1. Manuals
  2. Brands
  3. Bruker BioSpin Manuals
  4. Measuring Instruments
  5. Solid State NMR
  6. User manual

Bruker BioSpin Solid State NMR User Manual

Nmr spectroscopy
Hide thumbs
Table of Contents

Advertisement

Quick Links

Download this manual
Bruker
BioSpin
Solid State NMR
AVANCE Solids
User Manual
Version
002
NMR Spectroscopy
think forward

Advertisement

Table of Contents
loading
Need help?

Need help?

Do you have a question about the Solid State NMR and is the answer not in the manual?

Questions and answers

Related Manuals for Bruker BioSpin Solid State NMR

Summary of Contents for Bruker BioSpin Solid State NMR

  • Page 1 Bruker BioSpin Solid State NMR AVANCE Solids User Manual Version NMR Spectroscopy think forward...
  • Page 2 The information in this manual may be altered without notice. BRUKER BIOSPIN accepts no responsibility for actions taken as a result of use of this manual. BRUKER BIOSPIN accepts no liability for any mistakes contained in the manual, leading to coincidental damage, whether during installation or operation of the instrument.

  • Page 3: Table Of Contents

    Cross Polarization Setup and Optimization for a Real Solid: Glycine ......79 Some Practical Hints for CPMAS Spectroscopy ............85 Field Setting and Shift Calibration ................87 4.10 Literature ........................88 Decoupling Techniques ..............89 Heteronuclear Decoupling .................... 89 User Manual Version 002 BRUKER BIOSPIN...
  • Page 4 HETCOR with Cross Polarization under LG Offset ............. 135 RFDR ....................137 10.1 Experiment ........................ 138 10.2 Set-up ........................138 10.3 Data Acquisition ......................139 10.3.1 Set-up 2D Experiment ....................139 10.4 Spectral Processing ....................141 BRUKER BIOSPIN User Manual Version 002...
  • Page 5 Describing Relaxation ....................201 16.2 T1 Relaxation Measurements ..................202 16.2.1 Experimental Methods ....................202 16.2.2 The CP Inversion Recovery Experiment ..............203 16.2.3 Data Processing ......................205 16.2.4 The Saturation Recovery Experiment ................208 User Manual Version 002 BRUKER BIOSPIN...
  • Page 6 Multiple Pulse Sequences ..................271 21.3 W-PMLG and DUMBO ....................272 21.4 Quadrature Detection and Chemical Shift Scaling ............273 CRAMPS 1D ..................275 22.1 Pulse Sequence Diagram of W-PMLG or DUMBO ............275 BRUKER BIOSPIN User Manual Version 002...
  • Page 7 Proton-Proton DQ-SQ Correlation ................296 24.6 Pulse Sequence Diagram ................... 297 24.7 Data Processing ......................299 24.8 Examples ........................299 Appendix ................... 303 Form for Laboratory Logbooks ..................303 Figures ....................309 Tables ....................315 Index ....................319 User Manual Version 002 BRUKER BIOSPIN...
  • Page 8 Contents BRUKER BIOSPIN User Manual Version 002...

  • Page 9: Introduction

    Introduction This manual is intended to help the users set up a variety of different experiments that are nowadays more or less standard in solid state NMR. Previously, the manuals described the hardware in some detail, and also basic setup procedures. Armed with this knowledge, it was assumed the users would be in a position to manage the setup of even complicated experiments themselves.

  • Page 10: Disclaimer

    Please refer to the corresponding user manuals for any hardware mentioned in this manual for relevant safety information. Contact for Additional Technical Assistance For further technical assistance please do not hesitate to contact your nearest BRUKER dealer or contact us directly at: BRUKER BioSpin GMBH am Silberstreifen D-76287 Rheinstetten Germany Phone:...

  • Page 11: Test Samples

    CT 300 kHz wide as hydroquinon CPMAS d1>5s Clathrate gas in air single pulses overnight, 1s MQMAS dep. on crystal water 2-5 lines MQMAS AlPO-14 MQMAS d1 05-1s, 4 lines User Manual Version 002 BRUKER BIOSPIN 11 (327)

  • Page 12: Test Samples

    100scans,0.5s α-glycine sensitivity, 4ms contact,4s labelled for fast setup WL,MAS pulse determ., 100 scans 100 scans in a >=500 MHz instr. MAS,WL 100 scans, narrow line. 47/49 Anatas MAS,WL 100 scans 12 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 13: Test Samples

    1scan, 500s, finely powdered AgSO CPMAS 50 ms contact, 10 s repetition, 1 scan. Y(NO CPMAS 10ms contact, d1>10s Literature: J.M. Hook, P.A.W. Dean and L.C.M. van Gorkom, Magnetic Resonance in Chemistry, 33, 77 (1995). User Manual Version 002 BRUKER BIOSPIN 13 (327)
  • Page 14 Test Samples 14 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 15: General Hardware Setup

    For solids and liquids there should normally be different sets of preamplifiers. Liq- uids preamplifiers (HPPR, High Performance Preamplifiers) are not suitable for some of the requirements of solid state NMR. Where CP/MAS applications are the only solids applications, it is however possible to use liquids preamplifiers for X- observation.

  • Page 16: Figure 3.1. All Connections To The Back Of The Preamplifier

    (multi- receive setup only). The orange colored cable is the high voltage supply for the HPLNA pream- plifier. Figure 3.1. All Connections to the Back of the Preamplifier 16 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 17: Figure 3.2. Transmitter Cables (Only) Wired To Back Of The Preamplifier

    (type edasp setpre- amp, NMRSU password required). Figure 3.2. Transmitter Cables (only) Wired to Back of the Preamplifier User Manual Version 002 BRUKER BIOSPIN 17 (327)

  • Page 18: Figure 3.3. The Edasp Setpreamp Display

    General Hardware Setup Figure 3.3. The edasp setpreamp Display Note for Figure 3.3.: Transmitter to preamplifier wiring must reflect hardware con- nections! 18 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 19: Figure 3.4. Additional Connections To The Preamplifier Stack

    3. Tune RF in (from SGU 2 aux out) 8. High voltage DC for HPLNA-preamp 4. PICS probe ID cable to probe 9. Additional controls for multi-receiver 5. ATMA and AUX connectors Figure 3.4. Additional Connections to the Preamplifier Stack. User Manual Version 002 BRUKER BIOSPIN 19 (327)

  • Page 20: Rf Connections Between Preamplifier And Probe

    30 cm, and that no force is exerted on the RF connectors. Adapters should be avoided; since every connector may change the impedance to deviate from the required 50 Ω. Cables with loose connectors should be discarded, unless they 20 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 21: Rf-Filters In The Rf Pathway

    Usually, one filter per RF channel is required. Both filters should mutually exclude the frequency of the other channel(s). Usual attenuations of the frequency to be suppressed should be around > 80 dB, in special cases, when both frequencies User Manual Version 002 BRUKER BIOSPIN 21 (327)

  • Page 22: Figure 3.6. Standard Double Resonance Cp Experiment, Bypassing The Proton Preamp

    (about 20%!) The following figures illustrate the most common filter combinations. Figure 3.6. Standard Double Resonance CP Experiment, Bypassing the Proton Preamp Figure 3.7. Standard CP Experiment, Proton Preamp in Line 22 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 23: Figure 3.8. Triple Resonance Experiment, Without X-Y Decoupling

    Care should be taken that the two bandpass filters mutually exclude the other frequency as efficiently as possible. Low pass filters will not allow X or Y observe while Y or X is decoupled!). User Manual Version 002 BRUKER BIOSPIN 23 (327)

  • Page 24: Figure 3.10. Triple Resonance 1H/19F-Experiment

    F preamplifier will not allow long 19F pulses through it! For short pulses it is ok, for decoupling it must be bypassed, or a dedicated F pre- amp must be used. Figure 3.11. 19F/1H Combiner/Filter Set 24 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 25: Connections For Probe Identification And Spin Detection

    PICS cable are shown in Figure 3.13. for a WB and in Figure 3.14. for a SB probe. 1. PICS probe connector 2. Spin rate monitor cable Figure 3.13. PICS Probe Connector and Spin Rate Monitor Cable on a WB Probe User Manual Version 002 BRUKER BIOSPIN 25 (327)

  • Page 26: Mas Tubing Connections

    The maximum throughput de- pends on the experimental conditions and the probe type. 26 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 27: Connections

    The major difference between DVT and VTN/WVT probes is that for VTN/WVT probes the bearing gas is used for temperature control, whereas for DVT probes, bearing, drive and VT gas are separate. User Manual Version 002 BRUKER BIOSPIN 27 (327)

  • Page 28: Wide Bore (Wb) Magnet Probes

    Figure 3.15. WB DVT Probe MAS Tubing Connections 1. VT plus bearing gas 3. Drive gas 2. One thermocouple connector at stator inlet Figure 3.16. VTN Probe MAS Tubing Connections Note: WVT Probes are VTN- Type Probes 28 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 29: Figure 3.17. Wb Probes: Eject/Insert Connections

    2. Bearing gas in 5. Heater 8. Spin rate cable 3. Drive gas in 6. Heater cable in 9. Flush gas in Figure 3.18. WB Probes: DVT, Probe Connections for RT and HT Measurements User Manual Version 002 BRUKER BIOSPIN 29 (327)

  • Page 30: Standard Bore (Sb) Magnet Probes

    Bearing sense (to supervise bearing pressure, shut down in case of a pressure loss). For LT experiments, the ball joint at the heater dewar must be opened and the transfer line of the heat exchanger or the cooling unit must be connected. 30 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 31: Additional Connections For Vt Operation

    MAS probes are usually not as well insulated as for instance a wideline or PE stationary probe is. Therefore the probe outer shell warms/cools down during the experiment. The heat transfer between heater and probe electronics/probe environment must be kept at a safe level. User Manual Version 002 BRUKER BIOSPIN 31 (327)

  • Page 32: Figure 3.21. Wb Probe Mas Vtn And Wvt, And Dvt Probe Connections

    The following figures show the various connections to different probes. 1. Probe heater connector 3. TC connector (s) 2. VT gas in 4. Frame flush gas Figure 3.21. WB Probe MAS VTN and WVT, and DVT Probe Connections 32 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 33: Figure 3.22. Wb Probe Mas Dvt Connections

    (regul), located at stator inlet are connected. The VT unit must have the auxiliary sensor module to read more than one temper- ature. Only the TC labelled "regul" is used for regulation. User Manual Version 002 BRUKER BIOSPIN 33 (327)

  • Page 34: Figure 3.23. Sb Probe Mas Vtn

    General Hardware Setup 1. Probe heater connector 3. TC connector (s) 2. VT gas in 4. Frame flush gas Figure 3.23. SB Probe MAS VTN Figure 3.24. SB Probe MAS DVT Connections 34 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 35: Figure 3.25. Wb Wideline Or Pe Probes

    1. Bell shaped glass dewar around sample chamber 2. Insulating and sealing Al - felt ring 3. Cover for coil/sample compartment, fixed with plastic or metal screws Figure 3.26. WB Wideline or PE Probe Connections User Manual Version 002 BRUKER BIOSPIN 35 (327)

  • Page 36: Figure 3.27. Low Temperature Heat Exchanger For Vtn Probes (Old Style)

    In the figure above is a low temperature heat exchanger for VTN probes (old style): • 1 turn exchanger loop for SB probes; • 2 turn loop for WB probes; • 4 turn loop for DVT probes. 36 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 37: Figure 3.28. Low Temperature Heat Exchanger For Dvt Probes

    6 turns, the larger one may be used for high resolution probes. To use the spring loaded connection device shown in the close-up: 1. Compress the spring. 2. Move the hollow part over the ball joint. 3. Release the spring. User Manual Version 002 BRUKER BIOSPIN 37 (327)

  • Page 38: Figure 3.29. Low Temperature Liquid N2 Dewar With Dvt Probe/Heat Exchanger

    3. VT Gas flow from B-VT 3000 2. Transfer line to probe (DVT) 4. N2 level control (to B-VT 3000 temperature controller) Figure 3.29. Low Temperature Liquid N Dewar with DVT Probe/Heat Exchanger 38 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 39: Figure 3.30. Bottom View Of Low Temperature Dvt Probe/Heat Exchanger

