Regiospecificity of Immobilized Candida antarctica Lipase B (CAL-B) towards 2,3-Diacyl-1-O-alkyl Glyceryl Ether in Ethanol.

Highly pure 2,3-dioleoyl-1-O-alkyl glyceryl ether (DOGE), whose 1-position is a lipase-tolerant ether bond, was chemically synthesized and its detailed regioselectivity and acyl transfer were confirmed. During ethanolysis using immobilized Candida antarctica lipase B (CAL-B) with DOGE as the substrate, monooleoyl-1-O-alkyl glyceryl ethers (MOGEs) and a few 1-alkyl glyceryl ethers were formed upon consumption of the substrate. The structure of MOGE was confirmed using nuclear magnetic resonance spectroscopy and only the isomer of 2-MOGE was formed, indicating that CAL-B has complete α- regiospecificity. During ethanolysis, 3-MOGE was formed via acyl migration. These results indicate that the formation of 1-alkyl glyceryl ethers is not due to the imperfect regiospecificity of CAL-B, but rather due to ethanolysis of the formed 3-MOGE. The ethanolysis rate at the 3-α-position of DOGE was faster and the rate of acyl transfer was slightly slower for chain lengths greater than 14. These results show for the first time that both deacylation at the 3-position and acyl migration from the 2- to 3-position are affected by the structure of 1-position.

DBU-intercalated γ-titanium phosphate as a latent thermal catalyst in the reaction of glycidyl phenyl ether (GPE) and hexahydro-4-methylphthalic anhydride (MHHPA).

The capabilities and performance of γ-titanium phosphate (γ-TiP) with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a latent thermal catalyst were investigated by the copolymerization of glycidyl phenyl ether (GPE) and hexahydro-4-methylphthalic anhydride (MHHPA) at different temperatures for a period of one hour. Polymerization was not observed until the reactants were heated to 100 °C. Upon increasing the temperature to 120 °C, the conversion in the presence of γ-TiP·DBU as a catalyst showed 98% conversion in 1 h. The thermal stability of GPE and MHHPA reacted in the presence of γ-TiP·DBU at 40 °C for 144 h resulted in less than 7% conversion of GPE. The conversion of GPE did not show a significant increase at 40 °C.

Photo/Thermo Dual Stimulus-Responsive Liquid Marbles Stabilized with Polypyrrole-Coated Stearic Acid Particles.

In this study, we report on the fabrication of photo/thermo dual stimulus-responsive liquid marbles (LMs) that can be disrupted by light irradiation and/or heating. To stabilize the LMs, we synthesized micrometer-sized stearic acid (SA) particles coated with overlayers of polypyrrole (PPy) by aqueous chemical oxidative seeded dispersion polymerization. The SA/PPy core-shell particles could adsorb at the air-water interface to stabilize LMs by rolling water droplets on the particle powder bed. The presence of SA, known as a phase-change material, which undergoes a transition from solid to liquid by heating, and PPy, which can transduce light to heat, gives rise to the photo and thermo dual stimulus-responsive characters of the LMs. The disruption of the LMs could be induced in a cascade manner: light irradiation on the LM induced a temperature increase, followed by melting of the SA component on the LM surface, leading to its disruption and release of the inner water. The disruption time is linked to the PPy loading and light irradiation power, and it can be tuned from quasi-instantaneous to a few tens of seconds. The melting of SA due to a light-induced phase change from the solid to liquid state is a new mechanism to trigger the disruption of LMs. We finally demonstrated two applications of the LMs as a light-responsive microreactor and a sensor.

Oriented growth of stacking α-cobalt hydroxide salt continuous films and their topotactic-like transformation to oriented mesoporous films of Co3O4 and CoO.

Mesoporous metal oxide films composed of nanocrystal assemblies with an aligned crystallographic orientation are key nanostructures for efficient interfacial reactions; however, the development of a simple and versatile method for their formation on substrates still constitutes a challenge. Here we report the template-free centimetre-scale formation of novel cobalt oxide films of Co3O4 and CoO with a [111]-oriented mesoporous structure starting from stacking cobalt hydroxide continuous films. The cobalt hydroxide precursor is formed electrochemically on conductive substrates from a Co(NO3)2 aqueous solution at room temperature. A thorough characterization by means of scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV-vis-NIR spectroscopy, IR spectroscopy and Raman spectroscopy analyses reveals that the precursor film is an α-type layered cobalt hydroxide salt (α-Co-LHS) containing interlayer nitrate and hydrated water, i.e., α-Co(OH) x (NO3) y ·nH2O, with a [001]-oriented stacking film structure. Heat treatment of the [001]-α-Co-LHS films using different conditions, i.e., under air at 550 °C or under vacuum at 500 °C, results in the selective formation of Co3O4 or CoO mesoporous films, respectively. A plausible explanation for the observed centimetre-scale topotactic-like transformation from α-Co-LHS[001] to Co3O4[111] or CoO[111] is given according to the atomic framework similarity between the hydroxide precursor and the final oxides.

