In Situ Scanning Tunneling Microscopy on the Dynamic Process of the Replacement of Coronene on Au (111) by 6-Mercapto-1-Hexanol

The replacement of coronene monolayer on Au (111) by 6-mercapto-1-hexanol (MHO) was studied by in situ scanning tunneling microscopy (STM) in solutions. It was found that the rate of replacement depends strongly on the concentration of MHO. The replacement finished within a second at a higher concentration of MHO. At a lower concentration, the slow replacement could be followed by in situ STM. The replacement occurred initially near the elbow position of reconstructed Au (111) with the formation of pits in a single or several missing molecules. With the proceeding of replacement, these small pits expanded, and the surrounding coronene molecules were gradually substituted by MHO, which developed into ordered domains within a spatial confined environment. Meanwhile, the reconstruction of Au (111) was lifted. The replacement expanded fast along the reconstruction lines in the domain. For the fast replacement, a (root 3 x root 3) R30 degrees adlattice was observed, while a c(4 x 2) superlattice was observed for the slow replacement.

Investigation on relationship between charge transfer position and dielectric definition of average energy gap in Eu3+-doped compounds

The dielectric definition of average energy gap E-g of the chemical bond has been calculated quantitatively in Eu3+-doped 30 lanthanide compounds based on the dielectric theory of chemical bond for complex structure crystals. The relationship between the experimental charge transfer (CT) energy of Eu3+ and the corresponding average energy gap E-g has been studied. The results show that the CT energy increases linearly with increasing of the average energy gap E-g. The linear model is obtained. It allows us to predict the CT position of Eu3+-doped lanthanide compounds with knowledge of the crystal structure and index of refraction. Applied to the Ca4GdO(BO3)(3):Eu and Li2Lu5O4(BO3)(3):Eu crystals, the predicted results of CT energies are in good agreement with the experimental values, and it can be concluded that the lowest CT energy in Li2Lu5O4(BO3)(3):Eu originates from the site of Lu1.

Density functional study of the second row transition metal dimers

Equilibrium geometries, vibrational frequencies and dissociation energies of the second row transition metal dimers (from Y-2 to Cd-2 except Tc-2) ere studied by use of density functional methods B3LYP, BLYP, B3PW91, BHLYP, BP86, B3P86, SVWN, MPW1PW91 and PBE1PBE. The accuracy DFT methods is found to be highly dependent on the functional employed, in particular for vibrational frequency and dissociation energy. In most cases, the predicted bond distance is in general agreement with experiment and previous theoretical results. For van der Waals dimer Cd-2, B3LYP and BLYP have excellent performance in predicting the bond distance. For Ag-2, all density functional methods used in this study perform well in producing the bond distance, vibrational frequency and dissociation energy.

Predicting the position of the spin-forbidden band for Tb3+ ions in crystal hosts

The energy difference DeltaE between the spin-allowed and spin-forbidden states of Tb3+ in crystals is studied. The environmental factor he representing the character of the host is redefined by using the chemical band of complex crystals. The relationship between h(e) and DeltaE is found to be a linear relation. The results show that the energy difference between the spin-forbidden and spin-allowed states for Tb3+ ions in crystals can be predicted from the environmental factor.

Temperature dependence of the distribution of the first passage time: Results from discontinuous molecular dynamics simulations of an all-atom model of the second beta-hairpin fragment of protein G

More than 22 000 folding kinetic simulations were performed to study the temperature dependence of the distribution of first passage time (FPT) for the folding of an all-atom Go-like model of the second beta-hairpin fragment of protein G. We find that the mean FPT (MFPT) for folding has a U (or V)-shaped dependence on the temperature with a minimum at a characteristic optimal folding temperature T-opt*. The optimal folding temperature T-opt* is located between the thermodynamic folding transition temperature and the solidification temperature based on the Lindemann criterion for the solid. Both the T-opt* and the MFPT decrease when the energy bias gap against nonnative contacts increases. The high-order moments are nearly constant when the temperature is higher than T-opt* and start to diverge when the temperature is lower than T-opt*. The distribution of FPT is close to a log-normal-like distribution at T* greater than or equal to T-opt*. At even lower temperatures, the distribution starts to develop long power-law-like tails, indicating the non-self-averaging intermittent behavior of the folding dynamics. It is demonstrated that the distribution of FPT can also be calculated reliably from the derivative of the fraction not folded (or fraction folded), a measurable quantity by routine ensemble-averaged experimental techniques at dilute protein concentrations.

