A luminescent hybrid membrane-based logic device - ACS Publications

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Functional Inorganic Materials and Devices

A luminescent hybrid membrane-based logic device: from enantioselective discrimination to read-only memory for information processing Xiao Lian, and Bing Yan ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b09502 • Publication Date (Web): 09 Aug 2018 Downloaded from http://pubs.acs.org on August 20, 2018

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ACS Applied Materials & Interfaces

A Luminescent Hybrid Membrane-Based Logic Device: from Enantio-Selective Discrimination to Read-Only Memory for Information Processing Xiao Lian and Bing Yan* Shanghai Key Lab of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Tongji University, Siping Road 1239, Shanghai 200092, China Keywords: enantiomer recognition; luminescent hybrid membrane; logic circuit device; read-only memory; molecule computing

Corresponding author: Prof. Dr. Bing Yan, Email: [email protected] ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Abstract: Logic circuit device and molecule computer are idealized binary tools to implement manifold signals transformation and operation, which is a basic component of integrated circuits and widely used in computer, CNC (Computerized Numerical Control) and communication fields. By combining the advantages of the synthetic feasibility and enantio-selective luminescent recognition, a logic device based on the lanthanide functional membrane has been constructed, for effective recognize enantiomer and judge the enantiomer excess of chair drug mixture. In addition, it would be interesting if such logic circuit could be assembled into a loop circuit to realize intelligent control of Electronic component. A read-only memory (ROM) arrays built by the logic circuit are also actualized, which can be con-verted and stored binary strings. This work provides an active and universal approach to modulate luminescent device and logic circuit based on chemical sensor, with promising application for intelligent control, information processing and hu-man–machine interaction.

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Introduction Molecular logic and molecule compute was a continuously developing interdisciplinary field that captured worldwide interest, since the first example of the molecular logic gate was proposed 25 years ago.1,2 This is an ideal way of logic operation for processing information contained in photonic, electronic, and chemical signals.3 Applying the laws of Boolean arithmetic, various simple logic gates and multilevel networks are building up by employing organic molecules,4-6 polymers,7,8 nano-materials9-11 and biomolecules.12,13 To explore new dimensions of this interesting research area, metal-organic frameworks (MOFs) were integrated with different functional materials to construct logic gates.14,15 In recent years, chiral MOFs, as a kind of very promising candidate for selective recognition and separation,16-21 attracted the attention of many researchers around the world, due to their specific surface area, modifiable functional sites and diversity of host-guest interactions.22,23 The homochirality of MOFs could be constructed via distinct strategies. In the first way, chiral MOFs are synthesis from homochirality molecules as primary linkers or auxiliary ligands.24 On the other hand, post-synthetic modification (PSM) could also provide a valid strategy to prepare chiral MOFs.25 PSM strategies have been demonstrated as an attractive route for functionalization of MOFs,26,27 for instance, which will be able to construct enantio-selective response luminescent MOFs (Ln-MOFs). Ln-MOFs have brought bright promise to the development of luminescent functional materials, such as LED,28 chemical sensor,29-32 luminescent thermometer33,34 and biological detecting.35,36 Furthermore, because of the combination of multi-luminophores in framework, lanthanide MOFs can proceed to binary and multivalued information for multiparameter chemosensing and logic device processing.37,38 Herein, we describe a new strategy for the fabrication of enantio-selective membrane (Eu@1@ZnO) for logic circuit device. As a chiral metal-organic framework, the original MOFs (1) ACS Paragon Plus Environment


