Density functional theory study of the regio‐ and stereoselectivity of 1,3-dipolar cycloaddition reactions between 2-ethylthio-4-phenyl-1-azetin and some substituted nitrile oxides

The mechanism (regio- and stereoselectivity) of 1,3-dipolar cycloaddition (1,3-DC) of 2-ethylthio-4-phenyl-1-azetin 1 with benzonitrile oxide 2a, 2-aminobenzonitrile oxide 2b and 2-azidobenzonitrile oxide 2c has been investigated by density functional theory-based reactivity indices and activation energy calculations at B3LYP/6-31G(d,p) level of theory in the gas and solvent phase. Thermodynamic and kinetic parameters of the possible ortho/meta regioisomeric and endo/exo stereoisomeric pathways have been determined. In order to rationalize complete endo selective fashion provided by these 1,3-DC cycloadditions, a natural steric analysis between NLMOs i,j for TS1ox and TS1on and also a second-order interaction energy, E ², analysis between the donor–acceptor orbitals in these TSs were carried out. In all cases, the ortho pathways are more favorable compared to the meta alternatives and it is found that the endo pathway is preferred. Our results show that these cycloadditions follow an asynchronous one-step mechanism with a nonpolar character. Theoretical data are in good agreement with the experimental results.     

Dispersion-corrected DFT study on the carbon monoxide sensing by B<Subscript>2</Subscript>C nanotubes: effects of dopant and interferences

Electrical sensitivity of a boron carbon nanotube (B₂CNT) was examined toward carbon monoxide (CO) molecule by using dispersion-corrected density functional theory calculations. It was found that CO is weakly adsorbed on the tube, releasing energy of 3.5–4.1 kcal/mol, and electronic properties of the tube are not significantly changed. To overcome this problem, boron and carbon atoms of the tube were substituted by aluminum and silicon atoms, respectively. Although both Al and Si doping make the tube more reactive and sensitive to CO, Si doping seems to be a better strategy to manufacture CO chemical sensors due to the higher sensitivity without deformation of nanotube structure after adsorption procedure. Moreover, it was shown that some interference molecules such as H₂O, H₂S and NH₃ cannot significantly change the electronic properties of B₂CNT. Therefore, the Si-doped tube might convert the presence of CO molecules to electrical signal.     

Constructive Approximation in de Branges–Rovnyak Spaces

In most classical holomorphic function spaces on the unit disk in which the polynomials are dense, a function f can be approximated in norm by its dilates \(f_r(z):=f(rz)~(r<1)\). We show that this is not the case for the de Branges–Rovnyak spaces \(\mathcal{H}(b)\). More precisely, we exhibit a space \(\mathcal{H}(b)\) in which the polynomials are dense and a function \(f\in \mathcal{H}(b)\) such that \(\lim _{r\rightarrow 1^-}\Vert f_r\Vert _{\mathcal{H}(b)}=\infty \). On the positive side, we prove the following approximation theorem for Toeplitz operators on general de Branges–Rovnyak spaces \(\mathcal{H}(b)\). If \((h_n)\) is a sequence in \(H^\infty \) such that \(\Vert h_n\Vert _{H^\infty }\le 1\) and \(h_n(0)\rightarrow 1\), then \(\Vert T_{\overline{h}_n}f-f\Vert _{\mathcal{H}(b)}\rightarrow 0\) for all \(f\in \mathcal{H}(b)\). Using this result, we give the first constructive proof that, if b is a nonextreme point of the unit ball of \(H^\infty \), then the polynomials are dense in \(\mathcal{H}(b)\).     

Convergence Theorems for Pointwise Asymptotically Strict Pseudo-Contractions in Hilbert Spaces

A new class of contractive mappings called pointwise asymptotically ?-strict pseudo-contractions in Hilbert spaces is introduced and weak convergence of the sequence generated by Mann's iterative scheme to a fixed point of a uniformly Lipschitzian and pointwise asymptotically ?-strict pseudo-contractive mapping T in a Hilbert space is established. Also, a new kind of monotone hybrid method which is a modification of Mann's iterative scheme for finding a common fixed point of an infinitely countable family of uniformly Lipschitzian and pointwise asymptotically ?-strict pseudo-contractive mappings is proposed. Strong convergence of the sequence generated by the proposedmonotone hybrid method for an infinitely countable family of uniformly Lipschitzian and pointwise asymptotically ?-strict pseudo-contractive mappings in a Hilbert space is also shown. The results presented in this article extend and improve some known results in the literature.     

Chiral separation of three agrochemical toxins enantiomers by high-performance liquid chromatography on a vancomycin crystalline degradation products-chiral stationary phase

This work aims to evaluate for the enantiomeric separations of three agrochemical toxins: haloxyfop-methyl, fenoxaprop-p-ethyl and indoxacarb on crystalline degradation products-chiral stationary phase (CDP-CSP) of high-performance liquid chromatography (HPLC) under normal and polar organic phases. In the normal phase, the mobile phase was n-hexane with alcohols including methanol and isopropanol as polar modifiers. In the polar organic phase mode, the mobile phase was methanol with different percentages of triethylammunium acetate. The influence of flow rate (0.3-0.9 mL/min), analyte concentration and silica gel particle sizes (10, 15 and 30 microm) was investigated. This new chiral stationary phase showed excellent stereoselectivity for the two enantiomers of haloxyfop-methyl and fenoxaprop-p-ethyl and chiral recognition for indoxacarb under normal-phase mode. However, under polar organic phase, only indoxacarb was separated (alpha < 1.5). The chromatographic results were compared with commercial chiral columns.     

