Syringe-Injectable, Self-Expandable, and Ultraconformable Magnetic Ultrathin Films.

Syringe-injectable biomaterials and medical devices are important as minimally invasive implants for diagnosis, therapy, and regenerative medicine. Free-standing polymeric nanosheets with a thickness less than 1 µm and a flexural rigidity less than 10-2 nN m are a promising platform of syringe-injectable, implantable devices that provide conformable and long-term stable adhesion to the target biological tissues for in situ delivery of therapeutic materials. Here, we developed free-standing ultrathin films (<1 µm thick) based on polyurethane-based shape-memory polymer (SMP) and magnetic nanoparticles (MNP), termed MNP-SMP nanosheets. With the temperature-mediated shape-memory effect of SMP, we overcome the limitation in the manipulation of the conventional polymer nanosheets. In particular, we demonstrated the following four capabilities using the 710 nm thick MNP-SMP nanosheet with the glass transition temperature (Tg) of 25 °C: (1) syringe-injectability through the medical needles, (2) self-expandability after ejection, (3) conformability and removability on the biological surfaces, and (4) guidability in an external magnetic field. The MNP-SMP nanosheets were readily interfaced with an additional layer of poly(lactic-co-glycolic acid) (PLGA) to extend their functionality as a carrier of molecular and cellular drugs. The MNP-SMP nanosheets will contribute to the development of advanced syringe-injectable medical devices as a platform to deliver drugs, sensors, cells, and engineered tissues to the specific site or lesion in the body for minimally invasive diagnosis and therapy.

In situ manipulation of catalyst performance via the photocontrolled aggregation/dissociation state of the catalyst.

A diamide armed with a photochromic azobenzene unit and a nucleophilic pyridyl group varied its aggregation/dissociation state depending on the trans/cis geometry of the azobenzene. The catalytic activity of the pyridyl group was closely linked to the aggregation/dissociation state and hence photoirradiation could manipulate the catalytic performance.

Solvent-dependent self-discrimination of bis(2-hydroxyphenyl)diamides.

Solvent-dependent, self-discrimination of diamides is described. Mixing a solution of (R)-1a and (S)-1a, which are valine-derived, bis(2-hydroxyphenyl)diamide-bearing, multiple hydrogen-bonding modules, in dichloromethane immediately led to the formation of a thick suspension comprising a 1:1 heterochiral aggregate of 1a. The solubility of heterochiral 1a was substantially lower in halogenated solvents than in ethyl acetate. A perusal of racemic crystal structures obtained from chloroform and ethyl acetate revealed a significant difference in the crystal-packing pattern, which is likely to be the basis for the pronounced difference in solubility. Specific self-discrimination of 1 a in an ensemble of eight structurally related molecules showcased the specific aggregation through the hydrogen-bonding network of the bis(2-hydroxyphenyl)diamide framework. The low solubility of heterochiral 1a in halogenated solvent was exploited to achieve high stereoselectivity in a catalytic asymmetric reaction by using a low enantiomeric excess sample of 1a.

anti-Selective catalytic asymmetric nitroaldol reaction via a heterobimetallic heterogeneous catalyst.

Full details of an anti-selective catalytic asymmetric nitroaldol reaction promoted by a heterobimetallic catalyst comprised of Nd(5)O(O(i)Pr)(13), an amide-based ligand, and NaHMDS (sodium hexamethyldisilazide) are described. A systematic synthesis and evaluation of amide-based ligands led to the identification of optimum ligand 1m, which provided a suitable platform for the Nd/Na heterobimetallic complex. During the catalyst preparation in THF, a heterogeneous mixture developed and centrifugation of the suspension allowed for separation of the precipitate, which contained the active catalyst and which could be stored for at least 1 month without any loss of catalytic performance. The precipitate promoted a nitroaldol (Henry) reaction for a broad range of nitroalkanes and aldehydes under heterogeneous conditions, affording the corresponding 1,2-nitroalkanol in a highly anti-selective (up to anti/syn = >40/1) and enantioselective manner (up to 98% ee). Inductively coupled plasma (ICP) and X-ray fluorescence (XRF) analyses revealed that the precipitate indeed included both neodymium and sodium, which was further supported by high-resolution ESI TOF MS spectrometry.

Linking structural dynamics and functional diversity in asymmetric catalysis.

Proteins, the functional molecules in biological systems, are sophisticated chemical devices that have evolved over billions of years. Their function is intimately related to their three-dimensional structure and elegantly regulated by conformational changes through allosteric regulators and a number of reversible or unidirectional post-translational modifications. This functional diversification in response to external stimuli allows for an orderly and timely progression of intra- and extracellular events. In contrast, enantioselective catalysts generally exhibit limited conformational flexibility and thereby exert a single specific function. Exploiting the features of conformationally flexible asymmetric ligands and the variable coordination patterns of rare earth metals, we demonstrate dynamic structural and functional changes of a catalyst in asymmetric catalysis, leading to two distinct reaction outcomes in a single flask.

Asymmetric catalysis via dynamic substrate/ligand/rare earth metal conglomerate.

A highly enantio- and diastereoselective catalytic asymmetric Mannich-type reaction of alpha-cyanoketones and N-Boc imines promoted by an amide ligand/Sc(OiPr)3 catalyst is described. The similar reaction outcome is obtained with/without precomplexation of catalyst, suggesting that reaction components in a non-ordered conglomerate mixture orchestrate to form an ordered transition state during the reaction. Spectroscopic data and Eyring plot are consistent with this assumption.