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Multiple logic operations based on chemically triggered upconversion fluorescence switching
Journal Pre-proof Multiple logic operations based on chemically triggered upconversion fluorescence switching
Yang Yu, Sai Xu, Yuefeng Gao, Muhan Jiang, Jinsu Zhang, Xiangping Li, Xizhen Zhang, Baojiu Chen PII:
S1386-1425(20)30024-X
DOI:
https://doi.org/10.1016/j.saa.2020.118047
Reference:
SAA 118047
To appear in:
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
Received date:
2 December 2019
Revised date:
1 January 2020
Accepted date:
6 January 2020
Please cite this article as: Y. Yu, S. Xu, Y. Gao, et al., Multiple logic operations based on chemically triggered upconversion fluorescence switching, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy(2018), https://doi.org/10.1016/ j.saa.2020.118047
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© 2018 Published by Elsevier.
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Multiple Logic Operations Based on Chemically Triggered Upconversion Fluorescence Switching
Yang Yu1, Sai Xu1,*, Yuefeng Gao2, Muhan Jiang1, Jinsu Zhang1, Xiangping Li1, Xizhen Zhang1, Baojiu Chen1,* 1
School of Science, Dalian Maritime University, Dalian 116026, People's Republic of China
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College of Marine Engineering, Dalian Maritime University, Dalian 116026, People's Republic of China
Corresponding authors.
S. Xu [email protected] B. J. Chen
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[email protected]
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Journal Pre-proof Abstract The development of upconversion nanoparticles based logic systems, especially integrated logic systems is still a challenge until now. In this work, an upconversion nanocomposite system is developed and studied for the sensing abilities towards hydrion, hydroxyl ions, metal ions and anions (S2-, I-) by taking the advantages of turn-on and turn-off upconversion fluorescence switching response. Triggering by different kinds of ions, the upconversion system can act as a fluorescence switch due to the specific recognition abilities of Rhodamine 6G functionalized PEI for specific ions and the energy transfer process from upconversion nanoparticles to recognition molecules. Based on these results, multiple molecular logic gates, including single-input logic operation (YES, NOT), double-inputs logic operation (OR, AND, NOR, INHIBIT) and multiple-input integrative logic operation (INHIBIT+OR) are developed by employing hydrion, hydroxyl ions, metal ions and anions as inputs and the changes in the upconversion fluorescence intensity as output. The multiple logic operations are of great significance for the application in biomedical application and molecular calculation.
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KEYWORDS: Logic Gates; Upconversion Luminescence; Nanocomposite; Energy Transfer
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Journal Pre-proof 1. Introduction Molecular logic circuits are the foundation of molecular-scale computers that receive inputs representing true (input=1) or false (input=0) values to produce corresponding output signal and then carry out binary computational function. The mechanism is similar to the silicon-based electronic integrated circuits.[1-3] Recently, they have received continued attentions due to its beguiling prospects and potential applications in controllable drug release, metal ion detection, and molecular computing.[4-6] Compared to traditional logic circuit, molecular logic gates process information at the molecular level in theory, which can achieve device miniaturization and significantly enhance the sensitivity of the detection device. The first molecular logic AND gate used H+ and Na+ as chemical inputs and emission fluorescence intensity as optical output was reported by Silvain in 1993.[7] Following this pioneering work, a large amount of materials have been studied for molecular logic gates to achieve diverse logical operations.[8-11] In particular, fluorescent switch have been frequently employed in the rational design of molecular logic devices. Up to now, various organic fluorophores were employed to construct fluorescent-based Boolean logic gates. [12,13] However, organic fluorophores often suffer from drawbacks of high background noise and photo-bleaching. Rare earth doped upconversion nanoparticles (UCNPs), as novel luminescent nanomaterials with many distinctive physical and chemical properties, have recently aroused extensive research interests. Compared to semiconductor quantum dots and organic fluorophores, UCNPs have many advantages, such as high photochemical
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stability, low background noise and low biotoxicity.[14-16] With these advantages, UCNPs are widely used for bioimaging, biosensing and
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photodynamic therapy, etc.[17-20] UCNPs based simple logic gates, such as AND, OR and INHIBIT have been successfully established before [21,22], however integrated UCNPs based logic systems are rarely reported up to now. Therefore, it is necessary to design new UCNPs based
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logic systems that can construct simple and integrated operation platforms to increase the complexity of the logic system and meet the needs of diverse devices.
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In this study, an inventive nanocomposite was designed by mixing NaYF4: Tm3+, Yb3+ nanoparticles as energy transfer donors and
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Rhodamine 6G functionalized PEI (RFP) as energy transfer acceptors for establishing simple and integrated logic systems. Tm3+ and Yb3+ co-doped NaYF4 nanoparticles, in which Tm3+ ions act as the luminescent centers and Yb3+ ions as sensitizers, were synthesized by typical
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thermal decomposition method and modified with PAA for hydrophilicity. Polyethylenimine (PEI), a hydrosoluble cationic polymer, has been used for the development of fluorescence probes for the recognition of various metal ions, such as Cu2+, Zn2+, and Co2+. [23-25] The enrichment of amine in the structure of PEI is fit for chemical modification, and enable PEI to recognize specific elements. Specific recognition elements can conjugate onto PEI by rational design, leading to the increasement or decrement of fluorescence intensities by energy transfer or electron transfer. According to the previous reports, functionalized PEI was synthesized as energy transfer acceptors as well as ion recognizer to regulate the fluorescence on-off or off-on by adding different kinds of ions.[26-28] Based on the energy transfer process from UCNPs to RFP and the recognition capabilities of RFP for specific ions, in this report, an UC fluorescence system is developed to implement multiple molecular logic gates capable of single-input logic operation (YES, NOT), double-inputs logic operation (OR, AND, NOR, INHIBIT) and multiple-input integrative logic operation (INHIBIT+OR). 2. Experiment 2.1 Materials All the rare earth oxides including Yttrium oxide (Y2O3, 99%), ytterbium oxide (Yb2O3, 99%) and thulium oxide (Tm2O3, 99%) were obtained from Shanghai Second Chemical Reagent Factory (China). Sodium hydroxide (NaOH), ammoninm fluoride (NH4F), methanol, cyclohexane, absolute ethanol were provided by Tianjin Reagent Chemicals Co.Ltd (China). Oleic acid (OA, 90%), 1-octadecene (ODE, 90%), poly acrylic acid (PAA), diethylene glycol (DEG), rhodamine 6G (R6G) and polyethylenimine (PEI) were purchased from Aladdin. CuCl2·2H2O, CuCl, NaCl, KCl, CaCl2, ZnCl2，BaCl2，MnCl2·4H2O were purchased from Tianjin Damao Chemical Reagent Factory. In addition, RECl3·6H2O were obtained by dissolving the corresponding rare earth oxides in dilute HCl solution under continuous heating and the solution was 3
