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排序方式: 共有211条查询结果,搜索用时 46 毫秒
1.
Jan-Martin Heldt Michèle Salmain Gérard Jaouen 《Journal of organometallic chemistry》2004,689(25):4775-4782
The first poly(amidoamine) (PAMAM) dendrimers tethered with both (η5-cyclopentadienyl) rhenium tricarbonyl (CpRe(CO)3) units and polyethylene glycol (PEG) chains were prepared and characterized by combining NMR spectroscopy and Fourier-transform IR spectroscopy. Grafting of CpRe(CO)3 units was achieved by reductive amination of formyl-CpRe(CO)3 with the peripheral amines of generation 3 and 4 PAMAMs to yield dendrimers labeled with a variable number of CpRe(CO)3 units, ranging from 8 to 14 for PAMAM-G3 and 17-30 for PAMAM-G4. PEG chains of different lengths were then attached to some of the remaining peripheral amines, and their respective ability to improve the solubility of the metallodendrimers in aqueous buffered media was evaluated. These metallodendrimers represent new infrared probes designed to be coupled to immunological reagents for the amplification of the IR signal in carbonyl metallo immunoassay (CMIA). 相似文献
2.
3.
The thickness and the porosity of a deposit during ultrafiltration experiments are determined using an electrochemical method. Twenty microelectrodes are mounted flush to a ceramic plane membrane and maps of deposit thickness are determined for three inlet/outlet distributors configurations. Combining an electrochemical method and a step transient method, the determination of the thickness and the porosity of a particles deposit is performed. These local thickness and porosity values are analyzed thanks to wall shear stress local measurements obtained in a previous work [Sep. Sci. Technol. 37 (10) (2002) 2251]. The results emphasize the heterogeneity of the deposit thickness, especially in zones of low wall shear stress. Furthermore, the porosity values of the deposit are ranged between 0.3 and 0.8 as a function of the location at the membrane surface. 相似文献
4.
Top S el Hafa H Vessiéres A Huché M Vaissermann J Jaouen G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(22):5241-5249
In order to elucidate the extent to which recognition of the estrogen receptor is influenced by addition of an organometallic substituent at the 17 alpha position, modification of 17 beta-estradiol at this position was carried out by using the organometallic groups -C identical to C(eta 5-C5H4)RuCp, CH2-(eta 5-C5H4)RuCp, -C identical to C-(eta 5-C5H4)-W(CO)3(Me), -(C identical to CCHO)Co2(CO)6, and -(C identical to CCH2OH)Co2(CO)6. The relative binding affinity (RBA) values for estradiol receptor alpha showed that recognition was good (RBA between 20 and 13.5%) when the organometallic moiety was attached at the end of a rigid alkyne spacer. However, the affinity of the modified hormone for the receptor was severely reduced (RBA = 1%) for a substituent such as -CH2-(eta 5-C5H4)RuCP, in which the spacer is reduced to a single flexible sp3 carbon atom, allowing the organometallic moiety greater freedom of movement around the attachment point. The RBA values found were in agreement with results obtained from a molecular-modeling study in which 5, an organometallic hormone with a rigid spacer, or 7, a molecule with a flexible spacer, was inserted into the cavity of the recently characterized Ligand-Binding Domain of estrogen receptor alpha. 相似文献
5.
Top S Vessières A Leclercq G Quivy J Tang J Vaissermann J Huché M Jaouen G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(21):5223-5236
A series of ferrocene derivatives based upon the structure of the antiestrogenic drug tamoxifen or of its active metabolite hydroxytamoxifen has been prepared and named by analogy ferrocifens and hydroxyferrocifens. This series includes 1-[4-(O(CH(2))(n)NMe(2))phenyl]-1-phenyl-2-ferrocenyl-but-1-ene and 1-[4-(-O(CH(2))(n)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene, with n=2, 3, 5 and 8, and 1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenylethene. Most of these molecules have been synthesised by McMurry cross-coupling of the appropriate ketones, except for the ethene complexes, which were prepared by a four-step reaction sequence starting from the ferrocenylacetic acid. All these compounds were obtained as mixtures of Z and E isomers. The isomers were separated in the cases of the ferrocenyl derivatives of tamoxifen and hydroxytamoxifen (n=2). No isomerisation of the Z and E isomers occurred in DMSO after one day, while a 50:50 mixture of the isomers was obtained within one hour in chloroform. The X-ray structure of (E)-1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene has been determined. The relative binding affinity (RBA) values of the hydroxyferrocifens for the estrogen receptor alpha (ERalpha) was good to moderate, with values decreasing progressively with the length of the basic chain. The RBA values found for the estrogen receptor beta (ERbeta) are equal to or slightly less than those found for the alpha form. The lipophilicity of the hydroxyferrocifens are superior to the values found for estradiol and increase with lengthening of the chain. The antiproliferative effects of the four hydroxyferrocifens with n=2, 3, 5 and 8 were studied on four breast cancer cell lines (MCF7, MDA-MB231, RTx6 and TD5) possessing different levels of ERalpha. On MCF7 cells containing high levels of ERalpha, hydroxyferrocifens behave as antiestrogens. At a molarity of 1 microM the effect is close to that of hydroxytamoxifen (used for reference) when n=2 or 5, more marked when n=3, and weaker when n=8. Ferrocene alone has no effect. For the MDA-MB231 cells, classed as a hormone-independent breast cancer cell line, on the other hand, the hydroxyferrocifens show remarkable antiproliferative behaviour while the hydroxytamoxifen is completely inactive. Hydroxyferrocifens therefore show the unique property of being active both on hormone-dependent and on hormone-independent breast cancer cell lines. The molecular modelling study provides some clues for understanding of the antagonist effect of these molecules, while an additional cytotoxic effect due to the vectorised ferrocenyl unit is revealed in some occasions. 相似文献
6.
