No.R2201C312C(Bn)

*specifications subject change without notice.

Solid State NMR

Solid State NMR

1

New ideas from

JEOL RESONANCE offers a full range of Magic-Angle-Spinning (MAS) probes and tools matched

to a wide varity of solid-state NMR applications. JEOL RESONANCE MAS probes feature sample

tube diameters to match the user sample and sensitivity needs. JEOL RESONANCE narrow bore

MAS probes offer improved stability for high-speed spinning or for very large volumes.

The ECA Series NMR Spectrometer automatically updates the relavent spectrometer settings

for all NMR probes to speed switching to between solids and liquids NMR operation.

3.2 mm

Features and Appl icat ions

1 mmVery-high sample spinning speeds up to 80 kHz attained by the 1 mm rotor are required for high resolution 1H or multinuclear measurements of very small samples (800nl).

The combination of sample volume and increased spinning speed makes the 3.2 mm rotor ideal for NMR measurements at 500 MHz and above.

8 mmThe large volume allows high-sensitivity NMR measurements. This size is best suited for measurements at moderate spinning speeds--for example 29Si of synthetic minerals.

0.75 mmThe 0.75 mm rotor provides the ultra-high sample spinning speeds to 110 kHz required for high resolution 1H or multinuclear measurements of extremely small samples (290nl).

4 mmThis 4mm rotor provides a balanced combination of sample volume and spinning speed ideal for routine 13C-CPMAS, and other measure-ments at 400 MHz and 500 MHz.

2.5 mmThe 2.5 mm rotor permits higher sample spinning speeds required for 13C-CPMAS at high-fields, and high-resolution 1H measurements as well as improved rf performance for high performance MQMAS experients..

Max Speed Sample Volnme

8 kHz 616 μl

19 kHz 69 μl

24 kHz 49 μl

32 kHz 17 μl

80 kHz 0.8 μl

110 kHz 0.29 μl

2

Solid State NMR Applications:

Synthetic polymers

13C / ppm0100200300

5.0

4.0

3.0

2.0

1H T1 / s

ROSY spectrum

HX CPMAS probe p.3

ROSY p.10

0.75mm & 1mm p.4CPMAS probe

19F-MAS probe p.7

Pharmaceuticals

13C (ppm)150.0 100.0 50.0

13C NMR spectrum

HX CPMAS probe p.3

ROSY p.10

0.75mm & 1mm p.4CPMAS probe

19F-MAS probe p.7

Note: The photograph shows a simulated image.

Elastomers

FGMAS probe p.7

19F-MAS probe p.7 8mm MAS probe p.5

MAGIC p.9SHIMMING

ppm

13C NMR spectrum

180.0 160.0 140.0 120.0 100.0 80.0 60.0 40.0 20.0

ppm70.0 60.0 50.0 40.0 30.0 20.0

Inorganic materials

MQMAS probe p.6

19F-MAS probe p.7

STMAS probe p.6

27Al (ppm)100.0 80.0 60.0 40.0 20.0 0 -20.0

27AI-NMR spectrum

Quadruple bond

Sextuple bond

Foods

FGMAS probe p.7

MAGIC p.9SHIMMING

ppm8.0 6.0 4.0 2.0 0

1H-NMR spectrum

Note: The photograph shows a simulated image.

Batteries

0.75mm & 1mm p.4CPMAS probe

19F-MAS probe p.7

7Li (ppm)2.5 2.0 1.5 1.0 0.5 0

65 kHz

25 kHz

35 kHz

45 kHz

55 kHz

7Li-NMR spectrum

　Note: The photograph shows a

simulated image.

8mm MAS probe p.5

8mm MAS probe p.5 8mm MAS probe p.5

Sample : Monoethyl fumarateSpectrometer : JNM-ECA500Probe : 4 mm CPMAS probe

1H / ppm16.0 14.0 12.0 10.0 8.0 6.0 4.0 2.0 0 －2.0

1H-MAS spectrum (sample spinning speed: 15 kHz)

1H-wPMLG spectrum

-130.0 -135.0 -140.0

-130

.0-1

35.0

ppm

ppm

OH

OH

OH

CH3

H

H H

H

CH3 OH

O

CH3

13C / ppm150.0 100.0 50.0 0

3

HX CPMAS probe

CPMAS probes to match your application

CPMAS is the most widely used solid-state NMR experiment. The 4 mm, 3.2 mm and 2.5 mm HX CPMAS probes are ideally suited for these measurements. Probes with sample tubes up to 4 mm in diameter balance optimal CPMAS data collection with respectable high-resolution 1H NMR and MQMAS NMR perfromance.

