Lactate biosensors: current status and outlook

Many research efforts over the last few decades have been devoted to sensing lactate as an important analytical target in clinical care, sport medicine, and food processing. Therefore, research in designing lactate sensors is no longer in its infancy and now is more directed toward viable sensors for direct applications. In this review, we provide an overview of the most immediate and relevant developments toward this end, and we discuss and assess common transduction approaches. Further, we critically describe the pros and cons of current commercial lactate sensors and envision how future sensing design may benefit from emerging new technologies.     

Gate control characteristics in GaAs nanometer-scale Schottky wrap gate structures

Gate control characteristics of GaAs-based quantum wire transistors (QWRTrs) controlled by a nanometer-scale Schottky wrap gate (WPG) are investigated theoretically and experimentally. Gate bias dependence of the effective wire width of fabricated WPG QWRTrs determined theoretically as well as experimentally from Landau plots showed that the nanometer-scale WPG controls the potential very tightly near channel pinch-off and that the pinch-off threshold voltage is strongly dependent on the gate length, L_G, when L_G is shorter than 400 nm. The theory based on the three-dimensional (3D) potential simulation pointed out that Fermi level pinning on the semiconductor surface around the WPGs strongly affects the gate controllability in the nanometer-scale Schottky WPG structure.     

Multilayer lattice gas model in the quasichemical approximation

The multilayer lattice gas model is dealt with in the quasichemical approximation. A restriction on the atomic stacking is also introduced in the system so that an atom can occupy only a lattice site whose underlying nearest neighbor lattice sites are all occupied by atoms. The critical condensation of atoms is investigated as the substrate potential is varied. The theory is also applied to the surface roughening of the crystalline bulk.     

Specular reflection of helium and hydrogen molecular beams from the (111) plane of silver

The Debye—Waller (DW) factor in the specular reflection intensity of He and H₂ molecular beams from the Ag (111) plane has been studied experimentally and theoretically. A new expression for the DW factor corrected for a stationary part of the gas—surface interaction potential is derived kinematically and semi-classically by the use of a Morse potential. An analysis of the experimental data through the above DW factor yields a surface Debye temperature of 251 ± 20 K, which is unusually high, and potential depths of 1.5 ± 1.0 meV for He and 6.4 ± 2.9 meV for H₂, which seem slightly too small. These results are discussed on the basis of the nature of gas-surface interactions and in comparison with the results deduced from the conventional DW factor corrected for a constant attractive potential depth.     

Strategy for Molecular Design of Photochromic Diarylethenes Having Thermal Functionality

Thermal reactivities of photochromic diarylethene closed‐ring isomers can be controlled by the introduction of substituents at the reactive positions. Diarylethenes having bulky alkyl groups undergo thermal cycloreversion reactions. When bulky alkoxy groups are introduced, the diarylethenes have both thermal cycloreversion reactivities and low photocycloreversion quantum yields. Such photochromic compounds can be applied to thermally reusable photoresponsive‐image recordings. The thermal cycloreversion reactivity of the closed‐ring isomers can be evaluated using specific steric substituent constants and be correlated with the parameters. By introduction of trimethylsilyl or methoxymethyl groups at the reactive positions, the diarylethene closed‐ring isomers undergo thermal irreversible reactions to produce by‐products at high temperatures. These diarylethenes may be useful for secret‐image recordings. Furthermore, thiophene‐S,S‐dioxidized diarylethenes having secondary alkyl groups at the reactive positions undergo thermal by‐product formation reactions, in addition to the photostability of the colored closed‐ring isomers. Such materials may be used for light‐starting thermosensors. The thermal by‐product formation reactivity can be evaluated by the specific substituent constants and theoretical calculations of quantum chemistry. These results supply the strategy for the molecular design of the photochromic diarylethenes having thermal functionality.

     

Molecular dynamics simulation study on stabilities and reactivities of NADH cytochrome B5 reductase

Binding free energies between coenzyme (FAD and NADH) and the apoenzyme of NADH-cytochrome b5 reductase (b5R) were estimated by applying the continuum Poisson-Boltzmann (PB) model to structures sampled from molecular dynamics simulations in explicit water molecules. Important residues for the enzymatic catalysis were clarified using a computational alanine scanning method. The binding free energies calculated by applying an alanine scanning method can successfully reproduce the trends of the measured steady-state enzymatic activities kcatNADH/KmNADH. Significant decreases in the binding free energy are expected when one of the four residues Arg91, Lys110, Ser127, and Thr181 is mutated into Ala. According to the results of the molecular dynamics simulation, Thr181 is considered to be one of the key residues that helps NADH to approach the isoalloxazine in FAD. Finally, we have constructed very simplified model systems and carried out density functional theory calculations using B3LYP/LANL2DZ//ROHF(or RHF)/LANL2DZ level of theory in order to elucidate a realistic and feasible mechanism of the hydride-ion transfer from NADH to FAD affected by HEME(Fe3+) as an electron acceptor. Our calculated results suggest that the electron and/or hydride-ion transfer reaction from NADH to FAD can be accelerated in the presence of HEME(Fe3+).     

Pair Distribution Function from Liquid Jet Nanoparticle Suspension using Femtosecond X-ray Pulses

X-ray scattering data measured on femtosecond timescales at the SACLA X-ray Free Electron Laser (XFEL) facility on a suspension of HfO₂ nanoparticles in a liquid jet were used for pair distribution function (PDF) analysis. Despite a non-optimal experimental setup resulting in a modest Q_max of ~8 Å⁻¹, a promising PDF was obtained. The main features were reproduced when comparing the XFEL PDF to a PDF obtained from data measured at the PETRA III synchrotron light source. Refining structural parameters such as unit cell dimension and particle size from the XFEL PDF provided reliable values. Although the reachable Q_max limited the obtainable information, the present results indicate that good quality PDFs can be obtained on femtosecond timescales if the experimental conditions are further optimized. The study therefore encourages a new direction in ultrafast structural science where structural features of amorphous and disordered systems can be studied.     

Synthesis of Furoxans (1,2,5‐oxadiazole 2‐oxides) from Styrenes and Nitrosonium Tetrafluoroborate in Non‐Acidic Media and Mechanistic Study

Diverse furoxans (1,2,5‐oxadiazole 2‐oxides) were synthesized from the corresponding styrenes using nitrosonium tetrafluoroborate as the nitrosation reagent in pyridine (basic media) or dichloromethane (neutral media). Acid‐sensitive functional groups were tolerated under these conditions. The probable reaction mechanism was elucidated. The experimental results support an ionic reaction pathway in contrast to the conventional acidic conditions with a radical mechanism.     

Simple one-step extraction and cleanup by pressurized liquid extraction for gas chromatographic-mass spectrometric determination of pesticides in green leafy vegetables

A simple one-step extraction and cleanup using a pressurized liquid extraction method was developed for the gas chromatographic-mass spectrometric determination of pesticides in vegetables. The pressurized liquid extraction conditions were optimized and cleanup agents were evaluated. The investigated pesticides included six insecticides, chlorpyrifos methyl, pirimiphos-methyl, malathion, chlorpyrifos, O-ethyl O-4-nitrophenylphenyl phosphonothioate (EPN) and permethrins, a fungicide, isoprothiolane, and a herbicides, thiobencarb. The cleanup agent and a mixture of the vegetable and anhydrous sodium sulfate were separately packed in an extraction vessel. A transparent and colorless extract was obtained using graphitized carbon as the cleanup agent. The overall recoveries were 71-103% and the relative standard deviations ranged from 5.6 to 24%. The limit of detection values were 3-8 microg kg(-1). This method was successfully applied to green leafy vegetables.