Boolean Logic Networks Mimicked with Chimeric Enzymes Activated/Inhibited by Several Input Signals

Reactions catalyzed by artificial allosteric enzymes, chimeric proteins with fused biorecognition and catalytic units, were used to mimic multi-input Boolean logic systems. The catalytic parts of the systems were represented by pyrroloquinoline quinone-dependent glucose dehydrogenase (PQQ-GDH). Two biorecognition units, calmodulin or artificial peptide-clamp, were integrated into PQQ-GDH and locked it in the OFF or ON state respectively. The ligand-peptide binding cooperatively with Ca²⁺ cations to a calmodulin bioreceptor resulted in the enzyme activation, while another ligand-peptide bound to a clamp-receptor inhibited the enzyme. The enzyme activation and inhibition originated from peptide-induced allosteric transitions in the receptor units that propagated to the catalytic domain. While most of enzymes used to mimic Boolean logic gates operate with two inputs (substrate and co-substrate), the used chimeric enzymes were controlled by four inputs (glucose – substrate, dichlorophenolindophenol – electron acceptor/co-substrate, Ca²⁺ cations and a peptide – activating/inhibiting signals). The biocatalytic reactions controlled by four input signals were considered as logic networks composed of several concatenated logic gates. The developed approach allows potentially programming complex logic networks operating with various biomolecular inputs representing potential utility for different biomedical applications.     

Biofuel cell controlled by enzyme logic network — Approaching physiologically regulated devices

A “smart” biofuel cell switchable ON and OFF upon application of several chemical signals processed by an enzyme logic network was designed. The biocomputing system performing logic operations on the input signals was composed of four enzymes: alcohol dehydrogenase (ADH), amyloglucosidase (AGS), invertase (INV) and glucose dehydrogenase (GDH). These enzymes were activated by different combinations of chemical input signals: NADH, acetaldehyde, maltose and sucrose. The sequence of biochemical reactions catalyzed by the enzymes models a logic network composed of concatenated AND/OR gates. Upon application of specific “successful” patterns of the chemical input signals, the cascade of biochemical reactions resulted in the formation of gluconic acid, thus producing acidic pH in the solution. This resulted in the activation of a pH-sensitive redox-polymer-modified cathode in the biofuel cell, thus, switching ON the entire cell and dramatically increasing its power output. Application of another chemical signal (urea in the presence of urease) resulted in the return to the initial neutral pH value, when the O₂-reducing cathode and the entire cell are in the mute state. The reversible activation–inactivation of the biofuel cell was controlled by the enzymatic reactions logically processing a number of chemical input signals applied in different combinations. The studied biofuel cell exemplifies a new kind of bioelectronic device where the bioelectronic function is controlled by a biocomputing system. Such devices will provide a new dimension in bioelectronics and biocomputing benefiting from the integration of both concepts.     

DNA Computing Systems Activated by Electrochemically‐triggered DNA Release from a Polymer‐brush‐modified Electrode Array

An array of four independently wired indium tin oxide (ITO) electrodes was used for electrochemically stimulated DNA release and activation of DNA‐based Identity, AND and XOR logic gates. Single‐stranded DNA molecules were loaded on the mixed poly(N ,N ‐dimethylaminoethyl methacrylate) (PDMAEMA)/poly(methacrylic acid) (PMAA) brush covalently attached to the ITO electrodes. The DNA deposition was performed at pH 5.0 when the polymer brush is positively charged due to protonation of tertiary amino groups in PDMAEMA, thus resulting in electrostatic attraction of the negatively charged DNA. By applying electrolysis at −1.0 V(vs. Ag/AgCl reference) electrochemical oxygen reduction resulted in the consumption of hydrogen ions and local pH increase near the electrode surface. The process resulted in recharging the polymer brush to the negative state due to dissociation of carboxylic groups of PMAA, thus repulsing the negatively charged DNA and releasing it from the electrode surface. The DNA release was performed in various combinations from different electrodes in the array assembly. The released DNA operated as input signals for activation of the Boolean logic gates. The developed system represents a step forward in DNA computing, combining for the first time DNA chemical processes with electronic input signals.     

