Nuclear magnetic resonance (NMR) spectroscopy
CONTENTS
•SPECTROSCOPY
•NMR SPECTROSCOPY
•HISTORY
•THEORY
•PRINCIPLE
•INSTRUMENTATION
•SOLVENTS USED IN
NMR(PROTON NMR)
•CHEMICAL SHIFT
•FACTORS AFFECTING
CHEMICAL SHIFT
•RELAXATION PROCESS
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CONTD.
•SPIN-SPIN COUPLING
• 𝑛 + 1 RULE
•NMR SIGNALS IN VARIOUS
COMPOUNDS
•COUPLING CONSTANT
•NUCLEAR MAGNETIC
DOUBLE RESONANCE/ SPIN
DECOUPLING
•FT-NMR
•ADVANTAGES &
DISADVANTAGES
•APPLICATIONS
•REFERENCE
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SPECTROSCOPY
•SPECTROSCOPY IS DEFINED AS THE INTERACTION
BETWEEN MATTER & ELECTROMAGNETIC
RADIATION(EMR) OR LIGHT.
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CONTD.
•SPECTROMETRY IS THE APPLICATION OF
SPECTROSCOPY SO THAT THERE ARE QUANTIFIABLE
RESULTS THAT CAN THAN BE ASSESSED.
•SPECTROPHOTOMETER OR SPECTROMETER: THE
INSTRUMENT THAT IS USED TO MEASURE THE
AMOUNT OF ELECTRO MAGNETIC RADIATION
ABSORBED BY AN ORGANIC MOLECULE.
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NMR SPECTROSCOPY
•NMR IS BASED ON THE ABSORPTION OF ELECTROMAGNETIC
RADIATION IN THE RADIO FREQUENCY REGION 4-900𝑀𝐻𝑧 BY
NUCLEI OF THE ATOMS.
•PROTON IS PRESENT IN THE NUCLEI & PROTON SHOWS SPIN
MOMENT DUE TO THIS SPIN PROTON ACTS AS SMALL MAGNET.
•NMR ACTIVE COMPOUNDS: 1
1
𝐻, 6
13
𝐶, 7
14
𝑁, 8
17
𝑂, 9
19
𝐹, 15
31
𝑃, 17
35
𝐶𝑙
•NMR INACTIVE COMPOUNDS: 6
12
𝐶, 8
16
𝑂
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NMR
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HISTORY
1937 Rabi’s prediction & observation of NMR
1946 Discovery of NMR by Bloch (Stanford) & Purcell (Harvard)
1948 Russel Varian files patent for Earth’s-field NMR
magnetometer
1952 Russel Varian files patent for Earth’s-field NMR well logging
1953 Over Hauser NOE (nuclear Over Hauser effect)
1966 Ernst, Anderson Fourier transform NMR
1975 Jeener, Ernst 2D NMR
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CONTD.
1984 Nicholson NMR metabolomics
1985 Wuthrich first solution structure of a small protein (BPTI)
from NOE derived distance restraints
1987 3D NMR+ .
13
𝐶, .
15
𝑁 isotope labelling of recombinant proteins
1990 Pulsed field gradients
1996/7 Residual dipolar couplings (RDC) from partial alignment in
liquid crystalline media
2000s Dynamic nuclear polarisation (DNP) to enhance NMR
sensitivity
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NOBEL PRIZE PIONEERS
1944 Physics
Rabi (Columbia)
Resonance
method for
recording the
magnetic
properties of
atomic nuclei
1952 Physics Bloch
(Stanford), Purcell
(Harvard)
Development of new
methods for nuclear
magnetic precision
measurements &
discoveries in
connection
therewith.
1991 Chemistry
Ernst (ETH)
Development of
the methodology
of high resolution
NMR
spectroscopy
2002 Chemistry
Wuthrich (ETH)
Development of
NMR
spectroscopy for
determining the
3D- structure of
biological
macromolecules
in solution
2003 Medicine
Lauterbur
(University of
Illinois in Urbana),
Mansfield
(University of
Nottingham)
Discoveries
concerning
magnetic resonance
imaging
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THEORY
•SPIN QUANTUM NUMBER(I) IS RELATED TO THE
ATOMIC MASS & ATOMIC NUMBER OF THE NUCLEUS.
•ELEMENTS WITH EITHER ODD MASS OR ODD ATOMIC
NUMBER HAVE THE PROPERTY OF NUCLEAR SPIN.
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CONTD.
ATOMIC
MASS
ATOMIC
NUMBER
EXAMPLES
Half integer Odd Odd .
1 𝐻 1
2
Half integer Odd Even .
13 𝐶 1
2
Integer Even Odd .
2 𝐻 1
Zero Even Even .
12 𝐶 0
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NMR
active
NMR
inactive
PRINCIPLE
•SPINNING NUCLEUS: THE
PROTON PRESENT IN THE
NUCLEUS IS SPINNING &
ACTS AS MAGNETIC BAR.
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CONTD.
•EFFECT OF EXTERNAL
MAGNETIC FIELD:
PROTON WILL ALIGNED WITH
THE MAGNETIC FIELD (LOW
ENERGY & PARALLEL)
PROTON WILL OPPOSED THE
MAGNETIC FIELD (HIGH
ENERGY & ANTIPARALLEL)
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CONTD.
• PRECESSIONAL MOTION: PROTON WILL BE
SHOWING PRECESSIONAL MOTION DUE TO
INTERACTION OF SPIN & GRAVITATIONAL
FORCE OF EARTH→ GYROSCOPIC MOTION.
• ENERGY OF REOREINTATION OF
MAGNETIC DIPOLE
∆𝑬 = 𝒉𝒗
WHERE,
𝒉 = 𝒑𝒍𝒂𝒏𝒌′ 𝒔 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝒗 = 𝒇𝒓𝒆𝒒𝒖𝒆𝒏𝒄𝒚 𝒐𝒇 𝒓𝒂𝒅𝒊𝒂𝒕𝒊𝒐𝒏
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CONTD.
•PRECESSIONAL FREQUENCY:
SPINNING FREQUENCY OF
PROTON WILL BE SAME
PRECESSIONAL FREQUENCY 𝛼
EXTERNAL MAGNETIC FIELD
𝒗 𝜶 𝑩 𝒐
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CONTD.
•ENERGY TRANSITION:
IF PROTON’S PRECESSIONAL FREQUENCY WILL BE
EXACTLY SAME THEN ONLY IT WILL ABSORB RADIATION
(RADIO FREQUENCY) & RESONANCE TAKES PLACE WHICH
IS KNOWN AS NMR.
PROTON GOES TO LOW ENERGY LEVEL TO HIGH ENERGY
LEVEL.
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CONTD.
