The NMR Lab at the

School of Chemical Sciences

University of Illinois

Dean Olson

Director Andre Sutrisno

Solids NMR

Tracie Hubert

Technical Asst. Lingyang Zhu

Liquids NMR

55 Noyes

55 Noyes

Solution State NMR Spectrometers

400 MHz: Nalorac QUAD probes (H/F, C/P or P/B)

500 MHz: Nalorac QUAD probes H/F, C/P w PFG Z probe H/F, C/P probe

500 MHz: Varian HCN PFG Z probe

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600 MHz: AutoX BB and HCN probes

55 Noyes 146 RAL

Solid State NMR Spectrometers

300 MHz WB

Liquids/Solids:

• Varian 5mm H/X probe

• Chemagnetics 7mm/4mm

MAS probes

750 MHz WB:

• 1.6mm HFXY Fast MAS, HXYZ

Gradient Fast MAS and HXY Fast

MAS probes

• 3.2mm HCN Balun MAS and HXY

BioMAS probes

• 4mm T3 HXY MAS probe

500 MHz WB: • 3.2mm HCN Balun MAS probe

• 1.6mm HCDN Fast MAS probe

• 1.6mm HFXY Fast MAS probe

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55 Noyes A151 CLSL

Typically Rienstra Gp Typically Rienstra Gp

See Andre

Solution/Solid State 750 MHz NB

NMR Spectrometer

750 MHz NB:

• 5mm 1H{13C/15N} PFG probe

• 10mm 15N-31P BB probe

• 10mm 73Ge-15N BB probe

• 3mm 13C{1H} probe

• 3.2mm HCN Balun MAS probe

• 3.2mm HCN MAS probe

• 4mm 15N-31P CPMAS Probe

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A151 CLSL

See Lingyang

SCS NMR Website N

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NMR Training

Study and exercises;

Training by Liaison

Director e-mails 20 items: NMR principles, Mnova, i.p. address, etc.

Check-Out by

Director

Temperature Control

(VT) Training

by Director

UI500NB Training

by Director

(2D-NMR Prep)

Special 1D,

2D/3D-NMR Training

by Lingyang

Recommended for

UI500NB and required

for UI600

One key 2D document: UI500NB Advanced 1D and 2D NMR

Tuning and matching

pw90 calibration

Solvent suppression

T1 calibration

Get a booklet

and see Tracie

for paperwork

& ChemFOM

Solid State NMR

Training

by the Solids

Spectroscopist

A Common Problem

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From an MIT web document

A Common Problem

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Lower

Higher

A Few Under-Appreciated NMR

Data Processing Shortcuts

p7 references the chloroform 1H residual signal to 7.26 ppm (select peak first)

p77 references the chloroform 13C residual signal to 77.0 ppm (select peak first)

ga <return>

proc svf(‘filename’) e <return>

Use this after you’ve reviewed preliminary NMR data and you’re ready to

simply acquire. This series of commands does several things in a very

clever way:

• Acquires

• Processes the data

• Saves the file (so you don’t forget)

• Ejects the sample only if you have saved and named the data file in a

legal manner

• If you give the data file an illegal name, this is nicely called to your

attention by the sample failing to eject, and you can then fix the

problem.

• If you succeed on the first try, the sample pops up to confirm all is well.

• By the way, you can’t put the ga on the same line with the other

commands.

NMR user JLK is gratefully recognized for contributing this idea.

Handy NMR Command Sequence

Why Visit the NMR Lab?

“I wish I had done more NMR sooner.”

- Quote from a 5th year grad student

Bruker NMR - 500 MHz CryoProbe

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Coming Soon to an NMR Lab Near You (146 RAL)

Going where

the U400

is now:

Carver Bruker 500

Funding from the

Carver Charitable

Trust: $500K

Total Cost $895K

Bruker NMR - 500 MHz CryoProbe

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NMR Training Simulator

What NMR Can Do for You

• Structure Elucidation of Small Molecules(<1 kDa)

• Structure identification of synthetic compounds, intermediates, impurities, mixtures, unknowns, regiochemistry, rotamerization

• Quantitative NMR • Chemical exchange: Equilibrium or A(Di)ssociation constants • Reaction monitoring or reaction rates • Dynamics (T1, T2 and NOE) • Diffusion coefficients (DOSY NMR): monomer? dimer? • Enantiomeric purity determination • Absolute stereochemistry determination • Intramolecular hydrogen-bond determination

• Structure Determination and Dynamics of Macromolecules and Complexes

• NMR Screening (Protein-Ligand Interaction)

• Metabolites Analysis

by Lingyang Zhu

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Count the Numbers

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13C-APT

1H Spectrum

Long-Range Connectivity: 1H-13C gHMBC Spectrum

11 18 1 6 24 21

28

8

29,13209 25

29,25

28,25

22,25

26,2526,29

22,21

19,21

23,21

4,2

10,2

4,64,18

7,67,11

8,68,11

7,9

22,20

20,2424,18

6,1120,18

21,18

24,20

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Relative Stereochemistry: 1D 1H-1H NOE Experiment

This problem can also be

readily resolved by 1H-1H

J-coupling constants

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Regioisomer: 1H-19F NOE Experiment

NOE seen between 19F and proton at position 3, but not to the

pyrazole proton, suggesting the 5-position reaction, not 1-

position.

