Controlling Surface Interactions with Grafted Polymers

The interactions between surfaces modified with grafted polymers is studied theoretically. The aim of this work is to find polymer surface modifications that will result in localized attractive interactions between the surfaces. The practical motivation of the work is to find means to control the distance between bilayers and solid supports in supported membranes. Two theoretical approaches are used, the analytical treatment of Alexander and a molecular theory. It is found that grafting each end of the polymer to each surface results in an interaction with a well defined minimum. The location of the minima is found to be very close to the thickness of the polymer layer when the chains are grafted to only one of the surfaces. The predictions of the analytical theory are in excellent agreement with the molecular approach in this case. It is found that increasing the surface coverage increases the strength of the interaction. However, increasing the polymer chain length at fixed surface coverage results in a decrease of the free energy cost associated with separating the surfaces from their optimal distance. For the cases in which grafting to both surfaces is not possible, the molecular theory is used to study the effect of functionalizing segments of the chain to achieve an attractive well. It is found that by functionalizing the free end-groups of the polymers with segments attracted to the membrane, the range of the attractive interaction is significantly larger than the thickness of the unperturbed layer. Functionlizing the middle segments of the chains results in a shorter range attraction but of the same strength as in the end-functionalized layers. The optimal polymer modification is found to be such that the functionlized groups are attracted to the bare surface but are not attracted to the grafting surface. The relevance of the results to the design of experimental surface modifiers is discussed.     

Synergistic effects in mixed wormlike micelles of dimeric and single-chain cationic surfactants at high ionic strength

The mixed micellization between the cationic gemini surfactant [ C₁₂H₂₅( CH₃)₂N⁺( C₂H₄) N⁺( CH₃)₂ C₁₂H₂₅•2Br^-] and the cationic cetyltrimethylammonium bromide (CTAB) in 150 mM KBr solutions has been investigated. The variation of the cmc of the mixtures, measured by surface tension experiments, with composition revealed synergism in micelle formation. T-Jump and light scattering experiments performed in the vicinity of the crossover volume fraction showed the existence of two micellar populations, possibly linear and toroidal micelles. Rheological and dynamic light scattering experiments allowed to fully characterize the linear viscoelasticity of the mixtures. These measurements revealed synergistic gains in viscoelastic properties with a maximum of the stress-relaxation time around the equimolar composition. These effects are ascribed to a progressive intermicellar crosslinking resulting from a continuous increase of the end-cap energy with the 12-2-12 content in the mixture. Received: 18 November 2002 / Accepted: 8 April 2003 / Published online: 27 May 2003 RID="a" ID="a"e-mail: candau@fresnel.u-strasbg.fr     

On the NN final-state interaction in the <Superscript>16</Superscript>O (e,e<Superscript>′</Superscript>pp) reaction

The influence of the mutual interaction between the two outgoing nucleons (NN-FSI) in the ¹⁶O(e, e'pp) reaction has been investigated. Results for various kinematics are discussed. In general, the effect of NN-FSI depends on kinematics and the chosen final state in the excitation spectrum of ¹⁴C. Received: 19 December 2002 / Accepted: 6 February 2003 / Published online: 15 April 2003     

Femtosecond pump-probe experiments on non-stoichiometric sodium-fluoride clusters

In this paper we present two-color pump and probe spectroscopy on Na₂F, the smallest of the non-stoichiometric sodium-fluoride clusters (Na_nF_n-1), in molecular beams by employing femtosecond laser pulses. The molecules were pumped into the first excited state by one photonic transition and consecutively ionized from there by the second photon. We resolved the wavepacket oscillatory motion involving periodical structural rearrangements in the first excited state of Na₂F with a period of 185 fs. The time-resolved experiments show that sodium fluoride clusters provide interesting features which can be manipulated in optimal control experiments.     

Enhanced Ratiometric pH Sensing Using SNAFL-2 on Silver Island Films: Metal-enhanced Fluorescence Sensing

We have explored the opportunities for enhanced ratiometric pH sensing using the well-known carboxy seminaphthofluorescein (SNAFL-2) and silver island films (SiFs). Our results show that the metallic surfaces can provide up to a 40-fold increase in probe fluorescence intensity as compared to nonmetallic surfaces with the same probe coverage. However, while the S/N is significantly better for pH sensing, the emission wavelength ratiometric values are similar to that obtained in solution, due to the fact that the emission of both the acidic and basic forms of the probe are enhanced to similar extents. To the best of our knowledge this is the first report of enhanced ratiometric fluorescence sensing on metallic surfaces.     

Excitation functions of the analyzing power in elastic proton-proton scattering from 0.45 to 2.5 GeV

Excitation functions A_N(p_lab,_c.m.) of the analyzing power in elastic proton-proton scattering have been measured in an internal target experiment at the Cooler Synchrotron COSY with an unpolarized proton beam and a polarized atomic hydrogen target. Data were taken continuously during the acceleration and deceleration for proton kinetic energies T_lab (momenta p_lab) between 0.45 and 2.5 GeV (1.0 and 3.3 GeV/c) and scattering angles 30 ^° _c.m. 90^°. The results provide excitation functions and angular distributions of high precision and internal consistency. The data can be used as calibration standard between 0.45 and 2.5 GeV. They have significant impact on phase shift solutions, in particular on the spin triplet phase shifts between 1.0 and 1.8 GeV.     

Diffusion and ballistic contributions of electron-electron interaction to the conductivity in an Al0.26Ga0.74N/AlN/GaN heterostructure

The results of an experimental study of quantum correction of electron-electron interaction (EEI) to the conductivity of two-dimensional electron gas (2DEG) in an undoped heterostructure are reported. A small but significant decrease of the Hall slope with the increase of temperature was discovered. This is not due to the increase of electron concentration as temperature increases but to the EEI effect. Both diffusion and ballistic contributions of EEI to the conductivity of 2DEG were observed. As the temperature increases, the negative diffusion EEI correction to the conductivity increases in an absolute value while the ballistic EEI correction reduces to a renormalization of the transport mobility.     

3391 and 7699 laser generations and questions on the chaos

Summary In this report investigations are presented of laser generations at 3391 nm and 3391 and 7699 nm, or rather of changes induced by them in populations of the 5s′ [1/2] ₁ ⁰ , 4p′[3/2]₂ and 3d′[5/2] ₃ ⁰ levels, depending upon the angle of the tilted mirror of the He−Ne laser system. This writer has discovered that the above laser generations develop at a strongly tilted mirror, when the beam reflected from one mirror, in order to reach the other, has to be reflected many times on the inside walls of the discharge tube. The work was supported by CPBR 8.14.     

The effect of three-body interactions on thermal desorption spectra

Thermal desorption spectra are calculated for a one-dimensional chain and for a two-dimensional square lattice using the transfer-matrix technique and Monte Carlo simulations. Lateral interactions of adsorbed particles cause a splitting of spectra. The repulsive three-body interactions are shown to lead to an inequality of the integral intensities of the thermal desorption peaks.     

Elastic behaviour of lead fluoride under pressure

The variation of the second-order elastic constants (SOECs) and the longitudinal and shear modulii with hydrostatic pressure for the lead fluoride (PbF₂) has been investigated for the first time by means of a three-body force potential (TBP) model. The significance of three-body interactions (TBI) has been clearly demonstrated in reproducing the elastic constant variations and the pressure derivatives of SOECs of PbF₂. The equation of state for this crystal has also been reported.