Immobilized DNA aptamers as target-specific chiral stationary phases for resolution of nucleoside and amino acid derivative enantiomers

Recently, we described the use of a DNA aptamer as a new target-specific chiral stationary phase (CSP) for the separation of oligopeptide enantiomers (Michaud, M.; Jourdan, E.; Villet, A.; Ravel, A.; Grosset, C.; Peyrin, E. J. Am. Chem. Soc. 2003, 125, 8672). However, from a practical point of view, it was fundamental to extend the applicability of such target-specific aptamer CSP to the resolution of small (bioactive) molecule enantiomers. In this paper, immobilized DNA aptamers specifically selected against D-adenosine and L-tyrosinamide were used to resolve the enantiomers by HPLC, using microbore columns. At 20 degrees C, the adenosine enantioseparation was similar to that classically reported with imprinted CSPs (approximately 3.5) while a very high enantioselectivity was observed for the tyrosinamide enantiomers (the nontarget enantiomer was essentially nonretained on the CSP). The influence of temperature on solute binding and chiral discrimination was analyzed. The binding enthalpic contributions were determined from linear van't Hoff plots. Very large DeltaH values were obtained for the target enantiomers (-71.4 +/- 0.7 kJ/mol for D-adenosine and -139.4 +/- 2.0 kJ/mol for L-tyrosinamide). Such values were consistent with the formation of a tight complex between these analytes and the aptamer CSPs. This work demonstrates that target-specific aptamer CSPs constitute a powerful tool for the resolution of small (bioactive) molecule enantiomers.     

Sorption profile of Cd(II) ions onto beach sand from aqueous solutions

Sorption of traces of Cd(II) ions onto beach sand is investigated as a function of nature and concentration of electrolyte (10(-4) to 10(-2)M nitric, hydrochloric and perchloric acids, pH 2-10 buffers and deionized water), shaking time 5-40min, shaking speed 50-200strokes/min, dosage of sand (50-1000mg/15cm(3)), concentration of sorbate (1.04x10(-6) to 1.9x10(-4)M) and temperature (293-323K). Maximum sorption of Cd(II) ions (approximately 66%) is achieved from deionized water using 300mg/15cm(3) sand in 20min. The data are successfully tested by Langmuir, Freundlich and Dubinin-Redushkevich (D-R) sorption isotherms. The values for characteristic Langmuir constants Q=13.31+/-0.20micromol/g and of b=(6.56+/-0.53)x10(3)dm(3)/mol, Freundlich constants A=2.23+/-1.16mmol/g and 1/n=0.70+/-0.05 of (D-R) constants beta=-0.005068+/-0.000328kJ(2)/mol(2), X(m)=46.91+/-11.91micromol/g and energy E=9.92+/-0.32kJ/mol have been estimated. Kinetics of sorption has been studied by applying Morris-Weber, Richenberg and Lagergren equations. The sorption follows first order rate equation resulting 0.182+/-0.004min(-1) The thermodynamic parameters DeltaH=32.09+/-2.92kJ/mol, DeltaS=111.0+/-9.5J/molK and DeltaG=-1.68+/-0.02kJ/mol are evaluated. The influence of common ions on the sorption of Cd(II) ions is also examined. Some common ions reduce the sorption while most of the ions have very little effect. It can be concluded that beach sand may be used as an alternative for the expensive synthetic sorbents.     

Characterization of two types of silanol groups on fused-silica surfaces using evanescent-wave cavity ring-down spectroscopy

