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Hardware y Software Crio-Magneto superconductor Sonda superconductora RMN

Consola de Radiofrecuencia Computadora + Software RMN + Impresora/Plotter Solucin RMN Preparacin de la muestra Presentacin de los datos
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CRIOMAGNETOS SUPERCONDUCTORES

alambre superconductor
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SEGURIDAD CON LOS MAGNETOS DE RMN

Los magnetos de RMN siempre estn cargados! Los magnetos de RMN pueden interferir con dispositivos mdicos (p. ej. marcapasos, implantes metlicos) Los magnetos de RMN y las consolas de RF pueden interferir con dispositivos electrnicos y mecnicos y pueden daarlos (telfonos celulares, buscadores, relojes, llaves de autos, etc.) Los magnetos de RMN borrarn tarjetas de crdito,, tarjetas de identificacin, discos de 31/2, discos duros, USBs (I-pods, mp3). Atraen objetos ferromagnticos de cualquier tamao p. ej. clips, monedas, llaves, ploumas, tijeras, tornillos, sillas metlicas, cilindros de gas, etc.) y el espectrmetro y la gente pueden sufrir graves daos o lesiones, si se manejan sin cuidado.

 Los magnetos de RMN contener criognicos (helio y nitrgeno lquido) Los criognicos pueden causar quemaduras graves si no se maneja adecuadamente (use proteccin para los ojos y guantes). Crigenos se evaporan y pueden causar asfixia si no est bien ventilado el laboratorio. Cuando se apaga un imn se vaporizan hasta 100 litros de helio lquido en cuestin de minutos (2600 pies cbicos, 70,000 litros de gas) y puede causar asfixia, incluso si el laboratorio est bien ventilado. Si un imn se apaga, salga del laboratorio inmediatamente. No entre en pnico, el gas helio se elevar hasta el techo. Durante una recarga, la tubera se puede romper. Los tubos congelados de plstico se rompen como un cristal!

CONSOLA CON COMPUTADORA DE RMN

GENERADOR DE LA SEAL DE RADIOFRECUENCIA

Desacoplador (1H): Amplificador

Generador de Frecuencia

Transmisor: Amplificador

Generador de Frecuencia

Frequency Generators and Signal Amplifiers are required for each RF channel. Our spectrometers have 2 channels, modern spectrometers can have up to 8 channels.

SONDAS DE RMN
Magic angle (54.7)

Slidos Lquidos

Slidos

Lquidos
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MUESTRAS PARA RMN

Types of NMR sample holders Sample preparation Spectrum quality

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TIPOS DE PORTADORES DE MUESTRA PARA RMN

Solution NMR Sample Tube Spinners Solid State Sample Rotors

NMR Sample Tubes with Caps

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PREPARACIN DE LA MUESTRA PARA RMN

Tubes and Caps:

NMR tubes are a standard length (7 and 9 inch). When chipped (and reduced in length) they should not be reused as an unbalanced tube will not spin.

Always clean the tubes thoroughly after use. First use the solvent you were using to recover your previous sample, then rinse several times with acetone and finally dry the sample tube laying flat on a layer of kimwipes or placed upside-down on a kimwipe in a beaker or Erlenmeyer flask. Choose the container so the tubes stand vertically. Dont heat the tubes above 50 C, as the glass might warp. Always store unused, clean tubes uncapped and laying on a flat surface.
Tube caps are disposable and replacements can be easily obtained in bags of 100 ($5) or 1000 ($40 at www.wilmad.com).

Degassing Samples:

NMR spectra recorded using degassed solvents usually benefit from reduced half-height line-width and thus better S/N. (O2 gas is paramagnetic!)
There are several ways of degassing your sample:

the best is the freeze-pump-thaw technique, placing the sample in a ultrasonic bath works moderately well, bubbling nitrogen through or over the sample less well.
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PREPARACIN DE LA MUESTRA PARA RMN

Quantity:

For proton NMR spectra of small organic compounds (up to MW=500) anything between 1 and 20 mg of sample will be fine. Concentrated solutions can be viscous and may result in broad signals. Very dilute samples could be masked by impurities and solvent peaks. Carbon-13 is present at approximately 1.1 % natural abundance. It is intrinsically less sensitive than protons (approx. six thousand times). Please provide as much sample as possible, 50 - 100 mg (or more) is fine. Preparing two samples - one dilute sample for proton NMR and one concentrated sample for carbon NMR is a useful, but unnecessary practice. Solvent height (volume) should be uniform, 5 cm or 2 inches equal 0.5 ml. The ends of the sample distort the field homogeneity, shimming on each sample corrects this effect and takes just a minute or so. However, vastly different solvent heights (volumes) prevent complete correction and require many minutes shimming to achieve acceptable homogeneity. Samples prepared with too much solvent waste both time and money, and provide poorer S/N. However, If you have limited amounts of sample (less than 1 mg), using less solvent is permissible. Minimum height: 1 cm, however, this requires special positioning of the sample tube and very intensive shimming.
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PREPARACIN DE LA MUESTRA PARA RMN

