Influence of solvent on cyclic polynorbornene tacticity.

Tacticity is critical to polymer properties. The influence of solvent on tacticity in the catalytic synthesis of cyclic polynorbornene (c-PNB) is reported. In toluene cis,syndiotactic c-PNB forms; in THF, cis,syn/iso c-PNB forms.

Cis-Divacant Octahedral Fe(II) in a Dimensionally Reduced Family of 2-(Pyridin-2-yl)pyrrolide Complexes.

Four-coordinate transition-metal complexes can adopt a diverse array of coordination geometries, with square planar and tetrahedral coordination being the most prevalent. Previously, we reported the synthesis of a trinuclear Fe(II) complex, Fe3TPM2, supported by a 3-fold-symmetric 2-pyridylpyrrolide ligand [i.e., tris(5-(pyridin-2-yl)-1H-pyrrol-2-yl)methane] that featured a rare cis-divacant octahedral (CDO) geometry at each Fe(II) center. Here, a series of truncated 2-pyridylpyrrolide ligands are described that support mono- and binuclear Fe(II) complexes that also exhibit CDO geometries. Metalation of the tetradentate ligand bis[5-(pyridin-2-yl)-1H-pyrrol-2-yl]methane (H2BPM) in tetrahydrofuran (THF) results in the binuclear complex Fe2(BPM)2(THF)2 in which both Fe(II) ions are octahedrally coordinated. The coordinated THF solvent ligands are labile: THF dissociation leads to Fe2(BPM)2, which features five-coordinate Fe(II) ions. The Fe-Fe distance in these binuclear complexes can be elongated by ligand methylation. Metalation of bis[5-(6-methylpyridin-2-yl)-1H-pyrrol-2-yl]methane (H2BPMMe) in THF leads to the formation of four-coordinate, CDO Fe(II) centers in Fe(BPMMe)2. Further ligand truncation affords bidentate ligands 2-(1H-pyrrol-2-yl)pyridine (PyrPyrrH) and 2-methyl-6-(1H-pyrrol-2-yl)pyridine (PyrMePyrrH). Metalation of these ligands in THF affords six-coordinate complexes Fe(PyrPyrr)2(THF)2 and Fe(PyrMePyrr)2(THF)2. Dissociation of labile solvent ligands provides access to four-coordinate Fe(II) complexes. Ligand disproportionation at Fe(PyrPyrr)2 results in the formation of Fe(PyrPyrr)3 and Fe(0). Ligand methylation suppresses this disproportionation and enables isolation of Fe(PyrMePyrr)2, which is rigorously CDO. Complete ligand truncation, by separating the 2-pyridylpyrrolide ligands into the constituent monodentate pyridyl and pyrrolide donors, affords Fe(Pyr)2(Pyrr)2 in which Fe(II) is tetrahedrally coordinated. Computational analysis indicates that the potential energy surface that dictates the coordination geometry in this family of four-coordinate complexes is fairly flat in the vicinity of CDO coordination. These synthetic studies provide the structural basis to explore the implications of CDO geometry on Fe-catalyzed reactions.

Kinetic versus thermodynamic metalation enables synthesis of isostructural homo- and heterometallic trinuclear clusters.

Temperature-dependent metalation of the new hexadentate ligand (tris(5-(pyridin-2-yl)-1H-pyrrol-2-yl)methane; H3TPM) enables the selective synthesis of both mononuclear (i.e. Na(THF)4[Fe(TPM)], kinetic product) and trinuclear (i.e. Fe3(TPM)2, thermodynamic product) complexes. Exposure of Na(THF)4[Fe(TPM)] to FeCl2 or ZnCl2 triggers cluster expansion to generate homo- or heterometallic trinuclear complexes, respectively. The developed approach enables systematic variation of ion content in isostructural metal clusters via programmed assembly.

Iodosylbenzene Coordination Chemistry Relevant to Metal-Organic Framework Catalysis.

Hypervalent iodine compounds formally feature expanded valence shells at iodine. These reagents are broadly used in synthetic chemistry due to the ability to participate in well-defined oxidation-reduction processes and because the ligand-exchange chemistry intrinsic to the hypervalent center allows hypervalent iodine compounds to be applied to a broad array of oxidative substrate functionalization reactions. We recently developed methods to generate these compounds from O2 that are predicated on diverting reactive intermediates of aldehyde autoxidation toward the oxidation of aryl iodides. Coupling the aerobic oxidation of aryl iodides with catalysts that effect C-H bond oxidation would provide a strategy to achieve aerobic C-H oxidation chemistry. In this Forum Article, we discuss the aspects of hypervalent iodine chemistry and bonding that render this class of reagents attractive lynchpins for aerobic oxidation chemistry. We then discuss the oxidation processes relevant to the aerobic preparation of 2-(tert-butylsulfonyl)iodosylbenzene, which is a popular hypervalent iodine reagent for use with porous metal-organic framework (MOF)-based catalysts because it displays significantly enhanced solubility as compared with unsubstituted iodosylbenzene. We demonstrate that popular synthetic methods to this reagent often provide material that displays unpredictable disproportionation behavior due to the presence of trace impurities. We provide a revised synthetic route that avoids impurities common in the reported methods and provides access to material that displays predictable stability. Finally, we describe the coordination chemistry of hypervalent iodine compounds with metal clusters relevant to MOF chemistry and discuss the potential implications of this coordination chemistry to catalysis in MOF scaffolds.