are promising materials for enantioselective recognition because of its highly tunable structures and three-dimensional pores that can be precisely tailored for adsorption of specific guest molecules. In addition, as a sensitive luminescent probe for various chemicals, europium ion has strong narrow band emission and long fluorescence lifetime. Eu@1@ZnO will provide visual resolution for enantiomers, and membrane-based discrimination outperforms other chiral separation materials for the resolution of racemates because of its high efficiency, high throughput, low cost, recyclability and easy operation. This membrane exhibits preferential sensing performance to R-penicillamine (R-Pen) over S-penicillamine (S-Pen), with a ratiometric luminescence response. S-Pen is a valuable pharmaceutical for autoimmune disease like Wilson's disease and rheumatoid arthritis, however, the isoforms of the R- configuration may lead to gene mutation. Utilize the change of the fluorescence of sensing membrane, the design and application of a half-adder logic gate is actualized. Armed with this logic gate, a circular logic circuit is designed and implemented for intelligent control of LED. In addition, integrating Boolean operation and hybrid device, we assembling an intelligent molecular read-only memory (ROM) arrays for information processing and writing successfully for the first time. Our approach will provide possibility for devise and realizing intelligent molecular machine, and actualize the application of electronic detector, circulator, controller, and memorizer.


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Experimental Section Materials and Reagents EuCl3·6H2O was prepared by dissolving Eu2O3 into hydrochloric acid under stirred, subsequently evaporate the solution several times for crystallization. Penicillamine with different stereoisomerism were purchase form Aladdin (D-Pen, 98%) and TCI (L-Pen, 98%), respectively. Characterization and Instruments The scanning electron microscopy (Hitachi S-4800 SEM) was used to observe the morphology of the samples. Energy dispersive analysis of X-rays (EDX) spectrum and EDX-mapping image were obtained by the SEM operating at 15 kV. XPS (Axis Ultra DLD) measurements of samples were performed under ultrahigh vacuum. Powder X-ray diffraction (PXRD) patterns were recorded on a Bruker D8 ADVANCE diffractometer with Cu Kα radiation. Fluorescence measurement was carried on a FLS920 spectrometer with Xenon lamp (450 W). Synthetic Process ZnCar (1) powder: ZnCar (1) was synthesized in the light of a previously reported method with some modifications.39 Typically, 0.526 g of Zn(NO3)·6H2O (General-Reagent, AR) and 0.2 g of carnosine (β-alanyl-L-histidine, Adamas-beta, 98%) were solved in a mixing solvent of 20 mL DMF and 9 mL DI H2O. The mixing solution was loaded in a 50 mL polytetrafluoroethylene-lined steel autoclave. The autoclave was heated at 373 K for 12 h and was cooled down to room temperature in 2 h. The product was collected with centrifugation and washed with ethanol several times. 1-dk and Eu@1 powder: The product 1 (above 200 mg) was treated with an anhydrous mixture of 20 mL of cyclohexane, 5 mL of chloroform and 0.5 mL of diketene (Adamas-beta, 97%). The reaction was performed at 323 K for 3 days, and a flavescent or orange powder were obtained after centrifugation. For preparation of Eu@1, 1-dk (50 mg) and EuCl3·6H2O (10 mg) were added into a bottle with MeOH (10 mL), followed by continuous stirring for 12 h at 333K. ACS Paragon Plus Environment

40

The entire


preparation is displayed in Figure S1. Eu@1@ZnO membrane: The heterostructure membrane was prepared on ZnO support by the RS method.41,42 A typical synthesis procedure contained two steps. Seeding step: β-alanyl-L-histidine (0.2 g), DMF (20 mL) and DI H2O (9 mL) were mixed and stirred to a transparent solution. A ZnO support was placed in an autoclave (50 mL) with the precursor solution, and then the autoclave was placed in an oven at 373 K for 12 h. Second step: the seeded ZnO support was placed into a autoclave, and added the precursor solution (0.526 g Zn(NO3)·6H2O, 0.2 g β-alanyl-L-histidine, 20 mL DMF and 9 mL DI H2O) into it. Subsequently, the autoclave was heated at 373 K for 12 h and cooled down to room temperature in 2 h. The membrane was washed with ethanol and dried in air. For preparation of Eu@1@ZnO membrane, 1@ZnO membrane was placed in sealed Teflon bottle with a mixture of cyclohexane (20 mL), chloroform (5 mL) and diketene (1 mL), reacted for 3 days, and then treated with Eu3+ solution as mentioned earlier. Finally, a yellow membrane with red emission under UV light was obtained (Figure 1). Recognition for Pen enantiomer: the concentrations of the enantiomers were analysed with Edinburgh FLS920 spectrophotometer. The Pen solution with different concentrations or different enantiomeric excess (e.e.) were dripped to the luminescent membranes and tested by PL spectra. The enantiomeric excess (e.e.) was defined as Equation (S1): e. e. % = 100 ×

