Chiral Nanostructured Composite Films via Solvent-Tuned Self

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Chiral Nanostructured Composite Films via Solvent-Tuned Self-Assembly and Their Enantioselective Performances Kaiyue Chen, Tifeng Jiao, Junkai Li, Dongxue Han, Ran Wang, Guangjun Tian, and Qiuming Peng Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.9b00014 • Publication Date (Web): 07 Feb 2019 Downloaded from http://pubs.acs.org on February 7, 2019

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Chiral Nanostructured Composite Films via Solvent-Tuned Self-Assembly and Their Enantioselective Performances

Kaiyue Chen,a,b Tifeng Jiao,a,b,* Junkai Li,b Dongxue Han,b Ran Wang,b Guangjun Tian,c,* and Qiuming Penga

aState Key Laboratory of Metastable Materials Science and Technology, Yanshan University, 438West

Hebei Street, Qinhuangdao 066004, P. R. China bHebei

Key Laboratory of Applied Chemistry, School of Environmental and Chemical Engineering,

Yanshan University, 438West Hebei Street, Qinhuangdao 066004, P. R. China cKey

Laboratory for Microstructural Material Physics of Hebei Province, School of Science, Yanshan

University, 438West Hebei Street, Qinhuangdao 066004, P. R. China

*Corresponding authors *E-mail: [email protected] (T.J.). *E-mail: [email protected] (G.T.).

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ABSTRACT: Chiral nanostructures exhibited distinctive functions and attractive application in complex biological systems, which demonstrated the subject of many outstanding researches. In this work, various hierarchical composite films nanostructures were designed via supramolecular selfassembly using chiral amphiphilic glutamate derivatives and achiral porphyrin derivatives as well as their macroscopic enantioselective recognition properties were investigated. We have found that intermolecular hydrogen bonding interactions between water (donor and acceptor) and N,Ndimethylformamide (DMF) as well as chloroform (CHCl3) (acceptor only) and DMF could subtly alter the molecular packing, and significantly affected the supramolecular self-assembled nanostructures and triggered circular dichroism (CD) signal reversal. Present research work exemplified a feasible method to fabricate chiral flower-like and brick-like nanostructures films in different mixed solvents and large-scale chiral transfer from molecular level to complex structures, which also provided a facile approach to identify certain L-/D-amino acids by means of contact angle detection using present obtained self-assembled composted films.

KEYWORDS: self-assembled nanostructures, composite films, supramolecular chirality, solvent effect, enantioselectivity

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INTRODUCTION Chirality, as one of the most fascinating phenomena found in nature world, is existed in various hierarchical scales like molecular, macromolecular and supramolecular levels due to the control of chiral organization by molecular design.1,2 Most of biological systems through the change of conformations exhibit different chiral sense. In addition, the properties of organic materials are known to be not only related to their molecular structure but also to the way they are assembled.3 It is worth noting that both chiral and achiral molecules influenced by external conditions are possible to assemble into chiral nano/microstructures. Therefore, it is indispensable to fully understand the assembly mechanisms of chiral nanostructures in the field of science and biology.4 To obtain a diverse range of chiral nanostructures, supramolecular assemblies as an efficient “bottom-up” strategy are powerful methods.5,6 Artificial simulation of chiral nanostructures have been achieved based on molecular design and regulation of non-covalent bonds. For example, some peptides, nanoparticles, amino acid derivatives and achiral molecules have been designed into chiral nanostructures or hybrid materials by supramolecular assemblies under the synergistic effect of different kinds of intermolecular noncovalent interactions such as hydrogen bonds, electrostatic interactions, π-π stacking, van der Waals and hydrophobic forces, etc.7-12 In addition to the above mentioned, assembly rate, temperature, environmental pH value, chiral additives and solvent type have also been shown to have a remarkable effect on self-assembly processes and final morphologies.13-15 Solvents have different polar and hydrogen bonding abilities, which are key to regulating the thermal assembly process. In addition, the formation of hydrogen bonding between biomolecules and solvent molecules can dramatically influence supramolecular self-assembly. Depending on solvent types, various nanostructures including 3