    7. Transfer line 2. Frame flush 5. Heater 8. Read and regulation thermocouples 3. Shims 6. Magnet bore 9. Support for transfer line Figure 3.30. Bottom view of Low Temperature DVT Probe/Heat Exchanger User Manual Version 002 BRUKER BIOSPIN 39 (327)

  • Page 40: Figure 3.31. Low Temperature Setup With B-Cu X (Or B-Cu 05)

    Figure 3.31. Low Temperature Setup with B-CU X (or B-CU 05) In the figure above is the low temperature setup with a B-CU X (or B-CU 05) for DVT probes only, shown from the probe/magnet side. 40 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 41: Probe Setup, Operations, Probe Modifiers

    Choose the smallest coil diameter permitted by your sample, reduce the sample diameter if appropriate 2. Select the symmetrization insert such that the desired frequency is close to the upper end of the available tuning range User Manual Version 002 BRUKER BIOSPIN 41 (327)

  • Page 42: Shifting The Probe Tuning Range

    (removed) to achieve the full tuning range. The highest signal to noise is always reached with maximum inductance and minimum capacitance, i.e. at the high end of the tuning frequency achieved with maximum inductance. 42 (327) BRUKER BIOSPIN User Manual Version 002...
  • Page 43 4. Add a parallel coil to the NMR coil. This reduces the total inductance and shifts to higher frequency, however at the cost of filling factor. The bigger the parallel inductance, the smaller the high frequency shift and the loss. User Manual Version 002 BRUKER BIOSPIN 43 (327)

  • Page 44: Figure 3.34. Possible Modifiers For Probe Tuning Ranges (400 Mhz And Up Only)

    λ/4 can be tuned over the full range. All these modifications may be available for WB probes. In SB probes, they are usually built in (if necessary) and operated by a switch. 44 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 45: Figure 3.35. Λ/4 (Low Range) And Λ/2 Mode (High Range), 400 Mhz Probe

    (inner conductor) is connected to the coil, high voltage is required there. This means that the λ/4 point has low voltage but high current, whereas the λ/2 point is at high voltage and low current. A short between User Manual Version 002 BRUKER BIOSPIN 45 (327)

  • Page 46: Figure 3.36. A Λ/4 Only Probe (Left) And A Λ/4 - Λ/2 Probe (Right)

    λ/4-length shortens, the λ/4 point (1) moves inside the trans- mission line outer conductor (2). The screw (3) is used to set λ/4 (screw in) and λ/ 2 –mode (screw out). (4) proton tuning capacitor. 46 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 47: Figure 3.37. Without/With Parallel Capacitance To Shift The Tuning Range To Lower Frequency

    Capacitances may look different than the one shown in the picture. Fre- quently, two larger capacitances are used in series to form a smaller capacitance withstanding higher voltage. A parallel capacitance lowers and narrows the tuning range. User Manual Version 002 BRUKER BIOSPIN 47 (327)

  • Page 48: Adding A Frequency Channel To A Probe (Wb Probes Only)

    X-nuclei range). A triple probe X/F/H only has 2 RF connectors, because 1H and 19F are tuned to the same RF connector simultaneously. Likewise, a quadru- ple probe is an X/Y/F/H probe, with the X channel tuned to X and Y, and the pro- 48 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 49: Figure 3.39. Mounting A Triple Insert Into A Triple Probe

    (λ/2 (high range) or (λ/4 (low range)) mode. 1. X-Tuning capacitor 3. X-Y trap (stops X-frequency into 2. Y-Tuning capacitor Y-channel, but not Y into X-channel) Figure 3.39. Mounting a Triple Insert Into a Triple Probe User Manual Version 002 BRUKER BIOSPIN 49 (327)

  • Page 50: Mounting The Probe In The Magnet/Shim Stack

    It should also be possible to reach the probe tuning elements (since they need to be operated frequently) as easily as possible from the operators chair. Also, when tuning the probe, the video screen and the preamplifier display should be easily visible. 50 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 51: Edasp Display: Software Controlled Routing

    • Most routine applications will route correctly if the “default” button is pressed in the short menu version (receiver routing not shown). User Manual Version 002 BRUKER BIOSPIN 51 (327)

  • Page 52: Figure 3.41. Short Display, Pulse Routing Only For C/N/H Dcp Or Redor Experiment, Observing

    On AVIII instruments (with SGU/2), one SGU can produce two pulse trains (within the same NCO-frequency-setting range, 5 MHz). Figure 3.41. Short Display, Pulse Routing Only for C/N/H DCP or REDOR Experi- ment, observing C (above) and N (below) 52 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 53: Figure 3.42. Long Display, Pulse And Receiver Routing

    Dotted green lines: Possible (hardwired) routing are shown (“show RF rout- ing”). • Receiver routing: SGU3 used for transmit and receive (“show receiver rout- ing”). • Power indication: Maximum possible power output (as measured, “show pow- er at probe in”). User Manual Version 002 BRUKER BIOSPIN 53 (327)

  • Page 54: Figure 3.43. Pulse On F2, Observe On F1 - Routing

    In the figure above the edasp display for a system with two receiver channels, set for observe on C and N, while decoupling on protons. The same SGU is used for pulse and detection on both receiver channels. 54 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 55: Basic Setup Procedures

    3. Insert a spinner with finely ground KBr and spin at 5 kHz. It is assumed that these operations are known. If not, please refer to the following sources: • Probe manual. • MAS-II pneumatic unit manual in TopSpin/help. • SBMAS manual in TopSpin/help. User Manual Version 002 BRUKER BIOSPIN 55 (327)

  • Page 56: General Remarks

    The following setup steps need only be executed upon installation or after a probe repair. The test spectrum on glycine should be repeated in regular intervals to as- sure probe performance. 56 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 57: Setting The Magic Angle On Kbr

    1000 W output from the high power amplifier. In this menu, 4 RF channels are available. These 4 RF channels can be set up for 4 different frequencies. The two left most columns labelled frequency and logical User Manual Version 002 BRUKER BIOSPIN 57 (327)
  • Page 58 (for 500-800 MHz systems, it would be labelled for the frequency range 120-205 MHz). Con- nections are shown in the figure below: 58 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 59: Setting Acquisition Parameters

    The figure above shows the probe connections to the preamplifier with appropri- ate filters, placed on a table for better illustration. Setting Acquisition Parameters 4.2.2 Create a new data set for the experiment by typing edc in the command line. User Manual Version 002 BRUKER BIOSPIN 59 (327)

  • Page 60: Figure 4.3. Pop-Up Window For A New Experiment

    Spin the KBr sample moderately (~5, 2.5 mm: 10 kHz). In order to set up the ex- periment, type ased in the command line to open the table with parameters used for this experiment. 60 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 61: Figure 4.4. Ased Table With Acquisition Parameters For The Kbr Experiment

    4 (5) for a 300W or 500W transmitter. You can also check durations and power levels in a graphical display by clicking the experiment button in the Pulprog window as it is shown in the figure below. User Manual Version 002 BRUKER BIOSPIN 61 (327)

  • Page 62: Figure 4.5. Graphical Pulse Program Display

    Then match and tune the probe for this sample using the command wobb. This will start a frequency sweep over the range of SFO1+/-WBSW/2. The swept fre- quency will only be absorbed by the probe at the frequency to which it is tuned. 62 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 63: Figure 4.6. Display Example Of A Well-Tuned Probe

    Usually, turning the tuning knob counter clockwise (looking from below) will shift to higher tuning frequency. User Manual Version 002 BRUKER BIOSPIN 63 (327)

  • Page 64: Figure 4.7. Display Example Of An Off-Matched And Off-Tuned Probe

    Basic Setup Procedures Figure 4.7. Display Example of an Off-Matched and Off-Tuned Probe Figure 4.8. Display Example Where Probe is Tuned to a Different Frequency 64 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 65: Calibrating 1H Pulses On Adamantane

    5-10 kHz. Generate a new data set from the KBr data set by typing new. Set the instrument routing for C observe and H decoupling, as shown in the follow- ing figure: User Manual Version 002 BRUKER BIOSPIN 65 (327)

  • Page 66: Figure 4.10. Routing For A Double Resonance Experiment Using High Power Stage For H And X-Nu

    Note: the routing is only effective if the parameter powmod = high. To change to proton observe, click SwitchF1/F2. 66 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 67: Figure 4.11. Routing For A Double Resonance Experiment, Changed For Proton Observation

    Then acquire ns =2 scans on the protons of adamantane. User Manual Version 002 BRUKER BIOSPIN 67 (327)

  • Page 68: Figure 4.12. Proton Spectrum Of Adamantane At Moderate Spin Speed

    Basic Setup Procedures Figure 4.12. Proton Spectrum of Adamantane at Moderate Spin Speed Set the carrier frequency O1 on top of the biggest peak using the encircled button in TopSpin. 68 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 69: Figure 4.13. Setting The Carrier On Resonance

    User Manual Version 002 BRUKER BIOSPIN 69 (327)

  • Page 70: Figure 4.14. Expanding The Region Of Interest

    Click right mouse button in the Spectrum window. When the Save Display Re- gion to menu pops up, select Parameters F1/2 and OK or type dpl in the com- mand line. Figure 4.15. Save Display Region to Menu 70 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 71: Figure 4.16. The Popt Window

    Popt will generate a data set, where the selected expansion part of the spectrum is concatenated for all different parameter values (in this case, for p1). It will have a procno around 999. To achieve this, processing parameters are changed ap- User Manual Version 002 BRUKER BIOSPIN 71 (327)

  • Page 72: Figure 4.17. The Popt Display After Proton P1 Optimization

    Set the new pl1 as calculated and check whether 2*4.5 µsec for p1 will give a close to zero signal. This is a safe power level for all probes for pulses up to 100 msec. length. 72 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 73: Calibrating 13C Pulses On Adamantane And Shimming The Probe

    Pulse continuously using gs and shim the z gradient for highest FID integral. The gradient settings can be conveniently changed in the setsh display. Figure 4.18. and Figure 4.19. show the adamantane C FID without shims, with z-shim adjusted and the corresponding setsh displays. User Manual Version 002 BRUKER BIOSPIN 73 (327)

  • Page 74: Figure 4.18. Adamantane 13C Fid With 50 Msec Aq. Setsh Display

    T * and require much more shimming effort (only with older probes up to 400 MHz proton frequency). Figure 4.19. Adamantane C FID with 50 msec aq. setsh with Optimized Z-Shim Value 74 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 75: Calibrating Chemical Shifts On Adamantane

    Running spectra with the sweep on will superimpose spectra at different fields! One can set the sweep am- plitude to 0 in order to avoid such an accidental error condition. User Manual Version 002 BRUKER BIOSPIN 75 (327)

  • Page 76: Setting Up For Cross Polarization On Adamantane

    Start from the data set used for observing C under proton decoupling (1.4). Load the pulse program cp (in eda or typing pulprog cp). The pulse sequence is depicted in the following figure: Figure 4.20. A cp Pulse Sequence 76 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 77: Figure 4.21. Hartmann-Hahn Optimization Profile

    µsec) and pl1 (+/- 2 dB) for best signal. Fig. 21 shows a Hartmann-Hahn match optimization over 4 dB using a ramp contact pulse going from 50 to 100% ampli- tude. Figure 4.21. Hartmann-Hahn Optimization Profile User Manual Version 002 BRUKER BIOSPIN 77 (327)

  • Page 78: Figure 4.22. Hartmann-Hahn Optimization Profile Using A Square Proton Contact Pulse

    The sideband order 0 at 4.8 dB gives a rather small intensity. A ramp sweeping over 3.5-6.5 dB would cover both most efficient HH conditions. Note that increas- ing the spin rate would shift all maxima except the one at 4.8 dB further out. 78 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 79: Cross Polarization Setup And Optimization For A Real Solid: Glycine