− 1 +

The quenching ratio of the enantioselective fluorescence (e.f.) was defined as Equation (S2): e. f. =

− 2 −

where the I0 is the initial fluorescence intensity of Eu@1@ZnO membrane, the IR and IS are the fluorescence intensity of Eu@1@ZnO membranes after the addition of the same concentration of R-Pen and S-Pen, respectively.43


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Results and Discussion To illustrate the proof of principle, a water-stable chiral MOFs ZnCar (1) was synthesis from Zn(NO3)2·6H2O and the natural dipeptide carnosine.39 The luminescent recognize membrane was prepared through seeding step and growth step (Figure 1a-d and Figure S2).41,42 Eu3+@1@ZnO membrane was obtained via PSM method to formed pendant β-diketone arms (Figure S1), and Eu3+ incorporated subsequently.40 The powder X-ray diffraction (PXRD) study (Figure 1e) showed MOFs 1 to be isostructural with simulated pattern. To confirm the preparation of membrane, the crystal structure of Eu@1@ZnO was analysed. As showed in Figure 1e, the characteristic peaks of 1 can be observed in all two PXRD patterns of Eu@1@ZnO layer, and no impurity phases are found except for the ZnO (Figure S3). Nitrogen purging experiment was conducted for test macroscopic stability of the membrane. After one-hour purge of N2 at a flow rate of 25 L min-1 (0.15 MPa), the mass of the film only decreased by 0.7% (Figure S4). Air stability of Eu@1@ZnO membrane was demonstrated in Figure S5, after exposure to air for three days (R.T.), the XRD of the film did not change, which proved the good stability of the film in the air. The surface morphology of Eu@1@ZnO (Figure 1f) shows that regular crystal particles which are uniform spheres with loose pore structure (Figure S6) are uniformly deposited on the ZnO support. Figure 1g shows the cross-sectional microstructures of the prepared membranes, which elucidate that the membrane layer is well bonded on ZnO, and the thickness of MOFs layer is about 1 mm. Elemental analysis of Eu@1@ZnO was given by EDX spectra (Figure S7), and the EDX-mapping images show that the Eu3+ is distributed evenly (Figure 2a-c). XPS measurement was conducted (Figure S8) and the N 1s spectra are presented in Figure 2d and 2e. For N 1s spectra, the deconvolved peaks from low to high field are assigned to imidazole rings (398.8 eV), amino groups (399.4 eV), and C−N bond between amino groups and diketene ACS Paragon Plus Environment


