A Tho1
Points
Light:
P a w J. Tread0 and Michael D.
hlo&
Department of Chemisby
The University of Michigan
Ann Arbor. MI 48109-1055
Most chemists appreciate the impact of
the Fourier transform on chemical
analysis. IR spectroscopy and NMR
spectroscopy were revolutionized by
the introduction of multiplexing in-
strumentation that produced the Fou-
rier transform of the desired spectra.
Somewhat less familiar, but no less im-
portant, are image- and signal-process-
ing techniques that are based on the
Fourier transform. Not all chemists are
aware that the Fourier transform is just
one of several related linear trans-
forms. The Fourier transform is based
on sines and cosines; the other trans-
forms are based on other periodic func-
tions.
The Hadamard transform is the
most common of these alternative
transforms. Based on square waves
rather than on trigonometric functions,
this transform can be applied in three
different areas in analytical chemistry.
First, it is used to multiplex or encode
analytical signals so that many signals
.can he measured simultaneously. In
Hadamard techniques the multiplexer
turns elements on and off or makes
them switch between two values. The
same formalism describes multiplexing
schemes in which pseudorandom se-
quences are employed to excite a sys-
0003-2700/89/0361-723A/$01.5010
@ 1989 Amerlcan Chemical Society
,tern. In general, Fellgett's advantage,
the signalhoise ( S / N ) ratio improve-
ment from multiplexing many signals,
is sought. Fellgett's advantage can he
realized if the detector is noisy, because
one unit of detector noise is distributed
.among all the measured signals.
Second, the transform is used in
multiplexed imaging. Here, the goal is
usually to obtain spatially resolved sig-
nals without focusing a high-intensity
source on a sample. Fellgett's advan-
taee
~"~ ~-
mav he absent. A Dower distribu-
~~ ~ ~~
tion advantage is avhahle; source
powers can he 2 or 3 orders of magni-
tude higher than for tightly focused ra-
diation.
Finally, the Hadamard transform is
used in data transformations. Informa-
tion is redistributed so that signal com-
pression (i,e., truncation of the trans-
4
lNS~RUMEN7A7lON
form) can occur without loss of essen-
tial features. The transform is also used
before transmission of signals so that
the effects of corruption of one or more
data words are distributed over the en-
tire signal, rather than causina severe
localized loss of information. Here,
workers often emphasize the computa-
tional efficiency of the Hadamard
transform compared with that of the
Fourier transform.
These areas of application were de-
fined by about 1970. Analytical chem-
ANALYTICAL CHEMISTRY. VOL. 61. NO. 11. JUNE 1, 1989
ists are most familiar with the use of
Hadamard multiplexing schemes for
IR spectroscopy (I).Hadamard encod-
ing of the output of dispersive spec-
trometers proved less attractive than
multiplexing with a Michelson interfer-
ometer, which requires a Fourier trans-
form to recover a spectrum. Investiga-
tion of other applications of the Hada-
mard transform has continued in many
laboratories worldwide. Elegant tech-
nical advances in multiplexing technol-
ogy have suddenly revived interest in
spectroscopic applications. Increased
emphasis on spectroscopic microscopy
with laser and other intense sources
has spurred interest in Hadamard in-
aging.
Early developments in Hadamard
techniques were reviewed hy Decker
(2) and by Marshall and Comisarow
(3).There is extensive coverage L. --a.
damard transform spectroscopy, imag-
ing, and signal processing in Griffith's
1978 review volume (4). The 1979 Har-
wit and Sloane monograph (I)on spec-
troscopic and imaging .applications
.. of
Hadamard transforms remains the
standard comprehensive introduction
to both theory and practice in this
field. In this article we will emphasize
recent developments.
Hadamard multiplexing can be un-
derstood from the simple three-ele-
723A
INSTRLJMEN7A7ION
ment case shown in Figure 1. We can
illuminate the three resolution ele-
ments xl, x2, and x 3 one a t a time, as in
Figure la. Three measurements are re-
quired to define the signals at XI, x ~ ,
and x3. However, we can also illuminate
the elements two at a time, as shown in
Figure lb. In this case, we can com-
pletely define the system by a set of
I"
1 i=1
724A ANALYTICAL CHEMISTRY. VOL. 61, NO. 11, JUNE 1, 1989
three equations. These equations can The system can be solved by calculat-
be written in matrix form, as shown. ing the inverse of matrix X,according
The matrix inversion that recovers xl, to Equation 4.
xz,andxafrom themeasuredyl,yp,and
