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.     

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.     

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.     

Indazole,oxathiadiazole, and thiadiazine derivatives from thiosemicarbazides

4-Substituted thiosemicarbazides 1a–c reacted with 2,3-dicyano-5,6-dichloro-1,4-benzoquinone (DDQ, 2), 2,3,5,6-tetrachloro-1,4-benzoquinone (CHL-p, 6) and 2,3-dichloro-1,4-naphthoquinone (DCHNQ, 7) in ethyl acetate with admission of air and form the derivatives of 1,5,2,3-oxathiadiazole 8a–c, indazole 9a–c, 1,3,4-thiadiazine-6-one 10a–c, 1,3,4-thiadiazaphenanthren-9-one 11a–c, naphtho[1,2-e:4,3-è]bis1 Nogami, T., Yoshihara, K. and Nagakura, K. 1972. Bull. Chem. Soc. Jpn., 45: 122[Crossref] , [Google Scholar] 3 Belitskaya, L. D. and Kolesnikov, V. T. 1984. Zh. Org. Khim. (Eng. Translation), 20: 1753 [Google Scholar] 4 Foster, R., Kulevsky, N. and Wanigasekera, D. S. 1974. J. Chem. Soc., Perkin Trans., 1: 1318[Crossref] , [Google Scholar]thiadiazine 12 and dibenzo[b,i]thianthrene-5,7,12,14-tetraone 13. A rationale for the conversions observed is presented.     

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.     

Mechanical Effect of Acetic Acid Lignin Adsorption on Honeycomb-Patterned Cellulosic Films

Abstract

We have already fabricated honeycomb-patterned cellulosic films with cellulose I and II polymorphisms as a basal framework in order to create an artificial woody cell wall.^{[ 1} Nemoto, J., Uraki, Y., Kishimoto, T., Sano, Y., Funada, R., Obata, N., Yabu, H., Tanaka, M. and Shimomura, M. 2005. Production of mesocopically patterned cellulose film. Bioresour. Technol., 96: 1955–1958.  [Google Scholar] ^{, 2} Uraki, Y., Nemoto, J., Otsuka, H., Tamai, Y., Sugiyama, J., Kishimoto, T., Ubukata, M., Yabu, H., Tanaka, M. and Shimomura, M. 2007. Honeycomb-like architecture produced by living bacteria, Gluconacetobacter xylinus. Carbohydr. Polym., 69: 1–6. [Crossref], [Web of Science ®] , [Google Scholar] ^] The adsorption of an isolated lignin, acetic acid lignin (AL), was attempted onto the honeycomb films not only to develop materials further mimicking the cell wall but also to elucidate the mechanical effect of isolated lignin on the tensile strength of the cellulosic architecture. The tensile strengths of honeycomb-patterned cellulosic films were improved by the AL adsorption. Although the cellulosic films without lignin weakened under high moisture content conditions as compared with those under the low content conditions, the lignin-adsorbed cellulosic film maintained significant tensile strength even under the high content conditions. This result suggests that lignin contributes to reinforce the mechanical strength of cellulose framework, in particular high moisture conditions.     

Bias in Filter-Based Aerosol Light Absorption Measurements Due to Organic Aerosol Loading: Evidence from Laboratory Measurements

