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71.
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
72.
Effendy Marchetti F Pettinari C Pettinari R Ricciutelli M Skelton BW White AH 《Inorganic chemistry》2004,43(6):2157-2165
Adducts of the ligand bis(1,2,4-triazol-1-yl)methane (tz(2)(CH(2))) of the form AgX:tz(2)(CH(2)):ER(3):MeCN (1:1:1:x) (X = NO(3), R = Ph, E = P, As, or Sb, x = 1 or 2; X = NO(2), ClO(4), O(3)SCF(3), E = P, R = Ph, x = 0, 1 or 2; X = NO(3), ClO(4), E = P, R = cy, x = 1; X = ClO(4), E = As, R = Ph, x = 2) and AgNO(3):tz(2)(CH(2)):P(o-tolyl)(3) (2:2:1) have been synthesized and characterized in the solid state and in solution by analyses, spectral (IR, far-IR, (1)H and (13)C NMR, ESI MS data) data, and conductivity measurements. In the one-dimensional polymers (characterized by X-ray studies) AgNO(3):tz(2)(CH(2)):PPh(3):CH(3)CN (1:1:1:1), AgClO(4):tz(2)(CH(2)):PPh(3):CH(3)CN (1:1:1:2), AgNO(3):tz(2)(CH(2)):AsPh(3): CH(3)CN (1:1:1:2), and AgNO(3):tz(2)(CH(2)):SbPh(3):CH(3)CN (1:1:1:2), the silver atom can be regarded as four-coordinate, the tz(2)(CH(2)) ligands behaving as bridging groups rather than chelates, with no pair of ligands being dominant, quasi-trans, in their interactions. The AgNO(3):tz(2)(CH(2)):P(o-tolyl)(3) (2:2:1) adduct is a two-dimensional polymer containing two independent silver atoms, one four-coordinated unsymmetrically by a pair of triazolyl rings, one P(o-tolyl)(3), and a unidentate nitrate and the second by a quasi-symmetrical O(2)NO chelate and a pair of equivalent triazolyl rings. 相似文献
73.
74.
Dalvit C Mongelli N Papeo G Giordano P Veronesi M Moskau D Kümmerle R 《Journal of the American Chemical Society》2005,127(38):13380-13385
NMR-based binding and functional screening performed with FAXS (fluorine chemical shift anisotropy and exchange for screening) and 3-FABS (three fluorine atoms for biochemical screening) represents a potential alternative approach to high-throughput screening for the identification of novel potential drug candidates. The major limitation of this method in its current status is its intrinsic low sensitivity that limits the number of tested compounds. One approach for overcoming this problem is the use of a cryogenically cooled (19)F probe that reduces the thermal noise in the receiver circuitry. Sensitivity improvement in the two screening techniques achieved with the novel cryogenic (19)F probe technology permits an increased throughput, detection of weaker binders and inhibitors (relevant in a fragment-based lead discovery program), detection of slow binders, and reduction in protein and substrate consumption. These aspects are analyzed with theoretical simulations and experimental quantitative performance evaluation. Application of 3-FABS combined with the cryogenic (19)F probe technology to rapid screening at very low enzyme concentrations and the current detection limits reached with this approach are also presented. 相似文献
75.
Dalvit C Hadden DT Sarver RW Ho AM Stockman BJ 《Combinatorial chemistry & high throughput screening》2003,6(5):445-453
High-throughput ligand-based proton NMR screening performed in the presence of a spy molecule and a control molecule is a valuable tool for identifying drug leads. A limitation of the technique is represented by the severe overlap encountered in the screening of large chemical mixtures. An approach for overcoming this overlap problem is the use of multi-selective R(1) filtered and COSY or TOCSY experiments. Application of this methodology to compounds binding to the Sudlow site I of human serum albumin is presented. The screening is performed by simply monitoring the intensity of two signals. The precise measurement of the relative intensity of the two resonances permits determination of the binding constant of the NMR-hit. For a simple competition binding mechanism, the rapidly-derived NMR binding constants are in good agreement with the values derived from full-titration ITC and fluorescence spectroscopy measurements. 相似文献
76.