Hiqh quality 13C CPMAS spectra can be easily collected in a few minutes.

Sample : Cholic acidSpectrometer : JNM-ECA600Probe : 3.2 mm CPMAS probeMethodology : 13C-CPMASSample spinning speed : 19 kHzNumber of accumulations : 640

■ 13C-CPMAS

The 4 mm, 3.2 mm, and 2.5 mm CPMAS probes support high-resolution 1H measurements with wPMLG CRAMPS experiments.

■High-Resolution 1H Solids ■ 87Rb-MQMAS

The 4 mm, 3.2 mm, and 2.5 mm CPMAS probes support MQMAS measurements.

Sample : Rubidium nitrateSpectrometer : JNM-ECA600Probe : 4 mm CPMAS probe

Solid State NMR Medium-speed MAS (15 kHz) is not sufficient to narrow the line broadening caused by the strong 1H-1H dipole-dipole interaction; however, wPMLG CRAMPS NMR measurements easily yield high-resolution solid state 1H spectra.

1H (ppm)15.0 10.0 5.0 0

30 kHz

70 kHz

110 kHz

15.0 10.0 5.0

20.0

10.0

1H (SQ) /ppm

1 H (D

Q) /

ppm

15kHz

NH+

NHH

H 3N+

-O

O

1 2

NH1

NH2

NH3

34

1 H (

DQ

) /p

pm

1H (SQ) /ppm

NH1 NH2 1

NH3

2 OH 3, 4

NH1 / 1

NH1 / 3, 4

NH2 / 1

NH2 / 2

OH / 3, 4

2 / 3, 4

NH3 / 3, 4

NH3 / OH

σ1 + σNH2

σNH2

σ1

15.0 10.0 5.0

20.0

10.0

110 kHz

500

0

1500

1000

1H / ppm01020

14N

/ pp

m

HN

NH3+

-O

NH3+HN

O

O

CH3

4

0.75 mm & 1 mm CPMAS probes

Extreme-speed spinner technology achieves the highest available sample spinning speeds of 110 kHz and opens new solid-state NMR experiments.

JEOL RESONANCE's advanced high-speed spinner technology, announced April 2012, sets a new benchmark for solid-state NMR spinning speed: 110 kHz for a 0.75 mm, 290 nl sample rotor. The corresponding speed for a 1 mm sample tube holding 800 nl is 80 kHz. These two CPMAS probes for extremely small samples and ultra-fast sample spinning permit high-sensitivity microcoil measurements of limited samples and opens new solid-state NMR experiments that make effective use of ultra-fast sample spinning and high-strength RF magnetic fields.

Ultra-fast sample spinning at 80 kHz and above enables high-resolution 1H measurements without the need for CRAMPS decoupling. High-resolution quantitative measurements and 1H single-peak relaxation time determinations are only possible at very high spinning speeds. These speeds also make high-resolution 1H two-dimensional measurements practical without degrading sensitivity.

High-resolution 1H measurement with high-speed spinning

Sample : L-Histidine chlorideSpectrometer : JNM-ECA500Probe : 0.75 mm CPMAS Probes

Ultra-fast MAS lengthens the 1H transverse magnetization relaxation time (t2) effectively eliminating the 1H-1H dipole-dipole interaction, resulting in higher resolution spectra. Microcoils achieve high-sensitivity with large 14N RF magnetic fields and high mass sensitivity, this frees nitrogen NMR measurements from the difficulties of using 15N isotope labels.

1H-14N HMQC Measurements

Why 14N use instead of 15N?Although 14N is the most abundant Nitrogen isotope, 99.63%, most NMR observations have long used the rarer (0.37%) 15N. 14N's integer spin and nuclear quadrupole interactions have been difficult to overcome. In solution phase NMR, 14N-NMR quadrupole relaxation broadens spectra obscuring the results; in solid-state NMR the quadrupole interaction results in line widths of several MHz in conventional MAS probes. The JEOL RESONANCE 1mm and 0.75 mm MAS probes can overcome this difficulty resulting in high resolution 1H-14N correlation spectra without the need for 15N labeling.

Sample : L-Histidine chlorideSample volume : 0.29 µlSpectrometer : JNM-ECA600Probe : 0.75 mm CPMAS probe

Sample : Glycyl-L-alanineSample volume : 0.8 µlSpectrometer : JNM-ECA500Probe : 1 mm CPMAS probeSample spinning speed: 70 kHzMeasurement time: 2 minutes (approximately)

■ 1H DQ MAS spectrum

■ 1H MAS spectrum

■ 1H-14N HMQC spectrum

The 1 mm spinner module was developed with support from the Japan Science and Technology Agency's Industry-Academia Drive Innovation Program: Development of Systems and Technology for Advanced Measurement and Analysis.

