047–2051. [Web of Science ®] , [Google Scholar]), and (3 Horibe, H., Fukuda, Y., Kondo, K., Okuno, H., Murakami, Y. and Aoyama, T. 2004. Tetrahedron, 60: 10701–10709. [Crossref], [Web of Science ®] , [Google Scholar]) and to a mixture of compounds (4 Sakamoto, Y., Kondo, K., Tokunaga, M., Kazuta, K., Fujita, H., Murakami, Y. and Aoyama, T. 2004. Heterocycles, 63: 1345–1357. [Crossref], [Web of Science ®] , [Google Scholar]), (5 Sakamoto, Y., Kondo, K., Onozato, M. and Aoyama, T. 2006. Polycycl. Aromat. Comp., 26: 59–68. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]), (6 Kondo, K., Kazuta, K., Fujita, H., Sakamoto, Y. and Murakami, Y. 2002. Tetrahedron, 58: 5209–5214. [Crossref], [Web of Science ®] , [Google Scholar]), and (7 Gostam, T., Morean, C., Jutean, A., Guichard, E. and Delsuc, M. A. 2004. Magn. Reson. Chem., 42: 496–499.  [Google Scholar]). Although ¹ H NMR chemical shifts of the molecules in the mixtures resembled one another in the surrounding, we could distinguish signals of the individual molecules in each mixture on the basis of the NMR data and the values of the diffusion coefficient. Also, we could found the correlation of the measured diffusion coefficients and the calculated molecular volumes.     

Submicron Salt Particle Production in Bubble Bursting

Laboratory experiments of bubble bursting have shown that particle production increases with concentration for aqueous solutions of NaCl (Spiel 1998 Spiel, D. E. 1998. On the Births of Film Drops from Bubbles Bursting on Seawater Surfaces. J. Geophys. Res., 103: 24907–24918. [CROSSREF][CSA][Crossref], [Web of Science ®] , [Google Scholar]). Here, experiments with a submicron Na particle counter for three Na salts—NaCl, NaBr, and NaI—show comparable trends. Similarities in behavior are evident when the concentration for each salt is normalized to a threshold concentration (Lessard and Zieminski 1971 Lessard, R. R. and Zieminski, S. A. 1971. Bubble Coalescence and Gas Transfer in Aqueous Electrolytic Solutions. Indus. Engineer. Chem. Fund., 10: 260–269. [CROSSREF][CSA][Crossref] , [Google Scholar]). The number, size, and mass of particles produced increase with normalized solution concentration, suggesting that the same transition that controls ionic entropy and self-diffusion in aqueous solutions will govern the bubble bursting process. Further insight into the controlling forces is provided by the prediction of the number, size, and mass of particles produced from the Eotvos number, the ratio of buoyant to surface forces of the aqueous solution. The similarities among the parameterizations of particle properties to the Eotvos number for all three Na salts provide a strong indication that, for similar density solutions, particle production is dominated by surface forces, independent of chemical compositions. A complete mechanistic interpretation of particle production is limited by our inability to capture (theoretically or experimentally) both the macroscopic fluid mechanics of film rupture and the microscopic intermolecular interactions of strong ionic solutions. However, the parameterizations to dimensionless quantities of aqueous solutions presented here are sufficient to predict the essential characteristics of particle production. The collapse of the experimental results to common curves for several different salts shows the predictive ability of these parameterizations for other mixtures.     

On the Performance of the Fluctuation Test for Structural Change

Abstract

We discuss the performance of “closed-end” fluctuation tests, used to detect changes in the structural stability of a model, in the case where the time horizon is large and the observations do not possess high enough moments. It is demonstrated via a simulation study that, in the latter case, the choice of the boundary function should take into account the number of moments existing; otherwise the actual size of the test may exceed the nominal level. We suggest an alternative “open-end” fluctuation procedure and study its asymptotic behavior. It turns out that if an improper boundary function is chosen, then the null hypothesis may be rejected even if it is true. This means that an appropriate choice of the boundary function requires some prior information about the tail heaviness of the observations. This is different from the cumulative sum-based monitoring schemes suggested by Chu et al. (1996 Chu , C. S. J. , Stinchcombe , M. and White , H. ( 1996 ). Monitoring Structural Change , Econometrica 64 : 1045 – 1065 .[Crossref], [Web of Science ®] , [Google Scholar]) and further studied by Horváth et al. (2004 Horváth , L. , Hu?ková , M. , Kokoszka , P. , and Steinebach , J. ( 2004 ). Monitoring Changes in Linear Models , Journal of Statistical Planning and Inference 126 : 225 – 251 .[Crossref], [Web of Science ®] , [Google Scholar]).     

Selective Deflection and Localization of Flowing Aerosols onto a Substrate

Pulsed airflow cued by the fluorescence spectrum of a particular aerosol can be used to distinguish and deflect particles of biological origin out of an aerosol stream, permitting concentration of these particles for subsequent analysis (Pan et al. 2004 Pan, Y. L., Boutou, V., Bottiger, J. R., Zhang, S. S., Wolf, J. P. and Chang, R. K. 2004. A Puff of Air Sorts Bioaerosols for Pathogen Identification. Aerosol Sci. Technol., 38: 598–602. [CROSSREF][CSA][Taylor & Francis Online], [Web of Science ®] , [Google Scholar]). However, these high velocity pulses of air have an inherent tendency to scatter particles, confounding efforts to concentrate these deflected particles for analysis. The ability to concentrate large numbers of biological particles into a small area on a collection substrate is particularly important for more species-specific techniques such as Raman and FTIR (Fourier Transform Infra-Red) spectroscopy, which require long integration times due to their weak signal strength. In the present work, a simple method is developed for deflecting and localizing particles after classification by a pulsed airflow. The concept is both modeled and experimentally tested. A specially designed funnel is used to localize the scattered particles onto an area of substrate as small as 1 mm in diameter. Computational fluid dynamics simulations were performed to investigate the interaction of the pulsed airflow with the deflected particles and the localizing funnel, in order to gain insight into design parameters and operating conditions that affect the efficiency of this technique. The results show that the combination of pulsed airflow with a localizing funnel effectively deflects and localizes the concentrated bioaerosol onto a small area of substrate or an opening of a microfluidic cell.