Fluorescent phthalocyanine assembly distinguishes chiral isomers of

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Fluorescent phthalocyanine assembly distinguishes chiral isomers of different types of amino acids and sugars yuying jiang, Chenxi Liu, Xiqian Wang, Tianyu Wang, and Jianzhuang Jiang Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.7b01602 • Publication Date (Web): 04 Jul 2017 Downloaded from http://pubs.acs.org on July 9, 2017

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Fluorescent phthalocyanine assembly distinguishes chiral isomers of different types of amino acids and sugars Yuying Jiang, Chenxi Liu, Xiqian Wang, Tianyu Wang* and Jianzhuang Jiang* Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials. Department of Chemistry, University of Science and Technology Beijing, Beijing 100083 (P.R. China). KEYWORDS:

Interfacial

assembly;

Multi-object

chiral

recognition;

Phthalocyanine;

Fluorescence; Poly(L-lysine)

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ABSTRACT: The functions of some natural supramolecular architectures, such as ribosome, are dependent on the recognition of different types of chiral biomolecules. However, recognition of different types of chiral molecules (multi-object chiral recognition), such as amino acids and sugars, by independent and identically artificial supramolecular assembly, was rarely achieved. In this manuscript, simple amphiphilic achiral phthalocyanine was found to form supramolecular chiral assemblies with charged water-soluble polymers upon host-guest interactions at the air/water interface. Among these systems, one identical phthalocyanine/poly(L-lysine) assembly not only can distinguish enantiomers of difference amino acids, but also can recognize several epimers of monose. The chiral recognitions were achieved by either comparing the steady-state fluorescence intensity or fluorescence quenching rate of phthalocyanine/poly(L-lysine) assemblies, before and after interaction with different small chiral molecules. It was demonstrated that the interactions between poly(L-lysine) and different small chiral molecules could change the aggregation of phthalocyanines. And the sensitivity of fluorescence as well as the excellent multi-object chiral recognition properties of phthalocyanine/poly(L-lysine) assembly are dependent on subtle molecular packing mode and the cooperation of different noncovalent interactions.


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INTRODUCTION The important natural supramolecular architectures, such as hemoglobin or photosynthetic reaction center, are the assemblies of biomacromolecules and π-conjugated molecules.1-2 Considering the homochirality of most natural materials,1 chiral recognition on different types of biomolecules is essential for realizing the functions of many natural assemblies.3 Although chiral recognition has been investigated in different artificial supramolecular systems,4-12 one identical assembly being able to recognize several types of chiral molecules, especially for both amino acids and sugars, were rarely achieved. In theory, by mimicking natural supramolecular architectures, the assemblies of porphyrin/phthalocyanine with biomacromolecules could be good candidates for multi-object chiral recognition. However, despite the relatively extensive investigation on this type of artificial supramolecular assemblies,13-19 their multi-object chiral recognition properties were still not developed. In this study, we will show the first sample of simple phthalocyanine assembly discriminating chiral isomers as well as structural isomers of both amino acids and sugars. Incorporation of four crown ether substituents onto the phthalocyanine periphery results in H2Pc(15C5)4,20-21 which were selected to co-assemble with different charged biomacromolecules, such as negatively charged DNA and poly(L-lysine) containing positive charges in water (Scheme 1A). It is known that crown ether groups have relatively strong host-guest interactions with some charged organic molecules.22-24 For the formation of supramolecular assembly, crown ether moieties not only improve the amphiphilic properties of the molecular building blocks, but also can increase the flexibility of formed phthalocyanine assemblies. And the chirality of these charged biomacromolecules are expected to be transferred onto these co-assemblies. The


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corresponding phthalocyanine/biomacromolecules assemblies were prepared by means of air/water interfacial assembly and Langmuir-Blodgett technique, which are very useful for the fabrication of complex nanostructures as well as supramolecular devices with new properties.25-28 When DNA or poly(L-lysine) was dissolved in water, the amphiphilic phthalocyanine (H2Pc(15C5)4) could form supramolecular chiral assemblies with these biomacromolecules on water surface. Most interestingly, the poly(L-lysine)/H2Pc(15C5)4 assemblies showed broadspectrum molecular recognition and chiral recognition properties. Thus, depending on the relative fluorescence intensity and fluorescence quenching rate of poly(L-lysine)/H2Pc(15C5)4 assemblies, not only the enantiomers of various types of amino acids can be discriminated, several epimers of monose can also be clearly recognized (Scheme 1B).