Evanescent-wave cavity ring-down spectroscopy has been applied to a planar fused-silica surface covered with crystal violet (CV+) cations to characterize the silanol groups indirectly. A radiation-polarization dependence of the adsorption isotherm of CV+ at the CH3CN/silica interface is measured and fit to a two-site Langmuir equation to determine the relative populations of two different types of isolated silanol groups. CV+ binding at type I sites yields a free energy of adsorption of -29.9 +/- 0.2 kJ/mol and a saturation surface density of (7.4 +/- 0.5) x 10(12) cm(-2), whereas the values of -17.9 +/- 0.4 kJ/mol and (3.1 +/- 0.4) x 10(13) cm(-2) are obtained for the type II sites. The CV+ cations, each with a planar area of approximately 120 A2, seem to be aligned randomly while lying over the SiO- type I sites, thereby suggesting that this type of site may be surrounded by a large empty surface area (>480 A2). In contrast, the CV+ cations on a type II sites are restricted with an average angle of approximately 40 degrees tilted off the surface normal, suggesting that the CV+ cations on these sites are grouped closely together. The average tilt angle increases with increasing concentration of crystal violet so that CV+ cations may be separated from each other to minimize the repulsion of nearby CV+ and SiOH sites.     

Time-resolved fluorescence spectroscopic study of crude petroleum oils: influence of chemical composition

The fluorescence of crude petroleum oils is sensitive to changes in chemical composition and many different fluorescence methods have been used to characterize crude oils. The use of fluorescence lifetimes to quantitatively characterize oil composition has practical advantages over steady-state measurements, but there have been comparatively few studies in which the lifetime behavior is correlated with gross chemical compositional data. In this study, the fluorescence lifetimes for a series of 23 crude petroleum oils with American Petroleum Institute (API) gravities of between 10 and 50 were measured at several emission wavelengths (450-785 nm) using a 380 nm light emitting diode (LED) excitation source. It was found that the intensity average fluorescence lifetime (tau) at any emission wave-length does not correlate well with either API gravity or aromatic concentration. However, it was found that tau is strongly negatively correlated with both the polar and sulfur concentrations and positively correlated with the corrected alkane concentration. This indicates that the fluorescence behavior of crude petroleum oils is governed primarily by the concentration of quenching species. All the strong lifetime-concentration correlations are nonlinear and show a high degree of scatter, especially for medium to light oils with API gravities of between 25 and 40. The degree of scatter is greatest for oils where the concentrations (wt %) of the polar fraction is approximately 10 +/- 4%, the asphaltene component is approximately 1 +/- 0.5%, and sulfur is 0.5 +/- 0.4%. This large degree of scatter precludes the use of average fluorescence lifetime data obtained with 380 nm excitation for the accurate prediction of the common chemical compositional parameters of crude petroleum oils.     

Effect of air in the thermal decomposition of 50 mass% hydroxylamine/water

This paper presents experimental measurements of 50 mass% hydroxylamine (HA)/water thermal decomposition in air and vacuum environments using an automatic pressure tracking adiabatic calorimeter (APTAC). Overall kinetics, onset temperatures, non-condensable pressures, times to maximum rate, heat and pressure rates versus temperature, and mixture vapor pressures for the experiments in vacuum were similar when compared to the corresponding data for HA decomposition in air. Determined was an overall activation energy of 119+/-8 kJ/mol (29+/-2 kcal/mol), which is low compared to 257 kJ/mol (61.3 kcal/mol) required to break the H(2)N-OH bond reported in the literature. The availability of oxygen from air did not affect detected runaway decomposition products, which were H(2), N(2), N(2)O, NO, and NH(3), for samples run in vacuum or with air above the sample. A delta H(rxn) of -117 kJ/mol (28 kcal/mol) was estimated for the HA decomposition reaction under runaway conditions.     

Characterization of the interaction between 4-(tetrahydro-2-furanmethoxy)-N-octadecyl-1,8-naphthalimide and human serum albumin by molecular spectroscopy and its analytical application

