Towards supramolecular fixation of NOX gases: encapsulated reagents for nitrosation

The use of simple calix[4]arenes for chemical conversion of NO2/N2O4 gases is demonstrated in solution and in the solid state. Upon reacting with these gases, calixarenes 1 encapsulate nitrosonium (NO+) cations within their cavities with the formation of stable calixarene-NO+ complexes 2. These complexes act as encapsulated nitrosating reagents; cavity effects control their reactivity and selectivity. Complexes 2 were effectively used for nitrosation of secondary amides 5, including chiral derivatives. Unique size-shape selectivity was observed, allowing for exclusive nitrosation of less crowded N-Me amides 5 a-e (up to 95 % yields). Bulkier N-Alk (Alk>Me) substrates 5 did not react due to the hindered approach to the encapsulated NO+ reagents. Robust, silica gel based calixarene material 3 was prepared, which reversibly traps NO2/N2O4 with the formation of NO+-storing silica gel 4. With material 4, similar size-shape selectivity was observed for nitrosation. The N-Me-N-nitroso derivatives 6 d,e were obtained with approximately 30 % yields, while bulkier amides were nitrosated with much lower yields (<8 %). Enantiomerically pure encapsulating reagent 2 d was tested for nitrosation of racemic amide 5 t, showing modest but reproducible stereoselectivity and approximately 15 % ee. Given high affinity to NO+ species, which can be generated by a number of NOX gases, these supramolecular reagents and materials may be useful for NOX entrapment and separation in the environment and biomedical areas.     

氮原子在Ni平坦和缺陷表面上的吸附和振动

 构造了氮－镍相互作用的5－参数Morse势，研究了氮原子在Ni（\r\n100），Ni（110）和Ni（111）平坦表面的吸附和振动，获得了氮原子\r\n在三个低指数表面的吸附位、吸附构型、结合能和本征振动等数据，计\r\n算结果与实验结果非常吻合．同时，与Ni（100）表面对比，系统研究\r\n了氮原子在Ni（510）台阶面的吸附和扩散．计算结果表明，氮原子在\r\n台阶下部形成最稳定的吸附态，台阶对下台面上扩散的氮原子形成捕获\r\n势，对上台面上扩散的氮原子形成反射势．     

Effects of double substitution on the thermodynamic stabilities of nitrogen radicals

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Covalent Inorganic Azides

The chemistry of covalent inorganic azides originated with the synthesis of aqueous HN₃ solutions by Tony Curtis in 1890. A little later, in 1900, it proved possible to prepare iodine azide, IN₃, as the first member of the meanwhile complete series of halogen azides. Since then it has been possible to synthesize, in addition to HN₃ and the stable salt H₂NSbF, azide compounds of elements from Groups 13 to 17. In these compounds the N₃ moiety acts as a pseudohalogen and is primarily covalently coordinated to the nonmetal. Only a few organic azides, however, as well as HN₃, H₂N, and all halogen azides have been thoroughly studied with respect to structure and bonding. The combined application of diffraction methods (X-ray and electron diffraction) and microwave spectroscopy together with quantum chemical approaches such as ab initio SCF and density functional calculations have led in the last few years to an improved understanding of the molecular properties of numerous nonmetal azides, almost all of which are explosive. This interaction of theory and experiment has greatly enhanced the development of azide chemistry and has led to realistic expectations for the synthesis of as yet unknown nonmetal azides.     

Characterization of Titania/Silica Gel by Means of Low-Pressure Nitrogen Adsorption

Adsorbents synthesized by grafting of titania onto mesoporous silica gel surfaces at different temperatures were studied by means of nitrogen adsorption–desorption and water desorption. The pore size distribution f(R_p) of titania/silica gel depends on the titania concentration (C_TiO2) and the temperature of titania synthesis. Nonuniformity of TiO₂ phase is maximal at a low C_TiO2 value (3.2 wt.% anatase deposited at 473 K), and two peaks of the fractal dimension distribution f(D) are observed at such a concentration of titania, but at larger C_TiO2 values, only one f(D) peak is seen. More ordered filling of pores and adsorption sites by nitrogen, reflecting in the shape of adsorption energy distributions f(E) at different pressures of adsorbate, is observed for adsorbent with titania (rutile+anatase) grafted on silica gel at a higher temperature (673 K).     