    The glycine cp/mas 13C-spectrum taken under the same conditions as adaman- tane previously will look like in Figure 4.23., far from optimum: Figure 4.23. Display Showing α-Glycine Taken Under Adamantane Conditions, 4 scans User Manual Version 002 BRUKER BIOSPIN 79 (327)

  • Page 80: Figure 4.24. Optimization Of The Decoupler Offset O2 At Moderate Power, Using Cw Decoupling

    Check with 4 scans whether a close to zero signal is obtained. Compared to 4.5 µsec, a 2.7 µsec pulse requires about 4.5 dB more power (corresponding to almost 4 times more power!!!). 80 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 81: Figure 4.25. Glycine With Cw Decoupling At 90 Khz Rf Field

    A more efficient decoupling scheme is spinal64. Select cpdprg2 = spinal64, set pcpd2 to proton 180 degree pulse – 0.2 µsec for a start. A glycine spectrum as shown in Figure 4.26. is obtained. User Manual Version 002 BRUKER BIOSPIN 81 (327)
  • Page 82 B -field. The glycine lines show a broaden- ing proportional to B due to chemical shift dispersion. To make S/N values more comparable, this accounts for shorter T at higher field. 82 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 83: Figure 4.26. Glycine Spectrum With Spinal64 Decoupling At 93 Khz Rf Field

    On this triple probe, more than 100:1 is expected. What else needs to be opti- mized? Two more parameters are essential: 1. The power level at HH contact 2. The decoupling pulse pcpd2. User Manual Version 002 BRUKER BIOSPIN 83 (327)
  • Page 84 Write this information into the title file so it is stored with the data set as well as all other acquisition and processing parameters. Recalling this data set and acquir- ing a new data set should give the same spectrum within +/- 10% of S/N. 84 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 85: Some Practical Hints For Cpmas Spectroscopy

    Note: Higher RF power levels should only be applied if necessary and within specifications. For special probes, max. allowed RF fields may be lower. Check with your Bruker BioSpin applications support if in doubt. In order to have quantitative information about the precision of your magic angle,...
  • Page 86 Value of proton contact power level in dB and watt (sp0, sp0W). • Value of carbon contact power level (pl1, pl1W) and associated pulse length • S/N value obtained on glycine, SR value for shift calibration, line width on α- carbon in Hz. 86 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 87: Field Setting And Shift Calibration

    (from the current probe setting, so the appropriate probe must be se- lected in edhead). However: this will only work if all shim files contain the precisely determined field value for the same reference compound. User Manual Version 002 BRUKER BIOSPIN 87 (327)

  • Page 88: Literature

    4. K. Schmidt-Rohr, and H.W. Spiess, Multidimensional Solid-State NMR and Polymers, Academic Press (1994). 5. S.Hediger, B.H. Meier, R.R. Ernst, Adiabatic passage Hartmann-Hahn cross polarization in NMR un- der magic angle sample spinning, Chem. Phys.Lett 240, 449-456 (1995). 88 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 89: Decoupling Techniques

    At higher magnetic fields this becomes more evident, since the separation due to the mag- netic field increases. CW decoupling requires fairly high decoupling power to be efficient. User Manual Version 002 BRUKER BIOSPIN 89 (327)

  • Page 90: Tppm Decoupling

    Reference: 1. A.E. Bennett, C.M. Rienstra, M. Auger, K.V. Lakshmi, and R.G. Griffin; Heteronuclear decoupling in ro- tating solids, J. Chem. Phys. 103 (16); 6951 – 6958 (1995). 90 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 91: Spinal Decoupling

    Likewise, it can be used to decouple dilute spins or spins which are homonuclear decoupled by spinning ( Reference: 1. S.-F. Liu and K. Schmidt-Rohr, Macromolecules 34, 8416-8418 (2001). User Manual Version 002 BRUKER BIOSPIN 91 (327)

  • Page 92: Homonuclear Decoupling

    Hamiltonian around an effective field, aligned at the magic angle (arctan ) with respect to the Zeeman field in the rotating frame. The tilt is achieved by off resonance irradiation at the Lee Goldburg frequency f according to the Lee Goldburg condition. 92 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 93: Figure 5.2. Geometry For The Fslg Condition

    Since the hetero- nuclear X-H-coupling remains, there may be spinning sidebands from this cou- pling, in addition to CSA sidebands. User Manual Version 002 BRUKER BIOSPIN 93 (327)

  • Page 94: Figure 5.3. Fslg Decoupling Pulse Sequence Diagram

    Decoupling Techniques Figure 5.3. FSLG Decoupling Pulse Sequence Diagram Figure 5.4. Adamantane, FSLG-decoupled, showing the (downscaled) C-H J- couplings. 94 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 95: Table 5.1. Acquisition Parameters

    For ramped CP. pl12, p3 set for p3=90° sp0, pl1 set for cp 5-10m pl13 set for 70-100 kHz Optimize for best resolution. cnst20 70000-100000 Equals the applied RF-field. User Manual Version 002 BRUKER BIOSPIN 95 (327)

  • Page 96: Figure 5.5. Shape With Phase Gradients

    Figure 5.5. Shape with Phase Gradients In the figure above: Shape with phase gradients for positive and negative offsets and corresponding phase change, stdisp –display of lgs-1 shape. Amplitude is 100% throughout. 96 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 97: Dumbo

    ;calculate number of LG periods according to aq "count=aq/(p10)" 3 (p10:sp1 ph3):f2 ;p10 set by AU-program DUMBO (n*32 µsec) lo to 3 times count User Manual Version 002 BRUKER BIOSPIN 97 (327)

  • Page 98: Transverse Dephasing Optimized Spectroscopy

    Be careful not to exceed the maximum decoupling time with high power de- coupling. Reference: 1. G. De Paepe, N. Giraud, A. Lesage, P. Hodgkinson, A. Böckmann, and L. Emsley, Transverse De- phasing Optimized Solid-State NMR Spectroscopy, JACS 125, 13938 – 13939 (2003). 98 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 99: Practical Cp/Mas Spectroscopy On Spin 1/2 Nuclei

    - structural information about the molecular environment of the nucleus of in- terest: - mobility (rigid environment: expect long T and repetition delay), - proximity to protons (can one use cross polarization) User Manual Version 002 BRUKER BIOSPIN 99 (327)
  • Page 100 5. Now we know the minimum relaxation delay and the maximum contact time. With these parameters used as d1 and p15, the measurement is just a matter of patience. 100 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 101: Possible Approaches For Non-13C Samples

    Probe in triple mode C/N Si/79.5 41.7 Double mode low range C/100.5 62.5 Double mode low range C/100.5 Triple mode C/N Sn/149.1 62.5 Double mode high range P/161.9 71.4 Range switch up, double mode User Manual Version 002 BRUKER BIOSPIN 101 (327)

  • Page 102: Hints, Tricks, Caveats For Multi-Nuclear (Cp-)Mas Spectroscopy

    Setup for Standard Heteronuclear Samples 15N, 29SI, 31P N on α-glycine: calculate HH condition as described above. Else: Load α-glycine C reference spectrum, set observe nucleus N15 in edasp - add 2 dB to sp0 (spnam0=ramp.100) 102 (327) BRUKER BIOSPIN User Manual Version 002...
  • Page 103 P on ADP (ammonium dihydrogen phosphate NH - load α-glycine C reference spectrum - set observe nucleus to P in edasp - add 6 dB to pl1 - optimize HH condition, acquire 2 scans, reduce rg appropriately. User Manual Version 002 BRUKER BIOSPIN 103 (327)
  • Page 104 Practical CP/MAS Spectroscopy on Spin 1/2 Nuclei 104 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 105: Basic Cp-Mas Experiments

    Use glycine spinning at N kHz as before. When using POPT for such measure- ments the optimization type is “ZERO” so that the program looks for a zero cross- ing at the automatic data evaluation. To get nutation patterns without phase User Manual Version 002 BRUKER BIOSPIN 105 (327)

  • Page 106: Total Sideband Suppression Toss

    For TOSS B, d26 = 0.0773s/cnst31-p2, with cnst31 the rotation rate in Hz and p2 the 180º pulse width in µs. For TOSS A, d26 = 0.0412s/cnst31-p2, so the maximum spinning rate is lower. 106 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 107: Figure 7.2. Pulse Program For Cptoss

    Power level driving P2 on X-channel pl11 Spinning speed in Hz e.g. 5 kHz the entry would be 5000 cnst31 -Dtossb Tossb if needed because of high spinning speed or long p2 zgoptns User Manual Version 002 BRUKER BIOSPIN 107 (327)

  • Page 108: Figure 7.3. Comparison Of A Cptoss And Cpmas Experiment

    12.5 kHz sample rotation, depending, π of course, on the width of the employed – pulses. Figure 7.5. shows for a com- parison the results obtained with the 4 pulse sequence with 256 scans. 108 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 109: Figure 7.4. Cptoss243 Experiment On Tyrosine Hcl At 6.5 Khz

    4 mm CPMAS triple resonance probe at 500 MHz with 243 accumu- lated transients. No spinning sideband residuals can be observed, with a noise level below 2% peak to peak compared to the highest peak intensity. User Manual Version 002 BRUKER BIOSPIN 109 (327)

  • Page 110: Seltics

    For optimum suppression, the shortest pulse ( /24) of the sequences, τ π where is the rotor period, should be a /2 pulse or stronger. Choose pl11 ac- cordingly. Unlike TOSS, SELTICS is only 0.5 rotor periods long. 110 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 111: Figure 7.6. Pulse Program For Seltics

    In Figure 7.6. one can see that the SELTICS experiment takes only ½ rotor period compared to the 2 rotor periods required in the TOSS experiment. Use glycine or tyrosine.HCl at reasonable spinning speed. Figure 7.7. SELTICS at 6.5 kHz Sample Rotation on Tyrosine HCl. User Manual Version 002 BRUKER BIOSPIN 111 (327)

  • Page 112: Figure 7.8. Cholesterylacetate Spectrum Using Sideband Suppression

    Figure 7.8. is a cholesterylacetate spectrum using sideband suppression with the SELTICS sequence at 5 Hz sample rotation (upper spectrum). The lower spec- trum is the CPMAS spectrum at 5 kHz sample rotation. 112 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 113: Non-Quaternary Suppression (Nqs)

    Use glycine or tyrosine spinning at 11 kHz as before. Table 7.3. Acquisition Parameters Parameter Value Comments cpnqs, cptoss_nqs pulprog 180° pulse on X nucleus. Power level driving P2 on X-channel. pl11 30 – 80 µs Dephasing delay. User Manual Version 002 BRUKER BIOSPIN 113 (327)

  • Page 114: Figure 7.10. Glycine 13C Cpmas Nqs Experiment With A Dephasing Delay

    C CPMAS NQS Experiment with a Dephasing Delay Figure 7.10. is a glycine C CPMAS NQS experiment with a dephasing delayd3 = 40 µs so that the total dephasing time is 80 µs. Spinning sidebands are still visi- ble. 114 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 115: Figure 7.11. Tyrosine 13C Cpmas Nqs Experiment With Toss

    = 60 µs. Spinning sidebands are suppressed for a clean spec- trum. In this experiment the total dephasing time is 20 µs shorter than that used for the CPNQS experiment on glycine in Figure 7.10.. User Manual Version 002 BRUKER BIOSPIN 115 (327)

  • Page 116: Spectral Editing Sequences: Cppi, Cppispi And Cppircp

    Editing of 13C MAS NMR Spectra of Rigid Solids Using Cross-Polarization Methods, J. Magn. Reson. A 107, 67-78 (1994). Figure 7.12. Block Diagram of the CPPI Experiment. Typical pulse widths for the second part of the CP pulse with the phase inversion are 40 µs. 116 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 117: Figure 7.13. Cpmas Spectrum Of Tyrosine.hcl At 6.5 Khz

    Note: For more editing experiments consider the Solid State Attached Proton Test experiment, using the sostapt pulse program name, or look at 2D editing se- quences, based on the FSLG HETCOR experiment. User Manual Version 002 BRUKER BIOSPIN 117 (327)
  • Page 118 Basic CP-MAS Experiments 118 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 119: Fslg-Hetcor

    References: 1. H.J.M. deGroot, H. Förster, and B.-J. van Rossum, Method of Improving the Resolution in Two-Di- mensional Heteronuclear Correlation Spectra of Solid State NMR, United States Patent No 5,926.023, Jul. 20, 1999. 2. B.-J. van Rossum, H. Förster, and H.J.M. deGroot, High-field and high-speed CP-MAS...