•THE EMITTED RADIOFREQUENCY SIGNAL GIVE THE NMR
SPECTRUM OF THE CONCERED NUCLEUS.
THE EMITTED RADIOFREQUENCY IS DIRECTLY
PROPOTIONAL TO THE STRENGTH OF THE APPLIED
MAGNETIC FIELD.
𝑽 =
𝜸𝑩 𝒐
𝟐𝝅
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Where,
𝐵𝑜 = External magnetic field
𝛾 = Magnetogyric ratio
(ratio between magnetic moment & angular moment)
NMR SPECTRUM
•PLOT OF NMR SIGNALS 𝑉𝑠
MAGNETIC FIELG
(FREQUENCY) IN
REFERENCE TO TMS.
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INSTRUMENTATION
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CONTD.
•SAMPLE HOLDER:
5𝑚𝑚 GLASS TUBE IS USED, WHICH CAN HOLD 0.4𝑚𝑙 LIQUID
SAMPLE.
MICROTUBES ARE USED FOR LOW VOLUMES.
•MAGNET:
ACCURACY & QUALITY OF THE INSTRUMENT IS DEPENDENT ON
ITS STRENGTH.
RESOLUTION INCREASES WITH INCREASE IN THE FIELD
STRENGTH.
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CONTD.
THREE TYPES OF MAGNETS CAN BE USED
CONVENTIONAL MAGNET (30 − 60𝑀𝐻𝑧)
PERMANENT MAGNET (60,90, 100𝑀𝐻𝑧)
SUPER CONDUCTING MAGNET (470𝑀𝐻𝑧)
RELATIONSHIP BETWEEN 𝐵𝑜& 𝑣 CALCULATED BY (ARMOUR
EQUATION)
𝒗 =
𝜸
𝟐𝝅
𝑩 𝒐
•SWEEP GENERATOR: A SET OF SWEEP COIL IS LOCATED PARALLEL
TO THE MAGNET, WHICH ALLOWS THE MAGNETIC FIELD.
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CONTD.
•RF TRANSMITTER: IT IS A PAIR OF COILS MOUNTED
PERPENDICULAR TO THE PATH OF FIELD & RECIEVER
COIL.
•RECIEVER COIL & AMPLIFIER: AMPLIFIES THE RECEIVED
EMR BY 105 TIMES.
•DETECTOR: DETECTS THE SIGNAL PRODUCED BY
RESONATING NUCLEI.
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SOLVENTS USED IN NMR (PROTON
NMR)
• CHEMICALLY INERT
• SOLVENTS SHOULD BE MAGNETICALLY ISOTROPIC IN NATURE
• FREE FROM ANY HYDROGEN ATOM
• SOLVENT SHOULD BE ABLE TO DISSOLVE THE MOLECULA/ SAMPLE IN A
RESONABLE QUANTITY.
• COMMONLY USED SOLVENTS:
CARBON TETRACHOLRIDE(𝐶𝐶𝑙4), CARBON DISULPHIDE(𝐶𝑆2),
DEUTEROCHLOROFORM(𝐶𝐷𝐶𝑙3), HEXACHLOROACETONE( 𝐶𝐷𝐶𝑙3 2 𝐶𝑂),
DEUTEROBENZENE(𝐶6 𝐷6), DEUTERODIMETHYLSULFOXIDE( 𝐶𝐻3 2 𝑆𝑂)
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CONTD.
•HYDROGEN BONDING
INCREASE THE 𝛿 VALUE, & DESHIELDING OCCURS
HIGHER CONCENTRATION OF OH & NH GROUP LEADS
TO HYDROGEN BONDING & ELECTRON CLOUD
TRANSFER FROM HYDROGEN & ULTIMATELY
DESHIELDING TAKES PLACE.
 𝛿 VALUE OF SAME SAMPLE WILL BE DIFFERENT FOR
DIFFERENT SOLVENTS.
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CHEMICAL SHIFT (DENOTED BY𝛿, 𝑝𝑝𝑚
UNITS)
•NUMBER OF SIGNAL & POSITION OF SIGNAL PLAYS VERY
IMPORTANT ROLE IN NMR.
•POSITION OF PROTONS HELPS US TO UNDERSTAND THE
NATURE OF PROTON IN COMPOUNDS.
•DIFFERENT TYPES OF PROTONS ARE PRESENT IN THE
COMPOUNDS & THEY HAVE DIFFERENT ELECTRONIC
ENVIRONMENT, PROTONS GET ABSORB AT DIFFERENT
APPLIED MAGNETIC FIELD.
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CONTD.
•TMS (TETRAMETHYL SILANE)
REFERNCE COMPOUND
HIGH SHIELDING
MISCIBLE WITH ORGANIC
COMPOUND
HIGHLY VOLATILE
NOT TAKE PART IN CHEMICAL
NATURE
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CONTD.
• ALIPHATIC, ALICYCLIC 𝛿 = 0 − 2
• 𝛽 −SUBSTITUTED ALIPHATIC 𝛿 = 1 − 2
• ALKYNE 𝛿 = 2 − 3
• 𝛼 −MONOSUBSTITUTED ALIPHATIC 𝛿 =
2 − 5
• 𝛼 −DESUBSTITUTED ALIPHATIC 𝛿 = 2.5 −
7
• ALKENE 𝛿 = 4.5 − 7.5
• AROMATIC & HETEROATOMIC 𝛿 = 6 − 9
• ALDEHYDE 𝛿 = 9 − 10
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PROTON CHEMICAL SHIFTS
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CONTD.
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FACTORS AFFECTING CHEMICAL
SHIFT
• INDUCTIVE EFFECT(ELECTRONEGATIVITY):
GREATER THE ELECTRONEGATIVITY
GREATER IS THE DEDHIELDING
DELTA VALUE WILL BE MORE
• HYDROGEN BONDING:
• PROTONS THAT ARE INVVOLVED IN HYDROGEN BONDING ARE TYPICALLY
CHANGE THE CHEMICAL SHIFT VALUE.
• MORE HYDROGEN BONDING THE MORE PROTON IS DESHIELDED & CHEMICAL
SHIFT VALUE IS HIGHER.
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CONTD.
•VANDERWALL DESHEILDING/ STERIC EFFECT:
ELECTRON CLOUD OF BULKY GROUP WILL REPEL THE
ELECTRON CLOUD OF PROTON DUE TO ELECTROSTATIC
REPULSION.
DESHIELDING→ INCREASED DELTA VALUE
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CONTD.
•ANISOTROPIC(NON-UNIFORMITY) EFFECT:
CHEMICAL BONDS OF THE MOLECULES ARE ALSO HIGH
ELECTTRON DENSITY REGION & SETS OF MAGNETIC FIELD.
