Gas phase derivatization of endohedral metallofullerenes R@C-82 and R-2@C-80 (R = Nd, Ce)

Endohedral metallofullerenes Ce@C-82, Ce-2@C-80, Nd@C-82 and Nd-2@C-80 undergo gas phase ion/molecule reactions with the ion system from self-chemical ionization of vinyl acetate, and exohedral derivatives are thus generated, A new heterocycle is formed from metallofullerenes and a C2H3O+ cation, Endohedral metallofullerenes show much higher reactivities than empty fullerenes during the association and the charge and proton transfer processes, The strong electron-donating character of endohedral metallofullerenes is due to their unique super-atom-like electronic structures. (C) 1997 by John Wiley & Sons, Ltd.

FORMATION OF [C60C5H5] ADDUCT CATIONS AND THEORETICAL-STUDY OF THE ISOMERS

We study here the reactions between C-60 and planar C5H5+ cations that lead to the formation of [C60C5H5](+) adduct cations in the chemical ionization source of the mass spectrometer. The structures, stabilities and charge locations of some possible isomers of [C60C5H5](+): sigma-adduct, pi-complex, [1,4]- and [1,2]-addition cations, are studied by AM1 semiempirical molecular orbital calculations. We find that the most stable is the sigma-addition cation. Another interesting and stable structure is the pi-complex cation which is bonded by the electrostatic interaction at the inter-ring distance of 1.589 Angstrom with the C-5v symmetry. The C5H5+ cyclopentadienium cation seems to be an ''inverted umbrella'' sitting on a five-membered ring of the C-60 cage.

Photo-induced reactions in the ion-molecule complex Mg+-OCNC2H5

Ion - molecule complexes of magnesium cation with ethyl isocyanate were produced in a laser- ablation supersonic expansion nozzle source. Photo- induced reactions in the 1: 1 complexes have been studied in the spectral range of 230 - 410 nm. Photodissociation mass spectrometry revealed the persistent product Mg+ from nonreactive quenching throughout the entire wavelength range. As for the reactive channels, the photoproducts, Mg+OCN and C2H5+, were produced only in the blue absorption band of the complex with low yields. The action spectrum of Mg+(OCNC2H5) consists of two pronounced peaks on the red and blue sides of the Mg+ 3(2)P <-- 3(2)S atomic transition. The ground state geometry of Mg+ - OCNC2H5 was fully optimized at B3LYP/6- 31 - G** level by using GAUSSIAN 98 package. The calculated absorption spectrum of the complex using the optimized structure of its ground state agrees well with the observed action spectrum. Photofragment branching fractions of the products are almost independent of the photolysis photon energy for the 3P(x,y,z) excitations. The very low branching ratio of reactive products to nonreactive fragment suggests that evaporation is the main relaxation pathway in the photo- induced reactions of Mg+ (OCNC2H5). (C) 2003 American Institute of Physics.

One possible way to promote the bond-selective chemical-reactions by frequency-modulated lasers

It is proposed in this paper that we can use frequency-modulated (FM) lasers to realize bond-selective chemical reactions or to raise the efficiency of molecular isotope separation. Examples are given for HF molecule and the C–H bond in some hydrocarbons.

Isotope effect in proton-transfer and association-dissociation reactions for butylamine by ultrasonic relaxation methods

Ultrasonic absorption coefficients were measured for butylamine in heavy water (D2O) in the frequency range from 0.8 to 220 MHz and at concentrations from 0.0278 to 2.5170 mol dm(-3) at 25 degrees C; two kinds of relaxation processes were observed. One was found in relatively dilute solutions (up to 0.5 mol dm(-3)), which was attributed to the hydrolysis of butylamine. In order to compare the results, absorption measurements were also carried out in light water (H2O). The rate and thermodynamic parameters were determined from the concentration dependence of the relaxation frequency and the maximum absorption per wavelength. The isotope effects on the diffusion-controlled reaction were estimated and the stability of the intermediate of the hydrolysis was considered while comparing it with the results for propylamine in H2O and D2O. Another relaxation process was observed at concentrations greater than 1 mol dm(-3) in D2O. In order to examine the solution characteristics, proton NMR measurements for butylamine were also carried out in D2O. The chemical shifts for the gamma- and delta-proton in butylamine molecule indicate the existence of an aggregate. From profiles of the concentration dependence of the relaxation frequency and the maximum absorption per wavelength of sound absorption, the source of the relaxation was attributed to an association-dissociation reaction, perhaps, associated with a hydrophobic interaction. The aggregation number, the forward and reverse rate constants and the standard volume change of the reaction were determined. It was concluded from a comparison with the results in H2O that the hydrophobic interaction of butylamine in D2O is stronger than that in H2O. Also, the isotope effect on this reaction was interpreted in terms of the solvent structure.

