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1.
G. Giraudi Claudio Baggiani Antonella Cosmaro Emilio Santià Adriano Vanni 《Analytical and bioanalytical chemistry》1998,360(2):235-240
A very selective polyclonal antiserum against 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane (p,p′-DDT) was obtained by a careful choice of the haptenic structure (2,2-bis(4-chlorophenyl)-ethanol hemisuccinate). This hapten was conjugated to BSA to prepare the immunogen. The effects of different types of solid phases on the equilibrium reaction between the hapten on solid phase and the polyclonal antiserum were evaluated to obtain a fine tuning of the antiserum performances in terms of specificity for p,p′-DDT and sensitivity to low levels of this pesticide. The calibration curves obtained show that it is possible to set up a sensitive assay for p,p′-DDT, employing a p,p′-dichlorodiphenylacetic acid-based solid phase, with a detection limit of 0.12 ng/mL and a working range of about 0.21–40 ng/mL. Selectivity towards several p,p′-DDT-related substances was good (o,p-DDT 17%, p,p′-DDD 1.2% o,p-DDD 6.3%, p,p′-DDE 6.7%). 相似文献
2.
Spoto G Gribov E Bordiga S Lamberti C Ricchiardi G Scarano D Zecchina A 《Chemical communications (Cambridge, England)》2004,(23):2768-2769
Cu(I) ions in Cu-ZSM-5 form Cu+(H2) complexes, stable at room temperature and sub-atmospheric H2 pressure, which do not have any homogeneous analogue except for matrix-isolated [Cu(eta2-H2)Cl]. Comparison with the unstable Na+(H2) adducts formed in the parent Na-ZSM-5 zeolite allow the conclusion that the Cu(I)/H2 bond is governed by sigma-pi overlap forces. 相似文献
3.
Aschi M Lucente G Mazza F Mollica A Morera E Nalli M Paglialunga Paradisi M 《Organic & biomolecular chemistry》2003,1(11):1980-1988
The conformational study of a new group of synthetic peptides containing 4-amino-1,2-dithiolane-4-carboxylic acid (Adt), a cysteine-related achiral residue, has been carried out through a joint application of computational and experimental methodologies. Molecular Dynamics simulations clearly suggest the tendency of this molecule to adopt a gamma-turn conformation in vacuum and help in analyzing the complex and crucial conformational behaviour of the dithiolane ring which appears to preferentially adopt a C(S)-like structure. Electronic structure calculations carried out in solution using the Density Functional Theory also indicate the preservation of the gamma-like folding in apolar solvents and the helix-like one in more polar solvents. A comparison with the achiral 1-aminocycloalkane-1-carboxylic acid (Ac5c) has been carried out using the same computational tools. NMR and IR data on dipeptide derivatives containing the Adt or Ac5c residue show that in chloroform solution all the models prefer a gamma-turn structure, centered at the cyclic residue, stabilized by an intramolecular H-bond, whereas in a more polar solvent, i.e. dimethyl sulfoxide, this folding is not maintained. The experimental conformational studies, extended to N-Boc protected tripeptides, clearly indicate the remarkable tendency of both the five-membered C(alpha)-tetrasubstituted cyclic amino acids Adt and Ac5c to induce the gamma-turn structure also in models able to adopt the beta-bend conformation. 相似文献
4.
The halide anion effect on the adsorption of 1,2,3-triazole on Ag and Au colloidal nanoparticles has been investigated by means of surface enhanced Raman scattering (SERS), UV-visible absorption spectroscopy, and scanning electron microscopy. To interpret the SERS spectra, the vibrational spectra of 1,2,3-triazole were assigned with the help of density functional theoretical (DFT) calculations of the two tautomers of 1,2,3-triazole, both free and bound to Ag and Au adatoms. Upon addition of halide anions, both tautomers interact with the Ag surface through one nitrogen atom. Analogous behavior is observed in the case of basified Au colloids, whereas at the usual pH of these hydrosols (approximately 6) the adsorption of 1,2,3-triazole is the same of that observed in halide-free colloids. 相似文献
5.
3-Aryl-4-iodoisocoumarins, which were readily and efficiently prepared by regioselective iodolactonization of methyl 2-ynylbenzoates or the corresponding carboxylic acids, were used as precursors either to 3-arylisocoumarins, including naturally-occurring thunberginols A and B, or to unsymmetrical 3,4-disubstituted isocoumarins. On the other hand, (Z)- and (E)-3-iodomethylidenephthalides, which were regioselectively prepared by iodolactonization of methyl 2-ethynylbenzoate, were employed as starting materials for the stereospecific synthesis of (Z)- and (E)-3-ylidenephthalides, respectively. Some 3-arylisocoumarins and unsymmetrical 3,4-disubstituted isocoumarins showed certain cytotoxic activity against human cancer cell lines in vitro. 相似文献
6.
