Optical Probes of Crystal Growth Mechanisms: Intrasectoral Zoning

Chapter 10

Optical Probes of Crystal Growth Mechanisms: Intrasectoral Zoning 1

1

1,2

Richard W. Gurney , Miki Kurimoto , J. Anand Subramony , Loyd D. Bastin , and Bart Kahr 1

1,*

1

Department of Chemistry, University of Washington, Seattle, WA 98195-1700 Current address: Applied Materials, 3195 Kifer Road,M/S2955, Santa Clara,CA95051

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I m p u r i t i e s present i n c r y s t a l l i z i n g solutions m a y b e c o m e segregated within regions o f the resulting crystals that correspond to specific slopes o f growth hillocks. W h e n the impurities are dyes or luminophores, c h e m i c a l z o n i n g o f this sort results in distinct patterns o f color or light that serve to identify growth a c t i v e surface structures and c r y s t a l g r o w t h m e c h a n i s m s . Moreover, the optical probes reveal the specificity o f non-covalent interactions between molecules and anisotropic h i l l o c k s . These phenomena are illustrated herein for three crystals, potassium d i h y d r o g e n p h o s p h a t e , p o t a s s i u m sulfate, and α - l a c t o s e monohydrate, grown in the presence o f an azo dye, a luminescent benzene derivative, and a naturally o c c u r r i n g anthraquinone, respectively.

Introduction O p t i c a l probes are a mainstay o f the biochemical scientist eager to illuminate the specificity o f non-covalent interactions {1,2). A s crystal growth from solution is also governed by the specificity o f non-covalent interactions, we evaluate here to what extent dyes and luminophores can be used to reveal aspects o f non-covalent assembly during crystal growth. There is o f course an obvious distinction between the use o f optical probes for the study o f biochemistry and crystal growth: space. It is easy to imagine an optical label dangling from a protein o f interest into the cytoplasm as it makes its way about a cell. M o s t crystals, on the other hand, are close packed and can not easily accommodate guests o f arbitrary size. M i t s c h e r l i c h ' s Principle o f Isomorphism, a long-standing

© 2002 American Chemical Society

In Anisotropic Organic Materials; Glaser, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2001.

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constraint on the preparation o f solid solutions, asserts that m i x e d crystals shall be limited to components having similar sizes and shapes (3,4). The successful use o f the Principle o f Isomorphism in single crystal matrix isolation is w e l l illustrated by the host/guest hydrocarbon pairs in Figure 1. In the examples o f naphthalene in durene (5,6), diphenylmethylene in benzophenone (7,8,9), and pentacene in pterphenyl (10,11,12,13) exquisite matches o f hosts and guests enabled scientists to address particular scientific questions. M c C l u r e has also illustrated many examples o f the single crystal matrix isolation o f inorganic ions (14).

Guests

Hosts

b

d

f

Figure 1. Analyte guest and crystal host pairs in classic examples of single matrix isolation: (a) naphthalene, (c) diphenylmethylene, and (e) pentacene durene, (d) benzophenone, and (f) p-terphenyl, respectively.

crystal in (b)

In the aforementioned experiments it is t y p i c a l l y assumed that the guest is uniformly distributed throughout the host; however, this need not be the case. I f the crystal growth conditions are not carefully controlled or the relative concentration o f host and guest varies, the crystal is subject to concentric or temporal zoning in w h i c h composition changes during growth, Figure 2a. Favorable and unfavorable conditions for the incorporation o f an impurity may oscillate resulting in concentric polygons in cross section, Figure 2b. A s growth circles record a tree's history, concentric z o n i n g records a crystal's maturation and morphological history (15,16,17). In the fields o f mineralogy and petrology the concentric zoning o f trace metals or elemental ions within minerals has been studied in great detail (18,19). Heterogeneous incorporation o f impurities among crystal g r o w t h sectors, volumes o f a crystal that have grown in a particular direction through a specific face, is termed intersectoral zoning, Figure 2c. Here, the segregation is spatial as opposed to temporal (20,21,22). T h i s is a general feature o f impure crystals i n w h i c h s y m m e t r y distinct facets express different affinities for i m p u r i t i e s . While intersectoral zoning has been described in minerals with trace elements (18,19) and in synthetic crystals marked by dyes (23,24,25,26), a molecular level o f understanding was first presented by A d d a d i , Lahav, L e i s e r o w i t z , and their colleagues in their extensive studies o f solid solutions (27,28,29). Their 'Tailor-made A u x i l i a r i e s ' o f crystal growth demonstrated that nonsymmetry related facets must incorporate impurities differently, often resulting in a lowering o f the host's symmetry (30,31).


