AND logic gate application based on colorimetric screening of enzyme activity

A simple and novel DNA and gold nanoparticle (AuNPs) based colorimetric method has been developed for efficient detection of Deoxyribonuclease I (DNase-I) activity. For the detection process, the sample that contains DNase-I, which will cleave double stranded DNA into small pieces. Furthermore, the small pieces DNA sequences and water-soluble conjugated polymer cause the AuNPs aggregation (the solution change the color from red to blue). Thus, DNase-I could be detected by naked eyes or UV/Vis. Molecular substrates can be viewed as computational devices that process physical or chemical ‘inputs’ to generate ‘outputs’ based on a set of logical operators. Based on the assay, we have presented a DNA/AuNP based, multi-readout AND logic operations.     

A multi-receptor fluorescence signaling system exhibiting enhancement selectively in presence of Na(I) and Tl(I) ions

A PET fluorescence signaling system L₁ has been synthesized in the ‘Receptor1-Spacer-Fluorophore-Spacer-Receptor2’ format through attachment of a laterally non-symmetric heteroditopic cryptand and a 4,7,10,13-tetraoxa-1-azacyclopentadecane macrocycle at the 9- and 10-positions of anthracene. The cryptand receptor is derivatized with two 2,4-dinitrobenzene groups to impart structural rigidity. This system exhibits selective fluorescence enhancement in presence of Na(I) and Tl(I) ions simultaneously and mimics the AND logic function. The cryptand receptor also binds a Cu(II) ion outside the cavity and allows L₁ to perform as an INHIBIT chemical logic in presence of H⁺ and Cu(II) ions.     

‘Pourbaix sensors’: fluorescent molecular logic gates for pE and pH

Abstract

From the cross-fertilisation of fluorescent pH indicators and fluorescent redox switches, our group has established a new class of molecular sensor that operates as two-input molecular logic gates. These molecular sensors, known as ‘Pourbaix sensors’, are named in honour of Marcel Pourbaix, who developed the pH–potential diagrams for the various states of metal ion species in aqueous solution. This review highlights the evolution of ‘Pourbaix sensors’ based on anthracene and naphthalimide fluorophores. Potential applications of this class of molecule in fields such as corrosion science, cell biology and biomedical diagnostics are highlighted.     

Novel fused-LEDs devices as optical sensors for colorimetric analysis

The development of a novel, low power optical sensing platform based on light emitting diodes (LEDs) is described. The sensor is constructed from a pair of LEDs fused together at an angle where one LED functions as the light source and the other LED is reverse biased to function as a light detector. Sensor function is based on the level of light received by the detector diode, which varies with the reflectance of the interface between the device and its environment, or the chemochromic membrane that covers the device. A simple microprocessor circuit is used to measure the time taken for the photon-induced current to discharge the detector LED from an initial 5 V (logic 1) to 1.7 V (logic zero). This sensing device has been successfully used for colour and colour-based pH measurements and offers extremely high sensitivity, enabling detection down to the sub micro molar level of dyes.     

Ion diode logics for pH control

Electronic control over the generation, transport, and delivery of ions is useful in order to regulate reactions, functions, and processes in various chemical and biological systems. Different kinds of ion diodes and transistors that exhibit non-linear current versus voltage characteristics have been explored to generate chemical gradients and signals. Bipolar membranes (BMs) exhibit both ion current rectification and water splitting and are thus suitable as ion diodes for the regulation of pH. To date, fast switching ion diodes have been difficult to realize due to accumulation of ions inside the device structure at forward bias--charges that take a long time to deplete at reverse bias. Water splitting occurs at elevated reverse voltage bias and is a feature that renders high ion current rectification impossible. This makes integration of ion diodes in circuits difficult. Here, we report three different designs of micro-fabricated ion bipolar membrane diodes (IBMDs). The first two designs consist of single BM configurations, and are capable of either splitting water or providing high current rectification. In the third design, water-splitting BMs and a highly-rectifying BM are connected in series, thus suppressing accumulation of ions. The resulting IBMD shows less hysteresis, faster off-switching, and also a high ion current rectification ratio as compared to the single BM devices. Further, the IBMD was integrated in a diode-based AND gate, which is capable of controlling delivery of hydroxide ions into a receiving reservoir.     

