MIL-61 and Eu3+@MIL-61 as Signal Transducers To Construct an

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Functional Inorganic Materials and Devices

MIL-61 and Eu3+@MIL-61 as Signal Transducers to Construct an Intelligent Boolean Logical Library Based on Visualized Luminescent Metal Organic Frameworks Yu Zhang, and Bing Yan ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b00179 • Publication Date (Web): 15 May 2019 Downloaded from http://pubs.acs.org on May 15, 2019

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ACS Applied Materials & Interfaces

MIL-61 and Eu3+@MIL-61 as Signal Transducers to Construct an Intelligent Boolean Logical Library Based on Visualized Luminescent Metal Organic Frameworks

Yu Zhang and Bing Yan*

China-Australia Joint Laboratory of Functional Molecules and Ordered Matters, School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China

* Corresponding author: [email protected] (Bing Yan)

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Abstract MIL-61 and its post-synthesis product (Eu3+@MIL-61) are employed as signal transducers to construct a series of basic logic gates (NOT, NAND, INHIBIT, XNOR) on account of their simple synthetic process and fascinating luminescent properties. Also, a 2-outputs combinational logic gate and a cascaded logic gate can be constructed on these two signal transducer by changing the inputs. In this logic gate library system, the fluorescence of MIL-61 (395nm) or Eu3+@MIL-61 (615nm) is used as outputs with a threshold of 0.5. The advantages of this boolean logical library is that the two signal transducer are readily available and cost-effective. In addition, the luminescence change is visible to the naked eye under UV lamp which is more convenient in application. More importantly, it presents a new route for the design of molecular logic gates library based on luminescent metal organic frameworks (Ln-MOFs). And for further application, we experimentally construct two logic devices (a 4-to-2 encoder and a parity checker) based on Eu3+@MIL-61 to perform nonarithmetic information. Keywords: boolean logic library, visualized fluorescence center, luminescent MOFs, logic devices, nonarithmetic information.

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1. Introduction With the development of intelligent technology, people are increasingly demanding the density of electronic device. In 1974, the concept of molecular electronics was first reported by Aviram and Ratner when proposed molecular rectifier1. From then on, molecular computing has emerged as an indispensable technology for information processing2-5. Since the first molecular logic gate was successful introduced by deSilva and his coworkers6, various basic molecular logic gates, advanced circuits and even neural networks molecular logic gate have attracted significant research interest and have been efficiently applied in many different fields such as biomarker detection7, chemical sensing8,9, disease diagnostics and therapy10, and memory devices11. With the requirement of rapid development of intelligence, more and more complex combinatorial molecular logic gates have been continuously developing and applying in many fields12-17. All these excellent work make an important contribution to the application of molecules in logic circuits18-22. However, most molecular logic gate applications tend to focus on a single logic gate or simple combinational logic gate, such as AND, OR, INHIBIT and XNOR, so it is very difficult to realize more complicated electronic devices using them. In addition, most logic gate implementations are complicated to operate, costly and the outputs are not intuitive enough, so the quality of the reported logic gates needs to be further optimized. Luminescent metal organic frameworks (Ln-MOFs), is a very promising multifunctional luminescent material because of the combination of excellent luminescent features and many fascinating properties of MOFs, such as high specific surface areas, highly ordered structure and controlled pore size23-27. In the past few years, Ln-MOFs have been frequently employed as luminescent probes and sensors for the recognition and sensing of vapors28, pH values29, anions and cations30,31, organic small molecules32-34 and even temperature35. Well-defined structures, high sensing sensitivity due to the host framework-guest interactions and high surface areas which can be utilized to preconcentrate analytes36-38, all of these features make Ln-MOFs a special molecular system to be a signal transducer for the construction of logic devices. Up to now, lots of splendid works about logic gates and logic devices based on the Ln-MOFs have been reported39-42, our group have also made 3



