Solid State NMR News - Bruker · Innovation with Integrity Solid State NMR News •Solid State DNP...

Solid State NMR News

Peter Gierth, Bruker UK / Sebastian Wegner, Bruker BioSpin GmbH Bruker UK Users’ Meeting

Innovation with Integrity


• Solid State DNP NMR

• 111 kHz MAS NMR

• Adaptor kit for Varian and Chemagnetics probes

• MAS III firmware upgrades

• Application notes

• Training courses


Solid State DNP NMR

• Many applications in solid state NMR suffer from insufficient sensitivity

• Solid state DNP NMR today is the method of choice to solve this

– Biological systems (membrane proteins, fibrils etc.)

– Pharmaceuticals (13C and 15N 2D correlations at natural abundance

– Materials (frameworks, MOFs)


DNP of MOFs

• DNP-enhanced 15N{1H} CPMAS NMR spectra of UiO-66-NH2 (a), UiO-66-NH2 exposed to KCl (b), and Pt2+-loaded samples

• The –NH2 Pt peak grows linearlywith Pt loading of the MOF. Estimates of the ratio of free NH2 vs. –NH2 Pt can be made based on the relative peak intensities in the NMR spectra.


Solid-State DNP NMR Spectrometer Gyrotron and Klystron Options

Work in Progress: 263 GHz Klystron

• Offer a lower-price more compact

microwave source at 263 GHz

• Design compatible with possible upgrade later to gyrotron for full power performance

• Power output ~ 5 W • Available 2017

DNP with Gyrotron

DNP with Klystron (EIK)


111kHz - 0.7mm MAS Probe

• Highest available MAS rate

• High RF excitation in the 0.5MHz regime

• MAS stability of better than 0.25 ‰ at 111kHz (±28Hz max)

• 500nl Volume (350nl active volume)

• Available for SB/WB in HX / HXY / HCN configuration

• MAS 3 is mandatory !


MAS 3 – High Accuracy MAS regulation for 0.7 mm

• Standard deviation less than 4Hz

• Long term stability for more than 7 hours tested


Tools


Solution State / Solid State MAS NMR


BL 0.7 mm – first results hNH 2D correlation@ 111kHz

Coherence Lifetimes & Linewidths (Gb1)

Data courtesy of

Guido Pintacuda, ENS Lyon


• GB1 proved possibilities

• In 2016 unknown structures are targeted

• Picture shows a e.g.capsid

Data on the following slides courtesy of Guido Pintacuda, ENS Lyon

Structure Elucidation of a capsid protein

PNAS 2016 113 (33) E4757-E4758


1. Backbone Resonance Assignment


2. Elucidating Ha @ >100kHz MAS

15N-Linked Ha Detected Walk 13CO Linked Ha Detected Walk -> linking over prolines


15N-Linked Ha Detected Walk


3. Rapid Side Chain Assignment


4. Proximities Between Protons in Side-Chain


5. Automatic Structure Calculation with UNIO (T. Herrmann)


Paramagnetic Metalloproteins: Metal Ion Coordination


Paramagnetic Solids Large Offsets and Large Shift Anisotropies

pNMR Network


Lanthanide luminescent complexes



• Solid State DNP NMR

• 111 kHz MAS NMR

• Adaptor kit for Varian and Chemagnetics probes

• MAS III firmware upgrades

• Application notes

• Training courses


Support of Chemagnetics, Varian and Agilent MAS probes

• Bruker provides an adaptor kit for solid state NMR probes

from

• Easy integration of these probes into the Bruker workflow

• Full integration of the VT operation

• Full integration of the MAS operation

• Scope of the kit

• Probe adaptor plate

• VT adaptor for Johnston coupling

• Pneumatic adaptors and electrical interface for MAS

controller



• Probe probe adaptor

plate for WB system

• Probe adaptor plate mounted

to the probe transport frame



• Probe with adaptor plate mounted to the Bruker Shim coil



• Top: VT stack of a WB system with a

Bruker Johnson VT adaptor for

experiments above room temperature

• Right: poking out VT stack of WB

magnet. Includes black adaptor flange

on top of Bruker shim stack


New MAS III Firmware

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Different to former MAS units, MAS III firmware updates are straightforward:

1. open the Swiss FTP server ‘ftp://ftp.bruker.ch’ in an internet browser

2. go to: ‘/NMR/download/servtools/firmware/mas/’

3. download the latest firmware (e.g. to your desktop or home directory)



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4. open TopSpin and the MAS Display (‘masdisp’)

5. open the tab ‘Configuration’ in the MAS display

6. Click on ‘MAS firmware update’



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7. in the MAS webpage browse to the just downloaded firmware file

8. click on ‘Update’

mas3_20151008_1638.bin


Application Notes – 1H-Detection for Protein Samples

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• full set of ten 1H-detected experiments combined with (ultra-) fast MAS

• for protein backbone & side chain assignment

• available with at least TopSpin 3.2.7/ 3.5.3 (or on demand)

• 3 Application Notes explain theoretical and practical aspects:

Introduction to 1H-detection

Experiments explained in more detail

Straightforward optimization protocol


Application Notes – BSH CP for Protein Samples

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• Band-Selective Homonuclear Cross Polarization

• homonuclear C-C transfer in NCαCx and NCOCx experiments is essential for protein backbone assignment

• BSH CP represents a highly robust & efficient dipolar-based transfer method

• efficiently suppresses:

• unwanted sequential & long-range C-C transfers by dipolar truncation

• undesirable transfer to Cβ resonances

• five different experiments implemented from 1D up to 4D

• tested for protonated & deuterated samples

• available with at least TopSpin 3.2.6 / 3.5.2 or on demand


Application Notes – Where to find them? www.bruker.com

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Home . Products . Magnetic Resonance . NMR . Probes . Solids . Very Fast MAS . 0.7 mm . Learn More


Application Notes – Where to find them? www.theresonance.com

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application note


New TopSolids2 – Where to find Topsolids2


Solid State NMR Training Courses – www.bruker.com

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Other courses available upon request:

• 13C-detected solid state NMR on protein samples

• 1H-detected solid state NMR on protein samples

• TopSolids

• CRAMPS

We are always open for further suggestions: [email protected]


Acknowledgements

• core application people solid-state NMR:

Gerhard Althoff (DE)

Venita Decker (DE)

Sebastian Wegner (DE)

Barbara Perrone (CH)

Jochem Struppe (US) Fabien Aussenac (F) for DNP

+ all the other application people world wide!

• important E-mails:

[email protected]

mailto:[email protected]

mailto:[email protected]

Solid State NMR News - Bruker · Innovation with Integrity Solid State NMR News •Solid State DNP...

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