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91.
Poly(methyl acrylate)-b-poly(5,6-benzo-2-methylene-1, 3-dioxepane) (PMA-b-PBMDO) was synthesized by two-step atom transfer radical polymerization (ATRP). Firstly, ATRP of methyl acrylate (MA) was realized using ethyl α-bromobutyrate (EBrB) as initiator in the presence of CuBr/2,2'-bipyridine. After isolation, poly(methyl acrylate) withterminal bromine (PMA-Br) was synthesized. Secondly, the resulting PMA-Br was used as a macromolecular initiator in theATRP of BMDO. The Structure of block copolymer was characterized by ~1H-NMR spectroscopy. Molecular weight andmolecular weight distribution were determined on a gel permeation chromatograph (GPC). 相似文献
92.
Four kinds of AliBu_2OB' with different R' were synthesized. The effect of AliBu_2OR'/AliBu_3 mole ratio on the conversion, the [η] of copolymer and catalytic efficiency were studied. The conversion was increased obviously and the catalytic efficiency was 2.7 times higher than before. The effect of the amount of AliBu_2OR' on the valence state of vanadium ion and the change of the valence state of vanadium ion with reaction temperature and time were studied. The VIS and IR spectra of the trinary-component catalyst system were measured. The model of active center including AliBu_2OR' was proposed. The function of AliBu_2OB was explained. 相似文献
93.
Ivan Gutman 《Monatshefte für Chemie / Chemical Monthly》2005,136(6):1055-1069
Summary. The fact that cyclic arrangements of double bonds have a dramatic effect on the behavior of conjugated organic molecules is known since the 19th century. The fact that in monocyclic conjugated systems the size of the cycle and the number of -electrons involved is decisive for their stability (aromaticity) or lack of stability (antiaromaticity) is known since the 1930s. In polycyclic -electron systems several cyclic effects are present simultaneously and their separation became possible only recently. A molecular orbital method has been elaborated, by means of which the energy effects of individual cycles in polycyclic -electron systems can be estimated. This method is briefly outlined and illustrated by pertinent examples. An exhaustive bibliography of the topic considered is given. 相似文献
94.
95.
Organic photovoltaic (OPV) cells were fabricated via vacuum vapor deposition with {4-[2-(3-di-cyanomethylidene-5,5-dimethylcyclohexenyl)vinyl]phenyl}di(1-naphthyl)amine (DNP-2CN) as the electron donor, and fullerene (C60) as the electron acceptor. A thin film (10 nm) of tris(8-quinolinolato)aluminum (Alq3) was adopted as the buffer layer. A device based on this DNP-2CN exhibited an open circuit voltage (Voc) of 370 mV, a short-circuit current density (Jsc) of 0.61 mAocm 2, and a white-light power conversion efficiency ( η) of 0.09% (AM1.5, 75 mW.cm^- 2). 相似文献
96.
A. V. Ivanov P. A. Svinareva I. V. Zhukov L. G. Tomilova N. S. Zefirov 《Russian Chemical Bulletin》2006,55(2):281-286
A series of the earlier unknown diphthalocyanine complexes of rare-earth metals based on 4,5-isopropylidenedioxyphthalonitrile
were prepared. Their compositions and yields depend on the radius of the complexing ion. The synthesized compounds were studied
by spectroscopy and electrochemical methods. The redox potentials of the complexes studied change nonlinearly with a decrease
in the lanthanide ion radius.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 274—279, February, 2006. 相似文献
97.
