Constituents from the leaves of Phellodendron amurense and their antioxidant activity

Three new coumarins, phellodenols F-H (1-3) and a new glutaric acid derivative, phellodendric acid-A (4) were isolated from the leaves of Phellodendron amurense together with twenty-nine known compounds. Extensive 1D and 2D NMR experiments and other spectroscopic studies were employed to determine the structures of 1-4. The isolated compounds were screened for their antioxidant activity through DPPH (alpha,alpha-diphenyl-beta-picrylhydrazyl) radical scavenging assay. Compounds quercetin, quercetin-3-O-beta-D-glucoside, quercetin-3-O-beta-D-galactoside and kaempferol-3-O-beta-D-glucoside demonstrated significant radical scavenging activity comparable to vitamin E.     

Synthesis and properties of novel aromatic poly(ester-imide)s bearing 1,5-bis(benzoyloxy)naphthalene units

Two series of new aromatic poly(ester-imide)s were prepared from 1,5-bis(4-aminobenzoyloxy)naphthalene (p-1) and 1,5-bis(3-aminobenzoyloxy)naphthalene (m-1), respectively, with six commercially available aromatic tetracarboxylic dianhydrides via a conventional two-stage synthesis that included ring-opening polyaddition to give poly(amic acid)s followed by chemical imidization to polyimides. The intermediate poly(amic acid)s obtained in the first stage had inherent viscosities of 0.41-0.84 and 0.66-1.37 dl/g, respectively. All the para-series and most of the meta-series poly(ester-imide)s were semicrystalline and showed less solubility. Two of the meta-series poly(ester-imide)s derived from less rigid dianhydrides were amorphous and readily soluble in polar aprotic solvents, and they could be solution-cast into transparent and tough films with good mechanical properties. The meta-series polymers derived from rigid dianhydrides were generally semicrystalline and showed less solubility. Except for one example, the meta-series poly(ester-imide)s displayed discernible T_gs in the range 239-273 °C by DSC. All of these two series poly(ester-imide)s did not show significant decomposition below 450 °C in nitrogen or in air.     

Synthesis of well-aligned carbon nanotubes by inductively coupled plasma chemical vapor deposition

Uniform and well-aligned carbon nanotubes (CNTs) have been grown using a high density inductively coupled plasma chemical vapor deposition (ICP-CVD) system. A gas mixture of methane-hydrogen was used as the source and Ni as the catalyst for the CNT growth. The effect of process parameters, such as inductive RF power, DC bias voltage and CH₄/H₂ ratio, on the growth characteristics of CNTs was investigated. It was found that both plasma intensity and ion flux to the substrate, as controlled by the inductive RF power and DC bias voltage, respectively, can greatly affect the growth of CNTs. The relative importance of the generation of ions and the subsequent transport of ions to the substrate as serial process steps are considered as the two underlying factors in determining the growth characteristics of CNTs. PACS 81.05.Uw; 81.07.De; 81.15.Gh     

Bond energies, reaction volumes, and kinetics for σ- and π-complexes of MoCO5L

The photosubstitution reactions of molybdenum hexacarbonyl with σ and π donor ligands were investigated using photoacoustic calorimetry and computational methods in a series of linear alkane solvents (pentane, hexane, heptane, octane, decane, and dodecane). The results show that reaction volumes make a significant contribution to the photoacoustic signal and must be considered during thermodynamic calculations based on photoacoustic measurements. The enthalpies of CO substitution by an alkane solvent and subsequent substitution by each Lewis base were determined. Corresponding Mo-L bond energies (kcal mol(-1)) were calculated: L = linear alkanes (13), triethylsilane (26), 1-hexyne (27), 1-hexene (27), and benzene (17). The relative energies are in agreement with computational results. The experimental reaction volume for CO substitution by alkane was positive (15 mL mol(-1)) and negative or close to zero for alkane substitution by a Lewis base (for example, -11 mL mol(-1) for triethylsilane and 3.6 mL mol(-1) for benzene). The errors in the experimental and computational reaction volumes are large and often comparable to the reaction volumes. An improved calibration of the methods as well as a better understanding of the underlying physics involved is needed. For the Lewis bases reported in this study, the second-order rate constants for the displacement of a coordinated alkane are less than diffusion control (5 × 10(6)-4 × 10(7) M(-1) s(-1)) and decrease monotonically with the alkane chain length. The rate constants correlate better with steric effects than with bond energies. An interchange mechanism is consistent with the results.     

Structural and microscopic relaxations in glycerol: an inelastic x-ray scattering study

The THz dynamics of liquid glycerol has been probed by inelastic x-ray scattering at different pressure spanning the 0.66-3 Kbar range. A comparison with ultrasound absorption results available in literature leads us to identify the presence of two different relaxations, a structural (slow) relaxation and a microscopic (fast) one. Although the former has been already thoroughly studied in glycerol by lower frequency spectroscopic techniques, no hints on the latter are so far available in literature. We observe that the characteristic timescale of this fast relaxation ranges in the sub-picosecond, tends to decrease with increasing the wave-vector and seems rather insensitive to pressure changes. Finally, the timescale and strength of the fast relaxation have a direct link revealing the microscopic, single particle, nature of the involved process.     