A Supramolecular Approach on Using Poly(fluorenylstyrene)‐block‐poly(2‐vinylpyridine):PCBM Composite Thin Films for Non‐Volatile Memory Device Applications

Supramolecular composite thin films of poly[4‐(9,9‐dihexylfloren‐2‐yl)styrene]‐block ‐poly(2‐vinylpyridine) (P(St‐Fl)‐b‐P2VP):[6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) were prepared for write‐once‐read‐many times (WORM) non‐volatile memory devices. The optical absorption and photoluminescence results indicated the formation of charge transfer complexation between the P2VP block and PCBM, which led to the varied PCBM aggregated size and memory characteristics. The ITO/PCBM:(P(St‐Fl)‐b‐P2VP)/Al device exhibited the WORM characteristic with low threshold voltage (−1.6 to −3.2 V) and high ON/OFF ratio (10³ to 10⁵) by tuning the PCBM content. The switching behavior could be explained by the charge injection dominated thermionic emission in the OFF state and field‐induced charge transfer in the ON state. The present study provides a novel approach system for tuning polymer memory device characteristics through the supramolecular materials approach.

     

Molecular Logic Gates and Switches Based on 1,3,4‐Oxadiazoles Triggered by Metal Ions

Organic molecular devices for information processing applications are highly useful building blocks for constructing molecular‐level machines. The development of “intelligent” molecules capable of performing logic operations would enable molecular‐level devices and machines to be created. We designed a series of 2,5‐diaryl‐1,3,4‐oxadiazoles bearing a 2‐(para‐substituted)phenyl and a 5‐(o‐pyridyl) group (substituent X=NMe₂, OEt, Me, H, and Cl; 1 a – e ) that form a bidentate chelating environment for metal ions. These compounds showed fluorescence response profiles varying in both emission intensity and wavelength toward the tested metal ions Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, and Pb²⁺ and the responses were dependent on the substituent X, with those of 1 d being the most substantial. The 1,3,4‐oxadiazole O or N atom and pyridine N atom were identified as metal‐chelating sites. The fluorescence responses of 1 d upon metal chelation were employed for developing truth tables for OR, NOR, INHIBIT, and EnNOR logic gates as well as “ON‐OFF‐ON” and “OFF‐ON‐OFF” fluorescent switches in a single 1,3,4‐oxadiazole molecular system.     

Multiple logic gates based on electrically wired surface-reconstituted enzymes

The electrode functionalized with glucose oxidase (GOx) and microperoxidase-11 (MP-11) performs various Boolean logic operations (OR, XOR, AND-OR) upon addition of glucose and/or H2O2 and application of different potentials. The output signal coming from the electrically wired enzymes is electrochemically readable, allowing interfacing of biochemical computing systems with ordinary electronics.     

Covalent Functionalization of Black Phosphorus with Conjugated Polymer for Information Storage

Major disadvantages of black phosphorus (BP) are its poor air‐stability and poor solubility in common organic solvents. The best way to solve this problem is to incorporate BP into a polymer backbone or a polymer matrix to form novel functional materials that can provide both challenges and opportunities for new innovation in optoelectronic and photonic applications. As a proof‐of concept application, we synthesized in situ the first highly soluble conjugated polymer‐covalently functionalized BP derivative (PDDF‐g‐BP) which was used to fabricate a resistive random access memory (RRAM) device with a configuration of Au/PDDF‐g‐BP/ITO. In contrast to PDDF without memory effect, PDDF‐g‐BP‐based device exhibits a nonvolatile rewritable memory performance, with a turn‐on and turn‐off voltages of +1.95 V and ?2.34 V, and an ON/OFF current ratio of 10⁴. The current through the device in both the ON and OFF states is still kept unchanged even at 200th switching cycle. The PDDF/BP blends show a very unstable memory performance with a very small ON/OFF current ratio.     

Electrode interfaces switchable by physical and chemical signals for biosensing, biofuel, and biocomputing applications

This review outlines advances in designing modified electrodes with switchable properties controlled by various physical and chemical signals. Irradiation of the modified electrode surfaces with various light signals, changing the temperature of the electrolyte solution, application of a magnetic field or electrical potentials, changing the pH of the solutions, and addition of chemical/biochemical substrates were used to change reversibly the electrode activity. The increasing complexity in the signal processing was achieved by integration of the switchable electrode interfaces with biomolecular information processing systems mimicking Boolean logic operations, thus allowing activation and inhibition of electrochemical processes on demand by complex combinations of biochemical signals. The systems reviewed range from simple chemical compositions to complex mixtures modeling biological fluids, where the signal substrates were added at normal physiological and elevated pathological concentrations. The switchable electrode interfaces are considered for future biomedical applications where the electrode properties will be modulated by the biomarker concentrations reflecting physiological conditions.

