A fibrous hypercrosslinked sorbent prepared on PP-ST-DVB matrix via post-crosslinking reaction

A fibrous sorbent possessing abundant micropore structure was firstly prepared via post-crosslinking reaction on the PP-ST-DVB original fiber. Its micromorphology and sorptive properties were investigated, and the results demonstrated that the novel fibrous hypererosslinked sorbent has narrow pore-size distribution, small average porous radius （1.90 nm）, high specific surface area （362.31 m^2/g）, and fine sorptive properties for small organic molecules.     

Syntheses of sulfoxide derivatives in the benzodiazine series. Diazines. Part 37

Syntheses of new sulfinylcinnolines, quinoxalines, quinazolines and phtalazines have been investigated starting from the appropriate halogenobenzodiazine derivatives. The latter were converted in one step to the corresponding sulfanyl benzodiazines which upon oxidation with m-CPBA led to the corresponding sulfoxide derivatives of benzodiazines in moderate to good yields. In parallel to this study, an improved method for the synthesis of 2-methylsulfinylquinoxaline starting from 2-sulfanylquinoxaline is also described and in the quinazoline series a synthetic route has been developed to prepare 2-tert-butyl-5-phenylsulfinylquinazoline with satisfactory yield as well as 2-tert-butyl-5-tert-butylsulfinyl-4(3H)-quinazolinone and 2-tert-butyl-8-tert-butylsulfinyl-4(3H)-quinazolinone.     

PHOTOVOLTATC EFFICIENCIES OF MICROCRYSTALLINE AND ANHYDROUS CHLOROPHYLL a

Abstract— A thin layer of chlorophyll a (around 2000 Å). a p -type organic semiconductor. was sandwiched between two different metals. aluminum and silver. We used the photovoltaic effect in order to study the efficiency of light conversion by the crystalline and anhydrous forms of Chl a . When the photovoltaic cell is illuminated through the semi-transparent aluminum electrode. an action spectrum similar to the visible absorption spectrum of Chl a is obtained. The anhydrous form. always shows a maximum, in the red, at 672 nm and the crystalline one at 746 nm to 738 nm depending on the amount of water vapor present in the measuring area. The light conversion efficiency has been measured at the maximum absorption in the red for both forms of Chl a . For the anhydrous form, we found values as high as 0.036%, which is very significant even compared to 0.21%, the highest value found for the crystalline form. In both cases. the incident light power was approximately 10 μW on the cell. The light conversion efficiency of both forms of Chl a cells was found to depend on a combine effect of the nature of the gas (O₁. N₂. air. Ar. N₂O. SF ₆ , H₂) and the amount of water vapor present in the measuring area. The best conversion efficiency was obtained with O ₂ , or air saturated with water. This combined effect was very large for the crystalline form whereas the anhydrous form was only slightly affected.     

Preparation and Characterization of N-4-Nitrophenyl-L-prolinol Nanocrystals in Sol-Gel Matrices

Organic nanocrystals of N-4-nitrophenyl-l-prolinol (NPP) have been grown in sol-gel matrices prepared from silicon alkoxide precursors. Our process is based on the control of the nucleation and growth kinetics of the dye in the pores of dense gels. Nanocomposites gel-glasses are obtained with a high optical quality due to the small size of the nanocrystals (10-20 nm). Differential scanning calorimetry experiments evidenced clearly the melting point of NPP nanocrystals, which is registered 51°C above that of NPP powder. Micro-Raman and solid state NMR spectroscopies allowed us to demonstrate that our nanocrystallization process does not chemically modify NPP molecules. We specified also the nature of interactions existing between the NPP nanocrystals and the xerogels. These strong interactions, which explain the important increase of the melting point of the nanocrystals in comparison to the NPP powder, are hydrogen bonds between nitro groups of NPP and uncondensed silanol functions of the silicate network.     

