Article pubs.acs.org/crystal
Design of Heterogeneous Nuclei for Lateral Crystallization via Uniaxial Assembly of Cellulose Nanocrystals Zihao Lu,†,‡ Xiaoqing Qi,†,‡ Zhisen Zhang,§ Danqin Yang,†,‡ Qinwei Gao,†,‡ Yuan Jiang,*,† Xiaopeng Xiong,*,‡ and Xiang Yang Liu#,† †
Fujian Provincial Key Laboratory of Soft Functional Materials Research, Research Institute for Biomimetics and Soft Matter, College of Materials, ‡Department of Materials Science & Engineering, College of Materials, and §Fujian Provincial Key Laboratory of Soft Functional Materials Research, Research Institute for Biomimetics and Soft Matter, Department of Physics, Xiamen University, Xiamen 361005, China # Department of Physics, Faculty of Science, National University of Singapore, 117542, Singapore S Supporting Information *
ABSTRACT: Semicrystalline polymers (SCPs) represent a group of cheap heterogeneous nuclei for crystallization. Nevertheless, cellulose, the most abundant biogenic SCP, is notorious for its poor processability. This limits its application as the orientational guiding agent in crystallization of functional compounds. Different from current polymer engineering approaches to uniaxial SCP thin films, we explored a novel approach to the uniaxial cellulose thin film via the oriented assembly of cellulose nanocrystals (CNCs) by means of a simple dip-coating technique. This thin film successfully guides the lateral crystallization of two drug compounds, which in turn reflects the uniformity of the uniaxial CNC alignment on the macroscopic scale. Furthermore, unlike traditional SCP thin films, the assembly route driven by different external forces can lead to CNC thin films with distinct orientational characters for fabrication of patterned drug thin films. The emerging colloidal assembly route to a uniaxial SCP substrate leads to unprecedented access to design heterogeneous nuclei for oriented crystallization of functional hybrids.
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INTRODUCTION Functionality of crystalline thin films is highly affected by the molecular arrangement in each single crystalline microdomain and the lateral alignment of multiple domains across the macroscopic distance.1−6 Therefore, it is ultimately important to explore rational strategies of lateral deposition of various compounds into crystalline thin films to satisfy the increasing functional requirement. Among various coating methods, solution coating becomes increasingly important due to its great potential for developing low-cost manufacturing of flexible electronics and healthcare.1−3 A pioneer study on the porphyrin assembly verified that a dewetting process could lead to patterned nanowires in a distance of hundreds of micrometers.7 From then on, various methods of lateral deposition were rapidly explored, among which those employing emerging nanotechnology have been attracting increasing attention due to their effectiveness in precise control of the ordering and positioning of nanocrystalline domains.3,6,8,9 For example, spatial confinement provided by lithographically induced nanochannels could produce patterned, oriented nanostripes of spin-crossover compounds10 or organic semiconductors11,12 in a dewetting-induced lateral crystallization process. Alternatively, the Ward group reported that oriented nanocrystal arrays of model organic compounds can be © 2016 American Chemical Society
achieved in cylindrical nanopores in an evaporation-induced crystallization process.4,5,13,14 In both approaches, solvent evaporation occurring in the one-dimensional (1D) nanoconfining environment spontaneously generates the consistent shearing force, which functions synergistically with the crystallization behavior of target compounds to produce the ordering relative to the shearing direction. Nevertheless, the nanoscopic domain size and low crystal number density in both approaches can be problematic in practical applications. Meanwhile, it remains technically challenging to fabricate macroscopic, continuous, single crystalline domains of organic semiconductors, which can highly increase the charge mobility.15 Interestingly, employment of functional organic compounds with strong intermolecular interactions could effectively facilitate deposition of continuous single crystalline domains on the macroscopic scale.3,8,9 For instance, Diao applied a micropillar-patterned printing blade to promote the fast, dynamic, and shearing-induced crystallization of an organic semiconductor to achieve single crystalline domains in a large area.9 A dewetting process, coupled with a deliberate patterning Received: May 9, 2016 Revised: June 20, 2016 Published: July 12, 2016 4620
DOI: 10.1021/acs.cgd.6b00707 Cryst. Growth Des. 2016, 16, 4620−4626