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nanospheres, nanowires and nanobelts were formed. For instance, Liu and co-workers found that the introduction of water could tune the helical nanostructures and supramolecular chirality in organogels.16 Krone and co-workers have reported that a small amount of solvent can cause denaturation of proteins and self-assembly into various aggregates, which are responsible for diseases such as Alzheimer's disease and type II diabetes.17 However, it remains a challenge to tune the morphology of the assembled nanostructures by using solvent effects and how chirality is transferred during such process. It is well known that porphyrins belong to heterocyclic compounds composed of four pyrrole rings through four carbon atoms. Porphyrins and related compounds demonstrated unique planar and rigid molecular geometry as well as excellent components for the construction of organic nanostructures, displaying wide range of potential applications in catalysis, sensing and solar energy conversion due to their excellent photophysical, photochemical, electrochemical and structural properties.18-21 Porphyrin also played an important role in in human, plants, and microorganism, which four N atoms were easily coordinated with many metal atoms to form metal complexes, such as Ironcontaining red, magnesium chlorophyll and vitamin B12. Until now, all sorts of sophisticated porphyrin-containing nanomaterials have been fabricated. For examples, Wan and colleagues found that the porphyrin-based hollow hexagonal nanoparticles could be prepared in N,Ndimethylformamide/chloroform (DMF/CHCl3) system with the addition of surfactants, and the threedimensional structure could also be further formed.22 Jiang and coworkers have demonstrated that porphyrin and amphiphilic histidine could be fabricated into microflower structure through a selfassembly process in DMF/water mixed solvents.23 L-Glutamide derivative, as a amphiphilic molecule, displayed a chiral carbon atom and amino groups, which could easily interact with carboxylic acid 4


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groups through the hydrogen bonding. In this study, we prepared 5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin (TCPP)/N-(4Aminobenzoyl)-L-glutamic acid diethyl ester (L-GDE) composite films (abbreviated as TCPP/L-GDE) with different self-assembled nanostructures. Chemical structures of TCPP and L-GDE along with their space-filling models were shown in Figure 1. We demonstrated that the used solvents could efficiently tune morphological self-assembly via facile processing approach. We selected two solvent systems: DMF/CHCl3 and DMF/H2O. And by adjusting the ratios between good and poor solvents and solute concentrations, we obtained stable aggregated nanostructures such as microflower and bricklike structures, which were verified via scanning electron microscopy (SEM) and Transmission electron microscopy (TEM).24 Interestingly, these molecules formed chiral composite structures films through non-covalent bonds because of the chiral transfer in the self-assembly process, and the resulting nanostructured supramolecular chirality was not necessarily related to the molecular chirality in used molecules, which was characterized by circular dichroism (CD) spectra. We have also investigated the fluorescence lifetime measurements and a plausible formation of well aggregated mode has been proposed. In addition, we found that microflowers and brick-like could recognize certain amino acids. The obtained results will provide an important thread to the design and prepared building blocks of chiral structures by hierarchical self-assembly process.

MATERIALS AND METHODS Materials. 5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin (TCPP) and N-(4-aminobenzoyl)-Lglutamic acid diethyl ester (L-GDE) were purchased from Aladdin Chemicals (Shanghai, China). N,NDimethylformamide (DMF) and Trichloromethane (CHCl3) were supplied by Sigma-Aldrich. Aspartic 5


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acid (Asp), Glutamic acid (Glu), Tyrosine (Tyr), Phenylalanine (Phe), Arginine (Arg), and Alanine (Ala) were purchased from Aladdin Chemicals (Shanghai, China). The de-ionized water (DI water) was obtained via a Milli-Q water purification system with resistivity of 18.2 MΩ cm-1. Preparation of hierarchical self-assembled composite films. Various morphologies of TCPP with L-GDE were investigated in the mixed solvents of different volume ratios, including DMF/water and DMF/CHCl3. In a typical procedure, 0.5 mM TCPP and 2 mM L-GDE (molar ratio of 1:4) were dispersed in DMF, and then water or CHCl3 was added dropwise into DMF solution in the state of heating (60 C) for 3 min. Subsequently, the resulting solution was naturally cooled to room temperature. During the preparation of the composite films, the solvent evaporated naturally at room temperature. Computational simulation. Density functional theory (DFT) calculations were performed to investigate the interaction between TCPP and L-GDE in various solvents. In order to make the calculations affordable, the glutamate side chain in L-GDE was replaced by a C-H bond. Four such simplified molecules were placed close to the four -COOH groups of the TCPP molecule. The whole system contains 154 atoms. The ωB97X-D functional which takes into account both empirical dispersion and long-range corrections were used in all of the DFT calculations together with a standard 6-31G* basis set.25 The solvent effect was taken into account through the Polarizable Continuum Model (PCM). Three types of solvents (water, CHCl3 and DMF) which were described by the default parameters of Gaussian 16, has been considered. All of the structures were fully relaxed and no imaginary frequencies have been found in the vibrational analysis. All of the calculations were performed with the Gaussian 16 software. Characterization. Field-emission scanning electron microscope (SEM) (S-4800II, Hitachi, Japan) 6