THESE FIELDS ARE STRONGER IN ONE DIRECTION THAN
OTHERS & KNOWNS AS ANISOTROPIC
CHEMICAL SHIFT OF THE NEAR BY NUCLEI IS DEPENDENT ON
THE ORIENTATION OF THE NUCLEUS WITH RESPECT TO BOND.
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H-NMR SPECTRA 𝐶𝐻3 𝐵𝑟
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E
X
A
M
P
L
E
S
ACETONE
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E
X
A
M
P
L
E
S
METHYL ETHANOATE
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E
X
A
M
P
L
E
S
TERTIARY BUTYL BROMIDE
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E
X
A
M
P
L
E
S
1,1-DICHLOROETHANE
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E
X
A
M
P
L
E
S
BROMOPROPANE
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E
X
A
M
P
L
E
S
ISOPROPANOL
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E
X
A
M
P
L
E
S
RELAXATION PROCESS:
•RELAXATION IS PROCESS BY WHICH THE SPINS IN THE SAMPLE
COME TO EQUILLIBRIUM WITH THE SURROUNDINGS.
•RATE OF RELAXATION:
DETERMINES HOW FAST AN EXPERIMENT CAN BE REPEATED
INFLUENCED BY THE PHYSICAL PROPERTIES OF MOLECULE &
THE SAMPLE
•AN UNDERSTANDING OF RELAXATION PROCESSES IS IMPORTANT
FO THE PROPER MEASUREMENT & INTERPRETATION OF NMR
SPECTRA.
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RELAXATION PROCESSSPIN LATTICE/
LONGITUDINAL
RELAXATION
•CHARACTERISED BY 𝑇1 NUCLEI
IN UPPER STATE STARTS TO
LOSE ENERGY TO THE
SURROUNDING.
SPIN-SPIN/ TRANSVERSE
RELAXATION
•CHARACTERISED BY 𝑇2 DOESN’T
LEAD TO A CHANGE IN UPPER &
LOWER ENERGY LEVEL.
A NUCLEI IN THE UPPER STATE
STARTS TO TRANSFER ITS
ENERGY TO A NUCLEI IN LOWER
ENERGY LEVEL.
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SPIN-SPIN COUPLING
•WHEN SPIN OF 2 PROTONS ARE COUPLED, THEN IT IS
KNOWN AS SPIN-SPIN COUPLING.
•FOR SPIN-SPIN COUPLING MINIMUM 2 SETS OF
PROTONS ARE REQUIRED.
•DUE TO SPIN-SPIN COUPLING BETWEEN THE NEAR BY
PROTONS, SPLITTING OF SIGNAL WILL BE OBSERVED.
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CONTD.
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CONTD.
•IF NO PROTON IS PRESENT IN THE ADJACENT
CARBON THEN THAT SET OF PROTON WILL GIVE
SINGLET. E.G.𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝐶𝐻3 (𝑆𝐼𝑁𝐺𝐿𝐸𝑇)
•PEAK INTENSITIES OF VARIOUS MULTIPLETS.
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PASCAL’S TRIANGLE
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𝑛 + 1 RULE:
•MULTIPLICITY OF SIGNAL IS CALCULATED BY USING 𝑛 + 1 RULE.
•ONE OF THE RULE TO PREDICT THE SPLITTING OF PROTON
SIGNALS. THIS IS CONSIDERED BY THE NEAR BY HYDROGEN
NUCLEI.
∴ 𝒏 = 𝑵𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒑𝒓𝒐𝒕𝒐𝒏𝒔 𝒊𝒏 𝒏𝒆𝒂𝒓𝒃𝒚 𝒏𝒖𝒄𝒍𝒆𝒊
𝒘𝒉𝒆𝒓𝒆,
𝒁𝒆𝒓𝒐 𝑯 𝒂𝒕𝒐𝒎 𝒂𝒔 𝒏𝒆𝒊𝒈𝒉𝒃𝒐𝒖𝒓 𝒏 + 𝟏 = 𝟎 + 𝟏 = 𝟏 𝑺𝒊𝒏𝒈𝒍𝒆𝒕
𝑶𝒏𝒆 𝑯 𝒂𝒕𝒐𝒎 𝒂𝒔 𝒏𝒆𝒊𝒈𝒉𝒃𝒐𝒖𝒓 𝒏 + 𝟏 = 𝟏 + 𝟏 = 𝟐 𝑫𝒐𝒖𝒃𝒍𝒆𝒕
𝑻𝒘𝒐 𝑯 𝒂𝒕𝒐𝒎 𝒂𝒔 𝒏𝒆𝒊𝒈𝒉𝒃𝒐𝒖𝒓 𝒏 + 𝟏 = 𝟐 + 𝟏 = 𝟑 𝑻𝒓𝒊𝒑𝒍𝒆𝒕
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NMR SIGNALS IN VARIOUS
COMPOUNDS
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CONTD.
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COUPLING CONSTANT(J)
•THE DISTANCE BETWEEN THE CENTRES OF THE 2 ADJACENT
PEAKS IN A MULTIPLET IS CONSTANT & IT IS KNOWN AS
COUPLING CONSTANT.
•THE VALUE OF THE COUPLING CONSTANT IS INDEPENDENT
BECAUSE THERE IS NO EFFECT OF EXTERNAL/ APPLIED
MAGNETIC FIELD.
•IT IS USED TO DIFFERENTIATE BETWEEN TWO SINGLET &
ONE DOUBLET, TWO DOUBLET & ONE QUARTET.
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CONTD.
•UNITS OF COUPLING CONSTANT IS 𝐻𝑧, 𝐶𝑦𝑐𝑙𝑒𝑠 𝑃𝑒𝑟 𝑆𝑒𝑐𝑜𝑛𝑑 (𝑐𝑝𝑠)
•GENERALLY VALUE OF COUPLING CONSTANT IS UPTO 20𝐻𝑧
•IT CAN BE
POSITIVE: IF THE ENERGY IS LOWER WHEN THE 2 NUCLEI
HAVE OPPOSITE SPIN
NEAGTIVE: IF THE ENERGY IS LOWER WHEN THE 2 NUCLEI
HAVE PARALLEL SPIN
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CONTD.
•VALUE OF COUPLING
CONSTANT DEPENDS UPON
NUMBER OF COVALENT
BONDS
STRUCTURAL
RELATIONSHIP BETWEEN
THE COUPLE PROTONS
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NUCLEAR MAGNETIC DOUBLE
RESONANCE/ SPIN DECOUPLING
•IT IS A TECHNIQUE WHICH INVOLVED IRRADIATION OF
PROTONS OR SET OF PROTONS; THIS IRRADIATION IS
DONE BY INTENSE RADIOFREQUENCY ENERGY.
•THE ENERGY ELIMINATES SPIN-SPIN COUPLING
AMONGST PROTONS.