Wholly aromatic polyamides by the direct polycondensation reaction using triphenyl phosphite in the presence of poly(4-vinylpyridine)

The polycondensation reaction of aromatic dicarboxylic acids and diamines by using triphenyl phosphite were carried out in N-methylpyrrolidone (NMP) in the presence of poly(4-vinylpyridine) (P4VP). The reaction, especially of terephthalic acid (TPA), was markedly facilitated to give the absence of P4VP. The reaction promoted by P4VP was further favored by the addition of various pyridine derivatives; of the pyridines examined, pyridine was most effective, giving the best results at a high level (pyridine/P4VP values up to 26). P4VP of the molecular weight in the range of 1.3 × 10⁴?3.0 × 10⁵ did not affect the viscosity of the resulting polymer. These favorable additive effects of P4VP on the reaction of TPA were not observed in the reactions of isophthalic acid, and m -and p-aminobenzoic acids.     

Electrochemical mechanism of spiro and zwitterionic Meisenheimer compounds: A potential fluorescence molecular switching system

The reaction between picric acid and an excess of diisopropylcarbodiimide yields a stable red–orange fluorescent zwitterionic spiro Meisenheimer complex of 1,3,5-trinitrobenzene (ZW1). The acidic character of the iminium/guanidium moiety of the triazine ring in ZW1 permits to obtain the corresponding non-fluorescent spiro Meisenheimer Complex (MC2). The redox properties of both ZW1 and MC2 have been studied using electrochemical oxidation–reduction mechanism (established by cyclic voltammetry; classical and with ultramicroelectrodes) and controlled-potential electrolysis. A potential fluorescence switching system has been established, since fluorescent properties can be reversibly modulated by conversion of both states (ON, ZW1) and (OFF, MC2) upon reduction of ZW1 or oxidation of MC2.     

Stimuli‐Responsive Biointerface Based on Polymer Brushes for Glucose Detection

The construction and characterization of a biosensor based on polymer brushes is reported. The use of polymer brushes combined with nanoparticles was applied to show its suitability as a biosensor platform – with glucose oxidase as an enzyme probe. The biosensor demonstrated a pH‐sensitive on‐off property, and it was further used to control or modulate the electrochemical responses. In terms of the kinetic behavior, we were able to show the changing in the kinetic parameters of glucose oxidase operating in “on” and “off” state of the polymer brushes. The performance of the bioelectrode was investigated by chronoamperometry, impedance electrochemistry and cyclic voltammetric techniques. At optimized experimental conditions the dynamic concentration range was 2.0 to 16.0 mmol L^?1 with a detection limit of 5.6×10–⁶ mol L^?1. The repeatability of current responses for injections of 5.0 mmol L^?1 glucose was evaluated to be 5.3 % (n=10). The resulting biosensor seemed to provide the enzymes with a biocompatible nanoenvironment as it sustained the enhanced enzyme activity for an extended time and promoted possible good electron transfer through the polymer brushes to the electrode.     

Electrochemical oxidation of catechol at poly(indole-5-carboxylic acid) electrode

In this work we examined the electrochemical properties of poly(indole-5-carboxylic acid), PIn₅COOH. The polymer was produced by electrochemical polymerisation using cyclic voltammetry (CV). It was shown that PIn₅COOH is electroactive in aqueous solutions showing two redox processes in acidic solution and one redox process in solutions with pH > 4. The oxidation of catechol (CT) on Pt/In₅COOH modified electrodes was investigated by cyclic voltammetry (CV) and rotating disc electrode (RDE) voltammetry. It was established that CT was oxidised only after the oxidation of polymer film was initiated and that polymer significantly enhanced the oxidation and reduction peak currents in comparison with bare Pt electrode. The variation of peak currents (i _pa, i _pc) as a function of CT concentration was found to be linear up to 6 mM. Experiments with a rotating disk electrode show that the oxidation reaction of catechol occures not only at the polymer/electrolyte interface but also in the polymer film.     

Raman spectroelectrochemical study on the kinetics of electrochemical degradation of polyaniline

The kinetics of electrochemical degradation of polyaniline and a copolymer of aniline and metanilic acid have been studied by in situ Raman spectroscopy at a gold electrode. It has been concluded that probably no drastic changes in polymer structure occur on prolonged electrochemical treatment of polymer films at a high electrode potential (0.8 V vs. Ag/AgCl). Instead, most prominent changes relate to a gradual decrease of an overall intensity of spectra, viz. to gradual degradation of a polymer layer. The degradation proceeds faster at pH 1.0, compared to pH 7.0. The kinetic results obtained have been analyzed following simple 2- or 3-parameter exponential decay equations, and compared with the known degradation rate constants.     

