Multiarm Star-Shaped Polydimethylsiloxanes with a Dendritic Branching Center.

New multiarm stars have been synthesized based on polylithium derivatives of high-generation carbosilane dendrimers. In the synthesis of multiarm stars based on the eighth-generation dendrimer, steric hindrances were observed even during the synthesis of a polylithium initiator. Subsequently, this led to chain transfer reactions between growing arms, as well as other side effects. As a result, dense nanogel formations with a higher tendency of ordering than in classical objects of this type were isolated from the reaction mixture. The study of the rheology of multiarm stars based on sixth-generation dendrimers made it possible to determine the activation energies of viscous flow in these objects, which makes it possible to consider them as objects with a macromolecular nature and a reptation flow mechanism.

Cryostructuring of Polymeric Systems: 67 Properties and Microstructure of Poly(Vinyl Alcohol) Cryogels Formed in the Presence of Phenol or Bis-Phenols Introduced into the Aqueous Polymeric Solutions Prior to Their Freeze-Thaw Processing.

Poly(vinyl alcohol) (PVA) physical cryogels that contained the additives of o-, m-, and p-bis-phenols or phenol were prepared, and their physico-chemical characteristics and macroporous morphology and the solute release dynamics were evaluated. These phenolic additives caused changes in the viscosity of initial PVA solutions before their freeze-thaw processing and facilitated the growth in the rigidity of the resultant cryogels, while their heat endurance decreased. The magnitude of the effects depended on the interposition of phenolic hydroxyls in the molecules of the used additives and was stipulated by their H-bonding with PVA OH-groups. Subsequent rinsing of such "primary" cryogels with pure water led to the lowering of their rigidity. The average size of macropores inside these heterophase gels also depended on the additive type. It was found also that the release of phenolic substances from the additive-containing cryogels occurred via virtually a free diffusion mechanism; therefore, drug delivery systems such as PVA cryogels loaded with either pyrocatechol, resorcinol, hydroquinone, or phenol, upon the in vitro agar diffusion tests, exhibited antibacterial activity typical of these phenols. The promising biomedical potential of the studied nanocomposite gel materials is supposed.

Cross-Linked Luminescent Polymers Based on ß-Diketone-Modified Polysiloxanes and Organoeuropiumsiloxanes.

Nowadays, luminescent materials attract wide attention due to their valuable characteristics and broad area of potential application. Luminescent silicone-based polymers possess unique properties, such as flexibility, hydrophobicity, thermal and chemical stabilities, etc., which allow them to be utilized in various fields, such as optoelectronics, solid-state lasers, luminescent solar concentrators, sensors, and others. In the present work, a metal-ligand interaction approach was applied to obtain new cross-linked luminescent polymers based on multiligand polysiloxanes with grafted ß-diketone fragments and organoeuropiumsiloxanes containing various organic substituents. Organoeuropiumsiloxanes were utilized as a source of Eu3+ ions due to their compatibility with the silicon matrix. All synthesized polymers were fully characterized and their physicochemical, mechanical, self-healing, optical, and thermal properties were studied.

Polydimethylsiloxanes with Grafted Dibenzoylmethanatoboron Difluoride: Synthesis and Properties.

A method for the preparation of polydimethylsiloxanes with grafted methoxy-substituted dibenzoylmethanatoboron difluoride has been described. The structures of prepared polymers were confirmed using NMR, IR spectroscopy and gel permeation chromatography methods. Their thermal properties were investigated using thermal gravimetric analysis, differential scanning calorimetry and thermomechanical analysis. The prepared polymers had good thermal (Td5% up to 393 °C) and thermo-oxidative (Td5% = 413 °C) stability. The polymers started to transit in a viscous flow state at about 40 °C (for 3 a) and at about 20 °C (for 3 b). The viscoelastic characteristics of prepared polymers were determined in the sinusoidal oscillating vibrations mode. It was shown that the studied polymers at low frequencies at room temperature are viscoelastic fluids (G' < G″). Increasing the frequency led to inversion (crossover) of dependences G' and G″, which indicated the transition of polymers from viscous to elastomeric behavior characteristics, and the beginning of the formation of a physical network. Optical properties were studied using electron absorption, steady-state and time-resolved fluorescence spectroscopy. It was shown that intramolecular H-dimers exist in the ground state. The polymers studied had a bright fluorescence in the solution and in the solid state, consisting of bands of monomer and excimer emission. Thermally-activated delayed fluorescence was observed in the solution and the solid state. The prepared polymers possess intriguing properties that make them useful as optical materials, sensors or imaging agents.