  • Page 120: Pulse Sequence Diagram For Fslg Hetcor

    H chemical shifts evolve, the cross polariza- tion sequence, during which the information of the H spin magnetization is transferred to the X-spins, followed by observation of the X-spins under proton de- coupling. 120 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 121: Setting Up Fslg Hetcor

    Usually, l3 is set to 2-4 in order to reduce the F1 sampling width to a reasonable value. Cnst24 is usually set to -1000 - - 2000 in order to move the spectrum away from the center ridge in F1. User Manual Version 002 BRUKER BIOSPIN 121 (327)

  • Page 122: Figure 8.3. The Ased Display

    FSLG-HETCOR Figure 8.3. The ased Display 122 (327) BRUKER BIOSPIN User Manual Version 002...
  • Page 123 =in0 as calculated Set according to value calculated by ased. in_f1 F2 13C acquisition Recycle delay. 310ppm Sweep width direct dimension. 16-20 msec 10000-15000 Hz At 100 kHz RF, 15 kHz is ok. masr User Manual Version 002 BRUKER BIOSPIN 123 (327)

  • Page 124: Table 8.2. Processing Parameters For Fslg-Hetcor (On Tyrosine-Hcl)

    Table 8.2. Processing Parameters for FSLG-HETCOR (on tyrosine-HCl) Parameter Value Comment F2 direct dim 13C 2-4 k QSINE SSB 2, 3 or 5 ph_mod F1 indirect 1H 256-1048 STATES-TPPI QSINE 3, 5 ph_mod 124 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 125: Results

    FSLG-evolution. Cnst24 is used to separate the proton spectrum from this ridge. The contact time of 300 µsec shows many long range couplings. The next figure shows the region of interest excluding the center ridge and the spin- ning sidebands. User Manual Version 002 BRUKER BIOSPIN 125 (327)

  • Page 126: Figure 8.5. Fslg Hetcor Spectrum Tyrosine Hcl

    The figure above shows a FSLG Hetcor Spectrum Tyrosine HCl with parameters as shown in Table 8.1./Table 8.2.. Full transform with slight resolution enhance- ment, qsine/SSB=3. Proton shifts calibrated as 2.5 and 12 (most high field/low field peak). Expansion plot. 126 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 127: Modifications Of Fslg Hetcor

    RF field during the spin lock contact pulse. This modifies the HH condition, which must be reestablished using the pulse program lgcp. In the following sections, the specifics of these modified sequences are dis- cussed. User Manual Version 002 BRUKER BIOSPIN 127 (327)

  • Page 128: Carbon Decoupling During Evolution

    Natural abundance tyrosine-HCl was run with 50 µsec contact time. Reference: 1. A. Lesage and L. Emsley, Through-Bond Heteronuclear Single-Quantum Correlation Spectroscopy in Solid-State NMR, and Comparison to Other Through-Bond and Through-Space Experiments, J. Magn. Res. 148, 449-454 (2001). 128 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 129: Hetcor With Dumbo, Pmlg Or W-Pmlg, Using Shapes

    2. Vinogradov, E.; Madhu, P. K.; Vega, S., High-resolution proton solid-state NMR spectroscopy by phase modulated Lee-Goldburg experiment, Chem. Phys. Lett. (1999), 314(5,6), 443-450. 3. E. Vinogradov, P.K. Madhu and S. Vega, Proton spectroscopy in solid state NMR with windowed phase modulated Lee-Goldburg decoupling sequences, Chem. Phys. Lett. (2002), 354, 193.

  • Page 130: Figure 9.2. Hetcor Using Windowless Phase Ramps

    Proton spin nutation frequency with PL13. cnst20 1000-3000 Place carrier within proton spectrum for evolution. cnst24 Power level channel 1 for contact pulse. Power level channel 2 TPPM/SPINAL decoupling. pl12 Power level channel 2 PMLG decoupling. pl13 130 (327) BRUKER BIOSPIN User Manual Version 002...
  • Page 131 Processing Parameters for pmlg-HETCOR (as for FSLG on tyrosine-HCl) Parameter Value Comment F2 direct dim 2-4 k QSINE SSB 2, 3 or 5. ph_mod F1 indirect 256-1048 STATES-TPPI QSINE 3, 5 ph_mod User Manual Version 002 BRUKER BIOSPIN 131 (327)

  • Page 132: W-Pmlghet

    Start value 0, incremented during expt. 2- 4 Multiples of FSLG-periods, increment per row. =in0 as calculated Set according to value calculated by ased. in_f1 C acquisition Recycle delay. 310ppm sweep width direct dimension. 16-20 msec 132 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 133: Edumbohet

    CPDPRG2 SPINAL64/TPPM15 Decoupling sequence. H indirect Start value 0, incremented during expt. 2- 4 Multiples of e-DUMBO period, increment per row. =in0 as calculated Set according to value calculated by ased. in_f1 User Manual Version 002 BRUKER BIOSPIN 133 (327)

  • Page 134: Dumbohet

    Shape for contact pulse channel f2. spnam0 set to pl13 100 kHz for default duration 32 µs. dumbo_1+0 Both include one DUMBO cycle. spnam1 2.5 – 3 µsec 90º pulse channel 2 at pl12. 134 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 135: Hetcor With Cross Polarization Under Lg Offset

    Any standard ramp is possible, but a flat ramp (70-100% or 90-100%) is preferred. Usually, calculating the required RF field for the HH match can be done in the following way: User Manual Version 002 BRUKER BIOSPIN 135 (327)

  • Page 136: Figure 9.3. Hetcor On Tyrosine *Hcl Without (Left) And With Lg Contact (1Msec Contact)

    6. Set up a 2D data set with the pulse program lgcphetfq. The figures below com- pare spectra taken with and without LG-offset during cp. Figure 9.3. HETCOR on tyrosine *HCl without (left) and with LG contact (1msec contact) 136 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 137: Rfdr

    J. Chem. Phys. 108, 9463-9479 (1998). 4. B. Heise, J. Leppert, O. Ohlenschläger, M. Görlach and R. Ramachandran, Chemical shift correlation via RFDR: elimination of resonance offset effects, J. Biomol. NMR 24, 237-243 (2002). User Manual Version 002 BRUKER BIOSPIN 137 (327)

  • Page 138: Experiment

    XY-8 phase cycling =XYXY YXYX). Consequently, the number of rotor periods for the mixing time (L1) must be a multiple of 8. 138 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 139: Data Acquisition

    The “123” icon in the menu bar of the data windows acquisition parameter page (see Figure 10.2.)is used to toggle to the different data acquisition modes, 1D, 2D and 3D if so desired. User Manual Version 002 BRUKER BIOSPIN 139 (327)
  • Page 140 Number of rotor cycles for mixing time. F2 direct Left column. Number of complex points. 200 ppm Sweep width direct dimension. F1 indirect Right column. Number of real points. Rotor synchronized sweep width, or = 2 sw. 140 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 141: Spectral Processing

    F2 indirect Right column. Zero fill. STATES or STATES TPPI. Phase correction if needed. ph_mod Automatic baseline correction. bc_mod Figure 10.3. C Histidine Signal Decay as a Function of the RFDR Mixing Time User Manual Version 002 BRUKER BIOSPIN 141 (327)

  • Page 142: Figure 10.4. 2D Rfdr Spectrum Of 13C Fully Labelled Histidine (Rfdr Mixing Time 1.85 Ms)

    RFDR Figure 10.4. 2D RFDR Spectrum of C fully Labelled Histidine (RFDR mixing time 1.85 ms). 142 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 143: Proton Driven Spin Diffusion (Pdsd)

    Radio Frequency DRiven spin diffusion (see "RFDR" on page 137). RFDR provides similar infor- mation to PDSD but with a different mixing period. Here the term “frequency driv- User Manual Version 002 BRUKER BIOSPIN 143 (327)
  • Page 144 NMR applied to protein studies. More elaborate derivatives of PDSD are also known in bio-molecular NMR, where the unspecific spin diffusion within the proton spin system is filtered through a double quantum selection (Lange et al.).

  • Page 145: Pulse Sequence Diagram

    5. Optimize contact time, o1 and o2 on a C 1D CP experiment if necessary. 6. Create a new experiment with either iexpno or edc. 7. Change to a 2D data set. User Manual Version 002 BRUKER BIOSPIN 145 (327)

  • Page 146: 2D Experiment Setup

    Note that longer mixing times will result in S/N deterioration, as the mixing time approaches the of the observed nuclei. 146 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 147: Acquisition Parameters

    RAD calculate the required power level using calcpowlev, or use the setup pro- cedure shown in 11.7. 15. Start the experiment. Acquisition Parameters 11.3 Sample: C labelled histidine (labelled tyrosine-HCl). Experiment time: 90 min. (20 min.). User Manual Version 002 BRUKER BIOSPIN 147 (327)
  • Page 148 Number of rotor cycles for mixing time. AQ_MOD TD {F1} Number of points. SW{F1} usually = SW =MASR if possible. NUC1{F1} =NUC1 TD {F2} Number of points. Not required in TopSpin 2.1. FnMode TPPI/States/States-TPPI 148 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 149: Processing Parameters

    3. Use the au program calcpowlev to calculate the power level required for a pro- ton decoupling RF field of n × masr, using p3 and pl12 as reference values. Refer to chapter "Basic Setup Procedures" on page 55 for more informa- tion). User Manual Version 002 BRUKER BIOSPIN 149 (327)

  • Page 150: Figure 11.3. Popt Result For The Cw Decoupling Power Variation

    An RF field of 2 × proton chemical shift range is on the safe side. 5. Enter the power level determined above as pl14 recoupling power for DARR or RAD. 6. Using DARR or RAD shorter mixing times are possible. 150 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 151: Example Spectra

    Proton Driven Spin Diffusion (PDSD) Example Spectra 11.5 Figure 11.4. C CPSPINDIFF of fully labeled tyrosine*HCl, spinning at 22 kHz, 4.6 msec mix. Upper: PDSD, lower: DARR User Manual Version 002 BRUKER BIOSPIN 151 (327)

  • Page 152: Figure 11.5. Comparison Of Darr/Pdsd

    Traces from below: DARR at 4.6 msec mix, PDSD at 4.6 msec mix, DARR at 20 msec mix, and PDSD at 20 msec mix. Note that some cross peak intensities differ substantially! 152 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 153: Figure 11.6. 13C Darr Of Fully Labelled Ubiquitine Spinning At 13 Khz

    Proton Driven Spin Diffusion (PDSD) Figure 11.6. C DARR of Fully Labelled Ubiquitine Spinning at 13 kHz User Manual Version 002 BRUKER BIOSPIN 153 (327)
  • Page 154 Proton Driven Spin Diffusion (PDSD) 154 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 155: Redor

    With very strong dipolar couplings, the signal intensity may be lost after very few or only one refocusing pulse, so the decay curve cannot be User Manual Version 002 BRUKER BIOSPIN 155 (327)
  • Page 156 P pulses than vice versa, because the effect on caused by 1.1% of C would be max. 1.1%, a very small change which would re- quire extremely high S/N and extremely high stability in signal generation and spin rate. 156 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 157: Pulse Sequence

    MAS rate: 5-10 kHz. The MAS spinning speed should be stable within 1 to 2 Hz in order to get a well refocused echo. Overall Experimental time, including setup procedure: 3-5 hours. User Manual Version 002 BRUKER BIOSPIN 157 (327)
  • Page 158 HH condition f1 power level for contact pulse f1 power level for π pulse pl11 according to specs for HH condition power level for H ramp not used 158 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 159: Data Acquisition

    The setup procedure of these sequences is identical to the ones explained earlier, but you can skip the CP optimization procedure, which is replaced by a p/2 pulse on the observe channel. User Manual Version 002 BRUKER BIOSPIN 159 (327)