Journal Pre-proof recrystallized for several times to evaporating the solvent. 2.2 Synthesis of PAA modified NaYF4: Tm 3+, Yb3+ nanoparticles OA capped NaYF4: Tm 3+, Yb3+ nanoparticles were systhsized according to former literature with some modifications.[29] In brief, 2 mmol RE3+ chlorides with crystal waters (molar radio of YCl3·6H2O/TmCl3·6H2O/YbCl3·6H2O was 79.5/0.5/20) were dissolved in 100 ml three-necked flask containing 12 ml OA and 30 ml ODE and the mixture solution was vacuumed 0.5 hour under continuous stirring. Then the mixture solution was heated to 160 ℃ to dissolve completely. After cooling, a mixture of NH4F (8 mmol) and NaOH (5 mmol) in 10 ml of methanol solution was added dropwise into the flask under nitrogen protection. Later on, the mixture solution was heated to 100 ℃ and maintained for 60 min to remove the methanol. Then the solution was heated to 310 ℃ and kept for 90 min. After the mixture solution naturally cooled down to room temperature, the products were collected by centrifugation (8000 rpm, 10 min) and washed three times with ethanol and cyclohexane. The samples were stored in cyclohexane for the next step. Next, the NaYF4: Tm3+, Yb3+ nanoparticles were modified with PAA for hydrophilicity. In brief, PAA (1 g) and DEG (15 ml) were put into a three-necked flask and then the mixture solution was heated up to 110 ℃ under nitrogen atmosphere. After cooling, NaYF4: Tm3+, Yb3+ nanoparticles synthesized above were slowly added to the mixture solution. Then the mixture was heated to 150 ℃ with reflux for 2 h.
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Subsequently, the mixture was maintained at 240 ℃ for 1h. Finally, the products were precipitated by centrifugation and washed three times with
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ethanol and DI water. The nanoparticles were dispersed in 5 ml DI water for further use. [14] 2.3 Synthesis of RFP
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15ml of ethanol containing R6G (0.02 g) and PEI (1 g) was kept reflux for 24 h at 80 ℃. After cooling down to room temperature, the mixture was dialyzed in DI water for 72 hours to wipe off unreacted R6G. Then, ethanol in the solution was removed under vacuum distillation.
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Finally, the final product was store at 4 ℃.
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2.4 Characterization
The powder X-ray diffraction (XRD) was examined by Shimadzu X-ray diffractometer equipped with Cu-Kα1 radiation source (λ=0.15406).
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The XRD patterns were recorded with a scanning step of 0.02 °/s in the 2θ range of 10-80°. The morphologies of the synthesized samples were observed by a Joel-2100 high resolution transmission electron microscopy (TEM) at an acceleration voltage of 200 kV. The UC emission spectra were measured by a Hitachi F-4600 fluorescence spectrometer equipped with an external 980 nm laser as excitation source. The absorption spectra were recorded by a UV-VIS-NIR spectrophotometer (Shimadzu UV-3600). 3. Results and discussion 3.1 Structure and morphology of UCNPs
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Figure 1 (a) XRD patterns of OA-capped NaYF4: Tm 3+/Yb3+ nanoparticles and PAA modified NaYF4: Tm 3+/Yb3+ nanoparticles with the
/Yb3+
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standard cards for β-NaYF4 for comparison, TEM images of (b) OA-capped NaYF4: Tm 3+/Yb3+ nanoparticles and (c) PAA modified NaYF4: Tm
In order to confirm the crystal structure of the synthesized upconversion nanoparticle samples. The XRD patterns of the OA capped and
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PAA-modified NaYF4: Tm3+, Yb3+ nanoparticles samples were measured and exhibited in Fig. 1 (a). It can be seen that all diffraction peaks
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coincide well with standard card (JCPDS No. 28-1192). No diffraction peaks of any other phases or impurities are observed, thus, indicating that the obtained products are hexagonal-phased NaYF4 nanocrystals, the doping of rare earth ions and modification of PAA have no significant
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influence on the crystal structure.
To further study the obtained products, the morphologies of the samples were measured via TEM, and the images are shown in Fig. 1(b) and (c). As shown in Fig. 1(b), OA capped UCNPs display a uniform hexagonal plate-like morphology with an average size of 31.59 nm. After modification with PAA, the nanoparticles maintain the monodispersion in water without changes in shape and size (Fig. 1(c)). 3.2 Mechanism of logic gate construction
Figure 2 Luminescence emission spectra of (a) NaYF4: Tm 3+/Yb3+ under the excitation of 980 nm, (b) RFP-H+ under the excitation of 500 nm, (c) RFP and absorption spectra of (d) RFP-H+, and (e) RFP 5
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The design of upconversion logic gate is based on the upconversion Förster resonance energy transfer (UC-FRET) principle, which uses upconversion nanoparticles as donors and various types of materials such as gold, organic dyes, graphene oxides, and semiconductors as acceptors.[30-32] As an efficient FRET process, the acceptor absorption spectrum should overlap with the donor emission spectrum. [17] As shown in Figure 2, the UC emission spectrum of NaYF4: Tm3+, Yb3+ ranges from 430 nm to 500 nm under the excitation of 980 nm, however, there are no obvious absorption and emission peak for RFP. After acidizing RFP with HCl (pH=3.0), it exhibits a strong absorption band ranges from 420 nm to 700 nm, which overlaps well with the UC emission band of UCNPs. The emission peak of acidized RFP centers at 580 nm under the excitation of 500 nm. When RFP and NaYF4 are uniformly mixed in acidic environment with an appropriate ratio, it is expected that, energy transfer takes place from UCNPs to acidized RFP, a new broad emission band in the range of 525 nm to 635 nm will appear under the external
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Figure 3 (a) Emission spectra of NaYF4-RFP system with different concentrations of H+ and (b) fluorescence intensity responses for Tm3+ ions
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(430-500 nm) and RFP (525 nm-635 nm) of NaYF4-RFP system toward H+ in aqueous solution.