y3 is called an inverse Hadamard trans- x=s-1.y (4)
form. The operation connecting the xi The matrix S-I is computationally easy
with they; is the Hadamard transform to generate and is given by Equation 5.
itself.
In a practical multiplexing system,
hundreds or even thousands of ele-
ments are multiplexed. The principles Here W is a matrix that has -1's where
remain the same whatever the number S T bas 0's and +l's where ST has +l's.
of multiplexed elements. What is im- Matrix S, called a Sylvester matrix,
portant is that the multiplexing in- is derived from a Hadamard matrix,
volves switching some elements on (i.e., which contains elements +1 and -1
multiplication by +1) while leaving only. Despite this, the operation is
others off (i.e., multiplication by 0). called a Hadamard transform. Rules
The multiplexing sequence is a system- and algorithms for generating suitable
atic set of combinations of odoff ele- combinations of elements sij have been
ments. Physically, this combination described by Harwit and Sloane ( I ) .
can be realized with mechanical masks, The Hadamard transform may be
electronic or electrwptical switches, or viewed as describing functions using a
any appropriate kind of onloff switch- basis set of square waves. In contrast,
ing system. Fourier transforms use sine waves for
In practice, cyclic systems are used. the basis set. The Hadamard variable
Each Combination is generated from corresponding to frequency is termed
the previous one by shifting its ele- sequency. Many of the familiar proper-
ments one position to the left (or right)ties of Fourier transforms are observed
and placing the overflow in the vacant with Hadamard transforms. The gen-
position. In Figure IC,shifting the five-eral theory of Hadamard transforms
element mask to the left one unit at a and the uses of the transform and se-
time generates the three combinations quency in image and signal processing
of Figure lb. have been discussed by Harmuth (5).
We can generalize the system of Fig- As with the Fourier transform, there
ure 1. Any Hadamard code generates is a fast Hadamard transform (FHT).
the sum of signals from each element In both cases, the matrix defining the
weighted by 0 or 1. transform must be factorable. In the
" case of the Sylvester matrices, the FHT
yj = qjxXi (1) can be defined if the number of ele-
;=I
ments is equal to Zk - 1,where k is an
integer. For the Hadamard matrix,
In Equation 1, yj is the signal from containing +l's and -I%, the FHT is
the j-th combination of onloff ele- defined if the number of elements is
ments, and x ; is the signal generated at some 2k. Because the FHT requires
the i-th element. The vector sj = (s~j, only addition and subtraction, it exe-
su, . . ., s,J has values 1 for each on- cutes about 8-10 times faster than the
element and 0 for each off-element. fast Fourier transform (FFT)on a gen-
To recover all n signals, we need n eral-purpose computer.
measurements. These can be defined In general, Hadamard transform
by the n linear independent equations multiplexing bas the same kinds of ad-
that completely define the system. vantages and limitations as multiplex-
ing using Fourier encoding. Fellgett's
advantage, for example, can be ob-
tained in a spectroscopic system where
detector noise is dominant, but not in a
Yz =c "
%Xi (2.2)
shot noise limited system. Fellgett's
advantage is ahout the same order of
magnitude for both multiplexing
schemes. In each case, the instrument
... analog-to-digital converter dynamic
range must be increased by fi,where n
is the number of channels or signals
multiplexed relative to the require-
ments of a single-channel measure-
ment.
In matrix notation, Equations 2.1-2.n The choice between Fourier and Ha-
may be written as Equation 3. damard encoding depends largely on
the kind of experiment. A Michelson
Y=S.X (3) interferometer automatically produces
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ANALYTICAL CKMSTRY, VOL. 61. NO. 11. JUNE 1, 1989 725A
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a Fourier encoding. For imaging appli-
cations, the simplest spatial encoding
is a system of open and closed aper-
tures, which automatically produces a
Hadamard encoding. Arguments about
small differences in multiplex advan-
tage or even about computation time
are overshadowed by the requirements
of the experiment.
How Hadamard -y and
imaging are dare
Both spectroscopic and imaging appli-
cations require a sequence of Hada-
mard masks that encode the informa-
tion. Either one-dimensional or two-di-
mensional encodings are possible, as