A novel 4-(tetrahydro-2-furanmethoxy)-N-octadecyl-1,8-naphthalimide (TNN) was synthesized as a spectrofluorimetric probe for the determination of proteins. The effect of different solvents on the spectral characteristics of TNN was investigated. The results showed that TNN displayed dependent solvent polarity properties due to the effect of internal charge transfer. The interactions between TNN and human serum albumin (HSA) were studied by fluorescence and absorption spectroscopy. Fluorescence data revealed that the fluorescence quenching of HSA by TNN was the result of the formation of TNN-HSA complex. The binding parameters of interactions between TNN and HSA at different temperatures were obtained according to the Stern-Volmer equation. The thermodynamic parameters, enthalpy change (ΔH) and entropy change (ΔS), for the interactions were calculated to be -7.31 kJ mol(-1) and 72.75 J mol(-1) K(-1) according to the van't Hoff equation, indicating that the hydrogen bonds and hydrophobic interactions were the dominant intermolecular force in stabilizing the complex. The effect of TNN on the conformation of HSA was analyzed by circular dichroism and synchronous fluorescence spectroscopy. Furthermore, the results of displacement experiments using warfarin indicated that TNN could bind to site I of HSA. The fluorescence of TNN could be largely quenched by HSA, based on which a new fluorometric method for detecting HSA in the HCl-Tris buffer solution (pH = 7.4) was developed. The linear ranges of the calibration curves were 0.1~14.2 μM for HSA, 0.1~13.0 μM for bovine serum albumin (BSA), 0.2~9.7 μM for γ-globulin, and 0.3~11.3 μM for hemoglobin (Hb), with detection limits (3σ) of 1.37 × 10(-10) M for HSA, 1.84 × 10(-10) M for BSA, 3.14 × 10(-10) M for γ-globulin, and 6.86 × 10(-10) M for Hb. The effect of metal cations on the fluorescence spectra of TNN in ethanol was also investigated. The method has been applied to the determination of total proteins in human serum samples collected from the hospital and the results were in good agreement with those reported by the hospital.     

Synthesis,characterization and thermal studies of (Ni/Co) metal salts of hydrazine: potential initiatory compounds

Nickel hydrazinium nitrate (NiHN) and cobalt hydrazinium nitrate (CoHN) were prepared by reacting their respective metal nitrates with hydrazine hydrate at 25 and 65 degrees C. The compounds were characterized by metal content and infrared (IR) spectroscopy. Differential thermal analysis (DTA) results suggest that the nickel complex is relatively more stable than the cobalt complex. The activation energy determined by DTA and ignition delay measurements corresponds to an energy of activation (E(a)) of 80+/-4 kJ/mol for NiHN and that of 150+/-8 kJ/mol for CoHN. Thermo gravimetry (TG) also revealed more rapid decomposition of NiHN than that of CoHN in the temperature region of 215-235 degrees C. High temperature Fourier transform-infrared (FT-IR) studies indicated rupture of the Ni-Co-N bond as the primary step in the thermolysis. As regards sensitivity to mechanical stimuli, NiHN was found to be less impact sensitive while CoHN exhibited less friction sensitivity. The study revealed that NiHN could be used alone as well as in combination with oxidizer/fuel as initiators depending upon the specific requirements. The effect of silver azide and glass on the sensitization of NiHN was also studied. CoHN appears to be an effective ballistic modifier in enhancing burning rates of composite propellants.     

Adsorption of reactive dye onto carbon nanotubes: equilibrium, kinetics and thermodynamics

The adsorption efficiency of carbon nanotubes for Procion Red MX-5B at various pHs and temperatures was examined. The amount adsorbed increased with the CNTs dosage; however, the adsorption capacity initially increased with the CNTs dosage (<0.25 g/l) and then declined as the CNTs dosage increased further (>0.25 g/l). The linear correlation coefficients and standard deviations of Langmuir and Freundlich isotherms were determined and the results revealed that Langmuir isotherm fitted the experimental results well. Kinetic analyses were conducted using pseudo first- and second-order models and the intraparticle diffusion model. The regression results showed that the adsorption kinetics were more accurately represented by a pseudo second-order model. Changes in the free energy of adsorption (DeltaG degrees ), enthalpy (DeltaH degrees ) and entropy (DeltaS degrees), as well as the activation energy (E(a)) were determined. DeltaH degrees and DeltaS degrees were 31.55 kJ/mol and 216.99J/molK, respectively, at pH 6.5 and 41.47 kJ/mol and 244.64 J/molK at pH 10. The activation energy was 33.35 kJ/mol at pH 6.5. DeltaH degrees, DeltaG degrees and E(a) all suggested that the adsorption of Procion Red MX-5B onto CNTs was by physisorption.     

