Alternating copolymerization of carbon dioxide and propylene oxide by single-component cobalt salen complexes with various axial group

A series of single-component cobalt salen complexes, N,N'-bis(salicylidene)-1,2phenylenediamino cobaltIII X(X = Cl (1a), Br (1b), NO3 (1c), CF3COO (1d), BF4 (le), and N3 (If)) (SalphCoX), were prepared for alternating copolymerization of carbon dioxide and propylene oxide(PO) under mild condition. The axial anion X group of the SalenphCoX played important role in tailoring the catalytic activity, polymeric/cyclic carbonate selectivity, as well as stereochemistry of carbonate unit sequence in the polymer chain. SalenphCoX with an electron-withdrawing axial X group (complex 1c) was an ideal catalyst for the copolymerization of CO2 and PO to selectively produce polycarbonate with similar to 99% carbonate linkage and over 81% head-to-tail structure.

Calculating the equation of state parameters and predicting the spinodal curve of isotactic polypropylene/poly(ethylene-co-octene) blend by molecular dynamics simulations combined with Sanchez-Lacombe lattice fluid theory

Molecular dynamics simulations are adopted to calculate the equation of state characteristic parameters P*, rho*, and T* of isotactic polypropylene (iPP) and poly(ethylene-co-octene) (PEOC), which can be further used in the Sanchez-Lacombe lattice fluid theory (SLLFT) to describe the respective physical properties. The calculated T* is a function of the temperature, which was also found in the literature. To solve this problem, we propose a Boltzmann fitting of the data and obtain T* at the high-temperature limit. With these characteristic parameters, the pressure-volume-temperature (PVT) data of iPP and PEOC are predicted by the SLLFT equation of state. To justify the correctness of our results, we also obtain the PVT data for iPP and PEOC by experiments. Good agreement is found between the two sets of data. By integrating the Euler-Lagrange equation and the Cahn-Hilliard relation, we predict the density profiles and the surface tensions for iPP and PEOC, respectively. Furthermore, a recursive method is proposed to obtain the characteristic interaction energy parameter between iPP and PEOC. This method, which does not require fitting to the experimental phase equilibrium data, suggests an alternative way to predict the phase diagrams that are not easily obtained in experiments.

The combined effects of temperature and food supply on Calanus sinicus in the southern Yellow Sea in summer

The effects of temperature and food availability on the life history strategy of the planktonic copepod Calanus sinicus in the southern Yellow Sea in summer were studied in this paper. The fifth copepodite stage (CV) dominates the population in the central part of the southern Yellow Sea, where the Yellow Sea Cold Water Mass (YSCWM) occurs below the thermocline. Incubation experiments were conducted on CV C. sinicus caught from the YSCWM to examine the effects of temperature and food availability. Temperature at the surface (27degreesC) is lethal to CVs regardless of food availability. At the temperature in the middle of the thermocline (18degreesC), survival time of the specimens depends on food availability, being similar to20 days in treatments without extra food supply. At the temperature in the YSCWM (9degreesC), most animals survive at the end of 27 day incubation even in treatments without food supply. Developmental rate of CVs at 9degreesC without extra food supply is extremely low. The increase of either temperature or food supply promotes the developmental rate of CVs. According to these results, the surface layers with high temperature and low food abundance are detrimental for the survival and reproduction of C. sinicus. Low temperature and low food availability in the YSCWM help CV to maintain a much lower developmental rate and higher survival rate. The ecological trait of C. sinicus in the southern Yellow Sea in summer cannot be sufficiently explained solely by the effects of temperature.

Influential Factors of Loess Liquefaction and Pore Pressure Development

The liquefaction of loess under dynamic loading is studied experimentally with a dynamic triaxial test system. The effects of over-consolidation ratio (OCR), saturation degree and the frequency of dynamic loading upon loess liquefaction are investigated. The development of pore pressure within loess samples is also discussed. Based on the experimental results, the empirical relationship between pore pressure ratio and loading cycle number ratio is established for normal consolidated saturated loess.

A Discussion on Modeling Shape Memory Alloy Embedded in A Composite Laminate as Axial Force and Elastic Foundation

In this paper, the possible error sources of the composite natural frequencies due to modeling the shape memory alloy (SMA) wire as an axial force or an elastic foundation and anisotropy are discussed. The great benefit of modeling the SMA wire as an axial force and an elastic foundation is that the complex constitutive relation of SMA can be avoided. But as the SMA wire and graphite-epoxy are rigidly bonded together, such constraint causes the re-distribution of the stress in the composite. This, together with anisotropy, which also reduces the structural stiffness can cause the relatively large error between the experimental data and theoretical results.

