Explorations of translational molecular dynamics by NMR MGSE/OSGE methods
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1 Exploraons of ranslaonal molecular dynamcs by NMR MGSE/OSGE mehods Janez Sepšnk Unersy of Ljubljana, FMF, and J. Sefan Insue, Ljubljana, Sloena BC 3 BC AMPERE_School,CUBRIC_semnar 7
2 Modulaed Graden Spn Echo Velocy auocorrelaon funcon s a key uany of he dynamc sysems conanng deals of he underlyng naure of molecular neracons. By applyng he graden/radofreuency seuence, whch properly modulaes he spaal dscord of spn phase, we can oban he power specrum of he elocy auocorrelaon funcon from he spn aenuaon E Ee, d Mehod was used o sudy: Flow and molecular dynamcs of luds n porous meda Low freuency dynamcs of polymers and luds Imagng he morphology and acy of neurons n he bran Granular moon AMPERE_School,CUBRIC_semnar 7
3 Spns n nhomogeneous magnec feld E L Cos e B L L E B(r) e L r grad Br. r G. r L L AMPERE_School,CUBRIC_semnar 7
4 Pulsed graden spn echo (PGSE) Saonary spns E G e. r d Mong spns d d E G e. r d AMPERE_School,CUBRIC_semnar 7
5 Spn moon encoded n he spn phase G () G eff Spn phase dscord ' G eff d' E G r d eff e e Numerouse spns Velocy s a random arable ranslaonal moon E e d. d AMPERE_School,CUBRIC_semnar 7
6 Bloch-Torrey euaon / d d spn echo H.C. Torrey. Bloch euaons wh dffuson erms, Phys. Re., 4, , 956 m B r, m r m m=magnezaon densy =self-dffuson ensor E e. d M o e G d M o e b PGSE of dffuson n a porous medum E.L.Hahn, Spn-echoes, Phys. Re. 8, (95), H. Y. Carr and E. M. Purcell, Effecs of dffuson on free precesson n nuclear magnec resonance, Phys. Re. 94, (954) AMPERE_School,CUBRIC_semnar 7
7 Varous nerpreaons of dffuson weghed MRI ffuson kuross E E e b. AC b AC. AK b= G AC = apparen dffuson coeffcen Anomalous dffuson E E e b. C ffuson propagaor P r r E,, e r r o d AMPERE_School,CUBRIC_semnar 7
8 Molecular self-dffuson and elocy auocorrelaon Ensen s defnon: xx x( ) lm d d x( ) x ( ) x ( ) d / d d spn echo AC = apparen dffuson coeffcen d Green-Kubo relaon: xx x ( ) x x ( () ) x ( d d ) d x( ) Molecular elocy auocorrelaon conans deals of he underlyng naure of molecular neracons. AMPERE_School,CUBRIC_semnar 7
9 Velocy auocorrelaon Velocy auocorrelaon Velocy auocorrelaon funcon VAF of lud c ~ s d ( ) me VAF of resrced dffuson me Ineracons wh boundares se he long al of VAF AMPERE_School,CUBRIC_semnar 7
10 Velocy auocorrelaon Specrum of elocy auocorrelaon Velocy auocorrelaon Specrum of elocy auocorrelaon Velocy auocorrelaon specra VAF of lud c ~ s d ( ) NMR e d me khz d freuency VAF of resrced dffuson NMR me freuency khz AMPERE_School,CUBRIC_semnar 7
11 d d '. c '. d. e... ' AMPERE_School,CUBRIC_semnar 7 Cumulan expanson n he Gaussan phase approxmaon Gaussan phase approxmaon e phase grang d e E. / =random arable
12 d d '. c '. d. e... ' AMPERE_School,CUBRIC_semnar 7 Cumulan expanson n he Gaussan phase approxmaon Gaussan phase approxmaon e d e E., d e d e c Velocy auocorrelaon specrum Specrum of spn dephasng *,.., d J.Sepšnk, Analyss of NMR self-dffuson measuremens by densy marx calculaon, Physca 4B (98) Velocy auocorrelaon funcon
13 Modulaed Graden Spn Echo (MGSE) π/ π π π π π π π π m, d rf +G() () me T P.T. Callaghan, J. Sepšnk, Freuency-doman analyss of spn moon usng modulaed graden NMR, J. of Mag. Res. A 7, 8- (995) AMPERE_School,CUBRIC_semnar 7
14 Modulaed Graden Spn Echo (MGSE) Gaussan phase approxmaon E e X m, d π/ π π π π π π π π rf +G() () me Mehod enables a sroboscopc ew o he molecular moon AMPERE_School,CUBRIC_semnar 7
15 Velocy correlaon specrum of flows hrough a porous medum by MGSE mehod Graden mm (beads -3 mm) Flow π/ π π π π π π π π rf +G() E e j j m m T sperson specra for waer flow hrough on-exchange-resn bead pack a dfferen eloces as measured by MGSE seuence (d=7ms). P.T. Callaghan, J. Sepšnk, J. of Mag. Res. A 7, 8-(995) AMPERE_School,CUBRIC_semnar 7