Light absorption by soot or nigrosin dye aerosol particles were measured in the laboratory using a particle soot absorption photometer (PSAP) and a photo-acoustic spectrometer (PAS) to assess the influence of non-absorbing organic aerosol (OA) on the PSAP measurements. For the PSAP, particle light absorption is measured after collection on a filter, whereas for the PAS light absorption is measured while the particles remain suspended in the gas phase. OA was generated from the reaction of α -pinene with ozone. It was observed that the presence of this OA in an external mixture of absorbing aerosol and OA can cause an increase in the light absorption measured by the PSAP, relative to that measured by the PAS, by more than a factor of two. This enhancement in the PSAP absorption was found to increase as the amount of OA increased relative to the absorbing compound. Additionally, experiments where absorbing aerosol was deposited on a PSAP filter prior to addition of OA demonstrated that the non-absorbing OA can actually appear as if it were absorbing, with measured single scattering albedo values as low as 0.92. These results indicate that filter-based measurement techniques may significantly overestimate light absorption by aerosols in the atmosphere under conditions where the organic loading is large, with consequent implications for understanding and calculating the Earth's radiation budget. These laboratory experiments aid in the interpretation of results from a recent field study, discussed in a companion article (Lack et al. 2008 Lack, D. A., Cappa, C. D., Baynard, T., Massoli, P., Covert, D. S., Sierau, B., Bates, T. S., Quinn, P. K., Lovejoy, E. R. and Ravishankara, A. R. 2008. Bias in Filter-Based Aerosol Absorption Measurements Due to Organic Aerosol Loading: Evidence from Ambient Measurements. Aerosol Sci. and Technol., 42: 1033–1041. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]).     

Factorial Optimization of the Effects of Melt-Spinning Conditions on As-spun Aliphatic-Aromatic Copolyester Fibers I. Spin Draw Ratio,Overall Orientation and Drawability

According to our previous studies [1 Younes , B. , Fotheringham , A. , and EL-Dessouky , H. M. Polymer Engineering & Science 49 , 2492 ( 2009 ). [Google Scholar],2 Younes , B. , Fotheringham , A. , and EL-Dessouky , H. M. Journal of Applied Polymer Science 118 , 1270 ( 2010 ).[Web of Science ®] , [Google Scholar]], the optimum melting conditions have been achieved and lower melt flow index grade has been utilized in this work. In order to characterize the melt-spun AAC fibers, spin-draw ratio, optical birefringence and drawability were measured. The statistical optimization of fiber properties helps to produce the most satisfactory properties in the final fibers as an environmentally friendly attractive alternative to commercial chemical fibers. The importance of this model is in controlling the production process to optimize and enhance fiber properties, which may improve the quality and cost of biodegradable fibers.     

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.     

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     

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.     

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.     

DETECTION OF KNOWN PHOTOCHEMICAL DECOMPOSITION PRODUCTS OF PAH IN PARTICULATE MATTER FROM POLLUTION EPISODES IN SEOUL,KOREA