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some exploration constructing logic gates based on MOFs39, 42, 43-45. In general, our previous work mainly focused on sensing various chemicals based on Ln-MOFs, then further designed logic gate as an advanced analytical device. But there are few Ln-MOFs which can realize the implementation of several basic logic gates and more complex combinational gate simultaneously to date, not to mention the implementation of logic devices. Inspired by the previous work which can realize the various logic gates and multiple logic devices18, 19, 46

and logic devices based on sensing various chemicals using Ln-MOFs, a boolean logical library

based on metal organic frameworks was constructed the first time in this paper. In this library, MIL61 and its post-synthesis product (Eu3+@MIL-61) are employed as signal transducers of which the luminescence change is visible to the naked eye under UV lamp. The library embodies some basic logic gates (NOT, NAND, INHIBIT, XNOR), a 2-outputs combinational logic gate and a cascaded logic gates. Moreover, we have also constructed an encoder (convert data to code) and a parity checker (distinguish even numbers and odd numbers) which can perform nonarithmetic information for further application. The new route for the design of molecular logic gates library based on Ln-MOFs proposed a new possibility for the application of it. More importantly, this attempt can further close the gap between Ln-MOFs and electrical circuitries and expanded the application of Ln-MOFs in the field of molecular logic gates.

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2. Experimental section 2.1 Materials and Measurements Eu(NO3)3·6H2O was prepared by dissolving the Eu2O3 in a certain amount of concentrated nitric acid followed by evaporation and crystallization. Other chemicals were purchased from the commercial sources and used without further purification. The powder X-ray diffraction (PXRD) patterns were recorded with a Bruker D8 diffractometer using CuKa radiation with 40 mA and 40 kV and the dates were collected within the 2θ range of 5 – 50. Thermal gravimetric analysis (TGA) were carried out on a Netzsch STA 449C system at a heating rate of 5 K min−1 from 40 C temperature to 800 C under nitrogen atmosphere in the Al2O3 crucibles. Morphological analysis energy dispersive analysis of X-rays (EDX) was performed using Philips XL30 scanning electron microscope (SEM). UV-vis diffuse reflectance spectra were recorded by a JASCO V-750 spectrophotometer. X-ray photoelectron spectroscopy (XPS) experiments were carried out on a RBD upgrated PHI-5000C ESCA system (Perkin Elmer) with MgKa radiation (hυ¼ = 1253.6 eV). Luminescence excitation and emission spectra of the samples are obtained on Edinburgh FLS920 spectrophotometer using a 450 W xenon lamp as excitation source. 2.2 Synthesis of MIL-61 and Eu3+@MIL-61 MIL-61 was synthesized according to the previously reported procedure47. Ga(NO3)3·xH2O (3.5 mmol, 0.8951 g) with H4btec (1.75 mmol, 0.445 g) and distilled water (277.8 mmol, 5 mL) were added in sealed Teflon-lined steel autoclave at 200 C for 24 h. The white product was obtained by centrifugation at 10000 rpm for 3 min, after washed three times with distilled water, the product was dried in a vacuum at 60 C overnight. Eu3+@MIL-61 was synthesized by dispersing MIL-61 (100 mg) into the ethanol solution of Eu(NO3)3·6H2O (10 mL, 1 mmol). The solution was stirred for 48 h at 60 C. After separation by centrifugation and washing three times with distilled water for removal of residual Eu3+, the resulting white powder was dried at 60 C for 12 h. 2.3 Process of fluorescence experiment 5



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The cationic solutions (3 ml) used in the experiments were prepared from their chloride or nitrates salts, while the anion solutions (3 mL) were formulated from their sodium salts. The concentration of all chemicals used as inputs in the experiment was 10-2 mol·L-1. Then 3 mg of MIL-61 or Eu3+@MIL61 was immersed in these solutions and make sure that the concentrations of MIL-61 or Eu3+@MIL61 are always 3 mg/mL (If there is more than one solution, make sure they are added at the same time). Immediately, the mixtures were sonicated for 30 minutes to make them homogenize. The photoluminescent spectra of the suspensions were obtained at room temperature.