Electrical bistability of organic devices with a polymeric thin film for nonvolatile data storage

In this study, organic memory devices with a single active layer between the two external electrodes were fabricated using an electron‐donor type conjugated polymer and an electron‐acceptor type small organic molecule. The active layer of the memory device was prepared by blending polystyrene, poly[10‐(2′‐ethylhexyl)phenothiazine‐3,7‐diyl], and tetracyanoquinodimethane in 1,2‐dichlorobenzene. The device initially showed a low‐conductance state (OFF state) in the low‐voltage range, and an abrupt current increase, corresponding to the transition to a high‐conductance state (ON state), occurred at a certain voltage (V_th). The ON state could be reverted to the OFF state by applying a voltage higher than V_th. The current ratio between the two states was about 10³ (up to 10⁵). After this transition, the device remained in the ON state even after the applied voltage was removed, and this indicated the nonvolatile characteristics of the device. There was no sharp current degradation in the OFF or ON states for 4500 s of continuous bias. The device‐to‐device performance fluctuation was measured, and the conduction mechanisms in the ON and OFF states were examined by fitting the data to well‐known theoretical models. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Distinguishing normal cells from cancer cells via lysosome-targetable pH biomarkers with benzo[a]phenoxazine skeleton

In this paper, the design of a lysosome-targetable pH probe that has a fluorescent OFF (pH = 4) to ON (pH = 5–6) response is described to identify lysosomes in normal cells. The mechanism of photoinduced electron transfer with a fluorophore-based reaction (FBR-PET) was proposed. Benzo[a]phenoxazines with electro-donating aryl groups were selected, its (2,5-dimethoxyphenyl)imino-, (2-hydroxyphenyl)imino- and (2-hydroxy-5-methoxyphenyl)- imino-derivatives (probes 1a−c) were prepared and their optical responses towards pH were evaluated; their fluorescence pH titration experiments gave regularly changes with the increasing electro-donating abilities at the linked aryl groups, the (2-hydroxy-5-methoxyphenyl)iminobenzo[a]phenoxazine (probe 1c) exhibited a nearly OFF−ON response at 580–800 nm. All probes were reversible, and they showed excellent selectivity toward the proton over other competitive species. Fluorescence confocal images were performed with HeLa, KB cancer cells and V79 normal cells, probes 1a−c are all lysosome-targetable pH probes, and benzo[a]phenoxazine with (2-hydroxy-5-methoxyphenyl)imino-group (probe 1c) has potential applications in selective differentiation of normal cells from cancer cells.     

Temperature-Responsive Electrocatalysis Based on Poly(N-Isopropylacrylamide)-Modified Graphene Oxide (PNIPAm-GO)

Poly(N-isopropylacrylamide)-modified graphene oxide (PNIPAm-GO), which is a type of thermally responsive GO, was designed and synthesized through a covalent “grafting-from” strategy. The as-prepared modified nanosheets integrated the individual advantages of two components, such as the thermal sensitivity of the PNIPAm terminal as well as the conductivity and the open 2D structure of the GO substrate. PNIPAm-GO was able to perform the reversible regulation of hydrophilicity/hydrophobicity in aqueous solution upon variations in the temperature. Such a unique property might also lead to the utilization of PNIPAm-GO as an intelligent electrode material to achieve a switchable electrochemical response toward a [Fe(CN)₆]^3−/4− probe. The PNIPAm-GO modified glassy carbon electrode (PNIPAm-GO/GC electrode) was able to exhibit better electrochemical performance in an ON/OFF switching effect than the PNIPAm-modified glassy carbon electrode (PNIPAm/GC electrode) without GO owing to the intrinsic properties and large surface area of the introduced GO. Moreover, it was found that the PNIPAm-GO/GC electrode also displayed excellent thermally responsive electrocatalysis toward the detection of 1,4-dihydro-β-nicotinamide adenine dinucleotide (NADH) and dopamine (DA), which resulted in two different catalytic statuses on the same electrode. This kind of switchable catalytic performance of the PNIPAm-GO/GC electrode might greatly enhance the flexibility of its application, and thus it is expected to have wide potential for applications in the fields of biosensors and biocatalysis.     

