Pre-designed Properties Research Articles

Monodisperse covalent organic nanosheets by in-situ oxidation method for efficient ion/molecule separation

Two-dimensional (2D) covalent organic nanosheets (CONs) are layered crystalline porous polymers comprising periodically extended graphene-like structures, and have great application potential in membrane separation field due to the advantages of abundant optional monomers, tunable pore size and structure, facilely-tailored functionality and pre-designed properties. However, unlike graphene oxide (GO) membranes, it is hard to directly prepare 2D CON membranes by vacuum filtration because of the difficulties in preparation of ultra-thin, large-sized and well-dispersed 2D CONs. Herein, an improved buffering interlayer interface method was proposed to realize a facile one-step synthesis of GO-like CON oxides by using H2O2 as an in-situ oxidant in the buffer layer. The stereoscopic fulcrum-oxygen sites introduced into the structure of CONs lead to weaken interactions between CON layers and increased hydrophilicity, which contributes to subsequent preparation of monodisperse nanosheets. The membranes fabricated with the as-prepared monodisperse nanosheets can realize high-efficiency transport of metal ions with a precise charge-discriminated group separation ability and efficient ion rejection. The strategy of in-situ oxidation to prepare monodisperse CONs proposed in this study provides a valuable approach for the preparation of novel functionalized CONs and the achievement of fast membrane separation performance.

РЕАКЦІЯ ПІРИДО[2,1-a]ІЗОІНДОЛУ З (R)- І (S)- N-α-МЕТИЛБЕНЗИЛМАЛЕЇНІМІДАМИ

Selective chemical reactions create new possibilities for controlled synthesis of compounds with pre-designed properties for further use in medical chemistry, material science and other fields. This is especially useful for such synthetic methodology as [4+2] cycloaddition. Current work is dedicated to study of reactions between N-chiral maleinimides with cyclic dienes based on the pyridoisoindol. Pyrido[2,1-a]isoindol turned out to be the most practical object to study the first example of asymmetric variant of the Diels-Alder reaction involving condensed isoindols. Previously, we established that this heterocyclic system, in contrast to other azino- and azoloisoindols, upon undergoing cycloaddition with non-chiral maleinimides gives only rearranged adducts of the first type. This type of compounds have also interesting stereochemistry: in solid state they have twisted double bond (twist angle 7-10°), while in solution they exist as a mixture of athropodiastereomeres due to the asymmetric Carbon atom and hindered rotation around С–С bond between exocyclic double bond and 2-(α-pyridil)phenyl fragment. Initial expectation was that chiral induction would influence the ratio of corresponding athropodiastereomeres. Calculations show that there are four possible athropodiastereomeres due to the chiral center and sterically hindered chiral axis. In case of non-chiral dienophiles, reaction results in two major diastereomeres (for our purposes marked as A and B) with 70:30 ration and two minor isomers (marked С and D respectively), the latter constituting less than 5% of the total amount. Major and minor isomers are in constant complex equilibrium, controlled via slow rotation of around corresponding С-С bond on one hand (which is the reason for athropodiastereomeres between major forms A and B, shown via NMR spectra at different temperatures), and on the other hand – fast equilibrium due to the 1,5-sigmatropic shift (cause for the minor forms C and D). Target reaction was studied under standard conditions for this rearrangement and under the kinetic control in the inert atmosphere at -80°С using TiCl4 as catalyzer. We therefore show that reaction pathway is similar to our previous examples and results in rearranged adducts of the first type. Ratio of athropodiastereomeres (both major and minor forms) is different from previous examples using non-chiral 2-substituted maleimides. Asymmetric induction spontaneously transfers from influencing the Diels-Alder reaction to influencing synchronic sigmatropic rearrangement, which is the final stage in the formation of the rearranged adduct of the first type in condensed isoindol systems.

On the Influence of Inhomogeneous Interphase Layers on Instabilities in Hyperelastic Composites.