•TWO RADIOFREQUENCY IS USED, SO KNOWN AS DOUBLE
RESONANCE.
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CONTD.
•THIS TECHNIQUE IS A POWERFUL TOOL FOR
SIMPLYFYING THE SPECTRUM.
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FT-NMR (FOURIER TRANSFORM
NMR)/ PULSE NMR• THE SAMPLE IS IRRADIATED PERIODICALLY WITH BRIEF, HGHLY INTENSE
PULSE OF RADIOFREQUENCY RADIATION, FOLLOWING WHICH THE FREE
INDUCTION DECAY SIGNAL (A CHARACTERTIC EMISSION SIGNAL STIMULATED
BY IRRADIATION) IS RECORDED AS A FUNCTION OF TIME..
• A MATHEMATICAL TECHNIQUE THAT RESOLVES A COMPLEX FID (FREE
INDUCTION DECAY) SIGNAL INTO THE INDIVIDUAL FRQUENCIES THAT ADD
TOGETHER TO MAKE IT.
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FT-NMR INSTRUMENTATION
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COMPONENTS OF FT-NMR
• THE CENTRAL COMPONENT OF THE INSTRUMENT IS A HIGHLY STABLE MAGNET
IN WHICH THE SAMPLE IS PLACED.
• THE SAMPLE IS SURROUNDED BY THE TRANSMITTER/RECEIVER COIL.
• A CRYSTAL CONTROLLED FREQUENCY SYNTHESIZER HAVING AN OUTPUT
FREQUENCY OF 𝑉𝑐 - PRODUCES RADIO-FREQUENCY RADIATION.
• THIS SIGNAL PASSES INTO A PULSE SWITCH & POWER AMPLIFIER, WHICH
CREATES AN - INTENSE & REPRODUCIBLE PULSE OF RF CURRENT IN THE
TRANSMITTER COIL.
• RESULTING SIGNAL IS PICKED UP BY THE SAME COIL WHICH NOW SERVES A AS -
RECEIVER.
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CONTD.
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CONTD.
• THE SIGNAL IS THEN AMPLIFIED & TRANSMITTED TO A PHASE SENSITIVE
DETECTOR.
• THE DETECTOR CIRCUITRY PRODUCED THE DIFFERENCE BETWEEN THE
NUCLEAR SIGNALS 𝑉𝑛 & THE CRYSTAL OSCILLATOR OUTPUT 𝑉𝑐 WHICH
LEADS TO THE LOW FREQUENCY TIME-DOMAIN SIGNAL.
• THIS SIGNAL IS DIGITALIZED & COLLECTED IN THE MEMORY OF THE
COMPUTER FOR ANALYSIS BY A FOURIER TRANSFORM PROGRAM &
OTHER DATA ANALYSIS SOFTWARE.
• THE OUTPUT FROM THIS PROGRAM IS PLOTTED GIVING A FREQUENCY
DOMAIN SPECTRUM.
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ADVANTAGES OF FT-NMR
•MORE SENSITIVE & CAN MEASURE WEAKER SIGNALS
•PULSED FT-NMR IS MUCH FASTER COMPARE TO CONTINUOUS
WAVE NMR.
•READINGS CAN BE OBTAINED WITH LESS THAN 0.5𝑚𝑔 OF THE
COMPOUND.
•FT METHOD ALSO GIVES IMPROVED SPECTRA FOR SPARINGLY
SOLUBLE COMPOUNDS.
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ADVANTAGES & DISADVANTAGES OF
NMR
ADVANTAGES
• ONLY FLUIDS ARE VISIBLE TO NMR
TECHNOLOGY SO POROSITY
MEASUREMENT IS INDEPENDENT
OF THE LITHOLOGY.
• A BETTER MESUREMENT OF
PERMEABILITY IS POSSIBLE THAN
TRADITIONAL PLOT.
• NON-DESTRUCTIVE
DISADVANTAGES
•EXPENSIVE
•SLOWER LOGGING SPEEDS
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APPLICATIONS
•PHARMACEUTICAL SCIENCE:
STUDY PHARMACEUTICALS & DRUG METABOLISM
•CHEMISTRY:
DETERMINE MOLECULAR STRUCTURE OF DIFFERENT
COMPOUNDS
IDENTITY PRODUCTS OF CHEMICAL REACTIONS
•BIOLOGY
PROTEIN NMR
OBTAIN STRUCUTURAL INFORMATION ON COMPLEX PROTEINS
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CONTD.
•MEDICINE:
MRI
INSIGHT INTO THE STRUCTURAL INFORMATION OF THE
HUMAN BODY
SHARP CONTRAST IN SOFT TISSUE
•ENZYMOLOGY:
TO STUDY THE BIOLOGICAL ACTIVITIES OF ENZYME
STUDY OF CONFORMATIONAL DYNAMIC PROCESS IN ENZYMES
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REFERENCE
• INTRODUCTION TO SPECTROSCOPY BY PAVIA.
• A TEXTBOOK OF ORGANIC CHEMISTRY BY BAHL ARUN & BAHL B.S.