Mass spectrometric studies of metallofullerene

The endrohel metallofullerene, Gd@C-82, Gd@C-80, Gd-2@C-80 were synthesized by using K-H method. The technique of two-step of high pressure and high temperature extraction with 1, 3, 5-trimethylbenzene (first step) and pyridine(second step) has been successfully utilized to extract metallofullerene of Gd@C-82 The gas-phase negative ions of fullerenes C-n(n= 60, 70, 78, 82, 84...) and metallofullerene (Gd@C-82) have been studied by the ESI-MS, REC-MS and MALDI-TOF-MS. The differences among the mass spectra of ESI-MS, REC-MS and MALDI-TOF-MS have been observed and explained. In contrast to the empty fullerene C-82 , the metallofullerene Gd@C-82 should have a larger HOMO-LUMO gap. Experimental results suggest that Gd@C-82 is polarized and Gd3+ located in the off-center position of C-82 cage after Gd3+ is trapped into C-82 cage.

Calculations of cross sections of resonant two-photon transitions to the second excited 4f5d state in Pr3+: Y3Al5O12 using density matrix theory

The density matrix resonant two-photon absorption (TPA) theory applicable to laser crystals doped with rare earth ions is described. Using this theory, resonant TPA cross sections for transitions from the ground state to the second excited state of the 4f5d configuration in cm(4)s Pr3+:Y3Al5O12 are calculated. The peak value of TPA cross section calculated is 2.75 x 10(-50) cm(4)s which is very close to the previous experimental value 4 x 10(-50) cm(4) s. The good agreement of calculated data with measured values demonstrates that the density matrix resonant TPA theory can predict resonant TPA intensity much better than the standard second-order perturbation TPA theory.

Gas permeability and permselectivity of polyimides prepared from phenylenediamines with methyl substitution at the ortho position

Polyimides were prepared from diamines: 2,4,6-trimethyl-1,3-phenylenediamine (3MPDA) and 2,3,4,5-tetramethyl-1,4-phenylenediamine (4MPDA). 1,4-Bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 3,3'-4,4'-diphenylsulphone tetracarboxylic dianhydride (SO(2)PDA), 3,3',4,4'-diphenylsulphide tetracarboxylic dianhydride (SPDA), pyromellitic dianhydride (PMDA), and 2,2'-bis(3,4-dicarboxyphenyl)hexa-fluoroisopropane dianhydride (6FDA) were used as dianhydride. The gas permeabilities of H-2, O-2 and N-2 through the polyimides were measured at temperatures from 30 degrees C to 90 degrees C. The results show that as methyl and trifluoromethyl substitution groups densities increase from 7.73 x 10(-3) molcm(-3) to 13.50 x 10(-3)molcm(-3), the peameability of H-2 increases 10-fold at 60% loss of permselectivity of H-2/N-2 however, the permeability of O-2 increases 20-fold at 20% loss of permselectivity of O-2/N-2. For O-2/N-2 separation, PMDA-3MPDA has similar performance to 6FDA-3MPDA and 6FDA-4MPDA; all have higher permeabilities for O-2 than normal polyimides, and the P(O-2)/alpha(O-2/N-2) trade-off relationships lie on the upper bound line for polymers. (C) 1999 Society of Chemical Industry.

Factor analysis used to peak position optimization and spectral interference correction in inductively coupled plasma atomic emission spectrometry

Target transformation factor analysis was used to correct spectral interference in inductively coupled plasma atomic emission spectrometry (ICP-BES) for the determination of rare earth impurities in high purity thulium oxide. Data matrix was constructed with pure and mixture vectors and background vector. A method based on an error evaluation function was proposed to optimize the peak position, so the influence of the peak position shift in spectral scans on the determination was eliminated or reduced. Satisfactory results were obtained using factor analysis and the proposed peak position optimization method.

