I would like to introduce the new NMR program for spectra analysis
on the any PC (see below). DEMO version of this program can be FTPed:
bloch.CChem.Berkeley.Edu:/pub/nmr/ms-dos/nmrloop/nmrloop.zip (203.8 K).
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Welcome to NMRLoop 5.0
_______________________
NMRLoop 5.0 is a professional software for NMR Lineshape
Analysis oriented on IBM PC-AT personal computers.
NMRLoop package covers the one-dimensional NMR
applications of most general interest such as NMR,DNMR,
and Quadrupole Relaxation Broadened Lineshape Analysis.
Theory
______
NMR LINESHAPE. In contrast to other iterative NMR programs such
as PANIC (Bruker), SPINS (Varian) that fit nmr parameters to line
positions, NMRLoop is a lineshape-fitting program and does not
require any of the assignment of experimental lines. Such
approach gives the most exact results in analyzing high
resolution static NMR Lorentzian shapes.
The next feature is that NMRLoop permits the lineshape
calculations of isomeric mixtures with different ratios of
species and spin systems containing nucleus with different
natural abundance (Pt,Pb,Os etc).
DNMR LINESHAPE. The calculations of a theoretical dnmr lineshape
are based on the unified theory of exchange effects on the nmr
lineshape of strongly coupled spin system developed by G.Binsch
(ref.1). In contrast to other well-known programs such as DNMR5
(ref.2) et al we used the representation of static spin
Hamiltonian eigenfunctions instead the representation of basis
functions. In the representation of basis functions the Liouville
complex matrix to be diagonalized contains off-diagonal imaginary
elements, which correspond to the coupling constants. The order
of this matrix is defined by product of the orders of two static
Hamiltonians that satisfy to transition condition, and can't be
reduced. In the representation of eigenfunctions (used in
NMRLoop) the Liouville matrix does not contain off-diagonal
imaginary elements and its order may be strongly reduced by
neglecting of the weak intensity lines. As a consequence the
complex Liouville matrix can be constructed in such way that its
order is equal to the number of lines observed in the static nmr
spectrum. For example, the order of the largest Liouville matrix
of the [ABCDE]2 spin system is equal to 200x200. Using the
representation of eigenfunctions the order of Liouville matrix
may be reduced to 60x60 by neglecting of combination transition
only. So such approach has a great advantage in dnmr lineshape
calculations of complex spin systems containing the large number
of combination transitions that have a negligible intensities as
usually.
QUADRUPOLAR RELAXATION BROADENED LINESHAPE. The calculations of
the high-resolution nmr lineshape of the spin-1/2 region of spin
systems containing nuclei of spin-1/2, which are scalar coupled
to one or more nonequivalent quadrupolar nuclei (spin > 1/2), are
based on the relaxation matrix method. It is known that there are
two different approaches to lineshape calculations for such spin
systems, namely relaxation matrix method based on solving of the
equation of motion of the density matrix in the Liouville
representation (ref.4) and a stochastic approach based upon
analogy with chemical exchange (ref.5). The relaxation matrix
method is applicable to all spin systems of such kind, both first
and second order, and for all region of quadrupole relaxation
rates, whilst a stochastic approach is only applicable to
first-order systems. Both methods give identical results for
spin-1/2 region in cases: a) spin system contains a single
quadrupolar nuclei; b) in the limit of very rapid quadrupole
relaxation for systems, containing more than one quadrupolar
nucleus. NMRLoop has a switch to select one of the theoretical
approaches to have ability to compare lineshapes arising from the
one of used method.
FITTING. The fitting algorithm utilizes a standard non-linear
least-squares approach with mixed Gradient and Newton methods to
minimize the squared deviation function. A least-squares fit of
the experimantal data is performed to find the best set of NMR
parameters such as chemical shifts, coupling constants, effective
relaxation times, relaxation times of the quadrupolar nuclei,
populations, exchange rate constants. The number of the fitting
parameters is not limited.
