Electrochemically oriented immobilization of antibody on poly-(2-cyano-ethylpyrrole)-coated gold electrode using a cyclic voltammetry

Using quartz crystal microbalance (QCM) as an immunosensor, this work investigates the contribution of a cyclic voltammetry (CV) on the proper immobilization of antibodies with the aim of enhancing its target recognition and binding ability. Primarily, CV in the range of −0.1 to 0.9 V was applied to form a layer of poly-(2-cyano-ethylpyrrole) (PCEPy) on gold quartz crystal electrode. Then the efficiencies of antibodies (anti-IgG, AIgG) immobilized electrochemically with CV applied in 0-0.65 V were compared to those immobilized via physical adsorption, by observing relative affinity towards AIgG-Fab and AIgG-Fc fragments. The results showed antibody-AIgG-Fab interaction could be enhanced about 4 times when CV is applied (11.2 ± 1.3 vs 41.6 ± 3.4 relative fluorescence unit). On the contrary, physisorbed antibodies showed a higher degree of affinity towards AIgG-Fc indicating inappropriate orientations of physisorbed antibodies. AIgG immobilized PCEPy-gold QC electrode was characterized further for its sensitivity towards a new target bovine albumin with both a QCM and fluorescence measurement. Such electrode exhibited a good sensitivity as well as a large linear dynamic range, from 0.4 μg/ml to 1.0 μg/ml and from 0.5 μg/ml to 10.0 μg/ml, at QCM and fluorescence measurement, respectively.     

Kinetic and theoretical studies on alkaline ethanolysis of 4-nitrophenyl salicylate: effect of alkali metal ions on reactivity and mechanism

Pseudo-first-order rate constants (k(obsd)) for reactions of 4-nitrophenyl salicylate (7) with alkali metal ethoxides (EtOM, M = K, Na, and Li) in anhydrous ethanol have been measured spectrophotometrically. Interestingly, the k(obsd) value decreases significantly as the concentration of EtOM increases. Because the phenolic moiety of substrate 7 would be deprotonated and exist as an anionic form (i.e., 7(-)) under kinetic conditions, the ground-state stabilization of 7(-) through formation of a six-membered cyclic complex with M(+) (i.e., 8) is proposed to be responsible for the decreasing k(obsd) trend. The k(obsd) value at a given concentration of EtOK increases steeply upon addition of [18]crown-6 ether (18C6) up to [18C6]/[EtOK] = 1 in the reaction mixture and then remains relatively constant thereafter. In contrast, k(obsd) decreases upon addition of salts (e.g., LiClO(4) or KSCN) to the reaction mixture, which indicates that M(+) ions inhibit the reaction. However, in the presence of 18C6, the k(obsd) value is independent of the concentration of EtOK but remains constant, which indicates that the reaction proceeds through a unimolecular mechanism in the presence of the complexing agent. Although two conceivable unimolecular pathways (formation of ketene 9 and lactone 10) can account for the kinetic results, the reaction has been concluded to proceed via formation of ketene 9 as the reactive intermediate on the basis of theoretical calculations.     

Discrimination between genetically identical peony roots from different regions of origin based on 1H-nuclear magnetic resonance spectroscopy-based metabolomics: determination of the geographical origins and estimation of the mixing proportions of blended samples

Sixty peony root training samples of the same age were collected from various regions in Korea and China, and their genetic diversity was investigated for 23 chloroplast intergenic space regions. All samples were genetically indistinguishable, indicating that the DNA-based techniques employed were not appropriate for determining the samples’ regions of origin. In contrast, ¹H-nuclear magnetic resonance (¹H-NMR) spectroscopy-based metabolomics coupled with multivariate statistical analysis revealed a clear difference between the metabolic profiles of the Korean and Chinese samples. Orthogonal projections on the latent structure-discrimination analysis allowed the identification of potential metabolite markers, including γ-aminobutyric acid, arginine, alanine, paeoniflorin, and albiflorin, that could be useful for classifying the samples’ regions of origin. The validity of the discrimination model was tested using the response permutation test and blind prediction test for internal and external validations, respectively. Metabolomic data of 21 blended samples consisting of Korean and Chinese samples mixed at various proportions were also acquired by ¹H-NMR analysis. After data preprocessing which was designed to eliminate uncontrolled deviations in the spectral data between the testing and training sets, a new statistical procedure for estimating the mixing proportions of blended samples was established using the constrained least squares method for the first time. The predictive procedure exhibited relatively good predictability (adjusted R ²?=?0.7669), and thus has the potential to be used in the quality control of peony root by providing correct indications for a sample’s geographical origins.

Energy-Momentum and Equivalence Principle in Non-Riemannian Geometries

We introduce an energy-momentum density vector which is independent of the affine structure of the manifold and whose conservation is linked to observers. Integrating this quantity over time-like surfaces we can define Hamiltonian and momentum for the system which coincide with the corresponding ADM definitions for the case of irrotational Riemannian manifolds. As a consequence of our formalism, a Weak Equivalence Principle version for manifolds with torsion appears as the natural extension to non-Riemannian geometries from the Equivalence Principle of General Relativity.     