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DI water for 2−4 days until the pH value remained constant for around 1 h. The mixture in the membrane was treated with ultrasound (Qsonica sonicator, model Q55) in an ice bath to avoid overheating. Finally, the aqueous dispersion was filtered through a 0.45 μm Sartorius cellulose acetate membrane and then was stored in refrigerator at 4 °C. The final aqueous dispersion obtained had a mass fraction of ∼2%. For further use, the dispersion can be concentrated by the means of osmotic compression in a dialysis tube (Spectra/Por CE Float-a-Laser, MWCO 1000) in the presence of a 20 wt % aqueous PEG 20000 solution. Deposition of nematic CNC substrates: A volume of 20 μL of 1.0 wt % CNC dispersion was first added onto the coverslip 1.2 cm2 in size. As the solvent evaporated at ambient temperature, nematic CNC thin films bearing typical “Schlieren” patterns were obtained. Deposition of CNC thin films via a dip-coating process: The vertically aligned coverslip was immersed in a 4.6 wt % CNC dispersion and then was raised up with a constant rate. The waveshaped and uniaxially aligned CNC thin films were achieved at the lifting rates at 53 and 27 mm/min, respectively. The temperature and humidity were 25 ± 1 °C and 40−60%, respectively. Additionally, silanized CNC films were obtained by sealing the CNC thin film, together with the underneath coverslip, into a desiccator in the presence of the phenyltrimethoxysilane vapor for 24 h. Deposition of CNC thin films via a spin-coating process: A volume of 20 μL of 1 wt % CNC dispersion was dropped on a 1.2 cm2 coverslip for the spin-coating process with the spin rate at 4000 rpm for 40 s. Deposition of drug thin films: A volume of 20 μL of 10 g/L INNethanol solution was dropped on a CNC thin film, followed by a spincoating process with the spin rate at 4500 rpm for 40 s. The film was then exposed to an ethanol/water vapor mixture within a sealed desiccator to promote crystallization. Precisely, the vapor was generated by a mixture of ethanol and DI water with the volume ratio at 10:1. The needle-shaped α-INN crystals were observed after a reaction period of 5 h. The CBZ (form II) crystalline thin film was obtained by using the same procedure with a 10 g/L CBZ-alcoholic solution. Characterization. (Polarized) Optical microscopy images were taken on an Olympus BX53 microscope equipped with a chargecoupled device (CCD) camera (Nikon DXM1200). Atomic force microscopy images were taken with an atomic force microscope (AFM, DI Multimode, Veeco Inc.) in tapping mode. Scanning electron microscopy (SU-70, Hitachi) was used to scan CNC thin films and drug crystals. XRD patterns were recorded on an X-ray diffractometer system (X’pert PRO, PANalytical) with the Cu-ka radiation generated at 30 mA and 40 kV with the step size of 0.016°.
tool, remains an empirical approach to fabricating lateral crystalline thin films. Most of all, this approach does not guarantee vertical orientation control and thus usually leads to polycrystalline thin films in a dynamic deposition process. Alternatively, deposition on an underneath template including Langmuir membranes,16−18 self-assembled monolayers,19−21 semicrystalline polymers,22−27 and crystalline facets28−30 provides various robust approaches to orientational control in lateral and/or vertical directions. Among various matrices, uniaxial semicrystalline polymers (SCPs) obtained via stretching26,31,32 or rubbing22,33,34 have long been used extensively to template crystallization to realize three-dimensional (3D)-oriented thin films across the macroscopic distance.32 Nevertheless, both above-mentioned approaches meet the difficulty in treating cellulose and chitintwo abundant biopolymers with poor processability, unless their soluble derivatives were employed for processing.32,35,36 As a comparison, the β-chitin layer in Nautilus repertus shells is the laterally aligned fibrils in favor of the oriented growth of nacreous columns on their a and b crystallographic axes under biogenic control, which decreases the probability of occurrence of structural defects between nacreous columns.37,38 Promisingly, exploration of a straightforward, environmentally benign approach to coating a uniaxial cellulose or chitin thin film which functions as heterogeneous nuclei of lateral crystallization can expand their applications in drug delivery and biomedical applications.37,38 It is noted that cellulose and chitin, though they remain difficult for processing, can be decomposed to obtain their nanocrystalline forms, which can spontaneously assemble into liquid crystalline domains in the dispersion or thin film form.39,40 Theoretically, alignment of cellulose nanocrystals (CNCs) can provide an assembly method for fabrication of uniaxial cellulose thin films for lateral crystallization uses. Nevertheless, it remains challenging to obtain a uniaxial CNC thin film across the macroscopic distance.41,42 Very recently, we developed a simple dip-coating approach to a uniaxial CNC thin film on the macroscopic scale for the coalignment of single-walled carbon nanotubes.43 In the current study, the uniaxial CNC thin film and other patterned ones were employed as heterogeneous nuclei for lateral crystallization of two typical drug compounds. To our knowledge, this study provides the first nanoparticulate assembly method to obtain a uniaxial SCP thin film, which functions as the heterogeneous nuclei of lateral crystallization.