  • Page 160: Data Processing

    Figure 12.2. 2D data set after “xf2” processing. In the figure above the data set contains the alternating S’ and S experiments 160 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 161: Figure 12.3. T1/T2 Relaxation For Further Analysis Of The Data Figure And The Analysis Interface

    (Figure 12.5.). Here the value for number of points has to be set to the td2 value and the list file name has to be switched to auto, otherwise the data User Manual Version 002 BRUKER BIOSPIN 161 (327)

  • Page 162: Figure 12.5. Setting The Correct Analysis Parameter

    /S’ set within the 2D data set). In this experiment MAS spinning speed was 10 kHz resulting in data points every 200ms. Note, only the analysis of the low field shifted peak is shown here, corresponding to the alpha-glycine modification of the measured sample. 162 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 163: Figure 12.6. Plot Of The Normalized Signal Intensity Versus The Evolution Time

    0.3 area of the curve (it here may be useful to use a more efficient REDOR technique for strong dipolar coupled systems, like CT-RE- DOR, see e.g. reference 7.). User Manual Version 002 BRUKER BIOSPIN 163 (327)

  • Page 164: Figure 12.7. Experimental Data For The Glycine 13C{15N}-Redor

    C), leading to a slightly too high theoretical REDOR curve compared to the actual experiment. The green curve shows the same simulation assuming pulse errors of 10% on both channels, corresponding very well with the experi- mental data. 164 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 165: Figure 12.8. Comparison Of Experimental Data To A Simulation With Reduced Dipolar Coupling

    (Eq. 12.3) Using this equation you end up with the values given in Table 12.2. for the dis- tances and the second moments. The M values given in brackets for the simulat- User Manual Version 002 BRUKER BIOSPIN 165 (327)

  • Page 166: Figure 12.9. Experimental Data With The Corresponding M2 Parabolic Analysis

    Afterwards the data sets can be combined before running the interpretation process. 166 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 167: Final Remarks

    Of course a qualitative comparison within a set of samples is always possible with the same set of experimental parameters without doing a full calibration run. User Manual Version 002 BRUKER BIOSPIN 167 (327)
  • Page 168 Analysis and Calorimetry 66, 699-715 (2001). 10. M. Bertmer, H. Eckert, Dephasing of spin echoes by multiple heteronuclear dipolar interactions in rota- tional echo double resonance NMR experiments, Solid State Nuclear Magnetic Resonance 15,139- 152 (1999). 168 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 169: Super

    Chemical-Shift Anisotropy Powder Patterns in Magic-Angle-Spinning NMR, J. Magn. Reson. 155, 15-28 (2002). 2. R. Tycko, G. Dabbagh, and P.A. Mirau, Determination of Chemical-Shift-Anisotropy Lineshapes in a Two-Dimensional Magic-Angle-Spinning NMR Experiment, J. Magn. Reson. 85, 265-274 (1989). User Manual Version 002 BRUKER BIOSPIN 169 (327)

  • Page 170: Pulse Program

    256. 6. Run 1D experiment and make sure everything is set properly. 7. Create a new experiment with either iexpno or edc. 8. Change to 2D data set: 170 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 171: Setup 2D Experiment

    13. Set p2 to be a 180× pulse at pl1 for the TOSS sequence. 14. Set l5 for the gamma integral, typically = number of spinning sidebands nor- mally 4. 15. Start the experiment. User Manual Version 002 BRUKER BIOSPIN 171 (327)

  • Page 172: Figure 13.3. The Acquisition Parameter Window (Eda)

    SUPER Figure 13.3. The Acquisition Parameter Window (eda) 172 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 173: Data Acquisition

    – typically number of SSB’s. F2 direct (left column). 2048 Number of complex points. 300 ppm Sweep width direct dimension. F1 indirect Right column. 32 - 64 Number of real points. FnMode TPPI, STATES or STATES-TPPI. User Manual Version 002 BRUKER BIOSPIN 173 (327)

  • Page 174: Spectral Processing

    DC offset correction. Alpha For shearing the spectrum. F2 indirect Right column. Zero fill. STATES-TPPI QSINE Squared sine bell. 90º shifted sine bell. PH_mod Phase correction if needed. BC_mod Automatic baseline correction. 174 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 175: Figure 13.4. The Super Spectrum Of Tyrosine Hcl After Processing Using "Xfb

    SUPER Figure 13.4. The SUPER Spectrum of Tyrosine HCl After Processing Using “xfb” User Manual Version 002 BRUKER BIOSPIN 175 (327)

  • Page 176: Figure 13.5. Super Spectrum After Tilting The Spectrum Setting "1 Alpha" = -1

    Figure 13.5. SUPER spectrum after tilting the spectrum setting “1 alpha” = -1 The figure above is a SUPER spectrum after tilting the spectrum setting “1 alpha” = -1 and using the command “ptilt1” repeatedly until the CSA lines are within the spectral range. 176 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 177: Figure 13.6. Various Cross Sections From The Upper 2D Experiment

    SUPER Figure 13.6. Various Cross Sections from the Upper 2D Experiment The figure above illustrates various cross sections from the upper 2D experiment, from which CSA parameters can be determined. User Manual Version 002 BRUKER BIOSPIN 177 (327)
  • Page 178 SUPER 178 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 179: Symmetry Based Recoupling

    A possible trick is also to use off-resonant LG decoupling during the recoupling sequence. This enhances the effective proton field (vector sum of RF field and offset), and sharpens the HH condition since the homonuclear couplings are suppressed. User Manual Version 002 BRUKER BIOSPIN 179 (327)
  • Page 180 J. Chem. Phys. 117, 4974 (2002) 8. C. E. Hughes, S. Luca, and M. Baldus, RF driven polarization transfer without heteronuclear decou- pling in rotating solids, Chem. Phys. Letters, 385, 435-440 (2004). 180 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 181: Pulse Sequence Diagram, Example C7

    Usually, fully enriched samples are used, some- times diluted in natural abundance samples to reduce nonspecific long range interactions. As always, rotary resonance conditions (overlap of side- and center bands) should be avoided unless specifically desired. User Manual Version 002 BRUKER BIOSPIN 181 (327)

  • Page 182: Table 14.1. Recommended Probe/Spin Rates For Different Experiments And Magnetic Field

    HH condition. 6. Maximum RF field for decoupling 7. +LG means cw decoupling with optimized LG-offset frequency at the given RF field in order to avoid HH contact. 182 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 183: Spectrometer Setup For 13C

    120 if the spin rate suffices to omit decoupling. Set cnst20 = corresponding decoupling RF field. 5. Optimize pl11 for maximum signal intensity. 6. Optimize l0 for optimum signal intensity. In a multi-site spectrum the optima may differ for different spin pairs. User Manual Version 002 BRUKER BIOSPIN 183 (327)

  • Page 184: Figure 14.2. Optimization Of The Rf Power Level For Dq Generation/Reconversion On Glycine

    The glycine α-peak is usually hard to get off HH, so it is frequently too small. Optimise the LG-decoupling condition on the glycine α-peak (step 12). Figure 14.3. Variation of DQ-generation/reconversion time on a uniformly C la- beled peptide (fMLF). 184 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 185: Setup Of The 2D Sq-Dq Correlation Experiment

    10. Generate a new data set, set the mode to 2D using the 123 button in eda. Load the pulse program spc5cp2d. 11. Make sure C is selected as nuc1 in the F1 dimension, set FnMode =STATES-TPPI. User Manual Version 002 BRUKER BIOSPIN 185 (327)

  • Page 186: Data Acquisition

    Nucleus on f2 channel 2-3 ppm H offset for > 50 kHz ν Power level for f1 channel CP and p1 PL11 dep. on masr Power level for f1 channel recoupling power 186 (327) BRUKER BIOSPIN User Manual Version 002...
  • Page 187 Sweep width direct dimension, adjust to experimental require- ments F1 indirect (right column) 128 - 512 Number of experiments in indirect dimension see para. 17 Sweep width indirect dimension above STATES-TPPI, not required. In TS 2.1 User Manual Version 002 BRUKER BIOSPIN 187 (327)

  • Page 188: Spectral Processing

    δ ppm) to shift the spectrum suitably along F1. Setting 1 sr = 2*sr+o1 will set the referencing along F1 correctly (just type sr, and in f1 en- ter the value of sr for F2 and add *2+o1). 188 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 189: 13C Single Quantum Correlation With Dq Mixing

    RFDR experiments (see "Proton Driven Spin Diffusion (PDSD)" and "RFDR") as a NOESY-type correlation will be generated. Similarly, the MELODRAMA (see Bennett et al., Dusold et al.) sequence with ν = 5*ν may be used here. rotor User Manual Version 002 BRUKER BIOSPIN 189 (327)

  • Page 190: Data Acquisition

    Sweep width direct dimension, adjust to experimental require- ments. F1 indirect (right column) 128 - 512 Number of experiments in indirect dimension. usually = sw (F2) Sweep width indirect dimension. STATES-TPPI, not required in TS 2.1. 190 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 191: Spectral Processing

    AV III 700 SB. Left: 84 rotor periods DQ mixing, right:56 rotor periods mixing. The 84 periods mixing time show relayed correlations (positive, blue) which are absent at 56 periods mixing (except for the SSB cross peaks). Direct correlations are negative (red). User Manual Version 002 BRUKER BIOSPIN 191 (327)
  • Page 192 Symmetry Based Recoupling 192 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 193: Pisema

    Simulations of the spin dynamics show that the heteronuclear term in the Hamilto- nian leads to a complicated spectrum for small heteronuclear dipolar couplings (usually introduced by remote protons), see Z. Gan's paper for more information. User Manual Version 002 BRUKER BIOSPIN 193 (327)

  • Page 194: Pulse Sequence Diagram

    PISEMA References: 1. C.H. Wu, A. Ramamoorthy, and S.J. Opella, High-Resolution Heteronuclear Dipolar Solid State NMR Spectroscopy, J. Magn. Reson. A 109, 270-272 (1994). 2. A. Ramamoorthy, C.H. Wu, and S.J. Opella, Experimental Aspects of Multidimensional Solid State NMR Correlation Spectroscopy, J. Magn. Reson. 140, 131-140 (1999) 3.

  • Page 195: Setup

    HH match. For the new nutation frequency (B1 field for LG condition): θ sin( the offset frequency for the Lee-Goldburg condition is: θ cos( with the inverse of a 360º pulse. τ π User Manual Version 002 BRUKER BIOSPIN 195 (327)
  • Page 196 Use the calculated value and set inf1 in the eda win- dow correspondingly. Since dipolar couplings between H and N can be up to 15 kHz, the spectral width (including the experiment scaling factor) should be min. around 20 kHz. 196 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 197: Table 15.1. Acquisition Parameters

    No of points. Dwell time in t2. F1 indirect 1H ************** (right column). Number of points. IN_F1 L3*2*p5*SF or Scaling factor for PISEMA 0.82 = sin(54.7 deg.) calcu- L3*2.5*p5*SF lated by pulse program. User Manual Version 002 BRUKER BIOSPIN 197 (327)

  • Page 198: Processing

    Processing Parameters for the Pisema Experiment Parameter Value Comment F2 acquisition ************** Left column. Number of complex points in direct dimension. Apodization in t2. ************** Right column. F1 indirect Number of complex points in indirect dimension. 198 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 199: Figure 15.2. Pisema Spectrum Of 15N Labeled Acetylated Valine And Fid In T1 Over 3.008 Ms 64 Data Points

    N Labeled Acetylated Valine, B) FID in t1 over 3.008 ms 64 Data Points Figure 15.2. PISEMA Spectrum of N Labeled Acetylated Valine and FID in t1 over 3.008 ms 64 Data Points User Manual Version 002 BRUKER BIOSPIN 199 (327)

  • Page 200: Figure 15.3. Pisema Spectrum Of 15N Labeled Kdpf Transmembrane Protein

    N Labeled Kdpf Transmembrane Protein. PISEMA spectrum of N labeled Kdpf transmembrane protein aligned in DMPC (courtesy of NHMFL, Dr. T. Cross) membrane between glass plates using an FREE 700 MHz probe. 200 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 201: Relaxation Measurements