shown in Figure 2. The most common
dask technology is a series of apertures
that are fabricated on a transparent
substrate. Metal films on glass, quartz,
or silicon have been used. Slots milled
in thin sheets of metal have also been
employed. These systems all use cyclic
encodings so that the mask is translat-
ed or rotated by one aperture width to
generate sequential endings. This
principle is illustrated in Figure 2a for a
one-dimensional encoding. The active
aperture area is defmed by a framing
mask. After collection of a complete set
of data points, an inverse Hadamard
transform is calculated to recover the
desired spectrum or image.
Spectroscopy is performed by using
Hadamard masks to encode the dis-
persed output of a grating spectrome-
ter for presentation to a single detector.
Imaging is performed either by encod-
ing the source radiation or by encoding
the image itself.
The same principle can be used to
generate two-dimensional mask se-
quences, as shown in Figure 2b. Here,
the mask is folded. For the 15-element
sequence shown, the f i s t five elements
form one row, the next five form the
second, and the last five form the third
row. The mask is translated one unit
aperture width, as with the one-dimen-
sional sequence. The mathematical op-
erations are the same as for the one-
dimensional sequence. If a plot of the
data is required, it must he rearranged
from a linear sequence into the appro-
priate (+, y) coordinates. It is also pos-
sible to fold the sequence twice, as
shown in Figure 2c. This results in a
more compact mask but requires trans-
lation in two dimensions.
The Fateley group (6-9)has demon-
strated that optical shutter arrays
(OSAs) can he used as Hadamard mask
systems. An OSA, which is also called a
spatial light modulator, contains a ma-
trix of electronically addressable,
switchable elements that can be made
transparent or opaque. A transparent
element represents a 1in a Hadamard
sequence; an opaque element is a 0. An
OSA can generate a complete set of Ha-
damard sequences but requires no me-
chanical movement.
The OSA can be used to construct
multiplexed spectrometers or imaging
devices with no moving parts. Such de-
vices are more compact than mechani-
cal mask systems, provide excellent
spectral subtraction capability, and
may he more rugged. In addition, the
OSA allows selective filtering by leav-
ing certain elements always off, that is,
opaque (9). Here, important opportu-
nities for S/N ratio improvement exist.
! (6). They fabricated a 63-element va-
OSA technology is currently limited to
certain wavelength ranges. For exam-
ple, liquid crystal devices work in the
visible and near-IR hut not in the UV
or through most of the fingerprint re-
gion of the IR.
Hadamard encoding is not limited to
optical or beam spectroscopies. Hada-
mard sequences can he used to define
pseudorandom excitation sequences.
For example, Hadamard sequences of
potential pulses can be used to make
electrode impedance measurements.
Hadamard sequences of rf pulses can
be used for NMR spectroscopy.
Of course, any data set can be sub-
jected to Hadamard transformation.
Image transmission from the early days
of the space program employed this
technique. It is used in pattern recogni-
tion, image compression, and other
postprocessing applications.
Recent s p d m m p l c a p p l h t h
Sugimoto (10) has proposed a slitless
low-resolution near-IR (1-1.8 pm) Ha-
damard spectrometer using a Hada-
mard-encoded 16-element array of
light-emitting diodes (LEDs) as the
source and a 32-element array of ger-
manium diodes as the detector system.
The encoded LEDs replace the slits of a
conventional spectrometer, thus im-
proving the throughput. Here, the mul-
tiplexing provides a Jacquinot or
throughput advantage rather than the
Fellgett's advantage obtained by mul-
tiplexing the dispersed output onto a
single detector. The output of the LED
array is collimated so that a remote
0.25-m spectrometer with a 1-km path
length can be used. With this system,
the minimum detectable absorbance is
2 X 10-5 with a 1-s integration time.
Sugimoto calculates that an absor-
bance of 5 X 10-7 could be reached with
a 30-min integration time. As config-
ured for environmental measurements,
the system is capable of monitoring
"3, CHI, CiH4, CsH8, and the HOz
radical with parts-per-billion detection
limits and 1-stime resolution.
The first grating instrument to em-
ploy stationary electrooptical encoding
masks at the output was an IR spec-
trometer described by Hammaker et al.
nadium dioxide thermodiachromatic
array, which was operated in the 750-

