Estrogen Derivatives of Transition-Metal Complexes for Analytical Detection Enhancement

Abstract

We report herein the labeling of 17a-ethynyl-l7#l-estradiol with a ''Co3(CO)g" fragment.The cluster exhibits fully reversible electrochemical behavior and is assayed by means of the square-wave voltammetric technique. During the condensation of metallocarbonyl fragments around the organic chain, elimination of the 17/3-OH group in the original molecule occurs, affording Co3(CO)g(dehydroxyethynylestradiol). This modification causes an important decrease of relative binding affinity for the receptors. However, the cluster can still be used for immunoassay of estradiol, since its cross reactivity for specific antibodies is high.

Luminescent Au(I)/Cu(I) Alkynyl Clusters with an Ethynyl Steroid and Related Aliphatic Ligands: An Octanuclear Au4Cu4 Cluster and Luminescence Polymorphism in Au3Cu2 Clusters

“…NMR spectra were obtained using Bruker Avance 400 and 500 MHz spectrometers with 1 H and 13 C NMR chemical shifts referenced to residual solvent peaks in CDCl 3 , CD 2 Cl 2 , or DMSO-d 6 . 31 P{ 1 H} NMR data are referenced to external 85% H 3 PO 4 . Mass spectra of bis(acetylide) gold(I) ions were measured on a Shimadzu 2010 series liquid chromatography mass spectrometer (LC/MS) under negative mode electrospray ionization (ESI).…”

“…While the ethynyl group of ethisterone is often modified for the attachment of a transition metal, a few examples exist in which the steroid is directly coordinated to the metal as an acetylide after deprotonation 35,44,49 or through the acetylene π system. 31,48 Among them, Au(PR 3 )(ethynylsteroid) complexes exemplify the same basic architecture as the gold(I) acetylide complexes mentioned above from which luminescent mixed-metal complexes are generated upon addition of Cu(I) ions. Analogues incorporating ethynylestradiol derivatives display significant binding affinities toward the estrogen receptor ligand binding domains.…”

“…The literature is rich in examples of organic and organometallic derivatives of estradiol − and ethisterone − that were prepared with the goal of developing therapeutic or imaging agents having significant affinity for the estrogen receptor. While the ethynyl group of ethisterone is often modified for the attachment of a transition metal, a few examples exist in which the steroid is directly coordinated to the metal as an acetylide after deprotonation ,, or through the acetylene π system. , Among them, Au(PR 3 )(ethynylsteroid) complexes exemplify the same basic architecture as the gold(I) acetylide complexes mentioned above from which luminescent mixed-metal complexes are generated upon addition of Cu(I) ions. Analogues incorporating ethynylestradiol derivatives display significant binding affinities toward the estrogen receptor ligand binding domains .…”

The Ferrocenylethynyl Unit: a Stable Hormone Tag

“…Synthesis. Our previous attempt to link the [Co 3 (CO) 9 C] moiety directly to ethynylestradiol (HCCÀE) did not produce the desired compound [Co 3 (CO) 9 CÀCCÀE], due to its instability [15]. However, the insertion of a spacer between the estradiol and the organometallic core gave positive results [8], yielding a more stable metal-attached hormone.…”

Synthesis of Transition-Metal Steroid Derivatives

“…Derivative 467 was produced in 35% yield by reacting the corresponding steroid 466 , quantitatively obtained by a pallado-catalyzed procedure, with Co 3 (CO) 9 CBr and CuI according to an established procedure . Modified steroid 468 was directly synthesized from estradiol and Co 2 (CO) 8 in acetone reflux with 30% yield. For 468 , the trans configuration of the CC bond was assigned on the basis of theoretical calculations.…”