Formation of organic peroxides in the photooxidation of CH_4

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Structure of Dimers and the Nature of Color in 4′-Nitro-4-dimethylaminoazobenzene Solutions

A mechanism is proposed for the formation of stable dimers of 4′-nitro-4-dimethylaminoazobenzene dye (4′-nitro-DAB)₂ in solution, the existence of which in a vapor phase was established in 1965. It is shown that (4′-nitro-DAB)₂ dimers are stable also in neutral and moderately acidic solutions. Their UV–Vis spectra are similar to the spectra of the same solutions of 4-dimethylaminoazobenzene (DAB) containing DAB₂ dimers as the ground state. Like DAB₂, (4′-nitro-DAB)₂ dimers are reversibly converted to di- and triprotonated dimers under conditions of low and moderate acidity. In the process, the yellow color of the initial solution changes to red. It is concluded that the great stability of the dimers in the liquid and vapor phases is due to their inter-monomer bonds being formed with the participation of electrons promoted from the sp²- orbitals of N-atoms in azo-groups N=N to the Rydberg 3s-orbitals of the N=N-group (Rydberg bonds). It is established that at high acidities, the triprotonated dimers (the red solution) decompose reversibly into diprotonated monomers (the yellow solution). Structural formulas are proposed for the protonated species.     

Two-Parameter Stochastic Resonance in a Model of Electrodissolution of Fe in H_2SO_4

IntroductionStochastic resonance (SR) is a nonlinear effect which describes the optimal detection of a weak periodic signal by the action of external noise in nonlinear systems. SR was originally proposed to account for periodicity in the Earth's ice ages1, and it has been observed in a wide range of biological2-4 , physical5 and chemical6 systems. The systems mentioned above which may give rise to SR have a denominator despite many examples of SR in different scientific areas. It is noted…     

Analytical Properties of 4, 4′-Biazobenzenediazoaminobenzene and its Applications in Spectrophotometry

Abstract

The spectral characteristics and analytical properties of 4, 4′-Biazobenzenediazoaminobenzene as a new chromogenic reagent have been described and the optimum conditions for reaction with eight metal ions are presented. In the presence of Triton X-100 and sodium tetraborate solution, the reagent can be used for the determination of Hg, Ni, Cd. The molar absorptivities are 1.8×10⁵ l.mol^?1. cm^?1 at 515 nm for mercury, 2.0×10⁵ l.mol^?1. cm^?1 at 540 nm for nickel, and 1.8×10⁵ l.mol^?1.cm^?1 at 526 nm for cadmium. The recommended procedure has been used for the spectrophotometric determination of cadmium in waste water.     

Potentiometric investigation of NaSO 4 − ion pair formation in NaClO4 medium

The ion pair formation of NaSO ₄ ⁻ has been investigated potentiometrically in 1M NaClO ₄ medium at 25°C using two different sodium-selective indicator electrodes and a perchlorate reference electrode. The stability constant of NaSO ₄ ⁻ obtained in this study was . Although is small, it lowers the free sulfate concentration drastically in 1M NaClO ₄ medium and is a factor which should be considered in the use of NaClO ₄ as inert supporting electrolyte.     

Halogenation of Pyrazoles Using N‐Halosuccinimides in CCl4 and in Water

Reaction of pyrazoles with N‐halosuccinimides (NXS, X=Br, Cl) in either CCl₄ or water gave 4‐halopyrazoles in excellent yields. The reaction was carried out under mild conditions and did not require any catalysts or special precautions. The reaction provides an efficient method for 4‐C halogenation of pyrazoles.     

The mechanism and pathway of the ozonation of 4-chlorophenol in aqueous solution

Chlorophenols (CPs) have been widely used in dif- ferent formulations as preservatives, herbicides, insec- ticides, bactericides and solvents. Parts of chlorophe- nols were released to the natural environment during the usage. As a result, many water sources were con- taminated with CPs[1,2]. Furthermore, they also can be formed during the disinfection of phenol containing water by chlorination. Several CPs are recognized as the priority pollutants by the United States EPA (En- vironmenta…     

Theoretical Analyses of 4f11 →4f105d Excitation Spectra of Er3+ Doped in LiYF4

Spectral terms and J-spectral multiplet of low-spin 4f^105d configuration of Er^3 were obtained with the method of ligand field theory. According to the selection rules for dipole transitions, the excitation spectra of Er^3 doped in LiYF4 in vacuum ultraviolet region (120～160nm) of the spectrum were theoretically interpreted by applying the crystal field model, and the six bands were assigned to the spin-allowed transitions from the ground state (^4I15/2) to J-spectral multiplet of low-spin 4f^105d configuration of Er^3 ion.     