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3. Results and discussion 3.1 Characterization of MIL-61 and Eu3+@MIL-61 MIL-61 was synthesized by hydrothermal method from Ga(NO3)3·xH2O and H4btec according to the previous literature41. Eu3+@MIL-61 was generated through postsynthetic modification by incorporating Eu3+ into MIL-6148. The morphology observations in Figure S1 revealed that the MIL61 have a prismatic shaped particles with diameter in the range of 5 - 50 µm. The powder X-ray diffraction patterns (PXRD) of the two MOFs are identical with the simulated one as is illustrated in Figure S2, which means the successful synthesis of MIL-61 and the post-synthesis process did not change its structure. The X-ray photoelectron spectroscopy (XPS) data of MIL-61 and Eu3+@MIL-61 was also collected in Figure S3a, the O 1s peak of Eu3+@MIL-61 (529.7 ev) shows a certain displacement compared with MIL-61 (529.4 ev).This shift can be ascribed to the formation of Eu-O coordination bonds and can confirm the successful coordination between Eu3+ and O atom. The composition of Eu3+@MIL-61 is subsequently analyzed by energy dispersive X-ray analysis (EDX) spectroscopy Figure S3b, which can further prove the successful introduction of Eu3+. The thermogravimetric analysis (TGA) of MIL-61 and Eu3+@MIL-61 was examined under N2 atmosphere at a heating rate 5 K min−1 from 40 to 800 ◦C. Figure S4 shows two main weight loss at the temperature range of 200-425 ◦C and 425-600 ◦C The first loss could be assigned to the loss of free water molecules in the structure and the second loss could be ascribe to the removal of pyromellitic acid molecules41. UV-vis measurements of solid state MIL-61 and Eu3+@MIL-61 were also performed in Figure S5. The UV-vis spectrum of MIL-61 and Eu3+@MIL-61 were characterized by a band centered at 294 nm. The luminescence properties of MIL-61 and Eu3+@MIL-61 were studied in aqueous at room temperature. As is exhibited in Figure S6, arises from π - π* transitions of the ligands, MIL-61 shows a wide emission band centered at 395nm located at the blue region showed in CIE chromaticity diagram when excited at 297nm. After postsynthetic functionalization of Eu3+, the characteristic emission of Eu3+ appears in the emission spectrum of the product. In Figure S6b, the sharp lines centered at 580, 593, 615, 653, 701 nm can be ascribed to 5D0→7FJ (J = 0 - 4) transitions of Eu3+ 49,50. 7



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The most intense sharp 5D0→7F2 , which is located in 615nm, can yield an intense red color observed under UV-light irradiation which can be vividly showed in CIE chromaticity diagram. Figure S7 shows the structure stability of Eu3+@MIL-61 in aqueous environment from 0 h to 96 h. What we can conclude from the picture is that Eu3+@MIL-61 shows great structure stability in water after immersing for 96 hours. To verify the water stability of Eu3+ in Eu3+@MIL-61, the EDX spectroscopy of Eu3+@MIL-61 and Eu3+@MIL-61 after immersing in water for 96h were obtained in Figure S3b and Figure S3c. What we can conclude from Table S1 is that the weight percentage of Eu element does not changed a lot before and after immersing in water. The great water stability of it makes it a good candidate for future application. Simple synthesis process, stable structure, good fluorescence characteristics and excellent water stability, all of these advantages make MIL-61 and Eu3+@MIL-61 great signal transducers to further construct logic gates and logic devices. 3.2 Implementation of several basic logic gates (NOT, NAND, INHIBIT, XNOR) In terms of the above theoretical analysis, some of basic logic gates are designed below. In this boolean logical library, the fluorescence of MIL-61 (λ375nm) or Eu3+@MIL-61 (λ615nm) are used as the outputs with the threshold of 0.5. 3.2.1 The realization of NOT logic gate Of all basic logic gates, NOT logic gate is the simplest to implement using only one input. But it is an important member of the basic logic gates, and many complex logic calculations must rely on simple logic gate like it. In a NOT logic, the output is the opposite of the input45. Considering that Fe3+ is a fluorescence quencher to many MOFs from the literature46-48, we use Fe3+ as the input to construct a NOT gate based on Eu3+@MIL-61 while the fluorescence intensity of it is used as output。As a result, the fluorescence of Eu3+@MIL-61 was quenched as expected in showed in Figure 1b. Inspired by this, we designed a NOT logic gate using theλ615nm as the output while the input is Fe3+. The presence and absence of Fe3+ were denoted as ‘1’ and ‘0’ respectively, with a threshold value of 0.5. When Fe3+ was added to the system, the input can be denoted as ‘1’, the fluorescence of Eu3+@MIL-61 was quenched 8