光栅耦合外谐振腔调谐的半导体量子级连激光器

本文研究了由InGaAs/InAlAs材料组成,波长为4.6和5.1微米的量子级连中红外半导体激光器的光栅外耦合谐振腔的特性。在温度是80K时波长可调制宽度是激光中心波长的1.5%左右。对于这两个激光器而言,它们的波长可调制宽度随温度升高而减低。被调制的单模激光器的输出光功率是几个毫瓦,激光的谱线宽度是1到2个微米。激光阈值电流随波长缓慢变化,然而激光输出效率在短波长时更加优化。     

Alkali‐Metal Ion Catalysis and Inhibition in SNAr Displacement: Relative Stabilization of Ground State and Transition State Determines Catalysis and Inhibition in SNAr Reactivity

We report here the first observation of alkali‐metal ion catalysis and inhibition in S_NAr reactions. The plot of k_obsd versus [alkali‐metal ethoxide] exhibits downward curvature for the reactions of 1‐(4‐nitrophenoxy)‐2,4‐dinitrobenzene with EtOLi, EtONa, and EtOK, but upward curvature for the corresponding reaction with EtOK in the presence of 18‐crown‐6‐ether (18C6). Dissection of k_obsd into the second‐order rate constants for the reactions with the dissociated EtO^? and the ion‐paired EtOM (i.e., k and k_EtOM, respectively) has revealed that the reactivity increases in the order EtOLi<EtONa<EtOK<EtO^?<EtOK/18C6. This indicates that the reaction is inhibited by Li⁺, Na⁺, and K⁺ ions but is catalyzed by 18C6 K⁺ ion. The reactions of 1‐(Y‐substituted‐phenoxy)‐2,4‐dinitrobenzenes have been proposed to proceed through a stepwise mechanism, in which expulsion of the leaving group occurs after the rate‐determining step based on the kinetic result that σ^o constants exhibit a much better Hammett correlation than σ^? constants. Alkali‐metal ion catalysis or inhibition has been discussed in terms of differential stabilization of ground‐state and transition‐state complexes through a qualitative energy profile. A π‐complexed transition‐state structure is proposed to account for the kinetic results.     

Enlargement of blue-phase stability for rod-like low-molecular-weight chiral nematic liquid crystal mixtures

In this study, we investigated the enlargement of liquid crystal (LC) blue-phase (BP) temperature range using the rod-like low-molecular-weight cyano phenyl-type chiral nematic LC with various core group and chiral dopant concentrations. Also, the electro-optic response time was investigated for them. We found that the BP temperature range was strongly dependent upon the core structure and the chiral dopant concentration for the chiral nematic LC mixtures having the same terminal group. Also, we found a stable BP with a wide temperature range (more than 6 K), including a BP-isotropic coexistence state over 13.5 K upon heating and cooling processes and very fast response time (less than 1 ms), by using the cyano phenyl-type chiral nematic LC mixture with a high molecular aspect ratio and a high chiral dopant concentration.     

Development of Real-Time PCR Primer and Probe Sets for Detecting Degenerated and Non-degenerated Forms of the Butanol-Producing Bacterium Clostridium acetobutylicum ATCC 824

Degeneration is one of the limiting factors in butanol fermentation, and it must be monitored and prevented for stable butanol production. In Clostridium acetobutylicum ATCC 824, the most well-known butanol-producing microorganism, degeneration is caused by the loss of the pSOL1 plasmid that carries essential genes involved in solvent production. In this study, we designed two specific primer and probe sets for real-time qPCR (RT-qPCR) detection of C. acetobutylicum ATCC 824 (the C. aceto set) and pSOL1-possessing C. acetobutylicum ATCC 824 (the DGS set). Specific primer and probe sets were designed on the basis of the 16S rDNA sequence and pSOL1 sequence. The number of degenerated C. acetobutylicum could be quantified by subtracting the number of C. acetobutylicum ATCC 824 containing pSOL1 from the total number of C. acetobutylicum ATCC 824. The primer and probe sets permitted the specific detection and quantification of degenerated C. acetobutylicum and total butanol-producing C. acetobutylicum by RT-qPCR.     

The effect of an electric field on the local stoichiometry of front waves in an ionic chemical system

A model based on an autocatalytic, two-step reaction mechanismincluding two ionic components (of the same charge) and twonon-ionic components, where both reactions are of second orderoverall, is considered when an electric field is applied tothe system. The model is motivated by experimental observationson the iodate-arsenous acid system. The travelling wave equationsare examined first and conditions obtained for the existenceand form of these waves. These conditions are then used to interpretthe results obtained from numerical simulations of the fullsystem. These results display all the main features observedexperimentally, the change in the local stoichiometry and thepossible wave annihilation for sufficiently strong fields. Themodel provides a clear explanation for these features as wellas predicting new features not reported from the experiments.The main one of which is the occurrence of an internal wavepropagating in the reacted part of the system in the directioninduced by the applied field.