CF3C(O)F水合作用的热力学和动力学理论研究

由于氟氟烃（CFCs）对大气臭氧层有破坏作用，人们拟以另外的化合物来代替它，CF3CX2H（X＝H，CI，F）可能是一类合适的取代物．但人们对它及其反应产物对大气的影响还不清楚.CFaC（0）F是CFaCX。H大气光氧化过程的终产物之一[1－3］，其在大气中的后继反应行为将直接关系到CF2     

Synthesis of Spherical Titanium Dioxide Particles by Homogeneous Precipitation in Acetone Solution

Titania powders were synthesized by thermal hydrolysis of titanium tetrachloride in a mixed solvent was studied. The dielectric constant was tuned by regulating the acetone/water volume ratio (R/H ratio) and temperature of the solvent. Hydroxypropyl cellulose (HPC) was used as a steric dispersant. The synthesis were carried out at R/H ratios of 0–4, temperatures of 70–90°C, TiCl₄ concentrations of 0.05–0.2 M, HPC concentrations of 0–5 × 10^–3 g/cm³, and synthesis times of 15–60 min. The TiO₂ particles obtained at an R/H ratio of 0, i.e., pure water system, were fine and agglomerated. In contrast, the TiO₂ particles prepared at an R/H ratio of 3 were uniform and spherical. The TiO₂ particle size increased with increasing TiCl₄ concentration. The synthesis temperature did not influence the particle size, but greatly influenced the morphologyof the TiO₂. Adding HPC to the solution yielded more uniform and spherical particles. In addition, the synthesis time should be longer than 30 min to obtain the most uniform and spherical particles. The dielectric constant of the acetone-water mixed solvent at 28 gave the most uniform and spherical TiO₂ particles. The powders prepared at the condition of 0.1 M TiCl₄, R/H ratio of 3, HPC concentration of 0.001 g/cm³, temperature of 70°C, and synthesis time of 1 h exhibited the most uniform and spherical morphology. The as-synthesized powder was anatase and retained the phase below 400°C. It transformed to the rutile phase after calcination at 700°C.     

17O NMR Investigation of Chemical Homogeneity in Hybrid Systems

¹⁷O NMR experiments using enriched water were performed to followthe hydrolysis-condensation process of dimethyldiethoxysilanetetraethoxysilane and a 1/1 mixture of dimethyldiethoxysilane andtetraethoxysilane (H₂O/OEt = 0.5; pH = 2). The spectrarecorded over several hours time period were simulated to followquantitatively the variations of residual water, hydroxyl groups(Si–¹⁷ H) and oxo bridges (Si–¹⁷ –Si). Presence of a resonance signal due oxo bridges between di- andtetrafunctional Si units clearly demonstrates that co-condensationreactions occur to a large extent between the two alkoxides, and that thesebonds are stable during the aging period.     

Disproportionation of 6,8-Dialkyl-3-thia-2,4,6,8-tetraazabicyclo[3,3,0]octan-7-one 3,3-Dioxides under Conditions of Acid Hydrolysis and Acetylation

Acid hydrolysis and acetylation of 6,8-dialkyl-3-thia-2,4,6,8-tetraazabicyclo[3,3,0]octan-7-one 3,3-dioxides have been studied. 6,8-Dialkyl-3-thia-2,4,6,8-tetraazabicyclo[3,3,0]octan-7-one 3,3-dioxides disproportionate to 4,4'-sulfonyldiiminobis(1,3-dialkylimidazolidin-2-ones) and sulfamide when treated with acid at pH 1 or with acetyl chloride. The kinetics of the disproportionation have been studied.     

N- and O-Alkylation of 3-indolylcyclopropylacetic acid derivatives

2,2-Dimethyl-3-(2-methyl-3-indolyl)cyclopropylacetic acid, its amide and esters, and the corresponding alcohol, viz., the product of ester reduction by LiAlH₄, were synthesized. The chemoselectivity of N- and O-alkylation of these compounds was studied. Selective monoalkylation at the nitrogen atom of the heterocycle, O-alkylation to the side chain, or dialkylation at both nucleophilic sites can be carried out under conditions of phase-transfer catalysis. The N-acylation at the indole fragment of nitrile of this acid occurs only under the Vilsmeier—Haak formylation conditions.     

Nanostructured pure gamma-Fe2O3 via forced precipitation in an organic solvent

Pure maghemite, gamma-Fe(2)O(3), was prepared as ultra fine particles in the nanometer-sized range via the forced precipitation method in an organic solvent. The precipitation of iron(III) ions, from iron(III) chloride in 2-propanol led selectively to highly dispersed particles of ferrihydrite, which upon treatment with temperatures higher than 200 degrees C under dynamic vacuum resulted in high-surface-area particles of gamma-Fe(2)O(3). Precipitation in water also led to ferrihydrite, but the final product, after heating at 300 degrees C, contained a mixture of gamma-Fe(2)O(3) and alpha-Fe(2)O(3) (hematite). The precipitation from iron(III) nitrate in water resulted in goethite which was converted to hematite upon heating. On the other hand, the final product in 2-propanol was a mixture of maghemite and hematite. The products were characterized by FTIR, TGA, XRD, and gas sorption analysis. Nitrogen gas adsorption studies for the pure gamma-Fe(2)O(3) samples revealed mesoporous particles with high surface areas in the range of 70-120 m(2) g(-1) after heat treatment at 300 degrees C. The gamma-Fe(2)O(3) particles retained their gamma-phase as well as their mesoporous structure at relatively high temperatures, as high as 400 degrees C.     