Scheme. 1 (A) Molecular structures of phthalocyanine (H2Pc(15C5)4) and biomacromolecules (poly(L-lysine) and DNA); (B) Schematic illustration shows phthalocyanine/poly(L-lysine)


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assemblies, which discriminate chiral isomers of both amino acids and sugars upon the changes of fluorescence. Although strong π-π interactions between phthalocyanine molecules always quench the fluorescence of phthalocyanine assemblies,29 the co-assembly of phthalocyanine containing crown ether substituents with poly(L-lysine) still renders good fluorescence characteristics even in solid state. Most importantly, due to the complex multiple noncovalent interactions within the poly(L-lysine)/H2Pc(15C5)4 assemblies, their fluorescence is very sensitive to external stimulation, such as the interaction with additional chiral small molecules. Therefore, the chiral recognition can be achieved upon the changing of fluorescence of poly(L-lysine)/H2Pc(15C5)4 assemblies.

EXPERIMENTAL SECTION Materials. 2,3,9,10,16,17,23,24-tetrakis (15-crown-5) phthalocyanine (H2Pc(15C5)4) was prepared by following the method previously reported.21 Salmon sperm DNA, ε-poly(L-lysine), monose (glucose, galactose, mannose) as well as chloroform were purchased from Acros Organics. Ltd. and used without further purification. Amino acids (glutamic acid, aspartic acid, arginine, histidine, phenylalanine) were purchased from Inno Chem, Co., Ltd. Milli-Q water (18.2 MΩcm-1) was used in all the process. And the specific rotation value ([α]25D) of ε-poly(Llysine) is 57.10°(C=1, H2O).

Apparatus and Measurements. Measurements of surface pressure–area (π–A) isotherms and film depositions were carried out on a Nima 516 trough (Nima system, UK) at 25 oC. A Lambda 750 UV-vis spectrophotometer and JASCO J-815 CD spectropolarimeter were used for the


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UV−vis and CD spectral measurements, respectively. In the process of CD spectral measurement, the sample was placed perpendicular to the light path and continuously rotated within the plane, using an attachment to avoid the possible linear dichroism (LD).26 F-4500 FL spectrophotometer was used for fluorescence spectral measurement. FT-IR spectra were recorded with a Bruker Tensor 37 spectrometer. X-ray diffraction (XRD) was achieved on a Rigaku TTRⅢ X-ray diffractometer (Japan) with Cu Kα radiation (λ= 1.54 Å), which was operated at 45 kV, 100 mA. AFM images were recorded from Bruker Multimode 8 system with a silicon cantilever by using the tapping mode. All AFM images are shown in the height mode without any image processing except flatting. Procedures. The chloroform solution of (H2Pc(15C5)4) (5 ×10-5 M) was spread onto the surface of aqueous subphases to form the air/water interfacial assemblies. The subphases are either Milli-Q water (18.2 MΩcm-1) or aqueous solution of poly(L-lysine) (10-3 M) and DNA (2×10-6 M). After evaporation of chloroform for 20 minutes, the surface pressure-molecular area (π-A) isotherm was measured by compressing the floating film with a rate of 20 cm2 min-1. And the assemblies were transferred onto different solid substrates at different surface pressures. By horizontal lifting method, 10-layer LS films were transferred onto quartz substrates for UV−vis and circular dichroism (CD) spectral measurements. 30-layer LS films were transferred onto silicon wafer plates for XRD measurements. And 50-layer LS films were transferred onto CaF2 optical windows and subject to the FT-IR measurements. In addition, monolayer LB films for AFM measurements were deposited on a freshly cleaved mica surface by vertical lifting method with the lifting speed of 3mm/min.