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with a 5-15 kV accelerating voltage was used to characterize different morphologies of obtained samples. Transmission electron microscopy (TEM, HT7700, High-Technologies Corp., Ibaraki, Japan) was performed to further characterize the TCPP with L-GND. The TCPP/L-GND films were used for X-ray diffraction (XRD) analysis, which was performed on an X-ray diffractometer equipped with a Cu Kα X-ray radiation source and a Bragg diffraction setup (SMART LAB, Rigaku, Sakishima, Japan). FTIR spectra were recorded by using Fourier infrared spectroscopy (Thermo Nicolet Corporation) using the KBr tablet method at room temperature. The aggregates of L-GND /TCPP were analyzed using UV−vis spectrophotometer (SHIMADZU). Circular dichroism (CD) spectra of the samples were carried out on a JASCO J-810 CD spectrometer. During the measurement of the CD spectra, the composite films were perpendicular to the optical path and rotated in the plane of film to avoid polarization-dependent reflections and eliminate the possible angular dependence of the CD signals.26,27 The fluorescence lifetime measurements were performed on Edinburg FLS-980 fluorescence spectrometer using time-correlated single photon counting (TCSPC). Fluorescence spectra were recorded in quartz cuvettes on a Hitachi F-4500 fluorescence spectrophotometer. The appropriate amounts of aggregation solutions were slowly casted on the surface of copper foil, and forming flower-like or brick-like structure, and then naturally evaporate the solvent. An OCA20 machine (Data Physics, Germany) was used to measure amino acid and water contact angles at room temperature with optimized 2 μL of liquid drop. The obtained digital photographs were taken by a Nikon (Tokyo, Japan) D90 single lens reflex camera.

Results and discussion 7


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The co-assemblies of TCPP with amphiphilic glutamate formed diverse structures with the variation of volume ratio of present mixed solvents and solvent types. The scanning electron microscopy (SEM) images of the TCPP with L-GDE fabricated from the DMF/CHCl3 solvents, as shown in Figure 2. Depending on the solvent, those nanostructures formed remarkably different morphologies. When the volume ratio of the solvents (DMF/CHCl3) is > 3/7, it is clearly seen that the films with wrinkles are presented. While the ratio of the solvents reaches 2/8, microflowers structures that consisted of nanolayers are obtained. When the ratio of the solvents is < 2/8, the microflowers structures gradually disappear. Figure 3 showed morphological changes of TCPP/L-GDE assemblies fabricated from DMF/H2O with various volume ratios. When the volume ratio of DMF/H2O is > 5/5, wrinkled films similar to that mentioned above can be obtained. It is interesting to find that rectangular sheet structures begin to appear when the ratio of mixed solvents reaches 5/5. By decreasing of solvent volume ratio to 3/7, brick-like structures are observed. In addition, when the ratio of the solvents (DMF/H2O) is less than 3/7, the brick-like structure gradually disappeared. Consequently, it is shown that by simply modifying the solvent conditions, remarkably different morphologies can be easily obtained. Moreover, the hydrogen-bonding nature of solvent can also affect the self-assembled nanostructure. CHCl3 molecule is proton acceptor that can occupy the proton donors in L-GDE molecules, leading to the formation of flower-like structures of TCPP with L-GDE. On the contrary, water molecule display both a proton donor and an acceptor, which can form brick-like self-assembled structures with closely packed TCPP molecules.28 On the other hands, solvents can affect intermolecular interactions, leading to different microcosmic assembly modes. Figure 4 demonstrated the TEM images of TCPP/L-GDE at the volume ratio of DMF/CHCl3 at 2/8 and DMF/H2O at 3/7. It future confirmed that self-assembled flower-like and brick-like structures were formed. In this work, 8