L 2D array stepped horizontally and 1000-cm-' region with 3-cm-' resolu-

venically past the framing mask tion. They demonstrated the expected
Fellgett's advantage and described the
-
Flaure 2. One- wdimensional Hr rd encadinos
(a) A 15-eiemerd linear Wtem of endlngs. Each e n d i n g is formed by shining the mask sequence one
merits of stationary mask systems. Be-
cause of limitations on the size of the
elemsnt to the lm. (b) A twc-dinmnslonal e n d i n g is fwmad ky folding the onedimensional sequence mask, the entire fingerprint region
into Wee mws ot five slemsnrs each. The entire m a y 1s shined me element to me len to generate the could not be sampled at once. It may
next enmding In the sequence. (c)Two foldings genarete a more compact mechanical Implementation.
The flrst five endings are generaad by hwimntal shIS only. The next five encadlngs are generated by
prove difficult to design a spectrograph
shining a m Urn dawn and tollowinghe same hwizonmi shin sequence.The final five encodinga we gen- with a sufficiently flat field or to find a
aretd by shiltlng one m e Unit dorm and folbwiq he same horizontal shnt s~qwnce. material for mask fabrication to allow

ANALYTICAL CHEMISTRY, VOL. 61. NO. 11, JUNE 1. 1989 727A

INSTRUMEN7A7lON
Wavenumbem (cm-1)
Flgure 3. The effect of Rayleigh line re-
jection on Hadamard transform Raman
spectra.
(a) Spctrum of 2-nitropmpane vim m significant
Raylei€& scattered light peMed by the multi-
plexer. (b) and IC)The same spctrum. but wim
increasingly large m n 1 8 of Rayleim a l t e r
peMed by the munipiexer. (Adapted vim pnmir-
6ion horn Rehnence 9.)
acquisition of a complete spectrum.
The limited spectral coverage of
many electmaptical masks can he an
advantage in routine monitoring. Here,
only a narrow spectral region is usually
needed. In contrast, an interferometer,
without prior spectral filtering, records
information from the entire spectrum
at once, generating both excess noise
and some additional computational
burden to recover only the region
sought. In this area the Hadamard in-
strument may he both theoretically su-
perior and cost-effective.
In visible and near-IR spectrosco-
pies, Fateley and co-workers (6-9,II)
have used liquid crystal optical shutter
arrays (LC-OSAs) as stationary Hada-
mard mask systems. Current commer-
cial devices are useful at wavelengths
above -530 nm, but future versions
may operate further in the blue. With
an LC-OSA this group has demonstrat-
ed Hadamard Raman and atomic emis-
sion spectroscopies. The Fateley group
has encoded the output of a 1-m suh-
tractive double spectrometer equipped
with 1180 groove-per-millimeter grat-
ings. Because the LC-OSA used has a
0.6-mm aperture, the available resolu-
tion was about 30 cm-1.
Raman spectroscopy is a difficult ex-
periment for any multiplex technique,
as practitioners of FT-Raman have
pointed out (12).The source noise on
728A ANALYTICAL CHEMISTRY, VOL. 61, NO. 11. JUNE 1, 1989
the intense Rayleigh line is redistribut-
ed across the entire spectrum by either
Hadamard or Fourier multiplexing.
This problem is exacerbated with the
LC-OSA, because the device has appre-
ciable off-state transmission (7,8).Ha-
damard encoding allows rejection of
much of this noise by placement of an
extra mask in front of the OSA ele-
menta, which encode the line. The ef-
fect can be seen in the 2-nitropropane
Raman spectra shown in Figure 3. Mul-
tiplexing allows acquisition of Raman
spectra using visible or near-IR excita-
tion. Fateley and co-workers have dem-
onstrated that multiplexing generates
excellent S I N ratio Raman spectra
with uncooled silicon photodiodes as
detectors.
As with IR spectroscopy, a real ad-
vantage of Hadamard multiplexing
over Folvier multiplexing is that the
entire spectrum need not be encoded at
once. Hadamard Raman spectroscopy
may prove superior to FT-Raman for
routine monitoring over a restricted
wavenumber range. Using current
technology at least, it is easier to gener-
ate a complete multiplexed Raman
spectrum interferometrically than with
a Hadamard mask system.
There is an exact analog of dispersive