Zeolitic Imidazolate Frameworks as Latent Thermal Initiators in the Curing of Epoxy Resin.

The curing of a mixture of glycidyl phenyl ether (GPE) and hexahydro-4-methylphthalic anhydride (MHHPA) with zeolitic imidazolate frameworks (ZIFs)-ZIF-7, ZIF-8, ZIF-11, and ZIF-14-as latent thermal initiators has been critically evaluated. For ZIF-8 and ZIF-14, the % conversion values for GPE were 92 and 93%, respectively, for curing at 100 °C and for 1 h. With regard to the stability of ZIF-8 and ZIF-14 in the GPE-MHHPA mixture, the % conversion values for GPE were 11 and 12% for storage over 8 days at 25 °C. The ZIF-8 and ZIF-14 initiators exhibited excellent thermal latency for heating at 100 °C and showed good stability for storage at 25 °C. To evaluate the practicality of the resin curing system, the reactions of 2,2-bis(4-glycidyloxyphenyl)propane (DGEBA) and MHHPA with ZIFs were studied by differential scanning calorimetry. Prominent exothermic peaks for ZIF-8 and ZIF-14 were observed at 157 and 162 °C, respectively; by comparison, for the commercially available microencapsulated latent thermal initiators HX-3088 and HX-3722, the respective peak maxima were 177 and 181 °C, respectively. The exothermic peak maxima for ZIF-8 and ZIF-14 were lower than those for HX-3088 and HX-3722. The ZIF-8 and ZIF-14 initiators can be stored in precured epoxy resin at 25 °C and cured by lower temperatures compared with commercially-available initiators HX-3088 and HX-3722.

Mechanistic Study on Allylic Arylation in Water with Linear Polystyrene-Stabilized Pd and PdO Nanoparticles.

The catalytic cycle of allylic arylation in water catalyzed by linear polystyrene-stabilized Pd or PdO nanoparticles (PS-PdNPs or PS-PdONPs) was investigated. Stoichiometric stepwise reactions indicated that the reaction did not proceed stepwise on the surface of the catalyst. In the case of the reaction with PS-PdNPs, the leached Pd species is the catalytically active species and the reaction takes place through a similar reaction pathway accepted in the case of a complex catalyst. In contrast, allylic arylation using PS-PdONPs as a catalyst occurs via a Pd(II) catalytic cycle.

Poly(tetrafluoroethylene)-Stabilized Metal Nanoparticles: Preparation and Evaluation of Catalytic Activity for Suzuki, Heck, and Arene Hydrogenation in Water.

Poly(tetrafluoroethylene)-stabilized Pd nanoparticles (PTFE-PdNPs) were prepared in water with 4-methylphenylboronic acid as a reductant and characterized using powder X-ray diffraction, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy, and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Small PdNPs with a fairly uniform size were obtained in the presence of PTFE, whereas aggregation of palladium was observed in the absence of PTFE. PTFE-PdNPs showed high catalytic activity for the Suzuki coupling reaction in water and were reused without any loss of activity. No palladium species were observed by ICP-AES analysis in the reaction solution after the reaction, nor was any change in particle size observed after the recycle experiment. PTFE-PdNPs also exhibited excellent catalytic activity and reusability for the Heck reaction in water. Although palladium species were not detected in the reaction solution after the reaction, aggregates and smaller sizes of PdNPs were observed in the TEM image of the recovered catalyst. PTFE was also useful as the stabilizer of rhodium nanoparticles (RhNPs) prepared by reduction with NaBH4. PTFE-RhNPs showed high catalytic activity and reusability toward arene hydrogenation under mild conditions.

Recyclable polymer-supported nanometal catalysts in water.