Use of a modified cyclodextrin host for the enantioselective detection of a halogenated diether as chiral guest via optical and electrical transducers

In an alkaline rebreathing circuit, the inhalation anesthetic sevoflurane degrades into at least two products, one of them being the chiral halodiether 1,1,1,3,3-pentafluoro-2-(fluoromethoxy)-3-methoxypropane (halodiether B). Using octakis(3-O-butanoyl-2,6-di-O-n-pentyl)-y-cyclodextrin (Lipodex E) as chiral host diluted in the polysiloxane PS255, an exceptional large chiral separation factor alpha of 9.7 at 30 degrees C was found for halodiether B by capillary gas chromatography (cGC). Hence, the interaction of the single enantiomers and the racemic mixture of the halodiether B with Lipodex E was selected as a model system to study the enantioselective recognition by thickness shear mode resonators (TSMR), surface acoustic wave sensors, surface plasmon resonance (SPR), and reflectometric interference spectroscopy. Further investigations of the recognition process by using chemical sensors confirmed the preferential enrichment of the S-enantiomer resulting in 9-fold higher signals. Based on the distinction between enantioselective and nonenantioselective sorption, thermodynamic complexation constants of the single enantiomers with Lipodex E could be determined. The difference in Gibbs free energy -deltaE2,E1(deltaG) of the complexation of the enantiomers of halodiether B with pure Lipodex E was determined at 30 degrees C by TSMR and SPR to be 5.7 or 5.9 kJ/mol, respectively, agreeing well with that determined by cGC, i.e., 5.7 kJ/mol at 30 degrees C.     

Determination of vapor pressure of low-volatility compounds using a method to obtain saturated vapor with coated capillary columns

The vapor pressures of O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX), O-isobutyl S-2-diethylaminoethyl methylphosphonothiolate (RVX), and 2,4-dinitrotoluene (2,4-DNT) were determined with the gas saturation method in temperatures ranging from -12 to 103 degrees C. The saturated vapor was generated using a fused-silica column coated with the compound. This column was placed in a gas chromatograph, and the vapor pressure was determined directly from the detector signal or by sampling on Tenax tubes that were subsequently analyzed. From the linear relationships obtained by plotting log P vs 1/T, the enthalpies of vaporization (deltaHvap) and the vapor pressures at selected temperatures were determined. The vapor pressure of VX at 25 degrees C was 0.110 Pa and the deltaHvap 77.9 kJ x mol(-1). The corresponding results for RVX were 0.082 Pa and 76.6 kJ x mol(-1). The vapor pressure of 2,4-DNT at 72 degrees C (melting point) was determined to 6.0 Pa, and the enthalpies of the solid and the liquid state were 94.2 and 75.3 kJ x mol(-1), respectively. Using capillary columns to generate saturated vapors has three major advantages: short equilibrium time, low consumption of sample, and safe handling of toxic compounds.     

Thermal polymerization of uninhibited styrene investigated by using microcalorimetry

Calorimetric studies on the bulk polymerization of uninhibited styrene monomer under low temperature conditions from 50 to 85 degrees C were reported. Various thermograms acquired by either dynamic scanning or isothermal ageing were characterized by differential scanning calorimetry (DSC) or thermal activity monitor (TAM). Isothermal curve demonstrating an autocatalytic phenomenon associated with a characteristic induction time was detected. Heat of thermal polymerization of styrene between 50 and 85 degrees C was measured to be 670+/-11 J g(-1). The findings of this study include: (1) Exothermic phenomenon of thermal-initiation and chain transfer steps in thermal polymerization were corroborated by using calorimetric investigation extended to the temperature as low as 50 degrees C; (2) activation energies in the steps of thermal-initiation and chain transfer were determined to be 125+/-6 and 60+/-5 kJ mol(-1) by using Arrhenius plot, respectively; (3) apparent activation energy was verified to be 84 kJ mol(-1) related to the individual steps of thermal-initiation and chain transfer conformed. These kinetic parameters work well in simulating the adiabatic runaway behaviors of uninhibited styrene and in good agreement with other studies.     

