Hybridization of Particulate Methane Monooxygenase by Methanobactin-Modified AuNPs.

Particulate methane monooxygenase (pMMO) is a characteristic membrane-bound metalloenzyme of methane-oxidizing bacteria that can catalyze the bioconversion of methane to methanol. However, in order to achieve pMMO-based continuous methane-to-methanol bioconversion, the problems of reducing power in vitro regeneration and pMMO stability need to be overcome. Methanobactin (Mb) is a small copper-chelating molecule that functions not only as electron carrier for pMMO catalysis and pMMO protector against oxygen radicals, but also as an agent for copper acquisition and uptake. In order to improve the activity and stability of pMMO, methanobactin-Cu (Mb-Cu)-modified gold nanoparticle (AuNP)-pMMO nanobiohybrids were straightforwardly synthesized via in situ reduction of HAuCl4 to AuNPs in a membrane fraction before further association with Mb-Cu. Mb-Cu modification can greatly improve the activity and stability of pMMO in the AuNP-pMMO nanobiohybrids. It is shown that the Mb-Cu-modified AuNP-pMMO nanobiohybrids can persistently catalyze the conversion of methane to methanol with hydroquinone as electron donor. The artificial heterogeneous nanobiohybrids exhibited excellent reusability and reproducibility in three cycles of catalysis, and they provide a model for achieving hydroquinone-driven conversion of methane to methanol.

Tertiary amine-directed and involved carbonylative cyclizations through Pd/Cu-cocatalyzed multiple C-X (X = H or N) bond cleavage.

A novel Pd/Cu-cocatalyzed carbonylative cyclization by C-H activation and N-dealkylative C-N bond activation has been developed for the chemoselective construction of synthetically useful heterocycles. The N,N-dimethylamine group on o-indolyl-N,N-dimethylarylamines was found to act as both the directing group and reactive component in this C-H carbonylative cyclization reaction. Furthermore, a unique C-H oxidation/carbonylative lactonization of diarylmethylamines is firstly demonstrated under modified reaction conditions, which could be easily applicable to the one-step synthesis of multi-substituted phthalides bearing an N,O-ketal skeleton that is difficult to access by previously reported methods. Mechanistic studies implicate that Pd/Cu-cocatalyzed C-H oxidation/carbonylative lactonization is a sequential reaction system via Cu-catalyzed C(sp3)-H oxidation and Pd-catalyzed oxidative carbonylation of the C(sp2)-H bond. It was found that trace amounts of water are essential to promote the Cu-catalyzed C(sp3)-H oxidation of diarylmethylamine for the formation of the hydroxyl group, which could act as an in situ-formed directing group in the intramolecular carbonylative lactonization step.

Palladium-catalyzed olefination of aryl/alkyl halides with trimethylsilyldiazomethane via carbene migratory insertion.

The direct olefination of aryl/alkyl halides with trimethylsilyldiazomethane (TMSD) as a C1- or C2-unit was achieved successfully via a metal carbene migratory insertion process, which offered a new access to afford (E)-vinyl silanes and (E)-silyl-substituted α,ß-unsaturated amides in good yields and high chemoselectivity.

Methanobactin-mediated synthesis of bimetallic Au-Pd/Al2O3 toward an efficient catalyst for glucose oxidation.

A green bioreductive approach with methanobactin was adopted to fabricate bimetallic Au-Pd/Al2O3 catalysts for solvent-free oxidation of glucose to gluconic acid with H2O2 at atmospheric pressure. The catalyst was characterised by diffuse reflectance UV-vis spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction techniques to understand synergistic interactions between Au and Pd. Effects of Au to Pd molar ratio on the catalytic activity of Au-Pd/Al2O3 were investigated. The Au-Pd/Al2O3 catalyst with Au/Pd molar ratio of 0.8:0.2 exhibited excellent catalytic performance. With the catalyst, the oxidation activities of glucose to gluconic acid 2856 mmol min-1 g-1 and selectivity 99.6% were attained at 323 K with H2O2. The results indicated the activity and selectivity was affected by the ratio of Au/Pd on the Al2O3. The formation of Au0.8Pd0.2/Al2O3 was favourable for the catalytic reaction.