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and the output is ‘0’. The switch effect of Fe3+ on the fluorescence intensity is in line with the principle of the NOT gate. The electronic equivalent circuitry and truth table of the NOT gate is also depicted in Figure 1. 3.2.2 The realization of NAND logic gate As we know that the digital NAND logic gate is the inverse of an AND gate，the output signal is ‘0’ only if all inputs are ‘1’. Using this concept we have constructed a NAND logic gate based on MIL61. In this NAND logic gate, H+, Fe2+ and S2O82- are employed as three inputs and the fluorescence of MIL-61 (λ375nm) is the output with a threshold of ‘0.5’. What we can draw from Figure 2c, only when all these three ions were added in the MIL-61 system (the input is (1/1/1)) was the fluorescence quenched, thus resulting output ‘0’. Upon the addition of S2O82- and H+ in the solution of MIL-61 contained Fe2+, Fe2+ can be oxidized to Fe3+. Fe3+ has a quenching effect on the fluorescence as mentioned above46-48, the fluorescence was weak in the presence of these three inputs. We can see that only when the three of them coexist does the fluorescence intensity of MOF change and result in the output ‘0’, so the effect of these three ions is in line with the design principles of NAND logic gates. The truth table is showed in Figure 2d. 3.2.3 The realization of INHIBIT logic gate Figure 3a shows the design of a INHIBIT gate by using Eu3+@MIL-61 as signal transducer with the output of λ615nm. An INHIBIT gate is a special case of AND gate，the difference between INHIBIT and the AND gate is that in INHIBIT gate one of the two input lines have an inversion system (NOT gate). In this work, Ag+ and cysteine was designed as two inputs to construct the INHIBIT gate because of the Ag-thiols interaction between them. As can be seen from the histogram in Figure 3c, only the presence of Ag+ caused the fluorescence increase greatly. This is because the presence of Ag+ (0/1) can induce more efficient energy transfer from the ligand to Eu3+ ions, which can result in a great enhancement of fluorescence49. As we all know, there is an Ag-thiols interaction between Ag+ and cysteine16, so the presence of both Ag+ and cysteine (1/1) can destroy the induction of Ag+ and make fluorescence quenched. As for the inputs of (0/0) and (1/0), although the fluorescence is not quenched, 9



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the intensity of fluorescence can’t reach the threshold, the output is still remaining ‘0’. Therefore, the interaction between silver ions and cysteine, which can affect the fluorescence intensity of MOF, is in accordance with the design principles of INHIBIT logic gates. 3.2.4 The realization of XNOR logic gate XNOR can be seen as an exclusive NOR gate. In a XNOR gate, the output is “true” if the inputs are same and the output is “false” if the inputs are different. Which means, the output is ‘1’ when all of the inputs presence or absence. Figure 4a depicts the construction of the XNOR logic gate. What we can conclude from the photoluminescent (PL) spectra in Figure 4b is that both the lower pH (pH = 2) and higher pH (pH = 12) can weak the fluorescence of Eu3+@MIL-61. So we constructed a XNOR logic gate based on this. When the deionized water (0/0) and equimolar solutions of pH = 2 and pH = 12 (1/1) are added, the fluorescence of Eu3+@MIL-61 is not affected, because the equal amount of acid and base mix makes the solution neutral. The effect of pH = 2 and pH = 12 is also in line with the design principles of XNOR logic gates. While Eu3+@MIL-61 is exposed to a strong acid or a strong base, the inputs is (1/0) or (0/1), we speculate that strong acidity and alkalinity can disrupt the energy transfer between Eu3+ and the ligand56,57，so the fluorescence is quenched.

