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The interaction of 4-hydroxy metabolites of estrogens with DNA leads to the formation of DNA adducts. These adducts are believed to play an important role in the incidence of breast and endometrial cancer. In order to be able to analyze these adducts in in vivo samples a method based upon the coupling of miniaturized liquid chromatography (LC) to electrospray tandem mass spectrometry (ES-MS/MS) was developed for the analysis of the adducts formed with 4-hydroxyequilenin. In vitro synthesized adducts obtained by the reaction of 4-hydroxyequilenin with the main 2'-deoxynucleosides were separated on a Hypersyl C(18) BDS nano-HPLC column (15 cm x 75 microm i.d.) at a flow-rate of 300 nl min(-1) using gradient elution with CH(3)OH--0.2% CH(3)COOH in H(2)O. The column was coupled, in combination with a column switching system, to a nano-electrospray interface. Analysis of the low- and high-resolution low-energy collision-activated dissociation product ion spectra of normal and deuterated adducts supported earlier data demonstrating equilenin to form different isomeric adducts, except with thymidine, for which no adducts were found. The nano-HPLC column-switching ES-MS system was tested for its sensitivity on a triple-quadrupole instrument, and detection limits down to 197 fg in the single reaction monitoring mode were obtained for semi-preparatively isolated equilenin--2'-deoxyguanosine adduct. 相似文献
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Richard A. Bartsch David A. Babb Bronislaw P. Czech Dhimant H. Desai Eddy Chapoteau Carl R. Gebauer Wolodymyr Zazulak Anad Kumar 《Journal of inclusion phenomena and macrocyclic chemistry》1990,9(2):113-123
Four novel chromogenic benzocryptands and one side-armed chromogenic cryptand have been synthesized and their complexing abilities for alkali metal cations are described. 相似文献
4.
Stereodivergent Carbamate Synthesis by Selective in Situ Trapping of Organic Carbonate Intermediates
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Dr. Eddy Martin Eduardo C. Escudero‐Adán Prof. Dr. Arjan W. Kleij 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(5):1722-1727
Trans carbamates have been prepared in a diastereoselective approach by a judicious one‐pot combination of organic carbonates, prepared in situ, and suitable amine reagents under appropriate reaction conditions. This unprecedented approach allows for stereodivergence from a single oxirane substrate with easy access to both cis and trans carbamate isomers with high stereoselectivity (>19:1 d.r.). Key to the control of the diastereoselective nature of the conversions that lead to the trans carbamates is the in situ formation of trans‐configured oligo/polycarbonates through Al catalysis, which provides the targeted products after aminolysis. The present results demonstrate the valorization of a renewable carbon‐based reagent (CO2) into new valuable scaffolds and an unusual stereocontrol exerted through carbonate intermediates. A series of control experiments support the proposed mechanistic rationale towards the trans carbamate products, which is based on the trapping of an in situ formed trans‐configured oligo/polycarbonate. 相似文献
5.
Dr. Eddy W. T. Yemeli Dr. Graeme R. Blake Dr. Alexios P. Douvalis Prof. Thomas Bakas Gert O. R. Alberda van Ekenstein Dr. Petra J. van Koningsbruggen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(72):16766-16776
The iron(III) spin-crossover compounds [Fe(Hthsa)(thsa)] ⋅ H2O ( 1 ), [Fe(Hth5Clsa)(th5Clsa)2] ⋅ H2O ( 2 ), and [Fe(Hth5Brsa)(th5Brsa)2] ⋅ H2O ( 3 ) (H2thsa=salicylaldehyde thiosemicarbazone, H2th5Clsa=5-chlorosalicylaldehyde thiosemicarbazone, and H2th5Brsa=5-bromosalicylaldehyde thiosemicarbazone) have been synthesized and their spin-transition properties investigated by magnetic susceptibility, Mössbauer spectroscopy, and differential scanning calorimetry measurements. The three compounds exhibit an abrupt spin transition with a thermal hysteresis effect. The more polarizable the substituent on the salicylaldehyde moiety, the more complete is the transition at room temperature with an increased degree of cooperativity. The molecular structures of 1 and 2 in the high-spin state are revealed. The occurrence of the light-induced excited-spin-state trapping phenomenon appears to be dependent on the substituent incorporated into the 5-position of the salicylaldehyde subunit. Whereas the compounds with an electron-withdrawing group (-Br or -Cl) exhibit light-induced trapped excited high-spin states with great longevity of metastability, the halogen-free compound does not, even though strong intermolecular interactions (such as hydrogen-bonding networks and π stacking) operate in the system. For compound 2 , the surface level of photoconversion is less than 35 %. In contrast, compound 3 displays full photoexcitation. 相似文献
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William F. Eddy Mark Fitzgerald Christopher Genovese Nicole Lazar Audris Mockus Joel Welling 《Journal of computational and graphical statistics》2013,22(3):545-558
Abstract Functional magnetic resonance imaging of the human brain in action presents large statistical and computational challenges. Here we describe those challenges and provide references to a number of other papers where detailed methods developed to meet them are reported. The first seven sections of this paper were written in 1995 when our work was in its infancy. The last four sections were written more recently, to update the earlier sections and to show the directions we have gone and the directions we intend to go. 相似文献
9.
Shu‐Xian Hu Jian‐Guo Yu Eddy Y. Zeng 《International journal of quantum chemistry》2013,113(8):1128-1136
Calculations using density functional theory were performed to explore the mechanisms for atmospheric degradation of isopropyl methyl methylphosphonate (IMMP). The potential energy surface profiles for OH‐initiated reaction of IMMP were constructed, and all possible degradation channels were considered. Rate constants were further calculated using transition state theory. It was established from these calculations that H‐abstractions from alkyl groups have much lower energy barriers than substitutions of alkoxyl groups, and four possible H‐abstraction channels are competitive. Investigations into the secondary reactions under the presence of O2/NO were also performed. It is shown that O2 addition, reaction of peroxide radicals with NO to form RO radicals, and removal of ·RO are the major degradation pathways for alkyl radicals. Four selected products, CH3OP(O)(CH3)OC(O)CH3, CH3OP(O)(O)CH3, (CH3)2CHOP(O)(CH3)OH, and (CH3)2CHOP(O)(CH3)OCH?O, are predicted to be the major products in this study. © 2013 Wiley Periodicals, Inc. 相似文献
10.
Dr. Martha V. Escárcega‐Bobadilla Dr. Marta Martínez Belmonte Eddy Martin Eduardo C. Escudero‐Adán Prof. Dr. Arjan W. Kleij 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(8):2641-2648
A tetraoxo bis‐Zn(salphen) supramolecular host can bind various divalent metal salts, thereby providing access to trinuclear bifunctional systems that incorporate both Lewis acid sites and dynamically bound nucleophilic anions. The formation of these trinuclear species was investigated and their stability features were also determined. The application of these trinuclear complexes as bifunctional catalysts was evaluated in the formation of cyclic organic carbonates from epoxides and CO2. The catalytic data, in combination with control experiments, clearly demonstrate that these trinuclear compounds show much higher recycling potential compared to various control compounds and they can be used in up to five cycles without an observable loss in activity. Furthermore, this new recyclable catalytic system does not require any additives and can be applied under solvent‐free conditions. 相似文献