Biosynthesis of (S)-naproxen starch ester by Carica papaya lipase in intermittent opening reaction mode.

Inorder to brought S-naproxen into small intestine, an optically pure (S)-naproxen starch ester was produced by lipase through enantio-selective trans-esterification of racemic naproxen methyl ester with pretreatment starch in solvent system. With carefully selection of the reaction medium (isooctane), lipase (Carica Papaya Lipase, CPL) and the reaction mode (intermittent opening), a high conversion rate (48.6%) and enantiomeric excess of product (99.6%) was obtained. The slow release macromolecular (S)-Naproxen had been synthesized to improve the efficacy of racemic naproxen and overcome its side effects. The enanitomeric ratio of CPL (E=52.5) was higher than CRL (E=22) and greatly influenced by the byproduct methyl alcohol. The intermittent opening reaction mode was the effective way to remove the inhibition of methyl alcohol and to improve the enantio-selectivity of CPL. S-naproxen starch was confirmed by HPLC and 1H NMR. This method may also apply to preparation the other optically pure 2-phenylpropionic acid derivatives. S-naproxen starch was a new optically pure derivatives possessing emulsifying and slow release properties would be widely applied to the food, pharmaceutical and biomedical industries.

Synthesis of L-Ascorbyl Flurbiprofenate by Lipase-Catalyzed Esterification and Transesterification Reactions.

The synthesis of L-ascorbyl flurbiprofenate was achieved by esterification and transesterification in nonaqueous organic medium with Novozym 435 lipase as biocatalyst. The conversion was greatly influenced by the kinds of organic solvents, speed of agitation, catalyst loading amount, reaction time, and molar ratio of acyl donor to L-ascorbic acid. A series of solvents were investigated, and tert-butanol was found to be the most suitable from the standpoint of the substrate solubility and the conversion for both the esterification and transesterification. When flurbiprofen was used as acyl donor, 61.0% of L-ascorbic acid was converted against 46.4% in the presence of flurbiprofen methyl ester. The optimal conversion of L-ascorbic acid was obtained when the initial molar ratio of acyl donor to ascorbic acid was 5 : 1. kinetics parameters were solved by Lineweaver-Burk equation under nonsubstrate inhibition condition. Since transesterification has lower conversion, from the standpoint of productivity and the amount of steps required, esterification is a better method compared to transesterification.

Asymmetric Michael Addition of Aldimino Esters with Chalcones Catalyzed by Silver/Xing-Phos: Mechanism-Oriented Divergent Synthesis of Chiral Pyrrolines.

The mechanism-oriented reaction design for the divergent synthesis of chiral molecules from simple starting materials is highly desirable. In this work, aromatic amide-derived nonbiarylatropisomer/silver (silver/Xing-Phos) complex was used to catalyze the Michael addition of glycine aldimino esters to chalcones and successfully applied to the subsequent cyclocondensation to afford substituted cis-Δ(1)-pyrroline derivatives with up to 98 % ee. Besides the inherent performance of the chiral Ag/Xing-Phos catalyst system, it was found that the workup of such reactions played an important role for the stereoselective construction of stereodivergent Δ(1)-pyrrolines, in which an epimerization of the cis-Δ(1)-pyrrolines to the trans-isomers during was revealed.

Aromatic amide-derived non-biaryl atropisomers as highly efficient ligands in silver-catalyzed asymmetric cycloaddition reactions.

The synthesis of a series of aromatic amide-derived non-biaryl atropisomers with a phosphine group and multiple stereogenic centers is reported. The novel phosphine ligands exhibit high diastereo- and enantioselectivities (up to >99:1 d.r., 95-99 % ee) as well as yields in the silver-catalyzed asymmetric [3+2] cycloaddition of aldiminoesters with nitroalkenes, which provides a highly enantioselective strategy for the synthesis of optically pure nitro-substituted pyrrolidines. In addition, the experimental results with regard to the carbon stereogenic center as well as the amide stereochemistry confirmed the potential of hemilabile atropisomers as chiral ligand in catalytic asymmetric [3+2] cycloaddition reaction.