Polymer-based three-dimensional (3D) printing—such as the UV-assisted layer-by-layer polymerization technique—enables fabrication of deformable microstructured materials with pre-designed properties. However, the properties of such materials require careful characterization. Thus, for example, in the polymerization process, a new interphase zone is formed at the boundary between two constituents. This article presents a study of the interphasial transition zone effect on the elastic instability phenomenon in hyperelastic layered composites. In this study, three different types of the shear modulus distribution through the thickness of the interphasial layer were considered. Numerical Bloch-Floquet analysis was employed, superimposed on finite deformations to detect the onset of instabilities and the associated critical wavelength. Significant changes in the buckling behavior of the composites were observed because of the existence of the interphasial inhomogeneous layers. Interphase properties influence the onset of instabilities and the buckling patterns. Numerical simulations showed that interlayer inhomogeneity may result in higher stability of composites with respect to classical layup constructions of identical shear stiffness. Moreover, we found that the critical wavelength of the buckling mode can be regulated by the inhomogeneous interphase properties. Finally, a qualitative illustration of the effect is presented for 3D-printed deformable composites with varying thickness of the stiff phase.

Effect of controlled tacticity of polyacrylonitrile (co)polymers on their thermal oxidative stabilization behaviors and the properties of resulting carbon films

Due to the spatial alignment of the nitrile groups and their involvement in the cyclization reactions during thermal oxidative stabilization (TOS) procedures, stereoregularity of polyacrylonitrile (PAN) precursors is one of the most important structural parameters to afford carbon materials. To elucidate this, PAN and poly(acrylonitrile-co-itaconic acid) with higher degree of isotacticity were prepared through template-assisted free-radical polymerization in the presence of MgCl2. Fourier-transform infrared spectroscopy was employed to quantitatively track the structural evolutions of the PAN (co)polymer precursors during their TOS procedures. The improved TOS efficiencies of the precursors were evidenced by high extents of cyclization, high concentrations of cyclized rings and enhanced oxygen uptakes of the isotactic PAN (co)polymers during the TOS procedures. The isotactic PAN (co)polymer precursors also exhibited relatively large heat evolutions with broad exothermic curves in differential scanning calorimetry observations, further suggesting efficient TOS procedures with safer processing conditions. The efficient TOS procedures of the isotactic PAN (co)polymer precursors resulted in carbon materials with high degrees of crystallinity and high amounts of sp2 clusters, affording much improved electrical conductivities. This study provided knowledge on the structural characteristics of the precursors for carbon materials with pre-designed properties, which is critical for their success in high-end applications.

Triclinic nematic colloidal crystals from competing elastic and electrostatic interactions.

The self-assembly of nanoparticles can enable the generation of composites with predesigned properties, but reproducing the structural diversity of atomic and molecular crystals remains a challenge. We combined anisotropic elastic and weakly screened electrostatic interactions to guide both orientational and triclinic positional self-ordering of inorganic nanocrystals in a nematic fluid host. The lattice periodicity of these low-symmetry colloidal crystals is more than an order of magnitude larger than the nanoparticle size. The orientations of the nanocrystals, as well as the crystallographic axes of the ensuing triclinic colloidal crystals, are coupled to the uniform alignment direction of the nematic host, which can be readily controlled on large scales. We examine colloidal pair and many-body interactions and show how triclinic crystals with orientational ordering of the semiconductor nanorods emerge from competing long-range elastic and electrostatic forces.

Functionally Graded TiC-Based Cermets

A well-known approach for manufacturing ceramic-metal composites is based on infiltration of a ceramic preform by a molten metal. The particular properties of the TiC x -M system (M is an infiltrating metal) allow to follow two different strategies in order to generate functionally graded structures. According to the first approach a graded distribution of porosity is generated in the carbide preform by taking advantage of the dependence of the sinterability on the carbon content (x). Liquid metal infiltration generates a varying ceramic-to-metal ratio and a concurrent property profile According to the second approach, a pre-designed spatial carbon variation in a TiC x preform generates a corresponding affinity variation towards an infiltrating carbon containing molten alloy, e.g. a carbon steel. By appropriate heat treatments and as a function of the carbon content, one can induce significant variations and produce pre-designed property profiles in the metallic component and, thence, in the ceramic-metal composite. Examples will be put forward in order to illustrate the two approaches.