Three-Dimensional Modeling of Heat Transfer and Fluid Flow in Laminar-Plasma Material Re-Melting Processing

Modeling study is performed concerning the heat transfer and fluid flow for a laminar argon plasma jet impinging normally upon a flat workpiece exposed to the ambient air. The diffusion of the air into the plasma jet is handled by using the combined-diffusion-coefficient approach. The heat flux density and jet shear stress distributions at the workpiece surface obtained from the plasma jet modeling are then used to study the re-melting process of a carbon steel workpiece. Besides the heat conduction within the workpiece, the effects of the plasma-jet inlet parameters (temperature and velocity), workpiece moving speed, Marangoni convection, natural convection etc. on the re-melting process are considered. The modeling results demonstrate that the shapes and sizes of the molten pool in the workpiece are influenced appreciably by the plasma-jet inlet parameters, workpiece moving speed and Marangoni convection. The jet shear stress manifests its effect at higher plasma-jet inlet velocities, while the natural convection effect can be ignored. The modeling results of the molten pool sizes agree reasonably with available experimental data.

Stability Of Adhesion Clusters And Cell Reorientation Under Lateral Cyclic Tension

This work is motivated by experimental observations that cells on stretched substrate exhibit different responses to static and dynamic loads. A model of focal adhesion that can consider the mechanics of stress fiber, adhesion bonds, and substrate was developed at the molecular level by treating the focal adhesion as an adhesion cluster. The stability of the cluster under dynamic load was studied by applying cyclic external strain on the substrate. We show that a threshold value of external strain amplitude exists beyond which the adhesion cluster disrupts quickly. In addition, our results show that the adhesion cluster is prone to losing stability under high-frequency loading, because the receptors and ligands cannot get enough contact time to form bonds due to the high-speed deformation of the substrate. At the same time, the viscoelastic stress fiber becomes rigid at high frequency, which leads to significant deformation of the bonds. Furthermore, we find that the stiffness and relaxation time of stress fibers play important roles in the stability of the adhesion cluster. The essence of this work is to connect the dynamics of the adhesion bonds (molecular level) with the cell's behavior during reorientation (cell level) through the mechanics of stress fiber. The predictions of the cluster model are consistent with experimental observations.

Theory Of Phase Transformation And Reorientation In Single Crystalline Shape Memory Alloys

A constitutive model, based on an (n + 1)-phase mixture of the Mori-Tanaka average theory, has been developed for stress-induced martensitic transformation and reorientation in single crystalline shape memory alloys. Volume fractions of different martensite lattice correspondence variants are chosen as internal variables to describe microstructural evolution. Macroscopic Gibbs free energy for the phase transformation is derived with thermodynamics principles and the ensemble average method of micro-mechanics. The critical condition and the evolution equation are proposed for both the phase transition and reorientation. This model can also simulate interior hysteresis loops during loading/unloading by switching the critical driving forces when an opposite transition takes place.

On the mechanism of void growth and the effect of straining mode in ductile materials

Finite element analysis is employed to investigate void growth embedded in elastic-plastic matrix material. Axisymmetric and plane stress conditions are considered. The simulation of void growth in a unit cell model is carried out over a wide range of triaxial tensile stressing or large plastic straining for various strain hardening materials to study the mechanism of void growth in ductile materials. Triaxial tension and large plastic strain encircling around the void are found to be of most importance for driving void growth. The straining mode of incremental loading which favors the necessary strain concentration around void for its growth can be characterized by the vanishing condition of a parameter called "the third invariant of generalized strain rate". Under this condition, it accentuates the internal strain concentration and the strain energy stored/dissipated within the material layer surrounding the void. Experimental results are cited to justify the effect of this loading parameter. (C) 2000 Elsevier Science Ltd. All rights reserved.

Simple phenomenological determination of contact stiffness and elastic modulus of Ce-based bulk metallic glasses through nanoindentation

The viscoelastic deformation of Ce-based bulk metallic glasses (BMGs) with low glass transition temperature is investigated at room temperature. Contact stiffness and elastic modulus of Ce-based BMGs cannot be derived using the conventional Oliver-Pharr method [W. C. Oliver and G. M. Pharr, J. Mater. Res. 7, 1564 (1992)]. The present work shows that the time dependent displacement of unloading segments can be described well by a generalized Kelvin model. Thus, a modified Oliver-Pharr method is proposed to evaluate the contact stiffness and elastic modulus, which does, in fact, reproduce the values obtained via uniaxial compression tests. (c) 2007 American Institute of Physics.