-50.0 -100.0 -50.0 -100.029Si / ppm 29Si / ppm

3.2 mm MAS probe 8 mm MAS probe

0

2000

4000

6000

8000

10000

0 50 100 150 200 250 300 350

Spin

ning

spe

ed (k

Hz)

Drive air pressure (kPa)

0 10 20 30 40 50 607999.0

7999.5

8000.0

8000.5

8001.0

Time (s)

Spin

ning

spe

ed (H

z)

0 10 20 30 40 50 6049.0

49.5

50.0

50.5

51.0

Spin

ning

spe

ed (H

z)

Time (s)

±0.2 Hz

±0.5 Hz

Low spinning speed characteristics High spinning speed characteristics

Spinning profileOperation is simple because spinning control uses only drive pressure adjustment.

(The bearing pressure remains the same regardless of the spinning speed.)

5

High-Sensitivity Measurements with Largest Available Sample Rotor in a Narrow Bore Magnet

Increasing the sample volume can reduce the solid-state NMR magic angle spinning performance at high spinning speeds. The JEOL RESONANCE 8 mm MAS probes can achieve spinning speeds up to 8 kHz without compromising spinning stability in spite of the large 616 µl sample volume. The 8mm MAS spinner module is stable over a broad range of spinning speeds from 50 Hz up to 8 kHz.

High-Sensitivity Measurements with Larger Sample Volume Rotors

High spinning speed & highly stable spinning

Increasing the sample volume is a simple and cost effective effective way to boost the sensitivity of samples with weak NMR properties. JEOL RESONANCE therefore utilized the latest in fluid dynamics simulation technologies to develop stable 8 mm MAS Solid State NMR probes with the largest sample volume available for narrow bore (54 mm) magnets. These probes are especially effective for 29Si, low-gamma nuclei, and other nuclei with low sensitivitiy. The JEOL RESONANCE 8mm MAS State NMR probes are available in single tune X only or double tune HX configurations for optimal NMR sensitivity.

Sample: Synthesized tobermoriteSpectrometer : JNM-ECA500Repetition time : 10 sNumber of accumulations: 128

Samples courtesy of Asahi Kasei Corporation

■ 8 mm 29Si MAS spectrum with 1H Decoupling

8 mm MAS Probes

200.0 0 -200.043Ca / ppm

200.0 0 -200.043Ca / ppm

4 mm MAS probe 8 mm MAS probe

■ 8 mm 43Ca MAS spectrum

Sample: Synthesized tobermoriteSpectrometer : JNM-ECA600Repetition time : 0.5 sMeasurement time: 2 days (approximately)

43Ca nucleus characteristicsLow gyromagnetic ratio-1.8×107 rad/s (approximately 1/15 that of 1H)Low natural abundance: 0.145%Semi-integral spin: I = 7/2

Samples courtesy of Asahi Kasei Corporation

JEOL RESONANCE's unique high-frequency circuit technology

The patented JEOL RESONANCE balanced resonance design, pushes RF circuit ef ficiency to highest limits. T h e b a l a n c e d r e s o n a n c e circuit ef ficiently generates large RF magnetic fields leading to improved sensitivity and line shape for MQMAS measurements.

Electromagnetic Field Analysis Simulation Results

0 ‒20.0 ‒40.0

23N

a / p

pm 010

.0

23Na / ppm0 ‒20.0 ‒40.0 0 ‒20.0 ‒40.0

Sample: Na2SO4

No displacement 0.005° 0.01°

Effect of magic angle displacement on STMAS spectrum

6

MQMAS ProbesProbes designed specially for MQMAS measurements

provide high perfromance results.The NMR spectra of many inorganic materials are complicated by the second-order quadrupolar interaction from the spin I>1/2 nuclei contained in the material. The MQMAS experiment applied to half-integer spin quadrupolar nuclei effectively eliminates the second-order quadrupolar broadening to produce high resolution isotropic NMR spectra. The quality of the MQMAS NMR spectrum is strongly dependent on the applied RF magnetic field, larger RF magnetic fields lead to improved signal-to-noise ratio (S/N) and lineshape. The JEOL RESONANCE MQMAS probes with large RF fields are designed for high-performance MQMAS experiments in narrow bore magnets.