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The molecular recognition and chiral recognition on both amino acids and sugars is depending on the changes of fluorescence of poly(L-lysine)/H2Pc(15C5)4 assemblies. For this study, 20layer phthalocyanine LS films were transferred from poly(L-lysine) subphase onto quartz substrates with the surface pressure of 10 mN/m. These 20-layer H2Pc(15C5)4/poly(L-lysine) LS films were then subject to fluorescence spectral measurements. When these LS films were immersed in the aqueous solution of different chiral amino acids and sugars (1×10-2 M), the changes of fluorescence of poly(L-lysine)/H2Pc(15C5)4 assemblies were further analyzed. For the fluorescence measurements, the holder for membrane samples was used. And the excitation wavelength was set as 470 nm; excitation and emission slit were set to 5 and 10 nm respectively; the scan speed was set as 1200 nm/min. And the photomultiplier voltage was set to 700 V. For the time resolved fluorescence measurement, Time Scan mode was selected. The excitation wavelength was fixed at 470 nm, the fluorescence quenching rate of 706 nm emission was analyzed. The time unit was set to S (second), and the excitation and emission slit were also set to 5 and 10 nm respectively. All the fluorescence measurements were carried out at a room temperature of 25 oC. RESULTS AND DISCUSSION Air/water interfacial co-assembly of phthalocyanine with biomacromolecules. The assembly of H2Pc(15C5)4 was either performed on pure water or on the surface of poly(L-lysine) and DNA aqueous solution. And the surface pressure-area (π-A) isotherms of different assemblies were studied, as shown in Figure 1A. In the case of H2Pc(15C5)4 on pure water, the onset of the surface pressure was observed at 2.38 nm2/molecule. When the subphase was changed to poly(L-lysine) aqueous solution, the onset appeared at 2.61 nm2/molecule; while on the surface of DNA aqueous solution, the onset of surface pressure increased to 3.21


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nm2/molecule. Moreover, by extrapolating the linear part of the isotherm to zero surface pressure, the limiting area of H2Pc(15C5)4 on the surface of pure water, poly(L-lysine) solution and DNA solution were calculated as 1.97, 1.99 and 2.41 nm2/molecule, respectively. The change of limiting area clearly suggests the interaction between phthalocyanine and these charged biomacromolecules. The UV-vis spectra of the H2Pc(15C5)4 solution show strong split peaks at 702 and 663 nm with shoulders at 645 and 603 nm, which are the typical phthalocyanine Q-band.30 The phthalocyanine Soret band is at 349 nm, while the weak absorption at around 419 nm can be assigned to the n-π* transition of alkoxyl-substituted phthalocyanines (Figure 1B, C, D).31 Different from the UV-Vis spectrum of H2Pc(15C5)4 in solution, the Soret bands from the UVVis spectra of different H2Pc(15C5)4 LS films show clear blue-shifts, indicating the H aggregations of H2Pc(15C5)4 molecules within the LS films.26, 32 Notably, the strongest blueshifts can be found from the LS films deposited from the surface of poly(L-lysine) solution (Figure 1C), suggesting the interactions with positively charged biomacromolecules induced the phthalocyanines to form strong H aggregates. The circular dichroism (CD) spectra of H2Pc(15C5)4 LS films were also measured, as shown in Figure 1. For getting rid of the influence of the linear dichromism (LD), all the CD measurements were performed with rotation. Interestingly, although H2Pc(15C5)4 is achiral molecule, its LS films obtained from pure water subphase show CD signal with Cotton effect (CE) maxima at ca. 750 and 645 nm (Figure 1B), indicating the formation of supramolecular chiral assemblies upon symmetry breaking at the air/water interface.33, 34 Moreover, the clear CD signals were also detected from the H2Pc(15C5)4 LS films deposited from the surface of poly(Llysine) solution (Figure 1C) and DNA solution (Figure 1D). Notably, the LS films obtained from


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different subphases show different CD signals. For CD spectra of H2Pc(15C5)4/poly(L-lysine) LS films, only positive Cotton effect were detected from the corresponding Q-band, which is totally different from that of the assemblies obtained on pure water surface. Thus, poly(L-lysine) molecules have induced phthalocyanine to form different supramolecular chiral assembly, and chirality of poly(L-lysine) was transferred onto the assemblies. These results confirm the existence of strong interactions between H2Pc(15C5)4 and poly(L-lysine) at the air/water interface. It is worth mentioning that positive CD signals are also always detected from the LS films prepared from DNA subphase. Although DNA has negative charge, while H2Pc(15C5)4 does not has any positive charge groups, the H2Pc(15C5)4/DNA interaction is still not negligible.35,36 Certainly, since poly(L-lysine) molecules have positive charges, the interactions between H2Pc(15C5)4 and poly(L-lysine) are relatively strong.