3.3 Implementation of a 2-outputs combinational logic gate In consideration of accepting a high volume of information and constructing more complex circuits, basic logic gates tend to be incapable, so the implementation of combinational logic gate is urgently needed. In this work we experimentally realized a combinational logic gate composed of a NOT gate and a NAND gate. In this 2-outputs combinational logic gate, Fe3+ and EDTA are used as inputs respectively while the fluorescence of MIL-61 (λ375nm) or Eu3+@MIL-61 (λ615nm) are used as two outputs. From Figure 5b we can found that Fe3+ can quench the fluorescence of both MIL-61 (λ375nm) and Eu3+@MIL-61 (λ615nm) while EDTA can only quench the fluorescence at 615nm. So if the Fe3+ is present (the inputs are 1/1 and 0/1), both the two outputs are (0/0). Another situation is, if the Fe3+ is not present but EDTA is (the input is 1/0), because of the chelation to Eu3+ of EDTA, the fluorescence at 615 nm is quenched while 395 nm is still exit, and so the output is (1/0). When neither Fe3+ nor 10


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EDTA exists, neither of the fluorescence of MIL-61 (λ375nm) or Eu3+@MIL-61 (λ615nm) is affected, so the output is (1/1). In summary, the effect of EDTA and Fe3+ on the fluorescence intensity of the MOF is in line with the design principles of the combination of NOT and XAND.

3.4 Implementation of a cascaded logic gate Cascaded logic gate is another complex logic gate which is necessary for multi-level integrated circuits. In order to achieve the integrity of this logic gate library, a cascaded logic gate consisted by an INHIBIT gate and an AND gate was constructed in this work. In the operation of the combinatorial gate, Ag+, Fe3+, Na+ was chosen as input 1, input 2 and input 3 respectively. The enhancement of fluorescence by Ag+ and the quenching effect of Fe3+ on fluorescence have been mentioned before, and it can be seen from the PL spectra in Figure 6b that sodium ions have little effect on the fluorescence at 615 nm. We can clearly see through the truth table (Figure 6d) that only when the inputs were (0/0/1, 0/1/1), the output was ‘1’, whereas when the inputs are other than the case, the output is ‘0’.

3.5 Implementation of logic devices (4-to-2 encoder and parity checker) As we all know, one of the most important application of molecular logic gates is to perform nonarithmetic information processing. From this perspective, a 4-to-2 encoder and a parity checker based on this system were also implementated in this paper. An encoder is a device that processes signals or data into signals that can be used for communication, transmission, and storage. Herein, a 4-to-2 encoder based on MIL-61 and Eu3+@MIL-61 which can convert four inputs into two outputs was successfully constructed. In this encoder, the four inputs are consisted of Fe3+, EDTA, furazolidone and Na+ respectively while the outputs are the fluorescence of MIL-61 (λ 375nm) or Eu3+@MIL-61 (λ615nm). The effect of Fe3+, EDTA and Na+ on the fluorescence at 395 nm and 615 nm has been mentioned previously. In addition, we found that furazolidone can quench the light at 395 nm and only slightly weaken the light at 615 nm. What we can conclude from the truth table in Figure 7d, this encoder can encode four inputs (1/0/0/0, 0/1/0/0, 0/0/1/0, 0/0/0/1) into four outputs (0/0, 1/0, 0/1, 1/1) respectively. 11



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As for a parity checker, it can be used as a device to detect the presence of erroneous programs in data processing in addition to the simple application of identifying even numbers and odd numbers. In this parity checker, ten decimal numbers were transformed into corresponding binary numbers, and then, K+, Na+, Al3+, Ag+ were used as four inputs and act as four bits in the meantime. From the truth table in Figure 8d we can found that the inputs 0/0/0/1, 0/0/1/1, 0/1/0/1, 0/1/1/1, and 1/0/0/1 are encoded into the output‘1’with bright fluorescence, while the inputs 0/0/0/0, 0/0/1/1, 0/1/0/0, 0/1/1/0, and 1/0/0/0 are encoded into the output ‘0’ with weak fluorescence. From the PL spectra in Figure 8b we can more intuitively see that all the odd numbers correspond to strong fluorescence intensity, and all even numbers correspond to weak fluorescence intensity, so this parity checker is a logical device that can distinguish odd and even numbers conveniently and quickly. What’s more, this logical device can be applied to all natural number ranges because the parity of a natural number is determined by its single digit number.