■ 23Na-MQMAS

10.0 5.0 0 -5.0

10.0

5.0

ppm

ppm

23Na-MQMAS SpectrumSample : Sodium phosphateSpectrometer : JNM-ECA930Probe : 4 mm MQMAS probe

50.0 45.0 40.0 35.0 30.0 25.0

50.0

45.0

40.0

ppm

ppm

CS-a

xis QIS-axis

Amorphous components

Crystalline components

27Al-5QMAS SpectrumSample : Aluminum phosphateSpectrometer : JNM-ECA600Probe : 4 mm MQMAS probe

23Na / ppm20.0 10.0 0 ‒10.0 ‒20.0 ‒30.0

23N

a / p

pm15

.010

.05.

00.

0‒5

.0‒1

0.0

Sample : Na2SO4

Spectrometer : JNM-ECA600Probe : 3.2 mm STMAS probe

■ 23Na-STMAS spectrum

STMAS ProbesSTMAS NMR probes, the ultimate in quadrupolar nucleus analysis

STMAS NMR provides for higher sensitivity with the same high-resolution results for half-integer quadrupolar nuclei as MQMAS NMR. STMAS NMR measurements require extremely high magic angle precision and spinning stability. The JEOL RESONANCE STMAS NMR probes easily fulfill the demanding angle precision and spinning stability requirements of STMAS NMR experiments.

■ 27Al-MQMAS

Rubber

■ FGMAS Elastomers13C NMR spectrum

180.0 160.0 140.0 120.0 100.0 80.0 60.0 40.0 20.0

ppm70.0 60.0 50.0 40.0 30.0 20.0

ppm ppm70.0 60.0 50.0 40.0 30.0 20.0

13C NMR spectrum

13C-DEPT45 spectrum

13C-DEPT90 spectrum

13C-DEPT135 spectrum

ppm : 1H4.0 3.0 2.0 1.0 0

ppm : 13C

60.0

50.0

40.0

yselect 1H-13C HMQC spectrum with 13C presaturation

Crosslinking density : 1.36×10-4 mol/cm3

Samples courtesy of Prof. Kawahara Seiichi, Nagaoka University of Technology

Spectrometer : JNM-ECA600Probe : 4 mm FGMAS probeSample spinning speed : 17 kHz

-20.0 -40.0 -60.0 -80.0 -100.0 -120.0 -140.0 -160.0 -180.019F / ppm

7

19F-MAS ProbesLow 19F Background HX CPMAS probes are ideal for

analyzing fluorine containing samplesRecent years have seen the development of many fluorinated materials, pharmaceuticals, and other important compounds. JEOL RESONANCE low fluorine background HX CPMAS probes are ideal for analysing these samples without interference from fluorinated probe materials.

Sample : Fluoro-rubber pelletSpectrometer : JNM-ECA500

■ 19F-MAS Fluoro-Rubber

CPMAS probe19F-MAS probe

■ 19F-MAS Fluoro-Polymers

19F / ppm 0 -50.0 -100.0 -150.0 -200.0 -250.0

****

***

***

**

Sample : PCTFESpectrometer : JNM-ECA500Probe : 3.2 mm 19F-MAS probeSample spinning speed: 24 kHz

* Spinning Sideband

FGMAS ProbesHigh Resolution Field Gradient MAS NMR Probes for

semi-solids, tissue biopsies, and elastomers.

Soy milk mayonnaise

Primary ingredients: Canola oil, soy milk, apple cider vinegar, table salt, sugars

ppm10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0

1H-NMR spectrum

ppm180.0 160.0 140.0 120.0 100.0 80.0 60.0 40.0 20.0

ppm100.0 90.0 80.0 70.0 60.0

13C NMR spectrum

ppm : 1H10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

ppm : 13C

160.0140.0120.0100.0

80.0

60.0

40.0

20.0

ppm : 1H4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1

ppm : 13C

80.0

78.0

76.0

74.0

72.0

70.0

68.0

1H-13C HMQC spectrum

Spectrometer : JNM-ECA600Probe : 4 mm FGMAS probeSample spinning speed : 5 kHz

■ FGMAS Food Emulsion

8

This consists of a liquid nitrogen Dewar and cooling interface that attachs to the probe for low-temperature solid-state NMR measurements.

Low temperature VT solids accessory

Solid-state NMR frequently uses high sample spinning speeds. Spinning an unbalanced samples can damage the MAS NMR probe requiring expensive repairs. A bench spinner for test spinning outside the probe avoids this danger. It is a necessary accessory for films, pellets, and other samples that are especially difficult to balance.

Bench spinner

Many solid-state NMR applications require large rf fields. JEOL RESONANCE provides rf amplifiers for solid state NMR at 3 power levels: Standard, Middle, and High. These are designed to fit all experimental rf needs from routine CPMAS to high perfromance MQMAS experiments.