The UC emission spectra of the mixture solution of NaYF4: Tm3+, Yb3+ UCNPs and RFP (the concentration ratio of UCNPs to RFP is
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61.5:1) excited by external 980 nm laser changes with different pH values are shown in Fig. 3 (a). When adding H+ to the mixture solution (NaYF4-RFP system), the color of the solution gradually changes from colourless to pink, the emission band at the wavelength ranging between 525 nm and 635 nm appears when the pH value is adjusted to 5, and the intensity of the broadband increases as continuing adding H +. On the contrary, when slowly adding 2 mol/L NaOH solution to the mixture solution of the acidized composite system (NaYF4-RFP-H+ system) to adjust the hydrogen ion concentration of the solution, the emission band in this range disappears when the pH value is adjusted to 6, and the intensity is almost unchanged as continuing adding OH-. These results show that the reaction between RFP and hydrogen ions is reversible. The spectral integral area in the range of 430-550 nm for Tm3+ emission and in the range of 525-635 nm for RFP emission are calculated and shown in Figure 3(b). It can be seen that the emission intensity for Tm3+ gradually decreases and the emission intensity for RFP gradually increases with the adding of H+ in the pH value ranging from 3 to 6. However, the emission intensities are both almost unchanged in the pH value ranging from 6 to 10. These results further confirm the energy transfer process from Tm3+ to RFP occurs in acidic condition. The energy transfer efficiency can be calculated as
（1
I ） 100 % I0
(1)
which I and I0 represent the upconversion emission intensity in the range of 400-500 nm of the composite in the presence and absence of H+. According to the equation, the energy transfer efficiency is calculated as 54.6% when pH is 3
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Figure 4 (a) Emission spectra of NaYF4-RFP-H+ system with different concentrations of Cu2+ and (b) fluorescence responses of NaYF4-RFP-H+ system toward various metal ions in aqueous solution.
Figure 4 shows that the adding of Cu2+ can cause a distinct luminescence quenching in the NaYF4-RFP-H+ system. The formation of cupric amine complexes are through the combination of the amino groups at RFP and Cu2+, which is the main reason for fluorescence quenching of RFP by Cu2+ via energy transfer.[33] The sensing behavior of NaYF4-RFP-H+ composite system for copper ions was investigated. As shown in
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the inset of Figure 4 (a), the emission intensity change (ln (F0/F)) of NaYF4-RFP-H+ system versus the concentration of Cu2+ is calculated. The luminescence quenching by Cu2+ follows the modification Stern-Volmer (S-V) equation[34]:
F0 ) 1 K SV [Q] F
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ln (
(2)
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where F0 and F are the fluorescence intensities of RFP (525-635 nm) in the absence and presence of Cu2+, respectively, [Q] is the copper-ion concentration, and KSV is the S-V constant. The S-V plot for copper ions shows good linear relationship (R2=0.989) in the concentration range of
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0-2.6 mM, and KSV value is found to be 0.903 mM-1.
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In addition to examination the response of NaYF4-RFP-H+ system toward other common metal ions in aqueous solution, various metal chlorides were added to the mixture to maintain the metal ion concentration in the aqueous solution at 2 mM. The emission spectra were
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measured under the excitation of external 980 nm laser and the emission intensity changes (ln(F0/F)) dependent on various metal ions are shown in Fig. 4 (b). It is obvious to observe that only Cu2+ can cause a distinct fluorescence quenching in NaYF4-RFP-H+ system. Cu+ and other metal ions have little or no influence, demonstrating the system has good selectivity for Cu2+ detection. Additionally, for establishing multiple logic gates, the reversibility is very important. When adding S 2- or I- ions to the NaYF4-RFP-H+-Cu2+ system, obvious precipitation is produced. As shown in Figure S1, the broad emission band for RFP emission recovers again by adding S2- or Iions. It is because that S2- and I- ions have high affinities towards Cu2+, and the bound Cu2+ in RFP-H+-Cu2+ complex is sequestered by S2-or I-, which induces releasing of free RFP-H+. [35,36] Therefore, the composite system can be regarded as an ON-OFF-ON fluorescent switch by adding different ions.
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Scheme 1 Schematic representations for the synthesis of NaYF4-RFP and their sensing process toward various ions.
As a molecular logic gate, the system must possess the particular effect based on one or more inputs and a reliable output. Inspired by
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specific responses of the synthesized composite system to H+, OH-, Cu2+, S2- and I-. Multiple logic gates based on UC emission spectra are
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constructed, the operations are triggered by different combinations of the ions. The UC luminescence system are successfully achieving simple Boolean logic gates such as YES, NOT, AND, OR, NOR, and INHBIT, and sophisticated combination logic operations (INHIBIT+OR). In these
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logic operations, the absence or presence of these inputs are regarded as 0 or 1. The emission fluorescence intensity (the spectral integral
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intensity in the range of 525-635 nm) of NaYF4-RFP at pH=3 under the external 980 nm laser is defined as the threshold value. The output value
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is regarded as 1 when the relative emission intensity compared to the threshold value is above 0.3, otherwise the output value is defined as 0.
Figure 5. (a) The fluorescent spectra of NaYF4-RFP triggered by different inputs upon excitation of external 980 nm laser, inset: the corresponding response of normalized spectral integral area (525 nm-635 nm) in the presence of different input signals. The circuit diagram and truth table of the YES gate. (b) The fluorescent spectra of NaYF4-RFP-H+ triggered by different inputs upon excitation of external 980nm laser, inset: the corresponding response normalized spectral integral area (525 nm- 635 nm) in the presence of different input signals. The circuit diagram and truth table of the NOT gate.
