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51.
Stachurski ZH 《Physical review letters》2003,90(15):155502
It is proposed that two ideal amorphous structures, type I and type II, based on maximally random jammed packing of spheres of equal size, form a distinct class of ideal amorphous solids. The ideal amorphous structures contain wide variations in local density, limited by the condition of solidity. Four distinct characteristics, based on statistical geometry and topology, are shown to define this class. Voronoi tessellations carried out on simulated cells of random packed spheres and amorphous polymers give a broad distribution of individual volumes, skewed, with a tail at the high volume end. 相似文献
52.
Xin-tao Shuai Zbigniew Jedlinski Qiang Luo Nozirow Farhod Institute of Chemistry Chinese Academy of Sciences Beijing China Institute of Polymer Chemistry Polish Academy of Sciences - Zabrze Poland Institute of Synthetic Fibre Chinese Academy of Textile Sciences Beijing China 《高分子科学》2000,(1):19-23
A novel kind of copolymer with ABA-type block structure was synthesized by anionic ring-openingpolymerization of β-butyrolactone (β-BL) in the presence of a PEG-based dicarboxylates as macroinitiators which wereprepared by the esterification of aliphatic cyclic anhydride and poly(ethylene glycol) (PEG) oligomers (M_n=2000, 4000 and6000) and conversion of potassium dicarboxylates. The resultant copolymers as well as the intermediates were characterizedby IR,~1H-NMR and GPC. 相似文献
53.
Marek Daszkiewicz Zbigniew Staszak Adam Pietraszko Wiesława Bronowska Maria Cieślak-Golonka 《Structural chemistry》2006,17(6):599-608
Two polymeric complexes: catena(μ-CrO4-O,O′)[Co(HIm)3H2O] (1) and catena(μ-CrO4-O,O′)[Co0.43Ni0.57(HIm)3H2O] (2) (where HIm=imidazole) with a cis-bridging coordination mode of the CrO4
2− anion have been synthesized and characterized by X-ray and spectroscopic methods. These crystals were isolated from nine
systems of varying reagent molar ratios and three excluding anions: Cl−, NO3
− and SO4
2− exclusively as mer [M(HIm)3O3]-type isomers. The unit cell of these isostructural complexes (monoclinic crystal system P21
/n) contains two independent helixes, left- and right handed, stabilized by intrahelical and interhelical hydrogen bonding and
π–π interaction between pairs of the imidazole rings from neighbouring helixes. The Raman spectra at 77 K of 1 and 2 deconvoluted into lorentzian components revealed the block-type polymeric structure of the complexes. Moreover, the solution
studies at millimolar concentrations of 1 and 2 indicated their complete decomposition in water. Four K electronic spectral analysis of the crystals (band deconvolution
into gaussian components) enhanced with the data obtained in the polarized light allowed for assignment of the bands to the
respective d–d transition (D4h symmetry). It was found that the metallic centres are independently absorbing species, which supports the suggestion of a
block-type structure of the polymers. The respective crystal field parameters for Co and Ni were calculated. 相似文献
54.
Wojtczak BA Andrysiak A Grüner B Lesnikowski ZJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(34):10675-10682
A general approach to the synthesis of nucleoside conjugates containing carborane and metallocarborane complexes, based on Huisgen 1,3-dipolar cycloaddition ("chemical ligation"), is described. Boron-cluster-donors bearing terminal azide or ethynyl groups were prepared in the ring-opening reaction of dioxane-boron-cluster adducts and an azide anion or suitable alkynol-derived alcoholate nucleophile. Analogous derivatives bearing terminal sulfhydryl groups were also prepared. Nucleosides with various spacers containing terminal azide or ethynyl groups, located within nucleobases or sugar residues, were used as boron-cluster acceptors. The proposed methodology provides a convenient way to synthesize libraries of boron-cluster-modified nucleosides for various applications. 相似文献
55.
Pryjomska I Bartosz-Bechowski H Ciunik Z Trzeciak AM Ziółkowski JJ 《Dalton transactions (Cambridge, England : 2003)》2006,(1):213-220
The new phosphinite and phosphonite complexes (1-8) are very efficient catalysts for the methoxycarbonylation of iodobenzene and Heck cross-coupling of bromobenzene with butyl acrylate. High catalytic activity of these complexes can be explained by their in situ transformations during the reaction, stimulated by the presence of water, acid (HCl) or base (NEt(3)). Hydrolysis of phosphinite palladium complexes of the form trans-PdCl(2)[PPh(2)(OR)](2) (R = C(6)F(5), 2, (t)Bu 3, or O-menthyl 4) results in the formation of the dimeric complex [mu-ClPd(PPh(2)OH)(PPh(2)O)](2) 5, which is deprotonated by NEt(3), producing a polymeric complex of formula [Pd(P(O)PPh(2))(2)](n) 8. The reverse reaction, protonolysis of 8 with HCl, leads back to 5 and the monomeric complex 5a. The phosphinite complex PdCl(2)[PPh(2)(OBu)](2)1 with a more lipophilic ligand, PPh(2)(OBu), does not undergo hydrolysis under the same conditions. In the reaction of PdCl(2)(cod) with P(OPh)(2)(OH), the new dimer [mu-ClPd(P(OPh)(2)OH)(P(OPh)(2)O)](2) 6 was obtained, whereas reaction of Pd(OAc)(2) with P(OPh)(2)(OH) leads to the polymeric complex [Pd[P(O)(OPh)(2)](2)](n) 7. Protonolysis of 7 with HCl results in the formation of 6. 相似文献
56.
