Biomimetic hydrocarbon oxidation catalyzed by nonheme iron(III) complexes with peracids: evidence for an Fe(V)=O species

Mononuclear nonheme iron(III) complexes of tetradentate ligands containing two deprotonated amide moieties, [Fe(Me(2)bpb)Cl(H(2)O)] (3 a) and [Fe(bpc)Cl(H(2)O)] (4 a), were prepared by substitution reactions involving the previously synthesized iron(III) complexes [Et(3)NH][Fe(Me(2)bpb)Cl(2)] (3) and [Et(3)NH][Fe(bpc)Cl(2)] (4). Complexes 3 a and 4 a were characterized by IR and elemental analysis, and complex 3 a also by X-ray crystallography. Nonheme iron(III) complexes 3, 3 a, 4, and 4 a catalyze olefin epoxidation and alcohol oxidation on treatment with m-chloroperbenzoic acid. Pairwise comparisons of the reactivity of these complexes revealed that the nature of the axial ligand (Cl(-) versus H(2)O) influences the yield of oxidation products, whereas an electronic change in the supporting chelate ligand has little effect. Hydrocarbon oxidation by these catalysts was proposed to involve an iron(V) oxo species which is formed on heterolytic O-O bond cleavage of an iron acylperoxo intermediate (FeOOC(O)R). Evidence for this iron(V) oxo species was derived from KIE (k(H)/k(D)) values, H(2) (18)O exchange experiments, and the use of peroxyphenylacetic acid (PPAA) as the peracid. Our results suggest that an Fe(V)=O moiety can form in a system wherein the supporting chelate ligand comprises a mixture of neutral and anionic nitrogen donors. This work is relevant to the chemistry of mononuclear nonheme iron enzymes that are proposed to oxidize organic substrates via reaction pathways involving high-valent iron oxo species.     

Cholinesterase-based dipstick assay for the detection of organophosphate and carbamate pesticides

A cholinesterase (ChE)-based dipstick-type assay for the class-specific detection of organophosphate (OP) and carbamate (CM) pesticides was developed. The principle of the assay is based on inhibition of the activity of a ChE by these two families of pesticides, which is dependent on the concentration of pesticides. The proposed assay system is composed of a test strip with an acetylcholinesterase (AChE)-coated membrane and an enzyme substrate solution. The assay protocol involves incubation of the enzyme-coated strip in the pesticide-containing sample solution followed by incubation of the sample-treated strip in a chromogenic enzyme substrate solution. The color intensity is estimated by the naked eye or a reflectometer. Of the membranes tested as the enzyme support, Hybond N⁺ was the most suitable. Among the compounds tested as the enzyme substrate, indophenyl acetate was the best. The detectable concentration range of the dipstick assay for the OP and CM pesticides was 10⁻⁶-10² and 10⁻⁶-10⁰ μg mL⁻¹, respectively. The sensitivity of the dipstick assay to the oxidized form of parathion (paraoxon) was higher than to parathion. The strip showed a large matrix effect with pesticide-spiked lettuce samples, whereas it showed a small matrix effect with pesticide-spiked rice samples.     

Study of pH-dependent charges of soils by surface acid-base properties

The pH-dependent charges of Hungarian soils have been studied via surface acid-base properties. The intrinsic stability constants of protonation and deprotonation processes, as well as the concentration of surface sites, have been determined by surface complexation modeling. The protonation and deprotonation constants have been nearly the same for most soils. There is a relation between the concentration of surface sites and composition, expect for the freshly deposited soils with high primary silicate content. The results show that the concentrations of silanol and aluminol sites are different for each soil, the intrinsic stability constants of protonation and deprotonation processes, however, are nearly the same within experimental error. This can only be explained if these stability constants are real thermodynamic equilibrium constants. The fact that these constants are nearly the same supports the conclusion that we succeeded in excluding all processes that would disturb the measurements. The parameters characteristic of the edge sites of the soils are of two types: (a) the parameters depending on the quality and composition of the soils, (i.e.), the concentration of surface sites; (b) the parameters depending on the thermodynamically well-defined acid-base processes, independent of soil composition.     