Esterification and Selective Esterification in the Presence of TiCl4

A series of carboxylic acids was esterified to the corresponding esters with TiCl_4 as catalyst at room temperature,in high yields.This catalyst was highly effective for the selective esterification of primary alcohols with carboxylic acids,in the presence of secondary alcohols,and for the selective esterification of saturated acid with alcohol in the presence of conjugated acid or aromatic acid.On account of the high yield,high chemoselectivity,mild condition,and being free of other dehydrants,this is an efficient method.     

Routes of π-electron delocalization in 4-substituted-1,2-benzoquinones

The substituent effect in 4-substituted-1,2-benzoquinone is investigated by means of modeling using B3LYP hybrid functional in conjunction with the 6-311+G(d,p) basis set. The interrelation between different types of substituents, X = NO, NO(2), CN, CHO, H, Me, OMe, OH, NH(2), NHMe and N(Me)(2), and both CO groups has been characterized both qualitatively and then quantitatively by means of several measures of π-electron delocalization (HOMA, MCI, DI, FLU) based on structural and electronic properties of 4-substituted-1,2-benzoquinones chosen for analysis. Results of this analysis clearly show that only the meta-placed CO group is affected by substituents, whereas the para-placed CO group is rather insensitive to substitution. These observations may help to explain diversified chemical properties (including reactivity) of CO centers in o-benzoquinone derivatives. Among others, they may explain differences in proton-accepting properties of carbonyl O atoms, as it is shown for simple models in which carbonyl groups in o-benzoquinone act as proton acceptors in H-bonds of O···H-F type.     

Regioselective quaternization of N-alkyl-4-nitro- 1,2,3-triazoles in ButOH–HClO4 system

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Temperature dependence of broadening and shifts of methane lines in the ν4 band

We have recorded high-resolution absorption spectra of methane broadened by dry air and by N₂ at temperatures from −63 to 41°C using a Fourier transform spectrometer. These spectra have been analyzed to determine pressure broadening and line-shift coefficients, along with their temperature dependences, for 148 lines in the ν₄ fundamental band of ¹²CH₄. The experimental uncertainties for lines with J″≤10 are generally <2% for the broadening coefficient b⁰_L, 6–12% for its temperature dependence exponent n, 6–20% for the line-shift coefficient δ⁰, and 20–40% for its temperature dependence coefficient δ′; for J″> 10 the experimental uncertainties are somewhat larger. These results, especially for N₂-broadening, are in excellent agreement with other recent measurements. Since the present results cover a wide range of rotational quantum numbers (J″ up to 14), the variation of the temperature dependence of the half-widths and shifts from line to line within the ν₄ band is also examined.     

Effect of EDTA on the diffusion behavior of 99TcO4 − and ReO4 − in GMZ bentonite

Polyaminopolycarboxylate EDTA with powerful metal-binding property, which often presents in low and intermediate-level waste, can enhance the radionuclide migration. The effect of EDTA on the diffusion behavior of ⁹⁹TcO₄ ^? and ReO₄ ^? in Gaomiaozi (GMZ) bentonite was investigated by using through-diffusion method. For ⁹⁹TcO₄ ^? in present of EDTA, the D _e values was (1.2 ± 0.1) × 10^?11 m²/s, which was 4 times higher than that in absent of EDTA. It can be explained that the complexation between ⁹⁹TcO₄ ^? and EDTA might be formed. By contrast, the D _e values of ReO₄ ^? remained unchanged in present or absent of EDTA, indicating that ReO₄ ^? could not complex with EDTA. However, the diffusion of ReO₄ ^? could be increased in present of EDTA, the D _a value was found to be increased from 1.8 × 10^?10 to 5.4 × 10^?10 m²/s. It demonstrated that ReO₄ ^? need more drastic conditions to form the Re(VII)–EDTA complexes than those used for ⁹⁹TcO₄ ^?. For both ReO₄ ^? and ⁹⁹TcO₄ ^?, the rock capacity factor α is less than the total porosity ε _tot, indicating that they has little retention/sorption on the surface of bentonite.     

Discontinuous behavior of Rayleigh relaxation in supersaturated aqueous NH_4H_2PO_4 Solution

The algorithm of Rayleigh intensity correlation is employed for the elucidation of relaxa-tion time constants of the aqueous NH_4H_2PO_4 solution with various concentrations.The resultshows that there is a discontinuous(abrupt)increases in the relaxation time constant as the super-saturation state is reached.This quantity,the relaxation time constant,therefore,can be an orderparameter.Also discussed is the dependence of the relaxation time constant on the aggregationnumber n in(H_2PO_4~-)_n.This dependence is complicated and may be crucial in understanding theaggregation process in the supersaturation state.     