(401.6 eV). For 1@ZnO sample, the peak at 401.6 eV is also contributed to amide groups in dipeptide. By comparing the integral fraction of last peak (red solid line in Figure 2d and 2e) in 1@ZnO (4.35%) and Eu@1@ZnO (11.91%), we deduce that the grafting of dienone to form amides is feasible.44 Nuclear magnetic resonance (1H-NMR) was measured for powder product of PSM reaction (1-dk), which result from the digested 1-dk gives new resonance at 2.25 and 3.70 (Figure S9), confirming the formation of β-diketone. The peaks of stretching vibration absorption of C=O (1577 or 1562 cm-1) and C=C (1643 or 1622 cm-1) bonds in the spectra of 1-dk@ZnO and Eu@1@ZnO demonstrates the obtainment of β-diketone structure (Figure S10). In addition, the peak shifts of the spectrum of Eu@1@ZnO compared to that of 1-dk@ZnO reveal the coordinate interaction between Eu3+ and β-diketone. Similarly, compared with EuCl3·6H2O, the peak of Eu@1@ZnO in XPS Eu 3d spectra moves ca. 1.3 eV to lower binding energy region (Figure S11). This indicates an increase in the electron density of the Eu3+ ions, which reveals some difference of Eu3+ between EuCl3·6H2O and Eu@[email protected] Prior to further detectable application, the solid-state photoluminescence of Eu@1@ZnO is studied. As shown in Figure S12, the characteristic emissions of Eu3+ in the range of 580–710 nm are assigned to the 4f-4f transitions of the 5D0 excited state to 7FJ (J = 0, 1, 2, 3 and 4) levels. The weak emission band centered at 475 nm is associated with the π* → π transition of the organic framework 1 (Figure S13), and the substrate does not show emission band of ZnO due to the large band gap. The red fluorescence that visible from the naked eye can be used as a fluorescent probe (Figure 1d), especially, after prolonged immersion, its fluorescence intensity remains stable (Figure S14). The enantiomer recognition of Eu@1@ZnO membrane was measured by PL spectra toward R-Pen (Figure S15) and S-Pen (Figure S16) solutions with various concentrations. It is obvious that Eu@1@ZnO have showed conspicuous enantioselective recognition of Pen enantiomers. In addition, ACS Paragon Plus Environment

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when the concentrations of R-Pen were increased from 0 to 0.12 mM, the luminescence intensity of the emission at 615 nm (Ired) decreased, while the ligand emission (Iblue, λ = 475 nm) increased. However, the whole fluorescence spectra of Eu@1@ZnO membranes does not change with the concentration of S-Pen increased. The concentration of R-Pen was quantificational analysed using the luminescence respond signals, which defined as the ratio of Iblue to Ired (Figure S17 and Table S1). There was a good linear relationship (R2 = 0.9866) between the response signals and the R-Pen concentration in the range of 0 – 0.12 mM, and a LOD of 0.58 ppm was calculated according to the 3σ IUPAC criteria, the detailed calculative process was in Supporting Information. Considering the practical application of material, cycle experiment is also conduct to verify the recyclability of materials (Figure S18). After three cycles, the detection performance decreased significantly, which may be caused by the detachment of powder from the substrate under ultrasonic irradiation. Considering the quenching ratio of the enantioselective fluorescence (e.f.) of the membranal sensor is determined as 107.2,43 which means this sensor can distinguish two enantiomers of Pen with high selectivity. Nevertheless, enantiomeric composition of the analyte often also investigated, hence we go ahead with test e.e.% of R-Pen in the mixtures of Pen enantiomers. A study of the effect that emission of Eu@1@ZnO membranes influenced by enantiomeric compositions with various e.e.% (-100% - 100%) of R-Pen solutions was conducted. As we increase the e.e.% of R-Pen, the fluorescence of Iblue is linearly enhanced while the Eu3+ emission quenched (Figure 3). The linear curve of Iblue/Ired vs. e.e.% of R-Pen is shown in Figure S19 and gives a correlation coefficient (R2) of 0.9946, which is indicative of that e.e. of Pen enantiomers may be quantitatively analysed in whole ranges of e.e.%. The most frequently proposed mechanisms for enantio-selective sensor is the specific binding between R- and S- stereocenter,25 and the consequent energy transfer uncaged or forbidden. The carnosine ligands have been used to endow the pore structure with S configuration of the sensor ACS Paragon Plus Environment