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Figure 1. (A) π−A isotherms of H2Pc(15C5)4 spreading films on pure water, poly(L-lysine) solution (1×10-3 M) and DNA solution (2×10-6 M); (B-D) CD spectra (top) and UV-Vis spectra (bottom) of H2Pc(15C5)4 10-layer LS films (solid line) as well as H2Pc(15C5)4 in chloroform (dotted line). The subphases can be pure water (B), poly(L-lysine) solution (C) and DNA solution (D). And the H2Pc(15C5)4 LS films were deposited at 2 mN/m (black curve), 5 mN/m (red curve) and 10 mN/m (blue curve) respectively. These assemblies fabricated at the air/water interface were further studied by AFM measurements. For the H2Pc(15C5)4 LB films transferred from pure water, short nanofibers with the height of 1.2 nm were detected (Figure 2A). When the surface pressure was increased to 10 mN/m, much closely packed nanofibers formed. Notably, the hierarchical packing of these nanofibers could form diverse nanostructures (Figure 2B). Interestingly, the AFM images of LB films deposited from poly(L-lysine) systems show many small helical nanorods (Figure 2C, 2D).


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The relatively strong interactions between H2Pc(15C5)4 and poly(L-lysine) could transfer the molecular chirality of biomacromolecules into phthalocyanine co-assemblies and help the formation of helical nanostructures. And the chiral poly(L-lysine) could induce phthalocyanine assemble into helical nanostructures. The AFM images of DNA/H2Pc(15C5)4 systems show nanoribbons together with some spheres (Figure 2E, 2F).

Figure 2. AFM image of H2Pc(15C5)4 LB films on the mica surface. These LB films were deposited from the surface of pure water (A-B), poly(L-lysine) solution (C-D) and DNA solution (E-F), with the surface pressure at 5mN/m (A, C, E) and 10 mN/m (B, D, F). In order to understand the possible molecular packing mode within these supramolecular assemblies, the X-ray diffraction measurements were performed on these LS films (Figure 3A). For the H2Pc(15C5)4 LS films transferred from pure water and poly(L-lysine) solution, layered


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nanostructures with spacing distance of 1.23 and 1.26 nm respectively were detected, which are consistent with the results obtained from the AFM measurement. However, from the XRD patterns of DNA/H2Pc(15C5)4 assemblies, no clear diffraction peaks can be detected. The formation of phthalocyanine/biomacromolecules co-assemblies was further demonstrated by FTIR measurements. For the FT-IR spectra of different assemblies, the C=C, C=N and N–H vibration of phthalocyanine were detected at ca. 1639, 1450 and 3390 cm-1, respectively. And the bands at ca. 1274 and 1095 cm-1 are attributed to the antisymmetric vibrations of C–O–C of crown ether (Figure 3B). These results suggest that phthalocyanine is the major component of these assemblies. Nevertheless, for FT-IR spectra of H2Pc(15C5)4/poly(L-lysine) LS films, the characteristic peak of amide linkage of poly(L-lysine) were clearly detected at 1665cm-1, indicating the quite a lot of poly(L-lysine) molecules within the co-assemblies (Figure 3B).

Figure 3. (A) X-ray diffraction patterns of 30-layer LS films of H2Pc(15C5)4 from different subphase: (a) pure water; (b) Poly(L-lysine); (c) DNA; (B) FT-IR spectra of 50-layer LS films of H2Pc(15C5)4 from different subphase: (a) pure water; (b) Poly(L-lysine); (c) DNA.


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The air/water interfacial assembly of phthalocyanine containing four crown ether substituents (H2Pc(15C5)4) could form H-aggregates with weak supramolecular chirality upon symmetry breaking. And chiral biomacromolecules dissolved in water subphase could help H2Pc(15C5)4 form co-assemblies with different nanostructures and supramolecular chirality. Certainly, the interactions between phthalocyanine and poly(L-lysine) are relatively strong, which lead to much ordered molecular packing mode and helical nanostructures. Fluorescence properties and chiral recognition of poly(L-lysine)/H2Pc(15C5)4 coassemblies. When it was excited at 470 nm, poly(L-lysine)/H2Pc(15C5)4 LS films showed relatively strong fluorescence (Figure 4). It is worth mentioning that the fluorescence of H2Pc(15C5)4/poly(L-lysine) assemblies keeps unchanged, even though the LS films were immersed in pure water for 5 hours. Therefore, although the fluorescence intensity of many phthalocyanine systems is weak, the poly(L-lysine)/H2Pc(15C5)4 assemblies have good fluorescence properties. Presumably, due to the interactions between poly(L-lysine) and H2Pc(15C5)4, the phthalocyanine assemblies could not take very crowed molecular packing modes

and

thus

prevent

the

quenching

of

fluorescence.