Calculation of second-order nonlinear optical coefficients of KTiOPO4 and KTiOAsO4

The second-order nonlinear optical tensor coefficients of both KTiOPO4 (KTP) and KTiOAsO4 (KTA) are calculated from the chemical bond viewpoint. All constituent chemical bonds of both crystals are considered, and contributions of each type of bond to the total linearity and nonlinearity are determined. Calculated results agree satisfactorily with experimental data in both signs and numerical values. The calculation shows that though TiO6 groups and P(1)O-4 or As(1)O-4 groups have relatively larger linear contributions, they can only produce an advantageous environment for KOx (x = 8, 9) groups and P(2)O-4 or As(2)O-4 groups in nonlinear optical contributions. The origin of nonlinearity of KTP family crystals comes from the KOx (x = 8, 9) and P(2)O-4 groups in their crystal structures. Furthermore, the difference in optical nonlinearities of KTP type crystals is analyzed, based on the detailed calculation of nonlinearities of both KTP and KTA. (C) 1999 Academic Press.

Thermally stable interpenetrating polymer networks for second-order nonlinear optical materials

We report several kinds of interpenetrating polymer networks (IPNs) with nonlinear optical (NLO) properties. DMA spectra show that the two components of the IPNs have good compatibility with each other. The NLO materials have good optical transparency. The thermal stability of alignment was improved and the poled order remained very high. (C) 1999 John Wiley & Sons, Inc.

A ZINDO-SOS study on the nonlinear second-order optical properties of substituted silanes series molecules

On the basis of ZINDO methods,according to the sum - over - states( SOS) expression, we divise the program for the calculation of nonlinear second - order optical susceptibilities beta(ijk) and study how the different substituents on the phenyl ring attached to the atom silicon influence or; the nonlinear second - order optical properties for substituted silanes series molecules. The property of (CH3)(3)Si is Studied particularly. The effect of length of silica chains on the calculated beta values is studied too. The regularity summarized from calculated results has been explained micromechanically.

A theoretical study on the nonlinear optical second-order properties of azobenzene series molecules

On the basis of AM1 and INDO/CI methods, we devise the program for the calculation of nonlinear second-order optical susceptibilities beta(ijk) and perform systematic theoretical studies on the nonlinear optical second-order properties of azobenzene series molecules, i. e. on the basis of [GRAPHICS] we induced different donors on the left side of phenyl ring, and different accepters on the right side of phenyl ring, and examined the rule of beta variation. The regularity summarized from the calculated results has been explained micromechanically. Finally, a molecule having a big nonlinear second-order optical susceptibility has been designed.

DILUTE SOLUTION PROPERTIES OF RING-SHAPED POLYSTYRENE II. THE SECOND VIRIAL COEFFICIENTS

Using a low angle laser light scattering photometer (LALLS) the second virial coefficients(A_2) of ring-shaped and linear polystyrene (RPS and LPS) samples were determined in both toluene and butanone solutions. The A_2 of RPS in the good solvent (toluene) is smaller than that of LPS with the same molecular weight, but in the poor solvent (butanone) these two are very close. For RPS in the molecular weight range of 4×10~4——2.2×10~5, we haveA_(2r)=1.28×10~(-2)M_w~(-0.283) (Toluene 25℃) and A_(2r)=5.06×10~(-2...

The expression of peptidoglycan recognition protein-S1 gene in the scallop Chlamys farreri was enhanced after a second challenge by Listonella anguillarum

A more rapid and powerful response against repeated exposure of same pathogen in vertebrates is usually considered as the reflection of immunological memory, but it is not well understood in invertebrates. In the present Study, the temporal expression profiles of Chlamys farreri peptidoglycan recognition protein-S1 (CfPGRP-S1) gene after two challenges of Listonella anguillarum were examined to evaluate priming response in scallops. The up-regulation of CFPGRP-S1 mRNA occurred 3 h earlier, and the expression level was significant higher (P < 0.05), after the second challenge than that after the first challenge. The preliminary results Provided new insights into invertebrate immunological memory, and they also would be helpful to develop strategies for disease control. (C) 2008 Elsevier Inc. All rights reserved.