Ion‐selective Electrodes with 3D Nanostructured Conducting Polymer Solid Contact

Until now both ion‐to‐electron transducers as well as large surface area nanostructured conducting materials were successfully used as solid contacts for polymer‐based ion‐selective electrodes. We were interested to explore the combination of these two approaches by fabricating ordered electrically conducting polymer (ECP) nanostructures using 3D nanosphere lithography and electrosynthesis to provide a high surface area and capacitive interface for solid contact ion‐selective electrodes (SC‐ISEs). For these studies we used poly(3,4‐ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT(PSS)) films with 750 nm diameter interconnected pores as the intermediate layer between a glassy carbon electrode and a Ag⁺ ‐selective polymeric membrane. We also investigated the feasibility of loading the voids created in the polymer film with a lipophilic redox mediator (1,1’‐dimethylferrocene) to provide the respective ISEs with well‐defined/controllable E⁰ values. These expectations were fulfilled as the standard deviation of E⁰ values were reduced with almost an order of magnitude for 3D nanostructured SC‐ISEs filled with the redox mediator as compared to their redox mediator‐free analogs. The detrimental effect of the redox mediator extraction into the plasticized PVC‐based ion‐selective membrane (ISM) was efficiently suppressed by replacing the PVC‐based ISMs with a low diffusivity silicone rubber matrix.     

In Situ Measurement of Electrode Slope and Gravimetric Multiple Standard Addition Analysis by Ion Selective Potentiometry Without Prior Calibration of Electrode

Abstract

Two methods of calculation for the determination of an unknown concentration by gravimetric multiple standard addition analysis using ion selective potentiometry without prior calibration of the electrode have been described. These are based on simple calculation procedures involving linear least square fitting to Gran's equation to evaluate first the actual electrode slope ‘in situ’, then the unknown concentration and the cell constant. One method is iterative and the other is noniterative. The applicability of the methods has been demonstrated by processing the experimental data obtained by using fluoride and uranyl ion selective electrodes.     

Cooperative Catalysis for Selective Alcohol Oxidation with Molecular Oxygen

The activation of dioxygen for selective oxidation of organic molecules is a major catalytic challenge. Inspired by the activity of nitrogen‐doped carbons in electrocatalytic oxygen reduction, we combined such a carbon with metal‐oxide catalysts to yield cooperative catalysts. These simple materials boost the catalytic oxidation of several alcohols, using molecular oxygen at atmospheric pressure and low temperature (80 °C). Cobalt and copper oxide demonstrate the highest activities. The high activity and selectivity of these catalysts arises from the cooperative action of their components, as proven by various control experiments and spectroscopic techniques. We propose that the reaction should not be viewed as occurring at an ‘active site’, but rather at an ‘active doughnut’–the volume surrounding the base of a carbon‐supported metal‐oxide particle.     

La théorie exacte de la flexion des plaques

A new approach is introduced for the analysis and computation of homogeneous, isotropic elastic plates subjected to any bending loads. This approach is based upon a partitioning, which is independent of thickness, of the 3D reference solution into both a part with large variation length and localized effects, whose generalized stress-displacement values are zero. The part with large variation length can easily be computed from data as well as from generalized quantities that represent ‘averages’ in the thickness. These generalized quantities coincide with those obtained from the 3D reference solution; they constitute the solution to an ‘exact’ theory of plate bending.     

Enzyme-Coupled Nanoparticles-Assisted Laser Desorption Ionization Mass Spectrometry for Searching for Low-Mass Inhibitors of Enzymes in Complex Mixtures

In this report, enzyme-coupled magnetic nanoparticles (EMPs) were shown to be an effective affinity-based tool for finding specific interactions between enzymatic targets and the low-mass molecules in complex mixtures using classic MALDI-TOF apparatus. EMPs used in this work act as nonorganic matrix enabling ionization of small molecules without any interference in the low-mass range (enzyme-coupled nanoparticles-assisted laser desorption ionization MS, ENALDI MS) and simultaneously carry the superficial specific binding sites to capture inhibitors present in a studied mixture. We evaluated ENALDI approach in two complementary variations: ‘ion fading’ (IF-ENALDI), based on superficial adsorption of inhibitors and ‘ion hunting’ (IH-ENALDI), based on selective pre-concentration of inhibitors. IF-ENALDI was applied for two sets of enzyme–inhibitor pairs: tyrosinase–glabridin and trypsin–leupeptin and for the real plant sample: Sparrmannia discolor leaf and stem methanol extract. The efficacy of IH-ENALDI was shown for the pair of trypsin–leupeptin. Both ENALDI approaches pose an alternative for bioassay-guided fractionation, the common method for finding inhibitors in the complex mixtures.

