CHIRALITY 21:E28–E36 (2009)

Review Article
Experimental Aspects of Solid State Circular Dichroism
ETTORE CASTIGLIONI,1,2 * PAOLO BISCARINI,3 AND SERGIO ABBATE2
1
JASCO Corporation, 2967-5 Ishikawa-cho, Hachioji-shi, Tokyo 192-8537, Japan
2
Dipartimento di Scienze Biomediche e Biotecnologie, Università di Brescia, Brescia 25123, Italy
3
Dipartimento di Chimica Fisica e Inorganica, Università di Bologna, Bologna 40136, Italy

Contribution to the Special Thematic Project ‘‘Advances in Chiroptical Methods’’

ABSTRACT The interest of circular dichroism in the solid state is stimulated by sev-
eral needs, such as the desire to get solvent free spectra, the insolubility of the sample or
the intrinsic process in which the sample itself is prepared or manipulated. We approach
the argument on the basis of the sampling technique, since each different case calls for
specific care in getting proper results. Chirality 21:E28–E36, 2009. V C 2009 Wiley-Liss, Inc.

KEY WORDS: circular dichroism; single crystals; Nujol Mulls; pellets; diffuse
reflectance; suspensions; films; absorption flattening; scattering

INTRODUCTION sample and the selected sampling technique. We will

Lately there has been a revived interest in the proper- therefore review here the topic of solid-state CD following
ties of chiral materials in the solid state. Scientists the different sampling methods, while in the appendix we
employing different techniques, like x-ray crystallogra- will discuss the most used theoretical treatment on the ori-
phy,1 dynamic light scattering,2 or from different areas gin of anisotropy artifacts from conventional spectrometers.
like spectroscopy and separation science3 have dealt
with optical active aggregates of chiral molecules in the
DISCUSSION OF THE LITERATURE AND RESULTS
solid state. Yet the main techniques are optical rotatory
Single Crystals
dispersion and circular dichroism (CD), and scientists
listed above are aware of this and ask for help and col- The ability to obtain reliable CD spectra on single crys-
laboration from experts in the field: this is what has tals along directions other than the optical axis has been a
motivated us in writing this review. Besides Pescitelli difficult task for many years. The target was achieved by a
and coworkers have recently reported that solid-state dedicated spectrometer (J-800KCM) based on an exten-
CD on natural products shows advantages with respect sively modified commercial unit,10,11 which is suitable only
to solution phase CD, when comparing with TDDFT cal- for relatively large sized crystals.
culations, since the number of conformations is reduced The idea of a dedicated CD microscope was tried in the
to the solid-state structure.4,5 past,12 with questionable results, but the dream has been
A previous review on solid-state CD had been published made possible by the innovative development of a CD
10 years ago in this journal by Reiko Kuroda.6 The same imaging microscope,13–15 the idea behind this has also
author gave further important contributions on this subject been patented.16
with other extended texts in different books edited from Both approaches, together with the sister HAUP tech-
2000 to 2008.7–9 nique17-19 (High Accuracy Universal Polarimetry) make
Revisiting today the same argument gives us an oppor- use of a rather different hardware from the common CD
tunity to present a few further developments, but at the spectrometers. The same is true for the promising thermal
same time it allows us to extend the interest originally lens microscope which has not been yet applied on single
focused on inorganic samples. In addition today CD is no crystals.20 On the other hand extensive modifications to a
longer limited to the UV-vis range (ECD) since CD in the commercial spectrometer (JASCO J-820) has recently
IR range (VCD) has become an established, routine tech- allowed CD applications on solid samples (60 3 60 lm
nique: here too solid-state sampling may be important. size) with CCD imaging of the selected sampling area.21
CD spectroscopy has been mainly applied to samples
*Correspondence to: Ettore Castiglioni, JASCO Corporation, 2967-5
in solution phase, which means perfectly isotropic sam- Ishikawa-cho, Hachioji-shi, Tokyo 192-8537, Japan.
ples. On the contrary, solid state samples are often far E-mail: ettore.castiglioni@jasco-europe.com
from ideal in this respect. When using general purpose Received for publication 21 April 2009; Accepted 17 June 2009
DOI: 10.1002/chir.20770
commercial CD spectrometers, potential artifacts may be Published online 31 August 2009 in Wiley InterScience
present in the obtained spectra according to the type of (www.interscience.wiley.com).
C 2009 Wiley-Liss, Inc.
V
 SOLID STATE CD E29

