Self-assembled dendrimers with uniform structure

Calix[4]arenes substituted at their wide rim by four aryl urea residues (1) form hydrogen-bonded dimers in apolar solvents. Replacement of one urea residue by an acetamido moiety leads to calix[4]arene derivatives (5) which form hydrogen-bonded tetramers under the same conditions. Both self-assembly processes occur independently. Therefore, molecules have been prepared in which a tetra-urea calix[4]arene and a tri-urea mono acetamide derivative are covalently connected between their narrow rims by a long, mainly aliphatic chain [-O-(CH(2))(n)-C(O)-NH-(CH(2))(m)-O-] (7). In the presence of an equimolar amount of tetra-tosyl urea calix[4]arene () they form dendritic assemblies since the well known heterodimerization of tetra-tosyl and tetra-aryl urea calix[4]arenes prevents the formation of a cross-linked structure. Covalent connection of adjacent urea residues leads to tetra-loop derivatives (3) that cannot form homodimers, but instead form heterodimers with tetra-aryl or tetra-tosylureas. Therefore, similar dendrimers should be available using the selective dimerization observed for 3. The formation of a single, structurally uniform dendrimer from eight building blocks is confirmed by (1)H NMR spectra, showing only peaks that are also found for respective model assemblies. Translational diffusion coefficients of the assemblies have been determined using (1)H DOSY NMR.     

Guest exchange in dimeric capsules formed by tetra-urea calix[4]arenes

Ten tetra-urea calix[4]arene derivatives with different ether residues (methyl, pentyl, benzyl, all combinations of methyl and pentyl, 1,3-dibenzyl-2,4-dipentyl), including also the tetrahydroxy compound and the 1,3-dipentyl ether, were synthesised. Their urea groups were substituted with a lipophilic residue to ensure sufficient solubility in cyclohexane. Thus, kinetics for the exchange of the included guest (benzene) against the solvent (cyclohexane) could be followed by 1H NMR spectroscopy. The apparent first order rate constants decrease with increasing size of the ether residues from methyl to benzyl by more than three orders of magnitude. This can be understood by a decreasing flexibility/mobility of the calixarene skeleton. In line with this explanation is the rather slow exchange for the tetrahydroxy compound, where the cone conformation is stabilised by a cyclic array of intramolecular OH...OH hydrogen bonds.     

Preparation of biodegradable polymer nanoparticles by miniemulsion technique and their cell interactions

The emulsion/solvent evaporation method and miniemulsion technique were combined and applied in the formulation of biodegradable monodisperse nanoparticles at high solid contents using different biocompatible and biodegradable polymers such as poly(L-lactide) (PLLA), poly[(D,L-lactide)-co-glycolide] 50:50 (PLGA), and poly(epsilon-caprolactone) (PCL). Differences between the results of various polymers are found in terms of the particle size and size distribution as well as in the degradation time. An encapsulated hydrophobic fluorescent dye was used as a model marker in order to study the entrapment efficiency and diffusion yield out of the particle. Cellular uptake of the obtained particles was observed in Jurkat and HeLa cells. In the investigated particle size range of 80-200 nm, the surfactant on the particles' surface had a greater influence than the particle size. Uptake kinetics reveals that the PLLA and PCL particles are endocytosed much faster than polystyrene particles.     

Synthesis of fluorescent polyisoprene nanoparticles and their uptake into various cells

Fluorescent polyisoprene nanoparticles were synthesized by the miniemulsion technique as marker particles for cells. The uptake of the non-functionalized polyisoprene nanoparticles, without any transfection agents, into different adherent (HeLa) and also suspension (Jurkat) cell lines is strikingly efficient and fast compared to other polymeric particles, and leads to high loading of the cells. The intracellular polyisoprene particles are localized as single particles in endosomes distributed throughout the entire cytoplasm. The uptake kinetics shows that particle internalization starts during the first minutes of incubation and is finished after 48 h of incubation. Since (unfunctionalized) polystyrene particles show a comparable, low uptake behavior in cells, the uptake rates can be tuned by the amount of polystyrene in polyisoprene/polystyrene copolymer particles. As polyisoprene nanoparticles are internalized by different cell lines that are relevant for biomedical applications, they can be used to label these cells efficiently if a marker is incorporated in the particles. As polyisoprene is not or is hardly biodegradable the particles should be suited for long-term applications.     