Star-Shaped Polydimethylsiloxanes with Organocyclotetrasilsesquioxane Branching-Out Centers: Synthesis and Properties.

New non-crystallizable low-dispersity star-shaped polydimethylsiloxanes (PDMS) containing stereoregular cis-tetra(organo)(dimethylsiloxy)cyclotetrasiloxanes containing methyl-, tolyl- and phenyl-substituents at silicon atoms and the mixture of four stereoisomers of tetra[phenyl(dimethylsiloxy)]cyclotetrasiloxane as the cores were synthesized. Their thermal and viscous properties were studied. All synthesized compounds were characterized by a complex of physicochemical analysis methods: nuclear magnetic resonance (NMR), FT-IR spectroscopy, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), viscometry in solution, rheometry, and Langmuir trough study.

Tris-cis-tris-trans-dodeca[organo(dimethylorganosiloxy)]cyclododecasiloxanes {RSi(O)[OSiMe2R']}12. Self-ordering features.

The molecular order and thermotropic transitions of tris-cis-tris-trans-dodeca- [organo(dimethylorganosiloxy)]cyclododecasiloxanes {RSi(O)[OSiMe(2)R']}(12) (R = Ph, R' = Me, CH(2)Cl, Vi; R = Me, Et, Vi, R' = Me) have been investigated using differential scanning calorimetry, thermogravimetric analysis, and X-ray scattering. The cyclododecasiloxanes with phenyl side groups (R = Ph) can form mesomorphic structures within a very wide temperature range. Compounds with R = Me and Vi are liquids and exhibit microphase separation above their glass transition temperature because of the different nature and structure of the organic R and trimethylsiloxy OSiMe(3) side groups. When the side group R = Et, a mesomorphic structure is formed in a substantially more narrow temperature region than that for cycles containing phenyl groups. Thus, the type of side group R in organocyclododecasiloxanes determines their ability for self-ordering into mesomorphic structures and the thermal stability of the mesomorphic state.

Hybrid Polycarbosilane-Siloxane Dendrimers: Synthesis and Properties.

A series of carbosilane dendrimers of the 4th, 6th, and 7th generations with a terminal trimethylsilylsiloxane layer was synthesized. Theoretical models of these dendrimers were developed, and equilibrium dendrimer conformations obtained via molecular dynamics simulations were in a good agreement with experimental small-angle X-ray scattering (SAXS) data demonstrating molecule monodispersity and an almost spherical shape. It was confirmed that the glass transition temperature is independent of the dendrimer generation, but is greatly affected by the chemical nature of the dendrimer terminal groups. A sharp increase in the zero-shear viscosity of dendrimer melts was found between the 5th and the 7th dendrimer generations, which was qualitatively identical to that previously reported for polycarbosilane dendrimers with butyl terminal groups. The viscoelastic properties of high-generation dendrimers seem to follow some general trends with an increase in the generation number, which are determined by the regular branching structure of dendrimers.

Cryostructuring of Polymeric Systems. 49. Unexpected "Kosmotropic-Like" Impact of Organic Chaotropes on Freeze⁻Thaw-Induced Gelation of PVA in DMSO.