Moreover,

since

the

H2Pc(15C5)4/poly(L-lysine) chiral assemblies with fixed handedness were obtained, the application of these systems for chiral recognition was investigated. The proposed strategy is dependent on the changes of fluorescence of H2Pc(15C5)4/poly(L-lysine) assemblies upon the interaction with other small chiral molecules. Another worth noting is that poly(L-lysine) was found to have good potential for molecular sensing,37-38 which should also be helpful for achieving chiral recognition. As a type of polypeptide, poly(L-lysine) is expected to have subtle interactions with different amino acids. Therefore, the most representative amino acids, including acidic, basic, heterocyclic


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and aromatic amino acids, were firstly selected as objects for molecular recognition and chiral recognition. Indeed, when H2Pc(15C5)4/poly(L-lysine) LS films were dipped in the aqueous solution of different amino acids, the corresponding fluorescence spectra changed dramatically depending on the molecular structures and chirality of the amino acids (Figure 4, 5). Thus, the H2Pc(15C5)4/poly(L-lysine) assembly not only recognize amino acids with different molecular structures and properties, but also clearly discriminate enantiomers of some amino acids (Figure 4).

Figure 4. (A-C) The changes of fluorescence of H2Pc(15C5)4/poly(L-lysine) LS films upon dipping in the aqueous solution of different amino acids. The black curve represents the original fluorescence of H2Pc(15C5)4/poly(L-lysine) assemblies; (D) molecular structures of glutamic acid, aspartic acid and proline. The most interesting results were observed from the systems of acidic amino acids. When H2Pc(15C5)4/poly(L-lysine) LS films were immersed into the aqueous solution of L-glutamic acid, the fluorescence intensity increased dramatically (Figure 4A). In contrast, D-glutamic acid always induces remarkably decrease in the fluorescence of H2Pc(15C5)4/poly(L-lysine) assemblies (Figure 4A). Therefore, the chiral recognition for glutamic acid is achieved upon the


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changes

of

fluorescence

intensity

of

phthalocyanine.

The

chiral

recognition

of

H2Pc(15C5)4/poly(L-lysine) assemblies also works very well for aspartic acid (Figure 4B), which is another typical acidic amino acid. The interactions between acidic amino acids (such as glutamic acid) and positively charged poly(L-lysine) could influence the fluorescence of phthalocyanine assemblies. Presumably, the interactions between poly(L-lysine) and the enantiomers of acidic amino acids is also different, rendering the successful chiral recognition. It is worth mentioning that H2Pc(15C5)4/poly(L-lysine) assemblies can also clearly differentiate Land D-Proline upon the change of fluorescence (Figure 4C). Considering proline derivatives have been widely used for supramolecular chiral catalysis,39 chiral recognition of proline by using simple supramolecular systems could meet important applications. These results suggest that the chiral recognition of H2Pc(15C5)4/poly(L-lysine) assemblies is able to be applied to the broader molecular systems. In contrast, the typical basic amino acids such as arginine cannot change the fluorescence of H2Pc(15C5)4/poly(L-lysine) LS films (Figure 5A), perhaps due to the weak interactions between basic amino acids and poly(L-lysine). On the other hand, when the H2Pc(15C5)4/poly(L-lysine) assemblies were dipped in the aqueous solution of amino acids containing aromatic moieties, such as phenylalanine and histidine, the decrease in the fluorescence intensity can be detected (Figure 5B, 5C). Notably, the interactions with different aromatic amino acids lead the different quenching degree of the fluorescence, which differentiate phenylalanine from histidine. However, the enantiomers of aromatic amino acids, such as L-phenylalanine and Dphenylalanine, cannot be discriminated by the changes of steady-state fluorescence. Considering the fluorescence of H2Pc(15C5)4/poly(L-lysine) LS films was quenched largely by both Lphenylalanine and D-phenylalanine, we wonder if chiral recognition on aromatic amino acids