material, which could be bonded to amino acids with opposite configuration (R configuration) by hydrogen bonding. It is easier for R-penicillamine to enter the pores and then get trapped in the framework. On the other hand, the lack of hydrogen bonding interactions between S-amino acid guests and the chiral framework result in the unbound optical isomer. Thus, the enantioselective recognition of penicillamine was realized, because of the similar structure of penicillamine with chiral amino acids. After recognition experiments, the UV-Vis spectrum of Eu@1@ZnO shows a new absorption band in ultraviolet region, compared to the original spectrum (Figure S20). We speculate that this is due to the combination of R-Pen and Eu@1@ZnO, and the fluorescence quenching effect was not affected by Pen analogues or derivatives (Figure S21). The fluorescence decay curves (Figure S22 and S23) indicate that there is no change in the lifetime of emission of Eu3+, and the lifetime of Emblue is increased (Table S2), which means a stable binding structure between R-Pen and detecting membrane is forming, and it was proved that static quenching for 4f-4f transition occurs together with forbidden energy transfer from ligand to Eu3+. Consequently, the luminescent colour of the membrane can be observed from red to blue. Inspired by the enantiotropic induced colour change of the Eu@1@ZnO membranes, we also show that the enantio-selective response membrane is applicable for the logic circuit and to applicated in enantiomer monitor, circulating control electrocircuit and ROM arrays. At first, a logic gate circuit (GC-1) as a half-adder (Figure 4a and Figure S24), was designed based on the emission change of Eu@1@ZnO membrane. In consideration of the inputs, the existence and absence of R-Pen are defined as input signals “1” and “0” respectively. Ultraviolet excitation is a necessary condition for producing fluorescence, which can be regarded as constant input “1” in logic statements. The normalized fluorescence intensities of Emblue and Emred are regard as output signal, and select the threshold value as 0.5 (Figure S25). Emblue and Emred keep their original states when P-Pen is absent, and export the output (0, 1). In the presence of R-Pen, Emblue intensity increased and ACS Paragon Plus Environment

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Emred intensity decreased, generating the output (1, 0). The truth table of the half-adder logic circuit is given in the Figure 4b. The quantitative input of R-Pen is also applicable for GC-1, the column diagram for selecting threshold and truth table is shown in Figure S26 and Table S3. A more sophisticated detecting strategy was proposed subsequently, the content (e.e.%) of R-Pen replaced the input value 0 or 1, and the fluorescence intensity at 0% e.e. was chosen as the threshold (Figure 4c). The changes of the output signals of the logic device provides direct analysis for R-Pen levels in the enantiomer mixture. As shown in Table S4, the output (0,1) triggered by the negative e.e.%, and the output value of the raceme was defined as (0,0). When the e.e.% was go up to positive value, the output gates (1,0) appeared, and the colour of Eu@1@ZnO was changed to blue region (Figure S27). The as-prepared logic circuit could implement well for analysis R-Pen levels though discriminating colour changes. For more convenient analysing R-Pen, the colour changes can be expressed in RGB values, and the truth table of GC-1 with RGB as output is also provided (Figure S28 and Table S5). Whereafter, it is also designed and actualized that a reverse gate circuit with input “Emblue” and “Emred” and output “e.e.%”. As shown in Figure 5a and Figure S29, a gate circuit (GC-2) which was constituted of three-state gate and NAND gate could output three signals: “0”, “1” and “Z” (high impedance). By selecting the same threshold as GC-1, GC-2 could output signal “1” in presence of Emblue only. In the presence of Emred input only, the GC-2 would output the signal “0” which indicates the negative value of e.e.%. The signal “Z” is a special output of three-state gate, which means that the circuit is in the open circuit at this time. The signal “Z” is output only when the input signal is (1,1), indicating that the detected mixture is a raceme (e.e.% = 0%). The truth table for this logic gate are given in Figure 5b. Interestingly, input and output of GC-1 and GC-2 are exactly one-to-one correspondence, and they can make up a reversible cycle circuit. The cycle circuit GC-3 is exhibited in Figure 6a, the red and blue dotted boxes are GC-1 and GC-2 respectively, and they formed a closed loop together. As a ACS Paragon Plus Environment