Pure (7E,9Z-7, 9-dodecadien-1-yl acetate (1), the sex pheromone of Lobesiabotrana, has been prepared in 21.6% overall yield by a reaction scheme involving; (i) the cross-coupling of (E) - 8 - (2 - tetrahydropyranyloxy) -1 - octenyldisiamylborane with 1 - bromo - 1 - butyne, in the presence of a Pd (O) catalyst and base; (ii) the acetylation of the crude product of this reaction; (iii) the (Z)-stereoselective reduction of the obtained conjugated (E)-enyn-1-yl acetate. (E)-9,11-Dodecadien-1-yl acetate (2), a sex pheromone component of Diparopsiscastanea, has been analogously obtained (in 54.3% overall yield) by cross-coupling of (E) - 10 - (2 - tetrahydropyranyloxy) - 1 - decenyl borane with vinyl bromide, in the presence of a Pd (O) catalyst and base, followed by acetylation of the crude product. Compound 2, which was 87.7% chemically pure, was purified by column chromatography over SiO2-AgNO3. Chemically pure (9Z, 11E) - 9,11 - tetradecadien - 1 - yl acetate (3), a sex pheromone component of Spodopteralittoralis, has been prepared (in 30.2% overall yield) by reaction of 10 - (2 - tetrahydropyranyloxy) - 1 - decynylamagnesium bromide with (E)-1-iodo-1-butene, in the presence of a Pd (O) catalyst, followed by acetylation of the crude product and by (Z)-stereoselective reduction of the obtained (E)-enyn-1-yl acetate.The stereoisomeric purity of 1, 2 and 3 has been evaluated by glc analysis on glass capillary columns or by reverse phase hplc analysis. 相似文献
7.
G. Giraudi Claudio Baggiani Antonella Cosmaro Emilio Santià Adriano Vanni 《Fresenius' Journal of Analytical Chemistry》1998,360(2):235-240
A very selective polyclonal antiserum against 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane (p,p′-DDT) was obtained by a careful choice of the haptenic structure (2,2-bis(4-chlorophenyl)-ethanol hemisuccinate). This hapten
was conjugated to BSA to prepare the immunogen. The effects of different types of solid phases on the equilibrium reaction
between the hapten on solid phase and the polyclonal antiserum were evaluated to obtain a fine tuning of the antiserum performances
in terms of specificity for p,p′-DDT and sensitivity to low levels of this pesticide. The calibration curves obtained show that it is possible to set up
a sensitive assay for p,p′-DDT, employing a p,p′-dichlorodiphenylacetic acid-based solid phase, with a detection limit of 0.12 ng/mL and a working range of about 0.21–40
ng/mL. Selectivity towards several p,p′-DDT-related substances was good (o,p-DDT 17%, p,p′-DDD 1.2% o,p-DDD 6.3%, p,p′-DDE 6.7%).
Received: 4 November 1996 / Revised: 9 June 1997 / Accepted: 16 June 1997 相似文献
8.
This perspective article discusses structural features of iodine(iii) compounds as a prelude to presenting their use as umpolung reagents, in particular as pertains to their ability to promote the selective coupling of two nucleophilic species via 2e− oxidation.This perspective article discusses structural features of iodine(iii) compounds as a prelude to presenting their use as umpolung reagents, to promote the selective coupling of two nucleophilic species via 2e− oxidation. 相似文献
9.
(S)-β-Bisabolene, (S)-1, was synthetized by a synthetic route in which (S)-4-methyl-3-cyclohexene carboxylic acid, (S)-10, which was the key intermediate, was prepared via a highly diastereoselective TiCl4-catalyzed Diels-Alder reaction between isoprene and the acrylate of commercial (R)-pantolactone, followed by hydrolysis. Compound (S)-10 was then converted into ketone (S)-13 using two different procedures. The best one of these, as regards the degree of stereospecificity, involved the reaction of (S)-10 with 2 equiv of 4-methyl-3-penten-1-yllithium, 14, in the presence of CeCl3, and gave (S)-13 having ca. 84% ee. The Zr-promoted methylenation of this ketone afforded highly enantiomerically enriched (S)-1. 相似文献
10.
Alex Yong Sheng Eng Adriano Ambrosi Chun Kiang Chua Filip Šaněk Prof. Zdeněk Sofer Prof. Martin Pumera 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(38):12673-12683
Graphene and graphene oxides are materials of significant interest in electrochemical devices such as supercapacitors, batteries, fuel cells, and sensors. Graphene oxides and reduced graphenes are typically prepared by oxidizing graphite in strong mineral acid mixtures with chlorate (Staudenmaier, Hofmann) or permanganate (Hummers, Tour) oxidants. Herein, we reveal that graphene oxides pose inherent electrochemistry, that is, they can be oxidized or reduced at relatively mild potentials (within the range ±1 V) that are lower than typical battery potentials. This inherent electrochemistry of graphene differs dramatically from that of the used oxidants. Graphene oxides prepared using chlorate exhibit chemically irreversible reductions, whereas graphene oxides prepared through permanganate‐based methods exhibit very unusual inherent chemically reversible electrochemistry of oxygen‐containing groups. Insight into the electrochemical behaviour was obtained through cyclic voltammetry, chronoamperometry, and X‐ray photoelectron spectroscopy experiments. Our findings are of extreme importance for the electrochemistry community as they reveal that electrode materials undergo cyclic changes in charge/discharge cycles, which has strong implications for energy‐storage and sensing devices. 相似文献