Piotr Kurcok Andrzej Matuszowicz Zbigniew Jedliski 《Macromolecular rapid communications》1995,16(3):201-206
The anionic polymerization of 2-oxetanone and 4-methyl-2-oxetanone initiated with the potassium hydride/18-crown-6 complex was investigated. The α-proton abstraction of the monomer was found to proceed at the initiation step of this polymerization. The salt of the unsaturated carboxylic acid formed initiates further propagation, leading to functionalized polyesters with unsaturated, dead end-groups. 相似文献
57.
Marcin Kubisiak Karolina Zelga Wojciech Bury Iwona Justyniak Krzysztof Budny-Godlewski Zbigniew Ochal Janusz Lewiński 《Chemical science》2015,6(5):3102-3108
This paper reports a series of comparative experiments on the activity of carbon- and oxygen-centred radical species in a model reaction of the radical addition of THF to imines mediated by a series of zinc alkyl/air reaction systems. The study strongly contradicts the notion that generally R˙ radicals are the initiating species in organic reactions mediated by RnM/air systems, and simultaneously demonstrates that oxygen-centred radical species are the key intermediates responsible for the initiation process. In addition, a new efficient RZn(L)/air initiating system for radical organic reactions exampled by a model reaction of radical addition of THF to imines is developed. Moreover, the isolation and structural characterization of the first zinc alkylperoxide supported by a carboxylate ligand, [Zn4(μ3-OOtBu)3(μ4-O)(O2CEt)3]2, as well as the novel octanuclear zinc oxo(alkoxide) aggregate with entrapped O–THF species, [Zn4(μ4-O)(μ3-2-O–THF)(O2CEt)5]2, provide clear mechanistic signatures for the mode of function of the RZn(O2CR′)/air system. 相似文献
58.
The compatibility of cycloaliphatic and aromatic multifunctional epoxides with several epoxide resins allows the development of a wide range of cationic radiation‐curable formulations. The influence of different “epoxide resin‐monomer” systems UV‐cured in the presence of suitable cationic photoinitiators on the resulting physicochemical film properties was studied, and the results are stated. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
59.
Nowicka AM Zabost E Donten M Mazerska Z Stojek Z 《Analytical and bioanalytical chemistry》2007,389(6):1931-1940
A method is presented for the electroanalytical characterization of interactions of dsDNA with a drug, under conditions that
both agents are dissolved in the phosphate buffer solution and both are electroactive. Normal pulse, square wave, differential
pulse, and cyclic voltammetries were employed in the measurements of the drug and dsDNA oxidation signals at carbon electrodes.
UV–Vis spectroscopy was used as a non-electrochemical method to support the electroanalytical data. An anticancer drug, C-1311
(5-diethylaminoethyl-amino-8-hydroxyimidazoacridinone), has been selected for the examination. Normal pulse voltammetry was
particularly useful in showing that under the conditions employed neither dsDNA nor the drug were adsorbed at the electrode
surface. Necessary conditions for the appearance of the well-defined dsDNA voltammetric signal (guanine peak) are: rigorous
chemical and biological purity in the cell and appropriate purity of DNA. An analysis of the obtained results confirmed that
there were two modes of interaction between C-1311 and dsDNA: by intercalation and electrostatically. In the presence of excess
NaCl the electrostatic interactions deteriorate. The binding constants (K
1 and K
2, respectively) and the number (n) of nucleic base pairs (bp) and the number (m) of phosphate groups (pg) interacting with one molecule of drug have been determined. For strong interactions (intercalation)
the values of the binding constant, K
1, and the binding-site size, n, equal 3.7 × 104 M−1 and 2.1, respectively. For the weak electrostatic interactions the K
2 and m parameters equal 0.28 × 104 M−1 and 4.7. The intercalation process is rather slow and its rate (the conditions of pseudo-first-order reaction) was estimated
to equal 7 × 10−4 s−1. The possibility of independent determination of both interacting agents was very useful in the study.
Figure Intercalation of C-1311 into a dsDNA fragment 相似文献
60.
Olejniczak AB Plesek J Leśnikowski ZJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(1):311-318
A general approach to the synthesis of nucleoside conjugates between derivatives of thymidine (T), 2'-O-deoxycytidine (dC), 2'-O-deoxyadenosine (dA), and 2'-O-deoxyguanosine (dG), and metallacarborane complexes is described. Metallacarborane-nucleoside derivatives are prepared by reaction of the dioxane-metallacarborane adduct with a base-activated 3',5'-protected nucleoside. In the case of T and dG a mixture of regioisomers, which is easily separable by chromatographic methods, is obtained, thus yielding a series of modifications containing metallacarborane groups at the 2-O, 3-N, 4-O and 1-N, 2-N, 6-O locations, respectively; dC and dA are alkylated at the exo-amino function. The proposed methodology provides a route for the synthesis and study of nucleic acids modified with metallacarboranes at designated locations and a versatile approach to the incorporation of metals into DNA. 相似文献