Bifurcations on potential energy surfaces of organic reactions

A single transition state may lead to multiple intermediates or products if there is a post-transition-state reaction pathway bifurcation. These bifurcations arise when there are sequential transition states with no intervening energy minimum. For such systems, the shape of the potential energy surface and dynamic effects, rather than transition-state energetics, control selectivity. This Minireview covers recent investigations of organic reactions exhibiting reaction pathway bifurcations. Such phenomena are surprisingly general and affect experimental observables such as kinetic isotope effects and product distributions.     

Nontotally symmetric trifurcation of an SN2 reaction pathway

A new type of reaction pathway which involves a nontotally symmetric trifurcation was found and investigated for a typical S_N2‐type reaction, NC^‐ + CH₃X → NC? CH₃ + X^‐ (X = F, Cl). A nontotally symmetric valley‐ridge inflection (VRI) point was located along the C_3v reaction path. For X = F, the minimum energy path (MEP) starting from the transition state (TS) leads to a second‐order saddle point with C_3v symmetry, which connects three product minima of C_s symmetry. For X = Cl, four product minima have been observed, of which three belong to C_s symmetry and one to C_3v symmetry. The branching path from the VRI point to the lower symmetry minima was determined by a linear interpolation technique. The branching mechanism is discussed based on the reaction path curvature and net atomic charges, and the possibility of a nonotally symmetric n‐furcation is discussed. © 2015 Wiley Periodicals, Inc.     

Geometric and electronic structures of silicon fluorides (N = 4 – 6) and potential energy surfaces for dissociation reactions → SiF4 + F– and → + F–

The geometric and electronic structures of a series of silicon fluorides (n = 4 ? 6) were computationally studied with the aid of density functional theory (DFT) method with B3LYP and M06‐2X functionals and coupled cluster (CCSD and CCSD(T)) methods with 6‐311++G(d,p) basis set. The nature of the Si‐F bonds in these compounds was analyzed in the framework of the natural bond orbital theory and natural resonance theory. Energy characteristics (heats of reactions and energy barriers) of the dissociation reactions → SiF₄ + F^– and → + F^– were calculated using the DFT and CCSD methods. The potential energy surface of elimination of a fluoride anion from has a specific topology with valley‐ridge inflection points corresponding to bifurcations of the minimal energy reaction path. © 2016 Wiley Periodicals, Inc.     

Ultrasound‐assisted emulsification microextraction based on a solidified floating organic droplet for the rapid determination of 19 antibiotics as environmental pollutants in hospital drainage and Gomti river water

Antibiotics that are used excessively and disposed of improperly are categorized as emerging pollutants. The determination of micropollutants in water with an accurate and precise method is always a big challenge. Hence, a simple, rapid, sensitive, economical and almost eco‐friendly method is proposed for the quantitative determination of 19 antibiotics. The proposed method, ultrasound‐assisted emulsification microextraction and solidified floating organic droplet coupled with liquid chromatography and triple quadrupole mass spectrometry, has only a 3 min chromatographic run time for the determination of the 19 antibiotics. We report for the first time the use of the developed method for the quantitative determination of the antibiotics in waste water samples with better results in terms of higher sensitivity, cost‐effectiveness, better detection limits and a greener approach compared to the earlier reported methods. The limits of detection and quantification were in the range of 0.003–0.236 and 0.013–0.834 μg/L, respectively, with good linearity in the concentration range of 0.01–64.0 μg/L. The correlation coefficient was ≥0.987–0.99 for each analyte. The developed method has been successfully applied for the determination of antibiotics in water samples.     

Confirmation Studies on Polychlorinated Biphenyls (PCB) From River Waters Using Mass Fragmentography

Abstract

A specific and sensitive method to confirm the presence of polychlorinated biphenyls (PCB) in river water is described. Mass fragmentography is shown to be a proper technique especially when utilizing naturally occurring stable isotopes of chlorine. Synthesized tetrachloro-, pentachloro-and hexachlo-ro biphenyls were used to focus the mass spectrometer at three selected masses so called multiple ion detection (MID).     

