Formation of diagnostic product ions from cyanobacterial cyclic peptides by the two-bond fission mechanism using ion trap liquid chromatography/multi-stage mass spectrometry

Product ions obtained by tandem mass spectrometry (MS/MS) are quite effective for the amino acid sequencing of linear peptides. However, in the case of cyclic peptides, the fragmentation pattern is complicated because the cleavages occur randomly and product ions are generated as a(n), b(n), c(n), x(n), y(n) and z(n) series ions; therefore, the authors have never obtained sufficient sequence information. In order to overcome this problem, we applied ion trap liquid chromatography/multi-stage mass spectrometry (LC/MS(n)) and characterized the product ions obtained from anabaenopeptins and aeruginopeptins as the cyclic peptides. For the anabaenopeptins, MS(2) analysis did not provide sufficient sequence information on the cyclic structure, and MS(3) analysis was applied to sequence the constituent amino acids. Diagnostic product ions were obtained by the MS(3) analysis and were quite effective for obtaining the sequence information of the constituent amino acids. MS(2) analysis was, however, sufficient to obtain the sequence information of the aeruginopeptins. In both cases, the resulting product ions obtained from the cyclic structures were formed by the two-bond fission mechanism of the precursor ion, in which an initial fission of the cyclic structure to a linear one and subsequent fission(s) at the peptide bonds are included. The fragmentations were similar for the structurally related compounds, indicating that the cleavages occurred at definite peptide bonds. In addition, the resulting product ions are generated as b(n) series ions and the mass difference facilitates the amino acid sequencing. Thus, ion trap LC/MS(n) provides sequence information, and the resulting product ions are reproducible among the structurally related compounds and reliable for the sequencing of the constituent amino acids of the cyclic structure.     

Measuring the tensile strain of wood by visible and near-infrared spatially resolved spectroscopy

Cellulose - Strain measurement is critical for wood quality evaluation. Using conventional strain gauges constantly is high cost, also challenging to measure precious wood materials due to the use...     

Sodium D2 resonance radiation in single-pass sum-frequency generation with actively mode-locked Nd:YAG lasers

We report on a sodium D(2) resonance coherent light source achieved in single-pass sum-frequency generation in periodically poled MgO-doped stoichiometric lithium tantalate with actively mode-locked Nd:YAG lasers. Mode-locked pulses at 1064 and 1319 nm are synchronized with a time resolution of 37 ps with the phase adjustment of the radio frequencies fed to acousto-optic mode lockers. An output power of 4.6 W at 589.1586 nm is obtained, and beam quality near the diffraction limit is also achieved in a simple design.     

Dynamics of water in partially crystallized polymer/water mixtures studied by dielectric spectroscopy

The dielectric relaxation process of water was investigated for polymer/water mixtures containing poly(vinyl methyl ether), poly(ethyleneimine), poly(vinyl alcohol), and poly(vinylpyrrolidone) with a polymer concentration of up to 40 wt % at frequencies between 10 MHz and 10 GHz in subzero temperatures down to -55 degrees C. These polymer/water mixtures have a crystallization temperature TC of water at -10 to -2 degrees C. Below TC, part of the water crystallized and another part of the water, uncrystallized water (UCW), remained in a liquid state with the polymer in an uncrystallized phase. The dielectric relaxation process of UCW was observed, and reliable dielectric relaxation parameters of UCW were obtained at temperatures of -26 to -2 degrees C. At TC, the relaxation strength, relaxation time, and relaxation time distribution change abruptly, and their subsequent changes with decreasing temperature are larger than those above TC. The relaxation strength of UCW decreases, and the relaxation time and dynamic heterogeneity (distribution of relaxation time) increase with decreasing temperature. These large temperature dependences below TC can be explained by the increase in polymer concentration in the uncrystallized phase C(p,UCP) with decreasing temperature. C(p,UCP) is independent of the initial polymer concentration. In contrast to the relaxation times above TC, which vary with the chemical structure of the polymer and its concentration, the relaxation times of UCW are independent of both of them. This indicates that the factor determining whether the water forms ice crystals or stays as UCW is the mobility of the water molecules.     