• HTTP://WWW.CHEM.UCALGARY.CA/COURSES/350/CAREY5TH/CH13/CH13-NMR-2B.H
• HTTPS://TEACHING.SHU.AC.UK/HWB/CHEMISTRY/TUTORIALS/MOLSPEC/NMR1.HTM
• HTTPS://ORGSPECTROSCOPYINT.BLOGSPOT.COM/P/BASIC-1D-NMR-SPECTRA-SMALL-
AND-SIMPLE.HTML
• HTTPS://EN.WIKIPEDIA.ORG/WIKI/NUCLEAR_MAGNETIC_RESONANCE
• WWW.YOUTUBE.COM
• WWW.SLIDESHARE.COM
• WWW.GOOGLE.COM
27-12-2019V.K. VIKRAM VARMA 64
27-12-2019V.K. VIKRAM VARMA 65

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Nuclear magnetic resonance (NMR) spectroscopy

  • 2. CONTENTS •SPECTROSCOPY •NMR SPECTROSCOPY •HISTORY •THEORY •PRINCIPLE •INSTRUMENTATION •SOLVENTS USED IN NMR(PROTON NMR) •CHEMICAL SHIFT •FACTORS AFFECTING CHEMICAL SHIFT •RELAXATION PROCESS 27-12-2019V.K. VIKRAM VARMA 2
  • 3. CONTD. •SPIN-SPIN COUPLING • 𝑛 + 1 RULE •NMR SIGNALS IN VARIOUS COMPOUNDS •COUPLING CONSTANT •NUCLEAR MAGNETIC DOUBLE RESONANCE/ SPIN DECOUPLING •FT-NMR •ADVANTAGES & DISADVANTAGES •APPLICATIONS •REFERENCE 27-12-2019V.K. VIKRAM VARMA 3
  • 4. SPECTROSCOPY •SPECTROSCOPY IS DEFINED AS THE INTERACTION BETWEEN MATTER & ELECTROMAGNETIC RADIATION(EMR) OR LIGHT. 27-12-2019V.K. VIKRAM VARMA 4
  • 5. CONTD. •SPECTROMETRY IS THE APPLICATION OF SPECTROSCOPY SO THAT THERE ARE QUANTIFIABLE RESULTS THAT CAN THAN BE ASSESSED. •SPECTROPHOTOMETER OR SPECTROMETER: THE INSTRUMENT THAT IS USED TO MEASURE THE AMOUNT OF ELECTRO MAGNETIC RADIATION ABSORBED BY AN ORGANIC MOLECULE. 27-12-2019V.K. VIKRAM VARMA 5
  • 6. NMR SPECTROSCOPY •NMR IS BASED ON THE ABSORPTION OF ELECTROMAGNETIC RADIATION IN THE RADIO FREQUENCY REGION 4-900𝑀𝐻𝑧 BY NUCLEI OF THE ATOMS. •PROTON IS PRESENT IN THE NUCLEI & PROTON SHOWS SPIN MOMENT DUE TO THIS SPIN PROTON ACTS AS SMALL MAGNET. •NMR ACTIVE COMPOUNDS: 1 1 𝐻, 6 13 𝐶, 7 14 𝑁, 8 17 𝑂, 9 19 𝐹, 15 31 𝑃, 17 35 𝐶𝑙 •NMR INACTIVE COMPOUNDS: 6 12 𝐶, 8 16 𝑂 27-12-2019V.K. VIKRAM VARMA 6
  • 8. HISTORY 1937 Rabi’s prediction & observation of NMR 1946 Discovery of NMR by Bloch (Stanford) & Purcell (Harvard) 1948 Russel Varian files patent for Earth’s-field NMR magnetometer 1952 Russel Varian files patent for Earth’s-field NMR well logging 1953 Over Hauser NOE (nuclear Over Hauser effect) 1966 Ernst, Anderson Fourier transform NMR 1975 Jeener, Ernst 2D NMR 27-12-2019V.K. VIKRAM VARMA 8
  • 9. CONTD. 1984 Nicholson NMR metabolomics 1985 Wuthrich first solution structure of a small protein (BPTI) from NOE derived distance restraints 1987 3D NMR+ . 13 𝐶, . 15 𝑁 isotope labelling of recombinant proteins 1990 Pulsed field gradients 1996/7 Residual dipolar couplings (RDC) from partial alignment in liquid crystalline media 2000s Dynamic nuclear polarisation (DNP) to enhance NMR sensitivity 27-12-2019V.K. VIKRAM VARMA 9
  • 10. NOBEL PRIZE PIONEERS 1944 Physics Rabi (Columbia) Resonance method for recording the magnetic properties of atomic nuclei 1952 Physics Bloch (Stanford), Purcell (Harvard) Development of new methods for nuclear magnetic precision measurements & discoveries in connection therewith. 1991 Chemistry Ernst (ETH) Development of the methodology of high resolution NMR spectroscopy 2002 Chemistry Wuthrich (ETH) Development of NMR spectroscopy for determining the 3D- structure of biological macromolecules in solution 2003 Medicine Lauterbur (University of Illinois in Urbana), Mansfield (University of Nottingham) Discoveries concerning magnetic resonance imaging 27-12-2019V.K. VIKRAM VARMA 10
  • 11. THEORY •SPIN QUANTUM NUMBER(I) IS RELATED TO THE ATOMIC MASS & ATOMIC NUMBER OF THE NUCLEUS. •ELEMENTS WITH EITHER ODD MASS OR ODD ATOMIC NUMBER HAVE THE PROPERTY OF NUCLEAR SPIN. 27-12-2019V.K. VIKRAM VARMA 11
  • 12. CONTD. ATOMIC MASS ATOMIC NUMBER EXAMPLES Half integer Odd Odd . 1 𝐻 1 2 Half integer Odd Even . 13 𝐶 1 2 Integer Even Odd . 2 𝐻 1 Zero Even Even . 12 𝐶 0 27-12-2019V.K. VIKRAM VARMA 12 NMR active NMR inactive
  • 13. PRINCIPLE •SPINNING NUCLEUS: THE PROTON PRESENT IN THE NUCLEUS IS SPINNING & ACTS AS MAGNETIC BAR. 27-12-2019V.K. VIKRAM VARMA 13
