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Gel incorporation inside of organic single crystals grown in agarose
hydrogels†
Published on 16 June 2010. Downloaded by Technische Universiteit Delft on 07/06/2016 03:30:48.

Hanying Li,a Yuzo Fujiki,b Kazuki Sada‡b and Lara A. Estroff*a

Received 20th April 2010, Accepted 20th May 2010
DOI: 10.1039/c0ce00118j

Calcium tartrate tetrahydrate and a-glycine single crystals grown in matrix, it is necessary to know how general this gel-incorporation
agarose hydrogels incorporate agarose polymer networks, resulting phenomenon is. In this work, we investigate two model crystals to see
in polymer/single-crystal composites. whether or not they incorporate the gel matrix when grown within
agarose hydrogels. Glycine and calcium tartrate tetrahydrate (CTT)
crystals are typical models for the study of crystal growth. Glycine is
Crystal growth in gels has interested scientists for more than one useful for polymorph and crystallographic orientation selection
century. As ‘‘the best and most versatile growth media’’ for crystals, studies,6 while CTT is commonly used for the study of crystal growth
gels have advantages over solution growth because they can control in gels.1,7
both nucleation and growth during crystallization.1 In a gel, nucle- Glycine crystals were grown in 1 w/v% agarose hydrogel by
ation is suppressed and only a limited number of nuclei grow into diffusing ethanol vapor into the hydrogel, which was made from
large crystals in a stable, diffusion-dominated mass-transport envi- a glycine solution (60 mg mL!1). Millimetre-sized solids were
ronment. A large variety of gel-grown crystals have been prepared obtained (Fig. 1a) and a block of solid was randomly cut for crys-
and studied.1 Among these crystals, calcite was found, surprisingly, tallographic investigation using single crystal X-ray diffraction
by Nickl and Henisch to incorporate the silica-gel media and become (XRD) (Table 1). The results show that the block of solid diffracts
a gel/single-crystal composite.2 More recently, we have demonstrated X-rays as a single crystal, and the solved unit cell parameters are
that calcite crystals grown in agarose gels also incorporate the poly- consistent with reported data for the a-phase of glycine.8 Therefore,
mer network, and that these crystals maintain their long-range order the as-grown solid is a single crystal of a-glycine. The internal
(single-crystal nature).3 In this respect, the gel-grown calcite crystals,
as Henisch pointed out, are similar to biogenic calcite single crystals
that have biomacromolecules such as proteins and polysaccharides
occluded.4 Calcite was, therefore, thought to be ‘‘unique’’ in the sense
that it incorporates gel media while others do not. This apparent
uniqueness was maintained until Garcia-Ruiz et al. reported that gel-
grown protein single crystals trapped silica and agarose gels and
Petrova and Swift found that sodium bromate crystals might incor-
porate agarose gels.5 Until now, however, the types of crystals known
to incorporate gels have been limited.
The discovery of single crystals with incorporated polymer
networks challenges our traditional understanding of single crystals,
which are usually defined as faceted solids with homogeneous
compositions. It also provides a potential approach to prepare new
composite materials with complementary properties of rigid single
crystals and flexible polymers. Nevertheless, given that a very limited
number of crystals have been demonstrated to incorporate a gel

a
Department of Materials Science and Engineering, Cornell University,
Ithaca, New York, 14853, USA. E-mail: lae37@cornell.edu
b
Department of Chemistry and Biochemistry, Graduate School of
Engineering, Kyushu University, Nishi Ku, Fukuoka, 819039, Japan
† Electronic supplementary information (ESI) available: Complete
experimental details and Fig. S1. See DOI: 10.1039/c0ce00118j Fig. 1 (a) An optical microscopy (OM) image of an a-glycine crystal
‡ Current address: Department of Chemistry, Faculty of Science, grown from an 1 w/v% agarose hydrogel; (b and c) FESEM images of
Hokkaido University, Kita 10, Nishi 8, Sapporo, Hokkaido, 060-0810 a gel-grown a-glycine crystal after etching in ethanol for 4 days. White
Japan. arrows highlight the incorporated gel fibers.