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we fixed the solvents at 2/8 (DMF/CHCl3) and 3/7 (DMF/H2O) as an optimal condition to fabricate the organized flower-like and brick-like structures for the following performance characterizations. Furthermore, we have explored the effects of different concentrations of TCPP and L-GDE (the molar ratio is keep at 1:4) on morphology. Figure 5 and Figure 6 showes the SEM images of L-GDE, which concentration is ranging from 1 mM to 5 mM, with TCPP in DMF/CHCl3 or DMF/H2O mixed solvent. When L-GDE concentration is 2 mM, we can clearly observe the microflowers and brick-like structures, indicating that higher or lower concentration cannot induce formation of these kinds of structures with homogeneity. And the obtained changed morphologies at different concentrations demonstrate the interactions between the carboxylic acid group of TCPP and the amino group of LGDE. Notably, these images unambiguously confirm that depending on the concentration, selfassembled structures can form different patterns. Figure 7a showed the XRD curves of L-GDE with TCPP co-assemblies in different solvents, which were measured to investigate internal organized structures of the prepared composites. The XRD pattern of the TCPP cast film shows Bragg peaks at 2θ value of 6.3° in the low angle range, which is assigned to (100) plane and the width of TCPP is calculated by Bragg equation 2dsinθ = λ, which consequence is 1.42 nm.29 In the wide angle region, the Bragg peaks appeared at 2θ values of 12.7°, 18.9°, which were indexed to the (200), (300) lattice planes, respectively. In addition, the sharp peak at 2θ =25.1° (0.363 nm) can be attributed to the stacking distance between neighboring porphyrin rings along the direction perpendicular to the porphyrin rings. The XRD patterns of cast film with the ratio of DMF to CHCl3 of 2/8 are similar to the composite film fabricated in DMF/H2O (3/7). While compared to TCPP, the XRD patterns of composite films are obviously changed and the diffraction peaks at (100) plane moved to the left to 5.09° (1.73 nm), which may be due to L-GDE works as a 9


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“glue” to attach TCPP. And the peaks at 0.363 nm (25.1°) of two composite films are relatively weak, which can be clearly seen that interplanar spacing of TCPP is larger to some extent.30 The FT-IR measurements offered more information regarding the interaction of the selfassembled nanostructures that were formed in different mixed solution, as shown in Figure 7b. The peak around 1726 cm−1 is assigned to the ester carbonyl group (O-C=O) stretching vibration in L-GDE. And the L-GDE shows features corresponding to the methyl, amide I and amide II bands near 1295, 1627 and 1603 cm−1, respectively.31 TCPP shows a typical peak in the vicinity of 1697 cm−1, which corresponds to the C=O stretch. Comparing to TCPP, C=O vibration band of TCPP with L-GDE shifts from 1697 to 1688 cm−1, indicating that there are stronger hydrogen bonds between glutamate with carboxylic acid of TCPP.30,32 The cast film of TCPP and TCPP/L-GDE were further monitored by UV−vis spectra, as shown in Figure 7c. A dilute solution of TCPP in DMF, existing as monomer, shows a Soret band (B-band) at 434 nm and four relatively weak Q bands are at 523, 559, 597 and 650 nm ranging from 500 to 700 nm. It is reported that Soret and Q absorption band, corresponding to the electronic transitions of S0S2 and S0-S1 respectively, both arise from π-π* electronic transitions.33 Compared to the absorption in solution, a wide absorption band of cast film of TCPP moved red shift to 435 nm. The broad red shift demonstrates the π-π stacking between molecules and molecules in the film. In contrast, the B-band of TCPP/L-GDE cast film fabricated from different mixed solvent is quite different from TCPP cast film that obtained in DMF solution. The Soret absorption band position of TCPP with L-GND coassemblies in DMF/H2O mixed solvent shifted from 434 to 423 nm, which demonstrated that TCPP with L-GDE assemblies were formed via H-type aggregation. Nevertheless, the B-band of TCPP/LGDE in DMF/CHCl3 mixed solvent shows a slightly red shift from 434 to 444 nm, which implied the 10