Synthesis and properties of 1-(6-methoxy)-2-benzothiazolyl)-2-pyridones

Substituted ]-(6-methoxy-2-benzothiazolyt)-2-pyridones were prepared from 2-amino-6-methoxybenzathiazate through N-(6-methoxy-2-benzothiazotyl) cyanvorearmileaznd-3-aryl-N-(6-methoxy-2-benzothiazolyt)-2-cyano-2-propenamides. The cyclization of the latter with malonodinitrile in the presence of piperidine gave the corresponding pyridones. The structures of the synthesized compounds were confirmed by¹H NMR and mass spectral data.Department of Organic Chemistry, Mass Spectrometry Laboratory, Slovak Technical University, 812 37 Bratislava, Slovakia. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1402–1404, October, 1995. Original article submitted August 24, 1995.     

A theoretical study of the formation of the parent phosphinine C5H5P from the flash vacuum thermolysis of diallylvinylphosphine

The gas-phase decomposition of diallylvinylphosphine 1 into C5H5P 12 is studied by DFT/6-311+G(d,p) calculations with the B3LYP functional, followed by single-point energy-only calculations at the CCSD(T)/6-311+G(d,p) level. According to these calculations, the first step involves a retro-ene elimination that yields 3-phosphahexatrienes 2Z and 2E. Both compounds equilibrate through the formation of 1,2- and 3,4-dihydrophosphetes 3 and 4, and it is shown that the formation of 2Z is favored by the exothermic formation of the 3,4-dihydrophosphinine 5 through a 6pi-electrocyclization. Though 5 can easily isomerize into 2,3- (6) and 1,2-diyhydrophosphinines (7) by successive 1,5-hydrogen shifts, the formation of 12 from 5, 6, or 7 through an elimination of H2 is found to be a high energy process. It is also shown that the elimination of H2 from lambda5-phosphinine 8 following a C2v pathway is a symmetry-forbidden process. Finally, 1,4-dihydrophosphinine 9, which can be formed through a 1,4-hydrogen shift from lambda5-phosphinine 8, is found to be a convenient precursor of 12 through a 1,4-elimination of H2. The formation of 9 from 5 involves the intermediary formation of 3-phosphabicyclo[3.1.0]hex-2-ene 10. The mechanism eventually proposed for the formation of 12 from 2Z is given in Scheme 16 at the CCSD(T) level.     

氟硅烷自组装单分子膜的制备及其摩擦学性能

利用分子自组装技术制备了全氟辛酰胺丙基硅烷单分子膜,用X射线光电子能谱(XPS)对组装膜的表面元素进行了表征;接触角测试表明,该组装膜具有很好的疏水-疏油性,其对水的接触角高达105°,对正十六烷的接触角为50°.摩擦磨损实验结果表明,全氟辛酰胺丙基硅烷自组装单分子膜可以大大降低基片的摩擦系数,使载玻片的摩擦系数从0.85左右降低到0.14左右,而且低负荷下具有很好的耐磨性.     

Immobilization of protein on ferromagnetic Dacron

Ferromagnetic Dacron (polyethyleneterephthalate) is proposed as a matrix to immobilize proteins covalently. Dacron in powder was magnetized by reacting ferrous (Fe+2) and ferric (Fe+3) ions with its hydrazide form at pH 8.3. Ferromagnetic hydrazide Dacron was converted to ferromagnetic azide Dacron and amyloglucosidase (E.C. 3.2.1.3) was covalently bound through the latter group. The catalytic property of the enzyme was preserved (8% of the specific activity estimated for the soluble enzyme) and all the magnetic amyloglucosidase Dacron derivative was recovered by using a magnetic field. No activity was detected in the supernatant.     

New mono- and bis-carbene samarium complexes: synthesis, X-ray crystal structures and reactivity

New samarium carbene complexes have been synthesized and characterized by X-ray diffraction analysis; the carbenic nature was assessed by reactivity studies.     

Quaternarisation de l'atome d'azote de systemes tautomeres de la serie des oxo-4 thiazoles. Cycloadditions dipolaires 1,3 des thiazoles mesoioniques formes in situ

4-Hydroxythiazoles and N-acylimino 4-thiazolidinones show similar tautomeric behaviour to azlactones. However, the mechanism of their reaction with dimethylacetylenedicarboxylate or with ethyl vinyl ether differs fundamentally. In the thiazole series, the first step is the quaternization of the nitrogen atom. The mesoionic thiazole intermediate is then trapped by a second molecule of the dipolarophile.