As illustrated in Fig. 5, the fluorescence output state of only NaYF4-RFP system (without input) is regarded as “0” state. By adding H+ to the system, the fluorescence response of the system is triggered on. The addition of H+ leads to the formation of a delocalized xanthenes moiety of 8
Journal Pre-proof the rhodamine group due to the opening of the spirolactam ring.[37] This leads to the turn-on fluorescence of the NaYF4-RFP system in acidic solution. Thus, the fluorescence output state of the system in presence of H+ is regarded as “1”. The result is according with the Boolean logic gate “YES”, which output will be “1” only if the input is “1”, otherwise it is “0”. On the other hand, the addition of Cu 2+ to NaYF4-RFP-H+ system can trigger off the system. The fluorescence output state of the system in presence of Cu2+ is regarded as “1”, otherwise it is “0”. This obeys the Boolean logic gate “NOT”, which output signal is the opposite of the input signal. In order to demonstrate that the constructed molecular logic gate can be widely used in multi-function devices and can achieve more functions in practical applications. The logic gate should be triggered by different combinations of the inputs, transforming different configurations to perform different purposes. As shown in Fig. 6(a), AND gate is developed, setting NaYF4: Yb3+, Tm3+ as gate system. Neither RFP nor H+ can be separately triggered the fluorescence turn-on response of the broadband emission under 980 nm laser. NaYF4: Yb3+, Tm3+ alone also cannot produce emission spectra between 525 nm and 635 nm. The system only exhibit obvious broadband emission in the presence of two inputs of RFP and H+, which is corresponding well with the Boolean operation of AND logic gate. When setting NaYF4-RFP-H+-Cu2+ composite as gate system, either input of I- or S2- can lead to the fluorescence recovery of the broadband emission. In the presence of any input, the fluorescence output state of the system is regarded as “1”. The results shown in Figure 6(b) is
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according to the Boolean operation of OR logic gate, which output is “1” when there is in the presence of any inputs, otherwise it is “0”.
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As shown in Fig. 6(c), opposite to the OR logic operation, either Cu2+ or OH- can quench the emission band of NaYF4-RFP-H+, causing the output to be 0. In other words, in the absence of any input, the fluorescence output state of the system is regarded as “1”. The result obeys the
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Boolean operation of NOR logic gate, which output is “1” only if the input is “0”, otherwise it is “0”. The binary Boolean operation of INHIBIT logic gate, which output is “1” only when one specific input is in absence and the other is in
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presence. Here, NaYF4-RFP composite is set as gate system, H+ (input 1) and Cu2+ (input 2) are set as double inputs, which function through the
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NaYF4-RFP system, as shown in Fig. 6(d). As demonstrated in Scheme 1, the addition of H+ can lead to the turn-on fluorescence response of 525 nm-635 nm and Cu2+ can specifically bind to RFP to quench the fluorescence signal. So, only when H+ is absent and Cu2+ is present (input = 1,
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0), the fluorescence output signal is 1. In other cases, the output is 0.
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Figure 6 (a) The fluorescent spectra of NaYF4 triggered by different inputs upon excitation of external 980 nm laser, inset: the corresponding response of normalized spectral integral area (525 nm-635 nm) in the presence of different input signals. The circuit diagram and truth table of the AND gate. (b) The fluorescent spectra of NaYF4- RFP-H+-Cu2+ triggered by different inputs upon excitation of external 980 nm laser, inset: the corresponding response of normalized spectral integral area (525 nm-635 nm) in the presence of different input signals. The circuit diagram and truth table of the OR gate. (c) The fluorescent spectra of NaYF4-RFP-H+ triggered by different inputs upon excitation of external 980 nm laser, inset: the corresponding response of normalized spectral integral area (525 nm-635 nm) in the presence of different input signals The circuit diagram and truth table of the NOR gate. (d) The fluorescent spectra of NaYF4-RFP triggered by different inputs upon excitation of external 980 nm laser, inset: the corresponding response of normalized spectral integral area (525 nm-635 nm) in the presence of different input signals The circuit diagram and truth table of INHIBIT gate.
The construction of sophisticated logic system with multiple inputs is still a challenge. When there are more inputs integration, the connection of different logic gates can implement versatile higher functions. However, the sophistication of logic operations will be increased, so the integration of different logic gates are rarely reported. Herein, three inputs are introduced to the composite system to construct a more sophisticated logic system. As shown in Scheme 1, the addition of H+ leads to the turn-on fluorescence response of the broadband emission of the NaYF4-RFP system, while either Cu2+ or OH- leads to the quenching of the fluorescence response. An integrative logic system can be
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(0,0,1) and (0,1,1), the fluorescence output state of the system is regarded as “0”. When only H + is in presence in the system
(input= 1,0,0), the output of the system is regarded as “1”. In the presence of H+, either of Cu2+ or OH- can cause fluorescence quenching. In other words, When the input is (1,1,0), (1,0,1), and (1,1,1), the output of the system is regarded as “0”. Because of the advantages of dual response of NaYF4-RFP to different ions inputs, a complicated three-inputs logic system, which is combination of OR and INHIBIT, is
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successfully established.
Figure 7 The fluorescent spectra of NaYF4-RFP triggered by different inputs upon excitation of external 980 nm laser, inset: the corresponding response of normalized spectral integral area (525 nm-635 nm) in the presence of different input signals. The circuit diagram and truth table of the INHIBIT+OR gate.
4. Conclusions The Boolean logic systems including single-input logic gates (YES, NOT), dual-input logic gates (AND, OR, NOR, INHIBIT), and multiple-input complex logic gate (INHIBIT+OR) are constructed successfully. The molecular logic operations rely on energy transfer from NaYF4: Tm3+, Yb3+ nanoparticles to RFP, and the recognition ability of RFP to different kinds of ions. The ions (H+, OH-, Cu2+, I-, S2-) are performed as chemical inputs, the output results are implemented by observing UC fluorescence broadband emission. These logic systems can construct simple and integrated operating platforms to increase the complexity of the realized logic functions and meet the needs of diverse
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Acknowledgement This work is supported by National Natural Science Foundation of China (11704056, 11774042), Fundamental Research Funds for the Central Universities (3132019338, 3132019186), China Postdoctoral Science Foundation (2018T110212, 2016M591420), Natural Science Foundation of Liaoning Province (2019MS029), and the Open Fund of the State Key Laboratory of Integrated Optoelectronics (IOSKL2019KF06) References 1.
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Journal Pre-proof Declaration of interests
☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
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☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:
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Journal Pre-proof Author contributions Yang Yu: carried out the experiment, analyzed and interpreted the experimental data, and drafted the article. Sai Xu and Baojiu Chen: supervised the experiments and provided financial support for the project. Muhan Jiang, Jinsu Zhang and Xizhen Zhang: helped collating experimental data.
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Xiangping Li and Yuefeng Gao: helped interpreting the data and revising the articles. All the authors reviewed the manuscript.