Power amplifier H F L F

Standard 100 W 300 W

Middle 200 W 500 W

High 500 W 1000 W

JEOL RESONANCE's unique solid-state NMR sample packing tools simplify sample packing and unpacking for all rotors from 8 mm to 0.75 mm.

Solid-state sample packing tools

Accessories

MAS controller

Speed(Hz) Bearing(kPa) Drive(kPa)300

250

200

150

100

50

0

kPa25000

20000

15000

10000

5000

0

Hz

±1Hz

20005

20003

20001

19999

19997

19995

1H / ppm15.0 10.0 5.0

1H / ppm

30.0

20.0

10.0

0

High-precis ion Magic -Angle -Spinning controller for all JEOL RESONANCE MAS probes from 0.75 mm to 8 mm. Spinning stability control for 3.2 mm CPMAS probe

¹H-DQ CRAMPS spectrumThis measurement methodology requires high spinning speed stability to properly narow the 1H peaks.

9

Easy, quick, & reliable shimming for Magic-Angle-Spinning NMR

Magic Shimming

Unlike solution NMR, solid-state NMR has lacked access to automatic shim adjustment (auto shim) or gradient shimming resulting in large amounts of time spent shimming by hand with less than optimal results. Magic shimming is an innovative approach that achieves high resolution with field gradient mapping as in solution NMR. This allows the operator to easily and quickly adjust the shims to levels that are difficult to obtain with manual shimming. This advancement in sample shimming technology from JEOL RESONANCE will improve the quality of your measurements.

Static

mag

netic

field

B0z-axis

Solution NMR

Adjust Z1-Z6

Static

mag

netic

field

B 0

MAS NMR

Adjust Y1,X2,Z3

z-axisMagic angle

54.74°

What is Magic Shimming?

Magic shimming is gradient shimming for magic angle spinning NMR spectroscopy. Like solution NMR gradient shimming Magic Shimming uses a field gradient or homo-spoil pulse to map the magnetic field inside the sample rotor. The axial Z1-Z6 shims are used for solution NMR are very weak along the magic angle spinning rotor axis, therefore the tesseral (radial) Y1, X2, axial Z3, and other shims which are stronger along the magic angle spinning axis are used to optimize the magnetic field.

ppm0100150 50200

13 C-NMR of natural rubber

39.0 38.5 38.0

~40 seconds

Adamantane,

ppm

Why is the 1H longitudinal magnetization relaxation time T1 uniform in solid samples?

Within a single domain of a sample the homonuclear dipole -dipole interactions between the 1H nuclei form strongly coupled spin networks. At moderate spinning speeds this causes the 1H magnetization rapidly diffuses over the entire network of spins in the domain. The domains can be a single crystal form of a pure chemical or an isolate amorphous region in a sample mixture. The 1H spin diffusion causes the domain to have a single uniform 13C detected 1H T1 value for all sites that are part of the domain.

10

Latest answer for solid mixture analysis from JEOL RESONANCE

Analyzing mixtures by NMR is difficult; however, DOSY is well established for analyzing mixtures in solution. Recently JEOL RESONANCE developed ROSY to analyze mixtures in the solid state. ROSY, Relaxation Ordered SpectroscopY, relies on differences in 1H T1 relaxation in the solid state to separate the components of a mixture. This eliminates the complications and time spent to physically separate the mixture into pure substances. This new technology, from JEOL RESONANCE, promises to find application in analyzing crystal polymorphism, crystalline-amorphous mixing, and other solid state mixtures.

ROSY = Relaxation Ordered SpectroscopY

High molecular weight composite polymers applications

1H1H

1H1H

1H1H

1H

1H1H

1H

1H1H

1H1H

1H1H

1H

1H1H

1H1H

1H

1H1H

1H

1H

1H

1H

1H

1H 1H

1H

1H

1H

1H

1H

1H

1H

1H

1H

13C

1H1H

1H

13C

13C

Spin diffusion simulation

PET/Ny-6 Compound Fiber

PBT/PMMA Nanolayer Film

２µm

PETNy-613C / ppm

0100200300

5.0

4.0

3.0

2.0

1H T1 / s

Ny-6

13C / ppm0100200300

13C / ppm0100200300

PET

13C / ppm0100200300

2.5

2.0

1.5

1.0

1H T1 / s

PMMA

13C / ppm0100200300

PBT

13C / ppm0100200300

Dark: PBTLight: PMMA

Samples courtesy of Teijin Limited