145 impurities may also inhomogeneously deposit w i t h i n a single growth sector depending on the crystal's surface topography. Surfaces o f crystals g r o w n in the lower supersaturation regime often propagate through a dislocation w h i c h produces g r o w t h spirals or h i l l o c k s : s h a l l o w stepped pyramids w i t h single or m u l t i p l e dislocations at the apex (32,33). Polygonization o f hillocks partitions the parent face into v i c i n a l regions, each having slightly different inclinations. Impurity partitioning w i t h i n vicinal regions, intrasectoral zoning, results from the selective interactions o f impurities with particular stepped h i l l o c k slopes, Figure 2e. Intrasectoral z o n i n g therefore provides more detailed information about recognition mechanisms because the active growth surfaces at the time o f incorporation are more fully defined. The identification o f intrasectoral z o n i n g patterns enabled the determination o f the mechanism o f trace element partitioning in the minerals calcite [ C a ( C 0 ) ] , topaz [ A l S i 0 ( F , O H ) ] and apatite [ C a F ( C a ( P 0 4 ) 2 ) 3 ] (18,19,34,35,36,37,38).


3

2

4

2

2

3

Figure 2. Idealizations of compositional zoning in an orthorhombic crystal from seed: (a,b) concentric, (c,d) intersectoral, and (e,f) intrasectoral zoning. represent cross sections, indicated by broken lines in (a,c,e), respectively.

grown (b,d,f)

In recent years we have explored in detail the intersectoral z o n i n g o f dyes in simple, transparent host crystals. W e showed how structural studies o f dyed K S 0 crystals (39) led to the design o f new mixed crystals with prescribed properties such as lasing (40). D y e d acetate crystals were used as models for the study o f matrixassisted r o o m temperature phosphorescence (41) and o p t i c a l probes i n s i d e ferroelectric crystals such as Rochelle salt were used to monitor phase transitions (42). W e reinvestigated molecular crystal hosts for dyes (43,44) and also studied b i o m o l e c u l e s w i t h intrinsic chromophores (45). Y e t , despite the hundreds o f examples o f intersectoral zoning o f dyes and luminophores we had observed, not a single unambiguous case o f intrasectoral zoning was encountered. Zaitseva and coworkers perfected K H P 0 ( K D P , space group l-42d) (46) crystal g r o w t h conditions as a prerequisite to the development o f the N a t i o n a l Ignition Facility. In their hands, amaranth (1), Figure 3, an anionic dye that we had shown to have an exclusive affinity for the {101} surfaces o f K D P (47,48,49), was both interand intrasectorally zoned (50). This observation required introduction o f the dye 2

2

4


4

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during late growth thereby coloring only a thin surface layer so that patterns were not confounded by moving dislocation cores, Figure 4a. Figure 4b highlights the (101) face o f the K D P / 1 crystal in Figure 4a. The stripes result from 1 partitioning w i t h i n the A and Β regions o f the p o l y g o n i z e d h i l l o c k s prevalent on the pyramidal faces, Figure 4d. A differential interference contrast ( D I C )

Figure 3. Amaranth

(1).

Figure 4. a) Top, Left: Photograph of KDP/L b) Top, Right: The heterogeneous incorporation in the (101) pyramidal growth sector is apparent in this closer view (linear dimension 3.25cm). c) Bottom, Left: DIC micrograph of a pure KDP hillock (linear dimension 0.15mm), d) Bottom, Right: Schematic representation of (b).