Urea (URE) and guanidine hydrochloride (GHC) possessing strong chaotropic properties in aqueous media were added to DMSO solutions of poly(vinyl alcohol) (PVA) to be gelled via freeze⁻thaw processing. Unexpectedly, it turned out that in the case of the PVA cryotropic gel formation in DMSO medium, the URE and GHC additives caused the opposite effects to those observed in water, i.e., the formation of the PVA cryogels (PVACGs) was strengthened rather than inhibited. Our studies of this phenomenon showed that such "kosmotropic-like" effects were more pronounced for the PVACGs that were formed in DMSO in the presence of URE additives, with the effects being concentration-dependent. The additives also caused significant changes in the macroporous morphology of the cryogels; the commonly observed trend was a decrease in the structural regularity of the additive-containing samples compared to the additive-free gel sample. The viscosity measurements revealed consistent changes in the intrinsic viscosity, Huggins constant, and the excess activation heat of the viscosity caused by the additives. The results obtained evidently point to the urea-induced decrease in the solvation ability of DMSO with respect to PVA. As a result, this effect can be the key factor that is responsible for strengthening the structure formation upon the freeze⁻thaw gelation of this polymer in DMSO additionally containing additives such as urea, which is capable of competing with PVA for the solvent.

A Novel Ziegler⁻Natta-Type Catalytic System-TiCl4/2,2'-Dimethoxy-1,1'-Binaphthalene/Et3Al2Cl3/Bu2Mg for Production of Ultrahigh Molecular Weight Polyethylene Nascent Reactor Powders, Suitable for Solvent-Free Processing.

A series of ultrahigh molecular weight polyethylenes with viscosity-average molecular weights in the range of 1.6⁻5.6 × 106 have been prepared by using a novel Ziegler⁻Natta-type catalytic system-TiCl4/2,2'-dimethoxy-1,1'-binaphthalene/Et3Al2Cl3/Bu2Mg at different temperatures (Tpoly) in the range between 10 and 70 °C in toluene. The morphology of the nascent reactor powders has been studied by scanning electron microscopy, wide-angle X-ray diffraction, and the DSC melting behavior. Polymers are suitable for the modern processing methods-the solvent-free solid-state formation of super high-strength (tensile strength over 1.8⁻2.5 GPa) and high-modulus (elastic modulus up to 136 GPa) oriented film tapes. With decrease of Tpoly, the drawability of the reactor powders increased significantly.

Titanium(III, IV)-Containing Catalytic Systems for Production of Ultrahigh Molecular Weight Polyethylene Nascent Reactor Powders, Suitable for Solventless Processing-Impact of Oxidation States of Transition Metal.

Catalytic systems containing TiCl4 or TiCl3, THF, organomagnesium (n-Bu2Mg) and organoaluminum compounds capable of producing ultrahigh molecular weight polyethylene (UHMWPE) were developed. The resulting polymers were characterized by a molecular weight in the range of (1.8⁻7.8) × 106 Da and desirable morphology, suitable for modern methods of polymer processing-the solvent-free solid-state processing of superhigh-strength (tensile strength up to 2.1 GPa) and high-modulus (elastic modulus up to 125 GPa) oriented films and film tapes. The impacts of a THF additive, the oxidation state of the titanium atom, and the composition and nature of the nontransition organometallic compounds on the formation of catalytic systems for UHMWPE production were evaluated. The results indicate the suitability of individual titanium chloride tetrahydrofuran complex application for the formation of THF-containing catalytic systems. This approach also results in a significant increase in the system catalytic activity and mechanical properties of UHMWPE. The catalysts based on Ti(III) were inferior to systems containing Ti(IV) in productivity but were markedly superior in the mechanical properties of UHMWPE.

Thermodynamic and structural properties of tuber starches from transgenic potato plants grown in vitro and in vivo.

Potato plants harboring Phytochrome B (PHYB) gene from Arabidopsis thaliana or rol genes from Agrobacterium rhizogenes were used to study the effect of transgene expression on structure and properties of starch in tubers. Thermodynamic characteristics of starch (melting temperature, enthalpy of melting, thickness of crystalline lamellae) were shown to be variable depending on the transgene expression and plant culturing mode: in vitro or in soil. The expression of rolB or rolC genes in in vitro cultured plants evoked opposite effects on starch melting temperature and crystalline lamellae thickness. AtPHYB or rolB expression in the soil-grown potato led to the formation of more defective or more ordered starch structures, respectively, in comparison with starches of the same lines grown in vitro. On the whole, our study revealed genotype-dependent differences between starches extracted from tubers of in vitro or in vivo grown plants.