Over the past two decades, significant efforts have been expended to identify the photochemical decomposition products of the OH radical reactions of various polycyclic aromatic compounds (PAC), such as naphthalene, methylnaphthalenes, acenaphthene and phenanthrene (1 Lane, D. A. and Tang, H. 1994. Photochemical degradation of polycyclic aromatic compounds. I. Naphthalene.. Polycycl. Aromat. Comp, 5(1): 131–138. [Taylor & Francis Online] , [Google Scholar], 2 Bunce, N. J., Liu, L., Zhu, J. and Lane, D.A. 1997. Reaction of naphthalene and its derivatives with hydroxyl radicals in the gas phase.. Environ. Sci. Technol, 31(8): 2252–2259.  [Google Scholar], 3 Sasaki, J., Aschmann, S.M., Kwok, E.S.C., Atkinson, R. and Arey, J. 1997. Products of the gas-phase OH and NO3 radical-initiated reactions of naphthalene.. Environ. Sci. Technol, 31(11): 3173–3179.  [Google Scholar], 4 Sauret-Szczepanski, N. and Lane, D.A. 2004. Smog chamber study of acenaphthene: Gas/particle partition measurements of the products formed by reaction with the OH radical.. Polycycl. Aromat. Comp, 24(3): 161–172. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar], 5 Banceu, C. E., Mihele, C.M., Lane, D.A. and Bunce, N.J. 2001. Reactions of methylated naphthalenes with hydroxyl radicals under simulated atmospheric conditions.. Polycycl. Aromat. Comp, 18(4): 415–426. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar], 6 Wang, L., Atkinson, R. and Arey, J. 2007. Dicarbonyl products of the OH radical-initiated reactions of naphthalene and the C1- and C2-alkylnaphthalenes.. Environ. Sci. Technol, 41(8): 2803–2810.  [Google Scholar], 7 Lee, J. Y. and Lane, D.A. 2009. Unique products from the reaction of naphthalene with the hydroxyl radical. Atmos. Environ., 43: 4886–4893. [Crossref] , [Google Scholar]). Although these parent PAC are predominantly found in the gas phase, many of their oxidation products have been found largely in the particle phase (4 Sauret-Szczepanski, N. and Lane, D.A. 2004. Smog chamber study of acenaphthene: Gas/particle partition measurements of the products formed by reaction with the OH radical.. Polycycl. Aromat. Comp, 24(3): 161–172. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar], 7 Lee, J. Y. and Lane, D.A. 2009. Unique products from the reaction of naphthalene with the hydroxyl radical. Atmos. Environ., 43: 4886–4893. [Crossref] , [Google Scholar], 8 Mihele, C. M., Wiebe, H.A. and Lane, D.A. 2002. Particle formation and gas/particle partition measurements of the products of the naphthalene-OH radical reaction in a smog chamber. Polycycl. Aromat. Comp., 22: 729–736. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]). These products include diones, hydroxy-, and nitrated products as well as many products resulting from ring-opening steps. It is, or should be, the goal of every laboratory study on atmospheric processes to apply the laboratory results to real world samples. To this end, we have obtained particulate matter air samples, as well as some smog episode samples, from Seoul Korea and have searched for the known decomposition products of the above mentioned PAC. To eliminate the use of chlorinated solvents used in the extraction and analysis of particulate matter samples, we have been utilizing the direct thermal desorption of small (4 mm diameter) punches of filters followed by Multidimensional Gas Chromatography-Time of Flight Mass Spectrometry (TD-GCxGC-TOFMS) for the analysis of the desorbed compounds. So far, we have detected 14 of the known decomposition products of naphthalene, acenaphthene and phenanthrene in the Seoul pollution episode samples. These include: 1-hydroxynaphthalene, (E) 2-formylcinnamaldehyde, phthalic anhydride, phthalide, 1,2-naphthalic anhydride, 9-hydroxyphenanthrene and dibenzopyrone.     

DNA ADDUCTS OF BENZO[A]PYRENE- AND DIBENZO[A,L]PYRENE-DIOL EPOXIDES IN HUMAN LUNG EPITHELIAL CELLS: KINETICS OF ADDUCT REMOVAL,EFFECTS ON CELL CYCLE CHECKPOINTS,AND GENE EXPRESSION