Sorptive removal of endocrine-disruptive compound (estriol, E3) from aqueous phase by batch and column studies: kinetic and mechanistic evaluation

Endocrine disruptive compounds (EDC) are a wide variety of chemicals which typically exert effects, either directly or indirectly, through receptor-mediated processes. They mimic endogenous hormones by influencing the activities of hormone activities even at nanogram concentrations and reported to disrupt the vital systems (e.g., the endocrine system) in aquatic organisms. The EDC are present in aquatic water bodies and sediments mainly due to the release of human and animal excreted waste. Estriol (E3) removal by adsorption process was investigated in this study to evaluate the potential of activated charcoal as adsorbent. Agitated non-flow batch sorption studies showed good E3 removal efficiency. Sorption kinetic data illustrated good fit with pseudo-first-order rate equation. Experimental data confirmed to linear Langmuir's isotherm model. Neutral pH condition showed comparatively good sorption of E3. Adsorption capacity showed a consistent increasing trend with increase in the operating temperature [DeltaH degrees , -9.189 kJ/mol); DeltaS degrees , 0.492 J/mol K) suggesting exothermic nature of E3 sorption process. Free energy (DeltaG degrees ) increased from 2.51 to 2.97 kJ/mol with increase in temperature from 0 to 50 degrees C. Further, E3 spiked distilled water, untreated domestic sewage and treated domestic sewage were studied in fixed bed column to assesses the potential of sorption process as tertiary unit operation in the ETP system. Total E3 concentration was determined quantitatively by employing direct competitive enzymatic-immuno assay (EIA) procedure.     

Development of infrared electroabsorption spectroscopy and its application to molecular structural studies

We have constructed an infrared electroabsorption spectroscopic system employing the alternating current (AC) coupled dispersive method developed previously in our laboratory. It is highly sensitive, measuring electric-field-induced infrared absorption changes as small as 6 x 10(-8) in the mid-infrared region of 4000-820 cm(-1). Infrared electroabsorption spectra of liquids and solutions can be measured at room temperature. The system was first applied to liquid acetone to observe the orientational as well as the electronic polarization signals. These signals show distinct behaviors that are exactly predicted by theory. It was then applied to liquid 1,2-dichloroethane, for which electric-field-induced gauche/trans equilibrium changes were detected as infrared absorption changes. The gauche/trans ratio in room-temperature liquid 1,2-dichloroethane has been determined for the first time as 1.4 +/- 0.2. This equilibrium constant has led to the free energy difference deltaG of 0.9 +/- 0.4 kJ mol(-1) (deltaG = G(g) - G(t)) and the entropy difference of deltaS = -3.0 +/- 1.4 J K(-1) mol(-1) with the known enthalpy difference deltaH approximately 0.0 kJ mol(-1). Finally, the system was applied to 1,4-dioxane solutions of N-methylacetamide. The dipole moments of the monomer as well as that of the dimer of N-methylacetamide have been determined separately and a head-to-tail structure of the dimer has been clarified. The instrumentation and the theoretical basis of infrared electroabsorption spectroscopy are described in detail together with the above-mentioned experimental results.     