Nujol Mulls
The Nujol mull technique is widely used in IR and less
often in UV-vis absorption spectroscopies: a thin layer of
Nujol (refined mineral oil) film sandwiched between suita-
ble optical windows is transparent all over the UV-vis
range down to well below 200 nm and in most of the IR
range. Fluorolube (perfluorohydrocarbon) is occasionally
used as Nujol alternative, but is far less transparent in the
UV region.
With some care during sample preparation, finely
ground chiral nonracemic powders easily give fair CD
spectra in Nujol mulls: Figure 1 shows the CD spectra of
Binaphtol enantiomers, quality mirror image spectra can
be quickly obtained, since the finely dispersed sample
may be considered of isotropic nature. The main drawback
of the technique is reported to be scattering, a way to com-
pensate had been proposed in the past22,23 using the Shi-
bata opal glass technique,24 which calls for placing a spe-
cial diffuser just after the sample to homogenize the effect.
A good alternative practice is to put the sample as close as
possible to the photomultiplier tube surface (typically
much larger than sample beam) to increase the solid angle
collection and, in instruments with focused sampling
geometry, to place the sample where the beam size is
large enough to compensate patchy sample distribution.
With both these approaches we have however no way
to correct absorption flattening (AF) coming from
inhomogeneous particles distribution in the mull. As a
consequence the simplest approach is to run several spec-
tra at various sample concentrations, since AF is strictly
related to sample absorbance.25 In any case the real main
‘‘diagnostic’’ point is to collect the absorption spectra to-
gether with the CD data, directly or through the conver- Fig. 1. CD spectra (top) and UV spectra (bottom) of (S) and (R) enan-
sion of the high voltage applied to the photomultiplier tiomers of 1,10 -binaphtols in Nujol in black and gray respectively. Notice
that different absorption intensities correspond fairly to different CD inten-
tube. Any distortion in the absorption spectra will indicate sities. Spectra taken with a JASCO J-815SE at the University of Brescia,
either AF effects influencing also CD intensity or abnor- with 1 nm SBW, 1 sec response and 50 nm/min scanning speed.
mal scattering typically limiting the signal-to-noise ratio of
the CD data. In the absorption spectra the two effects go
into different directions: a larger scattering will produce
apparent higher absorbance, while a larger AF will IR transparent pellets. KBr, CsI and KCl are the most fre-
depress the absorption intensity. These simple rules apply quently used ‘‘inert’’ materials, the latter being more UV
to UV-vis CD experiments, while in the IR range there is transparent than the most used KBr. Pellet preparation
no way to increase the solid angle collecting geometry requires a minimum of practice. Samples must be mixed
given the small surface of the detectors, but in this region with KBr or other transparent salts at a concentration of
scattering artifacts are much lower. Properly obtained few percents and mixed so as to obtain a particle size
Nujol mulls from randomly oriented particulate systems ideally lower then the measuring wavelength. The mixture
allow, in quite a few instances, direct comparison between must then be pressed in an evacuable die (to remove hu-
solid state and solution spectra and several examples have midity and to obtain transparent pellets with minimum scat-
been published in the UV-vis26–29 and IR field.30 tering) equipped with separate anvils (in order not to rotate
An unusual application of solid state CD in Nujol mulls the powder when pressure is applied, since this may ‘‘ori-
has been reported under high pressure,31 these experi- ent’’ the sample). The obtained pellet includes two compo-
ments are however very challenging due to the potential nents diffusing the incoming light: the sample itself and the
induced artifacts. salt, so the Shibata opal glass approach suggested for mulls
is in this case performed by the grinded salt itself.
As in the case of Nujol mulls, pellets should be placed
Pellets in the UV-vis CD spectrometers as close as possible to the
There are cases in which the sample is dissolved or is photomultiplier tube surface; in addition some users rotate
chemically modified when it is put in contact with mineral pellets around the light propagation axis at discrete angles
oil. An alternative preparation method is based on mixing to compensate for non constant pellet thickness/surface
the sample with an inert matrix and for pressing UV-VIS/ parallelism and take the average of the different runs.
Chirality DOI 10.1002/chir
E30 CASTIGLIONI ET AL.