Volatile organic compounds of Angelica gigas Nakai, Korean medicinal herb

The study was performed to find out the profile of volatile flavor components from the aromatic medicinal plant, Angelica gigas Nakai. The volatile organic compounds of A. gigas Nakai were extracted by simultaneous steam distillation and extraction (SDE) method, and identified by gas chromatograph/mass spectrometric (GC/MS) analysis. A total of 116 compounds, including 40 hydrocarbons, 37 alcohols, 15 esters, 12 aldehydes, 7 ketones, and 5 miscellaneous were identified and quantified. Among them, 75 volatile organic compounds were detected which make up 90.52% of total volatile content. alpha-Pinene was detected as the prime volatile component which accounted for 30.89% of total volatile content and 2,4,6-trimethyl heptane, camphene, alpha-limonene, beta-eudesmol, vervenol, alpha-murrolene, and sphatulenol were detected as the major components of A. gigas Nakai.     

Effect of the Linking Structure of Nonlinear Optical Side Groups on the Phase Behavior of an Aromatic Polyester Backbone

Summary: The phase behavior of poly(p‐phenylene terephthalate)s (PPT) with pendant side groups, N‐(4‐nitrophenyl)ethylaminoethanol (NPE) and N‐(4‐nitrophenyl)‐L ‐prolinol (NPP) has been studied by using differential scanning calorimetry (DSC), wide‐angle X‐ray scattering (WAXS), and second harmonic generation (SHG). PPT‐NPE showed a layered liquid crystalline morphology while PPT‐NPP showed a completely amorphous structure. Compressive or shear stress applied on the polymer melt surface at 210 °C induced a more prominent layered structure of PPT‐NPE whereas the amorphous structure of PPT‐NPP remained unchanged under the stress. In order to understand this phase difference in terms of the repeat structure, we attempted theoretical ab initio Hartree‐Fock, and DFT calculations for the monomers and molecular dynamics for the bulk state. The results indicated that molecular configurations are a good way of microscopically understanding the phases of rigid backbone polymers with functional side groups: The NPT (constant particle number, pressure, and temperature) simulation data at 210 °C agree qualitatively with the experimental data and the difference between PPT‐NPE and PPT‐NPP could be understood using rotational energy barrier, steric hindrance and inter‐chain interactions. X‐ray diffractometer (XRD) simulation patterns for the oligomers are also in qualitative agreement with the experimental WAXS data and the structural parameters of stacks of PPT‐NPE chains are estimated to be layer distance (4.6 Å), backbone distance (21.5 Å), and side distance (12 Å).

     

Static and dynamic behaviour of nonlocal elastic bar using integral strain-based and peridynamic models

The static and dynamic behaviour of a nonlocal bar of finite length is studied in this paper. The nonlocal integral models considered in this paper are strain-based and relative displacement-based nonlocal models; the latter one is also labelled as a peridynamic model. For infinite media, and for sufficiently smooth displacement fields, both integral nonlocal models can be equivalent, assuming some kernel correspondence rules. For infinite media (or finite media with extended reflection rules), it is also shown that Eringen's differential model can be reformulated into a consistent strain-based integral nonlocal model with exponential kernel, or into a relative displacement-based integral nonlocal model with a modified exponential kernel. A finite bar in uniform tension is considered as a paradigmatic static case. The strain-based nonlocal behaviour of this bar in tension is analyzed for different kernels available in the literature. It is shown that the kernel has to fulfil some normalization and end compatibility conditions in order to preserve the uniform strain field associated with this homogeneous stress state. Such a kernel can be built by combining a local and a nonlocal strain measure with compatible boundary conditions, or by extending the domain outside its finite size while preserving some kinematic compatibility conditions. The same results are shown for the nonlocal peridynamic bar where a homogeneous strain field is also analytically obtained in the elastic bar for consistent compatible kinematic boundary conditions at the vicinity of the end conditions. The results are extended to the vibration of a fixed–fixed finite bar where the natural frequencies are calculated for both the strain-based and the peridynamic models.     