PVC‐Based Ion‐Selective Electrodes with Enhanced Biocompatibility by Surface Modification with “Click” Chemistry

We report here on plasticized ion‐selective poly(vinyl chloride) membranes with increased biocompatibility by means of a copper(I)‐catalyzed azide‐alkyne cycloaddition (‘click chemistry’) on the surface of finished membranes. We aimed for increasing the hydrophilicity of the surface and the application of NO releasing molecules. Employing the first principle, sodium selective membranes based on azide‐substituted PVC were modified with different length poly(ethylene glycol) (PEG) chains. For the second, cysteine groups were used as a nitrous oxide releasing substance. Surface modification was confirmed by Electrochemical Impedance Spectroscopy (EIS). Potentiometric measurements in undiluted whole blood showed an increased sensor stability in comparison to unmodified PVC. Membrane surfaces after 18 h contact with blood were analyzed with Scanning Electron Microscopy (SEM) and revealed a reduced level of blood cell adsorption on membranes modified with tetraethylene glycol (TEG) and PEGs. In contrast, cysteine modified membranes did not exhibit improved fouling resistance, suggesting that nitric oxide release by itself is not a sufficiently efficient mechanism.     

Dicyanomethylene-4H-pyran chromophores for OLED emitters, logic gates and optical chemosensors

Dicyanomethylene-4H-pyran (DCM) chromophores are typical donor-π-acceptor (D-π-A) type chromophores with a broad absorption band resulting from an ultra-fast internal charge-transfer (ICT) process. In 1989, Tang et al. firstly introduced a DCM derivative as a highly fluorescent dopant in organic electroluminescent diodes (OLEDs). Integration of ICT chromophore-receptor systems based on DCM chromophores with ion-induced shifts in absorption or emission is a convenient method to perform the logic expression for molecular logic gates. In recent years, various DCM-type derivatives have been explored due to their excellent optical-electronic properties and diverse structural modification. This feature article provides an insight into how the structural modification of DCM chromophores can be utilized for OLED emitters, logic gates and optical chemosensors. In addition, the aggregation-induced-emission (AIE) of DCM derivatives for further optical applications was also introduced.     

A Logic Gate Based on a Flexible Metal–Organic Framework (JUK-8) for the Concomitant Detection of Hydrogen and Oxygen

We present an autonomous, chemical logic gate based on a switchable metal–organic framework (MOF) composite, containing carbon nanoparticles and a Pt catalyst. The switchable MOF composite performs as AND logic gate. Hydrogen and oxygen gas streams serve as binary inputs. Catalytically formed water induces a structural transition (crystal volume expansion) of the MOF, and as a consequence, a detectable drop in conductance of the composite as a ‘true’ output only if both gases come in contact with the composite.     

The lipid bilayer concept and its experimental realization: from soap bubbles,kitchen sink,to bilayer lipid membranes

The inspiration for lipid bilayer research, without question, comes from the biological world. Although self-assembled bilayer lipid membranes (BLMs) in vitro, were first reported in 1961, experimental scientists have been dealing with BLM-type interfacial adsorption phenomena since Robert Hooke’s time (1672). BLMs (of planar lipid bilayers) have been used in a number of applications ranging from basic membrane biophysics including transport, practical AIDS research, and ‘microchips’ studies, to the conversion of solar energy via water photolysis, to biosensor development using supported bilayer lipid membranes (s-BLMs), and to photobiology comprising apoptosis and photodynamic therapy. This paper presents an overview of the origin of the lipid bilayer concept and its experimental realization, as well as the studies of our laboratory and recent research of others on the use of BLMs as models of certain biomembranes. In addition, we describe briefly our present work on supported BLMs as biosensors and molecular devices; the experiments carried out in close collaboration with colleagues on s-BLMs are delineated.     

Description of the Effects of Non‐ion‐exchange Extraction and Intra‐membrane Interactions on the Ion‐selective Electrodes Response within the Interface Equilibria‐triggered Model

The recently proposed interface equilibria‐triggered dynamic diffusion model of the boundary potential has proven its high predictive efficiency for quantification of the ion exchange and co‐extraction effects at the interface, as well as of the trans‐membrane transfer effect, on the electrode response. It is applicable for both ion exchanger‐based and neutral carrier‐based electrodes. In this communication, the adaptability of this model to more complex cases, when non‐ion‐exchange extraction processes at the interface (partition of organic acids’ and bases’ molecular forms and extraction of ionic associates) are coupled with protolytic equilibria in the aqueous phase and with self‐solvation process in the membrane phase, is demonstrated. By the example of electrodes reversible to ions of highly lipophilic physiologically active bases and acids (amiodarone, verapamil, vinpocetine, salicylic acid), it is shown that the peculiarities of their functioning, such as a very strong pH effect on the potential of cation‐selective electrodes, non‐monotonic pH dependence of the potential and super‐Nernstian response slope in certain pH region for a salicylate‐selective electrode, are well described within the model.     