    The return of the z-magnetization to equilibrium is termed longitudinal relaxation, or spin-lattice relaxation, and the return of trans- User Manual Version 002 BRUKER BIOSPIN 201 (327)

  • Page 202: T1 Relaxation Measurements

    FID is recorded. The intensity of a particular signal in the resulting spectrum depends on the initial intensity, the relaxation delay, and the re- laxation time constant T as follows: − − exp( (Eq. 16.1) 202 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 203: The Cp Inversion Recovery Experiment

    The data shown here were all acquired at an approxi- mate temperature of 20° C. The form of the pulse program is shown in the follow- ing figure. Figure 16.1. The CPX T1 Pulse Sequence User Manual Version 002 BRUKER BIOSPIN 203 (327)
  • Page 204 FIDs at each relaxation delay. For the glycine sample, a suitable list of times would be: 100ms, 220ms, 450ms, 1s, 2.2s, 4.5s, 10s, 22s, 45s. 204 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 205: Data Processing

    1000 Limits for baseline correction. ABSF2 -1000 Should cover entire F2 width. F1 – relaxation dimension Smallest power of 2 greater than Must be 2n, but any zeros will be TD(F1) ignored. User Manual Version 002 BRUKER BIOSPIN 205 (327)
  • Page 206 Unless there is obvious overlap of peaks, the assumption is usually that each peak corresponds to a single nuclear site, and thus a single T value. 206 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 207: Figure 16.2. Relaxation Of Alpha-Carbon Signal In Glycine

    18.5s and 6.4s for the carbonyl and alpha-carbon signals respectively - at other field strengths the numbers will be somewhat different. If the signals are really un- dergoing mono exponential relaxation, the curve should be a good fit to the mea- sured data. User Manual Version 002 BRUKER BIOSPIN 207 (327)

  • Page 208: The Saturation Recovery Experiment

    >20x aq – 1 second is reasonable in this case. If the experiment is run without de- coupling, then the saturation period is the only significant period of high-power pulsing, and d1 can be shorter. Acquire the 2D spectrum with zg. 208 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 209: T1P Relaxation Measurements

    If apparently non exponential decay is observed, this may result from such alternative relaxation processes. Experiment setup Sample: Glycine Spinning speed: 10 kHz Time: 20 minutes User Manual Version 002 BRUKER BIOSPIN 209 (327)

  • Page 210: Indirect Relaxation Measurements

    , a proton saturation-recovery step is inserted prior to the cross- polarization step in a standard CP sequence. The proton magnetization immedi- ately prior to CP, and thus the observed carbon signal, depends on the extent of 210 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 211: Indirect Proton T1 Measurements

    T1 values for the two sets of peaks. At 500 MHz, the proton relaxation time should be approximately 520 ms at room temperature. User Manual Version 002 BRUKER BIOSPIN 211 (327)
  • Page 212 Relaxation Measurements 212 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 213: Basic Mq-Mas

    CT selective 90° pulse p3. In the 4- pulse sequence, however, the conversion pulse p2 changes 3Q coherency to 1Q coherency which then passes through a Z-filter of two CT selective 90° pulses in a p3-d4-p3 sequence. User Manual Version 002 BRUKER BIOSPIN 213 (327)

  • Page 214: Figure 17.1. A 3-Pulse Basic Sequence With Z-Filter

    (mp3qzfil.av). p1 is the same, p2 is usually somewhat shorter than in the three pulse sequence. Corresponding power level pl11 should be set to achieve at least 150 kHz RF field amplitude. p3 should be some tens of µs, corre- 214 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 215: Data Acquisition

    On the other hand the corresponding RF field amplitude of a 20 µs 90° pulse will be 1/(80 µs*(I+1/2))=12.5 kHz/(I+1/2). This means that w <<w as a prerequi- User Manual Version 002 BRUKER BIOSPIN 215 (327)

  • Page 216: Table 17.1. Some Useful Samples For Half-Integer Spin Nuclei

    Note that in the latter the spinning sidebands from the satellite transition are no longer visi- ble which is used as an indication that it is not excited. 216 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 217: Figure 17.3. Comparison Of 87Rb Mas Spectra Of Rbno3 Excited With Selective And Non-Selective

    Figure 17.4. shows the nutation profiles of a non-selective and a selective pulse, respectively. Note that for the selective pulse a fairly precise 180° pulse of a length of 2*τ can be determined whereas for a non-selective pulse this is not 90° the case. User Manual Version 002 BRUKER BIOSPIN 217 (327)

  • Page 218: Figure 17.4. Nutation Profiles Of Selective And Non-Selective Pulses

    In the case of 300 W amplifiers the maximum signal amplitude may not be ob- tained even at full power, with the chosen pulse lengths. 218 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 219: Figure 17.5. Example For Popt Set-Up For Optimization Of P1 And P2

    For more details about using the popt procedure to optimize a series of parame- ters please refer to the manual. Figure 17.6. shows the signal amplitudes as func- tions of pulse lengths p2 and p1. User Manual Version 002 BRUKER BIOSPIN 219 (327)

  • Page 220: Two Dimensional Data Acquisition

    Used in mp3qzfil.av only. IN10 =in0*7/9 Used in mp3qzfil.av for nuclei with spin I=3/2 only, so that no shearing FT is required. Note the difference in increment handling in Topspin 2.1 and higher. 220 (327) BRUKER BIOSPIN User Manual Version 002...
  • Page 221 Therefore, rotor synchronization together with States or States-TPPI phase sensitive acquisition helps to fold spinning sidebands from outside back onto centre bands or other side bands. User Manual Version 002 BRUKER BIOSPIN 221 (327)

  • Page 222: Data Processing

    AU program prompts for “Apply ABS2?” and “F1 shift in ppm:”. It is ad- visable to calculate a baseline correction after F2 Fourier transform. Note that the range defined by ABSF1 and ABSF2 is used for this. You should make sure that 222 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 223: Figure 17.7. 2D 87Rb 3Qmas Spectrum Of Rbno3

    2D spectrum. The spectral range shown in F1 corresponds to the spinning frequency. Spectra are taken on AV500WB at a Larmor frequency of 163.6 MHz with a 2.5 mm CP/MAS probe, spinning at 25 kHz. User Manual Version 002 BRUKER BIOSPIN 223 (327)

  • Page 224: Figure 17.8. Comparison Of Differently Processed 2D 23Na 3Q Mas Spectra Of Na4P2O7

    +5 ppm. Spectra are taken on an AV500WB at a Larmor frequency of 132.3 MHz with a 4 mm CP/MAS probe spinning at 10 kHz. Note that the F1 range equals the spinning frequency of 10 kHz in both cases. 224 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 225: Obtaining Information From Spectra

    B increasing from left to right; the y axis increases from bottom to top. δ Plot A is for identical , plot B for identical quadrupole coupling and. In plots C User Manual Version 002 BRUKER BIOSPIN 225 (327)

  • Page 226: Table 17.5. Values Of |R-P| For Various Spins I And Orders P

    The spectral width in the MQ dimension of the sheared spectrum is given by spin- ning speed / ⎜R-p ⎜ in a rotor synchronized experiment. A 5Q experiment e.g. gives a 7.08/1.42 = 5 times smaller spectral range in the indirect dimension than a 3Q experiment. 226 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 227: Table 17.6. Chemical Shift Ranges For All Mq Experiments For All Spins I

    2D spectra. Figure 17.10. shows 2D O 3QMAS spectra at 11.7 T and 18.8 T where the Lar- mor frequency of this nucleus is 67.8 and 108.4 MHz, respectively. The sample is User Manual Version 002 BRUKER BIOSPIN 227 (327)

  • Page 228: Figure 17.10. 17O Mqmas Of Napo3 At 11.7 T (67.8 Mhz) On The Left And 18.8 T (108.4 Mhz) On The

    Figure 17.11. shows the results of the fitting with the solids line shape analysis package included in TopSpin. The spectra used for that have been extracted from rows of the 2D spectrum shown in Figure 17.10.. 228 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 229: Figure 17.11. Slices And Simulations Of The 18.8 T 17O Mqmas Of Napo3

    F2 axis. This is the dotted black line in Figure 17.12.. The shift value that is read from the F1 axis at this position is the isotropic chemical shift of that particu- lar site, and the Qis is then given by (Eq. 17.2). User Manual Version 002 BRUKER BIOSPIN 229 (327)

  • Page 230: Figure 17.12. Graphical Interpretation Of The Spectrum From Figure 17.10

    2D spectrum decreases to ≈ -30 ppm, whereas it cannot be determined graphical- ly anymore for the upper peak since the chemical distribution broadens the peak of ≈ -5 ppm. in the F1 dimension more than the theoretical δ 230 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 231: Mq-Mas: Sensitivity Enhancement

    180° pulse is applied. This is shown in Figure 18.1.. The FID generated by the initial 90° pulse is not sampled, but after it is decayed it is refocused with a 180° User Manual Version 002 BRUKER BIOSPIN 231 (327)

  • Page 232: Figure 18.1. Hahn Echo Pulse Sequence And Coherence Transfer Pathway

    The best method is to phase the spectrum to give minimum signal intensity and add or subtract 90° to the obtained value (click 90 or -90 in the TopSpin phasing interface). 232 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 233: Implementation Of Dfs Into Mqmas Experiments

    PL11 and PL21 are already calibrated as described in the chapter "Basic MQ-MAS" on page 213. Starting from this set-up a data set should be created into which either of the two DFS pulse programs is loaded. User Manual Version 002 BRUKER BIOSPIN 233 (327)

  • Page 234: Figure 18.3. Four Pulse Sequence And Coherence Transfer Pathway For The 3Q Mas Experiment

    = 0*6 90*6 180*6 270*6 receiver = {0 180}*3 {90 270}*3 {180 0}*3 {270 90}*3 {180 0}*3 {270 90}*3 {0 180}*3 {90 270}*3. Figure 18.4. Three Pulse Sequence and Coherence Transfer Pathway 234 (327) BRUKER BIOSPIN User Manual Version 002...
  • Page 235 CNST2: End frequency (in kHz) of the sweep; the sweep should cover the satellite transition, but this is often broader than the band width of the probe of approxi- mately 1 MHz. Therefore, it does not make sense to have this value bigger than 1000. User Manual Version 002 BRUKER BIOSPIN 235 (327)

  • Page 236: Table 18.1. Initial Parameters For The Dfs Experiment

    Number of rotor cycles for synchronization used in mp3qdfs.av only. cnst1 see text Start frequency of sweep (in kHz). cnst2 see text End frequency of sweep (in kHz). cnst3 (in ns) timing resolution for sweep. cnst31 “masr” Spinning frequency. 236 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 237: Figure 18.5. Example For Popt To Set-Up For Optimization Of Dfs

    This is true when the spinning frequency is kept constant and the sweep is a smaller fraction of a rotor period and when the sweep is kept at e.g. User Manual Version 002 BRUKER BIOSPIN 237 (327)

  • Page 238: 2D Data Acquisition

    FT can be performed for processing. However, no shearing is required in case of nuclei with spin I=3/2 where a split-t experiment can be per- formed, in which case IN10 must be set correctly. 238 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 239: Table 18.2. Parameters For 2D Data Acquisition Of 3-Pulse Shifted Echo Experiment Mp3Qdfs.av

    For spin I = 3/2, for all other spin I. IN11 For spin I = 3/2, =IN0*19/12 For spin I = 5/2, =IN0*101/45 For spin I = 7/2, =IN0*91/36 For spin I = 9/2. User Manual Version 002 BRUKER BIOSPIN 239 (327)

  • Page 240: Data Processing

    PHC1. This gives an approximate value, which can be precisely adjusted in the interactive phase correction routine. The phase of the spectrum must be corrected such that there is no signal in the imaginary part, as described above. 240 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 241: Table 18.4. Processing Parameters

    DFS enhanced spectra is the same as from the standard MQMAS experiments. Please refer to the chapter "Basic MQ-MAS" on page 213 for further details regarding the shearing transformation and the information ob- tained from MQMAS spectra. User Manual Version 002 BRUKER BIOSPIN 241 (327)