Not-XOR (NXOR) Logic Gate Realized with Enzyme-Catalyzed Reactions: Optical and Electrochemical Signal Transduction

The studied enzyme-based biocatalytic system mimics NXOR Boolean logic gate, which is a logical operator that corresponds to equality in Boolean algebra. It gives the functional value true ( 1 ) if both functional arguments (input signals) have the same logical value ( 0 , 0 or 1 , 1 ), and false ( 0 ) if they are different ( 0 , 1 or 1 , 0 ). The output signal producing reaction is catalyzed by pyrroloquinoline quinone-dependent glucose dehydrogenase (PQQ-GDH), which is inhibited at acidic and basic pH values. Two other reactions catalyzed by esterase and urease produce acetic acid and ammonium hydroxide, respectively, shifting solution pH from the optimum pH for PQQ-GDH to acidic and basic values ( 1 , 0 and 0 , 1 input combinations, respectively), thus switching the enzyme activity off (output 0 ). When the input signals are not applied ( 0 , 0 combination) or both applied compensating each other ( 1 , 1 combination) the optimum pH is preserved, thus keeping PQQ-GDH running at the high rate (output 1 ). The biocatalytic cascade mimicking the NXOR gate was characterized optically and electrochemically. In the electrochemical experiments the PQQ-GDH enzyme communicated electronically with a conducting electrode support, thus resulting in the electrocatalytic current when signal combinations 0 , 0 and 1 , 1 were applied. The logic gate operation, when it was realized electrochemically, was also extended to the biomolecular release controlled by the gate. The release system included two electrodes, one performing the NXOR gate and another one activated for the release upon electrochemically stimulated alginate hydrogel dissolution. The studied system represents a general approach to the biocatalytic realization of the NXOR logic gate, which can be included in different catalytic cascades mimicking operation of concatenated gates in sophisticated logic circuitries.     

Novel high‐performance polymer memory devices containing (OMe)2tetraphenyl‐p‐phenylenediamine moieties

The functional polyimide (OMe)₂TPPA‐6FPI ( PI ) and the polyamide (OMe)₂TPPA‐6FPA ( PA ) consisting of electron‐donating N,N′‐bis(4‐aminophenyl)‐N,N′‐di(4‐methoxylphenyl)1,4‐phenylenediamine [(OMe)₂TPPA‐diamine] for memory application were prepared in this study. These polyimide and polyamide memory devices were fabricated with the sandwich configuration of indium tin oxide (ITO)/polymer/Al, and could be switched from the initial low‐conductivity (OFF) state to the high‐conductivity (ON) state with high ON/OFF current ratios of 10⁷ and 10⁹, respectively. PI exhibited dynamic random access memory (DRAM) performance, whereas PA showed static random access memory (SRAM) behavior. To get more insight into the memory behaviors of these two different types of polymer memory devices, molecular simulation on the basic unit was carried out. Furthermore, the differences of highest occupied molecular orbital (HOMO) energy level, lowest unoccupied molecular orbital (LUMO) charge density isosurfaces, dipole moment, and linkage conformation between PI and PA were found to affect the volatile memory behavior. Both polymer memory devices revealed excellent stability with long operation time of 10⁴ s at continuous applied voltage of ‐2 V. The effect of polymer thickness on the volatile memory behavior of PA was also investigated in this study. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Molecular Switches and Multiple Logic Gates Based on 4-(2-Pyridylazo)resorcinol

A simple‐structured 4‐(2‐pyridylazo)resorcinol (PAR) system presents interesting properties with dual fluorescent outputs. Modulated by solution pH two kinds of reversible switch behaviors, "ON‐OFF" and "OFF‐ON", were realized with the PAR system. Stimulated by different combination of external stimulus, such as metal ions, UV irradiation and solution pH, the PAR system could perform multiple logic functions including three inputs AND, two inputs INHIBIT and combinatorial "NOR/AND" in parallel. The operation of the designed system is very simple and detected with a high sensitive fluorescent signal.     

现场电聚合法制备锂二次聚合物电池的研究

基于1,3-二氧戊环(DOL)的可聚合特征, 提出了一种新的聚合物锂二次电池的现场制备方法, 并对其进行研究. 电化学实验表明: 在特定的电流密度下, 仅通过常规的恒电流充放电处理就能实现聚合物锂二次电池的现场组装, 得到的聚合物锂二次电池在电化学性能上与普通液态锂二次电池相当. 紫外-可见光谱表明, 通过一定的电化学处理, DOL能够发生电聚合, 扫描电镜以及交流阻抗测试也证明DOL的聚合不仅实现了液态电解液向聚合态的转变, 而且有助于在电极表面生成较为稳定的聚合物层.