A question about maximal non-valuation subrings

In this paper we pursue and deep the study of ring extensions \({R \subset S}\) such that R is a maximal non-valuation subring of S [Ben Nasr and Jarboui in Houston J Math, 2009 (in press)]. It is proved in Ben Nasr and Jarboui [Houston J Math, 2009 (in press), Theorem 3.2] that if R is integrally closed with finite Krull dimension, then R is a maximal non-valuation subring of qf (R) iff R is not local and |[R, qf (R)]| = dim(R) + 3. This result encourages us to pose the following question: Let n be a nonzero positive integer greater than 2 and let R be a finite-dimensional domain such that |[R, qf (R)]| = dim(R) + n, does there exists an overring S of R such that R is a maximal non-valuation subring of S? This paper deals mostly with this question. We solve this question in case R is integrally closed.     

U(SMes*)n, (n = 3, 4) and Ln(SMes*)3 (Ln = La, Ce, Pr, Nd): lanthanide(III)/actinide(III) differentiation in agostic interactions and an unprecedented eta3 ligation mode of the arylthiolate ligand, from X-ray diffraction and DFT analysis

Reaction of U(NEt(2))(4) with HS-2,4,6-(t)Bu(3)C(6)H(2) (HSMes) gave U(SMes)(3)(NEt(2))(py) (1), whereas similar treatment of U[N(SiMe(3))SiMe(2)CH(2)][N(SiMe(3))(2)](2) afforded U(SMes)[N(SiMe(3))(2)](3) (2) and U(SMes)(3)[N(SiMe(3))(2)]. The first neutral homoleptic uranium(IV) thiolate to have been crystallographically characterized, U(SMes)(4) (4), was isolated from the reaction of U(BH(4))(4) and KSMes. The first homoleptic thiolate complex of uranium(III), U(SMes)(3) (5), was synthesized by protonolysis of U[N(SiMe(3))(2)](3) with HSMes in cyclohexane. The crystal structure of 5 exhibits the novel eta(3) ligation mode for the arylthiolate ligand. Comparison of the crystal structure of 5 with those of the isomorphous lanthanide congeners Ln(SMes)(3) (Ln = La, Ce, Pr, and Nd) indicates that the U-S, U-C(ipso)(), and U-C(ortho)() bond lengths are shorter than the corresponding ones in the 4f-element analogues, when taking into account the variation in the ionic radii of the metals. The distance between the uranium and the carbon atoms involved in the U...H-C epsilon agostic interaction of each thiolate ligand is shorter, by approximately 0.05 A, than that expected from a purely ionic bonding model. The lanthanide(III)/actinide(III) differentiation was analyzed by density functional theory (DFT). The nature of the M-S bond is shown to be ionic strongly polarized at the sulfur for M = U and iono-covalent (i.e. strongly ionic with low orbital interaction), for M = Ln. The strength of the U...H-C epsilon agostic interaction is proposed to be controlled by the maximization of the interaction between U(+) and S(-) under steric constraints. The eta(3) ligation mode of the arylthiolate ligand is also obtained from DFT.     

Probing structural integrity of single walled carbon nanotubes by dynamic and static compression

We report on a first study of single walled carbon nanotubes (SWCNTs) after application of dynamic (shock) compression. The experiments were conducted at 19 GPa and 36 GPa in a recovery assembly. For comparison, an experiment at a static pressure of 36 GPa was performed on the material from the same batch in a diamond anvil cell (DAC). After the high pressure treatment the samples were characterized by Raman spectroscopy and transmission electron microscopy (TEM). After exposure to 19 GPa of shock compression the CNT material exhibited substantial structural damage such as CNT wall disruption, opening of the tube along its axis (“unzipping”) and tube shortening (“cutting”). Dynamic compression to 36 GPa resulted in essentially complete CNT destruction whereas at least a fraction of the nanotubes was recovered after 36 GPa of static compression though severely damaged. The results of these shock wave experiments underline the prospect of using SWCNTs as reinforcing units in material WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)