16 AMPERE_School,CUBRIC_semnar 7
17 Applcaons of MGSE/OGSE mehod Osclang graden spn echo (OGSE) AMPERE_School,CUBRIC_semnar 7
18 WMRI by PGSE and OGSE Coronal and sagal T-weghed mages and enlarged AC mages of he hppocampus and cerebeacured usng he PGSE and OGSE seuences and correspondng Nssl saned secons. M. Aggarwal, M. V. Jones, P. A. Calabres, S. Mor and J. Zhang, Probng mouse bran mcrosrucure usng oscllang graden dffuson MRI, Mag. Res n Med., 67, 98-9 () SPIN THRO THE HISTORY OF RESTRICTE IFFUSION Workshop, Cardff, January 7 a CUBRIC AMPERE_School,CUBRIC_semnar 7
19 MGSE seuences () Consan magnec feld graden () Adances n Magnec and Opcal Resonance ed. Waren S. Waren, Vol. 9, p , (996), Academc Press, London, New York, Toko, Sydney AMPERE_School,CUBRIC_semnar 7
20 Ηˆ Hamlonan of MGSE seuence-consan magnec feld Bo Iˆ z Br Iˆ Ηˆ RF Ηˆ o Transformaon no roang and ogglng frame ges he Hamlonan of effece graden Ηˆ GRT ' Iˆ cos b( ) Iˆ sn b( ) B r z x z b( ) -RF pulses d resonance off-se phase dscord () J. Sepšnk, I Ardelean, Journal of Magnec Resonance 7 (6) 7 AMPERE_School,CUBRIC_semnar 7
21 d n e N E *,.., MGSE and specrum of elocy auocorrelaon AMPERE_School,CUBRIC_semnar 7 m m n e G G / 8 ' ') ( cos 4 m m n m m n n n Sn d b d d d b ' ') ( cos G ()
22 Measuremen of resrced dffuson by MGSE hydrogel res sphere : p k b k k k r ; m.8; m p b b 4 r.46 4 m ( m ) 4 r x 9 m s.5..5 p =.6-9 m s - r =.57-6 m khz Theory hydrogel p x 9 m s p =.38-9 m s - r =.4-6 m khz AMPERE_School,CUBRIC_semnar 7
23 Use of nernal gradens by MGSE m ( ) / T π y π y π y π y π y π y π y π y π/ x 8 G z m m T 4 G z π y π y π y b Waer n ceramc wh magnec mpures ncluson Pore sze Relaxaon me Inernal graden J. Sepšnk, I Ardelean, Usage of nernal magnec felds o sudy he early hydraon process of cemen pase by MGSE mehod, Journal of Magnec Resonance 7 (6) 7 AMPERE_School,CUBRIC_semnar 7
24 Polymer mel chan enanglemen x y y y y y y RF+G T P.G. de Gennes, J. Chem.Phys. 55, (97), M. o and S. F. Edwards, J. Chem. Soc., Faraday Trans. 74, 789 (978) Tube (ω) of mono-dsperse poly(soprene-.4) mels wh dfferen molecular mass AMPERE_School,CUBRIC_semnar 7
25 Chan Rouse moon Tube Rouse moon dsengagemen Regme of moon n molen polymers P.G. de Gennes, J. Chem.Phys. 55, (97), M. o and S. F. Edwards, J. Chem. Soc., Faraday Trans. 74, 789 (978) Voy J., Rubnsen M. and Colby R., Macromolecules, 4 (99) x d X e 3 Rube x s ( ) Repaon J. Sepšnk, A. Mohorč, C. Maea, S. Sapf and Igor Serša,EPL, 6 (4) 77 AMPERE_School,CUBRIC_semnar 7
26 MGSE by he use of nernal graden n polymer mel Analyss by usng MGSE AMPERE_School,CUBRIC_semnar 7
27 Temporal dependence of VAS n luds waer oluene AMPERE_School,CUBRIC_semnar 7
28 Velocy auocorrelaon of waer of dsrbuon AMPERE_School,CUBRIC_semnar 7
29 VAS of glycerol by usng NMR MOUSE dece res k p b k k k long al 3/ a b Vorces of hydrodnamc flucuaon hnder he molecular dffuson moon AMPERE_School,CUBRIC_semnar 7
30 VAS of resrced dffusson s ensor E G m n e G n VAS of moon n ube AMPERE_School,CUBRIC_semnar 7
31 Concluson In porous meda MGSE measuremen of he specrum of elocy auocorrelaon funcon ges nformaon abou he -pore sze, -nernal gradens -pore sze dsperson, -relaxaon mes,, -S/V rao. Mehod prodes compleely new nformaon abou molecular dynamc of fluds: luds, mxures of luds, polymers d. In combnaon wh he magnec resonance magng makes possble o sudy he morphology and he acy neurons. Hgh freuency lm of mehod, whch depends on he srengh of appled graden, reaches a he presen sae he freuences range beyond khz o enable he measuremens of dffuson n nano-pore sysems. AMPERE_School,CUBRIC_semnar 7
32 Acknowledgemen š š č č AMPERE_School,CUBRIC_semnar 7
33 Thank you for your aenon! AMPERE_School,CUBRIC_semnar 7
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