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can be achieved by measuring fluorescence quenching rate. Therefore, the time scan mode fluorescence spectra of H2Pc(15C5)4/poly(L-lysine) assemblies in both L-phenylalanine or Dphenylalanine aqueous solution were studied (Figure 5D). Interestingly, the interactions with Dphenylalanine induce the faster fluorescence decay of H2Pc(15C5)4/poly(L-lysine) assemblies, which is different from the case of interacting with L-phenylalanine. Based on the dynamic changes of H2Pc(15C5)4/poly(L-lysine) fluorescence, the enantiomers of aromatic amino acids can also be distinguished. Notably, the diffusion of the phenylalanine molecules, as well as the change of molecular packing mode of phthalocyanine assemblies could be time-consuming, which results in the delay for fluorescence change (Figure 5D).

Figure 5. (A-C) The changes of fluorescence of H2Pc(15C5)4/poly(L-lysine) LS films upon dipping in the aqueous solution of different amino acids. The black curve represents the original fluorescence of H2Pc(15C5)4/poly(L-lysine) assemblies; (D) fluorescence quenching (706 nm emission) of H2Pc(15C5)4/poly(L-lysine) assemblies upon dipping in the aqueous solution of D-


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phenylalanine and L-phenylalanine; (E) molecular structures of arginine, histidine and phenylalanine. Depending on the changes of the fluorescence of H2Pc(15C5)4/poly(L-lysine) LS films, chiral recognition on different types of amino acids has been demonstrated. Certainly, the multi-object chiral recognition with discriminating chiral isomers of both amino acids and sugars is really attractive. Since carbohydrate molecules have many hydroxyl groups, the interactions between carbohydrate molecules and H2Pc(15C5)4/poly(L-lysine) assemblies should be strong enough to change the fluorescence of phthalocyanine. In this context, we select several typical monose molecules with the smallest structure and chirality differences for recognition. The molecular structures of D-glucose, D-galactose and Dmannose are very similar. Their differences are reflected on only one chiral carbon atom (Figure 6C). Firstly, the H2Pc(15C5)4/poly(L-lysine) LS films were dipped into the aqueous solution of D-glucose, D-galactose and D-mannose, respectively. And the fluorescence spectra of H2Pc(15C5)4/poly(L-lysine) assemblies were measured. The results show that the interaction with all these monose compounds could dramatically decrease fluorescence intensity of H2Pc(15C5)4/poly(L-lysine) assemblies. Moreover, over a sufficiently long time horizon the fluorescence quenching of all the cases are able to reach very large degree (Figure 6A). Therefore, these epimers still cannot be distinguished based on the steady-state fluorescence spectra.


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Figure 6. (A) The changes of fluorescence of H2Pc(15C5)4/poly(L-lysine) LS films upon dipping in the aqueous solution of D-glucose, D-galactose and D-mannose respectively. The black curve represents the fluorescence of original H2Pc(15C5)4/poly(L-lysine) assemblies; (B) fluorescence quenching (706 nm emission) of H2Pc(15C5)4/poly(L-lysine) assemblies upon dipping in the aqueous solution of D-glucose, D-galactose and D-mannose; (C) molecular structures of D-glucose, D-galactose and D-mannose. In order to discriminate chiral isomers of sugars, the dynamic changes of fluorescence spectra of H2Pc(15C5)4/poly(L-lysine) assemblies were investigated. Figure 6B shows the fluorescence quenching rates of H2Pc(15C5)4/poly(L-lysine) assemblies in D-glucose, D-galactose and Dmannose aqueous solution. Interestingly, upon interaction with different epimers of monose, the fluorescence quenching rates of H2Pc(15C5)4/poly(L-lysine) assemblies are totally different, suggesting the recognition of these chiral isomers. Notably, interaction with D-glucose leads the fastest fluorescence quenching, while interaction with D-mannose renders the lowest fluorescence quenching of H2Pc(15C5)4/poly(L-lysine) assemblies. Considering the difference between D-glucose and D-mannose is the orientation of only one hydroxyl group (Figure 6C), the

significant

difference

of

fluorescence

change

again

clearly demonstrates

that

H2Pc(15C5)4/poly(L-lysine) assembly is a very good system for chiral recognition.