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RESULTS A nanoparticulate assembly route was explored to design the uniaxial CNC thin film uniform on the centimeter scale, which subsequently guided lateral growth of crystalline drug thin films, indomethacin (INN) and carbamazepine (CBZ) (Figures 1a−d and s1). First, a uniaxial CNC thin film was fabricated via a typical dip-coating process under ambient condition.40,44 Afterward, a lateral drug thin film was achieved via a multistage crystallization route,45 passing through the formation and transformation of drug precursors on the CNC thin film. Compared with conventional stretching and rubbing approaches, the current colloidal route, based on a simple dipcoating method performed in water, is a novel and efficient alternative to a uniaxial SCP thin film across the macroscopic distance. It is proposed that this green strategy is extendable to an enormous range of functional compounds by using various depositions methods. Hence, it has the broad scope in fabrication of functional thin films in drug delivery, energy generation and storage, etc.
EXPERIMENTAL SECTION
Materials. Microcrystalline cellulose (MCC) and phenyltrimethoxysilane were obtained from Sinopharm Chemical. Indomethacin (INN) and carbamazepine (CBZ) were obtained from Sigma-Aldrich. The concentrated H2SO4 (96−98 wt %) and H2O2 (30 wt %) solutions were received from Xilong Chemical for cleaning coverslips. Ethanol absolute was purchased from Huada Chemical. All chemical reagents involved in this study were of analytical grade and were used without any purification unless otherwise stated. Deionized (DI) water (18 mΩ/cm) was used throughout the work. Experimental Section. Fabrication of CNC dispersions: The procedure was according to our previous study.43 MCC was hydrolyzed in sulfuric acid (1 g of MCC in 8.75 mL of 64 wt % aqueous H2SO4 solution) at 45 °C with vigorous stirring for 30 min. Afterward, cold DI water was used to dilute the mixture as well as to quench the hydrolysis. The supernatant was removed by centrifugation, and the remaining thick white layer was placed inside a dialysis membrane (Spectra/Por 2, MWCO 12000−14000) and dialyzed with 4621
DOI: 10.1021/acs.cgd.6b00707 Cryst. Growth Des. 2016, 16, 4620−4626
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Figure 2. (a−c) Rotational POM (a, b) and AFM (c, the amplitude error mode) images of a typical uniaxial CNC thin film. (d) Respective histogram for the number percentage of CNCs in leading angles with a reference of the dip-coating direction. The analysis was based on image c. White arrows in images a−c point to the lifting direction in a dipcoating process, and white crossed arrows in images a and b show the polarization direction.
Figure 1. (a) Cartoon indicating multistage heterogeneous nucleation on a uniaxial CNC thin film, including formation of a CNC thin film in a dip-coating process, deposition of drug precursors via a spin-coating method, and the vapor-promoted drug crystallization. (b) Scanning electronic microscopy (SEM) image of a typical uniaxial CNC thin film. (c) Optical microscopy (OM) image of a thin layer of solvated INN liquid precursors, which was obtained via a spin-coating process and showed a bicontinuous pattern. (d) OM image of lateral α-INN crystals on a uniaxial CNC thin film. The white and black arrows in images b and d, respectively, point to the lifting direction in a dipcoating process.