  • 14. CONTD. •EFFECT OF EXTERNAL MAGNETIC FIELD: PROTON WILL ALIGNED WITH THE MAGNETIC FIELD (LOW ENERGY & PARALLEL) PROTON WILL OPPOSED THE MAGNETIC FIELD (HIGH ENERGY & ANTIPARALLEL) 27-12-2019V.K. VIKRAM VARMA 14
  • 15. CONTD. • PRECESSIONAL MOTION: PROTON WILL BE SHOWING PRECESSIONAL MOTION DUE TO INTERACTION OF SPIN & GRAVITATIONAL FORCE OF EARTH→ GYROSCOPIC MOTION. • ENERGY OF REOREINTATION OF MAGNETIC DIPOLE ∆𝑬 = 𝒉𝒗 WHERE, 𝒉 = 𝒑𝒍𝒂𝒏𝒌′ 𝒔 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 𝒗 = 𝒇𝒓𝒆𝒒𝒖𝒆𝒏𝒄𝒚 𝒐𝒇 𝒓𝒂𝒅𝒊𝒂𝒕𝒊𝒐𝒏 27-12-2019V.K. VIKRAM VARMA 15
  • 16. CONTD. •PRECESSIONAL FREQUENCY: SPINNING FREQUENCY OF PROTON WILL BE SAME PRECESSIONAL FREQUENCY 𝛼 EXTERNAL MAGNETIC FIELD 𝒗 𝜶 𝑩 𝒐 27-12-2019V.K. VIKRAM VARMA 16
  • 17. CONTD. •ENERGY TRANSITION: IF PROTON’S PRECESSIONAL FREQUENCY WILL BE EXACTLY SAME THEN ONLY IT WILL ABSORB RADIATION (RADIO FREQUENCY) & RESONANCE TAKES PLACE WHICH IS KNOWN AS NMR. PROTON GOES TO LOW ENERGY LEVEL TO HIGH ENERGY LEVEL. 27-12-2019V.K. VIKRAM VARMA 17
  • 18. CONTD. •THE EMITTED RADIOFREQUENCY SIGNAL GIVE THE NMR SPECTRUM OF THE CONCERED NUCLEUS. THE EMITTED RADIOFREQUENCY IS DIRECTLY PROPOTIONAL TO THE STRENGTH OF THE APPLIED MAGNETIC FIELD. 𝑽 = 𝜸𝑩 𝒐 𝟐𝝅 27-12-2019V.K. VIKRAM VARMA 18 Where, 𝐵𝑜 = External magnetic field 𝛾 = Magnetogyric ratio (ratio between magnetic moment & angular moment)
  • 19. NMR SPECTRUM •PLOT OF NMR SIGNALS 𝑉𝑠 MAGNETIC FIELG (FREQUENCY) IN REFERENCE TO TMS. 27-12-2019V.K. VIKRAM VARMA 19
  • 21. CONTD. •SAMPLE HOLDER: 5𝑚𝑚 GLASS TUBE IS USED, WHICH CAN HOLD 0.4𝑚𝑙 LIQUID SAMPLE. MICROTUBES ARE USED FOR LOW VOLUMES. •MAGNET: ACCURACY & QUALITY OF THE INSTRUMENT IS DEPENDENT ON ITS STRENGTH. RESOLUTION INCREASES WITH INCREASE IN THE FIELD STRENGTH. 27-12-2019V.K. VIKRAM VARMA 21
  • 22. CONTD. THREE TYPES OF MAGNETS CAN BE USED CONVENTIONAL MAGNET (30 − 60𝑀𝐻𝑧) PERMANENT MAGNET (60,90, 100𝑀𝐻𝑧) SUPER CONDUCTING MAGNET (470𝑀𝐻𝑧) RELATIONSHIP BETWEEN 𝐵𝑜& 𝑣 CALCULATED BY (ARMOUR EQUATION) 𝒗 = 𝜸 𝟐𝝅 𝑩 𝒐 •SWEEP GENERATOR: A SET OF SWEEP COIL IS LOCATED PARALLEL TO THE MAGNET, WHICH ALLOWS THE MAGNETIC FIELD. 27-12-2019V.K. VIKRAM VARMA 22
  • 23. CONTD. •RF TRANSMITTER: IT IS A PAIR OF COILS MOUNTED PERPENDICULAR TO THE PATH OF FIELD & RECIEVER COIL. •RECIEVER COIL & AMPLIFIER: AMPLIFIES THE RECEIVED EMR BY 105 TIMES. •DETECTOR: DETECTS THE SIGNAL PRODUCED BY RESONATING NUCLEI. 27-12-2019V.K. VIKRAM VARMA 23
  • 24. SOLVENTS USED IN NMR (PROTON NMR) • CHEMICALLY INERT • SOLVENTS SHOULD BE MAGNETICALLY ISOTROPIC IN NATURE • FREE FROM ANY HYDROGEN ATOM • SOLVENT SHOULD BE ABLE TO DISSOLVE THE MOLECULA/ SAMPLE IN A RESONABLE QUANTITY. • COMMONLY USED SOLVENTS: CARBON TETRACHOLRIDE(𝐶𝐶𝑙4), CARBON DISULPHIDE(𝐶𝑆2), DEUTEROCHLOROFORM(𝐶𝐷𝐶𝑙3), HEXACHLOROACETONE( 𝐶𝐷𝐶𝑙3 2 𝐶𝑂), DEUTEROBENZENE(𝐶6 𝐷6), DEUTERODIMETHYLSULFOXIDE( 𝐶𝐻3 2 𝑆𝑂) 27-12-2019V.K. VIKRAM VARMA 24
  • 25. CONTD. •HYDROGEN BONDING INCREASE THE 𝛿 VALUE, & DESHIELDING OCCURS HIGHER CONCENTRATION OF OH & NH GROUP LEADS TO HYDROGEN BONDING & ELECTRON CLOUD TRANSFER FROM HYDROGEN & ULTIMATELY DESHIELDING TAKES PLACE.  𝛿 VALUE OF SAME SAMPLE WILL BE DIFFERENT FOR DIFFERENT SOLVENTS. 27-12-2019V.K. VIKRAM VARMA 25
  • 26. CHEMICAL SHIFT (DENOTED BY𝛿, 𝑝𝑝𝑚 UNITS) •NUMBER OF SIGNAL & POSITION OF SIGNAL PLAYS VERY IMPORTANT ROLE IN NMR. •POSITION OF PROTONS HELPS US TO UNDERSTAND THE NATURE OF PROTON IN COMPOUNDS. •DIFFERENT TYPES OF PROTONS ARE PRESENT IN THE COMPOUNDS & THEY HAVE DIFFERENT ELECTRONIC ENVIRONMENT, PROTONS GET ABSORB AT DIFFERENT APPLIED MAGNETIC FIELD. 27-12-2019V.K. VIKRAM VARMA 26
  • 27. CONTD. •TMS (TETRAMETHYL SILANE) REFERNCE COMPOUND HIGH SHIELDING MISCIBLE WITH ORGANIC COMPOUND HIGHLY VOLATILE NOT TAKE PART IN CHEMICAL NATURE 27-12-2019V.K. VIKRAM VARMA 27
