Characterization of fulvic acids by liquid chromatography-quadrupole time-of-flight mass spectrometry

Fulvic acid standards from Suwannee River, Pony Lake, Elliot Soil, Waskish Peat, and Nordic Reservoir were characterized by liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) operating in negative electrospray ionization mode. The method employed a commercially available stationary phase that resulted in a distinctive chromatographic peak for each of the fulvic acid samples that differed in width and retention time at peak maximum. The QTOF-MS, operating in TOF mode, revealed that the unique chromatographic peak shapes were the result of the relative fraction of hydrogen and oxygen contained in various fulvic acid components. Those species that contained larger amount of hydrogen displayed a larger mass defect and were retained longer on the LC column, indicating reduced polarity. This is supported by a reduction in the degree of fragmentation related to polar functional groups as the mass defect and retention time increased. Lastly, the analysis of even and odd mass (at m/z 1 greater) ion intensity ratios revealed a correlation to the percent nitrogen of the various standards.     

Acoustic attenuation, phase and group velocities in liquid-filled pipes: Theory, experiment, and examples of water and mercury

Del Grosso's [Acustica 24, 299-311 (1971)] formulation, which predicts the phase speed of propagating axisymmetric modes inside a liquid-filled tube, is here extended to the complex domain in order to predict the attenuation, as well as the sound speed, of the modes as a function of frequency. Measurements of the sound speeds and the attenuations of the modes were performed in a water-filled Poly (methyl methacrylate) (PMMA) tube of internal radius, b=4.445 cm, in the range of the wavenumber-radius product, k(1)b, from 2 to 10. Parts of three or four modes were investigated and the measured sound speeds and the damping of the modes were compared with the theoretical predictions. The theory was then used to estimate the modal sound speeds and attenuations in a stainless-steel pipe filled with mercury having the same dimensions as are used in the Spallation Neutron Source at Oak Ridge National Laboratory, Tennessee.     

Factors Affecting the Production of Aromatic Immonium Ions in MALDI 157 nm Photodissociation Studies

Immonium ions are commonly observed in the high energy fragmentation of peptide ions. In a MALDI-TOF/TOF mass spectrometer, singly charged peptides photofragmented with 157 nm VUV light yield a copious abundance of immonium ions, especially those from aromatic residues. However, their intensities may vary from one peptide to another. In this work, the effect of varying amino acid position, peptide length, and peptide composition on immonium ion yield is investigated. Internal immonium ions are found to have the strongest intensity, whereas immonium ions arising from C-terminal residues are the weakest. Peptide length and competition among residues also strongly influence the immonium ion production. Quantum calculations provide insights about immonium ion structures and the fragment ion conformations that promote or inhibit immonium ion formation.

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Application of ultrasound as pretreatment for extraction of podophyllotoxin from rhizomes of Podophyllum peltatum

The effect of high-power ultrasound pretreatment on the extraction of podophyllotoxin from Podophyllum peltatum was investigated. Direct sonication by an ultrasound probe horn was applied at 24 kHz and a number of factors were investigated: particle size (0.18-0.6 mm), type of solvent (0-100% aqueous ethanol), ultrasonic treatment time (2-40 min), and power of ultrasound (0-100% power intensity, maximum power: 78 W). The optimal condition of ultrasound was achieved with 0.425-0.6 mm particle size, 10 min sonication time, 35 W ultrasound power, and water as the medium. There was no obvious degradation of podophyllotoxin with ultrasound under the applied conditions, and an improvement in extractability was observed. The SEM microscopic structure change of treated samples disclosed the effect of ultrasound on the tissue cells. The increased pore volume and surface area after ultrasonic treatment also confirmed the positive effect of ultrasound pretreatment on the extraction yield of podophyllotoxin from the plant cells.     

Characterization of deep levels in a-plane GaN epi-layers grown using various growth techniques

To study the correlation between defects and deep levels in a-plane GaN films grown on r-plane sapphire substrates, transmission electron microscopy (TEM) and deep level transient spectroscopy (DLTS) have been performed on three types of a-plane GaN samples grown using modified two-step growth (sample I), SiN_x interlayer (sample II), and patterned insulator on sapphire substrate (sample III). From the microstructure evolution in cross-sectional TEM images, it was shown that combination of growth techniques is highly efficient in the reduction of dislocation densities. Average dislocation densities of samples I, II, and III were about 2.2×10⁹ cm^?2, 1.1×10⁹ cm^?2, and 3.4×10⁸ cm^?2, respectively. The trap a_t E_c–E_t～0.13 eV (E1) was observed in only sample I, and three electron traps at 0.28–0.33 eV (E2), 0.52–0.58 eV (E3), and 0.89–0.95 eV (E4) from the conduction band edge were measured common to all the samples. The analysis of trap properties indicated that E2 and E3 trap levels are strongly associated with the partial dislocations in a-plane GaN films.     

