Nanogel engineering for new nanobiomaterials: from chaperoning engineering to biomedical applications

Nanosize hydrogels (nanogels) are polymer nanoparticles with three‐dimensional networks, formed by chemical and/or physical cross‐linking of polymer chains. Recently, various nanogels have been designed, with a particular focus on biomedical applications. In this review, we describe recent progress in the synthesis of nanogels and nanogel‐integrated hydrogels (nanogel cross‐linked gels) for drug‐delivery systems (DDS), regenerative medicine, and bioimaging. We also discuss chaperone‐like functions of physical cross‐linking nanogel (chaperoning engineering) and organic‐inorganic hybrid nanogels. © 2010 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.201000008     

Nano‐Encapsulation of Lipase by Self‐Assembled Nanogels: Induction of High Enzyme Activity and Thermal Stabilization

The effects of self‐assembled polysaccharide nanogels on colloidal and thermal stability of lipase from Pseudomonas cepacia were investigated. The enzyme activity, especially k_cat, drastically increased in the presence of nanogels of cholesterol‐bearing pullulan (CHP). The thermostability of lipase complex increased because the denaturation temperature of lipase increased by more than 20 °C by complexation with CHP nanogels. Lipase denaturation and aggregation upon heating was effectively prevented by complexation with CHP nanogels. Moreover, complexation with CHP nanogels protected lipase from lyophilization‐induced aggregation. Nano‐encapsulation with CHP nanogel is a useful method for colloidal and thermal stabilization of unstable enzyme.

     

Study on thermal stability of tertiary pyridine resin

The fundamental properties of tertiary pyridine resin (TPR) and its mixtures with methanol/HCl and HNO₃ were investigated in order to evaluate the thermal stability of TPR and to determine the conditions necessary to avoid runaway reactions. Based on experimental DSC results, it was found that TPR with HCl was thermally stable, but strong decomposition was possible with TPR in the presence of HNO₃. From the results of heating tests on the gram scale, TPR with HNO₃ reacted violently under high temperature regardless of HNO₃ concentration and presence or absence of methanol. However, it was considered that the violent exothermic reaction could be controlled by heating temperature.     

Extended applications of di-tert-butylsilylene-directed alpha-predominant galactosylation compatible with C2-participating groups toward the assembly of various glycosides

The high versatility of di-tert-butylsilylene(DTBS)-directed alpha-predominant galactosylation have been extended to the construction of difficult glycan sequences. First, to investigate the compatibility of the alpha-predominant reaction with various glycosylation systems a variety of 4,6-O-DTBS-tethered galactosaminyl or galactosyl donors were synthesized efficiently, which have C2-participating groups with a wide variety of leaving groups such as alkylsulfenyl, halide, trichloroacetimidate groups. The results of the detailed examination of the glycosylation reaction using the glycosyl donors showed the wide scope of the 4,6-DTBS-directed alpha-galactosylation. In the next step, the stereoselective construction of alpha-GalN-Ser/Thr sequences was examined by employing the DTBS-directed glycosylation. As a result, various types of serine and threonine derivatives were glycosylated alpha-selectively, producing alpha-GalN-Ser/Thr sequences in high yields. Moreover, the DTBS-directed galactosylation was successfully applied for the synthesis of alpha-tetrasaccharyl-Ser segment of glycophorin A.     

Pd(OAc)2-catalyzed carbonylation of amines

A phosphine-free catalytic system [Pd(OAc)2-Cu(OAc)2-air] induced a substrate-specific carbonylation of amines in boiling toluene under CO gas (1 atm). Symmetrical N,N'-dialkylureas were obtained by the carbonylation of primary amines. N,N,N'-Trialkylureas were selectively formed by addition of a secondary amine to the above reaction vessel. Secondary amines did not give tetraalkylureas. However, dialkylamines with a phenyl group on their alkyl chains, such as N-monoalkylated benzylic amine or phenethylamine derivatives, underwent a direct aromatic carbonylation to afford five- or six-membered benzolactams. In the carbonylation, the chelation effect or steric repulsion between Pd(II) and the meta-substituent in the ortho-palladation and the ring sizes of cyclopalladation products that were formed prior to carbonylation were found to generate good site selectivity and increase the reaction rate. In contrast, carbonylation of omega-arylalkylamines with a hydroxyl group gave neither ureas nor benzolactams but instead produced 1,3-oxazolidinones smoothly. Hydrochlorides of amines also underwent carbonylation to afford the corresponding amides under the conditions used. This procedure made it possible to prepare ureas of amino acid esters and N-alkylcarbamates in practical yields.     

Highly Blood Compatible Titania Gel

We examined blood compatibility of titania gels prepared through a sol-gel processing or yielded on titanium substrates by treating with hydrogen peroxide or simple heating. The blood compatibility was evaluated in terms of blood clotting time and correlated to the crystalline phases, roughness, specific surface area, and wettability. The sol-gel derived titania gel heated above 200°C had good blood compatibility. Ti substrate treated with hydrogen peroxide and subsequently heated at 550°C showed the best blood compatibility among the Ti substrates with or without the chemical treatment and heat-treatment. The specimen consisted of rutile and anatase phases, and had hydrophilic surface.     

A rapid and effective synthesis of propylene carbonate using a supercritical CO2-ionic liquid system

The synthesis of propylene carbonate from propylene oxide and carbon dioxide under supercritical conditions in the presence of 1-octyl-3-methylimidazolium tetrafluoroborate was achieved in nearly 100% yield and 100% selectivity within 5 minutes, whose TOF value is 77 times larger than those so far reported.     

Sodium borosilicate glasses prepared by the sol-gel process

A sodium borosilicate gel of composition 80SiO₂·15B₂O₃·5Na₂O (wt%) was prepared from tetraethyl orthosilicate, trimethyl borate, sodium methylate, H₂O, and HCl as the catalyst. Variation of specific surface area and porosity as a function of heating temperature indicated that closed pores were opened at temperatures lower than 400°C and collapsed above 450°C. From TG and DTA curves, about 19% Si and B atoms are evaluated to have −OH bonds. X-ray diffraction patterns indicated crystallization of low-cristobalite out of the gel when it was heated at 700°C for 5 h, showing a difference from a melt-quenched glass of the same composition.