Some other users average the reading continuously by

spinning the pellet during the spectra acquisition.
In the pellet technique too the sample is in isotropic
conditions and artifacts from spurious linear polarization
components are largely excluded, but AF effects may well
be present so, as outlined above, it’s essential to extract
also the regular absorption data to verify the consistency
of the measurement.
Pellet techniques have been used in many laboratories,
for a variety of samples including biomolecules,32–43 both
in the UV-vis (ECD) and in the IR (VCD).

IR plates
Commercially available alkali halide sample support sub-
strates (International Crystal Laboratories- Garfield, NJ)
have been proposed in NaCl, KBr or KCl variants for fast
qualitative IR analysis for liquids, mulls, film casting from
solutions. These can be used in ECD and VCD too: a few
drops of a regular VCD solution of (2)-Camphor in CCl4
were dispersed on the NaCl surface and solvent was dried
out in a few minutes. The resulting VCD spectra (with Fig. 2. VCD spectra of R-camphor film deposited on ICL NaCl IR plate.
mild baseline correction) is shown in Figure 2. Spectra taken on JASCO FVS-4000 at the University of Brescia with 1000
accumulation.

Diffuse Reflectance (DR)

Diffuse reflectance (DR) is one of the oldest sampling
techniques in the Vis range; since 193544 color analysis Here too the best results come from very diluted mix-
has been performed using this approach. This is a poten- tures since AF is present; in addition the linearity range is
tial alternative to the pellet techniques with the advantage significantly smaller than in the transmission sampling
of easier sample preparation since a simple mixture methods.
between the grinded sample and the scattering powder Due to the above limitations and the fact that no regular
(or occasionally using only properly powdered sample) is commercial accessory is yet available, reported applica-
enough. When solid–solid chemical interaction between tions are still very few,46–52 but the easy way to get spectra
sample and KBr powder may be a problem,45 Teflon pow- from all sorts of materials may encourage the use of the
der is a suitable alternative for its good scattering proper- technique in the future. In Figure 3 we compare Nujol
ties and inert nature. mull and DR spectra of a Rhodium chiral complex.
The measuring principle is simple: circularly polarized In addition to DR, other reflectance type measurements,
radiation enters through an aperture of an integrating widely employed in IR spectroscopy could be used. A few
sphere, internally coated with BaSO4, MgO or made of years ago an attempt to measure CD in external reflec-
Teflon, and hits the sample placed at an aperture on the tance mode, at an angle close to grazing incidence, with
opposite side. The diffusely reflected radiation is collected an homemade experimental accessory, was reported,53
and reflected many times by the inside surface of the spectra included a lot of artifacts coming from linearly
sphere and at last reaches the photomultiplier tube placed polarized components, but still useful information was
on a third aperture. In an ideal sphere the area of the three extracted.
apertures is negligible with respect to the total area, to Attenuated total reflectance (ATR) is a widely used
allow the largest possible number of reflections: this sampling technique particularly in the IR region.54 No
means that a good sphere is not so efficient since most of CD data have been reported so far; just a simple feasibil-
the radiation is absorbed by the inner sphere surface. This ity experiment has been carried out with a JASCO J-815
limits the signal-to-noise performances particularly in the spectrometer inserting a right angle quartz prism in the
low UV region; several DR applications in the IR are possi- sample compartment and placing the photomultiplier
ble and have been pursued (Gold coated spheres) but no tube on the built-in 908 port. The incoming beam is
DR VCD has been so far reported, due to the expected internally reflected on the hypotenuse of the ATR crys-
sensitivity problems. tal, where an evanescent wave extends beyond the prism
Sample dilution with a transparent powder is necessary surface. If a sample is placed in close contact to the hy-
to reduce spurious influence of the specularly reflected potenuse surface it partially absorbs the evanescent radi-
component, proper grinding (as done for preparing Nujol ation, while most of the light is reflected. To carry on
mulls or pellets) is essential here too for the same reasons. the experiment, the aqueous solutions of the two enan-
Nevertheless qualitative data can occasionally be obtained tiomers of L-Co(en)3Cl3 complex (kind gift of Prof. Sven
without dilution and even with no grinding, but related E. Harnung of University of Copenhagen) were dried on
spectra must be treated with much care. the prism hypotenuse obtaining rather irregular films
Chirality DOI 10.1002/chir
 SOLID STATE CD E31