Distances entre exponentielles et puissances d’éléments de certaines algèbres de Banach

Let A be a Banach algebra which does not contain any nonzero idempotent element, let γ > 0, and let . We show that if then . We also show, assuming a suitable spectral condition on x, that if , then Received: 12 July 2006 Revised: 31 January 2007     

The Minimal Cqupling of Charged spin-3/2 Fields to an Extended Abelian Gauge Model

Charged spin-3/2 fields are coupled to an extended gauge model without the total suppression of the vector degrees of freedom which usually takes place as a consequence of simultaneously imposing the Maxwell and Rarita-Schwinger U(1) symmetries.     

Magnetic properties of nanostructured MnZn ferrite

Mn_0.5Zn_0.5Fe₂O₄ nanoparticles (10-30 nm) have been prepared via mechanochemical processing, using a mixture of two single-phase ferrites, MnFe₂O₄ and ZnFe₂O₄. SQUID measurements (field-cooled magnetization curves and hysteresis loops) were performed to follow the mechanically induced evolution of the MnFe₂O₄/ZnFe₂O₄ mixture submitted to the high-energy milling process. The resulting single MnZn nanoferrite phase was characterized by SQUID (M-H curve), Faraday balance (M-T curve) and transmission electron microscopy. The magnetic characteristics of the mechanosynthesized material were compared with those of bulk Mn_0.5Zn_0.5Fe₂O₄. It was found that the saturation magnetization of nanostructured Mn_0.5Zn_0.5Fe₂O₄ (87.2 emu/g) is lower than that of the bulk Mn_0.5Zn_0.5Fe₂O₄, but, the Néel temperature of the sample (583 K) is higher than that of the bulk Mn_0.5Zn_0.5Fe₂O₄.     

C-20 ketone reduction of hydrocortisone by rice field microalga <Emphasis Type="Italic">Chlorella vulgaris</Emphasis> MCCS 013

A unicellular microalga, Chlorella vulgaris, was isolated from rice field and applied in the biotransformation experiment of hydrocortisone (1). This strain has not been previously tested for hydrocortisone bioconversion. Fermentation was carried out in BG-11 medium supplemented with 0.05% substrate at 25°C for 14 days incubation. The products obtained were chromatographically purified followed by their characterization using spectroscopic methods. 11β,17α,20β,21-Tetrahydroxypregn-4-en-3-one (2), 11β,17β-dihydroxyandrost-4-en-3-one (3), and 11β-hydroxyandrost-4-ene-3,17-dione (4) were the main bioproducts in the hydrocortisone bioconversion. Bioreaction characteristics observed were 20-ketone reduction for accumulation of compound 2 and side chain degradation of the substrate to prepare compounds 3 and 4. Time course study showed the accumulation of the product 2 from the second day of the fermentation and 3 as well as 4 from the third day. All the metabolites reached their maximum concentration in seven days. Microalgal 18S rRNA gene was also amplified by PCR. PCR products were sequenced to confirm their authenticity as 18S rRNA gene of microalgae. The result of PCR blasted with other sequenced microalgae in NCBI showed 100% homology to the 18S small subunit rRNA of six strains of Chlorella vulgaris.     

Synthesis of new phosphorus ylides: Spectroscopic and X‐ray structural studies

Stable phosphoranes, Ar₃P = CHCOR (R = C₆H₅, C₆H₄NO₂, C₆H₄OCH₃, CH₃, OCH₂C₆H₅; Ar = p‐tolyl or phenyl), have been C‐acylated by acetic anhydride to obtain new types of phosphorus ylides. Synthesis and characterization of six phosphorus ylides of the type Ar₃PC(COCH₃)(COR) are reported. The reaction of {(p‐tolyl)₃PCHCOC₆H₅} ( I ), {(p‐ tolyl)₃PCHCOC₆H₄NO₂} ( II ), {Ph₃PCHCOC₆H₄NO₂} ( III ), {Ph₃PCHCOC₆H₄OCH₃} ( IV ), {(p‐tolyl)₃PCHCOCH₃} ( V ), and {Ph₃PCHCOOCH₂C₆H₅} ( VI ) with acetic anhydride in dry chloroform as solvent gives (p‐tolyl)₃PC(COMe)(COC₆H₅), α‐acetyl‐α‐benzoylmethy‐lenetriphenylphosphorane ( 1 ), {(p‐tolyl)₃PC(COMe) (COC₆H₄NO₂)} ( 2 ), {Ph₃PC(COMe)(COC₆H₄NO₂)} ( 3 ), {Ph₃PC(COMe)(COC₆H₄OCH₃)} ( 4 ), {(p‐tolyl)₃ PC(COCH₃)₂} ( 5 ), and {Ph₃PC(COMe)(COOCH₂ C₆H₅)} ( 6 ). Single crystal X‐ray analyses for ylides 2 , 5 , and 6 reveal the monoclinic ( 2, 5 ) and triclinic ( 6 ) crystal systems. Characterization of the obtained compounds was also performed by elemental analysis, IR, ¹H, ³¹P, and ¹³C NMR. The geometries of these compounds have been investigated using density functional theory (DFT). In addition, electronic parameters of these compounds such as HOMO and LUMO energy, Mulliken partial charge, and dipole moment were obtained. In this paper, the reactivity of these ylides is discussed in regard to the aforementioned data. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:475–485, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20633