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3

3 6

NOE spectrum

1H spectrum

Regioisomer: 15N Chemical Shifts

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Based on the 15N chemical Shifts and

the connectivity from 1H-15N HMBC spectrum

Variable Temperature Experiments:

Tautomer Identification

HN

O

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N11

12

13

14t

15t

16tN

O

R

HN

11

12

13

14

15

16

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HP

LC

D

ata

H

PLC

D

ata

5°C

25°C

qNMR: Determination of %TFA

by an Internal Standard

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qNMR: Determining [sample]

using NMR software

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Chemical Exchange in NMR:

Intra- and Inter-molecular process

Kassoc = kon/koff

k1

k-1

Keq determined by LW and Dd

kon

koff

+

Intra-

Inter-

Meyer: 2003

U. Ottawa NMR Facility

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Collaborations & Publications Publications:

• The interplay of Al and Mg speciation in advanced Mg battery electrolytes,

JACS, 2015 (Gewirth Group)

• Control of protein orientation on gold nanoparticles. JPC, 2015 (Murphy group)

• Structure, bioactivity, and resistance mechanism of streptomonomicin,

an unusual lasso peptide from an understudied halophilic actnomycete.

Chem & Biol, Cell Press 2015 (Mitchell Group)

• Synthesis and Characterization of the Platinum-Substituted Keggin Anion

α- H2SiPtW11O404-. Inorg. Chem 2014 (Klemperer)

• Alkyne Mechanochemistry: Putative Activation by Transoidal Bending. RSC

ChemComm. 2014 (Moore group)

• NMR structure of the S-linked glycopeptide sublancin 168. ACS Chem Biol. 2014

(van der Donk group)

• New Reactions of Terminal Hydrides on a Diiron Dithiolate. JACS 2014

(Rauchfuss group)

• Identifying lithium–air battery discharge products through 6Li solid-state MAS and 1H–13C solution NMR spectroscopy. JPS 2013 (Gewirth group)

Posters: • Quantify phases in Early-age Geopolymers by 29Si and 27Sl NMR. ACSC 2014 (Struble group)

• Expired Epinephrine Maintains Sterility and Chemical integrity. NAEMSP 2015 (Sweedler group)

• Determining Sodium ion mobility in model emulsion system using Single- and Double- Quantum Filtered 23Na NMR Spectroscopy. IFT 2015 (Schmidt group)

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Solid State NMR Spectroscopy

Non-Destructive / “precious” samples

Additional information not available from solution NMR

Solid/Semi-solid samples / Insoluble / No solvent needed

Native states = “as is” - no treatment, approach

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(3cos2θ-1)=0;

θ=54.74°

B0

Varian/Agilent NMR rotors Bruker NMR rotors

by Andre Sutrisno

Solid State NMR Spectroscopy

Need to create solution-like motion and narrow line widths

- Magic Angle Spinning (MAS)

- High power (kW) 1H decoupling

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Solution NMR:

sharp, well resolved peaks

molecular tumbling

averages out the NMR

interactions

600 400 200 0 -200 -400 ppm

Solution NMR

Solid state NMR:

broad powder patterns

reduce both resolution

and sensitivity

Solid-state NMR

B0

13C CPMAS NMR Depicts Degree of

Crystallinity

A

C

B

• CPMAS = Cross-Polarization MAS Able to transfer magnetization from nuclei

with high natural abundance to those with low

natural abundance for signal enhancement

due to dipolar interactions

• Measure line width

• narrower line width (sharper the peak),

more crystalline

• Measure relaxation parameters, T1r (spin-

lattice relaxation time)

• the longer T1r, the more crystalline

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Ability to Follow Slow Reaction

Processes (Kinetics)

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Follow the transformation of “enol” to “keto” that occurs at room temp

NMR Chemical Shifts and

Coordination

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δ (ppm) -60 -70 -80 -90 -100 -110 -120

Q4

Q3

Q2

Q0

Q1

Si(OAl)4 Si(OSi)4

δ (ppm) 80 70 60 50 40 30 20 10 0 -10

Al(IV) Al(V) Al(VI)

AlX4 AlX6

δ (ppm) -80 -90 -100 -110 -120

1Al

2Al

3Al

4Al

0Al

Well-established chemical shift ranges for different species

27Al 29Si

27Al MAS NMR Depicts Various

Transition Phases from Thermal

Treatment

-60-40-20020406080100120140 ppm

* *

* *

Aluminum Acetate

As-spun Nanofibers

Al2O3 Powder

525 °C

800 °C

1000 °C

1200 °C

10 20 30 40 50 60

2 Theta

θ γ γ γ θ θ

θ

α α

α α α

As-spun

525 °C

800 °C

1000 °C

1200 °C

Boehmite: γ→δ → θ+ α → α

XRD is an excellent complementary technique

AlIV AlV AlVI

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De-convolution of 29Si MAS peaks

provides structural information and

degree of reactivity 29Si 1D SSNMR spectra of fly ash geopolymers before and after reaction

βC2S

(Q0)

Quart

z

Q4(3Al

)

Q4(4Al

) Q1 (CSH?)

Q2 (CSH?)

Q4

FAGP (Si/Al = 3.0)

Fly

Ash

• Beginning to identify

structural components

via deconvolution of

the peaks

• Ratio between

different Q sites change

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LU

Thank you

Please visit us at http://scs.illinois.edu/nmr/

Questions Always Welcome

HuiHui, Xixi (crazy cat), and Lu (mellow cat)