Ideally selective diisocyanate building blocks: New perspectives for dendrimers and coating binders

Using zirconium (IV) salts as catalyst, the reaction of a diisocyanate carrying one tertiary and one primary isocyanate group (IMCI, DIMP) with alcohols can be conducted with complete regioselectivity. This unique selectivity enables the use of a diisocyanate building block in unprecedented ways. Incomplete regioselectivity of diisocyanates, as commonly encountered in currently commercial ones like IPDI and TDI, inevitably leads to polydisperse products in reaction with polyols. The ultimate monodisperse polymer architecture, dendrimers, can now be made in a facile, straightforward manner using IMCI as the ideal diisocyanate building block. Coating applications of this unique building block are not restricted to these perfect branching polymers, but also include isocyanate-functional coating resins. Without any increase in polydispersity, a hydroxyl-functional polyester can be end-capped with the IMCI diisocyanate and subsequently serve as a crosslinker in powder coatings.     

A Light‐Blue Phosphorescent Dendrimer for Efficient Solution‐Processed Light‐Emitting Diodes

We describe the preparation of a dendrimer that is solution‐processible and contains 2‐ethylhexyloxy surface groups, biphenyl‐based dendrons, and a fac‐tris[2‐(2,4‐difluorophenyl)pyridyl]iridium(III ) core. The homoleptic complex is highly luminescent and the color of emission is similar to the heteroleptic iridium(III ) complex, bis[2‐(2,4‐difluorophenyl)pyridyl]picolinate iridium(III ) (FIrpic). To avoid the change in emission color that would arise from attaching a conjugated dendron to the ligand, the conjugation between the dendron and the ligand is decoupled by separating them with an ethane linkage. Bilayer devices containing a light‐emitting layer comprised of a 30 wt.‐% blend of the dendrimer in 1,3‐bis(N‐carbazolyl)benzene (mCP) and a 1,3,5‐tris(2‐N‐phenylbenzimidazolyl)benzene electron‐transport layer have external quantum and power efficiencies, respectively, of 10.4 % and 11 lm W^–1 at 100 cd m^–2 and 6.4 V. These efficiencies are higher than those reported for more complex device structures prepared via evaporation that contain FIrpic blended with mCP as the emitting layer, showing the advantage of using a dendritic structure to control processing and intermolecular interactions. The external quantum efficiency of 10.4 % corresponds to the maximum achievable efficiency based on the photoluminescence quantum yield of the emissive film and the standard out‐coupling of light from the device.     

Dendron-functionalized perylene diimides with carrier-transporting ability for red luminescent materials

This paper presents a series of dendrimers via a convergent synthetic approach with three generations, which contain perylene diimide cores, Fréchet-type poly(aryl ether) dendrons, and carbazole (CZ) or oxadiazole (OXZ) peripheral functional groups. The higher generation dendrimer has an obvious site-isolation or dilution effect of dendrons, which results in a relatively small red-shift of absorption and emission spectra when it forms a solid thin film for applications. The interactions between peripheral units and perylene diimide core in the dendrimers are also studied by steady-state and time-resolved fluorescence spectra under both direct and indirect excitation. The fluorescence data show that there exist two possible mechanisms, Förster energy transfer (FRET) and photo-induced electron transfer (PET), for dendrimers bearing carbazole units. No enhanced core fluorescence is observed because the energy transfer or light-harvesting potential of peripheral carbazole is counteracted by PET. While for dendrimers bearing oxadiazole units, no PET can take place between OXZ and perylene diimide since both of them are high electron affinity. The FRET and higher light-harvesting ability of oxadiazole without PET interfering result in the distinct enhancement of core emission in higher generation dendrimers. DSC results indicate that the incorporation of Fréchet-type poly(aryl ether) dendrons can improve the amorphous property and increase glass transition temperature (T_g). The preliminary EL results with single-layer architectures demonstrate that these dendrimers could be utilized as a promising kind of active red luminescent emitters with carrier-transporting ability. EL emission has the same recombination zone as PL, indicating that the recombination of excitons in fabricated EL devices is not close to cathode or anode vicinity. It is suggested that the site-isolation effect of dendron wedges is attributed to prevent the core luminorphores from approaching electrodes efficiently.     

Immobilization of dendrimers on Si-C linked carboxylic acid-terminated monolayers on silicon(111)

Poly(amidoamine) dendrimers were attached to activated undecanoic acid monolayers, covalently linked to smooth silicon surfaces via Si-C bonds. The resulting ultra-thin dendrimer films were characterized by X-ray photoelectron spectroscopy (XPS), X-ray reflectometry (XR) and atomic force microscopy (AFM). XPS results suggested amide bond formation between the dendrimer and the surface carboxylic acid groups. XR yielded thicknesses of 10 Å for the alkyl region of the undecanoic acid monolayer and 12 Å for the dendrimer layer, considerably smaller than the diameter of these spherical macromolecules in solution. This was consistent with AFM images showing collapsed dendrimers on the surface. It was concluded that the deformation arose from a large number of amine groups on the surface of each dendrimer reacting efficiently with the activated surface, whereby the dendrimers can deform to fill voids while spreading over the activated surface to form a homogeneous macromolecular layer.     

