- Catalysis and inhibition of ester hydrolysis in the presence of resorcinarene hosts functionalized with dimethylamino groups
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Complexation and catalysis of two calixresorcinarene (RES) derivatives with nucleophilic N,N-dimethylamino functions attached to their upper rims in the hydrolysis of carboxylate and sulfonate esters of 4-nitrophenol and 2,4-dinitrophenol have been investigated. Rate constants obey the complexation equation: kobs = kb × Ks + k c[Host]/Ks + [Host] Values of the dissociation constant (Ks) of the complexes are within the range exhibited by other systems such as cyclodextrins-ester complexes. The reactions of sulfonate esters only exhibit inhibition by the macrocyclic hosts. The reactions of the carboxylate esters exhibit catalysis and inhibition depending on the pH of the system. It is proposed that the dimethylamino function in RES3 and RES5 behaves as a nucleophile to form a reactive acylammonium species which subsequently decomposes and regenerates the catalytic amine. In the reaction of substituted phenyl acetates with RES3 the effective charge on the leaving oxygen in the complexed state (+0.88) is slightly more positive than that in the free ester (+0.70). The effective charge on the leaving oxygen in the transition structure is substantially more positive (+0.04 units) than in a model intramolecular reaction of tertiary dimethylamines with aryl esters (-0.53 units). The influence of the host on the reaction in the complex includes an electronic component which is ascribed to solvation of the transition structure of the rate-limiting step by water molecules located within the cavity of the host. It is suggested that this solvation is stronger than that occurring in the transition state for the model intramolecular reaction. Copyright
- Cevasco, Giorgio,Thea, Sergio,Vigo, Daniele,Williams, Andrew,Zaman, Flora
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p. 630 - 636
(2008/02/08)
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- Identification of surrogate compounds for the emission of PCDD/F (I-TEQ value) and evaluation of their on-line realtime detectability in flue gases of waste incineration plants by REMPI-TOFMS mass spectrometry
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Correlations between products of incomplete combustion (PIC), e.g., chloroaromatic compounds, can be used to characterise the emissions from combustion processes, like municipal or hazardous waste incineration. A possible application of such relationships may be the on-line real-time monitoring of a characteristic surrogate, e.g., with Resonance-Enhanced Multiphoton Ionization-Time-of-Flight Mass Spectrometry (REMPI-TOFMS). In this paper, we report the relationships of homologues and individual congeners of chlorinated benzenes (PCBz), dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and phenols (PCPh) to the International Toxicity Equivalent (I-TEQ) of the PCDD/F (I-TEQ value) in the flue gas and stack gas of a 22 MW hazardous waste incinerator (HWI). As the REMPI detection sensitivity is decreasing with the increase of the degree of chlorination, this study focuses on the lower chlorinated species of the compounds mentioned above. Lower chlorinated species, e.g., chlorobenzene (MCBz), 1,4-dichlorobenzene, 2,4,6-trichlorodibenzofuran or 2,4-dichlorophenol, were identified as I-TEQ surrogates in the flue gas. In contrast to the higher chlorinated phenols, the lower chlorinated phenols (degree of chlorination 4) were not reliable as surrogates in the stack gas. The identified surrogates are evaluated in terms of their detectability by REMPI-TOFMS laser mass spectrometry. The outcome is that MCBz is the best suited surrogate for (indirect) on-line measuring of the I-TEQ value in the flue gas by REMPI-TOFMS. The correlation coefficient r of the MCBz concentration to the I-TEQ in the flue gas was 0.85.