direction. From the eq 2, for random orientation, = 0.5 leads to f = 0, and for perfect orientation, = 1 leads to f = 1. The histogram of orientational distribution of CNCs (Figure 2d) based on multiple AFM images concludes that the orientation factor of CNCs within a uniaxial substrate is 0.94 ± 0.05 (error bar is calculated from three 10 by 10 μm AFM images). An exemplary angle-distribution analysis shows that the orientation factor of CNCs within the AFM imageFigure 2c is as high as 0.98 (NCNC = 258, Figure 2d). We note that the proper moving rate of the meniscus in a dip-coating process is crucial for achieving a uniaxial colloidal thin film, according to a previous study.48 In comparison, a wave-shaped CNC thin film with the f value of 0.60 ± 0.14 (error bar is calculated from three 10 by 10 μm AFM images) along the lifting direction was achieved by decreasing the lifting rate to 27 mm/min, as confirmed in both POM and AFM images (see an exemplary image in Figure s2c,d). Afterward, a two-step crystallization method was deliberately employed for lateral growth of a drug thin film on the CNC substrate. The preliminary screening tests showed that spin coating (spin rate at 4500 rpm; both INN and CBZ concentrations at 10 mg/mL) of a drug alcoholic solution was suitable for generating and stabilizing liquid precursor domains on the CNC substrate for crystallization. Afterward, the substrate together with a precursor layer was sealed within a closed desiccator in the presence of ethanol/water vapor to promote crystallization in precursor domains. In both cases, lateral, needle-like INN and CBZ crystal arrays were obtained, as illustrated in Figures 1d and s1, respectively. Orientation factors of INN and CBZ needles are 0.96 (N = 22, N represents the total number of crystals in statistics to derive orientation factors) and 0.89 (N = 51), respectively, according to angledistribution analyses of Figures 1d and s1. Monitoring the orientation relationship of drug crystals on the CNC film is particularly helpful for understanding the underlying mechanism of lateral crystallization. The uniform birefringent contrast (Figure 3a,b) and the single set of the external crystal facets (Figure 3c,d) are strong evidence of single crystalline domains (Figure 1c). A significant advantage
The multistep procedure started with fabrication of the underneath CNC thin film. A large-scale uniaxial CNC thin film was achieved via a simple dip-coating approach, based on the shearing-induced assembly of 1D nanoitems.46,47 In a typical dip-coating experiment, a vertically aligned coverslip emerged in a CNC aqueous dispersion was raised upward at a constant rate driven by a motor. A uniaxial CNC thin film was achieved when a coverslip was lifted from a 46 mg/mL dispersion with the rate at 53 mm/min (Figure 1b). As the film was rotated 45° in each step, it presented a simultaneous brightness variation under polarized optical microscopy (POM), which corresponds to the birefringent nature that single crystals possess. This is due to the total contribution of birefringence of each CNC nanorod and, therefore, is distinct evidence of the high orientational order of CNCs along the lifting direction (Figure 2a,b). A sampling zoomed-in atomic force microscopy (AFM) image and the corresponding histogram of orientational distribution of CNCs unambiguously confirm the presence of the uniaxial alignment (Figure 2c,d). Furthermore, the order degree of a CNC thin film is quantitatively characterized using the orientation factor f, which is defined as f = 2⟨cos2 θ ⟩ − 1
(1)
In eq 1, the average orientation angle, , is given by 2
N
2
⟨cos θ ⟩ =
∑i = 1 cos2 θi NCNC
(2)
where NCNC is the total number of counted CNC nanorods, θ is the angle between the long axis of CNCs and the lifting 4622
DOI: 10.1021/acs.cgd.6b00707 Cryst. Growth Des. 2016, 16, 4620−4626
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mentioned characterization results. In the current study, the β-cellulose was used as a standard for molecular modeling. Figure 4a,b shows the MD simulation result of dual INN molecules adsorbing on the (100) plane of cellulose, which remarkably indicates a same adsorption configuration of dual INN molecules (Figure 4a,b). It suggests the dominance of Hbonding interactions between the carboxylic acid and hydroxy groups in INN and CNC, respectively (Figure 4a,b). Moreover, the 5-methoxyl-indoline groups in INN molecules are always parallel to the CNC (100) face (Figure 4a,b), indicating strong van der Waals interactions between the 5-methoxyl-indoline in INN and alkyl groups in CNC. The configuration