Early Life Epigenetic Programming and Later Psychological Ramifications: Programming Positivity

Epigenetics is the field of focus when determining how environmental and behavioral factors can directly impact the expression of genes that affect our behavior. Existing studies have examined links between eliciting stress behaviors in pregnant mice and the negative stress behavioral responses in offspring for several subsequent generations, which points to a disposition to adverse stress responses later in life due to early-life epigenetic modifi- cations. Similarly, research on both rats and humans has found early life trauma to be a large factor in both the hyper- and de-methylation of genes responsible for stress processing, which can be linked to depressive behav- ior later in life. The proposed study aims to address the lack of attention to positive psychology in this field of study by seeking to identify epigenetic markers such as hyper- or de-methylation in regions of the rat genome con- taining homologous genes to those in humans potentially linked to positive affect or life satisfaction. Rat offspring reared with either high or low levels of maternal care would be exposed to a novel stressful environment, and a microarray analysis would be performed to assess the differences in gene expression in the previously noted regions of the genome. Gene expression analysis may reveal that offspring who received more maternal care show increased expression of the serotonin transporter gene, down-regulation of genes for proinflammatory cytokines, and up-regulation of anti-viral re- sponse genes. These results would be consistent with the gene expression patterns previously seen in individuals with higher levels of life satisfac- tion, eudemonic pleasure, and optimism

Viscoplastic Modeling of Surface Relief Grating Growth on Isotropic and Preoriented Azopolymer Films

We report on solving of two intriguing issues concerning the inscription of surface relief gratings within azopolymer thin films under irradiation with SS, PP and RL interference patterns. For this, we utilize the orientation approach and viscoplastic modeling in combination with experimental results, where the change in surface topography is acquired in situ during irradiation with modulated light. First, the initial orientation state of polymer backbones is proved to be responsible for the contradictory experimental reports on the efficiency of the SS interference pattern. Different orientation states can influence not only the phase of SS grating but also its height, which is experimentally confirmed by using special pretreatments. Second, the faster growth of gratings inscribed by the RL interference pattern is shown to be promoted by a weak photosoftening effect. Overall, the modeled results are in good agreement with the order of relative growth efficiency: RL–PP–SS

Motion of Adsorbed Nano-Particles on Azobenzene Containing Polymer Films

We demonstrate in situ recorded motion of nano-objects adsorbed on a photosensitive polymer film. The motion is induced by a mass transport of the underlying photoresponsive polymer material occurring during irradiation with interference pattern. The polymer film contains azobenzene molecules that undergo reversible photoisomerization reaction from trans- to cis-conformation. Through a multi-scale chain of physico-chemical processes, this finally results in the macro-deformations of the film due to the changing elastic properties of polymer. The topographical deformation of the polymer surface is sensitive to a local distribution of the electrical field vector that allows for the generation of dynamic changes in the surface topography during irradiation with different light interference patterns. Polymer film deformation together with the motion of the adsorbed nano-particles are recorded using a homemade set-up combining an optical part for the generation of interference patterns and an atomic force microscope for acquiring the surface deformation. The particles undergo either translational or rotational motion. The direction of particle motion is towards the topography minima and opposite to the mass transport within the polymer film. The ability to relocate particles by photo-induced dynamic topography fluctuation offers a way for a non-contact simultaneous manipulation of a large number of adsorbed particles just in air at ambient conditions

Light-induced structuring of photosensitive polymer brushes

We investigate light-induced irreversible structuring of surface topographies in poly(3-sulfopropyl methacrylate/potassium salt) (PSPMK) brushes on flat solid substrates prepared by surface-initiated atom transfer radical polymerization. The brushes have been loaded with azobenzene-based surfactant comprised of positively charged headgroups and hydrophobic tail. The surfactant exhibits photoresponsive properties through photoisomerization from the trans to cis states leading to significant changes in physicochemical properties of grafted polymer chains. The azobenzene surfactant enables photoresponsive behavior without introducing irreversible changes to chemical composition of the parent polymer brush. Exposing these photosensitive brushes to irradiation with UV interference beams causes the polymer brush to form surface relief grating (SRG) patterns. The cationic surfactant penetrates only ∼25% of the upper portion of the PSPMK brush, resulting in the formation of two sections within the brush: a photoresponsive upper layer and nonfunctional buried layer, which is not affected by the UV irradiation. Using nano-FTIR spectroscopy, we characterize locally the chemical composition of the polymer brush and confirm partial penetration of the surfactant within the film. Strong optomechanical stresses take place only within the upper layer of the brush that is impregnated with the surfactants and causes surface topography alternation due to a local rupture of grafted polymer chains. The cleaved polymer chains are then removed from the surface by using a good solvent, leaving behind topographical grating on top of the nonfunctional brush layer. We demonstrate that photostructured polymer brush can be used for reversible switching of brush topography by varying external humidity

Light-Induced Deformation of Azobenzene-Containing Colloidal Spheres: Calculation and Measurement of Opto-Mechanical Stresses

We report on light-induced deformation of colloidal spheres consisting of azobenzene-containing polymers. The colloids of the size between 60 nm and 2 μm in diameter were drop casted on a glass surface and irradiated with linearly polarized light. It was found that colloidal particles can be deformed up to ca. 6 times of their initial diameter. The maximum degree of deformation depends on the irradiation wavelength and intensity, as well as on colloidal particles size. On the basis of recently proposed theory by Toshchevikov et al. [J. Phys. Chem. Lett. 2017, 8, 1094], we calculated the opto-mechanical stresses (ca. 100 MPa) needed for such giant deformations and compared them with the experimental results