Two types of polymer-supported nanometal catalysts with high catalytic activity and recyclability in water have been developed. One catalyst was composed of linear polystyrene-stabilized metal nanoparticles (PS-MtNPs). A palladium catalyst (PS-PdONPs) was prepared in water by the thermal decomposition of Pd(OAc)2 in the presence of polystyrene. The degree of immobilization of Pd, but not the size of the Pd nanoparticles, was dependent on the molecular weight and cross-linking of the polystyrene. The PS-PdONPs exhibited high catalytic activity for Suzuki, Heck, and Sonogashira coupling reactions in water and they could be recycled without loss of activity. Linear polystyrene was also suitable as a stabilizer for in situ generated PdNPs and PtNPs. The second catalyst was a polyion complex that was composed of poly[4-chloromethylstyrene-co-(4-vinylbenzyl)tributylammonium chloride] and poly(acrylic acid)-stabilized PdNPs (PIC-PdNPs). Aggregation and redispersion of PIC-PdNPs were easily controlled by adjusting the pH value of the solution.

Linear polystyrene-stabilized PdO nanoparticle-catalyzed Mizoroki-Heck reactions in water.

Linear polystyrene-stabilized PdO nanoparticles (PS-PdONPs) were prepared by thermal decomposition of Pd(OAc)(2) in the presence of polystyrene. X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicated the production of PdO nanoparticles. The loading of palladium was determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). PS-PdONPs exhibited high catalytic activity for Mizoroki-Heck reactions under air in water and could be recycled without loss of activity.

Linear polystyrene-stabilized palladium nanoparticles-catalyzed C-C coupling reaction in water.

Linear polystyrene-stabilized PdO nanoparticles (PS-PdONPs) were prepared in water by thermal decomposition of Pd(OAc)(2) in the presence of polystyrene. The immobilization degree of palladium was dependent on the molecular weight of polystyrene, while the size of the Pd nanoparticles was not. Linear polystyrene-stabilized Pd nanoparticles (PS-PdNPs) were also prepared using NaBH(4) and phenylboronic acid as reductants. The catalytic activity of PS-PdONPs was slightly higher than that of PS-PdNPs for Suzuki coupling reaction in water. PS-PdONPs exhibited high catalytic activity for Suzuki and copper-free Sonogashira coupling reactions in water and recycled without loss of activity.

Synthesis and characterization of polypyrrole-palladium nanocomposite-coated latex particles and their use as a catalyst for Suzuki coupling reaction in aqueous media.

Polypyrrole-palladium (PPy-Pd) nanocomposite was deposited in situ from aqueous solution onto micrometer-sized polystyrene (PS) latex particles. The PS seed particles and resulting composite particles were extensively characterized with respect to particle size and size distribution, morphology, surface/bulk chemical compositions, and conductivity. PPy-Pd nanocomposite loading onto the PS seed latex particles was systematically controlled over a wide range (10-60 wt %) by changing the weight ratio of the PS latex and PPy-Pd nanocomposite. Pd loading was also controlled between 6 and 33 wt %. The conductivity of pressed pellets increased with the PPy-Pd nanocomposite loading and four-point probe measurements indicated conductivities ranging from 3.0 x 10(-1) to 7.9 x 10(-6) S cm(-1). Hollow capsule and broken egg-shell morphologies were observed by scanning/transmission electron microscopy after extraction of the PS component from the composite particles, which confirmed a PS core and PPy-Pd nanocomposite shell morphology. X-ray diffraction confirmed that the production of elemental Pd and X-ray photoelectron spectroscopy indicated the existence of elemental Pd on the surface of the composite particles. Transmission electron microscopy confirmed that nanometer-sized Pd particles were distributed in the shell. The nanocomposite particles functioned as an efficient catalyst for Suzuki-type coupling reactions in aqueous media for the formation of carbon-carbon bonds.

Facile preparation of linear polystyrene-stabilized Pd nanoparticles in water.

Palladium nanoparticles can be readily stabilized onto linear polystyrene by a simple procedure. The resultant polystyrene-stabilized Pd has high catalytic activity for Suzuki-Miyaura cross-coupling reaction in water and can be reused without loss of activity.

"Beta-cis-SAr effect" on decarbonylation from alpha,beta-unsaturated acyl and aroyl complexes.

Lone pair of heteroatom located at the beta-cis position in alpha,beta-unsaturated acyl and aroyl group 10 metal complexes dramatically facilitated the stoichiometric and catalytic decarbonylation reactions.

Photo-and-thiol-driven trans insertion of phenylacetylene into H-Pt bonds.

The photo-and-thiol-driven trans insertion of phenylacetylene into H-Pt bonds of Pt(X)(H)(PPh3)2 (X = SAr, Cl, Br, and I) took place to afford Pt[(Z)-C(H)=CH(Ph)](X)(PPh3)2 in good yields.