Colorimetric detection of melamine based on methanobactin-mediated synthesis of gold nanoparticles.

A simple and rapid field-portable colorimetric method for the detection of melamine in liquid milk was reported. Methanobactin (Mb) could reduce Au (III) to Au (0) and mediate the synthesis of gold nanoparticles (Au-NPs). Upon the addition of melamine, melamine interacted with oxazolone ring of Mb, which interrupted the formation of Au-NPs. Melamine could also stimulate the aggregation of formed Au-NPs. In this paper, these characteristics have been used to detect melamine in liquid milk by naked eyes observation with a detection limit of 5.56 × 10(-6)M (0.7 mg/kg). Further, the plasmon absorbance of the formed Au-NPs allowed the quantitative detection of melamine by UV-vis spectrometer. A linear correlation was existed between the absorbance and the melamine concentration ranging from 3.90 × 10(-7)M to 3.97 × 10(-6)M with a correlation coefficient of 0.9685. The detection limit (3σ) obtained by UV-vis spectrum was as low as 2.38 × 10(-7)M (i.e., 0.03 mg/kg).

Methanobactin-mediated synthesis of gold nanoparticles supported over Al2O3 toward an efficient catalyst for glucose oxidation.

Methanobactin (Mb) is a copper-binding peptide that appears to function as an agent for copper sequestration and uptake in methanotrophs. Mb can also bind and reduce Au(III) to Au(0). In this paper, Au/Al2O3 catalysts prepared by a novel incipient wetness-Mb-mediated bioreduction method were used for glucose oxidation. The catalysts were characterized, and the analysis revealed that very small gold nanoparticles with a particle size <4 nm were prepared by the incipient wetness-Mb-mediated bioreduction method, even at 1.0% Au loading (w/w). The influence of Au loading, calcination temperature and calcination time on the specific activity of Au/Al2O3 catalysts was systematically investigated. Experimental results showed that decomposing the Mb molecules properly by calcinations can enhance the specific activity of Au/Al2O3 catalysts, though they acted as reductant and protective agents during the catalyst preparation. Au/Al2O3 catalysts synthesized by the method exhibited optimum specific activity under operational synthesis conditions of Au loading of 1.0 wt % and calcined at 450 °C for 2 h. The catalysts were reused eight times, without a significant decrease in specific activity. To our knowledge, this is the first attempt at the preparation of Au/Al2O3 catalysts by Mb-mediated in situ synthesis of gold nanoparticles.

Silicon-based bulky group-induced remote control and conformational preference in the synthesis and application of isolable atropisomeric amides with secondary alcohol or amine moieties.

Remote stereocontrol through conformational transmission along a carbon chain is highly important in synthetic systems and molecular architectures. In this work, the interactional reactivity between a remote silicon-based bulky group and an O-/N-containing functional group has been revealed and determined by lateral lithiation-substitution, desilylation, as well as desilylation-olefination with benzaldehyde. The results suggest considerable information transmission and steric hindrance that can be exploited for the controllable synthesis of atropisomeric molecules. Based on the remote steric effect of a functional group across the aromatic ring of an amide, the construction of isolable atropisomeric amides with functional groups, such as alcohol, amine, and olefin was successfully achieved. All these new atropisomers were obtained in reasonable yield in pure diastereomeric form, and the specific configuration of representative products was confirmed by X-ray crystallography.

Methanobactin-mediated one-step synthesis of gold nanoparticles.