Hadamard spectrometry available for
mass spectrometry (13, 14). The ions
dispersed by a conventional magnetic
sector instrument are passed through a
sequence of Hadamard masks con-
structed as slits in metal and mechani-
cally translated and then detected with
a single-channel detector. Fellgett's
advantage is obtained.
ask 1
R 4. Operation of a &element Hadamard imaging sysi
The 63 encodiw of the image of the nullzHai"2" are generated by 63 sB(IuencBs, which are rep868m-
~ row of the Sylvester nmtslx, S:The encodingr on average rep8wm abouf haif the imensw
ed by t h 63
in the image. ma Inverse Syiwstw matrix. S-', is multiplied by me vectw of the 63 encOded signaia to
IecOvBT he imgs Of the "Um(YBI.
Recent imaging appllcatians
Hadamard multiplexing is well suited
to multiplexed imaging. Two types of
imaging are possible: signal-encoded
imaging and source-encoded imaging.
In source encoding, the excitation
source is encoded with a sequence of
Hadamard masks. In signal encoding,
the signal image is multiplexed. The
operation of a two-dimensional signal-
encoded imager is depicted in Figure 4.
The image is projected through a series
of Hadamard masks, each containing
63 elements folded into 9 X 7 arrays.
The encoded signals are then projected
onto a single-element detector. Upon
reverse Hadamard transform of the 63
independent signals, the spatially re-
solved image can be recovered.
Image (signal) encoding offers ad-
vantages with optical spectrwopies
involving reflected, scattered, or emit-
ted light. The image flux is usually far
less intense than the source flux, so the
mask does not have to he rugged. A h ,
diffraction from the mask apertures of
the incoherent image is less severe than
that of the coherent laser source.
Where imaging detectors do not ex-
ist, source-encoded multiplexing,
which is generally applicable to any lin-
ear spectroscopy, is often the most
practical form of imaging. The alterna-
tive to source encoding is tight focusing
or other generation of a small-area
source and raster scanning of the
source across the image. Even when
there is theoretically little or no classi-
cal multiplex advantage, e n d i n g al-
lows use of unfocused beams. In that
Trp
Recovered
image
 case the local source flux or power den-
sity can be reduced by at least 2 or 3
orders of magnitude. High signal inten-
sities can be maintained, and the possi-
bility of sample damage is minimized.
Our group has called this a power dis-
tribution advantage, which perhaps is
as commonly sought as classical multi-
plex advantages in Hadamard imaging.
We have investigated the imaging
properties of Hadamard systems gen-
erally (15-17).We have shown that for
a system of uniform mask elements,
resolution is ideally determined by
convolution with a unit aperture. In an
optical system, an encoded source
beam can often be condensed to im-
prove resolution or an image can be
magnified before encoding. In these
ways diffraction-limited Hadamard
imaging, in principle, is possible.
IR and visible Hadamard imaging
was demonstrated by Harwit and co-
workers in the early 1970s. All of this
work used dispersive spectrometers to
achieve spectral resolution. However, 1
Kraenz and Kunath (18) coupled a Send foryour FREE 8 page
two-dimensional Hadamard imaging
system to an FT-IR micrhscope. By Condensed Catalogtodav!
taking a complete interferogram at I
each step of the Hadamard sequence,
they obtained complete spatialhpec-
tral images at spatial resolution up to
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Hadamard imaging for an important tion of instruments, technical sup- metals, and inorganics. Accuracy
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rectly over the sample being imaged to
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" EGzG
&*PRINCETON APPLIED RESEARCH
mard multiplexing is necessary. Ex-
cimer lasers can be used as sources for
UV imaging if the encoding masks are
able to withstand high peak power laser
intensities (21). Spatial distribution of
a Imlue. Circle 43 lo have a reprasematlve call.
Circle 42 l