Kinetics and mechanism of the exothermic first-stage decomposition reaction of 1,3-bis(2,2,2-trinitroethyl)-1,3-diazacyclopentanone-2

The thermal behavior, mechanism and kinetic parameters of the exothermic first-stage decomposition reaction of the title compound in a temperature-programmed mode have been investigated by means of DSC, TG-DTG and IR. The reaction mechanism was proposed. The kinetic model function in differential form, apparent activation energy (E(a)) and pre-exponential factor (A) of this reaction are (1-alpha)(2), 178.41 kJ mol(-1) and 10(17.06)s(-1), respectively. The critical temperature of thermal explosion of the compound is 184.99 degrees C. The values of DeltaS( not equal ), DeltaH( not equal ) and DeltaG( not equal ) of this reaction are 91.54 J mol(-1)K(-1), 176.86 kJ mol(-1) and 135.83 kJ mol(-1), respectively.     

Direct determination of lead isotopes (206Pb, 207Pb, 208Pb) in arctic ice samples at picogram per gram levels using inductively coupled plasma-sector field MS coupled with a high-efficiency sample introduction system

Adopting strict cleanroom procedures, ice samples from the Canadian High Arctic have been analyzed for Pb concentrations and Pb isotopes (206Pb, 207Pb, 208Pb) using ICP-SMS. The detection limit for Pb (0.06 pg g(-1)) was approximately 2 orders of magnitude lower than the lowest concentration of Pb in the ice samples (range, 4.3-1660 pg g(-1); median, 45 pg g(-1)). Acidification of ice samples with high-purity HNO3 for stabilization purposes contributed only 0.004 pg of Pb g(-1), which is an insignificant source of Pb. Using a new sample introduction system consisting of a heated (140 degrees C) minicyclonic spray chamber and a Peltier cooled condenser (2 degrees C) and by replacing the conventional sample cone with a high-performance cone, signal intensities for Pb were increased by approximately 1 order of magnitude. Thus, it was possible not only to measure Pb isotope ratios directly using ICP-SMS but also to achieve reasonable precision (approximately 0.2%) at low picogram per gram concentrations of total Pb. This precision is comparable to that achievable by thermal ionization mass spectrometry at such low Pb concentrations, but the ICP-SMS requires much less sample volume (approximately 2 mL), needs no sample pretreatment, and therefore is considerably faster and less expensive than the conventional approach. Even though absolute Pb concentrations in two ice samples dating from 1974 and 1852 were very similar (9 and 6 pg g(-1)) their fundamentally different isotopic signature (206Pb/207Pb: 1.169 +/- 0.002 vs 1.147 +/- 0.003) clearly indicates different sources of Pb. The analytical procedures described here, therefore, offer great promise for fingerprinting the predominant sources of atmospheric Pb in polar snow and ice.     

Nitric oxide adsorption and desorption on alumina supported palladium

The adsorption properties of nitric oxide (NO) on alumina supported palladium were studied by a simultaneous thermogravimetric-analysis and differential-scanning-calorimetry (TGA-DSC) in a temperature ranges between 220 and 470 K. Upon adsorption, NO molecules on both Pd/Al2O3 and Pd/NaOH-Al2O3 samples were molecularly adsorbed between 220 and 300 K. Some NO molecules were strongly adsorbed on Pd/NaOH-Al2O3 and possessed a higher enthalpy of adsorption [approximately 140 kJ (mol NO)(-1)] than Pd/Al2O3 [approximately 114 kJ (mol NO)(-1)]. Upon heating above 320 K, the adsorbed NO molecule on these palladium surface was dissociated. In addition, a temperature programmed desorption and mass spectrometer (TPD-MS) study in a temperature range between 300 and 1100 K further indicated that some strongly adsorbed NO molecules may stay on basic sites (*b) and Pd-NaOH interface sites (*i) to enhance the decomposition of NO.     