A boron-mediated syn- and anti-stereoselective aldol reaction giving rise to various beta-hydroxyenones was coupled to a Pd((II))-mediated oxidative cyclization to give 2,3,6-trisubstituted syn- and anti-dihydropyranones in good yields. The Pd((II))-mediated oxidative cyclization was expanded to alpha-hydroxyenones leading to furan-3(2H)-one derivatives, which include natural product bullatenone and a known precursor of geiparvarin. The sole product of the oxidative cyclization of alpha,beta-dihydroxyenone was a five-membered furan-3(2H)-one derivative, suggesting that the ring closure of these diols is both chemo- and regioselective. 相似文献
7.
Alan M Bond Enrico Mocellin Cherrie B Pascual Panit Wedkanjana Grard Jaouen Siden Top 《应用有机金属化学》1990,4(5):557-568
Electrochemical oxidation of α- and β-diastereomers of a range of steroid hormone receptor marker chromium tricarbonyl complexes, (steroid)Cr(CO)3, have been examined at platinum electrodes in dichloromethane. Data confirm the general nature of previously published conclusions on the oxidation of (arene)Cr(CO)3 complexes (arene = benzene or steroid). That is, with 0.1 M Bu4NPF6 as the electrolyte, and in the absence of nucleophiles, a reversible oneelectron process, (steroid)Cr(CO)3 ? [(steroid)Cr(CO)3]+ + e?, is observed, followed by an irreversible one-electron process at considerably more positive potentials. The reversible half-wave potentials (approximately E°-values) calculated for the [(steroid)Cr(CO)3]+/(steroid)Cr(CO)3 redox couple are shown to be dependent on whether the α- or β-diastereomer is oxidized. Similarly the rate of nucleophilic attack on the 17-electron cation [(steroid)Cr(CO)3]+ by nucleophiles such as ClO, PPh3 and bis(diphenylphosphine)methane confirms a previous observation that the stereochemistry of this class of compound is important with respect to redox, kinetic and hormone receptor properties. The nature of the electrochemical data obtained on the (arene)Cr(CO)3 complexes in the presence of nucleophiles suggests that reactions associated with the nucleophilic attack on the 17-electron cations are complex and that a range of reaction pathways occur simultaneously. Electrochemical studies on the oxidation of (benzene)Cr(CO)2PPh3 and (oestradiol)Cr(CO)2PPh3 confirm some aspects of the proposed mechanisms, although it is clear that a great deal still has to be learned concerning mechanistic aspects of nucleophilic attack on these 17-electron complexes. 相似文献
8.
We report the synthesis and characterisation of (S) and (R)-2′-formylcymantrenyl-17α-ethynylestradiol synthesized using the Sonogashira cross-coupling reaction between optically pure (S) and (R) 1-formyl-2-iodo cymantrenes and ethynylestradiol. (S) and (R) 1-formyl-2-iodo cymantrenes were obtained from the same precursor: (2R,4R)-4-(methoxymethyl)-2-cymantrenyl-1,3-dioxane. 相似文献
9.
[Re(CO)6][BF4] reacts with HMPA to form [Re(CO)3(HMPA)3][BF4] (4), whose structure was determined by X-ray crystallography and proves to be a key intermediate in the ligand exchange reaction between three CO and Cp; and may be related to other cations such as [Re(CO)3(H2O)3]+, [Re(CO)3(CH3CN)3]+, [Re(CO)3(DMSO)3]+, obtained by different ways, and important in the field of organometallic radiopharmaceuticals. 相似文献
10.
Konrad Kowalski Anne VessièresSiden Top Gérard Jaouen Janusz Zakrzewski 《Tetrahedron letters》2003,44(13):2749-2751
A synthetic pathway giving access to diphenyl ethylene organometallic derivatives possessing the ferrocifen precursor skeleton modified in the Cp′ ring is described. It relies on reaction of the (η5-propionylcyclopentadienyl) (η6-benzene)iron(II) salt 7 with substituted cyclopentadienyl anions or their heteroanalogs followed by the McMurry coupling reaction with 4,4′-dihydroxybenzophenone. Using this approach pentamethylcyclopentadienyl and 3,4-dimethylphospholyl analogs of ferrocifen precursor (10 and 11) have been synthesized. Even with the presence of the bulky and containing phosphorus η5-ligands these compounds are still recognized by the two subtypes of estrogen receptor(ERα and ERβ). 相似文献