Highly efficient microextraction of chlorophenoxy acid herbicides in natural waters using a decanoic acid-based nanostructured solvent prior to their quantitation by liquid chromatography–mass spectrometry

Solvents used in microextraction require high solubilising capability to efficiently extract the target compounds. In this article, nanostructured solvents made up of alkyl carboxylic acids (ACAs) aggregate are proposed for the efficient microextraction of acidic pesticides from natural waters. The target compounds were chlorophenoxy acid herbicides (CPAHs) widely used in agriculture, forestry and gardening (viz. 2,4-D, MCPA, MCPP, 2,4,5-T and MCPB). The supramolecular solvents (SUPRASs) tested were generated from solutions of reverse micelles of octanoic (OcA), decanoic (DeA) and dodecanoic (DoA) acid in THF by the addition of water, which acted as the coacervating agent. The DeA-based SUPRAS was the most efficient extractant for CPAHs; actual concentration factors (ACFs) of 260 for 2,4-D, 290 for MCPA, and 400 for MCPP, 2,4,5-T and MCPB were obtained. The explanation for so high ACFs can be found in the extremely efficient retention mechanisms that the DeA-based SUPRAS provides for CPAHs (i.e. formation of hydrogen bonds and hydrophobic interactions), and the high number of binding sites that it contains (i.e. the concentration of biosurfactant in the SUPRAS was 0.56 mg μL⁻¹). Both characteristics permitted to effectively extract the target analytes in a low volume of solvent (about 2 μL of solvent per mL of sample). Others assets of the proposed supramolecular solvent-based microextraction (SUSME) approach included recoveries no dependent on matrix composition, rapidity (sample treatment spent about 15 min), use of low volume of sample (63 mL per analysis) and simplicity (no special lab equipments was needed). Combination with liquid chromatography/ion–trap mass spectrometry [LC–(IT)MS] afforded method quantitation limits for CPAHs within the interval 22–30 ng L⁻¹. The precision of the method, expressed as relative standard deviation (n = 11, [CPAH] = 200 ng L⁻¹), was in the range 2.9–5.8%. The applicability of the method to the analysis of natural waters was assessed by determining the target analytes in fortified river and underground water samples.     

Computational water purification controls using second‐order adjoint equations with stability confirmation

This paper presents a computational method for water purification using second‐order adjoint equations. In Japan, the waters of polluted rivers are purified by conveying the waters from other rivers into the main rivers or by using outflows from sewage plants. The shallow water flow equation based on the water velocity and elevation and the advection diffusion equation of COD concentration are governing equations. The control problem involves finding a flow velocity into the main river that can reduce the COD concentration as close to the target value as possible. In other words, the problem is to find a water velocity to minimize the performance function, which is the square sum of the discrepancy between the computed and the observed COD concentrations. The present research was motivated by the need to apply water purification controls to practical projects. We have found that the controls occasionally tend to be unstable, and the stability of control must be ensured. By expanding the extended performance function into the Taylor series, the necessary condition for the stationary state is derived. Based on this condition, the first‐and second‐order adjoint equations can be obtained. The backward solution of the adjoint equation leads to the gradient and the Hessian product; these serve as the basis of the quasi‐Newton method. From the condition that the performance function must be minimum, the stability confirmation index can be determined. Using this index, we have derived the trust region method, the computation of which confirms the stability of control. Verification was carried out using a simple channel model. By varying the peak value of the inflow velocity, the outlet velocity has been determined such that the water elevation at the target point is zero. Depending on the peak value of the inflow, unstable control arises; this is determined by the stability confirmation index presented in this paper. The trust region method with the stability confirmation index is shown to be adaptable to judge the stability of control. The present method was applied to the water purification of Teganuma river in Japan. The steady fundamental state was computed with the inflow, outflow, and COD concentration at the inlet being specified. The control velocity at the control point can be determined for a fixed control duration with and without the stability confirmation index. The inflow, outflow, and COD concentration are specified as functions of time. It is shown that this method is suitable for practical use because control stability can be ensured. Moreover, it is also noted that the maximum flow velocity for stable control depending on the given control duration can be obtained. Copyright © 2011 John Wiley & Sons, Ltd.     