Fundamental Fraction Knowledge of Preservice Elementary Teachers: A Cross‐National Study in the United States and Taiwan

The purpose of this paper is to show the similarities as well as the differences of fundamental fraction knowledge owned by preservice elementary teachers from the United States (N= 89) and Taiwan (N= 85). To this end, we examined and compared their performance on an instrument including 15 multiple‐choice test items. The items were categorized into four different types of fundamental fraction constructs, including part–whole relationship, quotient, equivalence, and meanings of operations. Each item was embedded in the area, linear, or set model except for the items constructed out of the meaning of operations. Several items were featured with a pictorial illustration. Quantitative analysis showed that U.S. preservice teachers were significantly outperformed by their Taiwanese counterparts overall. The difference between the two groups was statistically significant on 12 of 15 items. Findings suggest that preservice elementary teachers from both countries need to be better prepared in their understanding of the meaning of fraction multiplication or division operations. Findings also suggest that U.S. preservice elementary teachers need to be more knowledgeable in dealing with fraction problems embedded in a linear model. Further research is suggested to study the issues raised from the findings.     

The free energy of a reaction coordinate at multiple constraints: a concise formulation

The free energy as a function of the reaction coordinate (rc) is the key quantity for the computation of equilibrium and kinetic quantities. When it is considered as the potential of mean force, the problem is the calculation of the mean force for given values of the rc. We reinvestigate the PMCF (potential of mean constraint force) method which applies a constraint to the rc to compute the mean force as the mean negative constraint force and a metric tensor correction. The latter allows for the constraint imposed to the rc and possible artefacts due to multiple constraints of other variables which for practical reasons are often used in numerical simulations. Two main results are obtained that are of theoretical and practical interest. First, the correction term is given a very concise and simple shape which facilitates its interpretation and evaluation. Secondly, a theorem describes various rcs and possible combinations with constraints that can be used without introducing any correction to the constraint force. The results facilitate the computation of free energy by molecular dynamics simulations.     

Characterization of Single-Phase Flow Through Carbonate Rocks: Quantitative Comparison of NMR Flow Propagator Measurements with a Realistic Pore Network Model

We report here the quantitative comparisons between the measured NMR flow propagator of a carbonate rock and the flow propagator calculated with a porous network extracted from the micro-CT image of the twin plug. We developed a numerical model based on a particle tracking algorithm in pore space. The particle tracking in throats is described using the first arrival time distribution. As pores have an important volume fraction in the sample considered, we implemented a time-delay mechanism for particle transport in the pores. We consider that the nodes have volume and there is a transport of the tracking particles inside the nodes, which leads to an “apparent” time-delay. Simulations of flow propagator show good agreement with low field NMR experiments performed on the twin plug of the sample used for pore network extraction with a single adjustable parameter (that describes the dynamics in the pores). These results lead us to a better understanding of the connection between pore structure and the behavior of NMR flow propagator in fluid-saturated rocks and are essential in interpreting the experimental data and correlating NMR parameters to petrophysical properties.     

Influence of humidity on the fabrication of high-quality colloidal crystals via a capillary-enhanced process

Three-dimensional colloidal crystals have attracted a great deal of attention because of their potential use in photonic crystal, sensors, and other applications, but the bottlenecks in fabricating colloidal crystals include longer processing time and the lack of large-area ordered samples. A proposed capillary-enhanced method, which is a novel, efficient process for fabricating high-quality colloidal crystals in 24 h, is reported. It is necessary for increasing the processing rate by elevating the evaporation temperature but commonly resulted in the deposition of less-ordered crystals. However, high-quality colloidal crystals can be obtained in a controlled high-humidity system, resulting from the existence of secondary capillary forces present in high ambient humidity. Furthermore, the effect of secondary capillary forces will be confirmed, and it will increase with increasing humidity levels according to the semiquantitative analysis view of the surface thermodynamic behavior of small particles, including the modified Kelvin and Young-Laplace equations. Therefore, it can fine tune the relative position of the neighboring particles in the microarray and efficiently decrease the number of defects, resulting in the formation of perfect colloidal crystals with the assistance of enhanced secondary capillary forces.     

Yields of O2(1Σg+) and O2(1Δg) in the H + O2 reaction system,and the quenching of O2(1Σg+) by atomic hydrogen

The generation of metastable O₂(¹Σg⁺) and O₂(¹Δg) in the H + O₂ system of reactions was studied by the flow discharge chemiluminescence detection method. In addition to the O₂(¹Σg⁺) and O₂(¹Δg) emissions, strong OH(v = 2) → OH(v = 0), OH(v = 3) → OH(v = 1), HO₂(²A′₀₀₀) → HO₂(²A″₀₀₀), HO₂(²A′₀₀₁) → HO₂(²A″₀₀₀), and H O₂(²A″₂₀₀) → HO₂(²A″₀₀₀) emissions were detected in the H + O₂ system. The rate constants for the quenching of O₂(¹Σg⁺) by H and H₂ were determined to be (5.1 ± 1.4) × 10^?13 and (7.1 ± 0.1) × 10^?13 cm³ s^?1, respectively. An upper limit for the branching ratio to produce O₂(¹Σg⁺) by the H + HO₂ reaction was calculated to be 2.1%. The contributions from other reactions producing singlet oxygen were investigated.