Direct observation of adsorption sites of protein impurities and their effects on step advancement of protein crystals

We measured noninvasively step velocities of elementary two-dimensional (2D) islands on {110} faces of tetragonal lysozyme crystals, under various supersaturations, by laser confocal microscopy combined with differential interference contrast microscopy. We studied the correlation between the effects of protein impurities on the growth of elementary steps and their adsorption sites on a crystal surface, using three kinds of proteins: fluorescent-labeled lysozyme (F-lysozyme), covalently bonded dimers of lysozyme (dimer), and a 18 kDa polypeptide (18 kDa). These three protein impurities suppressed the advancement of the steps. However, they exhibited different supersaturation dependencies of the suppression of the step velocities. To clarify the cause of this difference, we observed in situ the adsorption sites of individual molecules of F-lysozyme and fluorescent-labeled dimer (F-dimer) on the crystal surface by single-molecule visualization. We found that F-lysozyme adsorbed preferentially on steps (i.e., kinks), whereas F-dimer adsorbed randomly on terraces. Taking into account the different adsorption sites of F-lysozyme and F-dimer, we could successfully explain the different effects of the impurities on the step velocities. These observations strongly suggest that 18 kDa also adsorbs randomly on terraces. Seikagaku lysozyme exhibited a complex effect that could not alone be explained by the two major impurities (dimer and 18 kDa) present in Seikagaku lysozyme, indicating that trace amounts of other impurities significantly affect the step advancement.

Optimization of single attosecond x-ray pulses by genetic algorithm control of the chirp and initial phase of 5 fs laser pulses

We show that the peak intensity of single attosecond x-ray pulses is enhanced by 1 or 2 orders of magnitude, the pulse duration is greatly compressed, and the optimal propagation distance is shortened by genetic algorithm optimization of the chirp and initial phase of 5 fs laser pulses. However, as the laser intensity increases, more efficient nonadiabatic self-phase matching can lead to a dramatically enhanced harmonic yield, and the efficiency of optimization decreases in the enhancement and compression of the generated attosecond pulses. (c) 2006 Optical Society of America.

Numerical modeling of optical levitation and trapping of the "stuck" particles with a pulsed optical tweezers

We present the theoretical analysis and the numerical modeling of optical levitation and trapping of the stuck particles with a pulsed optical tweezers. In our model, a pulsed laser was used to generate a large gradient force within a short duration that overcame the adhesive interaction between the stuck particles and the surface; and then a low power continuous - wave (cw) laser was used to capture the levitated particle. We describe the gradient force generated by the pulsed optical tweezers and model the binding interaction between the stuck beads and glass surface by the dominative van der Waals force with a randomly distributed binding strength. We numerically calculate the single pulse levitation efficiency for polystyrene beads as the function of the pulse energy, the axial displacement from the surface to the pulsed laser focus and the pulse duration. The result of our numerical modeling is qualitatively consistent with the experimental result. (C) 2005 Optical Society of America.

Biological mechanisms driving the seasonal changes in the internal loading of phosphorus in shallow lakes

Because of the obvious importance of P as a nutrient that often accelerates growth of phytoplankton (including toxic cyanobacteria) and therefore worsens water quality, much interest has been devoted to P exchange across the sediment-water interface. Generally, the release mode of P from the sediment differed greatly between shallow and deep lakes, and much of the effort has been focused on iron and oxygen, and also on the relevant environmental factors, for example, turbulence and decomposition, but a large part of the P variation in shallow lakes remains unexplained. This paper reviews experimental and field studies on the mechanisms of P release from the sediment in the shallow temperate (in Europe) and subtropical (in the middle and lower reaches of the Yangtze River in China) lakes, and it is suggested that pH rather than DO might be more important in driving the seasonal dynamics of internal P loading in these shallow lakes, i.e., intense photosynthesis of phytoplankton increases pH of the lake water and thus may increase pH of the surface sediment, leading to enhanced release of P (especially iron-bound P) from the sediment. Based on the selective pump of P (but not N) from the sediment by algal blooms, it is concluded that photosynthesis which is closely related to eutrophication level is the driving force for the seasonal variation of internal P loading in shallow lakes. This is a new finding. Additionally, the selective pump of P from the sediment by algal blooms not only explains satisfactorily why both TP and PO4-P in the hypereutrophic Lake Donghu declined significantly since the mid-1980s when heavy cyanobacterial blooms were eliminated by the nontraditional biomanipulation (massive stocking of the filter-feeding silver and bighead carps), but also explains why TP in European lakes decreased remarkably in the spring clear-water phase with less phytoplankton during the seasonal succession of aquatic communities or when phytoplankton biomass was decreased by traditional biomanipulation. Compared with deep lakes, wax and wane of phytoplankton due to alternations in the ecosystem structure is also able to exert significant influences on the P exchange at the sediment-water interface in shallow lakes. In other words, biological activities are also able to drive P release from sediments, and such a static P release process is especially more prominent in eutrophic shallow lakes with dense phytoplankton.