MOLECULAR RECOGNITION1 Novel carriers for dicarboxilic acids on the basis of α- aminophosphonates and calix[4]arenes Ivan I.Stoikov, Igor S.Antipin, Alexander I.Konovalov

MOLECULAR RECOGNITION2 Source PhaseReceiving PhaseMembrane Phase Membrane Transport SubstrateCarrierSubstrate-Carrier Complex

MOLECULAR RECOGNITION3 Receptor for Organic Acids

MOLECULAR RECOGNITION4 Dicarboxylic Acids α-Hydroxy Acids α-Amino Acids Hydroden Bonding & Electrostatic Interactions

MOLECULAR RECOGNITION5 Phosphorus Chemical Shifts and Yields of Aminophosphonates NR1R1 R2R2 R3R3 R4R4 P, ppm. Yields (%) 1CH 2 Ph-(CH 2 ) 5 -С 5 Н CH 2 Ph-СН 3 С2Н5С2Н СН(СН 3 ) 2 -СН 3 С2Н5С2Н CH 2 Ph-(CH 2 ) 4 -С 5 Н CH 2 Ph-СН 3 С 5 Н CH 2 Ph-(CH 2 ) 4 -СН 2 СН(С 2 Н 5 )С 4 Н CH 2 Ph-(CH 2 ) 5 -СН 2 СН(С 2 Н 5 )С 4 Н CH 2 Ph-СН 3 СН 2 СН(С 2 Н 5 )С 4 Н CH 2 Ph-СН 3 -НСН 2 СН(С 2 Н 5 )С 4 Н CH 2 Ph-Н СН 2 СН(С 2 Н 5 )С 4 Н CH 2 PhС4Н9С4Н9 -НСН 2 СН(С 2 Н 5 )С 4 Н CH 2 PhСН 3 С 10 Н CH 2 Ph-Н С 10 Н CH 2 Ph-(CH 2 ) 5 -c-C 6 H CH 2 PhННc-C 6 H

MOLECULAR RECOGNITION6 Cylinder with membrane Termostated cell Glass thermostated cell for membrane extraction: 1- external thermostated vessel with source phase; 2-internal vessel with receiving phase; 3-ring; 4-supported liquid membrane (SLM); 5- magnetic stir bars; 6-flow- through cell; D-detector. Membrane Transport

MOLECULAR RECOGNITION7 Initial Glycolic Acid Fluxes through a Supported Liquid Membrane Impregnated by carrier: carrierXRJ. 10 6, mol h -1 cm -2 no carrier С 5 Н СН 2 СН(С 2 Н 5 )С 4 Н С 5 Н СН 2 СН(С 2 Н 5 )С 4 Н c-C 6 H СН 2 СН(С 2 Н 5 )С 4 Н С 10 Н СН 2 СН(С 2 Н 5 )С 4 Н СН 2 СН(С 2 Н 5 )С 4 Н СН 2 СН(С 2 Н 5 )С 4 Н c-C 6 H С 10 Н 21 30

MOLECULAR RECOGNITION8 The Complex Structure of Aminophosphonates with Oxy Acid.

MOLECULAR RECOGNITION9 Carriers: α-Aminophosphonates 1-8.Substrates d,l-Glutamic acid, lg P=-3.69, pKa=4.33 Sodium acetate, lgP=-4.24 Tartaric acid, lgP=-1.95, pKa=2.89 Oxalic acid, lgP=-0.53, pKa=1.25 Glycolic acid, lgP=-1.11, pKa =3.83 Malonic acid, lgP=-0.58, pKa=1.38 Succinic acid, lgP=-0.59, pKa=4.21 d,l-Mandelic acid, lgP=0.64, pKa=3.37

MOLECULAR RECOGNITION10 Дополнительно... ЯнвФевМарАпрМайИюнИюлАвгСенОктНоя Этап 1 Этап 2 Этап 3 Дек The histogram of enhancement coefficients in the processes of membrane extraction by α-aminophosphonates ε

MOLECULAR RECOGNITION11 The histogram of enhancement coefficients in the processes of membrane extraction by α-aminophosphonates ε

MOLECULAR RECOGNITION12 The histogram of enhancement coefficients in the processes of membrane extraction by α-aminophosphonates ε

MOLECULAR RECOGNITION13 Malonic acid Succinic acid Glycolic acid Tartaric acid The Influences of Concentrations of Substrate in Source Phase on Initial Fluxes of Organic Acids through a SLM (298K).

MOLECULAR RECOGNITION14 The Influences of Concentrations of Substrate in Source Phase on Initial Fluxes of Organic Acids through a SLM (298K). Mandelic acid Oxalic acid

MOLECULAR RECOGNITION15 h Calix[4]arenes

MOLECULAR RECOGNITION16 (13) R 1 =-t-Bu, R 2 =-CH 2 -Ph, (14) R 1 =-t-Bu, R 2 =- -CH 2 -naphtyl, (15) R 1 =-t-Bu, R 2 =-9-CH 2 -Flu, (16) R 1 =-t-Bu, R 2 =-trans-CH 2 -СH=CH-Ph, (17) R 1 =-t-Bu, R 2 =-4-CH 2 -С 6 Н 4 -NO 2, (18) R 1 =-t-Bu, R 2 =-4-CH 2 -С 6 Н 4 -CN, (19) R 1 =-t-Bu, R 2 =-4-CH 2 -С 6 Н 4 -COOEt, (20) R 1 =-t-Bu, R 2 =-CH 2 -COOEt, (21) R 1 =-NO 2, R 2 =-CH 2 -Ph (22) R 1 =-t-Bu, R 2 =4-CH 2 -Pyr (23) R 1 =-t-Bu, R 2 =-CH 2 -CH 2 -NH-C(O)-С 6 Н 5

MOLECULAR RECOGNITION17 ε ε The histogram of enhancement coefficients in the processes of membrane extraction by calix[4]arenes 13-23