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Graphical Abstract
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Journal Pre-proof Highlights ● An upconversion composite system was developed for sensing towards different ions ● Triggering by different ions, the system can act as a fluorescence switch ● Simple and integrated logic gates were exploited by sensing ability of the system
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● The molecular logic operations rely on energy transfer principle
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Yang Yu, Sai Xu, Yuefeng Gao, Muhan Jiang, Jinsu Zhang, Xiangping Li, Xizhen Zhang, Baojiu Chen PII:
S1386-1425(20)30024-X
DOI:
https://doi.org/10.1016/j.saa.2020.118047
Reference:
SAA 118047
To appear in:
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
Received date:
2 December 2019
Revised date:
1 January 2020
Accepted date:
6 January 2020
Please cite this article as: Y. Yu, S. Xu, Y. Gao, et al., Multiple logic operations based on chemically triggered upconversion fluorescence switching, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy(2018), https://doi.org/10.1016/ j.saa.2020.118047
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© 2018 Published by Elsevier.
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Multiple Logic Operations Based on Chemically Triggered Upconversion Fluorescence Switching
Yang Yu1, Sai Xu1,*, Yuefeng Gao2, Muhan Jiang1, Jinsu Zhang1, Xiangping Li1, Xizhen Zhang1, Baojiu Chen1,* 1
School of Science, Dalian Maritime University, Dalian 116026, People's Republic of China
2
College of Marine Engineering, Dalian Maritime University, Dalian 116026, People's Republic of China
Corresponding authors.
S. Xu [email protected] B. J. Chen
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[email protected]
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Journal Pre-proof Abstract The development of upconversion nanoparticles based logic systems, especially integrated logic systems is still a challenge until now. In this work, an upconversion nanocomposite system is developed and studied for the sensing abilities towards hydrion, hydroxyl ions, metal ions and anions (S2-, I-) by taking the advantages of turn-on and turn-off upconversion fluorescence switching response. Triggering by different kinds of ions, the upconversion system can act as a fluorescence switch due to the specific recognition abilities of Rhodamine 6G functionalized PEI for specific ions and the energy transfer process from upconversion nanoparticles to recognition molecules. Based on these results, multiple molecular logic gates, including single-input logic operation (YES, NOT), double-inputs logic operation (OR, AND, NOR, INHIBIT) and multiple-input integrative logic operation (INHIBIT+OR) are developed by employing hydrion, hydroxyl ions, metal ions and anions as inputs and the changes in the upconversion fluorescence intensity as output. The multiple logic operations are of great significance for the application in biomedical application and molecular calculation.
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KEYWORDS: Logic Gates; Upconversion Luminescence; Nanocomposite; Energy Transfer
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Journal Pre-proof 1. Introduction Molecular logic circuits are the foundation of molecular-scale computers that receive inputs representing true (input=1) or false (input=0) values to produce corresponding output signal and then carry out binary computational function. The mechanism is similar to the silicon-based electronic integrated circuits.[1-3] Recently, they have received continued attentions due to its beguiling prospects and potential applications in controllable drug release, metal ion detection, and molecular computing.[4-6] Compared to traditional logic circuit, molecular logic gates process information at the molecular level in theory, which can achieve device miniaturization and significantly enhance the sensitivity of the detection device. The first molecular logic AND gate used H+ and Na+ as chemical inputs and emission fluorescence intensity as optical output was reported by Silvain in 1993.[7] Following this pioneering work, a large amount of materials have been studied for molecular logic gates to achieve diverse logical operations.[8-11] In particular, fluorescent switch have been frequently employed in the rational design of molecular logic devices. Up to now, various organic fluorophores were employed to construct fluorescent-based Boolean logic gates. [12,13] However, organic fluorophores often suffer from drawbacks of high background noise and photo-bleaching. Rare earth doped upconversion nanoparticles (UCNPs), as novel luminescent nanomaterials with many distinctive physical and chemical properties, have recently aroused extensive research interests. Compared to semiconductor quantum dots and organic fluorophores, UCNPs have many advantages, such as high photochemical
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stability, low background noise and low biotoxicity.[14-16] With these advantages, UCNPs are widely used for bioimaging, biosensing and
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photodynamic therapy, etc.[17-20] UCNPs based simple logic gates, such as AND, OR and INHIBIT have been successfully established before [21,22], however integrated UCNPs based logic systems are rarely reported up to now. Therefore, it is necessary to design new UCNPs based
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logic systems that can construct simple and integrated operation platforms to increase the complexity of the logic system and meet the needs of diverse devices.
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In this study, an inventive nanocomposite was designed by mixing NaYF4: Tm3+, Yb3+ nanoparticles as energy transfer donors and
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Rhodamine 6G functionalized PEI (RFP) as energy transfer acceptors for establishing simple and integrated logic systems. Tm3+ and Yb3+ co-doped NaYF4 nanoparticles, in which Tm3+ ions act as the luminescent centers and Yb3+ ions as sensitizers, were synthesized by typical
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thermal decomposition method and modified with PAA for hydrophilicity. Polyethylenimine (PEI), a hydrosoluble cationic polymer, has been used for the development of fluorescence probes for the recognition of various metal ions, such as Cu2+, Zn2+, and Co2+. [23-25] The enrichment of amine in the structure of PEI is fit for chemical modification, and enable PEI to recognize specific elements. Specific recognition elements can conjugate onto PEI by rational design, leading to the increasement or decrement of fluorescence intensities by energy transfer or electron transfer. According to the previous reports, functionalized PEI was synthesized as energy transfer acceptors as well as ion recognizer to regulate the fluorescence on-off or off-on by adding different kinds of ions.[26-28] Based on the energy transfer process from UCNPs to RFP and the recognition capabilities of RFP for specific ions, in this report, an UC fluorescence system is developed to implement multiple molecular logic gates capable of single-input logic operation (YES, NOT), double-inputs logic operation (OR, AND, NOR, INHIBIT) and multiple-input integrative logic operation (INHIBIT+OR). 2. Experiment 2.1 Materials All the rare earth oxides including Yttrium oxide (Y2O3, 99%), ytterbium oxide (Yb2O3, 99%) and thulium oxide (Tm2O3, 99%) were obtained from Shanghai Second Chemical Reagent Factory (China). Sodium hydroxide (NaOH), ammoninm fluoride (NH4F), methanol, cyclohexane, absolute ethanol were provided by Tianjin Reagent Chemicals Co.Ltd (China). Oleic acid (OA, 90%), 1-octadecene (ODE, 90%), poly acrylic acid (PAA), diethylene glycol (DEG), rhodamine 6G (R6G) and polyethylenimine (PEI) were purchased from Aladdin. CuCl2·2H2O, CuCl, NaCl, KCl, CaCl2, ZnCl2，BaCl2，MnCl2·4H2O were purchased from Tianjin Damao Chemical Reagent Factory. In addition, RECl3·6H2O were obtained by dissolving the corresponding rare earth oxides in dilute HCl solution under continuous heating and the solution was 3
Journal Pre-proof recrystallized for several times to evaporating the solvent. 2.2 Synthesis of PAA modified NaYF4: Tm 3+, Yb3+ nanoparticles OA capped NaYF4: Tm 3+, Yb3+ nanoparticles were systhsized according to former literature with some modifications.[29] In brief, 2 mmol RE3+ chlorides with crystal waters (molar radio of YCl3·6H2O/TmCl3·6H2O/YbCl3·6H2O was 79.5/0.5/20) were dissolved in 100 ml three-necked flask containing 12 ml OA and 30 ml ODE and the mixture solution was vacuumed 0.5 hour under continuous stirring. Then the mixture solution was heated to 160 ℃ to dissolve completely. After cooling, a mixture of NH4F (8 mmol) and NaOH (5 mmol) in 10 ml of methanol solution was added dropwise into the flask under nitrogen protection. Later on, the mixture solution was heated to 100 ℃ and maintained for 60 min to remove the methanol. Then the solution was heated to 310 ℃ and kept for 90 min. After the mixture solution naturally cooled down to room temperature, the products were collected by centrifugation (8000 rpm, 10 min) and washed three times with ethanol and cyclohexane. The samples were stored in cyclohexane for the next step. Next, the NaYF4: Tm3+, Yb3+ nanoparticles were modified with PAA for hydrophilicity. In brief, PAA (1 g) and DEG (15 ml) were put into a three-necked flask and then the mixture solution was heated up to 110 ℃ under nitrogen atmosphere. After cooling, NaYF4: Tm3+, Yb3+ nanoparticles synthesized above were slowly added to the mixture solution. Then the mixture was heated to 150 ℃ with reflux for 2 h.