The semilocalized approach to chemical reactivity (J. Mol. Struct. (Theochem) 588 (2002) 99; Int. J. Quant. Chem. 94 (2003) 302) is applied to study the addition reaction of an electrophile or nucleophile to the butadiene molecule. In accordance with the classical concept of the reaction center and its neighborhood (substituent), only one of the two H2C=CH-fragments of butadiene is supposed to be under a direct attack of the reagent, whereas the remaining H2C=CH-group is assumed to play the role of the substituent and thereby to participate in the process indirectly by exerting certain electron-donating or accepting effect upon the former group and/or the reagent. The main aim of the study consists in revealing the role of the H2C=CH-substituent in the formation of the known higher reactivity of the terminal carbon atom of the attacked C=C-bond (as compared to the internal atom) irrespective of the nature of the reagent. To this end, we seek to obtain an explicit algebraic representation of the interdependence between the direction and the extent of the total influence of the H2C=CH-substituent, on the one hand, and the nature of the reagent, on the other hand. The expressions for electron density and bond order redistributions among separate fragments of contacting molecules derived previously in the form of power series are shown to yield the above-anticipated representation. On this basis, it is demonstrated that the electron-donating effect of the initially occupied (bonding) orbital of the substituent and the electron-accepting effect of its initially vacant (antibonding) orbital upon the remaining fragments of the whole reacting system may be considered independently whatever the nature of the reagent. However, a strong interdependence is established between the actual relative extents of these two components of the total effect of the H2C=CH-group and the electron-donating (accepting) properties of the reagent. Moreover, this group of atoms is shown to manifest itself as an electron-donating (accepting) substituent under influence of an electrophilic (nucleophilic) attack. Using this principal result of the paper, the actual reactivity of butadiene with respect to electrophile (nucleophile) is interpreted by invoking a model system of a substituted ethene containing a simple (one-orbital) electron-donating (accepting) substituent, and a terminal addition easily follows for both types of the reagent. 相似文献
98.
Bayó N Jiménez JC Rivas L Nicolás E Albericio F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(5):1096-1103
An optimized solid-phase strategy for the preparation of the cyclic lipononadepsipeptide [N-Mst(L-Ser1), D-Ser4, L-Thr6, L-Asp8, L-Thr9]syringotoxin is reported. The strategy is based on the use of a mild orthogonal protection scheme and the incorporation of the nonproteinogenic amino acid (Z)-Dhb into the peptide chain as the dipeptide Fmoc-Thr(tBu)-(Z)-Dhb-OH. The didehydrodipeptide was synthesized by a water-soluble carbodiimide-induced beta-elimination of a protected dipeptide containing a residue of Thr with its free hydroxy side chain unprotected. 相似文献
99.
The direct enzymatic synthesis of a cyclic trimethylene carbonate (1,3‐dioxane‐2‐one) monomer with/without a methyl substituent was carried out using dimethyl or diethyl carbonate and 1,3‐diol with the objective of producing aliphatic poly(trimethylene carbonate), a typical biodegradable synthetic plastic. The lipase‐catalyzed condensation of dimethyl or diethyl carbonate with aliphatic 1,3‐diols using immobilized Candida antarctica lipase (lipase CA) in an organic solvent at 70 °C afforded the corresponding methyl‐substituted and unsubstituted cyclic trimethylene carbonates. The cyclic trimethylene carbonates obtained by the reaction of dimethyl or diethyl carbonates with 1,3‐propanediol and 2‐methyl‐1,3‐propanediol were polymerized by lipase to produce the corresponding polycarbonates.
100.
Henk Buck 《International journal of quantum chemistry》2005,101(1):73-83
With semi‐empirical MO and ab initio calculations at different levels, we investigated the π conjugation of alternating X? Y bonds with X? Y for N/B and N/C combinations in an open and cyclic arrangement. Although the intrinsic symmetry is lost for the acyclic even‐membered compounds, the alternation is still reflected in its geometry and electron‐density transfer. For the cyclic π compounds, we focused our attention on borazine N3B3H6 (D3h symmetry), which is isoelectronic with benzene (D6h symmetry). Specific attention is given to the electrophilic behavior of borazine with respect to CH and SiMe. The dynamics based on the results of FT‐ICR mass spectrometry was studied in more detail. In addition, the results of the cyclic systems with 4n and 4n+2 π electrons concerning their geometries are compared with the corresponding carbon compounds. Attention is also given to the dication of borazine, because of the corresponding triplet ground state of the benzene dication. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献