Ion/neutral complex-mediated reactions generated from some ionized tetrahydroimidazole-substituted methylene beta-diketones

The dissociation of gaseous metastable ions of m/z 153 and the formation of ions of m/z 139 from the unimolecular fragmentations of ionized tetrahydroimidazole-substituted methylene beta-diketones were examined by tandem mass spectrometry. In addition, some other fragments accompanying the elimination of either an H2O molecule or an CHO. radical were also observed in the collision-induced dissociation spectra of molecular ions of the compounds bearing an aromatic ring. Collision-induced dissociation and isotopic labeling showed that these processes may involve reactions of intermediate ion/neutral complexes and multistep rearrangements. The corresponding mechanisms are discussed. (C) 1997 by John Wiley & Sons, Ltd.

Molecular Dynamics Simulation of Peeling a DNA Molecule on Substrate

Molecular dynamics (MD) simulations are performed to study adhesion and peeling of a short fragment of single strand DNA (ssDNA) molecule from a graphite surface. The critical peel-off force is found to depend on both the peeling angle and the elasticity of ssDNA. For the short ssDNA strand under investigation, we show that the simulation results can be explained by a continuum model of an adhesive elastic band on substrate. The analysis suggests that it is often the peak value, rather than the mean value, of adhesion energy which determines the peeling of a nanoscale material.

Visualization of molecule interaction between antigen and antibody - One of ellipsometric imaging applications

It is to investigate molecule interactions between antigen and antibody with ellipsometric imaging technique and demonstrate some features and possibilities offered by applications of the technique. Molecule interaction is an important interest for molecule biologist and immunologist. They have used some established methods such as immufluorcence, radioimmunoassay and surface plasma resonance, etc, to study the molecule interaction. At the same time, experimentalists hope to use some updated technique with more direct visual results. Ellipsometric imaging is non-destructive and exhibits a high sensitivity to phase transitions with thin layers. It is capable of imaging local variations in the optical properties such as thickness due to the presence of different surface concentration of molecule or different deposited molecules. If a molecular mono-layer (such as antigen) with bio-activity were deposited on a surface to form a sensing surface and then incubated in a solution with other molecules (such as antibody), a variation of the layer thickness when the molecules on the sensing surface reacted with the others in the solution could be observed with ellipsometric imaging. Every point on the surface was measured at the same time with a high sensitivity to distinguish the variation between mono-layer and molecular complexes. Ellipsometric imaging is based on conventional ellipsometry with charge coupled device (CCD) as detector and images are caught with computer with image processing technique. It has advantages of high sensitivity to thickness variation (resolution in the order of angstrom), big field of view (in square centimeter), high sampling speed (a picture taken within one second), and high lateral resolution (in the order of micrometer). Here it has just shown one application in study of antigen-antibody interaction, and it is possible to observe molecule interaction process with an in-situ technique.

Adsorption of formaldehyde molecule on the intrinsic and Al-doped graphene: a first principle study

To search for a high sensitivity sensor for formaldehyde (H2CO), We investigated the adsorption of H2CO on the intrinsic and Al-doped graphene sheets using density functional theory (DFT) calculations. Compared with the intrinsic graphene, the Al-doped graphene system has high binding energy value and short connecting distance, which are caused by the chemisorption of H2CO molecule. Furthermore, the density of states (DOS) results show that orbital hybridization could be seen between H2CO and Al-doped graphene sheet, while there is no evidence for hybridization between the H2CO molecule and the intrinsic graphene sheet. Therefore, Al-doped graphene is expected to be a novel chemical sensor for H2CO gas. We hope our calculations are useful for the application of graphene in chemical sensor.