As a caution: conventional stirring of a suspension in a

cuvette may create vortices with induced supramolecular
optical activity as pointed out recently.63–66
Another recent application deals with nanocrystalline
benzophenone67 where CD spectra in Nujol mull and in
suspension are compared, the experimental part is how-
ever not well described.

Films
The last, and sometimes more challenging, solid sam-
pling system is as films. The term film is rather generic
and includes very different types from stand alone thin
sheets, to solutions deposited and dried on a transparent
window, to Langmuir-Blodgett (LB) depositions, to thin
layers between quartz windows . . . .
Depending on the preparation process, the chiral sam-
ple may be more or less oriented and potential artifacts
due to anisotropic structure may be present in the
recorded CD spectra.
Fig. 3. Nujol mull transmission (black) and DR (gray) CD spectra of While cautions on interpretation of CD of aligned film
L-Rh[(S,S)Phbdtp]3 complex collected on the J-810 of the University of had been reported early,68 the problem was properly
Bologna, with 1 and 6 nm SBW respectively, 1 sec response, 100 nm/min
scanning speed. addressed by a article by Shindo in Biopolymers,69 criticiz-
ing a previous article on the same journal70 about the
and spectra have been scanned (Fig. 4). Considering the induced optical activity by Congo red.
experimental limitations (very poor quality of the sample The film technique has particular relevance for CD of
layer, approximate alignment of the prism in the com- biomolecules; in the IR region the obvious advantage is
partment) and the 458 incidence angle used which for removal of the overlapping water absorption in the amide I
Total Reflectance will be mainly measured, the results
are not so bad. Possible reasons of the different inten-
sities are attributed to AF, as estimated and measured in
transmission on the Nujol mull of the same compound.

Liquid Suspensions
Another form in which solid samples may be analyzed is
suspensions in a liquid, which means either insoluble chi-
ral powders or chiral molecules bound to insoluble par-
ticles, aggregates etc. This topic is of wide interest today
since it finds applications in the fields of biocatalysis or
even therapeutics as illustrated in the literature cited
below.
After an early experimental work54 with a manual/non-
scanning spectrometer, an interesting application
appeared using a liquid medium with the refractive index
matching that of the powder.55
The CD in the low UV of immobilized enzymes on silica
gel particles (tens to hundreds of microns large) has been
the subject of a well detailed article,56 with the aim to
obtain secondary structure estimates, with use of short
path cells close to the photomultiplier tube surface, to min-
imize scattering effects. Sample sedimentation had to be
avoided: this was achieved with a motor driven cylindrical
cell holder, continuously rotating the cell around the light
propagation axis. The AF effects were corrected on an em-
pirical basis, but the cited article stimulated a work of
ours57 and another article58 from one of the coworkers of
the original article on the AF subject.
When the particles have a still smaller diameter, as in Fig. 4. Reflectance-CD and absorption spectra of the L and D enan-
tiomers of Co(en)3Cl3 complex in black and gray respectively. Spectra
case of nanoparticles, experimental difficulties are much taken at JASCO Europe, Cremella, Italy on a modified geometry of the J-
less.59–62 815 apparatus. 2 nm SBW, 0.5 sec response, 100 nm/min scanning speed.
Chirality DOI 10.1002/chir
E32 CASTIGLIONI ET AL.

