|
|
|
|
| LEADER |
01000naa a22002652 4500 |
| 001 |
NLM154330736 |
| 003 |
DE-627 |
| 005 |
20231223065809.0 |
| 007 |
tu |
| 008 |
231223s2005 xx ||||| 00| ||eng c |
| 028 |
5 |
2 |
|a pubmed24n0515.xml
|
| 035 |
|
|
|a (DE-627)NLM154330736
|
| 035 |
|
|
|a (NLM)15779934
|
| 040 |
|
|
|a DE-627
|b ger
|c DE-627
|e rakwb
|
| 041 |
|
|
|a eng
|
| 100 |
1 |
|
|a Pastoriza-Gallego, M Jose
|e verfasserin
|4 aut
|
| 245 |
1 |
0 |
|a Dediazoniation in SDS/BuOH/H2O reverse micelles
|b structural parameters, kinetics, and mechanism of the reaction
|
| 264 |
|
1 |
|c 2005
|
| 336 |
|
|
|a Text
|b txt
|2 rdacontent
|
| 337 |
|
|
|a ohne Hilfsmittel zu benutzen
|b n
|2 rdamedia
|
| 338 |
|
|
|a Band
|b nc
|2 rdacarrier
|
| 500 |
|
|
|a Date Completed 14.06.2006
|
| 500 |
|
|
|a Date Revised 22.03.2005
|
| 500 |
|
|
|a published: Print
|
| 500 |
|
|
|a Citation Status PubMed-not-MEDLINE
|
| 520 |
|
|
|a Dediazoniation of o-methylbenzenediazonium tetrafluoroborate was investigated in SDS/BuOH/H2O (SDS = sodium dodecyl sulfate) reverse micelles, RMs, and, for comparison, in binary BuOH/H2O mixtures by employing a combination of spectrophotometric and chromatographic techniques. RMs were characterized by steady-state fluorescence; the data indicate that the aggregation number of the RMs increase upon increasing [SDS], while the radius of the water pool is mainly controlled by the amount of water in the system, and that the thickness of the interfacial region increases upon increasing the amount of BuOH in the system, in agreement with literature reports. Experimental evidence suggests that dediazoniation mainly takes place in the interfacial region of the RMs. Kinetic data show that a turnover from the heterolytic to the homolytic mechanism takes place about pH = 5; the variation of the observed rate constants, k(obs,) with pH following an S-shaped curve. At pH approximately 2, k(obs) values are insensitive to solvent composition both in RMs and in the binary mixture; however, k(obs) values in RMs are slightly lower than those in BuOH/H2O, probably due to the presence of SDS. High-performance liquid chromatography analyses of the reaction mixture indicate, in both RMs and in binary mixtures, the main dediazoniation products are the heterolytic ArOH and ArOBu, their yields depending on the composition of the system, and only small (<10%) amounts of the reduction ArH product were detected. The data at low pH are interpreted in terms of a DN + AN dediazoniation mechanism, i.e., a rate-limiting formation of an extremely reactive aryl cation that further reacts with available nucleophiles in the solvation shell
|
| 650 |
|
4 |
|a Journal Article
|
| 700 |
1 |
|
|a Bravo-Diaz, Carlos
|e verfasserin
|4 aut
|
| 700 |
1 |
|
|a Gonzalez-Romero, Elisa
|e verfasserin
|4 aut
|
| 773 |
0 |
8 |
|i Enthalten in
|t Langmuir : the ACS journal of surfaces and colloids
|d 1992
|g 21(2005), 7 vom: 29. März, Seite 2675-81
|w (DE-627)NLM098181009
|x 1520-5827
|7 nnns
|
| 773 |
1 |
8 |
|g volume:21
|g year:2005
|g number:7
|g day:29
|g month:03
|g pages:2675-81
|
| 912 |
|
|
|a GBV_USEFLAG_A
|
| 912 |
|
|
|a SYSFLAG_A
|
| 912 |
|
|
|a GBV_NLM
|
| 912 |
|
|
|a GBV_ILN_22
|
| 912 |
|
|
|a GBV_ILN_350
|
| 912 |
|
|
|a GBV_ILN_721
|
| 951 |
|
|
|a AR
|
| 952 |
|
|
|d 21
|j 2005
|e 7
|b 29
|c 03
|h 2675-81
|