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.     

Transformation of substituted 5-amino-1,3-oxazole-4-carbonitriles into new 3,4,5-triaminopyrazole derivatives

Reactions of accessible 5-alkylamino- and 5-arylamino-1,3-oxazole-4-carbonitriles with hydrazine hydrate on heating involved a complex transformation sequence resulting in the formation of 3,4,5-triaminopyrazole derivatives. The structure of the products was confirmed by their cyclocondensation with acetylacetone, leading to 2-alkyl(aryl)amino-3-acylamino-5,7-dimethylpyrazolo[1,5-a]pyrimidines which were identified by NMR spectroscopy using COSY, NOESY, HMQC, and HMBC techniques.     

Contact Interaction Between a Laminated Shell of Revolution and a Rigid or Elastic Foundation

A method is proposed to solve the contact problem for laminated anisotropic shells of revolution. The method is based on a two-dimensional model that accounts for transverse shears and reduction. Also the method is based on the method of successive approximations, the generalized pseudo-force method, and a numerical-analytical method of solving boundary-value problems. The results obtained for a cylindrical shell of complex thickness structure are compared with those obtained in three-dimensional formulation__________Translated from Prikladnaya Mekhanika, Vol. 41, No. 5, pp. 68–75, May 2005.     

Kinetic study on the living/controlled cationic polymerization of p‐methoxystyrene coinitiated by tris(pentafluorophenyl)borane

A kinetic study of the living cationic polymerization of p‐methoxystyrene using 1‐(4‐methoxyphenyl)ethanol ( 1 )/B(C₆F₅)₃ initiating system in a mixture of CH₃CN with CH₂Cl₂ 1:1 (v/v) at room temperature was carried out utilizing a wide variety of conditions. The polymerization proceeded in a living fashion even in the presence of a large amount of water ([H₂O]/[B(C₆F₅)₃] ratio up to 20) to afford polymers whose M_n increased in direct proportion to monomer conversion with fairly narrow MWDs (M_w/M_n ≤ 1.3). The investigation revealed that the rate of polymerization was first‐order in B(C₆F₅)₃ concentration, while a negative order in H₂O concentration close to ?2 was obtained. It was also found that the rate of polymerization decreased with lowering temperature, which could be attributed to a decreased concentration in free Lewis acid, the true coinitiator of polymerization. A mechanistic scheme to explain the kinetic behavior of living p‐methoxystyrene polymerization is proposed, which has been validated by PREDICI simulation on multiple‐data curves obtained by ¹H NMR in situ polymerization experiment. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6928–6939, 2008     

Syndiospecific polymerization of styrene in the presence of new titanium complexes with dialkanolamines: Titanocanes and bistitanocanes

The syndiospecific polymerization of styrene is studied in the presence of titanium complexes with dialkanolamines—bistitanocanes and titanocane—activated by individual MAO or the combined cocatalyst MAO/TIBA. It is shown that these catalysts are more active and stereospecific after their activation with the combined cocatalyst ([TIBA]: [MAO] ≤ 0.13) than that in the case of the activation with MAO: The activities of the catalysts are ≤18 and 9 kg PS/(mol Ti h), and the syndiotacticities of PS are ≤76 and 60%, respectively. Polymers synthesized in the presence of bistitanocanes are characterized by M _n ≤ 4.5 × 10⁴ and T _m ≤ 268°C and a narrow molecular-mass distribution (≤2.5).     

Strained germanium films in Ge/InGaAs/GaAs heterostructures: Formation of edge misfit dislocations at the Ge/InGaAs interface

Heterostructures of the “strained Ge film/artificial InGaAs layer/GaAs substrate” type have been grown by molecular beam epitaxy. A specific feature of these structures is that the plastically relaxed (buffer) InGaAs layer has the density of threading dislocations on a level of 10⁵–10⁶ cm⁻². These dislocations penetrate into the strained Ge layer to become sources of both 60° and 90° (edge) misfit dislocations (MDs). Using the transmission electron microscopy, both MD types have been found at the Ge/InGaAs interface. It has been shown that the presence of threading dislocations inherited from the buffer layer in a tensile-strained Ge film favors the formation of edge dislocations at the Ge/InGaAs interface even in the case of small elastic deformations in the strained film. Possible mechanisms of the formation of edge MDs have been considered, including (i) accidental collision of complementary parallel 60° MDs propagating in the mirror-tilted {111} planes, (ii) induced nucleation of a second 60° MD and its interaction with the primary 60° MD, and (iii) interaction of two complementary MDs after a cross-slip of one of them. Calculations have demonstrated that a critical layer thickness (h _c ) for the appearance of edge MDs is considerably smaller than h _c for 60° MDs.     

Synthesis of 3-amino-1-benzyl-4-benzenesulfonyl-2-carbonitrilo-1H-pyrrole and preparation of related pyrrolo[3,2-d]pyrimidines

A method for the synthesis of a new 4-phenylsulfonyl-substituted 3-aminopyrrole was developed and related pyrrolo[3,2-d]pyrimidine derivatives were synthesized.     

Effect of the production conditions on the size and magnetic characteristics of iron sulfide Fe<Subscript>3</Subscript>S<Subscript>4</Subscript> nanoparticles

It was shown that the reaction of the trinuclear complex [FeFe₂O(CH₃CO₂)₆(H₂O)₃]·₂H₂O with thiourea in tetraethylene glycol leads to the formation of nanoparticles of thiospinel Fe₃S₄, the size of which depends on the reaction conditions. It was established that the formed thiospinel particles exhibit superparamagnetic characteristics. It was shown that the size of the nanoparticles has an effect on their magnetic characteristics.