5 mm

Use clean + dry NMR tubes and caps

(tubes can be re-used, caps should not!) 0.5 ml deuterated solvent (i.e. CDCl3 ,C6 D6 , acetone-d6 ,etc.) substrate requirements for routine spectra: 10 mg for proton NMR 100 mg for carbon-13 NMR

min. filling height of tube: 2 inches (5 cm)

Cleaning of tubes: 1. rinse with solvent you were using 2. rinse with acetone 3. dry in (vacuum-)oven at low temperature
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PREPARACIN DE LA MUESTRA PARA RMN

Clean clear solution Suspension or opaque solution Precipitate Concentration gradient Two phases Not enough solvent

GOOD!

Bad Samples!

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PREPARACIN DE LA MUESTRA PARA RMN

Shimming
improves the magnetic field homogeneity
If the magnetic field is not uniform within the sample, molecules in different positions will experience different field strengths. This will produce broad, distorted, or additional signals.
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Espectros correctos e incorrectos en RMN

are the result of:
Homogeneity of magnetic field Sample preparation Choice of solvent Data acquisition parameters Processing procedures

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Espectro correcto!!
ppm

ppm 18

Espectro incorrecto?
ppm

Peak picking

Integrales

ppm scale

ppm 19

Espectro correcto!!
ppm

ppm 20

Espectro incorrecto?

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Espectro incorrecto!!

No units specified for axis and peak picking

Signal/Noise ratio bad

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Espectro incorrecto?

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Espectro incorrecto!!

Tall signals are cut off

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Espectro incorrecto?

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Espectro incorrecto!!

Signals too small

(only allowed when trying to compare signal intensities between different spectra)

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Espectro incorrecto?

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Espectro incorrecto!!
Broad signals
Possible reasons: poor shimming viscous sample sample too concentrated suspended particles in sample excessive line broadening may have been used during processing

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Espectro incorrecto?

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Espectro incorrecto!!
Signals are distorted Excessive peak picking
(low p.p. threshold, also due to improper phasing) (automatic phase correction is often insufficient)

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Espectro incorrecto?

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Bad spectrum ? Espectro incorrecto?

Areas without signals should be excluded. (If you want to print all your spectra with a default range, i.e. 0-10 ppm, dont forget to print detailed expansions.)

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Lab Assignments
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 2X2 hrs 3 hrs 2X2 hrs 3 hrs 2 hrs 2 hrs 3 hrs 2 hrs 3 hrs 2 hrs Comprehensive 1H NMR and Indirect 13C Observation X00 mg Pulse Width Calibration and B1 100 mg Rare spin NMR concentrated (80-90%) Decoupling 1H from 13C and B2 100 mg Spin Echo and Spin/Spin Relaxation, T2 100 mg Spin/Lattice Relaxation, T1 100 mg Nuclear Overhauser Effect 25 mg Polarization Transfer and DEPT 100 mg 13C CP/MAS in Solids (sample provided) HETCOR (1H/13C COSY) 100 mg
1H

11. 2 hrs

COSY / NOESY (optional)

25 mg

Use your own samples, if possible. Familiarize yourselves with the procedures for each experiment, before you come to the lab. Print the manuals.

http://www.chem.binghamton.edu/NMR

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In all assignments you are expected to report on the following information:

Signal-to-noise ratio Chemical shifts and method of reference in relation to structure J coupling (homo and heteronuclear) in relation to structure Peak intensity and area in relation to concentration and structure/dynamics/relaxation Effect of B0 / lab magnetic field strength, Larmor frequency and gyromagnetic ratio Effect of B0 inhomogeneity Pulse width and tip angle Magnitude of B1 and B2 fields / rf field strengths used Effect of B1 and B2 inhomogeneity Effects of O1 and O2 / frequency offsets Effects of sample spinning and location of spinning sidebands Method of decoupling if used as well as effectiveness Solvent and temperature used Pulse sequence and instrument control programming All critical instrument or data processing parameters Vector and spin diagrams, as needed. Note any experimental or instrumental anomalies

The spectrometer manual to be used in this course can be downloaded from:

http://www.chem.binghamton.edu/staff/schulte/CHEM585f/Chem585f-Bruker.doc

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