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Subsequently, the mixture was maintained at 240 ℃ for 1h. Finally, the products were precipitated by centrifugation and washed three times with
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ethanol and DI water. The nanoparticles were dispersed in 5 ml DI water for further use. [14] 2.3 Synthesis of RFP
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15ml of ethanol containing R6G (0.02 g) and PEI (1 g) was kept reflux for 24 h at 80 ℃. After cooling down to room temperature, the mixture was dialyzed in DI water for 72 hours to wipe off unreacted R6G. Then, ethanol in the solution was removed under vacuum distillation.
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Finally, the final product was store at 4 ℃.
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2.4 Characterization
The powder X-ray diffraction (XRD) was examined by Shimadzu X-ray diffractometer equipped with Cu-Kα1 radiation source (λ=0.15406).
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The XRD patterns were recorded with a scanning step of 0.02 °/s in the 2θ range of 10-80°. The morphologies of the synthesized samples were observed by a Joel-2100 high resolution transmission electron microscopy (TEM) at an acceleration voltage of 200 kV. The UC emission spectra were measured by a Hitachi F-4600 fluorescence spectrometer equipped with an external 980 nm laser as excitation source. The absorption spectra were recorded by a UV-VIS-NIR spectrophotometer (Shimadzu UV-3600). 3. Results and discussion 3.1 Structure and morphology of UCNPs
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Figure 1 (a) XRD patterns of OA-capped NaYF4: Tm 3+/Yb3+ nanoparticles and PAA modified NaYF4: Tm 3+/Yb3+ nanoparticles with the
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standard cards for β-NaYF4 for comparison, TEM images of (b) OA-capped NaYF4: Tm 3+/Yb3+ nanoparticles and (c) PAA modified NaYF4: Tm
In order to confirm the crystal structure of the synthesized upconversion nanoparticle samples. The XRD patterns of the OA capped and
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PAA-modified NaYF4: Tm3+, Yb3+ nanoparticles samples were measured and exhibited in Fig. 1 (a). It can be seen that all diffraction peaks
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coincide well with standard card (JCPDS No. 28-1192). No diffraction peaks of any other phases or impurities are observed, thus, indicating that the obtained products are hexagonal-phased NaYF4 nanocrystals, the doping of rare earth ions and modification of PAA have no significant
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influence on the crystal structure.
To further study the obtained products, the morphologies of the samples were measured via TEM, and the images are shown in Fig. 1(b) and (c). As shown in Fig. 1(b), OA capped UCNPs display a uniform hexagonal plate-like morphology with an average size of 31.59 nm. After modification with PAA, the nanoparticles maintain the monodispersion in water without changes in shape and size (Fig. 1(c)). 3.2 Mechanism of logic gate construction
Figure 2 Luminescence emission spectra of (a) NaYF4: Tm 3+/Yb3+ under the excitation of 980 nm, (b) RFP-H+ under the excitation of 500 nm, (c) RFP and absorption spectra of (d) RFP-H+, and (e) RFP 5
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The design of upconversion logic gate is based on the upconversion Förster resonance energy transfer (UC-FRET) principle, which uses upconversion nanoparticles as donors and various types of materials such as gold, organic dyes, graphene oxides, and semiconductors as acceptors.[30-32] As an efficient FRET process, the acceptor absorption spectrum should overlap with the donor emission spectrum. [17] As shown in Figure 2, the UC emission spectrum of NaYF4: Tm3+, Yb3+ ranges from 430 nm to 500 nm under the excitation of 980 nm, however, there are no obvious absorption and emission peak for RFP. After acidizing RFP with HCl (pH=3.0), it exhibits a strong absorption band ranges from 420 nm to 700 nm, which overlaps well with the UC emission band of UCNPs. The emission peak of acidized RFP centers at 580 nm under the excitation of 500 nm. When RFP and NaYF4 are uniformly mixed in acidic environment with an appropriate ratio, it is expected that, energy transfer takes place from UCNPs to acidized RFP, a new broad emission band in the range of 525 nm to 635 nm will appear under the external
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Figure 3 (a) Emission spectra of NaYF4-RFP system with different concentrations of H+ and (b) fluorescence intensity responses for Tm3+ ions
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(430-500 nm) and RFP (525 nm-635 nm) of NaYF4-RFP system toward H+ in aqueous solution.