LOADING OF SPECTRAL DATA. 1D spectral data resulting from Bruker
or Varian NMR Spectrometers may be loaded and processed (except
FFT). Spectral data resulting from Bruker NMR spectrometer must
be transfered into DOS file using KERMIT utility. Spectral data
resulting from Varian NMR spectrometer must be prepared on the
floppy standard formatted on Varian spectrometer.
X-Factorization and Magnetic Equivalence Factorization are
used in all theoretical model calculations.
Menu system and examples
_________________________
This part describes the most important menu items.
The program option may be selected from submenu "Options".
SubMenu "Options" Item Description
ͺ Simulation of the static high-resolution
NMR Simulation NMR spectra up to 12 magnetical
© equivalent groups spin-1/2.
Examples:
1. [ABCDX]2 - 5-spin system, where X-Pt with a natural
abundance
2. ABC - arbitrary 3-spin system
3. A2B3C3; 4. ABX3Z3; 5. ABCDX3Z3; 8. ABCMNZ3 - demonstrate
magnetic equivalence factorization
6. ABCDEF - arbitrary 6-spin system
7. [A2B2X6Z6]3 - demonstrates 3 conformer mixture of N,N,N,N-
tetramethyldihydrazide succinic acid (ref.6).
ͺ Simulation of the exchange-broadened
DNMR Simulation DNMR spectra.
©
Examples:
1. [AX]4 - demonstrates four-sites nonmutual exchange in
first-order system.
2. ABC=BAC - demonstrates mutual exchange in 3-spin
second-order system (nmr parameters used from
ref.1).
3. [ABC]2 - example 2 calculated as nonmutual exchange.
4. [ABMNX]2 - demonstrates Z,E-isomerization of 1-formyl,
2-[4-cloro,2,3,5,6-tetrafluoro]phenylhydrazine
(ref.3).
5. [A2B2X6Z6]4 - conformational exchange in N,N,N,N-
tetramethyldihydrazide succinic acid (ref.6).
6. [A2C2X6Z6]4 - example 5 calculated as first-order system
ͺ Simulation of the first-order nmr
QRB Simulation spectra spin-1/2 scalar coupled to
© a set of nonequivalent quadrupolar
nuclei with spin > 1/2.
Examples:
1. AXY - 3-spin system with two nonequivalent quadrupolar
nucleus with spin equal 1 (Ix=Iy=1).
2. AX - Ix = 3/2.
ͺ Lineshape analysis of the static high-
NMR Fitting resolution NMR spectra.
©
Examples:
1. [A2B2X6Z6]3 - lineshape analysis of example "NMR Simulation".7
at room temperature.
Varied parameters:
1. T2[A] - site 1
2. T2[X] - site 1
3. T2[A] - site 3
4. T2[X] - site 3
5. Population[1]
6. Population[2]
2. [A2B2X6Z6]3 - example 1 with the next varied parameters:
1. Chemical Shift[A] - site 1
2. Chemical Shift[X] - site 1
3. Chemical Shift[A] - site 2
4. Chemical Shift[X] - site 2
5. Chemical Shift[A] - site 3
6. Chemical Shift[B] - site 3
7. Chemical Shift[X] - site 3
8. Chemical Shift[Z] - site 3
9. J[A-B] - site 3
10. Population[1]
11.Population[2]
3. ABC - lineshape analysis of example "NMR Simulation".2.
Varied parameters:
1. Chemical Shift[A]
2. Chemical Shift[B]
3. Chemical Shift[C]
4. J[A-B]
5. J[A-C]
6. J[B-C]
ͺ Lineshape analysis of the exchange-
DNMR Fitting broadened DNMR spectra.