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Possible mechanism for the chiral recognition of H2Pc(15C5)4/poly(L-lysine) coassemblies. When H2Pc(15C5)4/poly(L-lysine) LS films were interacted with different types of amino acids or sugars showing changed molecular chirality, the variations of their fluorescence spectra could be different. And the chiral recognition was achieved either by measuring the steady-state fluorescence spectra or by comparing the fluorescence quenching rate of relevant H2Pc(15C5)4/poly(L-lysine) assemblies. One of the most typical examples is from differentiating enantiomers of glutamic acid. Although there is only slightly structural difference, interaction with L-glutamic acid can greatly increase the fluorescence intensity of H2Pc(15C5)4/poly(Llysine) assembly, while interaction with D-glutamic acid always gets quenching of fluorescence. Considering glutamic acid is small organic molecule without special photophysical properties, such gigantic changes of fluorescence should derive from the transformation of phthalocyanine aggregations.29 Due to the different molecular chirality of L or D-glutamic acids, the interactions between poly(L-lysine) and enantiomers of glutamic acid should be different. When D-glutamic acid was

interacted

with poly(L-lysine) or crown

ether groups of H2Pc(15C5)4,

phthalocyanine/poly(L-lysine) assembly may change into more tight aggregation, and the fluorescence of phthalocyanine was quenched (Figure 7). In contrast, the interactions between Lglutamic acid and H2Pc(15C5)4/poly(L-lysine) assembly could induce not too closely molecular packing mode, which lead the enhancement of fluorescence (Figure 7).


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Figure 7. Schematic illustration shows the possible mechanism of phthalocyanine/poly(L-lysine) assembly chiral recognition on enantiomers of glutamic acid. This issue has been demonstrated by the AFM images, UV-Vis spectra and CD spectra of H2Pc(15C5)4/poly(L-lysine) assemblies upon interaction with enantiomers of glutamic acid. The AFM images of H2Pc(15C5)4/poly(L-lysine) assembly upon interaction with D-glutamic acid show much larger nanoparticles (Figure 8B) compared with that of the systems treated with Lglutamic acid (Figure 8A), suggested that D-glutamic acid could lead stronger aggregation of phthalocyanine molecules. And the UV-Vis spectra of H2Pc(15C5)4/poly(L-lysine) assemblies show red-shifts at Q-band after dipping in glutamic acids solution, which prove the changes of phthalocyanine aggregation (Figure 8C). Notably, the red-shift triggered by D-glutamic acid is even larger than the case of L-glutamic acid/H2Pc(15C5)4/poly(L-lysine) system (Figure 8C). Moreover, the AFM images of H2Pc(15C5)4/poly(L-lysine) assemblies upon interaction with D-


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glucose were also studied. Very large particles with the height more than 7.0 nm were detected (Figure 8E). These results suggest that monose molecules could help phthalocyanine form large assemblies, which induce the quenching of fluorescence. And the red-shifts at Q-band were also detected from the UV-Vis spectra of H2Pc(15C5)4/poly(L-lysine) assemblies interacted with different monose. D-glucose molecules, which induce the fastest fluorescence quenching, make the largest red-shift of the UV-Vis spectra of H2Pc(15C5)4/poly(L-lysine) assemblies. In addition, no clear cotton effect can be detected from the CD spectra of H2Pc(15C5)4/poly(Llysine) systems upon interaction with enantiomers of glutamic acid and monose (Figure S1), which further demonstrates the changes of phthalocyanine aggregation.

Figure 8. (A, B, E) AFM image of H2Pc(15C5)4/poly(L-lysine) assemblies after dipping in the aqueous solution of L-glutamic acid (A), D-glutamic acid (B) and D-glucose (E); (C, D) UV-Vis spectra of H2Pc(15C5)4 10-layer LS films after treated by aqueous solution of glutamic acids (A) and monose (B).