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formation of TCPP J-type aggregation with the aid of L-GDE.34 Interestingly, the directions of movement of B-band are completely opposite in TCPP/L-GND in DMF/H2O and DMF/CHCl3 solvents. Moreover, it shows an obvious Cotton effect for TCPP/L-GDE system in CD spectra, as shown in Figure 7d. In DMF/CHCl3 system, an intensive CD splitting band is located at 446 nm, which is equally to the λ max of the absorption maximum obtained in the composite film, and a positive maxima CD signal at 452 nm with a minimum negative band at 433 nm.35 In addition, in DMF/H2O system, cast film shows an intensive negative CD band at 450 nm and a positive band at 437 nm with a crossover at 440 nm. More important, in comparison with TCPP/L-GDE system in DMF/H2O, the Cotton effect of TCPP with L-GDE assemblies in DMF/CHCl3 solvents are slightly red-shifted, which is in well accordance with data of UV-vis spectra. These results are likely to be induced by different solvents and the chiral sense of L-GDE effectively transferred to TCPP chromophores, which was induced by hydrogen bonding between L-GDE and TCPP.36 At the same time, it also indicates that the different orientations in the molecular packing causes the reversed supramolecular chirality. To gain further insight, TCPP/L-GDE systems together with TCPP itself were measured by fluorescence spectra, as shown in Figure 8a. In DMF solution, there appeared two emission bands including Q*X00 and Q*X01 at 652 nm and 716 nm for TCPP monomer at the excitation wavelength of 405 nm, which belonged to the characteristic bands of porphyrin molecules. The emission peak of TCPP in mixed solvent is quite different from that obtained in DMF solution, and the maximum intense emission band becomes red-shifted with the spectral broadening, which reveals that aggregation of the porphyrin molecules form in these systems.37 It is also observed that in comparison with TCPP in mixed solvent, the decrease in fluorescence intensity of composite film may be due to the transfer of electrons from TCPP to L-GDE.38 11


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For the sake of better understanding the excited state interactions between TCPP and L-GDE, we have measured the fluorescence decay, as shown in Figure 8b. The decay curves of TCPP monomer (DMF as solvent) can be fitted using mono-exponentially with the decay time of 11.10 ns. In case of DMF/H2O mixed solvent, the decay curves are fitted using a double exponential function and the other decay curves (DMF/CHCl3) are fitted by mono-exponential decay. The decay components of TCPP in DMF/H2O are 2.20 and 7.87 ns and the average decay time is 5.3 ns. The decay time of TCPP (DMF/CHCl3) is 8.86 ns. However, in the case of TCPP/L-GDE (DMF/H2O), the decay components are 3.39 and 8.26 ns and the average decay time is 6.64 ns. And the lifetime of TCPP/L-GDE (DMF/CHCl3) is reduced to 9.09 ns. The shortening of decay time unambiguously confirms the presence of TCPP aggregates and forming J-type aggregation.39 In addition, in mixed solvent, compared with TCPP, the increase of average decay time of composites demonstrated the partial Htype aggregation of TCPP molecules.40,41 Therefore, fluorescence decay results are similar to UV-vis spectra, which further indicated that TCPP/L-GDE complexes existed in the form of H- and J- type aggregation. In addition, the self-assembled units of TCPP/L-GDE were further investigated by simulating simplified glutamic acid derivative and TCPP in different solvents using a computational model (density functional theory, DFT), as shown in Figure 9. We have found that the stacking styles and patterns between TCPP and four L-GDE had changed a lot. According to the literature previously reported, surface recombination of polymers with chiral side chains can produce diverse wetting performances relying on the enantiomers within the droplets.42,43 Inspired by the above situation, we investigated the enantioselectivity of the TCPP/LGDE co-assemblies film for different chiral amino acid solutions as test liquids such as alanine (Ala), arginine (Arg), aspartic acid (Asp), glutamic acid (Glu), phenylalanine (Phe) and tyrosine (Tyr) by 12