ANALYTICAL CHEMISTRY, VOL. 61. NO. 11, JUNE 1, 1989 728A

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INSTRUMEN7A7ION

tor. Figure 6 is an image of polycrystal-

line benzoic acid obtained with this in-
strument.
Multiplexing can be advantageous in
combination with multichannel Ra-
man detectors. Two-dimensional
(CCD)detectors can provide complete
spectra that are spatially resolved in
one direction but not in two. Hada-
mard multiplexing may provide an in-
expensive route to two-dimensional
spectrdspatial Raman imaging with
these devices.
Several groups (25-ZS),primarily as-
tronomers, have used signal-encoded
Hadamard X-ray telescopes to im-
prove the S/N ratios in observations of
nebulae, solar flares, black holes in
space, and plasmas in nuclear reactors.
The masks are fabricated as holes in
metal foils, and the radiation is direct-
ed to counting detectors.

Figure 5. An image-encoded Hadamard Raman microscope. Hadatnardexcitation seqwnce

The sample 18 illuminated with an unlocuwrd laser beam. me Raman sulnw is coiieclec a r w @ a mn-
applications
b'mtkml canpaund mlomamps and presentedto a Hademard mask 88qyBnce before passage though a Hadamard sequences are pseudoran-
sP63rmWw. Spanal mlution depsnda on Um relation between mtal magnlflultion In the system and dom pulse sequences. Optical and X-
the size of a unn aperture in h e mask. ( m a d with parrnlsslon frm Reference 16.)
ray spectroscopy and imaging use
masks based on these sequences. How;
ever, they can be used to define pseu-
the h e r light is an attractive alterna- coded instrument. Hadamard images dorandom excitations of a system.
tive to attenuation of expensive laser have been obtained with nearly diffrac- An efficient form of ac polarography
power by 2 orders of magnitude. Masks tion-limited resolution. (29-31) uses Hadamard sequences of
containing hundreds of elements are Figure 5 is a diagram of a Hadamard small-amplitude sine-wave harmonics
easily generated and employed in these transform Raman miqroscope con- to exercise a dropping mercury elec-
multiplexing systems (15,22).There is structed in our laboratories. Unfocused trode. The dc response and the in-
little degradation of SlN ratio beyond laser light illuminates the sample. The phase and quadrature components can
that caused by the fador of two attenu- scattered signal is collected, magnified, be obtained simultaneously, allowing
ation of average power that occurs and projected to the encoding mask by complete specification of the cell im-
when masking is used. the microscope optics. Spectral resolu- pedance. The technique is equivalent
Most source-encoded imaging bas tion is provided by the monochroma- to conventional ac polarography, as

1-
been near-field imaging. The mask is
placed as close to the sample as physi-
c a y possible, and the sampled area is
equal to the aperture area This ap-
-,
proach offers limited resolution. For

-
the most part, minimum aperture di-
mensions are limited by fabrication
technologies and have been 50 pm on a
side, or larger. With any optical spec-
troscopy, it is possible to use coarse
masks to e n d e the beams and then to
condense the e n d e d beams, similar
to the way photolithography is done.
This approach has been applied to pho-
tothermal detection (16) and Raman
imaging (23).Masks with 150-400-pm
unit aperture dimensions have been
used to generate images with 13-pm
resolution (16).There is no reason that
diffraction-limited images with resolu-
tion of 0.5jun or less cannot be generat-
ed by this technique, so long as proper-
ly designed imaging optics are used.
Source-encoded Hadamard Raman
imaging (23)andsignal-encodedHada- Figure 6. The image of a benzoic acid crystal (992 cm-') obtained with the instru-
mard Raman microscopy (24) have ment of Figure 5.
been demonstrated. With a signal-en- (~daptedw h permissionhorn R B ~ W ~ C B
17 )