Metabolic engineering of Corynebacterium glutamicum for the production of glutaric acid, a C5 dicarboxylic acid platform chemical.

Corynebacterium glutamicum was metabolically engineered for the production of glutaric acid, a C5 dicarboxylic acid that can be used as platform building block chemical for nylons and plasticizers. C. glutamicum gabT and gabD genes and Pseudomonas putida davT and davD genes encoding 5-aminovalerate transaminase and glutarate semialdehyde dehydrogenase, respectively, were examined in C. glutamicum for the construction of a glutaric acid biosynthesis pathway along with P. putida davB and davA genes encoding lysine 2-monooxygenase and delta-aminovaleramidase, respectively. The glutaric acid biosynthesis pathway constructed in recombinant C. glutamicum was engineered by examining strong synthetic promoters PH30 and PH36, C. glutamicum codon-optimized davTDBA genes, and modification of davB gene with an N-terminal His6-tag to improve the production of glutaric acid. It was found that use of N-terminal His6-tagged DavB was most suitable for the production of glutaric acid from glucose. Fed-batch fermentation using the final engineered C. glutamicum H30_GAHis strain, expressing davTDA genes along with davB fused with His6-tag at N-terminus could produce 24.5 g/L of glutaric acid with low accumulation of l-lysine (1.7 g/L), wherein 5-AVA accumulation was not observed during fermentation.

Enhanced production of gamma-aminobutyrate (GABA) in recombinant Corynebacterium glutamicum strains from empty fruit bunch biosugar solution.

BACKGROUND: Recent interest has been focused on the production of platform chemicals from renewable biomass due to increasing concerns on global warming and depletion of fossil fuel reserves. Microbial production of platform chemicals in biorefineries has been suggested to be a promising solution for these problems. Gamma-aminobutyrate (GABA), a versatile bulk chemical used in food and pharmaceutical industry, is also used as a key monomer for nylon 4. GABA can be biologically produced by decarboxylation of glutamate. RESULTS: In this study, we examined high glutamate-producing Corynebacterium glutamicum strains as hosts for enhanced production of GABA from glucose and xylose as carbon sources. An Escherichia coli gadB mutant with a broad pH range of activity and E. coli xylAB genes were expressed under the control of a synthetic H36 promoter. When empty fruit bunch (EFB) solution was used as carbon source (45 g/L glucose and 5 g/L xylose), 12.54 ± 0.07 g/L GABA was produced by recombinant C. glutamicum H36GD1852 expressing E. coli gadB mutant gene and xylAB genes. Batch fermentation of the same strain resulted in the production of 35.47 g/L of GABA when EFB solution was added to support 90 g/L glucose and 10 g/L xylose. CONCLUSIONS: This is the first report of GABA production by recombinant C. glutamicum strains from co-utilization of glucose and xylose from EFB solution. Recombinant C. glutamicum strains developed in this study should be useful for an efficient and sustainable production of GABA from lignocellulosic biomasses.

Oxidation Catalysis by an Aerobically Generated Dess-Martin Periodinane Analogue.

Hypervalent iodine(V) reagents, such as Dess-Martin periodinane (DMP) and 2-iodoxybenzoic acid (IBX), are broadly useful oxidants in chemical synthesis. Development of strategies to generate these reagents from dioxygen (O2 ) would immediately enable use of O2 as a terminal oxidant in a broad array of substrate oxidation reactions. Recently we disclosed the aerobic synthesis of I(III) reagents by intercepting reactive oxidants generated during aldehyde autoxidation. In this work, aerobic oxidation of iodobenzenes is coupled with disproportionation of the initially generated I(III) compounds to generate I(V) reagents. The aerobically generated I(V) reagents exhibit substrate oxidation chemistry analogous to that of DMP. The developed aerobic generation of I(V) has enabled the first application of I(V) intermediates in aerobic oxidation catalysis.

Oxidase catalysis via aerobically generated hypervalent iodine intermediates.