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measuring the contact angle. And the concentrations of the amino acid aqueous solutions were 0.1 mM. More importantly, there was a versatile means to detect their chirality. The contact angle of water on the cast film (DMF/CHCl3 2/8) was 116.6°, while contact angle for cast film fabricated from DMF/H2O 3/7 was 99.1°, as shown in Fig. 10a. It was well known that the surface structure of composite films had a significant impact on contact angle of water. In other words, the surface roughness could enhance both the hydrophilicity and the hydrophobicity of the surfaces.44 To ensure accuracy, each of the chiral amino acid aqueous solutions was tested five times with one chiral composite film to get the representative averaged results. From the graphic illustration in Figure 10b, the L-Arg and D-Arg are dropleted on the TCPP/L-GDE (DMF/CHCl3 2/8) surface and the average contact angles are about 130.2° and 118.5°, respectively. And for enantiomeric aspartic acid (DMF/H2O 3/7), the average contact angles are 74.0° and 86.2°, as illustrated in Figure 10c. As shown in Figure 11a, the averaged contact angles for L-Asp and D-Asp are about 102.5° and 117.3°, while for the L-Phe and D-Phe are about 110.5° and 135.7°, which confirms that the surface containing micro-flower structures exhibit enantiomeric recognition of chiral arginine, aspartic acid and phenylalanine. However, the cast film surface (DMF/CHCl3 2/8) showed almost the same contact angle to enantiomeric Ala, Glu and Tyr. Analogously, the averaged contact angles of L-Ala, D-Ala are about 75.5°, 89.5° respectively, as shown in Figure 11b. It was found that the cast composite film (DMF/H2O 3/7) had recognition preference to enantiomeric Ala and Asp. It is important to note that microflower supramolecular structure are hydrophobic to the certain chiral amino acid, while the surface containing brick-like structures are hydrophilic to a portion of chiral amino acid. In addition, the additional contact angle tests for L-Arg and D-Arg on films made only L-GDE were measured. The obtained contact angle values showed minor change, indicating well enantioselective recognition 13


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in the composite films. A plausible self-assembly process of TCPP with L-GDE co-assembly in mixed solvents and their chiral recognition of enantiomeric amino acid were depicted in Figure 12. Based on the above FT-IR results, the hydrogen-bonding interaction between carboxylic groups of TCPP and amide of LGDE played a key role in the process of self-assembly. In addition, the self-assembled structures were also influenced by tightly bounded solvent molecules in the presence of the same molecules. Water molecule acted as both a proton donor and an acceptor, promoting an ordered arrangement of TCPPLGDE self-assembled unit, in which the main driving force could be aromatic - stacking and resulted in closely packed brick-like structures in DMF/H2O (3/7) solvents.37 By contrast, CHCl3 molecule displayed proton acceptor that could occupy the proton donors of L-GDE, preferentially forming three-dimensional less closely packed microflower structures. And the non-covalent bond interaction such as hydrogen bonding played an important role in the formation of their morphology in DMF/CHCl3 (2/8) solvents. These results indicated that the solvent could efficiently affect local interactions of TCPP/L-GDE self-assembly on the molecular level.45 Due to the differences in packing nanostructures in composite films, when some chiral amino acids interacted with these surfaces of films and changed the surface properties, corresponding contact angles could alter, which demonstrated enantioselective property of present obtained TCPP-L/GDE cast film via contact angle measurements. Present studies have provided new exploration for the design of self-assembled films and wide applications in composite materials.46-55

Conclusions We have systematically demonstrated the effects of different mixed solvents, solvent volume ratios 14


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and solute concentrations on self-assembled nanostructure films and chirality, which was confirmed by the above many characterization measurements. The chirality at the carbon center of L-GDE was transferred to TCPP chromophores through hydrogen bond in self-assembly process, which replaced the tedious organic synthesis required to introduce chiral units. In addition, microflowers and bricklike nanostructures were obtained, suggesting supramolecular chiral inversion in DMF/CHCl3 (2/8) and DMF/H2O (3/7) mixed solvents, respectively. These interesting self-assembled supramolecular nanostructures films further exhibited the excellent recognition of certain amino acids. Present work is expected to provide a significant clue in the design of functionalized chiral supramolecular nanostructures and wide application in nano-sensors as well as chiral devices.