ANALYTICAL CHEMISTRY, VOL. 61, NO. 11, JUNE 1. I989 731A


7
0.0 --
-I
Figure 7. Quadrature(top)and in-
0.1 M KCI, shown at 114.6 Hz.
Excltatlon w w form mplltllde, V, = 50 mV. (Adapted from Reference 30.)
shown in Figure 7, but is more efficient.
As with any Hadamard technique, the
required computations involve no mul-
tiplication or division. A laboratory mi-
crocomputer can perform them in real
time or near real time.
Hadamard pseudorandom excita-
tion has been proposed to improve the
efficiency of multichannel tandem
Fourier transform mass spectrometry
(FTMSAWMS). McLafferty and co-
workers (32,33)suggest the use of Ha-
damard weighted excitation functions
to dissociate differing combinations of
precursor ions. In each step, a different
set of half of the precursor ions is disso-
ciated, while product ion masses are
monitored. The FTMSAWMS spectra
for the product ions are recovered by
inverse Hadamard transform of the
multiplexed spectra. Hadamard trans-
form FTMSAWMS should provide a
Fellgett's advantage over single precur-
sor ion measurements. Other tandem
MS experiments can be similarly en-
hanced.
The Hadamard transform is a linear
transform. The usual inverse Hada-
mard transformation fails if the system
does not respond linearly. B l h i c h and
Ziessow describe techniques for treat-
ing nonlinear saturation effecta in Ha-
damard NMR spectrometry (34).Ha-
damard pulse sequences are useful in
NMR because they allow distribution
of the excitation power over the entire
data acquisition time. Both Hadamard
phase change and amplitude change se-
732A ANALYTICAL CHEMISTRY, VOL. 61,
.
. -
0 .
1 spatial data on samples. Fourier trans-
(bottom)ac polarcgrams of 0.1 mM
quences can be used. However, if high
pulse energies are used, it is necessary
to solve the Blocb equations numeri-
cally and introduce saturation correc-
tion terms into the data treatment for
recovery of the spectral line shapes.
Data lranrfarmations
Hadamard encoding of data sets for
image processing and image compres-
sion was one of the earliest applications
of the transform (35).The computa-
tional efficiency of Hadamard trans-
forms was a major force behind much
of this work. Computational consider-
ations have driven most applications to
chemical data transformations. It was
recognized early that the Hadamard
and Fourier transforma allowed about
the same amount of data compression
by truncation of high-frequency or se-
quency terms.
Recently Zupan and eo-workers (36)
demonstrated that Hadamard and
Fourier transformation are about
equally effective in compression of IR
spectra. Of course, calculation of the
Hadamard transform is about eight
times faster than calculation of the
Fourier transform. Figure 8 shows that
truncation of the high-sequency terms
in the benzenesulfonamide spectra
leads to broadened recovered spectra
with loss of detail. Compressed spectra
recovered a f k r Hadamard transforma-
tion have the high-intensity narrow
portions removed from the top of peaks
before broadening is noticeable.
NO. 11. JUNE 1, 1989
conclusions
Hadamard transformation remains a
field with proven areas of application
and many awaiting exploration. Tech-
nologies for fabrication of moving or
stationary masks are now available for
most of the electromagnetic spectrum.
Computer addressing of stationary
mask sequences (OSAs) is straightfor-
ward. Computer control of stepping
motors and piezoelectric translators is
routine. These advances make once-
difficult imaging and spectroscopic ap-
plications quite practical.
Hybrid multichannel/multiplex ex-
periments may become increasingly
important as ways to use multichannel
detectors to obtain complete spectral/
form spectral encoding and Hadamard
spatial encoding have been demon-
strated in IR spectral microscopy. A
similar approach could prove useful
with Raman spectroscopy.
Much Hadamard imaging has been
near-field imaging. It is now known
that near-field visible imaging can be
used to resolve features 2 orders of
magnitude smaller than the Rayleigh
diffraction limit (37,38).Yet sub-Ray-
leigh Hadamard imaging has not yet
been explored in any region of the elec-
tromagnetic spectrum.
With such exciting prospects we can
expect future progress in Hadamard
transform applications to be rapid and
far from random.
Flgure 8. Effect of truncation of the
Fourier transform (FFT) and Hadamard
transform (FHT) on the recovered 512-
point IR spectrum of benzenesulfona-
mide.
Trumllon of the FFT bmadens the opclrum;
buncallon of me FHT amnuales hlglntensitv
featues. (Adapled vim permiasion hom Refer-
*me 36.)
 ASA
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CIRCLE 32 ON READER SERVICE CARD
ANALYTICAL CHEMISTRY. VOL. 61, NO. 11, JUNE 1, 1989 raa~