  • Page 242: Fast Amplitude Modulation - Fam

    0 → -3 → -1, 0, +1 → -1. It has been shown that this leads to a substantial gain in sensitivity. However, it requires that data are acquired in echo/anti-echo mode in order to store the two different coherence transfer pathways in consecu- tive FID’s in the serial file. 242 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 243: Figure 18.7. Pulse Sequence And Coherence Transfer Pathways For Spam 3Qmas

    Not 20 µs like in mp3qzqf.av. Set by the pulse program, internally used counter. see text Number of anti-echos to be acquired 0 > L5 > td{F1}/2. For spin I = 3/2. For all other spins. User Manual Version 002 BRUKER BIOSPIN 243 (327)
  • Page 244 I = 3/2, or the second slice for all other nuclei. 2D processing is then done with the AU program xfshear. Alternatively xfshear can be used first, with a sub- sequent 2D interactive phase correction. 244 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 245: Stmas

    Figure 19.1. Principle of 2D Data Sampling in STMAS Experiments. The (blue) filled rectangle on the left symbolizes the first pulse, which starts the evolution period t . After each revolution of the rotor, rotational echo’s show up User Manual Version 002 BRUKER BIOSPIN 245 (327)
  • Page 246 θ from the magic angle the broadening is 3cos , which close to the magic √ θ angle is . The magnitude of the interaction that must be narrowed in the pres- 246 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 247: Pulse Sequences

    20 µs for z-filter, respectively. Phase lists are as follows, for phase sensitive detection in F1 the phase of the first pulse must be in- cremented by 90° in States or States-TPPI mode: User Manual Version 002 BRUKER BIOSPIN 247 (327)

  • Page 248: Figure 19.3. Four Pulse Sequence And Coherence Transfer Pathway

    FnMODE being QF: ph1 = 0 180 90 270 ph2 = 0*4 90*4 180*4 270*4 ph3 = 0*16 90*16 180*16 270*16 248 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 249: Experiment Setup

    70° C for a couple of hours before packing the rotor in order to eliminate crystal water completely. Recycle delays at 11.7 T, longer delays may be required at higher fields. User Manual Version 002 BRUKER BIOSPIN 249 (327)

  • Page 250: Table 19.3. Initial Parameters For The Set-Up Of Stmasdfqz.av

    For PL11 an initial value that corresponds to 150 to 300 W can be used. Optimiza- tion will be done on the first increment of the 2D sequence, which is calculated within the pulse program according to „D0=(1s*L0/CNST31)-P1/2-P4-0.3µ-P2/2“, 250 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 251: Two Dimensional Data Acquisition

    Since the magic angle is probably not yet perfect 32 to 64 FID’s will be suf- ficient initially. Processing parameters are described in the next section. User Manual Version 002 BRUKER BIOSPIN 251 (327)

  • Page 252: Figure 19.4. 87Rb Stmas Spectra Of Rbno3

    Figure 19.4. 87Rb STMAS Spectra of RbNO3 While the left spectrum has been obtained after adjusting the magic angle with KBr, the right spectrum can be obtained after several iterations of readjusting the angle and rerunning the 2Dspectrum. 252 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 253: Data Processing

    Using this procedure the shift positions in the indirect dimension are identical (in ppm) to all MQMAS exper- iments, and the information obtained is the same. User Manual Version 002 BRUKER BIOSPIN 253 (327)
  • Page 254 Table 19.7. Values of R and for the Various Spin Quantum Numbers Ob- tained in the STMAS Experiment |R-p| (p = ± 1) Spin I -8/9 1.889 7/24 0.70833 28/45 0.3777 55/72 0.263111 254 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 255: Double-Cp

    N Chemical Bonds by Double Cross-Polarization NMR, J. Magn. Reson.59,150-156 (1984). 3. M. Baldus, A.T. Petkova, J. Herzfeld, and R.G. Griffin, Cross Polarization in the tilted frame: assign- ment and spectral simplification in heteronuclear spin systems. Mol. Physics 5, 1197-1207 (1998). User Manual Version 002 BRUKER BIOSPIN 255 (327)

  • Page 256: Pulse Sequence Diagram, Double Cp (Dcp)

    The sample may be fully labelled or diluted with natural abundance gly- cine. A restricted volume rotor is preferred. If a different spin rate is used, a dif- ferent shape must be generated for the second CP step. 256 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 257: Figure 20.2. The Edasp Routing Tables For H-C-N Double Cp

    5. Set up for standard C CP operation in triple mode. Remember that a double tuned probe has better signal to noise and requires less power on X than a tri- ple probe. User Manual Version 002 BRUKER BIOSPIN 257 (327)

  • Page 258: Channel Setup

    11. When the HH condition is optimized, find the power level to achieve a 35 kHz RF field (7.14 μsec 90 ° pulse, carrier close to the N-resonance). It is essen- tial to optimize the first proton to nitrogen HH contact. This is not as trivial as 258 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 259: Setup Of The Double Cp Experiment

    Using a square pulse on the N channel is preferred, but the se- quence can be rewritten to use a C square pulse and have the shape on the N channel. User Manual Version 002 BRUKER BIOSPIN 259 (327)

  • Page 260: Table 20.1. Recommended Parameters For The Dcp Setup

    C, or square spnam2 square.100 or ramp45- square on N, or ramp/tangential pulse 55, tcn5500 cpdprg2 SPINAL64 SPINAL64 decoupling 2, 4, or 16 Number of scans 260 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 261: Figure 20.4. Shape Tool Display With Ramp Shape From 45 To 55

    8. Re-optimize p16, the optimum should be > 10 msec. If the signal gets worse with longer contact time, there is a loss due to direct H contact. Minimise this loss in the following way: User Manual Version 002 BRUKER BIOSPIN 261 (327)

  • Page 262: Figure 20.5. Shape Tool Display With A Tangential Shape For Adiabatic Cross Polarization

    +6 dB (4 fold power in TopSpin 3.0 and later), since the amplitude cor- responds directly to pulse voltage. 11. Optimize the DCP condition on the rectangular pulse, using 0.1 dB steps over a range of +/-1 dB around the optimum found with the ramp. 262 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 263: Figure 20.6. Double Cp Optimization Of Pl5 In Increments Of 0.1 Db

    Figure 20.7. Double CP yield, measured by comparing CPMAS and DCP ampli- tudes of the high field resonance. Note that the C carbon receives very little magnetization under these conditions, the transfer is rather selective. User Manual Version 002 BRUKER BIOSPIN 263 (327)

  • Page 264: Setup Of The 2D Double Cp Experiment

    N-C experiment transfers from the α-carbons to all (X) carbons α which are in close enough proximity to the α-carbons. Check with your applica- tions support for appropriate pulse programs. 264 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 265: 2D Data Acquisition

    Power level for Ramp HN contact pulse 1H spnam1 tcn5500 Tangential or ramp contact pulse spnam2 square.100 Shape on N channel cpdprg2 SPINAL64 SPINAL64 decoupling 2 or 16 Number of scans F2 direct (left column) Number of complex points User Manual Version 002 BRUKER BIOSPIN 265 (327)

  • Page 266: Spectral Processing

    (left column) 2-4k FT-size QSINE Squared sine bell Shifted square sine bell, >2: res. enhancement ph_mod Phase correction if needed F2 indirect (right column) 512-1024 Zero fill STATES-TPPI QSINE Squared sine bell 266 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 267: Example Spectra

    Double-CP Example Spectra 20.5 Figure 20.8. C-N correlation via Double CP in histidine (simple setup sample). 4mm Triple H/C/N Probe. User Manual Version 002 BRUKER BIOSPIN 267 (327)

  • Page 268: Figure 20.9. Ncαcx Correlation Experiment With 22 Ms Darr Mixing Period For Cα-Cx Spin Diffusion On Gb1 Protein Run Using An Efree-Probe

    C or C generates positive cross peaks, HORROR or α β DREAM transfer generates negative cross peaks. See the chapter on spin diffu- sion experiments for more information about DARR or PDSD. 268 (327) BRUKER BIOSPIN User Manual Version 002...
  • Page 269 See the chapter on recoupling experiments for the SPC5 setup and for more infor- mation about DQ recoupling sequences. Note the inverse phase of the cross peaks generated by the DQ-mixing step. User Manual Version 002 BRUKER BIOSPIN 269 (327)
  • Page 270 Double-CP 270 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 271: Cramps: General

    This condition can be achieved either by 4 л/2 pulses of suitable phase and spacing (multiple-pulse methods), or by off-resonance irradiation of suitable offset and RF-field (Lee- User Manual Version 002 BRUKER BIOSPIN 271 (327)

  • Page 272: W-Pmlg And Dumbo

    Lee-Goldburg experiment, Chem. Phys. Lett. 314, 443-450 (1999). 2. D. Sakellariou, A. Lesage, P. Hodgkinson and L. Emsley, Homonuclear dipolar decoupling in solid- state NMR using continuous phase modulation, Chem. Phys. Lett. 319, 253 (2000). 272 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 273: Quadrature Detection And Chemical Shift Scaling

    As the frequencies are always smaller than in the standard excitation/observation scheme, the chemical shift User Manual Version 002 BRUKER BIOSPIN 273 (327)
  • Page 274 An example of shift calibration, taking the scaling factor into ac- count, will be given in the practical chapter. 274 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 275: Cramps 1D

    45 degrees, adjust. φ sp1: set for 100-130 kHz WPMLG: p5, 1.2-1.5 µsec or calculated from cnst20=RF field DUMBO: p10 set by xau dumbo. φ CYCLOPS, 0 1 2 3 User Manual Version 002 BRUKER BIOSPIN 275 (327)

  • Page 276: Pulse Shapes For W-Pmlg And Dumbo

    500 MHz, it is recommended to replace the standard 32 µsec timing by 24 µsec timing and increasing the power level accordingly, since this has been found to give better results. Figure 22.2. PMLG Shape for wpmlg, sp1 276 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 277: Analog And Digital Sampling Modi

    DRU) down-conversion must be done to obtain data sets of reasonable sizes. The pulse programs dumboa and wpmlga are written for the pseudo analog mode without digital filtering, dumbod and wpmlgd are written for the digitally filtered mode. User Manual Version 002 BRUKER BIOSPIN 277 (327)

  • Page 278: Analog Mode Sampling

    CRAMPS 1D Analog Mode Sampling 22.3.1 Figure 22.4. Analog Sampling Scheme Digital Mode Sampling 22.3.2 Figure 22.5. Digital Sampling Scheme 278 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 279: Setup

    As for 100 kHz RF field. 1.2µsec 0.7 µsec To be optimized. cnst25 To be optimized. 4 – 2.6 µsec To be optimized. 1.5 µsec or calculated from cnst20 To be optimized. For α-glycine. User Manual Version 002 BRUKER BIOSPIN 279 (327)
  • Page 280 For α-glycine. l11=anavpt 2, 4, 8, 16 or 32. To be optimized. /2*(2*p9+p10)*0.5 To be corrected for proper scaling. 16-64 Up to 1024. digmod analog MASR 10-12 kHz Depending on cycle time. 280 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 281: Fine Tuning For Best Resolution

    Some pulse programs are written such that upon ased, the (approximately) correct sweep width is shown and can be set as an acquisi- tion parameter. User Manual Version 002 BRUKER BIOSPIN 281 (327)

  • Page 282: Digital Mode Acquisition

    Examples 22.10 Figure 22.6. Optimizing sp1 for Best Resolution 282 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 283: Figure 22.7. Optimizing Cnst25 For Minimum Carrier Spike, Optimized At 120°C

    CRAMPS 1D Figure 22.7. Optimizing cnst25 for Minimum Carrier Spike, Optimized at 120°C Figure 22.8. Optimizing p14 for Minimum Carrier Spike, Optimized at 0.6 µsec User Manual Version 002 BRUKER BIOSPIN 283 (327)

  • Page 284: Figure 22.9. Wpmlg-Cramps After Optimization, Digital Acquisition

    CRAMPS 1D Figure 22.9. WPMLG-CRAMPS After Optimization, Digital Acquisition 284 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 285: Modified W-Pmlg

    CYCLOPS, 1 2 3 0 pl12=set for around 100 kHz p1 around 2.5 µsec φ = 0 2 sp1: set for 100-130 kHz=cnst20 WPMLG: calculated from cnst20=RF field φ CYCLOPS, 0 1 2 3 User Manual Version 002 BRUKER BIOSPIN 285 (327)

  • Page 286: Pulse Shapes For W-Pmlg

    ##TITLE= m5p ##TITLE= m3p ##JCAMP-DX= 5.00 Bruker JCAMP library ##JCAMP-DX= 5.00 Bruker JCAMP library ##DATA TYPE= Shape Data ##DATA TYPE= Shape Data ##ORIGIN= Bruker BioSpin GmbH ##ORIGIN= Bruker BioSpin GmbH ##OWNER= <hf> ##OWNER= <hf> ##DATE= 2005/11/29 ##DATE= 2005/11/29 ##TIME= 14:47:39...