Hydrolysis of 1,2-disubstituted imidazolines in aqueous media

The kinetics of hydrolysis of 1,2-disubstituted imidazolines in aqueous media was studied (pH 2.0—12.5, T = 25—90 °C) by UV spectroscopy. The hydrolysis products were identified. The introduction of a branched substituent into position 2 of the imidazoline ring increases the hydrolytic stability of the compounds. The effect of the pH on the hydrolysis rate of imidazolines is discussed.     

On the Hydrolytic Stability of Organic Ligands in Al-, Ti- and Zr-Alkoxide Complexes

The complexation degrees of Al-, Ti- and Zr-butoxide (M) with unsaturated and saturated -diketones (3-allylpentane-2.4-dione-APD, acetylacetone-ACAC) and -ketoesters (methacryloxyethyl-acetoacetate-MEAA, allylacetoacetate-AAA, ethylacetoacetate-EAA) as organic ligands (L) were examined by IR and ¹³ C NMR spectroscopy and were found to be L:M 1.5. The hydrolytic stability of the ligands of the metal alkoxide complexes (L:M = 1) during hydrolysis/condensation reactions at the molar ratio h (H₂O : OR) = 0.5–2.0 decreases with increasing H$$₂O:complex ratio. Furthermore, the ligand stability depends on the type of metal in the complexes and decreases in the order Al- > Zr- > Ti-butoxide complexes at h=1. The ACAC ligand likewise shows in the Al-, Ti- and Zr-butoxide complexes a high hydrolytic stability (95–100%) at h=1 within 7 days. The Ti- and Zr-butoxide complexes with -ketoesters as ligand show at h=1> a release to a different extent e.g., up to 60% in the case of the MEAA-ligand in the Ti-butoxide complex after 2 days. In general, the hydrolytic stability of the ligands in the Ti-butoxide complexes (L:M = 1, h=1) decreases in the order ACAC > APD > AAA > EAA MEAA. The hydrolysis/condensation reaction of complexes having a weak ligand stability leads to larger particle sizes in the sols than those with stable ACAC ligands. The results contribute to a more controlled synthesis of sols and of new inorganic-organic hybrid polymers via the sol-gel process.     

Synthesis and transformations of metallocycles. 9. Regioselective and stereoselective synthesis of al-substitutedtrans-3,4-dialkylaluminocyclopentanes catalyzed by (η5-C5H5)2ZrCl2

A new stereoselective method is developed for the synthesis of 1-chloro-, 1-alkoxy-, and 1-N,N-dialkylaminoalumino-cyclopentanes from -olefins, metallic magnesium, and aluminum halides (AlCl₃, RO-AlCl₂, R₂N-AlCl₂) in the presence of catalytic amounts of Cp₂ZrCl₂ (Cp=⁵-C₅H₅). The products from hydrolysis and deuterolysis of the Al-substituted 3,4-dialkylaluminocyclopentanes (ACP) have the threo configuration.For Communication 8, see [1].Institute of Organic Chemistry, Urals Branch, Russian Academy of Sciences, 450054 Ufa. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1393–1397, June, 1992.     

Fractionation and purification of antioxidant peptides from Chinese sturgeon (Acipenser sinensis) protein hydrolysates prepared using papain and alcalase 2.4L

Protein hydrolysates have the potential to be natural and safer sources of bioactive peptides. In this study, two proteases were used to hydrolyze Chinese sturgeon (Acipenser sinensis) protein, and the hydrolysates were then purified to yield antioxidant peptides. The degree of hydrolysis of 23.56 % and 18.14 % was obtained using papain and alcalase 2.4L, respectivly, and hydrolysates had 96.80 % and 87.24 % total amino acid content, respectivly. The papain hydrolysate (PH) and alcalase 2.4L hydrolysate (AH) showed good antioxidant activity against DPPH^? (IC₅₀ of 3.64 and 3.15 mg/mL) and ABTS^?+ (IC₅₀ of 1.92 and 1.58 mg/mL), respectively. The low-molecular-weight (<1000 Da) fraction of both hydrolysates demonstrated the highest antiradical activity (IC₅₀ of 2.59 and 2.31 mg/mL, DPPH) and (IC₅₀ of 1.54 and 1.36 mg/mL, ABTS), respectively. Nine peptides were separated from both hydrolysates using reverse phase high performance liquid chromatography (RP-HPLC). The IC₅₀ for ABTS^?+ scavenging activity of peptide P5 with valine, glycine and asparagine (MW of 282.13 Da) from PH, and peptide P3 with histidine, glycine and alanine (MW of 302.74 Da) from AH was 0.89 and 0.72 mg/mL, respectively. The fractions and purified peptides obtained from Chinese sturgeon hydrolysates could be utilized as natural antioxidant substitutes in pharmaceuticals and food products.