©
Examples:
1. [AX]4 - lineshape analysis of example "DNMR Simulation".1
Varied parameters:
1. Population[1]
2. Population[3]
3. K[1-3] = K[2-3]
4. K[1-4] = K[2-4]
2. [A2C2X6Z6]3 - lineshape analysis of example "DNMR Simulation".5
at 318 K degree.
Varied parameters:
1. Population[1]
2. Population[2]
3. K[1-3] = K[1-4]
4. K[2-3] = K[2-4]
3. [A2C2X6Z6]3 - lineshape analysis of example "DNMR Simulation".5
at 328 K degree.
Varied parameters:
1. Population[1]
2. Population[2]
3. K[1-3] = K[1-4]
4. K[2-3] = K[2-4]
4. ABC=BAC - lineshape analysis of example "DNMR Simulation".2.
Varied parameter: K[1-2].
ͺ Lineshape analysis of the first-order
QRB Fitting nmr spectra spin-1/2 scalar coupled
© to a set of quadrupolar nuclei.
Examples:
1. AX - lineshape analysis of example "QRB Simulation".2.
Varied parameter: T2[X].
2. AX - lineshape analysis of example "QRB Simulation".2.
Varied parameters:
1. J[A-X]
2. T2[X]
SubMenu "File"
______________
ͺ
View File Browsing of any text file.
©
ͺ
Load Spectrum Loading of spectra in one of the followed
© format: 1) internal format; 2) Bruker
format; 3) Varian format.
ͺ
View data.Results Browsing of calculated nmr transitions.
©
SubMenu "Defaults"
__________________
The most part of this submenu items are disabled in demo
version.
ͺ
QRB method Switches on the theoretical method of lineshape
© calculation for spin systems, containing quadrupolar
niclei - "relaxation matrix method" or "stochastic
method".
ͺ
Param Editing of initial nmr parameters in any program
© option. In demo version input and editing of spin
system string is disabled. Other parameters may be
changed.
ͺ
Display Processing and drawing of simulated and/or fitting
© spectra. Processing of 1D spectral data arising from
Bruker or Varian spectrometers.
ͺ
Run Recalculation of nmr lineshape after initial nmr
© parameters have been changed.
System requirements
__________________
IBM PC-AT 286 or higher with a minimum of 1MB of memory, must be
used MS-DOS 5.0 or higher. Math coprocessor, hard disk, and
color VGA or VGA compatible monitor are required. Memory manager
HIMEM.SYS is strongly recommended. A mouse is optional but
recommended.
References
__________
1. G.Binsch, J.Amer.Chem.Soc., 91 (1969), 1304.
2. D.S.Stephenson, G.Binsch, J.Magn.Reson., 32, (1978), 145.
3. V.F.Galat, E.V.Titov, J.Mol.Stucture, 174, (1988), 303.
4. N.C.Pyper, Mol.Physics, 21, (1971), 977.
5. J.A.Pople, Mol.Physics, 1, (1958), 168.
6. V.F.Galat et al, Theor.&Exper.Chem., 31 (1995), 120.
For communication
_________________
Dr. Valerij F. Galat, Institute of Physical Organic & Coal
Chemistry, R.Luxemburg Str. 70, 340114 Donetsk, Ukraine.
Tel (0622)-558-144, (0622)-554-629(home)
E-mail kapkan@infou.donetsk.ua
Dr. Yuri A. Strelenko, N.D.Zelinsky Institute of Organic
Chemistry, Leninsky prospect 47, 117913 Moscow B-334,
Russia.
Fax (7-095) 135 5328
Tel (7-095) 135 9094
E-mail strel@nmr1.ioc.ac.ru
*********************************************************************
| Dr. Yuri A. Strelenko | |
| N.D.Zelinsky Institute | Fax (7-095) 135 5328 |
| of Organic Chemistry, | Tel (7-095) 135 9094 |
| Leninsky prospect 47, | e-mail strel@nmr1.ioc.ac.ru |
| 117913 Moscow B-334, | |
| Russia | |
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