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At least 703 records · Page 39Linked to original sources
PubMed2002

A density functional study of O-O bond cleavage for a biomimetic non-heme iron complex demonstrating an Fe(v)-intermediate.

Density functional theory using the B3LYP hybrid functional has been employed to investigate the reactivity of Fe(TPA) complexes (TPA = tris(2-pyridylmethyl)amine), which are known to catalyze stereospecific hydrocarbon oxidation when H(2)O(2) is used as oxidant. The reaction pathway leading to O-O bond heterolysis in the active catalytic species Fe(III)(TPA)-OOH has been explored, and it is shown that a high-valent iron-oxo intermediate is formed, where an Fe(V) oxidation state is attained, in agreement with previous suggestions based on experiments. In contrast to the analogous intermediate [(Por.)Fe(IV)=O](+1) in P450, the TPA ligand is not oxidized, and the electrons are extracted almost exclusively from the mononuclear iron center. The corresponding homolytic O-O bond cleavage, yielding the two oxidants Fe(IV)=O and the OH. radical, has also been considered, and it is shown that this pathway is inaccessible in the hydrocarbon oxidation reaction with Fe(TPA) and hydrogen peroxide. Investigations have also been performed for the O-O cleavage in the Fe(III)(TPA)-alkylperoxide species. In this case, the barrier for O-O homolysis is found to be slightly lower, leading to loss of stereospecificity and supporting the experimental conclusion that this is the preferred pathway for alkylperoxide oxidants. The difference between hydroperoxide and alkylperoxide as oxidant derives from the higher O-O bond strength for hydrogen peroxide (by 8.0 kcal/mol).

Ferric Compounds↗
PubMed2002

Biomimetic arrays of oriented helical ZnO nanorods and columns.

Extended helical or chiral nanostructures are usually associated with biomolecules but are mostly absent in synthetic materials. Here we report the first synthesis of unusual oriented and extended helical nanostructures in synthetic ceramics. Large arrays of oriented helical ZnO nanorods and columns are formed using simple citrate ions to control the growth habits of the ZnO crystal. This novel mechanism could lead to new approaches to control the orientation, the surface area, and the defect structure of synthetic materials that are critical for practical applications. The morphology generated in the helical ZnO nanostructure shows remarkable resemblance to the growth morphology of nacreous calcium carbonate and thus may shed new light on morphology and orientation control of biominerals.

Molecular Mimicry↗
PubMed2005

Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution.

The electrochemical hydrogen evolution reaction is catalyzed most effectively by the Pt group metals. As H2 is considered as a future energy carrier, the need for these catalysts will increase and alternatives to the scarce and expensive Pt group catalysts will be needed. We analyze the ability of different metal surfaces and of the enzymes nitrogenase and hydrogenase to catalyze the hydrogen evolution reaction and find a necessary criterion for high catalytic activity. The necessary criterion is that the binding free energy of atomic hydrogen to the catalyst is close to zero. The criterion enables us to search for new catalysts, and inspired by the nitrogenase active site, we find that MoS2 nanoparticles supported on graphite are a promising catalyst. They catalyze electrochemical hydrogen evolution at a moderate overpotential of 0.1-0.2 V.

Catalysis↗
PubMed2001

Biomimetic transport of simple olive biophenol and analogues through model biological membranes by differential scanning calorimetry.

The different interactions of p-hydroxybenzoic acid (1), a simple biophenol (BP) found in olives and their food products, and its substitute analogues, benzoic (2), anisic (3), and toluic (4) acids, with a model membrane represented by dimyristoylphosphatidylcholine (DMPC) multilamellar vesicles (MLV) was studied by differential scanning calorimetry (DSC). The influence of their different lipophilic character on transfer and absorption processes through an aqueous medium into a lipid bilayer was also investigated. DSC experiments allowed monitoring of the interaction of BP with biomembranes by considering the effects exerted on the thermotropic behavior of DMPC multilamellar and unilamellar vesicles at different pHs (4 and 7.4). The examined compounds affect the transition temperature (T(m)) of phospholipid vesicles, causing a shift toward lower values, which is modulated by the molecular fraction entering into the lipid bilayer, as well as by their molecular interaction with the lipids. Kinetic calorimetric measurements were performed on suspensions of blank liposomes immediately after being added to fixed weighed amounts of powdered compounds and after increasing incubation periods at 37 degrees C. T(m) shifts, due to molecular dissolution and transfer of the compounds into the membrane surface occurring during the incubation time, were compared with those determined by a fixed molar fraction of free compounds directly dispersed in the membrane. The results show that the kinetic process, involved in molecular release, transfer through aqueous medium, and uptake by the model membrane surface, is influenced by lipophilicity as well as by pH, acting on the acid solubility and membrane disorder, allowing us to gather useful information on the BP intake process of olive derived foodstuffs.

Calorimetry, Differential Scanning↗
PubMed2005

Biomimetic extraction of Bacillus thuringiensis insecticidal crystal proteins from soil based on invertebrate gut fluid chemistry.

Quantitative monitoring of Bacillus thuringiensis (Bt) insecticidal crystal proteins in soil has been hampered by the lack of efficient extraction/detection methods. A novel approach for simple and effective Bt protein extraction was explored by evaluating extraction solutions from invertebrate gut fluids. Marine worm gut fluids were identified as promising for extracting Bt protein from soil. An artificial gut fluid based on these marine worm gut fluids was developed using commercially available chemicals and was evaluated for its ability to extract Bt proteins from soil. On the basis of experiments with Cry1 proteins, the artificial gut fluid in combination with ELISA was highly effective for protein extraction and analysis in a variety of soil types and was well-correlated with bioassay results. Coupling of immunoassay with this extraction method provides, for the first time, an efficient, accurate, and quantitative assay for routine measurement of Bt protein residues in soil.