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4. Conclusions In conclusion, a boolean logical library containing four basic logic gates (NOT, NAND, INHIBIT, XNOR) and two combinational gates (a two outputs logic gate and a cascaded logic gate) based on MIL-61 and its post-synthesis product (Eu3+@MIL-61) were successfully constructed in this work for the first time. Besides, a 4-to-2 encoder and a parity checker that can perform more complicated nonarithmetic information were also constructed on Eu3+@MIL-61. This is the first time that the boolean logical library was realized based on visualized luminescent MOFs. Simple synthesis method, convenient operation process and visible fluorescence changes under UV lamp, all of which make MIL-61 and Eu3+@MIL-61 excellent signal transducers for implementing logic gates. More importantly, in this boolean logical library, the luminescence of MIL-61 (λ375nm) or Eu3+@MIL-61 (λ615nm) are used as outputs which is visible by naked eye under UV lamp. This is a new attempt for the design of molecular logic gates library based on luminescent metal organic frameworks (LnMOFs). Further studies about this are currently under way.

Associated content Supporting information Additional FTIR spectra; XPS spectra; TGA curves; EDX spectroscopy; UV-vis spectra; luminescence spectra; CIE coordinates; photographs; weight percentage of all elements determined by EDX.

Author information Corresponding Author *E-mail: [email protected]. ORCID Bing Yan: 0000-0002-0216-9454 Author Contributions 13



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Y.Z. and B.Y. 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 This work was supported by the National Natural Science Foundation of China (21571142), Developing Science Funds of Tongji University, and the Science & Technology Commission of Shanghai Municipality (14DZ2261100).

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Figure legends Figure 1 (a) The scheme and electronic equivalent circuitry of NOT logic gate. (b) PL spectra of the NOT gate with the input of Fe3+. (c) Column diagram of the fluorescence intensity: the dashed line shows the threshold (the green column represents the fluorescence of 615nm). (d) The truth table of the NOT gate. Figure 2 (a) The scheme and electronic equivalent circuitry of NAND logic gate. (b) PL spectra of the NAND gate with the inputs of H+, Fe2+ and S2O82-. (c) Column diagram of the fluorescence intensity: the dashed line shows the threshold (the blue column represents the fluorescence of 395nm). (d) The truth table of the NAND gate. Figure 3 (a) The scheme and electronic equivalent circuitry of INHIBIT logic gate. (b) PL spectra of the INHIBIT gate with the inputs of Ag+ and cysteine. (c) Column diagram of the fluorescence intensity: the dashed line shows the threshold (the green column represents the fluorescence of 615nm). (d) The truth table of the INHIBIT gate. Figure 4 (a) The scheme and electronic equivalent circuitry of XNOR logic gate. (b) PL spectra of the XNOR gate with the inputs of PH=2 and PH=12. (c) Column diagram of the fluorescence intensity: the dashed line shows the threshold (the green column represents the fluorescence of 615nm). (d) The truth table of the XNOR gate. Figure 5 (a) The scheme and electronic equivalent circuitry of the 2-outputs combinational logic gate (NOT+NAND) (b) PL spectra of the combinational logic gate (c) Column diagram of the fluorescence intensity: the dashed line shows the threshold (the blue column represents the fluorescence of 395nm while the green column represents the fluorescence of 615nm).

(d) The truth table of the 2-outputs

combinational logic gate. Figure 6 (a) The scheme and electronic equivalent circuitry of the cascaded logic gate (INHIBIT+AND) (b) PL spectra of the cascaded logic gate. (c) Column diagram of the fluorescence intensity: the dashed line shows the threshold (the green column represents the fluorescence of 615nm). (d) The truth table of the cascaded logic gate. Figure 7 (a) The scheme and electronic equivalent circuitry of the 4-to-2 encoder. (b) PL spectra of the 4-to-2 encoder. (c) Column diagram of the fluorescence intensity: the dashed line shows the threshold (the blue column represents the fluorescence of 395nm while the green column represents the fluorescence of 615nm). (d) The truth table of the 4-to-2 encoder. Figure 8 (a) The scheme and logic system of the parity checker. (b) PL spectra of the parity checker. (c) Column diagram of the fluorescence intensity: the dashed line shows the threshold (the green column represents the fluorescence of 615nm). (d) The truth table of the parity checker.

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Figure 1

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Figure 2

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Figure 3

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Figure 4

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Figure 5

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Figure 6

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Figure 7

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Figure 8

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MIL-61 and Eu3+@MIL-61 as Signal Transducers To Construct an

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