- Blumenstock,Zimmermann,Schramm,Kettrup
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p. 507 - 518
(2007/10/03)
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- Reactions within Association Complexes: The Reaction of Imidazole with Substituted Phenyl Acetates in the Presence of Detergents in Aqueous Solution
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The bimolecular rate constants for reaction of imidazole with phenyl acetates complexed with sodium dodecyl sulfate (SDS) or cetyltrimethylammonium bromide (CTAB) micelles obey Bronsted equations with βlg similar to that of the reaction in aqueous solution. The dissociation constants of ester (KS) and the hypothetical dissociation constant (KTS) of the transition state of the micelle complexes obey Hansch equations with similar sensitivities (p) to π (-0.66 and -0.589 for KS and -0.735 and -0.495 for KTS, respectively). The slopes also indicate that the microsolvation environments associated with the transition state and the complexed ester have aqueous character. The relative values of KTS and KS indicate that the transition state of the reaction of imidazole with ester is more weakly complexed to both micelles than is the reactant ester. Log KTS values are linear functions of log KS for reactions with both CTAB and SDS; the slopes are, respectively, -0.893 and -1.19 consistent with a slightly more "water-like" medium for the transition state than for the site of binding of ester with CTAB-micelle and slightly less for the SDS-micelle. The results for ester and transition state are consistent with the location of the phenyl residue in a hydrophobic region that possesses water molecules. It is concluded that the acetyl group in the complexed transition state is located in an aqueous part of the Stern region, whereas the phenyl residue is in a part of the Stern region that possesses alkane components. The derived kinetic and complexation parameters in these experiments refer to micelles with Stern regions that have been maintained at constant ionic compositions.
- Pirinccioglu, Necmettin,Zaman, Flora,Williams, Andrew
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p. 2537 - 2543
(2007/10/03)
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- Method of disinfecting premises from coccidial oocysts using generated ammonia
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A method of disinfecting premises from coccidial oocysts in which surface to be disinfected is thoroughly wetted with a first aqueous solution of ammonium salt containing approximately 0.5 to 1.5 molar of ammonium together with non-ionic surfactant and indicator having a color change in the region of pH 8 to pH 10 and the wetted surface is then covered with sufficient of a second aqueous solution of alkali metal hydroxide containing approximately 0.75 to 2.3 molar of hydroxide toether with phenolic bactericide to cause the indicator to change color on the treated surface. A preparation for use in such a method comprises a first package containing ammonium salt together with non-ionic surfactant and indicator and second package containing alkali metal hydroxide and phenolic bactericide, the molar amount of hydroxide in the second package being greater than the molar amount of ammonium in the first package.
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- Photochemistry of halogenated benzene derivatives. Part VI. Photoreactions of tetra- and pentachlorophenols in water-acetonitrile mixtures
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Laboratory photochemical studies of aqueous acetonitrile solution of some polychlorinated phenols (PCPs) such as 2,3,4,5-tetrachlorophenol (2,3,4,5-Cl4-Pn)(1), 2,3,4,6-Cl4-Pn(2), 2,3,5,6-Cl4-Pn(3), and pentachlorophenol (Cl5-Pn)(4) at λ>285 nm have been carried out for 6 and 24 h exposure times.All the investigated PCPs underwent reductive dechlorination.This process was dependent not only upon the position of OH group but also upon the relative positions of the Cl substituents on the benzene ring.The Cl4-Pn 2 (and 3) and Cl5-Pn (4) also yielded photoproducts of molecular formulae C8H4Cl3NO(M+.=235) and C8H3Cl4NO(M+.=269), respectively.Furthermore, phenol 3 is unique amongst the investigated PCPs; in addition to the above mentioned photoproducts, it yielded hexa-, hepta-, and octachlorodihydroxybiphenyl(s) as well as heptachlorohydroxydiphenyl ether.
- Choudhry, Ghulam Ghaus,Wielen, Frans W. M. van der,Webster, G. R. Barrie,Hutzinger, Otto
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p. 469 - 475
(2007/10/02)
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- THE REACTIONS OF UNACTIVATED ARYL HALIDES WITH SODIUM METHOXIDE IN HMPA; SYNTHESIS OF PHENOLS, ANISOLES, AND METHOXYPHENOLS
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Sodium methoxide reacts with dichlorobenzenes in HMPA to give the chloroanisoles as a result of a SNAr process.Excess MeONa then effects the demethylation of the ethers to give the chlorophenols via an SN2 reaction.With tri- and tetrachlorobenzenes the initially formed chloroanisoles can be dealkylated to chlorophenols or can suffer further substitution to give the chlorodimethoxybenzenes; these react with excess MeONa to give the chloromethoxyphenols.The results obtained with the various isomers of the di-, tri-, and tetrachlorobenzenes are presented and discussed on the basis of the electronic effects of the substituents.
- Testaferri, L.,Tiecco, M.,Tingoli, M.,Chianelli, D.,Montanucci, M.
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p. 193 - 198
(2007/10/02)
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