Dendrosome-based gene delivery

Gene transfer to humans requires carriers for the plasmid DNA, which can efficiently and safely carry the gene into the nucleus of the desired cells. The purpose of the present study was to design dendrosomes as a novel, non-viral, vesicular, gene delivery vector and to carry out a comparative study of the relative transfection efficiencies of dendrosomes with standard non-viral, gene delivery vectors.

Fourth-generation PAMAM dendrimers were synthesized by double the Michael addition reaction and extensively characterized. The dendrimer–DNA complex was prepared and was confirmed by CD spectroscopy. The dendrosomes were prepared by the reverse phase evaporation method and the entrapment efficiency of the dendrosomal formulation was estimated. In vitro toxicity of the formulation was evaluated by hemolytic toxicity and cytotoxicity studies. Transfection efficiency of the dendrosomal formulations was compared to standard non-viral gene delivery vectors in HEK-293 cell.

The results of hemolytic toxicity cytotoxicity studies demonstrated that the dendrosomes possess negligible toxicity as compared to the other formulations and are suitable for in vivo administration. The results of transfection of HEK-293 cell with PGL2 showed that the dendrosomal formulation DF3 possesses superior transfection efficiency against other delivery systems under study.

Dendrosomes possess tremendous potential as a novel non-viral and non-toxic gene delivery vector.     

Can dendrimer based nanoparticles fight neurodegenerative diseases? Current situation versus other established approaches

For several decades, the treatment of central nervous system (CNS) disorders such as, for instance, Alzheimer’s disease (AD), Huntington’s disease (HD), and Parkinson’s disease (PD) represented an important challenge due to the difficulty in delivering drug molecules and imaging agents to the brain. Two strategies have been developed aimed at achieving the efficient delivery of drugs to the brain: invasive (e.g., temporary osmotic Blood Brain Barrier (BBB) opening, direct local delivery of nanoparticles with encapsulated CNS drugs etc.) and noninvasive approaches. As a part of the noninvasive approach among systemic delivery of drug molecules across BBB using nanocarriers, dendrimers represent promising therapeutics agents per se or nanocarriers of CNS drugs and for gene therapies. This original review emphasizes and analyzes the use of dendrimers as promising systems in the treatment of AD and PD, ischemia/reperfusion injury, neuroinflammation including cerebral palsy, neurological injury after cardiac surgery and particularly after hypothermic circulatory arrest, and for retinal degeneration purposes.     

Cytoprotective activities of water-soluble fullerenes in zebrafish models

Using zebrafish (Danio rerio) embryos as a model system, we compared the antioxidant and cytoprotective effects of a series of new water-soluble fullerenes 1–12. Since zebrafish embryos are transparent during the first week of life, the effects of fullerenes on multiple organ systems, including CNS, PNS, and heart, could be assessed in situ. Both positively charged and negatively charged water-soluble fullerenes were added at concentrations between 1 and 500?µM to 96 well plates containing zebrafish embryos at 24–120 hours post fertilization (hpf). Direct toxicity of each fullerene compound was assessed by LC50. In addition, we assessed the ability of each fullerene to protect against toxicity induced by known chemical toxins in this system. Four different drug/chemical toxicity models were used in our study: (i) protection of neuromast hair cells from gentamicin-induced toxicity; (ii) protection of neuromast hair cells from cisplatinum-induced toxicity; (iii) protection of tyrosine hydroxylase-containing dopaminergic CNS neurons from 6-hydroxydopamine toxicity; and (iv) protection of total CNS neurons from 6-hydroxydopamine toxicity. Our results indicate that (i) positively charged water-soluble fullerenes tend to exhibit greater toxicity than negatively charged fullerenes with similar structures; (ii) toxicity varies considerably among negatively charged fullerenes from very low to moderate, depending on structural features; (iii) dendrofullerenes 2–7 (monoadducts of C₆₀) show stronger protection against cisplatinum toxicity in neuromast hair cells while then the e,e,e-trismalonic acid 1 (so called C3) shows stronger protection against gentamicin-induced cytotoxicity in the same cells; (iv) C3 (1) is relatively unstable in all aqueous solvents tested and breaks down mainly through decarboxylation reactions to form penta, tetra and tris carboxylated forms, which exhibit increased toxicity in vivo compared with C3 (1). Our findings indicate that water-soluble fullerenes can protect against chemical toxin-induced apoptotic cell death in a vertebrate, whole-animal model that may be useful for predicting the efficacy and toxicity of these compounds in mammals. Furthermore, the relative potential for pharmacologic use of these compounds varies considerably with respect to stability.     

Electrical switching and memory phenomena observed in redox dendrimer thin films

This article reports on the fabrication of dendrimer molecular thin film sandwich devices with electrical switching and memory properties. The storage media consists of a redox-gradient N,N?-(1,4-phenylene)bis(N,N′N′N″,N″-pentakis(4-methoxyphenyl)-1,3,5-benzenetriamine) (4AAPD) dendrimer layer sandwiched between two N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine (TPD) thin films. The TPD thin films are used as potential barriers. The 4AAPD layer acts as a potential well where redox-state changes and consequent electrical transitions of the embedded 4AAPD molecules can be effectively triggered. Experimental results indicate that electrical switching could be reproducibly obtained in the dendrimer sandwiches upon crossing a threshold bias voltage. After switching, the device conductivity can be increased more than three orders of magnitude, which is stable for several days in ambient conditions. This work demonstrates the possibility of using solid-state redox-gradient dendrimer layer as information storage media.