Facile Electrochemical Hydrogenation and Chlorination of Glassy Carbon to Produce Highly Reactive and Uniform Surfaces for Stable Anchoring of Thiolated Molecules

Carbon is a highly adaptable family of materials and is one of the most chemically stable materials known, providing a remarkable platform for the development of tunable molecular interfaces. Herein, we report a two‐step process for the electrochemical hydrogenation of glassy carbon followed by either chemical or electrochemical chlorination to provide a highly reactive surface for further functionalization. The carbon surface at each stage of the process is characterized by AFM, SEM, Raman, attenuated total reflectance (ATR) FTIR, X‐ray photoelectron spectroscopy (XPS), and electroanalytical techniques. Electrochemical chlorination of hydrogen‐terminated surfaces is achieved in just 5 min at room temperature with hydrochloric acid, and chemical chlorination is performed with phosphorus pentachloride at 50 °C over a three‐hour period. A more controlled and uniform surface is obtained using the electrochemical approach, as chemical chlorination is observed to damage the glassy carbon surface. A ferrocene‐labeled alkylthiol is used as a model system to demonstrate the genericity and potential application of the highly reactive chlorinated surface formed, and the methodology is optimized. This process is then applied to thiolated DNA, and the functionality of the immobilized DNA probe is demonstrated. XPS reveals the covalent bond formed to be a C?S bond. The thermal stability of the thiolated molecules anchored on the glassy carbon is evaluated, and is found to be far superior to that on gold surfaces. This is the first report on the electrochemical hydrogenation and electrochemical chlorination of a glassy carbon surface, and this facile process can be applied to the highly stable functionalization of carbon surfaces with a plethora of diverse molecules, finding widespread applications.     

Feasibility of self-correcting quantum memory and thermal stability of topological order

Recently, it has become apparent that the thermal stability of topologically ordered systems at finite temperature, as discussed in condensed matter physics, can be studied by addressing the feasibility of self-correcting quantum memory, as discussed in quantum information science. Here, with this correspondence in mind, we propose a model of quantum codes that may cover a large class of physically realizable quantum memory. The model is supported by a certain class of gapped spin Hamiltonians, called stabilizer Hamiltonians, with translation symmetries and a small number of ground states that does not grow with the system size. We show that the model does not work as self-correcting quantum memory due to a certain topological constraint on geometric shapes of its logical operators. This quantum coding theoretical result implies that systems covered or approximated by the model cannot have thermally stable topological order, meaning that systems cannot be stable against both thermal fluctuations and local perturbations simultaneously in two and three spatial dimensions.     

Electrochromic cells with iridium oxide display electrodes

We report the fabrication and electrochromic behavior of iridium oxide film electrodes, including a specific display electrode design compatible with the high peak ion-insertion current densities accepted by this material and necessary for the shortest possible response time. The configuration of a complete two-terminal display cell, in which the high capacity counter electrode behaves as a pseudo-reference electrode, is presented. Cell performance, including the use of IR compensated constant-voltage address when response time is limited by impedances external to the iridium oxide itself, is reported.     

Mannich reaction of secondary amines,aldehydes and alkynes in water using Cu/C nanoparticles as a heterogeneous catalyst

The use of 2 mol% of Cu/C nanoparticles, as an easily accessible and inexpensive heterogeneous catalyst, promoted a one-pot three-component condensation of an amine, aldehyde, and an alkyne in water to produce the corresponding propargylamine in good to high yields. This method was proved to be applicable to a wide range of substrates and is especially practical for the synthesis of new azacrown ether derivatives. The catalyst was quantitatively recovered from the reaction by a simple filtration and reused for at least ten times with almost consistent activity.     