Quantitative evaluation of lectin‐reactive glycoforms of α1‐acid glycoprotein using lectin affinity capillary electrophoresis with fluorescence detection

α₁‐Acid glycoprotein (AGP) was previously shown to be a marker candidate of disease progression and prognosis of patients with malignancies by analysis of its glycoforms via lectins. Herein, affinity capillary electrophoresis of fluorescein‐labeled AGP using lectins with the aid of laser‐induced fluorescence detection was developed for quantitative evaluation of the fractional ratios of concanavalin A‐reactive or Aleuria aurantia lectin‐reactive AGP. Labeled AGP was applied at the anodic end of a fused‐silica capillary (50 μm id, 360 μm od, 27 cm long) coated with linear polyacryloyl‐β‐alanyl‐β‐alanine, and electrophoresis was carried out for about 10 min in 60 mM 3‐morpholinopropane‐1‐sulfonic acid‐NaOH buffer (pH 7.35). Addition of the lectins to the anode buffer resulted in the separation of lectin‐reactive glycoform peaks from lectin‐non‐reactive glycoform peaks. Quantification of the peak area of each group revealed that the percent of lectin‐reactive AGP is independent of a labeling ratio ranging from 0.4 to 1.5 mol fluorescein/mol AGP, i.e. the standard deviation of 0.5% for an average of 59.9% (n=3). In combination with a facile procedure for micro‐purification of AGP from serum, the present procedure, marking the reactivity of AGP with lectins, should be useful in determining the prognosis for a large number of patients with malignancies.     

Diffusion of methane and carbon dioxide in carbon molecular sieve membranes by multinuclear pulsed field gradient NMR

Carbon molecular sieve (CMS) membranes are promising materials for energy efficient separations of light gases. In this work, we report a detailed microscopic study of carbon dioxide and methane self-diffusion in three CMS membrane derived from 6FDA/BPDA(1:1)-DAM and Matrimid polymers. In addition to diffusion of one-component sorbates, diffusion of a carbon dioxide/methane mixture was investigated. Self-diffusion studies were performed by the multinuclear (i.e., (1)H and (13)C) pulsed field gradient (PFG) NMR technique which combines the advantages of high field (17.6 T) NMR and high magnetic field gradients (up to 30 T/m). Diffusion measurements were carried out at different temperatures and for a broad range of the root-mean-square displacements of gas molecules inside the membranes. The diffusion data obtained from PFG NMR are compared with the corresponding results of membrane permeation measurements reported previously for the same membrane types. The observed differences between the transport diffusivities and self-diffusion coefficients of carbon dioxide and methane are discussed.     

High-voltage power supplies to capillary and microchip electrophoresis

Over the past years, the development of capillary electrophoresis (CE) and microchip electrophoresis (ME) systems has grown due to instrumental simplicity and wide application. In both CE and ME, the application of a high voltage (HV) is a crucial step in the electrokinetic (EK) injection and separation processes. Particularly on ME devices, EK injection is often performed with three different modes: gated, pinched, and unpinched. In all these cases, different potential values may be applied to one or multiple channels to control the injection of small sample volumes as well as the separation process. For this reason, the construction of reliable HV power supplies (HVPS) is required. This review covers the advances of the development of commercial and laboratory-built HVPS for CE and ME. Moreover, it intends to be a guide for new developers of electrophoresis instrumentation.     

Construction of supramolecular helical nanofibers using renewable biomaterials: self-assembly of a cytidylic acid-appended bolaamphiphile in lemon juice

We performed the self-assembly of a 1,18-cytidylic acid-appended bolaamphiphile (C18C) in lemon juice, which contained citric acid, and succeeded in forming left-handed helical nanofibers with diameters, lengths, and pitches of ca. 6-7 nm, several hundred nm to 5 μm, and ca. 30-40 nm, respectively.     

Solid-state supramolecular assemblies consisting of planar charged species

Pyrrole-based π-conjugated anion-responsive molecules provided various planar anionic structures by complexation with halide anions, resulting in the formation of solid-state assemblies with planar counter cations and exhibiting various modes of charge-by-charge assembly depending on the substituents of the anion receptors.     

Novel pyridino-α-pyrone sesquiterpene type pileotin produced by a sea urchin-derived Aspergillus sp.

A new metabolite, pileotin A, was isolated from a strain of Aspergillus fumigatus originally obtained from the sea urchin Toxopneustes pileolus together with the known compound oxalicine B. The relative stereostructure of pileotin A was elucidated based on spectroscopic analyses, including 1D and 2D NMR techniques. This unique pyridino-α-pyrone sesquiterpene type metabolite has spiro-δ-lactone at C-4.