Unexpected Temperature Behavior of Polyethylene Glycol Spacers in Copolymer Dendrimers in Chloroform

We have studied copolymer dendrimer structure: carbosilane dendrimers with terminal phenylbenzoatemesogenic groups attached by poly(ethylene) glycol (PEG) spacers. In this system PEG spacers areadditional tuning to usual copolymer structure: dendrimer with terminal mesogenic groups. Thedendrimer macromolecules were investigated in a dilute chloroform solution by 1H NMR methods(spectra and relaxations). It was found that the PEG layer in G = 5 generations dendrimer is “frozen”at high temperatures (above 260 K), but it unexpectedly becomes “unfrozen” at temperatures below250 K (i.e., melting when cooling). The transition between these two states occurs within a smalltemperature range (~10 K). Such a behavior is not observed for smaller dendrimer generations (G = 1and 3). This effect is likely related to the low critical solution temperature (LCST) of PEG and is caused bydendrimer conformations, in which the PEG group concentration in the layer increases with growing G.We suppose that the unusual behavior of PEG fragments in dendrimers will be interesting for practicalapplications such as nanocontainers or nanoreactors.</p

Comparison of AlN vs. SIO2/LiNbO3 Membranes as Sensitive Elements for the SAW-Based Acceleration Measurement: Overcoming the Anisotropy Effects

We propose the use of aluminum nitride (AlN) membranes acting as sensitive elements for the surface acoustic wave (SAW)-based acceleration measurement. The proposed solution is compared against existing prototypes based on the use of quartz (SiO2)/lithium niobate (LiNbO3) membranes that are characterized by extensive anisotropic properties. Using COMSOL Multiphysics 5.4 computer simulations we show explicitly that sensitive elements based on less anisotropic AlN membranes overcome both the low sensitivity limitations of SiO2 and low temperature stability of LiNbO3. Moreover, AlN membranes exhibit nearly double the robustness against irreversible mechanical deformations when compared against SiO2, which in turn allows for further 1.5-fold sensitivity enhancement over LiNbO3 based sensors. Taking into account their acceptable frequency characteristics, we thus believe that the AlN membranes are a good candidate forsensitive elements especially for high acceleration measurements

Mechanical relaxation of functionalized carbosilane dendrimer melts

International audienceFunctionalizing the internal structure of classical dendrimers is a new way of tailoring their properties. Using atomistic molecular dynamics simulations, we investigate the rheological behavior of functionalized dendrimers (FD) melts obtained by modifying the branching of carbosilane dendrimers (CSD). The time (relaxation modulus G(t)) and frequency (storage G' and loss G" moduli) dependencies of the dynamic modulus are obtained. Fourth generation FD melts present a region where G' > G". In contrast, their non-functionalized counterparts (i.e., classical dendrimers with a regular branching) do not show such a region. The comparative analysis of FD and CSD suggests that the internal densification due to functionalization prevents the penetration of branches and causes FD to behave like colloidal particles in a crowded environment. Since CSD have no special interactions, we expect that this effect will be common for other dendrimer macromolecules

Influence of the Chemical Structure on the Mechanical Relaxation of Dendrimers

The rheological properties of macromolecules represent one of the fundamental features of polymer systems which expand the possibilities of using and developing new materials based on them. In this work, we studied the shear-stress relaxation of the second generation PAMAM and PPI dendrimer melts by atomistic molecular dynamics simulation. The time dependences of relaxation modulus G(t) and the frequency dependences of the storage G′(ω) and loss G″(ω) moduli were obtained. The results were compared with the similar dependences for the polycarbosilane (PCS) dendrimer of the same generation. The chemical structure of the dendrimer segments has been found to strongly influence their mechanical relaxation. In particular, it has been shown that hydrogen bonding in PAMAM dendrimers leads to an entanglement of macromolecules and the region is observed where G′(ω) > G″(ω). This slows down the mechanical relaxation and rotational diffusion of macromolecules. We believe that our comprehensive research contributes to the systematization of knowledge about the rheological properties of dendrimers