of dual INN molecules in α-INN crystal (Figure 4c) is very similar to their adsorption configuration on the (100) plane of cellulose (Figure 4b). Combining to the lattice vectors of cellulose crystal (Figure 4b) and α-INN crystal (Figure 4c), the b, c lattice vectors of α-INN crystal induced by the (100) plane of cellulose would be favorable to align to the b, c lattice vectors of cellulose crystal, respectively. In addition, the α-INN crystal has a typical needle morphology, with its c-axis parallel to the long axis direction. As a consequence, the orientation of α-INN needles would be highly regulated by the orientation of CNCs, which is in good accordance with the experimental results. Interestingly, CNC thin films under the guidance of various external forces can show rich assembly forms including the uniaxial, wave-shaped, nematic, and radial ones (Figures 2a−c and s2a−e). Therefore, the distinct assembly behaviors of CNCs allow for fabrication of various patterned drug thin films, the latter of which, in turn, can be used as lateral indicators to “mirror” the assembly behavior in the underneath CNC layer. OM images show that all patterned α-INN crystals properly reflect lateral information on the underneath CNC substrate used (Figures 5a,b and 1d). For instance, INN needles show the meandering and winding-shaped textures on the nematic and wave-shaped CNC substrates, respectively (Figure 5a,b). Therefore, curved INN crystals macroscopic in size nicely reflect the local assembly behavior of CNCs microscopically. Unlike curved α-INN crystals, which nicely follow the curvature of the underneath CNC thin film, CBZ (form II) crystals are robust needles and roughly reveal the orientational information on the underneath CNC substrate (Figure 5c,d and s1). The angle-distribution analysis of Figure 5d shows that the orientation factor of CBZ rods on wave-shaped CNC film decreases to a value of 0.56 (N = 60), compared with that of 0.89 (N = 51) on the uniaxial one in Figure s1. Additionally, radial patterns of both INN and CBZ needles (Figure s4) were also fabricated on radially aligned CNC substrates, which were
Figure 3. (a, b) Rotational POM images of INN crystals on the uniaxial CNC thin film. (c, d) SEM images of INN (c) and CBZ (d) needles on each uniaxial CNC substrate. White arrows in both images point to the aligning direction of CNC nanorods. White arrows in images a−d point to the lifting direction in a dip-coating process, and white crossed ones in images a and b show the polarization direction.
of lateral growth on the CNC thin film lies in the visibility of the orientational relationship between the underneath heterogeneous nuclei and crystals on the top. SEM images showing the uniaxial alignment of drug needles (Figure 3c,d) are remarkably instructive because they show that needles grow along the long axis of CNCs. In the XRD pattern, only two peaks belonging to α-INN crystals exist, namely, (0 2 0) and (0 4 0) (Figure s3a). This reveals that the b axis of α-INN crystals is perpendicular to the substrates plane. The orientational information from the XRD pattern, together with that from microscopic observations, suggests that the α-INN crystals grown on the CNC film are fully oriented. The same orientational information is also confirmed in the CBZ-CNC hybrid thin film (Figure s3b). Hence, results from multiple tools indicate both drug crystals are fully oriented on the CNC substrate. The polymorphic outcomes of both drug crystals were determined as the α-INN49 and CBZ (form II),50,51 as confirmed by XRD patterns (Figure s3a,b). In addition to XRD, SEM, and OM characterization tools, molecular modeling was performed to identify the underlying mechanism of lateral growth of drug crystals on the CNC thin film. Because of the distinct crystallization behavior of each drug crystal, both the nucleation face and the absolute orientation are readily identified, based on the above-
Figure 4. Side- (a) and top-view (b) snapshots of dual INN molecules (bolded ones) absorbed on the (100) plane of CNC along the c-axis of cellulose, in which the lattice vectors of cellulose crystal are shown. (c) Crystal configuration of INN, and the lattice vectors of an α-INN crystal are shown. 4623
DOI: 10.1021/acs.cgd.6b00707 Cryst. Growth Des. 2016, 16, 4620−4626