(1) Harwit, M. Sloane, N.J.A. Ha&-
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m r d Tmnsform Optics; Academic: New
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(3) Marshall, A. G.; Comisarow, M. B.
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Spectrosc. 1988,42,897-901.
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Find it RA
(iYTdotta,D. C.; Hammaker, R.M.; Fate-
ley, W. G. Appl. Opt. 1987,26,4825-92.
(9) Tilotta, D. C.;heeman, R.D.; Fateley,
1980,52,154€-11.
C.: de Levie,
Chane. C. C.;
(30)Chang,
55-35659.
1983,55
isss, 35659.
Levie. R.Anal. Chem.
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FAST W. G. Appl. S ectmc. 1987,41,12t3&81.

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LabGuide (13) Arikawa, T.Jpn. J. Appl. Phys. 1919,

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IR 211-19
(14) Arikawa. T. In Electronic and Atomic
Collisions;Oda, N.; Takayanagi, J., Eds.
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The LabGuide is where more
than 140 suppliers say, "Here we
199-805.
(15) Fotiou, F. IC; Morris, M. D. Anal.
,&
(31) Harootunian. A.; Betzig, E.; Iaaacaon,
are. Compare our products with Chem. 1987,59,144662. M.; Lewis, A. Appl. Phys. Lett. 1986,49,
(16) Treado, P. J.; Morris, M. D. Appl. fi7A-m
those of our competitors."For Spectmc. 1988,42,1481-93.
example, you'll find typical product (38) Betzig, E.; Harootuninn, A,; Lewis, k,
(11) Treado, P. J.; Morris, M. D.Proc. Int. Ieaccson,
1900. M. Appl. Opt. 1986, 25, 1890-
line ads in the current LabGuide Laser Symp., IV, in press.
from the followingfirms: (18) Kraenz, M. E.; Kunath, D. J. Mol.
Struct. 19&2,79,4740. This work was supported in psrt by the National
(19) Coufal, H.; Moller, U.; Schneider, S. Institutes of Health through grant GM-37W.
AdwrUsers e
ACEGLASS ............... 131
ALLTECH .................... 62
BLUEM .................... 181
CHEMICAL DYNAMICS ..... 197
CONOSTAN .............. 27-28
ELDEX .................... 143
FLUKA CHEMICAL ......... 205
GILMONT .................. 111
GRAPHIC CONTROLS ..... 147
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UICINC. ................... 101 Patrick J . Treado (right) is a third-year graduate student at the University of
VALCO .................... 141 Michigan pursuing a Ph.D. in analytical chemistry. He received his B.S. degree in
WHEATON .............. 99,119 chemistry from Georgetown Universit) in 1985. His research interests are in
Roman spectroscopy, photothermol spectroscopy, and microscopy.
Michael D. Morris (left)is professor of chemistry at the University of Michigan.
The LabGuideIS your true one He received his B.A. degree in chemist0 from Reed College in 1960 and his Ph.D.
Ptop buying source for scientific in chemistry from Harvord University in 1964. After several years on the chemis-
PodUcts. try faculty at Penn State, he joined the University of Michigan in 1969. His
research interests are in analytical laser spectroscopj, with special emphasis on
Roman spectroscopy.

7S4A ANALYTICAL CHEMISTRY. VOL. El. NO. 11, JUNE 1, 1989