Electrochemically Induced Free‐Radical Polymerization for the Fabrication of Amperometric Glucose Biosensors

Electrochemically induced free radical polymerization was employed for the fabrication of amperometric glucose biosensors. Based on the electrochemical reduction of persulfate anion, an ultrathin poly(acrylic acid) (PAA) hydrogel coating was generated on both the bare and glucose oxidase (GOD) crosslinked platinum electrodes in a neutral phosphate buffer solution under a low ionic strength condition. This electrosynthetic approach offers a flexible and controllable way to prepare functional coatings for biosensors under a wide range of highly biocompatible conditions, significantly different from other electropolymerization technologies that usually cause the enzyme deactivation. Negatively charged PAA hydrogel coating not only results in a biosensor with good permselectivity and long‐term stability, but also remarkably enhances its sensitivity by improving the oxygen recycle supply and the enzyme activity. Combined with a simple drop‐evaporation procedure to control the GOD loading, the present method offers a versatile and biocompatible way for fabricating highly sensitive biosensor.     

Computation of deuterium isotope perturbation of 13C NMR chemical shifts of alkanes: a local mode zero-point level approach

Replacement of H by D perturbs the (13)C NMR chemical shifts of an alkane molecule. This effect is largest for the carbon to which the D is attached, diminishing rapidly with intervening bonds. The effect is sensitive to stereochemistry and is large enough to be measured reliably. A simple model based on the ground (zero point) vibrational level and treating only the C-H(D) degrees of freedom (local mode approach) is presented. The change in CH bond length with H/D substitution as well as the reduction in the range of the zero-point level probability distribution for the stretch and both bend degrees of freedom are computed. The (13)C NMR chemical shifts are computed with variation in these three degrees of freedom, and the results are averaged with respect to the H and D distribution functions. The resulting differences in the zero-point averaged chemical shifts are compared with experimental values of the H/D shifts for a series of cycloalkanes, norbornane, adamantane, and protoadamantane. Agreement is generally very good. The remaining differences are discussed. The proton spectrum of cyclohexane- is revisited and updated with improved agreement with experiment.     

Tunable hybridization at midzone and anomalous Bloch-Zener oscillations in optical waveguide ladders

We have studied the optical oscillation and tunneling of light waves in optical waveguide ladders (OWLs) formed by two coupled planar optical waveguide arrays. For the band structure, a midzone gap is formed owing to band hybridization, and its wavenumber position can be tuned throughout the whole Brillouin zone, which is different from the Bragg gap. By imposing a gradient in the propagation constant in each array, Bloch-Zener oscillation (BZO) is realized with Zener tunneling between the bands occurring at the midzone, which is contrary to the common BZO with tunneling at the center or edge of the Brillouin zone. The occurrence of BZO is demonstrated by using the field-evolution analysis. The tunable hybridization at the midzone enhances the tunability of BZO in the OWLs. This Letter may offer new insights into the coherent phenomena in optical lattices.     

Improved techniques for parametric and nonparametric evaluations of the first‐passage time for degradation processes

For degradation data in reliability analysis, estimation of the first‐passage time (FPT) distribution to a threshold provides valuable information on reliability characteristics. Recently, Balakrishnan and Qin (2019; Applied Stochastic Models in Business and Industry, 35:571–590) studied a nonparametric method to approximate the FPT distribution of such degradation processes if the underlying process type is unknown. In this article, we propose some improved techniques based on saddlepoint approximation, which enhance those existing methods. Numerical examples and Monte Carlo simulation studies are used to illustrate the advantages of the proposed techniques. Limitations of the improved techniques are discussed and some possible solutions to such are proposed. Some concluding remarks and practical recommendations are provided based on the results.     

Introduction of a triflate group into sterically-hindered positions in 1-aryl-4,6-diamino-1,3,5-triazines and their dimroth rearrangement products

Decomposition of 1-(azidophenyl)-4,6-diamino-1,3,5-triazines 11–13 and their 4-amino-6-(azidoanilino)-1,3,5-triazine isomers 31–33 in trifluoromethanesulphonic acid at 0° led to the introduction of the triflate group (OSO₂CF₃) into the aryl group. This method can be employed to introduce a bulky substituent into the hindered position ortho to the triazinyl substituent. Dimroth rearrangement of 1-(aryl)-4,6-diamino-1,3,5-triazines is best effected in refluxing ethanolic pyridine.     

Loss of trace impurities during NAA of liquid reagents

The loss of trace elements during NAA of five liquid reagents, hydrofluoric acid, hydrochloric acid, nitric acid, hydrogen peroxide and deioniyed water, has been investigated using 17 radioactive tracers of⁴⁶Sc,⁵¹Cr,⁵⁴Mn,⁵⁹Fe,⁶⁰Co,⁶⁴⁵Zn,⁷⁵Se,⁸⁵Sr,⁹⁵Zr,¹¹³Sn,¹²⁴Sb,¹⁵¹Eu,¹⁶⁰Yb,¹⁷⁷Lu,¹⁸²Ta,²³³Pa. Two kinds of container quartz and polyethylene have been used for irradiation and also for preconcentration of the reagents. The containers were cleaned before use by washing-leaching-rinsing procedure. The reagents were preconcentrated by subboiling evaporation under the infrared lamp in clean bench. The loss of trace elements has been revealed to be severer for the reagents of hydrochloric acid and nitric acid in the container of quartz than for the other cases, while that is lowest for hydrogen peroxide.     

Label-free fluorescent probing of G-quadruplex formation and real-time monitoring of DNA folding by a quaternized tetraphenylethene salt with aggregation-induced emission characteristics

Biosensing processes such as molecular beacons require non-trivial effort to covalently label or mark biomolecules. We report here a label-free DNA assay system with a simple dye with aggregation-induced emission (AIE) characteristics as the fluorescent bioprobe. 1,1,2,2-Tetrakis[4-(2-bromoethoxy)phenyl]ethene is nonemissive in solution but becomes highly emissive when aggregated. This AIE effect is caused by restriction of intramolecular rotation, as verified by a large increase in the emission intensity by increasing viscosity and decreasing temperature of the aqueous buffer solution of 1,1,2,2-tetrakis[4-(2-triethylammonioethoxy)phenyl]ethene tetrabromide (TTAPE). When TTAPE is bound to a guanine-rich DNA strand (G1) via electrostatic attraction, its intramolecular rotation is restricted and its emission is turned on. When a competitive cation is added to the G1 solution, TTAPE is detached and its emission is turned off. TTAPE works as a sensitive poststaining agent for poly(acrylamide) gel electrophoresis (PAGE) visualization of G1. The dye is highly affinitive to a secondary structure of G1 called the G-quadruplex. The bathochromic shift involved in the G1 folding process allows spectral discrimination of the G-quadruplex from other DNA structures. The strong affinity of TTAPE dye to the G-quadruplex structure is associated with a geometric fit aided by the electrostatic attraction. The distinct AIE feature of TTAPE enables real-time monitoring of folding process of G1 in the absence of any pre-attached fluorogenic labels on the DNA strand. TTAPE can be used as a K+ ion biosensor because of its specificity to K+-induced and -stabilized quadruplex structure.