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 , c-PNB forms; in THF, / c-PNB forms.
View Article and Find Full Text PDFTemperature-dependent metalation of the new hexadentate ligand (tris(5-(pyridin-2-yl)-1H-pyrrol-2-yl)methane; HTPM) enables the selective synthesis of both mononuclear (i.e. Na(THF)[Fe(TPM)], kinetic product) and trinuclear (i.
View Article and Find Full Text PDFHypervalent 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 O that are predicated on diverting reactive intermediates of aldehyde autoxidation toward the oxidation of aryl iodides.
View Article and Find Full Text PDFCorynebacterium 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.
View Article and Find Full Text PDFBackground: 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.
View Article and Find Full Text PDFCellular Fas-associated protein with death domain-like interleukin-1β-converting enzyme-inhibitory protein (c-FLIP), often strongly expressed in numerous cancers, plays a pivotal role in thwarting apoptosis and inducing chemotherapy resistance in cancer. An integrated approach combining chemotherapy with suppression of c-FLIP levels could prove paramount in the treatment of cancers with c-FLIP overexpression. In this study, we utilized a polymeric layer-by-layer (LbL) assembly of silica-supported mesoporous titania nanoparticles (MTNst) to co-deliver paclitaxel (PTX) and microRNA 708 (miR708) for simultaneous chemotherapy and c-FLIP suppression in colorectal carcinoma.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
June 2018
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 (O ) would immediately enable use of O 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.
View Article and Find Full Text PDFCadaverine 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.
View Article and Find Full Text PDFThe development of sustainable oxidation chemistry demands strategies to harness O as a terminal oxidant. Oxidase catalysis, in which O serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O reduction. Direct O utilization suffers from intrinsic challenges imposed by the triplet ground state of O and the disparate electron inventories of four-electron O reduction and two-electron substrate oxidation.
View Article and Find Full Text PDFThis 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.
View Article and Find Full Text PDFFlexible 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.
View Article and Find Full Text PDFTo 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.
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