AUTHOR INFORMATION Corresponding authors *E-mail: [email protected]. Tel.: 0086-335-8056854 (T.J.). *E-mail: [email protected] (G.T.).

Notes The authors declare no competing financial interest.

Acknowledgments We greatly acknowledge the financial supports of National Natural Science Foundation of China (Nos. 21872119, 21473153), Support Program for the Top Young Talents of Hebei Province, China Postdoctoral Science Foundation (No. 2015M580214), Research Program of the College Science & Technology of Hebei Province (No. ZD2018091), and Scientific and Technological Research and 15


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Development Program of Qinhuangdao City (No. 201701B004).

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Figure 1. Chemical structures of L-GDE and TCPP along with their space-filling models.

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Figure 2. SEM images of TCPP with L-GDE assembly at different volume ratios of DMF/CHCl3: a, 8/2; b, 6/4; c), 4/6; d, 3/7; e, 2/8; f, 1/9.

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Figure 3. SEM images of TCPP with L-GDE assembly at different volume ratios of DMF/H2O: a, 8/2; b, 6/4; c, 5/5; d, 4/6; e, 3/7; f, 2/8.

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Figure 4. TEM images of TCPP/L-GDE at the volume ratio of (a) DMF/CHCl3 at 2/8 and (b) DMF/H2O at 3/7, respectively.

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Figure 5. SEM images of TCPP/L-GDE assemblies in DMF/CHCl3 mixed solvents at various concentration of LGDE: (a) 1 mM, (b) 2 mM, (c) 3 mM, (d) 5 mM.

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Figure 6. SEM images of TCPP/L-GDE assemblies in DMF/H2O mixed solvents at various concentration of L-GDE: (a) 1 mM, (b) 2 mM, (c) 3 mM, (d) 5 mM.

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Figure 7. (a) XRD patterns of TCPP cast films and TCPP/L-GDE composite films in various mixed solvents. (b) FTIR spectra of TCPP/L-GDE composite films obtained in various mixed solvents as well as L-GDE and TCPP cast films. (c) UV-vis spectra of TCPP cast films, TCPP with L-GDE and TCPP solution. (d) CD spectra of TCPP/LGDE composite films in different mixed solvents.

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Figure 8. (a) Fluorescence spectra and (b) Fluorescence decay of TCPP and TCPP with L-GDE in different solvents.

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Figure 9. The calculated self-assembled stacking structures of TCPP with simplified glutamic acid derivative in (a,a’) DMF solution, (b,b’) DMF/CHCl3 2/8 and (c,c’) DMF/H2O 3/7 along with the top and side views.

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Figure 10. Contact angles tests of (a) H2O on composite films (DMF/CHCl3 2/8 and DMF/H2O 3/7), (b) L-Arg and D-Arg on composite film (DMF/CHCl3 2/8), (c) L-Asp and D-Asp on composite film (DMF/H2O 3/7)

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Figure 11. Contact angle comparison of H2O and L/D-amino acid droplets on the obtained composite films fabricated from (a) DMF/CHCl3 2/8 and (b) DMF/H2O 3/7, respectively.

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Figure 12. Schematic depiction of the pathway-dependent self-assembly behaviors of glutamic acid derivatives and TCPP in mixed solvents and their chiral recognition of enantiomeric amino acids.

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Figure-1 139x106mm (300 x 300 DPI)


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Figure-2 159x72mm (300 x 300 DPI)


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Figure-3 159x71mm (300 x 300 DPI)


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Figure-4 139x69mm (300 x 300 DPI)


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Figure-5 139x94mm (300 x 300 DPI)


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Figure-6 139x94mm (300 x 300 DPI)


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Figure-7 139x109mm (300 x 300 DPI)


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Figure-8 159x62mm (300 x 300 DPI)


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Figure-9 159x58mm (300 x 300 DPI)


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Figure-10 119x135mm (300 x 300 DPI)


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Figure-11 160x65mm (300 x 300 DPI)


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graphic Abstract 119x60mm (300 x 300 DPI)


Chiral Nanostructured Composite Films via Solvent-Tuned Self

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