Asymmetric Induction by β-Cyclodextrins in NaBH4 Reduction of Ketones

Asymmetric reduction of various prochiral ketones was achieved with sodium borohydride utilizing -CD or its derivative, mono-6-deoxy-6-[N-(2-aminoethyl)]amino--CD (-CD-en) as a chiral template. It was found that pre-equilibrium between ketone and -CD derivative and low reaction temperature increase asymmetric induction. The extent of asymmetric induction and the absolute configuration of the resulting secondary alcohols are highly dependent upon the nature of the ketones and also -CD derivatives. A mechanistic scheme is suggested to explain the dependency.     

Chemical Proteomic Profiling of Protein 4′-Phosphopantetheinylation in Mammalian Cells

Protein 4′-phosphopantetheinylation is an essential post-translational modification (PTM) in prokaryotes and eukaryotes. So far, only five protein substrates of this specific PTM have been discovered in mammalian cells. These proteins are known to perform important functions, including fatty acid biosynthesis and folate metabolism, as well as β-alanine activation. To explore existing and new substrates of 4′-phosphopantetheinylation in mammalian proteomes, we designed and synthesized a series of new pantetheine analogue probes, enabling effective metabolic labelling of 4′-phosphopantetheinylated proteins in HepG2 cells. In combination with a quantitative chemical proteomic platform, we enriched and identified all the currently known 4′-phosphopantetheinylated proteins with high confidence, and unambiguously determined their exact sites of modification. More encouragingly, we discovered, using targeted chemical proteomics, a potential 4′-phosphopantetheinylation site in the protein of mitochondrial dehydrogenase/reductase SDR family member 2 (DHRS2).     

Crystal Structure of Derivative of H_4′-NOBIN and the Applications in Hetero-Diels-Alder Reaction

Novel Schiff bases of H4′-NOBIN 5a and 5b were synthesized by condensation of 3 with aldehydes. Compound 5b was structurally characterized by single-crystal X-ray diffraction. The asymmetric hetero-Diels-Alder reactions were carried out with high yields and good enan-tioselectivities in the presence of Ti-(S)-5a complex as catalyst. Crystallographic data for 5b: C27H22BrNO, Mr = 456.37, triclinic, space group P1 with a = 9.1618(2), b = 10.3836(2), c = 12.7718(2), α = 105.4860(10),β = 94.6360(10), γ = 108.4610(10)o, V = 1092.32(4)3, Z = 2, Dc = 1.388 g/cm3, μ = 1.900 mm-1, F(000) = 468, R = 0.0476 and wR = 0.1248 for 3092 observed reflections (Ⅰ > 2σ(Ⅰ)).     

Estimation of uncertainty in measurement of boron in Zr–Nb alloy samples by BF4 − ion selective electrode

Boron doped zirconium–niobium alloy is employed for neutron reactivity control in advanced nuclear reactors. An accurate knowledge of the boron content and uncertainty associated with the measurement result is essential for reactivity calculations. In view of the refractory nature of the alloy, boron determination in these matrices is a challenging task for analytical chemists. Also due to non-availability of matrix-matched reference materials, direct solid analysis cannot be resorted to. With this in view, a simple and sensitive method based on potentiometric determination of boron as tetrafluoroborate with tetrafluoroborate ion selective electrode has been developed. After dissolving the sample, boron was quantitatively converted to BF₄ ⁻ with the addition of HF. Potential response was measured with Orion 9305 BN BF₄ ⁻ ion selective electrode. The response of the ion selective electrode was Nernstian in the range of 0.1–100.0 μg/g of boron in the solution. The method has been validated by two independent methods namely spectrophotometry and inductively coupled plasma-atomic emission spectrometry (ICP-AES). All identifiable sources of uncertainties in the methodology have been individually assessed. The combined uncertainty is calculated employing uncertainty propagation law. The expanded relative uncertainty in the measurement (coverage factor 2) is 6.50%.     

Experimental investigation of the formation of double phosphates in the LaPO4–NaF system

In the course of segregation smelting of rare-earth and rare metal raw materials with a fluxing agent (NaF), two immiscible melts form, one of which is a silicate melt and the other is a phosphate–salt melt. The silicate melt is enriched with Fe₂O₃, Al₂O₃, SiO₂, and Nb₂O₅, and the phosphate–salt melt is dominated by P₂O₅, TR₂O₃, Sc₂O₃, and Y₂O₃, and also with Ca, Sr, and Ba oxides. Chemical reactions between lanthanum orthophosphate and sodium fluoride in the LaPO₄–NaF system were studied for developing a technology for processing the phosphate–salt (rare-earth metal) melt. It was found that a metathesis reaction gives double phosphate Na₃La[PO₄]₂ and binary fluoride NaLaF₄. The products of crystallization of melts in the LaPO₄–NaF system decompose in weak mineral acids unlike those in conventional technology for processing monazite raw material.