Determination of Dialkyldimethylammonium Surfactants in Consumer Products and Aqueous Environmental Samples Using the Mixed Micelle-Based Methodology

Abstract

The determination of dialkyldimethylammonium surfactants (DDAS) based on the measurement of the critical micelle concentration (CMC) of mixed sodium dodecylsulphate (SDS)-DDAS aggregates in a basic medium ([NaOH]=4.8 × 10^?3 M) is proposed. The dye Coomassie Brilliant Blue G (CBBG) was used as a photometric probe for the rapid determination of CMCs. Formation of CBBG-DDAS and DDAS-SDS premicellar aggregates of well-defined stoichiometrics at cationic and anionic surfactant concentrations far below their CMCs is demonstrated. Increased SDS concentration in the titration medium results in the formation of DDAS-SDS mixed micelles. The strong interaction between the opposite charged head group of DDAS and SDS permits these cationic surfactants to be determined at the ng ml^?1 level with a nearly uniform response for all the DDAS tested (12–18 alkyl carbons). The relative standard deviation for 1.10 μg ml^?1 ditetradecyldimethylammonium bromide (DTDAB) was 1.5%. The mixed-micelle based methodology was applied to the determination of DDAS in softeners and aqueous environmental samples (river water and laundry effluents) with average recoveries ranged from 87.1 to 100.6 and from 96.3 to 104.0, respectively.     

Preserving bounded and conservative solutions of transport in one‐dimensional shallow‐water flow with upwind numerical schemes: Application to fertigation and solute transport in rivers

This work intends to show that conservative upwind schemes based on a separate discretization of the scalar solute transport from the shallow‐water equations are unable to preserve uniform solute profiles in situations of one‐dimensional unsteady subcritical flow. However, the coupled discretization of the system is proved to lead to the correct solution in first‐order approximations. This work is also devoted to show that, when using a coupled discretization, a careful definition of the flux limiter function in second‐order TVD schemes is required in order to preserve uniform solute profiles. The work shows that, in cases of subcritical irregular flow, the coupled discretization is necessary but nevertheless not sufficient to ensure concentration distributions free from oscillations and a method to avoid these oscillations is proposed. Examples of steady and unsteady flows in test cases, river and irrigation are presented. Copyright © 2007 John Wiley & Sons, Ltd.     

Concentrations and Sources of Polycyclic Aromatic Hydrocarbons in Water and Sediments from the Huaihe River,China

Surface water and sediments were collected from eleven locations on the middle region of Huaihe River to evaluate the environmental effects of urban and industrial activities. The concentrations of sixteen polycyclic aromatic hydrocarbons (PAHs) in water and sediments were between 1.2–5.1 µg/L and 72–139 ng/g, respectively. High levels of PAHs in water were recorded in comparison to those of other countries, while the concentrations in sediments were low to moderate levels. A weak positive correlation was observed (R² = 0.49, P = 0.13) between PAHs and total organic carbon in water. However, a significant positive correlation (R² = 0.79, P = 0.004) was found in sediments, which indicated that total organic carbon was a factor in PAH levels in sediments but not in water. The parent ratios were studied by principal component analysis that showed the PAHs from water were predominantly derived from coal combustion (34%), oil spills (49%), and vehicular emissions (17%), while the major PAH sources to sediments were coal combustion. Using the ecological toxic equivalency factor index, it was concluded that the PAHs levels may provide a potential risk in water but not in sediments.