region. After early studies on polypeptides using the dis-

persive type VCD apparatus in Chicago,71-73 in recent
years consistent progress has been reported by the group
of Polavarapu,74–76 where alternative types of film prepara-
tion have been proposed (supported films, free-standing
films, film-on-film, matrix assisted film formation) with re-
markable results.75 An additional approach, the ‘‘Spray-
Method’’, had been proposed by the Nafie’s group.77
In the UV range after the pioneering work of Fasman78
and Tunis-Schneider and Maestre,79 Brahms et al. studied
DNA films80 with an home-made spectrometer checking
the absence of linear dichroism parasitic effects. Cassim
et al. reported CD on films of purple membranes,81,82 pho-
toreceptor membranes. A process to create multilayer
films (isopotential spin-dry method) has been studied by
Clark et al.83,84 and the method was used by Bazzi and
Woody.85
More recently a-helix-bundle proteins have been stud-
ied as LB films (and in solution).86
Surface pressure effects in LB protein films were stud-
ied by CD and other techniques by Nicolini et al.87 Fig. 5. CD (top) and UV (bottom) spectra of commercial low fat yogurt
(left) and butter samples. Films obtained by squeezing the product
A tendency to increase b-sheet structure in proteins’ between two quartz plates. Spectra obtained at JASCO Europe, Cremella,
films dried on a thin quartz window compared to solution Italy, on a J-815 apparatus. 2 nm SBW, 1 sec response, 100 nm/min scan-
phase samples was observed by Hu et al.,88 whose results ning speed. Gray curves refer to the films placed in the normal sampling
position, black ones putting the sample as close as possible to the photo-
were however criticized by Harada and Kuroda89 using multiplier tube.
the dedicated J-800KCM instrument.10 Nakagawa et al.
studied amino acid films prepared with vacuum sublima-
tion technique.90 A far more detailed article on CD of poly- both VIS and IR range108; the literature on this subject is
methyl-glutamate LB films deposited on a quartz window, very large due to the potential industrial interest on these
with care to avoid linear orientation artifacts and employ- materials.109–111
ing long accumulation times to be able to obtain the weak Supramolecular assemblies J-aggregates in PVA/aque-
signal, was published by Nordén group.91 Ultra-thin pro- ous solution were dried as a film and mounted between
tein films on gold surfaces implied that the averaging of optical glass plates112: CD spectra were collected rotating
999 spectra was needed to get a CD signal of acceptable the sample around the optical axis and about the vertical
signal to noise.92 As an alternative, to increase the CD sig- axis. More recently Yao et al.113 revisited the same topics
nal, a stack of quartz slides with deposited LB films of pep- in solution phase detecting different conformers according
tides had been used.93 to the apparent CD measurements.
Oriented circular dichroism (OCD) as introduced by The apparent CD spectra had been used also by
Huang et al.94–97 is another sort of solid-state sampling Shindo114 to discriminate between achiral polymeric films
technique: membranes containing peptides/proteins are with one or with multiple layer structure, simply collecting
stacked to form a multilayer system and spectra are col- the CD spectra from front and back sides.
lected under controlled humidity and temperature condi- The spectral range in which film techniques are widely
tions. Other research groups are involved in this used is the vacuum ultraviolet region, to remove interfer-
tematic.98,99 ences from solvent absorption. Many applications have
A huge amount of literature data is available on CD film been reported using conventional dispersive,115,116 syn-
analysis and is often related to material sciences. chrotron radiation117,118 or polarizing undulator119,120
Thermal helix inversion in the solid thin films of helical based CD spectrometers.
polymers has been reported for poly(L-aspartic acid Film techniques may be subject to scattering effects
ester),100 poly(thiophene),101,102 poly(isocyanate),103 poly too: Figure 5 shows spectra of dairy products (low fat
(silane)104 and poly(phenylacetylene) spin-casted films by yogurt and butter) measured as a film between two
solvent vapor and heating.105,106 quartz plates in the UV region. Both these samples
Treated films of fluorene polymers show very strong have a very strong intrinsic scattering. Our spectra were
CD effects, spin coated films of different thickness had obtained placing the sample in the normal cell position
been showing a strong nonlinearity between absorption of the cell holder and, in a second run, rather close to
and CD.107 Linear birefringence and dichroism were the photomultiplier tube sensitive surfaces. The data
the probable reason of the phenomena, but no specific clearly show that, while the apparent absorbance spectra
measurement had been carried out. are obviously much less influenced by scattering in the
Photoinduced chirality on azomaterial films deposited close by position, the apparent shapes of the CD spectra
on quartz or BaF2 windows (by irradiation with circularly are substantially kept, despite the strong increase in the
polarized Ar1 laser source) was recently measured in noise.
Chirality DOI 10.1002/chir
 SOLID STATE CD E33