The electrophilic iodocyclization reaction of (Z)- and (E)-5-n-alkylsubstituted 4-alken-1-ols followed by base-induced hydrodeiodination reaction stereoselectively gave, respectively, (Z)- and (E)-alkylidentetrahydrofurans in high yield. Completely different outcomes were observed with (Z)- and (E)-6,6-dimethylhept-4-en-1-ol: their iodocyclization furnished, respectively, threo- and erythro-2-(1-iodo-2,2-dimetylpropyl)tetrahydrofuran with high stereoselectivity. The threo isomer gave clean formation of 6-tert-butyl-3,4-dihydro-2H-pyran by base-induced ring expansion, while erythro isomer underwent a base-induced ring contraction to 1-cyclopropyl-3,3-dimethylbutan-1-one. Moreover, (Z)- and (E)-5-cyclopropylpent-4-en-1-ol underwent a 6-endo-iodocyclization to threo- and erythro-2-cyclopropyl-3-iodotetrahydro-2H-pyran, respectively, that under the same basic treatment, gave two isomeric 6-cyclopropyldihydro-2H-pyrans in a stereoselective fashion. 相似文献
77.
Methyl or silyl dissociation in the CH(2)=CHCH(2)-XH(3) (a-XH(3)(*)(+)) and CH(2)=CHCH=CHCH(2)-XH(3) (p-XH(3)(*) (+)) radical cations (X = C, Si) yields a(+) or p(+) and XH(3)(*). Similarly, the radical anions a-CH(3)(*) (-) and p-CH(3)(*) (-) give the pi-delocalized anion and CH(3)(*) preferentially. In contrast, a-SiH(3)(*) (-) and p-SiH(3)(*-) prefer to dissociate into the pi-delocalized radical and silide. All reactions are endoergic: by 43-50 kcal mol(-)(1) in the radical cations, and easier to some extent in the radical anions, that require 29-33 (X = C) and 13-14 kcal mol(-)(1) (X = Si). The fragmentation energy profiles do not present significant barriers for the backward process in the case of the radical cations. All radical anions exhibit an energy maximum along the dissociation pathway, but the barrier is lower than the dissociation limit. Fragmentation is "activated" more in the anions than in the cations with respect to homolysis in the corresponding neutrals (that requires 72-81 kcal mol(-)(1)). Wave function analysis indicates that the C-X bond cleavage in the hydrocarbon radical ions, although formally comparable to a homolytic process, is at variance with this model, due to the spin recoupling of one of the two C-X bond electrons with the originally unpaired electron. This is basically true also for the silyl-substituted radical anions, in which the initial more delocalized charge distribution might suggest some heterolytic character of the bond cleavage. 相似文献
78.
Julio Belmar Claudio Jimnez C. Ruiz‐Prez F. S. Delgado Ricardo Baggio 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(10):o599-o601
In the title compound, C15H20N2O, the bond distances and angles are consistent with the presence of the hydroxy tautomer. This tautomer was unambiguously determined by the clear presence of a H atom bonded to oxygen, as well as the total absence of any residual electron density around the N atom in the heterocycle, thus precluding any possibility of desmotropism. 相似文献
79.
Lancelot N Elbayed K Raya J Piotto M Briand JP Formaggio F Toniolo C Bianco A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(6):1317-1323
A tetra- and a hepta-homopeptide from the C(alpha)-tetrasubstituted Aib (alpha-aminoisobutyric acid) residue were covalently linked to the POEPOP resin by the fragment-condensation approach. The conformational preferences of the two model peptides were determined for the first time on a solid support by means of high-resolution magic angle spinning NMR spectroscopy. The results obtained indicate that the Aib homopeptides adopt a regular 3(10)-helical structure even when they are covalently bound to a polymeric matrix, and thus confirm the remarkable conformational stability of the peptides rich in this amino acid. An ATR-FTIR spectroscopic investigation, performed in parallel, also confirmed that these polymer-bound peptides do indeed adopt a helical conformation. The results of this study open the possibility to exploit the peptide-resin conjugates based on C(alpha)-tetrasubstituted alpha-amino acids as helpful, structurally organized templates in molecular recognition studies or as catalysts in asymmetric synthesis. 相似文献
80.
Antonio L. Braga Helmoz R. Appelt Claudio C. Silveira Ludger A. Wessjohann Paulo H. Schneider 《Tetrahedron》2002,58(52):10413-10416
The enantioselective alkynylation reaction of aldehydes with alkynes and diethylzinc, catalyzed by chiral disulfide–oxazolidine ligands, provides a simple, practical and inexpensive method to access chiral propargylic alcohols in good yields and satisfactory ee's. 相似文献