  • 28. CONTD. • ALIPHATIC, ALICYCLIC 𝛿 = 0 − 2 • 𝛽 −SUBSTITUTED ALIPHATIC 𝛿 = 1 − 2 • ALKYNE 𝛿 = 2 − 3 • 𝛼 −MONOSUBSTITUTED ALIPHATIC 𝛿 = 2 − 5 • 𝛼 −DESUBSTITUTED ALIPHATIC 𝛿 = 2.5 − 7 • ALKENE 𝛿 = 4.5 − 7.5 • AROMATIC & HETEROATOMIC 𝛿 = 6 − 9 • ALDEHYDE 𝛿 = 9 − 10 27-12-2019V.K. VIKRAM VARMA 28
  • 31. FACTORS AFFECTING CHEMICAL SHIFT • INDUCTIVE EFFECT(ELECTRONEGATIVITY): GREATER THE ELECTRONEGATIVITY GREATER IS THE DEDHIELDING DELTA VALUE WILL BE MORE • HYDROGEN BONDING: • PROTONS THAT ARE INVVOLVED IN HYDROGEN BONDING ARE TYPICALLY CHANGE THE CHEMICAL SHIFT VALUE. • MORE HYDROGEN BONDING THE MORE PROTON IS DESHIELDED & CHEMICAL SHIFT VALUE IS HIGHER. 27-12-2019V.K. VIKRAM VARMA 31
  • 32. CONTD. •VANDERWALL DESHEILDING/ STERIC EFFECT: ELECTRON CLOUD OF BULKY GROUP WILL REPEL THE ELECTRON CLOUD OF PROTON DUE TO ELECTROSTATIC REPULSION. DESHIELDING→ INCREASED DELTA VALUE 27-12-2019V.K. VIKRAM VARMA 32
  • 33. CONTD. •ANISOTROPIC(NON-UNIFORMITY) EFFECT: CHEMICAL BONDS OF THE MOLECULES ARE ALSO HIGH ELECTTRON DENSITY REGION & SETS OF MAGNETIC FIELD. THESE FIELDS ARE STRONGER IN ONE DIRECTION THAN OTHERS & KNOWNS AS ANISOTROPIC CHEMICAL SHIFT OF THE NEAR BY NUCLEI IS DEPENDENT ON THE ORIENTATION OF THE NUCLEUS WITH RESPECT TO BOND. 27-12-2019V.K. VIKRAM VARMA 33
  • 34. H-NMR SPECTRA 𝐶𝐻3 𝐵𝑟 27-12-2019V.K. VIKRAM VARMA 34 E X A M P L E S
  • 36. METHYL ETHANOATE 27-12-2019V.K. VIKRAM VARMA 36 E X A M P L E S
  • 37. TERTIARY BUTYL BROMIDE 27-12-2019V.K. VIKRAM VARMA 37 E X A M P L E S
  • 41. RELAXATION PROCESS: •RELAXATION IS PROCESS BY WHICH THE SPINS IN THE SAMPLE COME TO EQUILLIBRIUM WITH THE SURROUNDINGS. •RATE OF RELAXATION: DETERMINES HOW FAST AN EXPERIMENT CAN BE REPEATED INFLUENCED BY THE PHYSICAL PROPERTIES OF MOLECULE & THE SAMPLE •AN UNDERSTANDING OF RELAXATION PROCESSES IS IMPORTANT FO THE PROPER MEASUREMENT & INTERPRETATION OF NMR SPECTRA. 27-12-2019V.K. VIKRAM VARMA 41
  • 42. RELAXATION PROCESSSPIN LATTICE/ LONGITUDINAL RELAXATION •CHARACTERISED BY 𝑇1 NUCLEI IN UPPER STATE STARTS TO LOSE ENERGY TO THE SURROUNDING. SPIN-SPIN/ TRANSVERSE RELAXATION •CHARACTERISED BY 𝑇2 DOESN’T LEAD TO A CHANGE IN UPPER & LOWER ENERGY LEVEL. A NUCLEI IN THE UPPER STATE STARTS TO TRANSFER ITS ENERGY TO A NUCLEI IN LOWER ENERGY LEVEL. 27-12-2019V.K. VIKRAM VARMA 42
  • 43. SPIN-SPIN COUPLING •WHEN SPIN OF 2 PROTONS ARE COUPLED, THEN IT IS KNOWN AS SPIN-SPIN COUPLING. •FOR SPIN-SPIN COUPLING MINIMUM 2 SETS OF PROTONS ARE REQUIRED. •DUE TO SPIN-SPIN COUPLING BETWEEN THE NEAR BY PROTONS, SPLITTING OF SIGNAL WILL BE OBSERVED. 27-12-2019V.K. VIKRAM VARMA 43
  • 45. CONTD. •IF NO PROTON IS PRESENT IN THE ADJACENT CARBON THEN THAT SET OF PROTON WILL GIVE SINGLET. E.G.𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝐶𝐻3 (𝑆𝐼𝑁𝐺𝐿𝐸𝑇) •PEAK INTENSITIES OF VARIOUS MULTIPLETS. 27-12-2019V.K. VIKRAM VARMA 45
  • 47. 𝑛 + 1 RULE: •MULTIPLICITY OF SIGNAL IS CALCULATED BY USING 𝑛 + 1 RULE. •ONE OF THE RULE TO PREDICT THE SPLITTING OF PROTON SIGNALS. THIS IS CONSIDERED BY THE NEAR BY HYDROGEN NUCLEI. ∴ 𝒏 = 𝑵𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒑𝒓𝒐𝒕𝒐𝒏𝒔 𝒊𝒏 𝒏𝒆𝒂𝒓𝒃𝒚 𝒏𝒖𝒄𝒍𝒆𝒊 𝒘𝒉𝒆𝒓𝒆, 𝒁𝒆𝒓𝒐 𝑯 𝒂𝒕𝒐𝒎 𝒂𝒔 𝒏𝒆𝒊𝒈𝒉𝒃𝒐𝒖𝒓 𝒏 + 𝟏 = 𝟎 + 𝟏 = 𝟏 𝑺𝒊𝒏𝒈𝒍𝒆𝒕 𝑶𝒏𝒆 𝑯 𝒂𝒕𝒐𝒎 𝒂𝒔 𝒏𝒆𝒊𝒈𝒉𝒃𝒐𝒖𝒓 𝒏 + 𝟏 = 𝟏 + 𝟏 = 𝟐 𝑫𝒐𝒖𝒃𝒍𝒆𝒕 𝑻𝒘𝒐 𝑯 𝒂𝒕𝒐𝒎 𝒂𝒔 𝒏𝒆𝒊𝒈𝒉𝒃𝒐𝒖𝒓 𝒏 + 𝟏 = 𝟐 + 𝟏 = 𝟑 𝑻𝒓𝒊𝒑𝒍𝒆𝒕 27-12-2019V.K. VIKRAM VARMA 47
  • 48. NMR SIGNALS IN VARIOUS COMPOUNDS 27-12-2019V.K. VIKRAM VARMA 48
  • 50. COUPLING CONSTANT(J) •THE DISTANCE BETWEEN THE CENTRES OF THE 2 ADJACENT PEAKS IN A MULTIPLET IS CONSTANT & IT IS KNOWN AS COUPLING CONSTANT. •THE VALUE OF THE COUPLING CONSTANT IS INDEPENDENT BECAUSE THERE IS NO EFFECT OF EXTERNAL/ APPLIED MAGNETIC FIELD. •IT IS USED TO DIFFERENTIATE BETWEEN TWO SINGLET & ONE DOUBLET, TWO DOUBLET & ONE QUARTET. 27-12-2019V.K. VIKRAM VARMA 50
  • 51. CONTD. •UNITS OF COUPLING CONSTANT IS 𝐻𝑧, 𝐶𝑦𝑐𝑙𝑒𝑠 𝑃𝑒𝑟 𝑆𝑒𝑐𝑜𝑛𝑑 (𝑐𝑝𝑠) •GENERALLY VALUE OF COUPLING CONSTANT IS UPTO 20𝐻𝑧 •IT CAN BE POSITIVE: IF THE ENERGY IS LOWER WHEN THE 2 NUCLEI HAVE OPPOSITE SPIN NEAGTIVE: IF THE ENERGY IS LOWER WHEN THE 2 NUCLEI HAVE PARALLEL SPIN 27-12-2019V.K. VIKRAM VARMA 51
