Biological and Material Solid State NMR

NHMFL NMR User Committee Meeting, Tallahassee,October 2, 2009

Zhehong Gan

Instrumentations and Capabilities900UWB: PISEMA/Bicelle

3.2mm VT HX MAS 3.2mm Bruker HCN MAS

830NB (Keck) 1.8, 4 and 7mm MAS 2.75mm HX MAS (Samoson)

600WB(1&2) PISEMA/Bicelle4mm HXY MAS (Bruker)4mm HFX MAS (Bruker)

(soon in 2009) 3.2mm HCN low-E MAS (funded by UCGP)

1.3mm HXY 60kHz ultrafast MAS (Bruker)

Enhancing Spectral Resolution of HETCOR Spectra at 900 MHz

Fu, R.; Gordon, E.D.; Hibbard, D.J.; and Cotten, M., J. Am. Chem. Soc. 131 (31), 10830-10831 (2009)

Myriam Cotten/Hamilton College; Riqiang Fu/NHMFL

Supported by NSF (CHE-0832571), Research Corporation, Dreyfus Foundation, & NIH R01 AI23007

HETCOR Spectra of Aligned T21G22 Piscidin 3 Peptide at 900 MHz

Myriam Cotten/Hamilton College; Riqiang Fu/NHMFL

M2 Protein Drug Target for Flu Virus • This 22-62 tetrameric construct (25kDa) has been shown to

function as a proton channel blockable by the anti-viral drug, amantadine.

• Below is a PISEMA spectrum of uniformly aligned, amino acid specific (15N Leu, 15N Val, 15N Phe) labeled sample in DOPC DOPE lipids. Spectra for the entire backbone have been obtained and assigned.

• Structure is very different from the solution NMR structure obtained in DHPC in that the amphipathic helix interacts interfaces with the lipid bilayer as opposed to forming a water soluble domain.

In collaboration with David Busath, BYU & Huan-Xiang Zhou, FSU Physics

A Model H-bonded Solid: NH4H2PO4 (ADP)

NPO4H

NMR Study of Structural Phase Transition on 900 MHz

Naresh Dalal/FSU; Riqiang Fu, Bill Brey, Jason Kitchen/NHMFL

Order-disorder behavior Isotropic chemical shift, δiso, is invariant to rotational and

translational changes.

Displacive behavior Any change in δiso detected at a phase transition implies a change in

the electronic structure of the molecular moiety.

High field, Probe and Pulse sequence Development for Material Applications

Gan et al, JMR, 200 (2009) 2, Sideris et al Science 321 (2008) 113

Efficient SPAM-MQMAS pulse sequence

Balanced probe circuit delivers high B1 field

Sensitivity enhancement with high B0, B1

and SPAM-MQMAS for low- nuclei

Optimizing QCPMG for low- wideline NMR at High Fields

I. Hung/NHMFL

35Cl QCPMG NMR spectra of (a) Cp2ZrCl2 , (b) Cp2TiCl2, (c) Cp2MoCl2 and (d) Cp2WCl2 acquired at 25 and 19.6 T

QCPMG NMR using Resistive Magnets

I. Hung, K. Shetty. W. Brey, Z. Gan/ NHMFL P. Ellis/PNNL, SSNMR submitted

Sc2O3

18

6 coord. Sc140

User highlight: High field, fast MAS and MQMAS ofIonic Conductors

L. Buannic, F. Blanc, C. Grey StonyBrooks

11.7T 19.6T36kHz MAS

1-pulse

Q-filtered spin-echo

SPAM-MQMAS

BZSc30

Low-field (500MHz) spectra at users’ lab show no sign of 5-coord Sc site of interest in Sc-doped Ba-Zr perovskites which has been found and measured under high magnetic field, fast MAS, Q-filtered, and SPAM-MQMAS pulse sequence.

14N NMR: indirect detection and PISEMA

AlaGlyGly, 600MHz, 4mm 10kHz MAS, 128 scans per point

14N PISEMA of N-acetyl-D-valine (600MHz, 128 t1/8 scans)

I. Hung, C. Qian, W. Brey, Z. Gan, Supported by UCGP

Users and Collaborators

Materials and Quadrupolar Nuclei

- C. Grey/StonyBrooks25Mg, 27Al, 89Y, 45Sc, clay, zeolite, ion-

conductor - L. Polles/Rennes

95Mo nanoparticle catalyst- S. Sen/UCDavis

73Ge glasses- H. Jakobsen/Aarhus

33S, 17O, instrumentation- Warwick, St Andrews/UK

Natural abundant 17O, 45Ca minerals and glasses

- G. Wu/Queensprotein-ion binding/39K MQMAS

- B. Chemlka/UCSB 25Mg, 45Ca, 67Zn, nanomaterials

- Amoureux/LilleLow- probe development

- Hernandez-Maldonado/Puerto Rico porous sorbent and catalyst

- Cheng, Yang/XiamenBattery materials

Bio-solids and membrane proteins

- S. Opella (UCSD)- G. Veglia (Minnesota)- A. Rammamoorthy (Michigan)- M. Cotten (Hamilton College)