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Nevertheless, only poorly oriented α-INN and CBZ (form II) needles were obtained with no clear evidence of multistage crystallization (Figure s5). This result highlights the importance of the surface-favored multistage crystallization, where metastable liquid precursors generated by a spin-coating method are crucial in the present study. The appearance of liquid precursors of drug compounds highly suggests that crystallization passes through a far-from-equilibrium process.45 Furthermore, our finding is among rare case studies that liquid precursors of INN can form from the solution phase in the absence of polymeric additive. In comparison, amorphous INN and CBZ domains were obtained via a melt crystallization or crystallization in the presence of a polymeric additive.52−54 To conclude, the current work shows that colloidal assembly of cellulose nanocrystals can be employed for fabrication of uniaxial SCP thin films, which function as heterogeneous nuclei of lateral crystallization of two typical drug compounds. Such CNC assemblies, bearing the exposed and regularly distributed hydroxy groups on each particle, well mimic the β-chitin layer in Nautilus repertus shells. Intriguingly, CNC substrates bearing distinct orientational characters can form various patterned drug thin films, which, in turn, properly “visualize” the lateral assembly behavior of the underneath substrate macroscopically. Hence, this technique opens a door for lateral growth of functional crystalline compounds on environmental-benign biomacromolecular thin films, which are difficult for processing with conventional approaches. For instance, lateral growth of drug crystals on the biomacromolecular thin film can be an efficient approach to obtaining drug-excipient hybrids thin films bearing the preferred alignment direction to facilitate drug manufacturing.
Figure 5. (a, b) OM images showing α-INN crystals on nematic (a) and wave-shaped (b) CNC substrates. (c, d) OM images of CBZ (form II) crystallized on nematic (c) and wave-shaped (d) CNC substrates. White arrows in images b and d point to the lifting direction in a dip-coating process.
obtained via a spin-coating approach according to a previous study.44 Favorable interactions between hydroxy groups on CNCs and the “paired” functional groups on drug molecules are assumedly essential for lateral growth of two drug compounds. A comparative crystallization experiment was performed on a silanized CNC thin film to examine structural outcomes of drug crystals. Though liquid precursors were still formed on the silanized CNC substrate, their number density was sharply decreased (Figure 6a) when compared with those formed on
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.6b00707. Simulation details, the XRD patterns of INN and CBZ, the supporting (P)OM images of INN and CBZ films, the supplementary POM and AFM images of CNC thin films (PDF)
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AUTHOR INFORMATION
Corresponding Authors
Figure 6. (a) OM image of domains of INN liquid precursors spincoated onto a silanized uniaxial CNC substrate. (b) POM image of γINN crystals obtained on the same substrate. The polymorphic judgment is empirically based on the characteristic shape and facet information on the γ-INN crystals.
*E-mail:
[email protected] (Y.J.). *E-mail:
[email protected] (X.X.). Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This research work was supported by National Natural Science Foundation of China (Nos. 21303144 and 51273166), Natural Science Foundation of Fujian Province, China (Nos. 2014J0101 and 2013J01206), the “111” Project (B16029), National Nature Science Foundation of China (No. U1405226), Fujian Provincial Department of Science & Technology (2014H6022), and the 1000 Talents Program from Xiamen University. Special thanks to Mr. Mingfeng Liu and Mr. Yu Huang for assistance in figure drawing and in crystallization. Prof. Daiyong Ye from South China University of Technology is acknowledged for providing CNC samples in the initial test studies.
the hydrophilic counterpart (Figure 1d). This difference should be attributed to the poor wetting behavior after the silanization treatment. The subsequent vapor-promoted crystallization led to formation of randomly oriented, sheet-like γ-INN crystals the thermodynamically stable form of INN at room temperature (Figure 6b). The failure in the lateral growth on the silanized CNC thin film demonstrates that hydroxy groups exposed on each CNC are essential for regulating lateral growth of α-INN crystals via H-bonding interactions. Besides molecular interactions, selection of the crystallization route is also crucial for lateral growth of drug crystals. An evaporation crystallization approach was used in the current study to deposit INN and CBZ crystals on the CNC substrate. 4624
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