11. Harada T, Shindo Y, Kuroda R. Crystal chirality of the non-

CONCLUSIONS chiral inorganic salt, a-Ni(H2O)6SO4. Chem Phys Lett 2002;360:217–
We have reviewed here the existing literature dealing 222.
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of single crystals, Mulls, Pellets, films on IR plates or else,
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as Suspensions or measured with DR or ATR/Total Reflec-
Circular dichroism imaging microscopy: application to enantiomor-
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E36 CASTIGLIONI ET AL.

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Development of vacuum-ultraviolet circular dichroism measurement The measured CD signal can be expressed in a simpli-
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Appl Spectrosc 2008;62:901–905.
advanced approach of Shindo10 calls for the careful
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vibrational circular dichroism measurement: use of a rotating half- true CD signal can then be extracted averaging the two
wave plate. Theor Chem Account 2008;119:69–79.
measurements obtained rotating the sample 1808 with
129. Tanaka M, Yagi-Watanabe K, Kaneko F, Nakagawa K. Accurate and
quick calibration method for polarizing-modulation spectroscopy
respect to the vertical axis.
using an ac-modulated polarizing undulator. Rev Sci Instrum 2008; Two recent articles on this subject,125,126 while related
79:083102–083109. to CD in the IR (VCD), make use of other similar sim-
plified approaches. Once again in the VCD field Lau-
rence Nafie proposed intriguing hardware modifica-
APPENDIX: ARE THERE WAYS TO CORRECT LINEAR tions,127,128 but still in line with the previously men-
ANISOTROPIES? tioned ideas (Nafie, personal communication). Similar
It’s well-known that solid state CD spectra measured effects of linear anisotropies have also been considered
with commercial spectrometers using polarization-modu- in VUV polarizing undulator.129 In any case a practical
lation technique may include artifacts originating from way to fully compensate large linear anisotropies does
the interaction between macroscopic sample anisotropies not exist with conventional spectrometers. The best
[linear dichroism (LD) and linear birefringence (LB)] approach requires at least the measurement not only of
coupled with the non ideal optical properties of the CD, but also of LD since similar shapes between the
components used in the current CD spectrometers, two spectra are likely to indicate the presence of arti-
which use photoelastic modulators for phase modulation facts in the CD spectra. Collection of both face and
spectroscopy. Several articles have dealt with these back sample orientation spectra is an additional, simple
aspects using Jones or Stokes-Mueller formalisms.121-124 to achieve, must.

Chirality DOI 10.1002/chir