Selecting ionization path by dynamic stark shift with strong laser pulse

Multiphoton ionization of NO via intermediate Rydberg states with ultra-short laser pulses is investigated with time-resolved photoelectron spectroscopy in combination with fermosecond pump-probe technology. The Rydberg states of NO, which are characterized by obvious ac-Stark shift in ultra-strong laser field, can be tuned in resonance to ionize NO molecule at one's will with identical laser pulses, i.e., one can 'select' resonance path to ionization. The results shown in this Letter demonstrate that the states holding notable dynamic Stark shift provide us another dimension to chemical control with strong laser field. (C) 2003 Elsevier Science B.V. All rights reserved.

Pressurized capillary electrochromatography separation of peptides with strong cation exchange and hydrophilic interaction

A pressurized capillary electrochromatography (pCEC) instrument with solvent gradient capability has been used for the separation of a peptide mixture. Retention mechanism and selectivity of the peptides were studied by pCEC using a strong cation exchange (SCX) column. The effects of applied voltage, supplementary pressure, organic modifier concentration, ionic strength,, and pH value on pCEC separation were investigated. It was found that the retention mechanism of the peptides in this system is based on a mixed mode of hydrophilic interaction, strong cation exchange, and electrophoresis. Compared with the separation results obtained by reverse phase pCEC and capillary electrophoresis (CE), this mixed-mode pCEC is more powerful for the separation of hydrophilic peptides with similar charge-to-mass ratio.

Theoretical studies of product polarization and state distributions of the H+HCl reaction

The angular momentum polarization and rotational state distributions of the H-2 and HCl products from the H + HCl reaction are calculated at a relative translational energy of 1.6 eV by using quasiclassical trajectories on two potential energy surfaces, one from G3 surface [T.C. Allison et al., J. Phys. Chem. 100 (1996) 13575], and the other from BW2 surface [W. Bian, H.-J. Werner, J. Chem. Phys. 112 (2000) 220]. Product rotational distributions obtained on the G3 potential energy surface (PES) are much closer to the experimental results (P.M. Aker et al., J. Chem. Phys. 90 (1989) 4795; J. Chem. Phys. 90 (1989) 4809) than the distributions calculated on the BW2 PES. The distributions of P(phi(r)) for the H-2 and HCl products obtained on the G3 PES are similar, whereas the rotational alignment effect of the H-2 product is stronger than that of the HCl product. In contrast to the polarization distributions obtained on the G3 PES, the rotational alignment effect of the two products calculated on the BW2 PES is similar. However, the abstraction reaction is dominated by out-of-plane mechanisms, while the exchange reaction is dominated by in-plane mechanisms. The significant difference of the product rotational polarization obtained on the G3 and BW2 PESs implies that the studies of the dynamical stereochemistry can provide a sensitive test for the accuracy of the PES. (C) 2002 Elsevier Science B.V. All rights reserved.

The effects of sediment transport on grain-size distributions

Changes in statistics (mean, sorting, and skewness) describing grain-size distributions have long been used to speculate on the direction of sediment transport. We present a simple model whereby the distributions of sediment in transport are related to their source by a sediment transfer function which defines the relative probability that a grain within each particular class interval will be eroded and transported. A variety of empirically derived transfer functions exhibit negatively skewed distributions (on a phi scale). Thus, when a sediment is being eroded, the probability of any grain going into transport increases with diminishing grain size throughout more than half of its size range. This causes the sediment in transport to be finer and more negatively skewed than its source, whereas the remaining sediment (a lag) must become relatively coarser and more positively skewed. Flume experiments show that the distributions of transfer functions change from having a highly negative skewness to being nearly symmetrical (although still negatively skewed) as the energy of the transporting process increases. We call the two extremes low-energy and high-energy transfer functions , respectively. In an expanded sediment-transport model, successive deposits in the direction of transport are related by a combination of two transfer functions. If energy is decreasing and the transfer functions have low-energy distributions, successive deposits will become finer and more negatively skewed. If, however, energy is decreasing, but the initial transfer function has a high-energy distribution, successive deposits will become coarser and more positively skewed. The variance of the distributions of lags, sediment in transport, and successive deposits in the down-current direction must eventually decrease (i.e., the sediments will become better sorted). We demonstrate that it is possible for variance first to increase, but suggest that, in reality, an increasing variance in the direction of transport will seldom be observed, particularly when grain-size distributions are described in phi units. This model describing changes in sediment distributions was tested in a variety of environments where the transport direction was known. The results indicate that the model has real-world validity and can provide a method to predict the directions of sediment transport

Dewetting behavior of polystyrene film filled with (C6H5C2H4NH3)(2)PbI4

The dewetting behavior of thin (about 30 nm) polystyrene (PS) films filled with different amount of (C6H5C2H4NH3)(2)PbI4 (PhE-PbI4) on the silicon substrate with a native oxide layer was investigated. For different additive concentrations, PhE-PbI4 showed different spatial distributions in the PS films, which had a strong influence on the film wettability, dewetting dynamics, and mechanism. With 0.5 wt % additive, PhE-PbI4 formed a noncontinuous diffusion layer, which caused a continuous hole nucleation in the film. With about 1 wt % additive, a continuous gradient distribution layer of PhE-PbI4 formed in the film, which inhibited the dewetting.

Microstructure and Deformation Behavior of Polyethylene/Montmorillonite Nanocomposites with Strong Interfacial Interaction

Deformation behavior of polyethylene/modified montmorillonites with polymerizable surfactant (PE/P-MMT) nanocomposite with strong interfacial interaction was studied by means of morphology observation and X-ray scattering measurements. The orientation of PE chains was accompanied by the orientation of well-dispersed MMT platelets due to the presence of strong interfacial interaction, and both of the orientations were parallel to the deformation direction. The high degree of orientation of MMT platelets and PE chains resulted from the synergistic movement of PE matrix and MMTs, which originated from the presence of a network-like structure.

Synthesis and Characterization of Hyperbranched Poly(ether amide)s with Thermoresponsive Property and Unexpected Strong Blue Photoluminescence

A facile and efficient strategy for the syntheses of novel hyperbranched poly(ether amide)s (HPEA) from multihydroxyl primary amines and (meth)acryloyl chloride has been developed. The chemical structures of the HPEAs were confirmed by IR and NMR spectra. Analyses of SEC (size exclusion chromatography) and viscosity characterizations revealed the highly branched structures of the polymers obtained. The resultant hyperbranched polymers contain abundant hydroxyl groups. The thermoresponsive property was obtained from in situ surface modification of abundant OH end groups with N-isopropylacrylamide (NIPAAm). The study oil temperature-dependent characteristics has revealed that NIPAAm-g-HPEA exhibits an adjustable lower critical solution temperature (LCST) of about 34-42 degrees C depending on the grafting degree. More interestingly, the work provided an interesting phenomenon where the HPEA backbones exhibited strong blue photoluminescence.

Kinetics and Statistical Distributions of Single-Molecule Conformational Dynamics

We developed a coarse-grained yet microscopic detailed model to study the statistical fluctuations of single-molecule protein conformational dynamics of adenylate kinase. We explored the underlying conformational energy landscape and found that the system has two basins of attractions, open and closed conformations connected by two separate pathways. The kinetics is found to be nonexponential, consistent with single-molecule conformational dynamics experiments. Furthermore, we found that the statistical distribution of the kinetic times for the conformational transition has a long power law tail, reflecting the exponential density of state of the underlying landscape. We also studied the joint distribution of the two pathways and found memory effects.