Preparation of gold nanoparticles with a narrow size distribution has enormous importance in nanotechnology. Methanobactin (Mb) is a copper-binding small peptide that appears to function as an agent for copper sequestration and uptake in methanotrophs. Mb can also bind and catalytically reduce Au (III) to Au (0). In this study, we demonstrate a facile Mb-mediated one-step synthetic route to prepare monodispersed gold nanoparticles. Continuous reduction of Au (III) by Mb can be achieved by using hydroquinone as the reducing agent. The gold nanoparticles have been characterized by UV-visible spectroscopy. The formation and the surface plasmon resonance properties of the gold nanoparticles are highly dependent on the ratio of Au (III) to Mb in solution. X-ray photoelectron spectroscopy (XPS), fluorescence spectra and Fourier transform-infrared spectroscopy (FT-IR) spectra suggest that Mb molecules catalytically reduce Au (III) to Au (0) with the concomitant production of gold nanoparticles, and then, Mb statically adsorbed onto the surface of gold nanoparticles to form an Mb-gold nanoparticles assembly. This avoids secondary nucleation. The formed gold nanoparticles have been demonstrated to be monodispersed and uniform by transmission electron microscopy (TEM) images. Analysis of these particles shows an average size of 14.9 nm with a standard deviation of 1.1 nm. The gold nanoparticles are extremely stable and can resist aggregation, even after several months.

Development of a novel multifunctional n,p ligand for highly enantioselective palladium-catalyzed asymmetric allylic etherification of alcohols and silanols.

CycloN2P2-Phos! The use of the multidentate phosphine, CycloN2P2-Phos, which contains four heteroatoms (two nitrogen and two phosphorus atoms), in the palladium-catalyzed asymmetric allylic etherification (AAE) of alcohols and silanols leads to excellent levels of enantioselectivity (up to 99 % ee).

Modulation of multifunctional N,O,P ligands for enantioselective copper-catalyzed conjugate addition of diethylzinc and trapping of the zinc enolate.

In this work, we have successfully synthesized a new family of chiral Schiff base­phosphine ligands derived from chiral binaphthol (BINOL) and chiral primary amine. The controllable synthesis of a novel hexadentate and tetradentate N,O,P ligand that contains both axial and sp3-central chirality from axial BINOL and sp3-central primary amine led to the establishment of an efficient multifunctional N,O,P ligand for copper-catalyzed conjugate addition of an organozinc reagent. In the asymmetric conjugate reaction of organozinc reagents to enones, the polymer-like bimetallic multinuclear Cu-Zn complex constructed in situ was found to be substrate-selective and a highly excellent catalyst for diethylzinc reagents in terms of enantioselectivity (up to >99 % ee). More importantly, the chirality matching between different chiral sources, C2-axial binaphthol and sp3-central chiral phosphine, was crucial to the enantioselective induction in this reaction. The experimental results indicated that our chiral ligand (R,S,S)-L1- and (R,S)-L4-based bimetallic complex catalyst system exhibited the highest catalytic performance to date in terms of enantioselectivity and conversion even in the presence of 0.005 mol % of catalyst (S/C = 20 000, turnover number (TON) = 17,600). We also studied the tandem silylation or acylation of enantiomerically enriched zinc enolates that formed in situ from copper-L4-complex-catalyzed conjugate addition, which resulted in the high-yield synthesis of chiral silyl enol ethers and enoacetates, respectively. Furthermore, the specialized structure of the present multifunctional N,O,P ligand L1 or L4, and the corresponding mechanistic study of the copper catalyst system were investigated by 31P NMR spectroscopy, circular dichroism (CD), and UV/Vis absorption.

Hydrosilane and bismuth-accelerated palladium catalyzed aerobic oxidative esterification of benzylic alcohols with air.

In a palladium-catalyzed oxidative esterification, hydrosilane can serve as an activator of palladium catalyst with bismuth, thus leading to a novel ligand- and silver-free palladium catalyst system for facile oxidative esterification of a variety of benzylic alcohols in good yields.

Biosysthesis of corn starch palmitate by lipase Novozym 435.

Esterification of starch was carried out to expand the usefulness of starch for a myriad of industrial applications. Lipase B from Candida antarctica, immobilized on macroporous acrylic resin (Novozym 435), was used for starch esterification in two reaction systems: micro-solvent system and solvent-free system. The esterification of corn starch with palmitic acid in the solvent-free system and micro-solvent system gave a degree of substitution (DS) of 1.04 and 0.0072 respectively. Esterification of corn starch with palmitic acid was confirmed by UV spectroscopy and IR spectroscopy. The results of emulsifying property analysis showed that the starch palmitate with higher DS contributes to the higher emulsifying property (67.6%) and emulsion stability (79.6%) than the native starch (5.3% and 3.9%). Modified starch obtained by esterification that possesses emulsifying properties and has long chain fatty acids, like palmitic acid, has been widely used in the food, pharmaceutical and biomedical applications industries.