The fjord-region PAH dibenzo[a,l]pyrene (DBP) is considerably more carcinogenic than the bay-region benzo[a]pyrene (BP). This fact can be ascribed to differences in DNA binding efficiency of their ultimate carcinogenic diol epoxide (DEs) intermediates, differences in structural features of the DNA adducts, and differences in DNA adduct recognition and the subsequent lesion removal by nucleotide excision repair (NER). In order to further substantiate previous findings in cell-free human systems (1 Buterin, T., Hess, M. T., Luneva, N., Geacintov, N. E., Amin, S., Kroth, H., Seidel, A. and Naegeli, H. 2000. Unrepaired Fjord Region Polycyclic Aromatic Hydrocarbon-DNA Adducts in Ras Codon 61 Mutational Hot Spots. Cancer Research, 60: 1849–1856.  [Google Scholar]), cultured cells (2 Luch, A., Kudla, K., Seidel, A., Doehmer, J., Greim, H. and Baird, W. M. 1999. The Level of DNA Modification by (+)-syn-(11S,12R,13S,14R)- and (?)-anti-(11R,12S,13S, 14R)-Dihydrodiol Epoxides of Dibenzo[a,l]pyrene Determined the Effect on the Proteins p53 and p21WAF1 in the Human Mammary Carcinoma Cell Line MCF-7. Carcinogenesis, 20: 859–865.  [Google Scholar]), and in rodents (3 Jankowiak, R., Ariese, F., Hewer, A., Luch, A., Zamzow, D., Hughes, N. C., Phillips, D., Seidel, A., Platt, K. L., Oesch, F. and Small, G. J. 1998. Structure, Conformations, and Repair of DNA Adducts from Dibenzo[a,l]pyrene: 32P-Postlabeling and Fluorescence Studies. Chemical Research in Toxicology, 11: 674–685.  [Google Scholar]) we have studied DNA adduct formation of anti-DE of DBP [(±)-anti-DBPDE], in A549 human epithelial lung carcinoma cells and monitored the levels of adducts as a function of time. A high-performance liquid chromatography (HPLC) procedure that allows monitoring of all cis- and trans-nucleoside adducts of dA and dG was used. Circular dichroism and UV-spectroscopy have been employed to gain information on adduct structural features. Incubation of cells with 0.1 μM (±)-anti-DBPDE resulted in rapid formation of adducts, followed by a decline. After 6 h of incubation about 20% of the adducts remained. Repeating the experiment with 0.01 μM (±)-anti-DBPDE resulted in a correspondingly lower adduct level initially, but in this case a larger proportion (35%) of the adducts remained after 6 h of incubation. Notably, at this time point, similar amounts of adducts are observed with both (±)-anti-DBPDE concentrations studied. Independent of diol epoxide concentration and incubation time, the dA/dG adducts were constant in number (～2.8). However, within the different adduct categories, the adduct distribution seemed to be time dependent. Although the data are preliminary, a selection with regard to adduct removal seems to have taken place. In comparative experiments with (+)-anti-BPDE, no significant difference in rates of adduct removal was evident. Preliminary results from global gene expression analysis, with focus on genes involved in DNA maintenance and cell cycle checkpoints, demonstrate interesting differences in the stress response elicited in the cells following exposure to the distorted and flexible nonplanar DBPDE or the rigid and planar BPDE molecule. As expected some major common induction events were clearly related to the activation of p53-dependent cell cycle checkpoint. However, distinct clusters of gene expression alterations were detected which mark one or other treatment specifically, indicating a high degree of subtlety in the stress response to closely related DNA adduct forming species.     

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.     

The Extended Peel Zone Model: Effect of Peeling Velocity

According to the peel zone model proposed by Pesika et al. [8 Pesika , N. S. , Tian , Y. , Zhao , B. , Rosenberg , K. , Zeng , H. , McGuiggan , P. , Autumn , K. , and Israelachvili , J. N. , J. Adhes. 83 , 383 – 401 ( 2007 ).[Taylor &; Francis Online], [Web of Science ®] , [Google Scholar]], the peel strength of an adhesive tape is proportional to the length of the peel zone or the bifurcation region at the peeling front between the tape backing and the substrate. In this study, the effects of the peel angle and peel velocity on the shape of the peel zone and the peel strength are further investigated theoretically and experimentally. The theoretical analysis on the angle at the edge of the peel zone, θ₀, and the peel strengths at different peel velocities and angles was compared with experimental tests using three different commercial tapes. The experimental results are in good agreement with the extended peel zone model, which provides a simple approach to predict the peel strength of adhesive tapes with different physical properties at different peel angles and velocities.     

Consistency and Traceability of Black Carbon Measurements Made by Laser-Induced Incandescence,Thermal-Optical Transmittance,and Filter-Based Photo-Absorption Techniques