Conjecture of Li and Praeger concerning the isomorphisms of Cayley graphs of A5

LetG be a finite group, andS a subset ofG \ |1| withS =S ^?1. We useX = Cay(G,S) to denote the Cayley graph ofG with respect toS. We callS a Cl-subset ofG, if for any isomorphism Cay(G,S) ≈ Cay(G,T) there is an α∈ Aut(G) such thatS ^α =T. Assume that m is a positive integer.G is called anm-Cl-group if every subsetS ofG withS =S ^?1 and | S | ≤m is Cl. In this paper we prove that the alternating groupA ₅ is a 4-Cl-group, which was a conjecture posed by Li and Praeger.     

Analysis of Phase Measurement Errors in Electro-Optic Holography

This paper presents the results of an error analysis in electro-optics holography. These errors include phase measurement errors due to the linear phase shifter errors in static electro-optic holography, and phase measurement errors due to the errors in the vibrating bias amplitude and phase in dynamic electro-optic holography. Through the error analysis, we found that the phase shifting errors in static electro-optic holography are twice as large as those in the conventional 4-bucket phase shifting algorithm, and the phase shifting errors in dynamic electro-optic holography are similar to those in the 4-bucket phase shifting algorithm.     

Direct Stereoconvergent Allylation of Chiral Alkylcopper Nucleophiles with Racemic Allylic Phosphates

Copper-catalyzed stereoconvergent allylation of chiral sp³-hybridized carbon nucleophiles with a racemic mixture of acyclic secondary allylic phosphates is reported. In the presence of a copper-catalyst complexed with chiral BenzP* ligand, tandem coupling reaction of vinyl arenes, bis(pinacolato)diboron, and racemic allylic phosphates provided β-chiral alkylboronates possessing (E)-alkenyl moiety through a direct stereoconvergent allylic coupling with concomitant generation of a C(sp³)-stereogenic center. A range of vinyl (hetero)arenes and secondary allylic phosphates bearing 1°, 2°, 3° alkyl and phenyl α-substituents were suitable for the reaction, forming products with high enantioselectivities up to 95 % ee. Density functional theory calculations were conducted in detail to elucidate the origin of the observed regioselectivity of borylcupration and stereoconvergent (E)-olefin formation from racemic allylic phosphates.     

Determination of stress-intensity factors by the method of caustics in anisotropic materials

This paper studied the applicability of the method of caustics to anisotropic materials under Mode I and mixed-mode static-loading conditions and introduced the procedure to obtain stress-intensity factors (SIF) in anisotropic materials by the method of caustics.The mapping equations for initial and caustic curves in anisotropic materials were introduced and their computer graphical images were compared to the experimental ones to check the validity of the mapping equations proposed in this paper. The agreement between them was found to be satisfactory.Two kinds of equations to determine SIF in anisotropic materials by the method of caustics are proposed in this paper. Corroborative experiments carried out by using the orthotropic materials under various loading conditions are presented. In the case of Mode I loading condition, the SIF's obtained by this paper's methods were found to be close to the results by another method, i.e., boundary-element method (BEM). And in the case of mixed-loading condition, the SIF's by this paper and BEM show little differences, (2.2–24.4 percent) with respect to the slanted angle of crack.     

Reductive Carbocyclization of Homoallylic Alcohols to syn‐Cyclobutanes by a Boron‐Catalyzed Dual Ring‐Closing Pathway

The organoborane‐catalyzed reductive carbocyclization of homoallylic alcohols has been developed by using hydrosilanes as reducing reagents to provide a range of 1,2‐disubstituted arylcyclobutanes. The reaction proceeds in a cis‐selective manner with high efficiency under mild conditions. Mechanistic studies, including deuterium scrambling and Hammett studies, and DFT calculations, suggest a dual ring‐closing pathway.