The development of sustainable oxidation chemistry demands strategies to harness O2 as a terminal oxidant. Oxidase catalysis, in which O2 serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O2 reduction. Direct O2 utilization suffers from intrinsic challenges imposed by the triplet ground state of O2 and the disparate electron inventories of four-electron O2 reduction and two-electron substrate oxidation. Here, we generate hypervalent iodine reagents-a broadly useful class of selective two-electron oxidants-from O2. This is achieved by intercepting reactive intermediates of aldehyde autoxidation to aerobically generate hypervalent iodine reagents for a broad array of substrate oxidation reactions. The use of aryl iodides as mediators of aerobic oxidation underpins an oxidase catalysis platform that couples substrate oxidation directly to O2 reduction. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis.

Characterization of a Whole-Cell Biotransformation Using a Constitutive Lysine Decarboxylase from Escherichia coli for the High-Level Production of Cadaverine from Industrial Grade L-Lysine.

Cadaverine is used for the synthesis of the novel bio-polyamides 54, 56, and 510. Here, we examine the feasibility of using a lysine decarboxylase (LdcC) from Escherichia coli for high-level production of cadaverine. After sequential optimization of whole-cell biotransformation conditions, recombinant E. coli-overexpressing LdcC (EcLdcC) could produce 1.0 M cadaverine from 1.2 M crude L-lysine solution after 9 h. EcLdcC retained a higher cadaverine yield after being reused 10 times at acidic and alkaline pH values than that of a recombinant E. coli strain overexpressing an inducible lysine decarboxylase (CadA), a conventional cadaverine producer (90 vs. 51% at pH 6 and 55 vs. 15% at pH 8). This study reveals that EcLdcC is a promising whole-cell biocatalyst for the bio-based production of cadaverine from industrial grade L-lysine in comparison to EcCadA.

Production of 5-aminovaleric acid in recombinant Corynebacterium glutamicum strains from a Miscanthus hydrolysate solution prepared by a newly developed Miscanthus hydrolysis process.

This study examined nine expired industrial Corynebacterium glutamicum strains with high lysine producing capability for enhanced production of 5-AVA. C. glutamicum KCTC 1857 exhibiting the highest lysine production was transformed with either original Pseudomonas putida davBA genes, encoding the 5-AVA biosynthesis pathway, or C. glutamicum codon-optimized davBA genes. C. glutamicum KCTC 1857 expressing the original genes had superior cell viability and 5-AVA production capability compared to the other strain. This strain produced 39.93g/L of 5-AVA, which is the highest titer reported to date in fed-batch fermentation from glucose. Indeed, Miscanthus hydrolysate solution prepared from a novel process, comprising pretreatment, hydrolysis, purification, and concentration, was used as feedstock for 5-AVA production. A total of 12.51g/L 5-AVA was produced from the Miscanthus hydrolysate; this value is 34.7% higher than that obtained from glucose in batch fermentation.

Exploration of Gate-Opening and Breathing Phenomena in a Tailored Flexible Metal-Organic Framework.

Flexible metal-organic frameworks (MOFs) show the structural transition phenomena, gate opening and breathing, upon the input of external stimuli. These phenomena have significant implications in their adsorptive applications. In this work, we demonstrate the direct capture of these gate-opening and breathing phenomena, triggered by CO2 molecules, in a well-designed flexible MOF composed of rotational sites and molecular gates. Combining X-ray single crystallographic data of a flexible MOF during gate opening/closing and breathing with in situ X-ray powder diffraction results uncovered the origin of this flexibility. Furthermore, computational studies revealed the specific sites required to open these gates by interaction with CO2 molecules.

Crystal-Size Effects on Carbon Dioxide Capture of a Covalently Alkylamine-Tethered Metal-Organic Framework Constructed by a One-Step Self-Assembly.

To enhance the carbon dioxide (CO2) uptake of metal-organic frameworks (MOFs), amine functionalization of their pore surfaces has been studied extensively. In general, amine-functionalized MOFs have been synthesized via post-synthetic modifications. Herein, we introduce a one-step construction of a MOF ([(NiLethylamine)(BPDC)] = MOFNH2; [NiLethylamine](2+) = [Ni(C12H32N8)](2+); BPDC(2-) = 4,4'-biphenyldicarboxylate) possessing covalently tethered alkylamine groups without post-synthetic modification. Two-amine groups per metal centre were introduced by this method. MOFNH2 showed enhanced CO2 uptake at elevated temperatures, attributed to active chemical interactions between the amine groups and the CO2 molecules. Due to the narrow channels of MOFNH2, the accessibility to the channel of CO2 is the limiting factor in its sorption behaviour. In this context, only crystal size reduction of MOFNH2 led to much faster and greater CO2 uptake at low pressures.