In this study, we show that black carbon (BC) mass concentrations measured by different techniques are consistent and traceable. First, we present the volatilities of 13 organic compounds passed through a heated inlet. These data were used to quantify the interference of organic aerosols on the BC measurement techniques. The masses of the refractory particles that incandesce (m*_ref) were used to calibrate BC mass measured by a single-particle soot photometer (SP2), which uses laser-induced incandescence. This calibration was influenced little by refractory organics and agreed well with that of fullerene soot, which indicates the consistency of the standards. We estimated the interference of pyrolyzed refractory organics on the BC measured with a filter-based absorption photometer continuous soot monitoring system (COSMOS) with a heated inlet to be small in Asia. This was also confirmed by the stable mass absorption cross section (MAC) obtained by the high correlations between BC mass concentrations measured by COSMOS (M _COSMOS) and those measured by the thermal-optical transmittance method (M _TOT) (Kondo et al. 2009 Kondo, Y., Sahu, L., Kuwata, M., Miyazaki, Y., Takegawa, N., Moteki, N., Imaru, J., Han, S., Nakayama, T., Hu, M., Kim, Y. J. and Kita, K. 2009. Stabilization of the Mass Absorption Cross Section of Black Carbon for Filter-Based Absorption Photometry by the Use of a Heated Inlet. Aerosol Sci. Technol., 43: 741–756. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]). M _COSMOS was also compared with total BC mass concentrations measured with an SP2 (M _SP2) in Tokyo in 2009. M _COSMOS and M _SP2 were highly correlated (r ²= 0.97) and agreed to within about 10% on average. These results demonstrate that M _SP2, M _COSMOS, and M _TOT were nearly identical. Use of the masses of incandescing refractory BC particles for calibration of BC mass concentrations determined by different techniques gave consistent results.     

Skylight Color Shifts due to Variations of Urban-Industrial Aerosol Properties: Observer Color Difference Sensitivity Compared to a Digital Camera

Simulations of the sky dome color shifts of a cloudless sky have been performed, assuming three urban-industrial tropospheric aerosol cases. Each of these aerosols is represented by the bimodal lognormal volume distribution (Dubovik et al. 2002 Dubovik, O., Holben, B., Eck, T. F., Smirnov, A., Kaufman, Y. J., King, M. D., Tanré, D. and Slutsker, I. 2002. Variability of Absorption and Optical Properties of Key Aerosol Types Observed in Worldwide Locations. J. Atm. Sci., 59: 590–608. [Crossref], [Web of Science ®] , [Google Scholar]). A total of ten parameters are used to control the aerosol characteristics. These ten parameters are perturbed and the resulting sky color shifts are estimated. All simulations have been performed relative to the reference cases that represent the time-averaged state of each aerosol case. We have simulated the sensitivity of the theoretical CIE (Commission Internationale de l′ Eclairage) standard human observer to discriminate sky color changes, due to changes of the aerosol control parameters. A Digital color Camera Model (DCM) has also been incorporated in the simulation scheme. The DCM simulates the performance of a camera-colorimeter created specifically to measure sky color. The DCM has been used to investigate whether a color digital camera can replicate the behavior of the CIE standard observer, with respect to sky color shifts. The standard observer is most sensitive to perturbations of the parameters of the aerosol fine mode, which are particles with diameters less than 0.6 μ m. However his sensitivity is highly variable, depending on the parameter varied, on the aerosol case and on the direction of the observation. The DCM was in excellent agreement with the behavior of the CIE standard observer. The camera simulated sky color measurement accuracy was high. The results show that the camera sensitivity in discriminating color differences is much better than that of the observer.     

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.     

Comparative Study of Thermal Degradation of N-vinylimidazole/Phenoxy- and Methoxyethylmethacrylate Copolymers

Copolymerization reactions involving N-vinylimidazole and its derivatives have stimulated great interest due to the wide possibilities of the preparation of new materials, including the synthetic analogues of biopolymers with imidazole fragments. The role of the imidazole group in polymers is very important, especially due to the high thermal stability at elevated temperatures when it is copolymerized with methacrylates, which contain highly electronegative atoms like oxygen [10 Machida , S. , Shimizu , Y. , and Makita , T. Jappan Tappi J. 21 , 352 ( 1967 ). [Google Scholar],11 Goksel , C. , Haciogler , B. , and Akbulut , U. J. Polym. Sci. Part A 35 , 3578 ( 1997 ). [Google Scholar]]. Accordingly, copolymers of N-vinylimidazole with phenoxy- and methoxyethylmethacrylate have been prepared and subjected to thermogravimetric analysis to discover their thermal stability. Copolymers are also characterized by FTIR and ¹H-NMR spectroscopic methods. Results show that the thermal stability is greater for N-vinylimidazole-co-phenoxyethylmethacrylate than for those with N-vinylimidazole-methoxyethylmethacrylate.