  • Page 287: Setup

    2, 4, 8, 16 or 32. 3 - 8 To be optimized. /2*(2*p9+10*p5)*0.47 To be corrected for proper scaling. 16-64 Up to 1024. digmod analog MASR 12-15 kHz Depending on cycle time. User Manual Version 002 BRUKER BIOSPIN 287 (327)

  • Page 288: Fine Tuning For Best Resolution

    Fine tuning is done by optimizing power levels, pulse widths and carrier offset as before, the carrier spike is gone, spikes at both sides may appear. Correcting for Actual Spectral Width 23.6 The modified sequence has a slightly different scaling factor of 0.47. 288 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 289: Digital Mode Acquisition

    The correction for the scaling factor must be done after acquisition, changing the status parameter swh by typing s swh and dividing the value by the scaling factor (about 0.47 for WPMLG and 0.5 for DUMBO). User Manual Version 002 BRUKER BIOSPIN 289 (327)
  • Page 290 Modified W-PMLG 290 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 291: Cramps 2D

    1D experiment on your sample (the recommended setup sample is gly- cine) and generate a 2D data set by clicking on the symbol 1, 2 in the headline of the acquisition parameters. User Manual Version 002 BRUKER BIOSPIN 291 (327)

  • Page 292: Pulse Sequence Diagram

    Table 24.1. Acquisition Parameters Parameter Value Comment pulprog wpmlg2d. AV 3 instruments only, topspin 2.1 or later. FnMODE STATES-TPPI. Any other method may be used with appropriate changes in ppg. NUC1, NUC2 292 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 293: Data Processing

    These values are set as status parameters before transform as indicated above. Table 24.3. Processing Parameters Parameter Value Comment STATES-TPPI QSINE Slight-moderate resolution enhancement is usually required. User Manual Version 002 BRUKER BIOSPIN 293 (327)

  • Page 294: Examples

    3 and 4 ppm will show at a mixing time as short as 50 µsec, the cross peaks to the NH -protons at 9 ppm require 200 -300 µsec to show. The mixing time here was 500 µsec. A sequence without carrier spike suppression was used here. 294 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 295: Figure 24.3. Spectrum Of Tyrosine-Hydrochloride

    Figure 24.3. Spectrum of Tyrosine-hydrochloride The mixing time was 300 µsec to show all connectivities. Full plot to show that smaller sweep widths can be chosen when the carrier can be conveniently placed within the spectrum. User Manual Version 002 BRUKER BIOSPIN 295 (327)

  • Page 296: Proton-Proton Dq-Sq Correlation

    Proton-Proton DQ-SQ Correlation 24.5 This experiment correlates proton shifts (F2) with double quantum frequencies (sum of shifts of the correlated sites). Double quantum transitions are excited and reconverted by a post-C7 or similar sequence. 296 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 297: Pulse Sequence Diagram

    98000, return. The output will be “change power level by 0.18 dB”. The power level for the p-C7 sequence is therefore 0.18 dB to higher attenuation than what is required for a 2.5 µsec pulse. User Manual Version 002 BRUKER BIOSPIN 297 (327)
  • Page 298 11,12 select φ CYCLOPS pl12 φ pl12 p11, ~45° φ pl12 φ sp1: set for 100-130 kHz RF- WPMLG: calculated via cnst20 field DUMBO: p10 set by xau dumbo. φ DQ selection 298 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 299: Data Processing

    These spectra were both taken without the modification according to "CRAMPS 2D" on page 291, so the offset is placed to the down field side and the spectrum width was chosen larger than necessary. The small plots show the full spectrum. User Manual Version 002 BRUKER BIOSPIN 299 (327)

  • Page 300: Figure 24.6. Glycine, Proton-Proton Dq-Sq Correlation Using Wpmlg In Both Directions

    CRAMPS 2D Figure 24.6. Glycine, Proton-Proton DQ-SQ Correlation Using WPMLG in Both Directions 300 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 301: Figure 24.7. 14.5 Khz W-Pmlg/Pc7 Dq/Sq Correlation At 600 Mhz With Tyrosine-Hydrochloride

    CRAMPS 2D Figure 24.7. 14.5 kHz W-PMLG/PC7 DQ/SQ Correlation at 600 MHz with Ty- rosine-Hydrochloride User Manual Version 002 BRUKER BIOSPIN 301 (327)
  • Page 302 CRAMPS 2D 302 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 303: Appendix

    Another copy may be printed for every user‘s own laboratory notebook. One form per probe used should be filled out. The following form serves as an example: User Manual Version 002 BRUKER BIOSPIN 303 (327)
  • Page 304 304 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 309: Figures

    Figure 3.36. A λ/4 only probe (left) and a λ/4 - λ/2 probe (right) ..........46 Figure 3.37. Without/with Parallel Capacitance to Shift the Tuning Range to Lower Frequency ... 47 Figure 3.38. Parallel Coil to Shift the Tuning Range to Higher Frequency ........48 User Manual Version 002 BRUKER BIOSPIN 309 (327)
  • Page 310 Pulse Program for Hahn Echo Sequence ..............98 Practical CP/MAS Spectroscopy on Spin 1/2 Nuclei Basic CP-MAS Experiments Figure 7.1. Pulse Program for CP with Flip-back Pulse ............105 Figure 7.2. Pulse Program for CPTOSS.................. 107 310 (327) BRUKER BIOSPIN User Manual Version 002...
  • Page 311 Figure 12.7. Experimental data for the glycine 13C{15N}-REDOR ..........164 Figure 12.8. Comparison of Experimental Data to a Simulation with Reduced Dipolar Coupling . 165 Figure 12.9. Experimental data with the corresponding M2 parabolic analysis......166 User Manual Version 002 BRUKER BIOSPIN 311 (327)
  • Page 312 Figure 18.2. Processing of Hahn Echo. Left is the Shifted Echo..........233 Figure 18.3. Four Pulse Sequence and Coherence Transfer Pathway for the 3Q MAS Experiment .. Figure 18.4. Three Pulse Sequence and Coherence Transfer Pathway ........234 312 (327) BRUKER BIOSPIN User Manual Version 002...
  • Page 313 Figure 22.9. WPMLG-CRAMPS After Optimization, Digital Acquisition ........284 Modified W-PMLG Figure 23.1. Pulse Sequence Diagram ..................285 CRAMPS 2D Figure 24.1. Pulse Sequence Diagram ..................292 Figure 24.2. Setup and Test Spectrum of Alpha-glycine .............294 User Manual Version 002 BRUKER BIOSPIN 313 (327)
  • Page 314 Figure 24.5. Pulse Sequence Diagram ..................297 Figure 24.6. Glycine, Proton-Proton DQ-SQ Correlation Using WPMLG in Both Directions ..300 Figure 24.7. 14.5 kHz W-PMLG/PC7 DQ/SQ Correlation at 600 MHz with Tyrosine-Hydrochloride ... Appendix 314 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 315: Tables

    Acquisition Parameters for e-DUMBO-HETCOR (on tyrosine-HCl) ......133 Table 9.5. Acquisition Parameters for DUMBO-HETCOR (on tyrosine-HCl)......134 RFDR Table 10.1. Acquisition Parameters ..................140 Table 10.2. Processing Parameters..................141 Proton Driven Spin Diffusion (PDSD) User Manual Version 002 BRUKER BIOSPIN 315 (327)
  • Page 316 Table 18.3. Parameters for 2D Data Acquisition of 4-pulse Z-filtered Experiment mp3qdfsz.av. 240 Table 18.4. Processing Parameters ..................241 Table 18.5. Parameters for FAM ....................242 Table 18.6. Further Parameters for 2D Data Acquisition of SPAM MQMAS Experiment mp3qspam.av ....................... 243 STMAS 316 (327) BRUKER BIOSPIN User Manual Version 002...
  • Page 317 Table 24.2. Phases, RF-levels, and Timings ................293 Table 24.3. Processing Parameters..................293 Table 24.4. Acquisition Parameters ..................298 Table 24.5. Phases, RF-Levels and Timing ................298 Table 24.6. Processing Parameters..................299 Appendix User Manual Version 002 BRUKER BIOSPIN 317 (327)
  • Page 318 Tables 318 (327) BRUKER BIOSPIN User Manual Version 002...

  • Page 319: Index

    BF1........................58 BLEW-12......................92 BN ........................11 Boric Acid ......................11 BR-24 ......................92, 272 breakthrough ....................... 56 bsmsdisp ......................75 bypassing the preamp..................73 C-24 ........................272 calcpowlev......................72 Calibrating ......................75 User Manual Version 002 BRUKER BIOSPIN 319 (327)
  • Page 320 133 experiment button ....................61 frequency ......................57 Frequency Switched Lee Goldburg ............. 92, 272 Frequency Switched Lee Goldburg Heteronuclear Correlation......119 FSLG ......................... 272 FSLG Decoupling....................92 FSLG pulse ....................... 119 320 (327) BRUKER BIOSPIN User Manual Version 002...
  • Page 321 KCl ........................12 KMnO4 ........................ 12 Lee Goldburg condition ..................92 LG Offset......................135 Li (org.)........................ 12 LiCl ......................11 – 12 local motions ..................... 202 logical channel ....................57 longitudinal relaxation ..................201 User Manual Version 002 BRUKER BIOSPIN 321 (327)
  • Page 322 ......................71 power conversion factor ..................101 Power Conversion Table................... 101 powmod......................58, 66 powmod high....................... 66 preamp ........................ 58 preamplifier ......................58 Profile ......................77 – 78 Proton Bandpass Filter..................59 322 (327) BRUKER BIOSPIN User Manual Version 002...
  • Page 323 ......................... 83 skip........................71 Skip optimization ....................71 Sm2Sn2O7......................11 Sn(cyclohexyl)4....................11 SnO2 ........................11 spin nutation frequencies ..................55 spin rate monitor ....................55 SPINAL ....................... 91 SPINAL decoupling ..................... 91 User Manual Version 002 BRUKER BIOSPIN 323 (327)
  • Page 324 WHH-4 ......................272 windowless sequences ..................92 wobb........................62 wobb high ......................67 W-PMLG ......................272 X Low Pass Filter ....................59 xau angle......................65 X-BB Preamplifier....................59 XiX decoupling ....................91 324 (327) BRUKER BIOSPIN User Manual Version 002...
  • Page 325 Index Y(NO3)3*6H2O ....................13 ZGoption –Dlacq ....................75 ZGOPTNS......................106 α-carbon at 43 ppm ..................... 80 α-glycine......................12, 79 γ-glycine ......................79 User Manual Version 002 BRUKER BIOSPIN 325 (327)
  • Page 326 Index 326 (327) BRUKER BIOSPIN User Manual Version 002...
  • Page 327 End of Document User Manual Version 002 BRUKER BIOSPIN 327 (327)
  • Page 328 With more than 40 years of experi ence meeting the professional scientific sector’s needs across a range of disciplines, Bruker BioSpin has built an enviable rapport with the scientific community and various specialist fields through understanding specific demand, and providing attentive and responsive service.

Table of Contents

Save PDF