147 micrograph (51) o f a representative {101} h i l l o c k is shown i n F i g u r e 4 c . A s illustrated in F i g u r e 4 d , the majority o f h i l l o c k centers terminated at the [010] intersection. The likely positions o f the centers are illustrated had they not been o v e r g r o w n . The horizontal band i n the center right o f Figure 4b presumably corresponds to a Β slope (52). A s the identification o f intrasectoral z o n i n g patterns was instrumental i n determining m i x e d crystal growth mechanisms o f minerals w i t h trace elements as w e l l as the partitioning o f 1 within the pyramidal growth sectors o f K D P , we sought other examples among our dyed crystals. B e l o w , we demonstrate how the analogous use o f a fluorescent probe for K S 0 crystals and a dye with α - l a c t o s e monohydrate crystals can be used to identify active growth surfaces. Downloaded by COLUMBIA UNIV on September 17, 2012 | http://pubs.acs.org Publication Date: November 2, 2001 | doi: 10.1021/bk-2001-0798.ch010

2

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Salt Crystals: Sulfonated Anilines and Potassium Sulfate E v e n though, to the best o f our knowledge, growth h i l l o c k s on K S 0 crystals have never before been observed, B u c k l e y commented on the "rounded and uneven" nature o f the {021} surfaces (25), w h i c h Tutton had earlier referred to as "striated and distorted (53,54)" W h e n crystals o f K S 0 , Figure 5, were grown from a solution containing m M quantities o f aniline-2-sulfonate (2), Figure 6, five distinct growth sectors {001}, {011}, {021}, {110} and {111} became luminescent, and each d i s p l a y e d a unique o p t i c a l signature (55). In addition to this h i g h degree o f intersectoral zoning, the {021} growth sectors displayed a pronounced blue banding characteristic o f intrasectoral z o n i n g where 2 was found in the Β but not the A regions, Figure 7. The partitioning o f 2 results from the selective recognition o f a specific slope o f the h i l l o c k s on the K S 0 (021) face, as e m p h a s i z e d in the comparative D I C and fluorescence micrographs in Figure 8. 2

2

4

4

2

4

a

Figure 5. K S0 crystals are typically bound by {021}(q') {110}(p), {010}(b), (lll}(o) and {011}(q) faces and occasionally display {001}(c), {031}(q"), {100}(a), {112}(o'), and (130}(p) facets. Indices are based on optical goniometry (a = 5.772 A,b = 10.072 A, c ^7.483 A, space group Pmcn) (25,56). 2

4

t


148


Figure 6. Aniline-2-sulfonate

(2).

=

Figure 7. (a) Left: Luminescence (Xjf . = 388 nm and Xphosp. 454 nm) of a K SO/2 mixed crystal illuminated with ultraviolet light (λ = 254 nm). Lateral dimension is 1.0 cm. Dark spot in the lower right hand corner of photo is epoxy used for mounting during goniometry. Emission from 2 does not correspond to growth sector boundaries but to vicinal regions on the {021} faces, (b) Right: Idealized representation of crystal shown on the left. llor

2

Figure 8. (a) Left: DIC micrograph of intrasectorally zoned KjSO/2 mixed crystal shown in Figure 7. The two "comet-like " objects are regions having slopes similar to the "top" portion of the image, (b) Right: Luminescence micrograph of the region shown on left. Luminescence of 2 is visibly confined to the steeper sloped region of the hillocks. The horizontal axis is parallel to the [100] direction, the top of the image is closer to (010) than (001).


149 The hillocks on the surface o f K S 0 / 2 m i x e d crystals are ideally represented in Figure 9. The step train propagating toward (010) has the largest advancement velocity, υ , and has straight steps. A s the steps begin to curve, Figure 10a, a boundary is formed between the A and Β vicinal faces: compare Figures 8, 9 and 10a. The step flats shown in the slice in Figure 9 index as (021) on either side o f the apex, w h i l e the step risers in the A and Β regions index as (031) and (011) faces, respectively. 2

4

Α

It is evident from D I C micrographs o f the {021} faces o f pure and m i x e d K S 0 crystals that 2 does not induce the formation o f the hillocks but affects their overall morphology, Figure 10. The doped crystals are often dominated by a small number o f macroscopic hillocks, while the pure K S 0 crystal surfaces are generally covered with a greater number o f smaller hillocks. 2


2

υΑ » υ Β

υ

Α

4

υΒ

Figure 9. Idealized representation

of K S0 2

4

{021}

hillock.