The UC emission spectra of the mixture solution of NaYF4: Tm3+, Yb3+ UCNPs and RFP (the concentration ratio of UCNPs to RFP is
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61.5:1) excited by external 980 nm laser changes with different pH values are shown in Fig. 3 (a). When adding H+ to the mixture solution (NaYF4-RFP system), the color of the solution gradually changes from colourless to pink, the emission band at the wavelength ranging between 525 nm and 635 nm appears when the pH value is adjusted to 5, and the intensity of the broadband increases as continuing adding H +. On the contrary, when slowly adding 2 mol/L NaOH solution to the mixture solution of the acidized composite system (NaYF4-RFP-H+ system) to adjust the hydrogen ion concentration of the solution, the emission band in this range disappears when the pH value is adjusted to 6, and the intensity is almost unchanged as continuing adding OH-. These results show that the reaction between RFP and hydrogen ions is reversible. The spectral integral area in the range of 430-550 nm for Tm3+ emission and in the range of 525-635 nm for RFP emission are calculated and shown in Figure 3(b). It can be seen that the emission intensity for Tm3+ gradually decreases and the emission intensity for RFP gradually increases with the adding of H+ in the pH value ranging from 3 to 6. However, the emission intensities are both almost unchanged in the pH value ranging from 6 to 10. These results further confirm the energy transfer process from Tm3+ to RFP occurs in acidic condition. The energy transfer efficiency can be calculated as
（1
I ） 100 % I0
(1)
which I and I0 represent the upconversion emission intensity in the range of 400-500 nm of the composite in the presence and absence of H+. According to the equation, the energy transfer efficiency is calculated as 54.6% when pH is 3
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Figure 4 (a) Emission spectra of NaYF4-RFP-H+ system with different concentrations of Cu2+ and (b) fluorescence responses of NaYF4-RFP-H+ system toward various metal ions in aqueous solution.
Figure 4 shows that the adding of Cu2+ can cause a distinct luminescence quenching in the NaYF4-RFP-H+ system. The formation of cupric amine complexes are through the combination of the amino groups at RFP and Cu2+, which is the main reason for fluorescence quenching of RFP by Cu2+ via energy transfer.[33] The sensing behavior of NaYF4-RFP-H+ composite system for copper ions was investigated. As shown in
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the inset of Figure 4 (a), the emission intensity change (ln (F0/F)) of NaYF4-RFP-H+ system versus the concentration of Cu2+ is calculated. The luminescence quenching by Cu2+ follows the modification Stern-Volmer (S-V) equation[34]:
F0 ) 1 K SV [Q] F
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ln (
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where F0 and F are the fluorescence intensities of RFP (525-635 nm) in the absence and presence of Cu2+, respectively, [Q] is the copper-ion concentration, and KSV is the S-V constant. The S-V plot for copper ions shows good linear relationship (R2=0.989) in the concentration range of
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0-2.6 mM, and KSV value is found to be 0.903 mM-1.
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In addition to examination the response of NaYF4-RFP-H+ system toward other common metal ions in aqueous solution, various metal chlorides were added to the mixture to maintain the metal ion concentration in the aqueous solution at 2 mM. The emission spectra were
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measured under the excitation of external 980 nm laser and the emission intensity changes (ln(F0/F)) dependent on various metal ions are shown in Fig. 4 (b). It is obvious to observe that only Cu2+ can cause a distinct fluorescence quenching in NaYF4-RFP-H+ system. Cu+ and other metal ions have little or no influence, demonstrating the system has good selectivity for Cu2+ detection. Additionally, for establishing multiple logic gates, the reversibility is very important. When adding S 2- or I- ions to the NaYF4-RFP-H+-Cu2+ system, obvious precipitation is produced. As shown in Figure S1, the broad emission band for RFP emission recovers again by adding S2- or Iions. It is because that S2- and I- ions have high affinities towards Cu2+, and the bound Cu2+ in RFP-H+-Cu2+ complex is sequestered by S2-or I-, which induces releasing of free RFP-H+. [35,36] Therefore, the composite system can be regarded as an ON-OFF-ON fluorescent switch by adding different ions.
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Journal Pre-proof 3.3 Construction of multiple logic gates
Scheme 1 Schematic representations for the synthesis of NaYF4-RFP and their sensing process toward various ions.
As a molecular logic gate, the system must possess the particular effect based on one or more inputs and a reliable output. Inspired by
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specific responses of the synthesized composite system to H+, OH-, Cu2+, S2- and I-. Multiple logic gates based on UC emission spectra are
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constructed, the operations are triggered by different combinations of the ions. The UC luminescence system are successfully achieving simple Boolean logic gates such as YES, NOT, AND, OR, NOR, and INHBIT, and sophisticated combination logic operations (INHIBIT+OR). In these
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logic operations, the absence or presence of these inputs are regarded as 0 or 1. The emission fluorescence intensity (the spectral integral
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intensity in the range of 525-635 nm) of NaYF4-RFP at pH=3 under the external 980 nm laser is defined as the threshold value. The output value
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is regarded as 1 when the relative emission intensity compared to the threshold value is above 0.3, otherwise the output value is defined as 0.
Figure 5. (a) The fluorescent spectra of NaYF4-RFP triggered by different inputs upon excitation of external 980 nm laser, inset: the corresponding response of normalized spectral integral area (525 nm-635 nm) in the presence of different input signals. The circuit diagram and truth table of the YES gate. (b) The fluorescent spectra of NaYF4-RFP-H+ triggered by different inputs upon excitation of external 980nm laser, inset: the corresponding response normalized spectral integral area (525 nm- 635 nm) in the presence of different input signals. The circuit diagram and truth table of the NOT gate.
As illustrated in Fig. 5, the fluorescence output state of only NaYF4-RFP system (without input) is regarded as “0” state. By adding H+ to the system, the fluorescence response of the system is triggered on. The addition of H+ leads to the formation of a delocalized xanthenes moiety of 8
Journal Pre-proof the rhodamine group due to the opening of the spirolactam ring.[37] This leads to the turn-on fluorescence of the NaYF4-RFP system in acidic solution. Thus, the fluorescence output state of the system in presence of H+ is regarded as “1”. The result is according with the Boolean logic gate “YES”, which output will be “1” only if the input is “1”, otherwise it is “0”. On the other hand, the addition of Cu 2+ to NaYF4-RFP-H+ system can trigger off the system. The fluorescence output state of the system in presence of Cu2+ is regarded as “1”, otherwise it is “0”. This obeys the Boolean logic gate “NOT”, which output signal is the opposite of the input signal. In order to demonstrate that the constructed molecular logic gate can be widely used in multi-function devices and can achieve more functions in practical applications. The logic gate should be triggered by different combinations of the inputs, transforming different configurations to perform different purposes. As shown in Fig. 6(a), AND gate is developed, setting NaYF4: Yb3+, Tm3+ as gate system. Neither RFP nor H+ can be separately triggered the fluorescence turn-on response of the broadband emission under 980 nm laser. NaYF4: Yb3+, Tm3+ alone also cannot produce emission spectra between 525 nm and 635 nm. The system only exhibit obvious broadband emission in the presence of two inputs of RFP and H+, which is corresponding well with the Boolean operation of AND logic gate. When setting NaYF4-RFP-H+-Cu2+ composite as gate system, either input of I- or S2- can lead to the fluorescence recovery of the broadband emission. In the presence of any input, the fluorescence output state of the system is regarded as “1”. The results shown in Figure 6(b) is
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according to the Boolean operation of OR logic gate, which output is “1” when there is in the presence of any inputs, otherwise it is “0”.