Multilayer graphene/chlorine‐isobutene‐isoprene rubber nanocomposites: the effect of dispersion

Multilayer graphene (MLG) is composed of approximately 10 sheets of graphene. It is a promising nanofiller just starting to become commercially available. The dispersion of the nanofiller is essential to exploit the properties of the nanocomposites and is dependent on the preparation method. In this study, direct incorporation of 3 parts per hundred of rubber (phr) MLG into chlorine‐isobutene‐isoprene rubber (CIIR) on a two‐roll mill did not result in substantial enhancement of the material properties. In contrast, by pre‐mixing the MLG (3 phr) with CIIR using an ultrasonically assisted solution mixing procedure followed by two‐roll milling, the properties (rheological, curing, and mechanical) were improved substantially compared with the MLG/CIIR nanocomposites mixed only on the mill. The Young's moduli of the nanocomposites mixed in solution increased by 38%. The CIIR/MLG nanocomposites produced via solution showed superior durability against weathering exposure. Copyright © 2016 John Wiley & Sons, Ltd.     

Lanthanide complexation with CMPO and CMPO-calix[4]arenes in solution: spectrophotometric and electrospray mass spectrometric approaches

The binding of lanthanide(III) cations with organophosphorous ligands like CMPO and related calix[4]arene-based derivatives have been investigated using two experimental methods. The stability constants of the lanthanum, europium and ytterbium complexes were first determined in methanol by UV absorption spectrophotometry in the presence of nitrate or chloride anions. The results showed that the stoichiometry and the stability of the complexes formed depend on the position of the CMPO moieties either on the wide or the narrow rim of the calixarene scaffold, the nature of the medium, the conformational mobility of the ligands. Complexation of lanthanum was also followed by ESI-mass spectrometry in the same solvent. This method confirmed the stoichiometry of the complexes, giving also structural information, like coordination of anion or solvent molecules to the complexes, and allowed the calculation of distribution curves in good agreement with those derived from the spectrophotometric results. This is an important result showing that ESI-MS can be used to provide with quantitative information when absorption spectrophotometry is not applicable, i.e. for systems where complexation leads to weak spectral changes.     

Oxygen-bridged hybrid metallocene-nonmetallocene polymetallic catalysts of group 4 metals for bimodal activity in olefin polymerization: synthesis, characterization, and theoretical investigation

This article describes the syntheses of two covalently linked oxygen-bridged hybrid metallocene-nonmetallocene polymetallic catalysts bearing two different catalytically active group 4 metals. The reactions of Cp*2(Me)Zr(OH) (2) with Ti(NMe2)4 and Hf(NMe2)4 led to the formation of a heterobimetallic compound Cp*2(Me)Zr(micro-O)Ti(NMe2)3 (7) and a trimetallic derivative Cp*2(Me)Zr(micro-O)Hf(NMe2)2(micro-O)Zr(Me)Cp*2 (9), respectively, under the elimination of Me2NH. The crystal data confirm the molecular structures of 7 and 9, which crystallize in the space groups P and P21/n, respectively. 9 is the first example of a crystallographically characterized heterotrimetallic complex having a Zr-O-Hf-O-Zr core. 7 bearing two active catalytic centers, namely, zirconium and titanium, exhibits bimodal activity in olefin polymerization when activated with methylalumoxane (MAO). It produces polyethylene largely controlled by the zirconium center, and polystyrene seems to be formed predominantly by the titanium center. DFT calculations were performed on the supposed cationic intermediates, revealing that a cation generated on the titanium center is sterically more accessible for monomer binding, though it is energetically less-favorable than that generated on the zirconium center.