steerable electronic component, LED is supervised by the output value of the circuit. For example, “0” as an initial value is input into GC-3, it will output “1” and make the LED turn on. The above-mentioned output will be transfromed to a new input and import into GC-3, thus a cycle has been completed. After the first cycle, the output of GC-3 will be changed to “0” and make the LED turn off. Consequently, “0”and “1” will be output by the GC-3 alternated and uninterrupted (Figure 6b), and the intelligent control of LED that uninterrupted scintillation between “ON” and “OFF” is achieved. Furthermore, the transformative circuit of GC-3 is applied in ROM arrays. ROM is a common information memory in a computer and using binary encoding to achieve huge information writing. As the chart shows (Figure 6c), the output of GC-1 was used as ROM decode, and a set of algorithms for decoding and writing information is designed (details of the algorithms are in Supporting Information). For example, when the signal (0,1) input into the ROM matrix, the “AND” logic gate code is calculated as (W0, W1, W2, W3 = 0, 1, 0, 0), and a string (D0, D1, D2, D3 = 1, 1, 0, 1) is written and stored in the ROM (Figure 6d). By controlling the e.e. % of R-Pen of solution, and further controlling the intensity of the blue and red emission, the function of information storage is realized. That means GC-3 logic device has been preliminarily applied through spectrometers.© By designing logic circuits and algorithms, the MOFs membrane can integrate ROM and store binary information. As far as we know, this is firstly that applying MOFs composite to the design logic elements for ROM arrays.

Conclusion In conclusion, a new luminescent enantiomer recognition membrane which consists of homochiral MOFs and ZnO substrate was successfully fabricated. We have constructed Boolean logic device that crucially, can implement well in analysing R-Pen levels via colour discrimination. In addition, ACS Paragon Plus Environment

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complex logic gate system could operate as cycling circuit to control the electronic device. For further application, we have constructed an intelligent molecular ROM arrays for information processing and writing. The platform based on Eu@1@ZnO membrane has achieved the combination of enantiomer discrimination and logic operation in hybrid materials to construct intelligent detector, circuit controller and information memorizer, which prove more approaches to develop artificial intelligence in molecular computing.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Physical characterization, mechanism discussion, circuit diagrams and truth tables, algorithms of ROM arrays (PDF)

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. ORCID Bing Yan: 0000-0002-0216-9454 Author Contributions ‡These authors contributed equally. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT ACS Paragon Plus Environment


This work is supported by the National Natural Science Foundation of China (21571142) and the Developing Science Funds of Tongji University.

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Figure 1. Photo images of 1@ZnO membrane under sunlight (a) and UV light (b); photo images of Eu@1@ZnO membrane under sunlight (c) and UV light (d); (e) PXRD patterns of simulated 1, as-synthesized 1 and Eu@1@ZnO membrane; (f) surface morphology of Eu@1@ZnO membrane; (g) the cross-sectional microstructures of the prepared membranes.



Figure 2. (a-c) EDX-mapping images of Eu@1@ZnO for element Zn (b) and Eu (c); (d) XPS N 1s spectrum of 1@ZnO; (e) XPS N 1s spectrum of Eu@1@ZnO.

Figure 3. Photoluminescence response spectra varying with e.e.% of R-Pen solutions.


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Figure 4. (a) circuitry for the half-adder GC-1 logic gate; (b) truth table corresponding to the GC-1 circuit; (c) Column diagram of the normalized fluorescence intensity of Iblue and Ired toward different e.e. % of R-Pen ranging from -100 % to 100 %.

Figure 5. (a) circuitry for the GC-2 logic gate; (b) truth table corresponding to the GC-2 circuit.



Figure 6. (a) circuitry for the half-adder GC-3 cycling system; (b) circuitry for the GC-3 cycling logic gate; (c) circuitry for the ROM arrays; (d) the decoding and writing information of ROM arrays based on the output A0 and A1.


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A luminescent hybrid membrane-based logic device - ACS Publications

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