Structural studies on C-amidated amino acids and peptides: function of amide group in molecular association in crystal structures of Val-Gly-NH2, Ser-Phe-NH2, Gly-Tyr-NH2 and Pro-Tyr-NH2 hydrochloride salts

As part of a series of elucidation of the structural features of peptides caused by C-terminal alpha-amidation, the crystal structures of H-Val-Gly-NH2, H-Ser-Phe-NH2, H-Gly-Tyr-NH2, and H-Pro-Tyr-NH2 hydrochloride salts were analyzed by the X-ray diffraction method. Although respective molecules take energetically allowable torsion angles concerning the backbone and side chains, their conformations are not necessarily the same as the corresponding unamidated ones. This results from the different molecular packing requirements, rather than from different conformational features inherent in the C-amidated and -unamidated peptides. As for the molecular packing feature, each peptide tended to form a repeated structure through those hydrogen bonds in which both amide NH and O=C groups participate. The chloride ions are located between the neighboring peptides and are hydrogen-bonded to the respective amide NHs, leading to the sheet structure. The hydrogen-bonding feature of the amide group and its function in molecular packing was discussed based on the results analyzed so far.     

Automatic analyzer for highly polar carboxylic acids based on fluorescence derivatization–liquid chromatography

A sensitive, versatile, and reproducible automatic analyzer for highly polar carboxylic acids based on a fluorescence derivatization–liquid chromatography (LC) method was developed. In this method, carboxylic acids were automatically and fluorescently derivatized with 4‐(N,N‐dimethylaminosulfonyl)‐7‐piperazino‐2,1,3‐benzoxadiazole (DBD‐PZ) in the presence of 4‐(4,6‐dimethoxy‐1,3,5‐triazin‐2‐yl)‐4‐methylmorpholinium chloride by adopting a pretreatment program installed in an LC autosampler. All of the DBD‐PZ‐carboxylic acid derivatives were separated on the ODS column within 30 min by gradient elution. The peak of DBD‐PZ did not interfere with the separation and the quantification of all the acids with the exception of lactic acid. From the LC‐MS/MS analysis, we confirmed that lactic acid was converted to an oxytriazinyl derivative, which was further modified with a dimethoxy triazine group of 4‐(4,6‐dimethoxy‐1,3,5‐triazin‐2‐yl)‐4‐methylmorpholinium chloride (DMT‐MM). We detected this oxytriazinyl derivative to quantify lactic acid. The detection limits (signal‐to‐noise ratio = 3) for the examined acids ranged from 0.19 to 1.1 µm , which correspond to 95–550 fmol per injection. The intra‐ and inter‐day precisions of typical, highly polar carboxylic acids were all <9.0%. The developed method was successfully applied to the comprehensive analysis of carboxylic acids in various samples, which included fruit juices, red wine and media from cultured tumor cells. Copyright © 2014 John Wiley & Sons, Ltd.     

Two-stage feedforward tracking control system with error-based disturbance observer for optical discs

Recently, the scaling up of the storage capacity and data transfer rate of digital storage media has been required. However, increasing in the storage capacity and transfer rate makes optical head control more difficult. Thus, a tracking control system for optical discs must exhibit a high degree of precision control. Consequently, a new two-stage feedforward control (TSFFC) system for high-precision control is proposed in this paper. The proposed system is constructed using two zero phase error tracking (ZPET) control systems based on error prediction and an error-based disturbance observer (EDOB) that uses a notch filter to suppress non periodic disturbances. The proposed control system is designed for DDU-1000 for digital versatile discs (DVDs). The experimental results demonstrate that the proposed system effectively suppresses tracking errors.     