Unexpected formation of novel organometallic hetero-cation crystals with a rare coordination mode.

The imitative synthesis of the ionic liquid [bmim][Co(CO)(4)], carried out in organic solvents instead of water, produced an unexpected liquid complex with partial crystallization. The resulting solid was confirmed to be the novel hetero-cation salt, [bmim]K[Co(CO)(4)](2) () and a crystallographic investigation revealed an extremely unusual (CO)(7)-K coordination mode. When the organic cation was replaced by [C(4)Py](+), similar crystallization was also obtained, forming [C(4)Py]K[Co(CO)(4)](2) (), which has an analogous structure. Both of these cases indicate an interesting influence that these organic cations have on the crystallization of organometallic structures that yields new structural examples.

Methanol production from CO(2) by resting cells of the methanotrophic bacterium Methylosinus trichosporium IMV 3011.

Methanol production from carbon dioxide was successfully achieved using resting cells of Methylosinus trichosporium IMV 3011 as biocatalysts. Carbon dioxide was reduced to methanol and extracellular methanol accumulation has been found in the carbon dioxide incubations. However, resting cells of methanotrophs have a finite or intrinsic methanol production capacity due to a limiting supply of intracellular reducing equivalent. It has been found that the catabolism of stored Poly-beta -Hydroxybutyrate (PHB) can provide intracellular reducing equivalents to improve the intrinsic methanol production capacity. The initial nitrogen and copper concentration in the culture medium were studied for the accumulation of PHB by M. trichosporium IMV 3011, to expand its potential uses in methanol production from carbon dioxide reduction. It appeared that the total methanol production capacity was increased with increasing PHB content in cells. Resting cells containing 38.6% PHB exhibited the highest total methanol production capacity. But higher PHB accumulation adversely affected the total methanol production capacity. The effects of methanol production process on the survival and recovery of M. trichosporium IMV 3011 were examined. The results showed that the methanol production from carbon dioxide reduction was not detrimental to the viability of methanotrophs.

Novel pyridinium based cobalt carbonyl ionic liquids: synthesis, full characterization, crystal structure and application in catalysis.

Through an optimized synthetic strategy, a series of novel alkylpyridinium cobalt tetracarbonyl salts, [C(1)Py][Co(CO)(4)] (), [C(4)Py][Co(CO)(4)] () and [C(16)Py][Co(CO)(4)] () (C(n)Py = N-C(n)H(2n+1)-pyridinium), were successfully prepared in good yields, using a water-organic biphasic system. All the three compounds melt well below 100 degrees C and could be classified as ionic liquids. The compounds were fully characterized using IR, UV-Vis, (1)H NMR, (13)C NMR, ESI-MS and elemental analysis, and was structurally characterized by X-ray single crystal analysis. Compound has been found to be an efficient and reusable catalyst for the alkoxycarbonylation of propylene oxide without the aid of a base additive.

Environmentally friendly, efficient resolution of racemic secondary alcohols by lipase-catalyzed enantioselective transesterification in ionic liquids in the presence of organic bases.

The lipase-catalyzed enantioselective transesterification of racemic secondary alcohols was studied using vinyl acetate as acyl donor in two imidazolium-based ionic liquids vs. hexane (Scheme), both in the absence and presence of catalytic amounts of organic bases such as triethylamine (Et(3)N) or pyridine. The organic bases generally enhanced both the rate and enantioselectivity of the reaction. Further, the system 1-butyl-3-methyl-1H-imidazolium hexafluorophosphate/Candida antarctica lipase B ([bmim][PF(6)]/CALB) could be readily recycled four times without significant loss in activity or enantioselectivity.