Classification of quantum phases and topology of logical operators in an exactly solved model of quantum codes

Searches for possible new quantum phases and classifications of quantum phases have been central problems in physics. Yet, they are indeed challenging problems due to the computational difficulties in analyzing quantum many-body systems and the lack of a general framework for classifications. While frustration-free Hamiltonians, which appear as fixed point Hamiltonians of renormalization group transformations, may serve as representatives of quantum phases, it is still difficult to analyze and classify quantum phases of arbitrary frustration-free Hamiltonians exhaustively. Here, we address these problems by sharpening our considerations to a certain subclass of frustration-free Hamiltonians, called stabilizer Hamiltonians, which have been actively studied in quantum information science. We propose a model of frustration-free Hamiltonians which covers a large class of physically realistic stabilizer Hamiltonians, constrained to only three physical conditions; the locality of interaction terms, translation symmetries and scale symmetries, meaning that the number of ground states does not grow with the system size. We show that quantum phases arising in two-dimensional models can be classified exactly through certain quantum coding theoretical operators, called logical operators, by proving that two models with topologically distinct shapes of logical operators are always separated by quantum phase transitions.     

Nonperturbative gadget for topological quantum codes

Many-body entangled systems, in particular topologically ordered spin systems proposed as resources for quantum information processing tasks, often involve highly nonlocal interaction terms. While one may approximate such systems through two-body interactions perturbatively, these approaches have a number of drawbacks in practice. In this Letter, we propose a scheme to simulate many-body spin Hamiltonians with two-body Hamiltonians nonperturbatively. Unlike previous approaches, our Hamiltonians are not only exactly solvable with exact ground state degeneracy, but also support completely localized quasiparticle excitations, which are ideal for quantum information processing tasks. Our construction is limited to simulating the toric code and quantum double models, but generalizations to other nonlocal spin Hamiltonians may be possible.     

Cystic fibrosis: a label-free detection approach based on thermally modulated electrochemical impedance spectroscopy

Cystic fibrosis is one of the most common genetically inherited diseases in northern Europe, with the DF508 mutation being the most common, and among the Caucasian population being responsible for almost 70% of cases. In this work, we report on the use of thermally modulated electrochemical impedance spectroscopy for the discrimination of the DF508 mutation from the wild-type sequence. DNA probes (15 and 21 bases long) were immobilised on the surface of gold electrodes and the variation of the charge-transfer resistance was monitored as a function of hybridisation. Two sets of targets were used in this work: synthetic 15-mer sequences and two single-stranded synthetic analogues of PCR products 82 (mutant) and 85 (wild type) bases long. Hybridisation with short targets resulted in very sequence specific charge-transfer-resistance variation with a discrimination factor at room temperature between fully complementary and mismatched sequences of approximately fivefold. However, in the case of the single-stranded synthetic PCR product analogues, a lower discrimination factor was recorded (1.5-fold). The effect of temperature was investigated to improve discrimination and the use of a posthybridisation wash at elevated temperature resulted in a fivefold improvement in the discrimination factor. Using an electrode array with probes immobilised against each of the mutant and wild-type sequences, we achieved an unequivocal detection of the DF508 mutation.     

Biofunctionalization of Polyoxometalates with DNA Primers,Their Use in the Polymerase Chain Reaction (PCR) and Electrochemical Detection of PCR Products

The bioconjugation of polyoxometalates (POMs), which are inorganic metal oxido clusters, to DNA strands to obtain functional labeled DNA primers and their potential use in electrochemical detection have been investigated. Activated monooxoacylated polyoxotungstates [SiW₁₁O₃₉{Sn(CH₂)₂CO}]^8? and [P₂W₁₇O₆₁{Sn(CH₂)₂CO}]^6? have been used to link to a 5′‐NH₂ terminated 21‐mer DNA forward primer through amide coupling. The functionalized primer was characterized by using a battery of techniques, including electrophoresis, mass spectrometry, as well as IR and Raman spectroscopy. The functionality of the POM‐labeled primers was demonstrated through hybridization with a surface‐immobilized probe. Finally, the labeled primers were successfully used in the polymerase chain reaction (PCR) and the PCR products were characterized by using electrophoresis.