A Remote ‘Imidazole’‐Based Ruthenium(II) Para‐Cymene Pre‐catalyst for the Selective Oxidation Reaction of Alkyl Arenes and Alcohols

Herein we disclosed the use of a remote ‘imidazole’‐based precatalyst [(para‐cymene)Ru^II(L)Cl]⁺, C‐1 where L=2‐(4‐substituted‐phenyl)‐1H‐imidazo[4,5‐f]^[1,10] phenanthroline) for the selective oxidation of a variety of alkyl arenes/heteroarenes and alcohols to their corresponding aldehydes or ketones in presence of tert‐butyl hydroperoxide (TBHP). The remote ‘imidazole’ moiety present in the complex facilitates the activation of oxidant and subsequent generation of active species via the release of para‐cymene from C‐1 , which in‐turn was less effective without the ‘imidazole’ moiety. The mechanistic features of C‐1 promoted oxidation of alkyl arenes were also assessed from spectroscopic, kinetic, and few control experiments. The substrate scope for C‐1 promoted oxidation reaction was assessed based on the selective oxidation of 27‐different alkyl arenes/heteroarenes and 25 different alcohols to their corresponding aldehydes/ketones in moderate to good yields.     

聚合物发光电化学池

聚合物发光电化学池(polymer light-emitting electrochemical cell,PLEC)作为一种新型的聚合物发光二极管(polymer light-emitting diodes,PLED),它的本质特征是在PLED活性层掺杂电解质以提高活性层载流子传输能力,由于其具有对电极金属功函数不敏感和量子效率高等诸多优点而受到广泛关注。本文从活性层配方的改良、电极金属及基板的表面处理、相容性的改善、固定p-n结的实现和引入热处理手段等方面综述了近几年PLEC的研究进展,分析了当前PLEC在电致发光领域面临的问题,并对PLEC的前景进行了展望。     

Differential capacitance of the electric double layer: mean-field modeling approaches

Electrolytes screen the charges carried by an electrode through the formation of a diffuse double layer. The corresponding differential capacitance reflects the change of the surface charge density with the applied surface potential. Mean-field modeling of the differential capacitance is an attempt to qualitatively explain experimental findings such as the camel-to-bell shape transition in terms of physical factors including the ion size and concentration, nonelectrostatic ion–ion interactions, electrostatic ion–ion correlations, and the influence of the electrode curvature. We highlight the central role of the lattice gas model as a conceptual tool to describe concentrated electrolytes and ionic liquids, and we briefly summarize how extensions and generalizations of this model give rise to concepts known as ‘overscreening’ and ‘underscreening’.     

Thin‐Layer Chemical Modulations by a Combined Selective Proton Pump and pH Probe for Direct Alkalinity Detection

We report a general concept based on a selective electrochemical ion pump used for creating concentration perturbations in thin layer samples (～40 μL). As a first example, hydrogen ions are released from a selective polymeric membrane (proton pump) and the resulting pH is assessed potentiometrically with a second membrane placed directly opposite. By applying a constant potential modulation for 30 s, an induced proton concentration of up to 350 mM may be realized. This concept may become an attractive tool for in situ titrations without the need for sampling, because the thin layer eventually re‐equilibrates with the contacting bulk sample. Acid–base titrations of NaOH and Na₂CO₃ are demonstrated. The determination of total alkalinity in a river water sample is carried out, giving levels (23.1 mM ) comparable to that obtained by standard methods (23.6 mM ). The concept may be easily extended to other ions (cations, anions, polyions) and may become attractive for environmental and clinical applications.     

A reversible fluorescence nanoswitch based on bifunctional reduced graphene oxide: use for detection of Hg2+ and molecular logic gate operation

Herein, we demonstrate the first use of a reduced graphene oxide (rGO)-organic dye nanoswitch for the label-free, sensitive and selective detection of Hg(2+) using bifunctional rGO as an effective nanoquencher and highly selective nanosorbent. Moreover, a reversible on-off INHIBIT rGO logic gate based on a cysteine-Hg(2+) system has also been designed.