Quantitative detection of individual cleaved DNA molecules on surfaces using gold nanoparticles and scanning electron microscope imaging

Single-nucleotide polymorphisms (SNPs) are the most frequent type of human genetic variation. Recent work has shown that it is possible to directly analyze SNPs in unamplified human genomic DNA samples using the surface-invasive cleavage reaction followed by rolling circle amplification (RCA) labeling of the cleavage products. The individual RCA amplicon molecules were counted on the surface using fluorescence microscopy. Two principal limitations of such single-molecule counting are the variability in the amplicon size, which results in a large variation in fluorescence signal intensity from the dye-labeled DNA molecules, and a high level of background fluorescence. It is shown here that an excellent alternative to RCA labeling is tagging with gold nanoparticles followed by imaging with a scanning electron microscope. Gold nanoparticles have a uniform diameter (15 +/- 0.5 nm) and provide excellent contrast against the background of the silicon substrate employed. Individual gold nanoparticles are readily counted using publicly available software. The results demonstrate that the labeling efficiency is improved by as much as approximately 15-fold, and the signal-to-noise ratio is improved by approximately 4-fold. Detection of individual cleaved DNA molecules following surface-invasive cleavage was linear and quantitative over 3 orders of magnitude in amount of target DNA (10(-18)-10(-15) mol).     

Chemical reduction of an unbuffered nitrate solution using catalyzed and uncatalyzed nanoscale iron particles

Uncatalyzed and catalyzed nanoscale Fe(0) systems were employed for the denitrification of unbuffered 40 mgN L(-1) nitrate solutions at initial neutral pH. Compared to microscale Fe(0) (<100 mesh), the efficiency and rate of nitrate removal using uncatalyzed and catalyzed nano-Fe(0) were highly promoted, in which the maximum promoted rate was obtained using copper-catalyzed nano-Fe(0) (nano-Cu/Fe). Nitrate first-order degradation rate constants (k(obs)) decreased significantly (>70%) with aged nano-Fe(0) and aged nano-Cu/Fe, and were recovered with NaBH(4) as reductants at levels of about 85 and 75%, respectively. Activation energies (E(a)) of nitrate reduction over the temperature range of 10-60 degrees C were 42.5 kJ mol(-1) for microscale Fe(0), 25.8 kJ mol(-1) for nano-Fe(0) and 16.8 kJ mol(-1) for nano-Cu/Fe. Unlike microscale Fe(0), the kinetics of denitrification by nano-Fe(0) and nano-Cu/Fe began to show characteristics of mass transport in addition to chemical reaction control. Ammonium was the predominant end product in all the systems. However, as for nitrite, 40% of the degraded nitrate persisted in the nano-Cu/Fe system. Thus, relative to nano-Cu/Fe, nano-Fe(0) is a potential reductant for denitrification of groundwater as far as toxic nitrite generation is concern.     

Oxidation of chlorinated ethenes by potassium permanganate: a kinetics study

The kinetics of oxidation of perchloroethylene (PCE), trichloroethylene (TCE), three isomers of dichloroethylene (DCE) and vinyl chloride (VC) by potassium permanganate (KMnO(4)) were studied in phosphate-buffered solutions of pH 7 and ionic strength approximately 0.05 M and under isothermal, completely mixed and zero headspace conditions. Experimental results have shown that the reaction appears to be second order overall and first order individually with respect to both KMnO(4) and all chlorinated ethenes (CEs), except VC. The degradation of VC by KMnO(4) is a two-consecutive-step process. The second step, being the rate-limiting step, is of first order in VC and has an activation energy (E(a)) of 7.9+/-1 kcal mol(-1). The second order rate constants at 20 degrees C are 0.035+/-0.004 M(-1) s(-1) (PCE), 0.80+/-0.12 M(-1) s(-1) (TCE), 1.52+/-0.05 M(-1) s(-1) (cis-DCE), 2.1+/-0.2 M(-1) s(-1) (1,1-DCE) and 48.6+/-0.9 M(-1) s(-1) (trans-DCE). The E(a) and entropy (DeltaS(*)) of the reaction between KMnO(4) and CEs (except VC) are in the range of 5.8-9.3 kcal mol(-1) and -33 to -36 kcal mol(-1) K(-1), respectively. Moreover, KMnO(4) is able to completely dechlorinate CEs, and the increase in acidity of the solution due to CE oxidation by KMnO(4) is directly proportional to the number of chlorine atoms in CEs.