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As shown in Fig. 6(c), opposite to the OR logic operation, either Cu2+ or OH- can quench the emission band of NaYF4-RFP-H+, causing the output to be 0. In other words, in the absence of any input, the fluorescence output state of the system is regarded as “1”. The result obeys the
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Boolean operation of NOR logic gate, which output is “1” only if the input is “0”, otherwise it is “0”. The binary Boolean operation of INHIBIT logic gate, which output is “1” only when one specific input is in absence and the other is in
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presence. Here, NaYF4-RFP composite is set as gate system, H+ (input 1) and Cu2+ (input 2) are set as double inputs, which function through the
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NaYF4-RFP system, as shown in Fig. 6(d). As demonstrated in Scheme 1, the addition of H+ can lead to the turn-on fluorescence response of 525 nm-635 nm and Cu2+ can specifically bind to RFP to quench the fluorescence signal. So, only when H+ is absent and Cu2+ is present (input = 1,
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Figure 6 (a) The fluorescent spectra of NaYF4 triggered by different inputs upon excitation of external 980 nm laser, inset: the corresponding response of normalized spectral integral area (525 nm-635 nm) in the presence of different input signals. The circuit diagram and truth table of the AND gate. (b) The fluorescent spectra of NaYF4- RFP-H+-Cu2+ triggered by different inputs upon excitation of external 980 nm laser, inset: the corresponding response of normalized spectral integral area (525 nm-635 nm) in the presence of different input signals. The circuit diagram and truth table of the OR gate. (c) The fluorescent spectra of NaYF4-RFP-H+ triggered by different inputs upon excitation of external 980 nm laser, inset: the corresponding response of normalized spectral integral area (525 nm-635 nm) in the presence of different input signals The circuit diagram and truth table of the NOR gate. (d) The fluorescent spectra of NaYF4-RFP triggered by different inputs upon excitation of external 980 nm laser, inset: the corresponding response of normalized spectral integral area (525 nm-635 nm) in the presence of different input signals The circuit diagram and truth table of INHIBIT gate.
The construction of sophisticated logic system with multiple inputs is still a challenge. When there are more inputs integration, the connection of different logic gates can implement versatile higher functions. However, the sophistication of logic operations will be increased, so the integration of different logic gates are rarely reported. Herein, three inputs are introduced to the composite system to construct a more sophisticated logic system. As shown in Scheme 1, the addition of H+ leads to the turn-on fluorescence response of the broadband emission of the NaYF4-RFP system, while either Cu2+ or OH- leads to the quenching of the fluorescence response. An integrative logic system can be
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Journal Pre-proof established by setting NaYF4-RFP as logic gate, H+, Cu2+ and OH- as three inputs. When H+ is in absence in the system, namely, the input is (0,0,0), (0,1,0),
(0,0,1) and (0,1,1), the fluorescence output state of the system is regarded as “0”. When only H + is in presence in the system
(input= 1,0,0), the output of the system is regarded as “1”. In the presence of H+, either of Cu2+ or OH- can cause fluorescence quenching. In other words, When the input is (1,1,0), (1,0,1), and (1,1,1), the output of the system is regarded as “0”. Because of the advantages of dual response of NaYF4-RFP to different ions inputs, a complicated three-inputs logic system, which is combination of OR and INHIBIT, is
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Figure 7 The fluorescent spectra of NaYF4-RFP triggered by different inputs upon excitation of external 980 nm laser, inset: the corresponding response of normalized spectral integral area (525 nm-635 nm) in the presence of different input signals. The circuit diagram and truth table of the INHIBIT+OR gate.
4. Conclusions The Boolean logic systems including single-input logic gates (YES, NOT), dual-input logic gates (AND, OR, NOR, INHIBIT), and multiple-input complex logic gate (INHIBIT+OR) are constructed successfully. The molecular logic operations rely on energy transfer from NaYF4: Tm3+, Yb3+ nanoparticles to RFP, and the recognition ability of RFP to different kinds of ions. The ions (H+, OH-, Cu2+, I-, S2-) are performed as chemical inputs, the output results are implemented by observing UC fluorescence broadband emission. These logic systems can construct simple and integrated operating platforms to increase the complexity of the realized logic functions and meet the needs of diverse
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Journal Pre-proof devices. Although there is still much work to do in this field, our work provides an practical prototype for UCNPs applications in complexity logic system design and holds great promise for future molecular computing.
Acknowledgement This work is supported by National Natural Science Foundation of China (11704056, 11774042), Fundamental Research Funds for the Central Universities (3132019338, 3132019186), China Postdoctoral Science Foundation (2018T110212, 2016M591420), Natural Science Foundation of Liaoning Province (2019MS029), and the Open Fund of the State Key Laboratory of Integrated Optoelectronics (IOSKL2019KF06) References 1.
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Journal Pre-proof Declaration of interests
☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
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☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:
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Journal Pre-proof Author contributions Yang Yu: carried out the experiment, analyzed and interpreted the experimental data, and drafted the article. Sai Xu and Baojiu Chen: supervised the experiments and provided financial support for the project. Muhan Jiang, Jinsu Zhang and Xizhen Zhang: helped collating experimental data.
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Xiangping Li and Yuefeng Gao: helped interpreting the data and revising the articles. All the authors reviewed the manuscript.
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Graphical Abstract
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Journal Pre-proof Highlights ● An upconversion composite system was developed for sensing towards different ions ● Triggering by different ions, the system can act as a fluorescence switch ● Simple and integrated logic gates were exploited by sensing ability of the system
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● The molecular logic operations rely on energy transfer principle
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