Development of biodegradable hyperbranched core-multishell nanocarriers for efficient topical drug delivery.

The topical application of drugs allows for a local application in skin disease and can reduce side effects. Here we present biodegradable core-multishell (CMS) nanocarriers which are composed of a hyperbranched polyglycerol core functionalized with diblock copolymers consisting of polycaprolactone (PCL) and poly(ethylene glycol) (mPEG) as the outer shell. The anti-inflammatory drug Dexamethasone (Dexa) was loaded into these CMS nanocarriers. DLS results suggested that Dexa loaded nanoparticles mostly act as a unimolecular carrier system. With longer PCL segments, a better transport capacity is observed. In vitro skin permeation studies showed that CMS nanocarriers could improve the Nile red penetration through the skin by up to 7 times, compared to a conventional cream formulation. Interestingly, covalently FITC-labeled CMS nanocarriers remain in the stratum corneum layer. This suggests the enhancement is due to the release of cargo after being transported into the stratum corneum by the CMS nanocarriers. In addition, the hPG-PCL-mPEG CMS nanocarriers exhibited good stability, low cytotoxicity, and their production can easily be scaled up, which makes them promising nanocarriers for topical drug delivery.

Dendritic nanocarriers based on hyperbranched polymers.

Hyperbranched polymers are obtained through one-step polymerization reactions and exhibit properties that are very similar to those of perfect dendrimer analogues. Therefore, hyperbranched polymers are a suitable alternative for perfect dendrimers as building blocks for dendritic nanocarrier systems. With regard to using soluble hyperbranched polymers as carrier systems, their flexible chains are a major benefit as they can adopt and compartment guest molecules. Upon encapsulation, the properties of the host decides the fate of the guest, e.g., solubility, but the host can also shield a guest from the environment and protect it, e.g., from degradation and deactivation. With regard to the advantages of using hyperbranched polymers as nanocarrier systems and their scalable synthesis, we will discuss different types of hyperbranched polymers and their application as nanocarrier systems for drugs, dyes, and other guest molecules.

Enantioselective Rh-catalyzed domino transformations of alkynylcyclohexadienones with organoboron reagents.

A new enantioselective rhodium-catalyzed domino reaction is described that gives access to fused heterocycles by desymmetrization of alkyne-tethered cyclohexadienones. Two new C-C bonds and two stereocenters are formed in one step with good enantioselectivity. In contrast to prior reports, it was found that a vinylidene is not involved in the product formation but that syn-addition of the rhodium-aryl species onto the alkyne takes place.

Towards recyclable NAD(P)H regeneration catalysts.

Rh(III)-TsDPEN, an immobilized analog of the well-known [Cp*Rh(bpy)(H(2)O)](2+) was evaluated as a heterogeneous, recyclable regeneration catalyst for reduced oxidoreductase cofactors [NAD(P)H]. Repeated use of this catalyst was established and the catalytic properties were initially investigated. Apparently, Rh(III)-TsDPEN is prone to severe diffusion limitations, necessitating further developments. Overall, a promising concept for chemoenzymatic redox catalysis is proposed, which may overcome some of the current limitations such as catalyst cost and incompatibility of Rh with some biocatalysts.

Quasi-homogeneous hydrogenation with platinum and palladium nanoparticles stabilized by dendritic core-multishell architectures.

Platinum and palladium nanoparticles, supported and stabilized by polymeric core-shell architectures, proved to be active catalysts for hydrogenation reactions. Here, two different reactions were used as probes to investigate the influence of the polymeric support: the hydrogenation of α-methyl styrene (AMS) to cumene and the partial hydrogenation of 1,5-cyclooctadiene (COD). We found that the stability of the nanoparticles and the rate of reaction are higher in the presence of a hydrophobic octadecyl shell within a three-shell polymer system. The kinetic study of AMS hydrogenation showed much higher activities for palladium nanoparticles than for platinum nanoparticles, and the obtained results (e.g., 35 kJ/mol for the activation energy) are of the same order of magnitude as reported earlier for palladium supported on alumina. A methanol/n-heptane biphasic mixture was tested for catalyst recycling and allowed for highly efficient catalyst separation with very low metal leaching.