Figure 10. DIC micrographs, (a) Left: K SOV2 mixed crystal (lateral dimension mm), (b) Right: pure K S0 crystal (lateral dimension 2.5 mm). 2

2

4

4


2.5

150


Sugar Crystals: C a r m i n i c A c i d and α-Lactose Monohydrate R e c e n t l y , we have shown that α - l a c t o s e monohydrate ( L M ) crystals incorporate b i o p o l y m e r s such as green fluorescent protein ( G F P ) in specific growth sectors, namely (010). The protein gains substantial kinetic stability since the large amplitude vibrations that precede denaturation are dampened in the crystal (57). In order to better understand the partitioning mechanism o f guests within L M crystals, we sought simpler compounds that displayed analogous behavior. α - L a c t o s e monohydrate ( L M ) is a simple disaccharide made from galactose and glucose, Figure 11. A n aqueous grown L M crystal (space group P2\) (58) is shaped like a hatchet with (010), {0-11}, {100}, {110}, {1-10}, {1-50} and (0-10) faces. L M crystals nucleate at the apex o f the hatchet and grow unidirectionally toward +b through a spiral growth mechanism with dislocations propagating along [010] (59), as confirmed by the recent observation o f hillocks on the (010) face by atomic force microscopy ( A F M ) (60,61).

Figure 11. α-Lactose (4-0-$-D-galactopyranosyl-a-D-glucopyranose) (top) and carminic acid (3) (7-fi-D-glucopyranosyl-9 10-dihydro-3,5,6,8-tetrahydroxyl-lmethyl-9,10-dioxo-2-anthracenecarboxylie acid) (bottom). t

D I C microscopy o f a pure L M crystal reveals a typical single polygonized h i l l o c k that partitions the (010) surface into four vicinal faces pairwise related by t w o - f o l d symmetry, Figure 12a. A n idealized representation o f the hillock based on A F M and D I C results is pictured in Figure 12b. The elementary growth steps have an average step height equal to the b dimension and have a greater advancement velocity in the Β and B ' vicinal faces as compared to the A and A ' vicinal faces. C a r m i n i c acid (3), Figure 11, a natural red dyestuff produced by the female C h o c h i n e a l beetle (Dactylopius coccus) (62), recognizes the (010) face o f L M exclusively, as does G F P . If the {0-11} face o f a L M / 3 crystal is observed obliquely 3 is seen to be partitioned w i t h i n two distinct bands, suggestive o f intrasectoral z o n i n g , Figure 13. T h i s partitioning was q u i c k l y interpreted w h e n b r i g h t f i e l d absorbance and corresponding D I C micrographs o f the (010) face o f the L M / 3 crystal


151


were compared, Figure 14. It is observed that 3 selectively interacts with the Β and B ' v i c i n a l faces o f the h i l l o c k , Figure 14a. Furthermore, it is conceivable that incorporation o f 3 is concurrent with the onset o f the dislocation because the color emanates from a point other than the nucleation sight, Figure 13. E v e n though the center o f the hillock cannot be located in the D I C micrograph due to etching, the dye reveals its location, Figure 14.

Figure 12 (a) Left: DIC Schematic representation regions A, A \ B, and Β direction of crystal is 0.6

9

Figure

micrograph of a pure LM crystal (010) surface, (b) Right: of the hillock on the (010) face illustrating the four vicinal pairwise related by two fold rotational symmetry. Lateral mm.

13. (a) Left: A brightfield reflected light micrograph

(1.2 (h) χ 0.8 (w) x0.5

3

(d) mm .

glare from the edges. Absorption sector boundaries,

of a LM/3 mixed

The image was electronically

processed

of 3 (λ™* = 500 nm) does not correspond

(b) Right: Idealized representation

of crystal in (a).


crystal

to remove to growth


152

Figure 14. Micrographs of LM/3 mixed crystal (010) surface: (a) Left: brightfield reflected light showing absorbance. b) Right: and reflected light with DIC. Lateral dimension of crystal is 0.6 mm.