Probing single-molecule by surface-enhanced resonance Raman scattering with linearly and circularly polarized laser

Rhodamine 6G (R6G) was incubated in silver sols with different low concentrations and its surface-enhanced resonance Raman scattering (SERRS) spectra, excited by linearly and circularly polarized light, respectively, were studied. At the single-molecule level the SERRS spectra were recorded in 10(-13) M dye colloidal solution. Spectral inhomogeneous behaviors from single-molecule were observed such as spectral polarization, spectral diffusion and intensity fluctuations of vibrational lines. Difference between SERRS spectra of R6G excited by linearly and circularly polarized light and the effect of the polarizing angle of Raman signal relative to the slit of spectrograph on the Raman spectral polarization were analyzed and measured experimentally. Circularly polarized laser and the correction of the polarizing angle of Raman signal are necessary to avoid fake results in the measuring of Raman spectral of single-molecule, which was not noticed in initial papers. (c) 2005 Elsevier B.V. All rights reserved.

Enhancement of ultrafast four-wave mixing in a polar molecule medium

We investigate the ultrafast four-wave mixing (FWM) with two-color few-cycle ultrashort pulses propagating in a two-level polar molecule medium. It is found that the enhancement of FWM can be achieved even for low intensity pulses due to the effects of permanent dipole moments (PDM) in polar molecules. Moreover, the conversion efficiency of FWM can be controlled by the carrier-envelope phases (CEP) of two ultrashort pulses. (c) 2006 Optical Society of America

Constitutive plasma membrane targeting and microdomain localization of Dok5 studied by single-molecule microscopy

In the present study, single-molecule fluorescence microscopy was used to examine the characteristics of plasma membrane targeting and microdomain localization of enhanced yellow fluorescent protein (eYFP)-tagged wild-type Dok5 and its variants in living Chinese hamster ovary (CHO) cells. We found that Dok5 can target constitutively to the plasma membrane, and the PH domain is essential for this process. Furthermore, single-molecule trajectories analysis revealed that Dok5 can constitutively partition into microdomain on the plasma membrane. Finally, the potential mechanism of microdomain localization of Dok5 was discussed. This study provided insights into the characteristics of plasma membrane targeting and microdomain localization of Dok5 in living CHO cells. (C) 2008 Elsevier B.V. All rights reserved.

Heterodimerization of integrin Mac-1 subunits studied by single-molecule imaging

Heterodimerization of integrin Mac-1 (alpha(M) beta(2)) Subunits plays important role on regulating leukocytes adhesion to extracellular matrix or endothelial cells. Here, using total internal reflection microscopy, we investigated the heterodimerization of integrin Mac-1 subunits at the single-molecule level in live cells. Individual alpha(M) subunit fused to the enhanced yellow fluorescent protein (eYFP) was imaged at the basal plasma membrane of live Chinese hamster ovary (CHO) cells. Through analysis of mean square displacement (MSD), diffusion coefficient, the size of restricted domain and fraction of molecules undergoing restricted diffusion, we found that as compared with the diffusion in the absence of beta(2) subunit, the diffusion of single-molecule of alpha(M)-YFP was suppressed significantly in the presence of beta(2) subunit. Thus, based on the oligomerization-induced trapping model, we suggested that in the presence of beta(2) subunit, the am subunit may form heterodimer with it. (C) 2008 Elsevier Inc. All rights reserved.

Single-molecule detection in a liquid by surface-enhanced resonance Raman scattering

Surface-enhanced resonance Raman scattering (SERRS) of Rhodamine 6G (R6G) adsorbed on colloidal silver clusters in a liquid has been studied. The first observation of single molecule resonance Raman scattering in a liquid in a probed volume of 10 pL was achieved. Anisotropy of SERRS spectra of single R6G molecule and huge SERRS spectra were observed and compared with that of single molecule fixed in the dried films of sols, which revealed the intricate complex interaction between R6G molecules and the environment in a liquid.

Carrier-envelope phase dependence of few-cycle ultrashort laser pulse propagation in a polar molecule medium

We theoretically investigate carrier-envelope phase dependence of few-cycle ultrashort laser pulse propagation in a polar molecule medium. Our results show that a soliton pulse can be generated during the two-photon resonant propagation of few-cycle pulse in the polar molecule medium. Moreover, the main features of the soliton pulse, such as pulse duration and intensity, depend crucially on the carrier-envelope phase of the incident pulse, which could be utilized to determine the carrier-envelope phase of a few-cycle ultrashort laser pulse from a mode-locked oscillator.