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Moreover, as a type of chiral polymer, the interactions between poly(L-lysine) and different small chiral molecules could be very important for the chiral recognition. And there should be relatively strong interactions between acidic amino acids (such as glutamic acid) and positively charged poly(L-lysine), which could further influence the fluorescence of phthalocyanine assemblies. The interactions between poly(L-lysine) and the enantiomers of acidic amino acids is also different, rendering the successful chiral recognition. In contrast, the interactions between positively charged basic amino acids (such as arginine) and poly(L-lysine) could be too weak to induce change in the fluorescence of the assembled phthalocyanine molecules. On the other hand, the interactions between phthalocyanine and different small chiral molecules also cannot be ignored. In the case of phenylalanine, presumably the π-π interactions between aromatic moieties and phthalocyanine molecules lead close packing of molecules and quench the fluorescence. Many hydroxyl groups on monose may have strong interactions with both H2Pc(15C5)4 and poly(L-lysine), which lead the aggregation of phthalocyanine and quenching of fluorescence, and achieve the chiral recognition for monoses. Notably, depending on different molecular structures of these monoses, the rate and degree for forming induced aggregations should be different. In principle, a monose molecule with more adjacent hydroxyl groups adopting same direction, could form better cooperative effect for interaction with H2Pc(15C5)4/poly(L-lysine) assemblies.40 Therefore, D-glucose molecules could induce stronger aggregation and the fastest fluorescence quenching. It is worth mentioning that the excellent multi-object chiral recognition properties of H2Pc(15C5)4/poly(L-lysine) assembly should be dependent on its subtle molecular packing mode and the cooperation of different non-covalent interactions. The planarity of the aromatic ring of phthalocyanine molecules could enhance the π-π interactions and induce the tendency of


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aggregation and fluorescence quenching. In contrast, the interactions between crown ether substituents and poly(L-lysine) tend to help the separation of phthalocyanine molecules. The balance of these two trends lead to the sensitivity of the fluorescence of H2Pc(15C5)4/poly(Llysine) assembly. Therefore, for the proline, even though interactions between proline and H2Pc(15C5)4/poly(L-lysine) assemblies are not significant, these relatively weak interactions are also able to discriminate chiral molecules by using H2Pc(15C5)4/poly(L-lysine) LS films. CONCLUSION In summary, the air/water interfacial assembly of achiral phthalocyanine containing four crown ether substituents not only can form H-aggregates with supramolecular chirality, but also can form complex with charged polymers, such as poly(L-lysine) and DNA. Most interestingly, depending on the changes of fluorescence of phthalocyanine/poly(L-lysine) assemblies, molecular recognition and chiral recognition of many different types of amino acids as well as monosaccharides could be achieved. These results not only help us to further understand the interaction within supramolecular systems, but also open a new strategy for multi-object chiral recognition by using simply supramolecular assemblies.


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AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] *E-mail: [email protected] Notes The authors declare no competing financial interest. ACKNOWLEDGMENT Financial support from the National Key Basic Research Program of China (Grant No. 2013CB933402), Natural Science Foundation of China (Nos. 21290174, 21631003, 21671017, 21301017, 21401009, and 21474118), Beijing Municipal Commission of Education, and University of Science and Technology Beijing is gratefully acknowledged. REFERENCES (1) Berg, J. M.; Tymoczko, J. L.; Gatto, G. J., Biochemistry. W. H. Freeman & Co Ltd., 2015. (2) Yu, F.; Cangelosi, V. M.; Zastrow, M. L.; Tegoni, M.; Plegaria, J. S.; Tebo, A. G.; Mocny, C. S.; Ruckthong, L.; Qayyum, H.; Pecoraro, V. L., Protein Design: Toward Functional Metalloenzymes. Chem. Rev. 2014, 114 (7), 3495-3578. (3) Banik, S. D.; Nandi, N., Chirality and protein biosynthesis. Top. Curr. Chem. 2013, 333 (Biochirality), 255-306. (4) Aviles-Moreno, J. R.; Quesada-Moreno, M. M.; Lopez-Gonzalez, J. J.; Martinez-Haya, B., Chiral Recognition of Amino Acid Enantiomers by a Crown Ether: Chiroptical IR-VCD Response and Computational Study. J. Phys. Chem. B 2013, 117 (32), 9362-9370.


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SYNOPSIS: Identical phthalocyanine/poly(L-lysine) supramolecular assembly fabricated at the air/water interface can distinguish both the enantiomers of different types of amino acids as well as epimers of monose, depending on the changes of fluorescence.


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Fluorescent phthalocyanine assembly distinguishes chiral isomers of

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