1060 | CrystEngComm, 2011, 13, 1060–1062 This journal is ª The Royal Society of Chemistry 2011
 View Article Online

Table 1 Unit cell dimensions of a-glycine and CTT crystals

a-Glycine CTT

Gel-grown crystal Solution-grown crystal8 Gel-grown crystal Solution-grown crystal9

a/Å 5.1050 " 0.0028 5.1020 " 0.0008 9.1847 " 0.0031 9.24 " 0.02
b/Å 11.8830 " 0.0059 11.9709 " 0.0017 10.5439 " 0.0036 10.63 " 0.02
c/Å 5.4760 " 0.0026 5.4575 " 0.0015 9.5835 " 0.0033 9.66 " 0.02
a/deg 90 90 90 90
b/deg 111.8640 " 0.0119 111.705 " 0.017 90 90
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g/deg 90 90 90 90

structure of the single crystals was studied by observing gently etched Contract #C050017), and the Cornell Center for Materials Research
crystals using field emission scanning electron microscopy (FESEM). (CCMR), a Materials Research Science and Engineering Center of
After etching in ethanol for 4 days, fiber networks are visible inside of the National Science Foundation (DMR 0520404). Particular
etch pits (Fig. 1b and c). Since etching reveals the gel networks inside acknowledgement is made of the use of the Optical Microscopy and
of the crystals, we conclude that gel-grown a-glycine single crystals Electron Microscopy facilities of CCMR. L.A.E. and H.Y.L. thank
incorporate the gel polymers.
CTT crystals were prepared by diffusing an aqueous sodium
tartrate solution (40 mM) into a 1 w/v% agarose hydrogel, which
already contained calcium chloride (40 mM). Millimetre-sized solids
precipitate at the solution/gel interface after 15 days (Fig. 2a). The
half of the crystal that grew into the gel (Fig. 2a, right) is more opaque
than the part of the crystal that grew into solution (Fig. 2a, left).
Similar methods as used for the glycine crystals were utilized to study
the crystallography and internal structure of the opaque gel-grown
CTT crystals. A block of solid from the opaque side was cut and
examined by single crystal XRD. The results show that the block of
solid diffracts X-rays as a single crystal of CTT (Table 1).9 Gently
etching the crystals in DI water for 2 days reveals that there are film-
like materials inside of the etch pits (Fig. 2d and e, arrows). These
materials are identified as the incorporated gel polymers. Another
piece of evidence to support gel incorporation is that after a block of
crystal (Fig. 2b) was totally dissolved in a 0.1 M HCl solution,
a transparent, gel-like material (Fig. 2c) similar to the shape of the
original crystal remained. Therefore, gel-grown CTT single crystals
also incorporate the gel polymers.
CTT crystals grown from silica hydrogels have been studied inten-
sively as a model crystal and described not to incorporate the silica-gel
media.1,7 However, this work shows that CTT crystals incorporate
agarose gels. The discrepancy might be due to different gel composi-
tions and/or different growth kinetics between the silica and agarose
gel systems. When a crystal grows in a gel media, whether it will
incorporate the gel matrix or not is mainly determined by three factors:
wetting between the crystal and gel matrix, growth rate, and strength of
gel network.10 Very possibly, by selecting gel-crystal pairs and growth
conditions, more and more crystals will be found to incorporate gel
media. In order to expand the diversity of organic crystals that can be
grown in gels, future work will need to consider using gels formed in
organic solvents (organogels)11 as matrices.
In summary, we grew a-glycine and CTT single crystals in agarose
hydrogels and found that agarose polymers were incorporated into
Fig. 2 (a) An OM image of a CTT crystal grown from an 1 w/v%
the crystals without significantly disrupting the crystalline lattices.
agarose hydrogel. White arrows highlight the interface between opaque
This work extends the generality of gel-incorporated single crystals
and clear parts of the crystal. See text for details; OM images of a block of
grown from hydrogels and shows that the gel method is a promising gel-grown CTT crystal after dissolving in 0.1 M HCl solution for (b) 10
method to prepare single-crystal composite materials, and to min and (c) 24 hours. Image (c) is roughly the mirror image of (b) because
construct single crystals with internal porous structures. the gel material flipped over before imaging; (d and e) FESEM images of
L.A.E. and H.Y.L. acknowledge partial support from the NSF a gel-grown CTT crystal after etching in DI water for 2 days. White
(DMR 0845212), J. D. Watson Investigator Program (NYSTAR arrows highlight the incorporated gel polymers.

This journal is ª The Royal Society of Chemistry 2011 CrystEngComm, 2011, 13, 1060–1062 | 1061

Emil Lobkovsky for assistance with the single-crystal X-ray diffrac-
tion. K.S. acknowledges partial support from Grant-in-Aid from the
Ministry of Education, Culture, Sports, Science and Technology,
Japan (MEXT), and Y.F. acknowledges the JSPS research fellowship
for young scientists and Kyushu University Global COE Program
‘‘Science for Future Molecular Systems’’ from MEXT.
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Published on 16 June 2010. Downloaded by Technische Universiteit Delft on 07/06/2016 03:30:48.
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