  • 52. CONTD. •VALUE OF COUPLING CONSTANT DEPENDS UPON NUMBER OF COVALENT BONDS STRUCTURAL RELATIONSHIP BETWEEN THE COUPLE PROTONS 27-12-2019V.K. VIKRAM VARMA 52
  • 53. NUCLEAR MAGNETIC DOUBLE RESONANCE/ SPIN DECOUPLING •IT IS A TECHNIQUE WHICH INVOLVED IRRADIATION OF PROTONS OR SET OF PROTONS; THIS IRRADIATION IS DONE BY INTENSE RADIOFREQUENCY ENERGY. •THE ENERGY ELIMINATES SPIN-SPIN COUPLING AMONGST PROTONS. •TWO RADIOFREQUENCY IS USED, SO KNOWN AS DOUBLE RESONANCE. 27-12-2019V.K. VIKRAM VARMA 53
  • 54. CONTD. •THIS TECHNIQUE IS A POWERFUL TOOL FOR SIMPLYFYING THE SPECTRUM. 27-12-2019V.K. VIKRAM VARMA 54
  • 55. FT-NMR (FOURIER TRANSFORM NMR)/ PULSE NMR• THE SAMPLE IS IRRADIATED PERIODICALLY WITH BRIEF, HGHLY INTENSE PULSE OF RADIOFREQUENCY RADIATION, FOLLOWING WHICH THE FREE INDUCTION DECAY SIGNAL (A CHARACTERTIC EMISSION SIGNAL STIMULATED BY IRRADIATION) IS RECORDED AS A FUNCTION OF TIME.. • A MATHEMATICAL TECHNIQUE THAT RESOLVES A COMPLEX FID (FREE INDUCTION DECAY) SIGNAL INTO THE INDIVIDUAL FRQUENCIES THAT ADD TOGETHER TO MAKE IT. 27-12-2019V.K. VIKRAM VARMA 55
  • 57. COMPONENTS OF FT-NMR • THE CENTRAL COMPONENT OF THE INSTRUMENT IS A HIGHLY STABLE MAGNET IN WHICH THE SAMPLE IS PLACED. • THE SAMPLE IS SURROUNDED BY THE TRANSMITTER/RECEIVER COIL. • A CRYSTAL CONTROLLED FREQUENCY SYNTHESIZER HAVING AN OUTPUT FREQUENCY OF 𝑉𝑐 - PRODUCES RADIO-FREQUENCY RADIATION. • THIS SIGNAL PASSES INTO A PULSE SWITCH & POWER AMPLIFIER, WHICH CREATES AN - INTENSE & REPRODUCIBLE PULSE OF RF CURRENT IN THE TRANSMITTER COIL. • RESULTING SIGNAL IS PICKED UP BY THE SAME COIL WHICH NOW SERVES A AS - RECEIVER. 27-12-2019V.K. VIKRAM VARMA 57
  • 59. CONTD. • THE SIGNAL IS THEN AMPLIFIED & TRANSMITTED TO A PHASE SENSITIVE DETECTOR. • THE DETECTOR CIRCUITRY PRODUCED THE DIFFERENCE BETWEEN THE NUCLEAR SIGNALS 𝑉𝑛 & THE CRYSTAL OSCILLATOR OUTPUT 𝑉𝑐 WHICH LEADS TO THE LOW FREQUENCY TIME-DOMAIN SIGNAL. • THIS SIGNAL IS DIGITALIZED & COLLECTED IN THE MEMORY OF THE COMPUTER FOR ANALYSIS BY A FOURIER TRANSFORM PROGRAM & OTHER DATA ANALYSIS SOFTWARE. • THE OUTPUT FROM THIS PROGRAM IS PLOTTED GIVING A FREQUENCY DOMAIN SPECTRUM. 27-12-2019V.K. VIKRAM VARMA 59
  • 60. ADVANTAGES OF FT-NMR •MORE SENSITIVE & CAN MEASURE WEAKER SIGNALS •PULSED FT-NMR IS MUCH FASTER COMPARE TO CONTINUOUS WAVE NMR. •READINGS CAN BE OBTAINED WITH LESS THAN 0.5𝑚𝑔 OF THE COMPOUND. •FT METHOD ALSO GIVES IMPROVED SPECTRA FOR SPARINGLY SOLUBLE COMPOUNDS. 27-12-2019V.K. VIKRAM VARMA 60
  • 61. ADVANTAGES & DISADVANTAGES OF NMR ADVANTAGES • ONLY FLUIDS ARE VISIBLE TO NMR TECHNOLOGY SO POROSITY MEASUREMENT IS INDEPENDENT OF THE LITHOLOGY. • A BETTER MESUREMENT OF PERMEABILITY IS POSSIBLE THAN TRADITIONAL PLOT. • NON-DESTRUCTIVE DISADVANTAGES •EXPENSIVE •SLOWER LOGGING SPEEDS 27-12-2019V.K. VIKRAM VARMA 61
  • 62. APPLICATIONS •PHARMACEUTICAL SCIENCE: STUDY PHARMACEUTICALS & DRUG METABOLISM •CHEMISTRY: DETERMINE MOLECULAR STRUCTURE OF DIFFERENT COMPOUNDS IDENTITY PRODUCTS OF CHEMICAL REACTIONS •BIOLOGY PROTEIN NMR OBTAIN STRUCUTURAL INFORMATION ON COMPLEX PROTEINS 27-12-2019V.K. VIKRAM VARMA 62
  • 63. CONTD. •MEDICINE: MRI INSIGHT INTO THE STRUCTURAL INFORMATION OF THE HUMAN BODY SHARP CONTRAST IN SOFT TISSUE •ENZYMOLOGY: TO STUDY THE BIOLOGICAL ACTIVITIES OF ENZYME STUDY OF CONFORMATIONAL DYNAMIC PROCESS IN ENZYMES 27-12-2019V.K. VIKRAM VARMA 63
  • 64. REFERENCE • INTRODUCTION TO SPECTROSCOPY BY PAVIA. • A TEXTBOOK OF ORGANIC CHEMISTRY BY BAHL ARUN & BAHL B.S. • HTTP://WWW.CHEM.UCALGARY.CA/COURSES/350/CAREY5TH/CH13/CH13-NMR-2B.H • HTTPS://TEACHING.SHU.AC.UK/HWB/CHEMISTRY/TUTORIALS/MOLSPEC/NMR1.HTM • HTTPS://ORGSPECTROSCOPYINT.BLOGSPOT.COM/P/BASIC-1D-NMR-SPECTRA-SMALL- AND-SIMPLE.HTML • HTTPS://EN.WIKIPEDIA.ORG/WIKI/NUCLEAR_MAGNETIC_RESONANCE • WWW.YOUTUBE.COM • WWW.SLIDESHARE.COM • WWW.GOOGLE.COM 27-12-2019V.K. VIKRAM VARMA 64