Thermochemistry of adducts of some bivalent transition metal bromides with 4-chloroaniline

The compounds [MBr₂(p-clan)₂] (where M is Mn(II), Fe(II), Co(II), Ni(II), Cu(II) or Zn(II); p-clan = 4-chloroaniline) were synthesized and characterized by melting points, elemental analysis, thermal analysis and electronic and IR spectroscopy. The enthalpies of solution of the adducts, metal(II) bromides and 4-chloroaniline in methanol, 1.2 M aqueous HCl or 25% (v/v) 1.2 M aqueous HCl in methanol were measures and by using thermochemical cycles, the following thermochemical parameters for the adducts have been determined: the standard enthalpies for the Lewis acid/base reactions (Δ_rH°), the standard enthalpies of formation (Δ_fH°), the standard enthalpies of decomposition (Δ_DH°), the lattice standard enthalpies (Δ_MH°) and the standard enthalpies of the Lewis acid/base reactions in the gaseous phase (Δ_rH°(g)). The mean bond dissociation enthalpies of the metal(II)-nitrogen coordinated bonds and the enthalpies of adduct formation in the gaseous phase have been estimated.     

Acid-catalyzed attack of the dinitrogen ligand in thecis-(Me2PhP)4Mo(N2)2 andtrans-(Ph2PCH2CH2PPh2W(N2)2 complexes by nitronium and nitrosonium cations with the formation of nitrogen oxides

The interaction of labeled dinitrogen complexescis-(Me₂PhP)₄Mo(¹⁵N₂)₂ andtrans-(dppe)₂W(¹⁵N₂)₂ with non-labeled nitronium and nitrosonium fluoroborates,¹⁴NO₂BF₄ and¹⁴NOBF₄, in sulfolane at room temperature in the presence of H₂SO₄ results in rapid formation of labeled nitrous and nitric oxides (¹⁵N¹⁴NO,¹⁵NO), as well as¹⁵N¹⁴N. The yield of the products depends on the reagent ratio and reaches 10–20 mol. % per mole of a complex under optimum conditions. The mechanism of the reactions found is proposed. It involves the step of protonation of the dinitrogen ligand to form the corresponding hydrazido(2–) derivatives, which are then attacked by nitronium or nitrosonium cations. In accordance with the mechanism proposed, it was established that the hydrazido(2–) complexes, (Me₂PhP)₃Mo(¹⁵N₂H₂)Cl₂ and (dppe)₂W(¹⁵N₂H₂)Cl₂, are capable of forming¹⁵N¹⁴NO,¹⁵NO, and¹⁵N¹⁴N under the action of¹⁴NO₂BF₄ and¹⁴NOBF₄ in the absence of an acid.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 13–13, July, 1995.     

Modification of Surface and Structural Properties of Ordered Mesoporous Silicates

Two simple modification methods for ordered mesoporous silicas were examined and compared. MCM-41 molecular sieve was physically coated with 4-cyano-4-biphenyl [4(4-pentenyloxy)]benzoate (CBPB) and chemically modified using trimethylethoxysilane. The structural and surface properties of the obtained materials were characterized using elemental analysis, thermogravimetry and nitrogen adsorption over a wide pressure range.It was shown that the pore size of the MCM-41 material was not decreased significantly after the coating procedure, even for high loadings of CBPB. Moreover, low pressure adsorption measurements indicated that significant fractions of the MCM-41 surface were not covered by CBPB, even for high CBPB loadings, which suggests that the attained coverage may be very nonuniform. The chemical bonding procedure led to a marked decrease in the pore size and change of surface properties.It was demonstrated that nitrogen adsorption measurements provide a means of a thorough characterization of modified MCM-41 materials, allowing to estimate the surface area, pore volume and pore size distribution. Moreover, low pressure adsorption data can be used to qualitatively or semiquantitatively assess the surface coverage of the coated/bonded organic groups, which may be used to estimate the uniformity of the coverage and therefore, the usefulness of the modification procedure.     

Analysis of nitriles at low parts per million levels by capillary gas chromatography

Two methods have been developed for the determination of trace levels of acetonitrile and propionitrile in light naphthas. One involves clean-up and preconcentration by medium pressure liquid chromatography (MPLC) in which nitriles are concentrated ten-fold while the complex hydrocarbon matris is removed. The concentrated solution is then analyzed by high resolution GC with flame ionization detection. The second method involves direct injection of samples into a capillary GC equipped with chemiluminescence nitrogen detection. The results and repeatability obtained from both methods are comparable. Preconcentration enables identification by GC-MS and simultaneous analysis of other polar species, with no need for selective detectors. Direct analysis is, on the other hand, much less time-consuming and requires less sample.     

Treatment of coke plant wastewater by A/O fixed biofilm system

The long-term environmental impacts of wastewa-ter from coke plant can be very high, especially due to the discharge of large amounts of wastewater. The composition of coke plant wastewater is complicated and varies from one factory to another, depending …