High-water-content mouldable hydrogels by mixing clay and a dendritic molecular binder.

With the world's focus on reducing our dependency on fossil-fuel energy, the scientific community can investigate new plastic materials that are much less dependent on petroleum than are conventional plastics. Given increasing environmental issues, the idea of replacing plastics with water-based gels, so-called hydrogels, seems reasonable. Here we report that water and clay (2-3 per cent by mass), when mixed with a very small proportion (<0.4 per cent by mass) of organic components, quickly form a transparent hydrogel. This material can be moulded into shape-persistent, free-standing objects owing to its exceptionally great mechanical strength, and rapidly and completely self-heals when damaged. Furthermore, it preserves biologically active proteins for catalysis. So far no other hydrogels, including conventional ones formed by mixing polymeric cations and anions or polysaccharides and borax, have been reported to possess all these features. Notably, this material is formed only by non-covalent forces resulting from the specific design of a telechelic dendritic macromolecule with multiple adhesive termini for binding to clay.

Conjugation effects of various linkers on Gd(III) MRI contrast agents with dendrimers: optimizing the hydroxypyridinonate (HOPO) ligands with nontoxic, degradable esteramide (EA) dendrimers for high relaxivity.

One essential requirement for more sensitive gadolinium-based MRI contrast agents is to slow the molecular tumbling of the gadolinium(III) ion, which increases the gadolinium's relaxivity (i.e., its ability to speed up the NMR relaxation of nearby water molecules). One route to this is through conjugation to high-molecular-weight polymers such as dendrimers. In this work, amine-functionalized TREN-bis(1,2-HOPO)-TAM-ethylamine and TREN-bis(1-Me-3,2-HOPO)-TAM-ethylamine ligands have been synthesized and attached to biocompatible 40 kDa esteramide (EA)- and poly-l-lysine (PLL)-based dendrimers capable of binding up to eight gadolinium complexes. These conjugates have T(1) relaxivities of up to 38.14 ± 0.02 mM(-1) s(-1) per gadolinium at 37 °C, corresponding to relaxivities of up to 228 mM(-1) s(-1) per dendrimer molecule. This relaxivity expressed on a "per Gd" basis is several times that of the small-molecule complexes and an order of magnitude higher than that of current commercial agents. Because of their high performance and low toxicity, these macromolecules may constitute an attractive complement to currently available gadolinium(III)-based contrast agents.

Acid-degradable cationic dextran particles for the delivery of siRNA therapeutics.

We report a new acid-sensitive, biocompatible, and biodegradable microparticulate delivery system, spermine modified acetalated-dextran (Spermine-Ac-DEX), which can be used to efficiently encapsulate siRNA. These particles demonstrated efficient gene knockdown in HeLa-luc cells with minimal toxicity. This knockdown was comparable to that obtained using Lipofectamine, a commercially available transfection reagent generally limited to in vitro use due to its high toxicity.

Two-photon degradable supramolecular assemblies of linear-dendritic copolymers.

Micelles of dendritic-linear copolymers have been developed to release a payload after infrared stimulus.

Doubly-dendronized linear polymers.

Doubly-dendronized polymers were synthesized by grafting polybenzyl ether dendrons onto a poly(hydroxy) styrene polymer with polyaliphatic esters.

Quinacridone-based molecular donors for solution processed bulk-heterojunction organic solar cells.

New soluble quinacridone-based molecules have been developed as electron donor materials for solution-processed organic solar cells. By functionalizing the pristine pigment core of quinacridone with solubilizing alkyl chains and light absorbing/charge transporting thiophene units, i.e., bithiophene (BT) and thienylbenzo[c][1,2,5]thiadiazolethienyl (BTD), we prepared a series of multifunctional quinacridone-based molecules. These molecular donors show intense absorption in the visible spectral region, and the absorption range and intensity are well-tuned by the interaction between the quinacridone core and the incorporated thiophene units. The thin film absorption edge extends with the expansion of molecular conjugation, i.e., 552 nm for N,N'-di(2-ethylhexyl)quinacridone (QA), 592 nm for 2,9-Bis(5'-hexyl-2,2'-bithiophene)-N,N'-di(2-ethylhexyl)quinacridone (QA-BT), and 637 nm for 4-(5-hexylthiophen-2-yl)-7-(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (QA-BTD). The change of molecular structure also influences the electrochemical properties. Observed from cyclic voltammetry measurements, the oxidation and reduction potentials (vs ferrocene) are 0.7 and -1.83 V for QA, 0.54 and -1.76 V for QA-BT, and 0.45 and -1.68 V for QA-BTD. Uniform thin films can be generated from both single component molecular solutions and blend solutions of these molecules with [6,6]-phenyl C70-butyric acid methyl ester (PC70BM). The blend films exhibit space-charge limited current (SCLC) hole mobilities on the order of 1×10(-4) cm(2) V(-1) S(-1). Bulk heterojunction (BHJ) solar cells using these soluble molecules as donors and PC70BM as the acceptor were fabricated. Power conversion efficiencies (PCEs) of up to 2.22% under AM 1.5 G simulated 1 sun solar illumination have been achieved and external quantum efficiencies (EQEs) reach as high as ∼45%.

Xenon biosensor amplification via dendrimer-cage supramolecular constructs.

Polyamidoamine dendrimers were synthesized with a single biotin moiety and used with cryptophane-A cages to form supramolecular biosensor constructs. These new biosensors amplified the NMR signals obtained from polarized xenon 8 times more than the original Xe biosensor.

A versatile new monomer family: functionalized 4-vinyl-1,2,3-triazoles via click chemistry.

Using facile, highly modular synthetic approaches, a new monomer family based on a 1,2,3-triazole-4-vinyl building block has been prepared, and various functional derivatives have been obtained. Subsequent homo- and copolymerization of these novel functionalized monomers gives polymeric materials with unique physical properties, combining many attractive features of more traditional monomers, such as styrene, vinylpyridine, and meth/acrylates.

Synthetic micelle sensitive to IR light via a two-photon process.

A micellar assembly of molecules constituted of poly(ethylene glycol) as the hydrophilic component and 2-diazo-1,2-naphthoquinone as the hydrophobic component was shown to be destroyed in a two-photon photoreaction triggered by infrared light with release of an encapsulated fluorescent probe molecule.

Dendronized linear polymers via "click chemistry".

Dendronized linear polymers are prepared from dendritic azides and poly(vinylacetylene) using "click chemistry." The Cu(I)-catalyzed Huisgen [2 + 3] cycloaddition is quantitative up to the third generation.