Use of chiral derivatization for the determination of dichlorprop in tea samples by ultra performance LC with fluorescence detection

Dichlorprop is available for agricultural use as a chiral pesticide. In this study, the stereoselective determination of dichlorprop enantiomers in tea samples such as green, black, jasmine, and oolong was developed by ultra performance LC with fluorescence spectrometry after covalent chiral derivatization. The separation was achieved on an Acquity BEH C18 column with the mobile phase consisting of 0.1% formic acid in acetonitrile/water at a flow rate of 0.4 mL/min. In the covalent chiral derivatization using (S)‐(+)‐4‐(N,N‐dimethylaminosulfonyl)‐7‐(3‐aminopyrrolidin‐1‐yl)‐2,1,3‐benzoxadiazole, the peak resolution between the S and R‐dichlorprop enantiomers was 2.6. LODs and LOQs values were 10 and 50 ng/mL standard solution. The linearity of the calibration curves yielded the coefficients (r² > 0.99, ranging from 0.05 to 5 μg/mL) of determination of each of the dichlorprop enantiomers. SPE extraction was used for the sample preparation of dichlorprop in various tea samples. Recoveries were in the range of 82.4–97.6% with associated precision values (within‐day: 82.4–95.8%, n = 6, and between‐day: 83.7–97.6% for 3 days) for repeatability and reproducibility. Based on this result, our method has been proven to be highly efficient and suitable for the routine assay of dichlorprop enantiomers in various tea samples. We propose that the ultra performance LC assay after covalent chiral derivatization would be the renewed tools in the era of chiral stationary platform for chiral pesticide residues in foods.     

Bisecting a 4-connected graph with three resource sets

Let G=(V,E) be an undirected graph with a node set V and an arc set E. G has k pairwise disjoint subsets T₁,T₂,…,T_k of nodes, called resource sets, where |T_i| is even for each i. The partition problem with k resource sets asks to find a partition V₁ and V₂ of the node set V such that the graphs induced by V₁ and V₂ are both connected and |V₁∩T_i|=|V₂∩T_i|=|T_i|/2 holds for each i=1,2,…,k. The problem of testing whether such a bisection exists is known to be NP-hard even in the case of k=1. On the other hand, it is known that if G is (k+1)-connected for k=1,2, then a bisection exists for any given resource sets, and it has been conjectured that for k?3, a (k+1)-connected graph admits a bisection. In this paper, we show that for k=3, the conjecture does not hold, while if G is 4-connected and has K₄ as its subgraph, then a bisection exists and it can be found in O(|V|³log|V|) time. Moreover, we show that for an arc-version of the problem, the (k+1)-edge-connectivity suffices for k=1,2,3.     

A simple and rapid method of collecting radionuclides from rain water

A column of mixed powdered ion-exchange resins (Powdex) is proposed for the collection of radionuclides from rain water. The radionuclides are collected efficiently for γ-ray spectrometry. The procedure takes about 1.5 h for 10 l of rain water.     

Separation assay of histamine and its metabolites in biological specimens

This review summarizes the determination methods for histamine and the metabolites in biological specimens by separation techniques, such as gas chromatography, liquid chromatography and capillary electrophoresis. The typical applications using these methods are also described in this review together with the characteristics of the methods. Copyright (c) 2008 John Wiley & Sons, Ltd.     

Capture of cationic ligands bound diffusely to base pairs during DNA refolding

We obtained the intrinsic binding affinity for metal ions, polyamines, and oligolysine peptides diffusely bound to base-paired sites in DNA by monitoring the shift of the hairpin-duplex equilibrium of the self-complementary DNA sequences, which can be widely used for capturing cationic ligands bound diffusely to nucleotide base pairs.     

Effect of DNA on filament formation of tau microtubule-binding domain: structural dependence of DNA

To examine whether or not DNA accelerates the paired helical filament (PHF) formation of tau, the effect of various types of DNAs on filament formations of three-repeated and four-repeated microtubule-binding domains (3RMBD and 4RMBD, respectively) of tau protein was investigated by monitoring the change of thioflavin S fluorescence intensity, that is parallel to the filament formation. Consequently, the followings were clarified: 1) the structurally rigid double-stranded DNA such as poly(dG-dC) or calf thymus DNA has the high potency of promoting the filament formations of 3RMBD and 4RMBD, 2) the filament formation of 3RMBD was more promoted than that of 4RMBD, due to the intermolecular dimer formation of 3RMBD, 3) the DNA-promoted filament formations of these MBDs were temperature-dependent, and the single-stranded DNA such as poly(dA) or poly(dT) reversely protected 4RMBD from the molecular assembly at 20 degrees C. These are the first report on the function of DNA for the PHF formation of tau protein.