Conclusion Recent studies, particularly by scanning probe microscopies, have revealed the role o f steps, kinks, and other emergent structures in directing the adsorption o f guests or impurities during crystal growth. Ward's studies o f ledge directed epitaxy (63,64), and H o l l i n g s w o r t h ' s demonstration o f spiral growth nucleated in incommensurate urea inclusion compounds (65) stand out as exemplary illustrations o f this sort. Here, we have shown that colored or light emitting molecules can under certain conditions also image growth active surface structures. In so doing, molecular probes reveal to the eye the macroscopic features o f crystal growth mechanisms. A t the same time, the selectivity o f molecular guests for vicinal slopes o f a given growth spiral stand out as previously underexplored examples o f molecular recognition. G i v e n the specificity o f the recognition processes illustrated herein, it is not surprising that the optical probes, once trapped inside o f the crystals, are h i g h l y oriented. W e do not have space in this account to discuss the orientation o f 1, 2, and 3 in their respective hosts, but we have studied the orientation o f these and other guests in crystals by measurements o f linear dichro\$m(39,44,47), fluorescence anisotropy, and in the case o f guests with long-lived triplet states, single crystal E P R (41,55). The formation o f "oriented gases" o f chromophores in this w a y is useful for the interpretation o f anisotropic physical properties, especially when the property to be measured is the electronic structure o f a dye, because molecules must be oriented and isolated from one another to avoid coupling and preserve the monomolecular characteristic o f interest. Thus, optical probes, " T a i l o r - M a d e A u x i l i a r i e s (31)" w i t h optical signatures easily administered to crystallization solutions, preserve dynamic information about crystal growth mechanisms, the subject emphasized in this report while the anisotropy o f the guests spectral properties preserve information about the microscopic interactions between guests and hillock slopes.


153 Experimental A l l chemicals were reagent grade, purchased from A l d r i c h C h e m i c a l C o . except for potassium phosphate monobasic ( P r o C h e m ) and potassium sulfate ( M a l l i n k r o d t ) . D e i o n i z e d water for crystallizations was distilled using a C o r n i n g Mega-Pure System MP-1. T y p i c a l growth solutions for K S 0 crystallizations contained > 25 m g guest per gram o f host. Guest concentrations in crystals were determined from the absorbance o f dissolved crystals. T y p i c a l m i x e d crystals were g r o w n in 5 to 7 days by s l o w evaporation from dishes inside an undisturbed cabinet. F o r K D P crystallizations see reference 50. Downloaded by COLUMBIA UNIV on September 17, 2012 | http://pubs.acs.org Publication Date: November 2, 2001 | doi: 10.1021/bk-2001-0798.ch010

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4

Ion-free α - l a c t o s e was prepared by passing the saturated lactose solution through both cation ( A m b e r l i t e IR120) and anion ( A m b e r l i t e I R A 4 0 1 ) exchange resins. T y p i c a l growth solutions for L M crystallizations contained 1 m g o f guest per gram o f host. T y p i c a l m i x e d crystals were grown in 3 to 4 days by slow evaporation from a 24 multi-well plate at room temperature inside an undisturbed cabinet. Crystals were indexed optically using a S T O E Darmstadt optical goniometer and a L e i c a D M L M reflected light microscope with spindle stage. Crystals were also indexed with x-rays using a N o n i u s K a p p a C C D Diffractometer. T o preserve surface structures, crystals were p u l l e d through a layer o f hexanes sitting atop the growth solution, washed with hexanes, and carefully dried with K i m w i p e s (32). Linear D i c h r o i s m measurements were performed on a SpectraCode M u l t i p o i n t Absorbance-Imaging ( M A I - 2 0 ) M i c r o s c o p e w h i c h consists o f an O l y m p u s B X 50 polarizing microscope connected to a Spectra Pro-300i triple grating monochrometer ( A c t o n Research Corporation). A fiber optic cable containing a linear stack o f 20 fibers connects the microscope to the monochrometer and Princeton Instruments C C D detector. The instrument is controlled using the program KestralSpec. U l t r a v i o l e t a b s o r p t i o n spectra were r e c o r d e d w i t h a H i t a c h i U - 2 0 0 0 spectrophotometer c o n t r o l l e d w i t h S p e c t r a C a l c software ( G a l a c t i c Industries). Differential interference contrast images were obtained with a L e i c a D M L M reflected light microscope and captured with a Diagnostic Instruments S P O T digital camera.

Acknowledgements We thank the National Science Foundation (CHE-9457374, C H E - 9 7 2 7 3 7 2 ) , the University o f Washington Royalty Research Fund, the donors o f the A m e r i c a n C h e m i c a l Society-Petroleum Research Fund (30688-AC6), the National Institutes o f Health ( G M 5 8 1 0 2 - 0 1 ) , and the University o f Washington Center for Nanotechnology for financial support. W e also thank Scott L o v e l l and D o n g Q i n for their assistance. We extend special thanks to Natalia Zaitseva for gifts o f K D P crystals and for advice on crystal growth techniques.


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