Atomic force microscopy measurements of topography and friction on dotriacontane films adsorbed on a SiO2 surface

doi:10.1063/1.2060707 (8 pages)We report comprehensive atomic force microscopy (AFM) measurements at room temperature of the nanoscale topography and lateral friction on the surface of thin solid films of an intermediate-length normal alkane, dotriacontane (n-C32H66), adsorbed onto a SiO2 surface. Our topographic and frictional images, recorded simultaneously in the contact mode, reveal a multilayer structure in which one to two layers of molecules adsorb adjacent to the SiO2 surface oriented with their long axis parallel to the interface followed by partial layers of molecules oriented perpendicular to the surface. The thicknesses of the parallel and perpendicular layers that we measured with the AFM agree with those inferred from previous x-ray specular reflectivity measurements on similarly prepared samples. We also observe bulk dotriacontane particles and, in contrast with our previous measurements, are able to determine their location. Above a minimum size, the bulk particles are separated from islands of perpendicularly oriented molecules by regions of exposed parallel layers that most likely extend underneath the particles. We find that the lateral friction is sensitive to the molecular orientation in the underlying crystalline film and can be used effectively with topographic measurements to resolve uncertainties in the film structure. We measure the same lateral friction on top of the bulk particles as on the perpendicular layers, a value that is about 2.5 times smaller than on a parallel layer. Scans on top of parallel layers indicate a constant height but reveal domains having different sublevels of friction. We explain this by the domains having different azimuthal orientations of the molecules.This work was supported by U.S. National Science Foundation under Grant Nos. DMR-0109057 and DMR-0411748, by the Chilean government under FONDECYTGrant Nos. 1010548 and 7010548, and by the Fundacion Andes Grant No. C-13768

High-resolution ellipsometric study of an n-alkane film, dotriacontane, adsorbed on a SiO2 surface

doi:10.1063/1.1429645Using high-resolution ellipsometry and stray light intensity measurements, we have investigated during successive heating-cooling cycles the optical thickness and surface roughness of thin dotriacontane (n-C32H66) films adsorbed from a heptane (n-C7H16) solution onto SiO2-coated Si(100) single-crystal substrates. Our results suggest a model of a solid dotriacontane film that has a phase closest to the SiO2 surface in which the long-axis of the molecules is oriented parallel to the interface. Above this "parallel film" phase, a solid monolayer adsorbs in which the molecules are oriented perpendicular to the interface. At still higher coverages and at temperatures below the bulk melting point at Tb = 341 K, solid bulk particles coexist on top of the "perpendicular film." For higher temperatures in the range TbTs, a uniformly thick fluid film wets to the parallel film phase. This structure of the alkane/SiO2 interfacial region differs qualitatively from that which occurs in the surface freezing effect at the bulk alkane fluid/vapor interface. In that case, there is again a perpendicular film phase adjacent to the air interface but no parallel film phase intervenes between it and the bulk alkane fluid. Similarities and differences between our model of the alkane/SiO2 interface and one proposed recently will be discussed. Our ellipsometric measurements also show evidence of a crystalline-to-plastic transition in the perpendicular film phase similar to that occurring in the solid bulk particles present at higher coverages. In addition, we have performed high-resolution ellipsometry and stray-light measurements on dotriacontane films deposited from solution onto highly oriented pyrolytic graphite substrates. After film deposition, these substrates proved to be less stable in air than SiO2.This work was supported by the Chilean government under CONICYT Grant No. 018/AT/005NSF and FONDECYT Grant No. 1980586 and by the U.S. National Science Foundation under Grant Nos. INT-9605227, DMR-9802476, and DMR-0109057

Nanoscale Observation of Alkane Delayering

Noncontact Atomic Force Microscopy and synchrotron x-ray scattering measurements on dotriacontane (n-C32H66 or C32) films adsorbed on SiO2-coated Si(100) wafers reveal a narrow temperature range near the bulk C32 melting point Tb in which a monolayer phase of C32 molecules oriented perpendicular to surface is stable. This monolayer phase undergoes a delayering transition to a three-dimensional (3D) fluid phase on heating to just above Tb and to a solid 3D phase on cooling below Tb. An equilibrium phase diagram provides a useful framework for interpreting the unusual spreading and receding of the monolayer observed in transitions to and from the respective 3D phases.Comment: 13 pages, 3 figure

Intramolecular diffusive motion in alkane monolayers studied by high-resolution quasielastic neutron scattering and molecular dynamics simulations

URL:http://link.aps.org/doi/10.1103/PhysRevLett.92.046103 DOI:10.1103/PhysRevLett.92.046103Molecular dynamics simulations of a tetracosane (n-C24H50) monolayer adsorbed on a graphite basal-plane surface show that there are diffusive motions associated with the creation and annihilation of gauche defects occurring on a time scale of ~0.1-4 ns. We present evidence that these relatively slow motions are observable by high-energy-resolution quasielastic neutron scattering (QNS) thus demonstrating QNS as a technique, complementary to nuclear magnetic resonance, for studying conformational dynamics on a nanosecond time scale in molecular monolayers.This work was supported by the NSF under Grants No. DMR-9802476 and No. DMR-0109057, by the Chilean government under FONDECYT Grant No. 1010548, and by the U.S. Department of Energy through Grant No. DE-FG02-01ER45912. The neutron scattering facilities in this work are supported in part by the National Science Foundation under Agreement No. DMR-0086210

Cardiovascular reactivity in a simulated job interview: the role of gender role self-concept

This study investigated the relation of gender role self-concept (G-SC) to cardiovascular and emotional reactions to an ecologically relevant stressor in a sample of graduating male and female university students. Thirty-seven men and 37 women completed the Personal Attribute Questionnaire and worked on four tasks designed to reflect common features of a job interview. Blood pressure and heart rate were measured at baseline, during, and after each task; subjective stress was measured at baseline and after each task. Subjective and objective stress scores were averaged across tasks and analyzed by sex and G-SC (i.e., instrumentality, expressiveness). Results indicated that women as a group demonstrated greater emotional reactivity, but did not differ in their physiological reactions when compared to men. Regardless of sex, participants’ instrumentality scores contributed significantly to the variation in subjective stress response: those scoring high on instrumentality reported less stress, but evidenced greater blood pressure reactivity than those scoring low on instrumentality. These results suggest that gender roles, particularly an instrumental self-concept, may play an important role in both subjective and objective reactions to an ecologically relevant stressor

Loss of thalamic serotonin transporters in early drug-naïve Parkinson’s disease patients is associated with tremor: an [123I]β-CIT SPECT study

In vitro studies revealed serotonin transporter (5-HTT) decline in Parkinson’s disease (PD). Yet, few studies investigated thalamic 5-HTT in vivo and its effect on PD heterogeneity. We analyzed thalamic [123I]β-CIT binding (mainly reflecting 5-HTT binding) in 32 drug-naïve PD patients and 13 controls with SPECT. Twenty-six patients were examined twice (17 months apart). Based on UPDRS scores, we identified subgroups of patients with moderate/severe tremor (PDT) and without tremor (PDWT) at the time of clinical diagnosis. Additionally, depressive symptoms were evaluated using the Beck Depression Inventory (BDI) at baseline. Mean thalamic specific to non-specific [123I]β-CIT binding ratio was lower in patients when compared to controls, and further decreased during follow-up. At baseline, average thalamic ratio was significantly lower in the PDT than in the PDWT subgroup. No correlation was found between BDI scores and thalamic binding ratios. Our findings show decline of [123I]β-CIT binding to thalamic 5-HTT in PD and its possible contribution to tremor onset