Animals↗
PubMed2006

Metalloporphyrins as biomimetic models for cytochrome p-450 in the oxidation of atrazine.

The aim of this work was to evaluate whether metalloporphyrin models could mimic the action of cytochrome P-450 in the oxidation of atrazine, a herbicide. The commercially available second-generation metalloporphyrins 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin metal(III) chloride [M(TDCPP)Cl] and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin metal(III) chloride [M(TFPP)Cl] (metal = Fe or Mn) and the oxidants iodosylbenzene and metachloroperbenzoic acid were employed in this study. Results showed that the metalloporphyrins used here can oxidize atrazine. Yields as high as 32% were obtained for the Mn(TFPP)Cl/PhIO system, which shows that these catalysts can mimic both the in vivo and the in vitro action of cytochrome P-450, with formation of the metabolites DEA and DIA. The formation of five other unknown products was also detected, but only one of them could be identified, since the other four were present in very low concentrations. The compound COA, identified by mass spectrometry, was the main product in most of the oxidation reactions.

Atrazine↗
PubMed2000

A biomimetic total synthesis of (-)-spirotryprostatin B and related studies.

The prenylated natural products spirotryprostatin A and B derived from the Trp-Pro diketopiperazine also feature an oxidative rearrangement of the indole to form a spirooxindole. Synthetically, formation of the oxindole ring was stereoselectively accomplished by reaction of the appropriate indole precursor with N-bromosuccinimide. For optimum results, the oxidation should be carried out prior to diketopiperazine cyclization. In this manner, we have synthesized the tetrahydro- and dihydro- analogues of spirotryprostatin B in four steps from L-tryptophan methyl ester. The dihydro derivative was then converted to spirotryprostatin B by unsaturation of the pyrrolidine ring to a pyrroline, thus unambiguously confirming the structure of the natural product.

Alkaloids↗
PubMed2001

A biomimetic approach to dihydrobenzofuran synthesis.

A method for an acid-catalyzed construction of dihydrobenzofuran heterocycles (14) from 2-(2'-hydroxyethyl)quinone precursors 10 is presented. The putative oxonium ion intermediate 17 formed by an intramolecular hydroxyl cyclization followed by dehydration is reduced in situ by an added dihydroquinone source. Good to excellent yields of cyclized products are realized in all cases except for highly electron deficient systems, and these suffer reduction prior to oxonium ion formation. All products are monomeric and derived from a two-electron transfer except for 10 g, which affords the dimeric dihydrobenzofuran. The amount of cyclization or reduction product is governed by the HOMO/LUMO gap between the quinone substrate and the dihydroquinone additive, and the product distribution can be adjusted by modifying the electronic properties of the added reducing agent.

Allyl Compounds↗
PubMed2002

New approach to biomimetic transamination using bifunctional [1,3]-proton transfer catalysis in thioxanthenyl dioxide imines.

A pyridoxamine equivalent, 9-aminothioxanthene 10,10-dioxide, has been designed that is capable of affording transamination in good to excellent yields of natural as well as artificial amino acids. Amidines and guanidines in catalytic amounts were capable of performing [1,3]-proton transfer in the imines under mild conditions, whereas various simple amines failed. The use of chiral catalysts resulted in modest asymmetric induction (ee < or = 45%). The electronic dependence in para-substituted phenyl glyoxylate imines, isotope effects, and computational studies support a stepwise, bifunctional mechanism for amidine and guanidine catalysts. Attempts toward an autocatalytic model system are described.

Amination↗
PubMed2002

Endo-oxacyclizations of polyepoxides: biomimetic synthesis of fused polycyclic ethers.

Boron trifluoride-etherate promotes the endo-selective oxacyclization of polyepoxides derived from various acyclic terpenoid polyalkenes, including geraniol, farnesol, and geranylgeraniol, providing an efficient and stereoselective synthesis of substituted oxepanes and fused polyoxepanes. The mechanism of the oxacyclization reaction probably involves intramolecular nucleophilic addition of epoxide oxygen to open another epoxide that is activated as an electrophile by the Lewis acid. These oxacyclizations proceed stereospecifically with inversion of configuration upon opening of each epoxide to provide trans-fused polycyclic products. The oxacyclization cascade is terminated by a tethered nucleophile, which may be the carbonyl oxygen of a ketone, ester, or carbonate, or a trisubstituted alkene. The best oxacyclization yields are generally observed with tert-butyl carbonate as the terminating nucleophile, although in some cases the oxacyclization products include formation of tert-butyl ethers as a minor product. The oxacyclization transformations described herein may mimic ring-forming steps in the biosynthesis of trans-syn-trans-fused polycyclic ether marine natural products.

Biological Factors↗
PubMed2002

A biomimetic approach to the synthesis of an antiviral marine steroidal orthoester.

Orthoesterol B, a marine natural product exhibiting antiviral activities, contains a [3.2.1]-bicyclic orthobutyrate bridging the steroid side chain and ring D. A biosynthetic reaction was proposed by which rearrangement of an epoxy ester results in the formation of the orthoester moiety. Steroidal model compounds incorporating 16-butyroxy and 20,22-epoxy groups were synthesized from tigogenin and were shown to rearrange to orthoesters under mild acidic catalysis.

Animals↗
PubMed2003

Total synthesis of (+/-)-cameroonan-7alpha-ol and biomimetic rearrangements to related nopsane sesquiterpenes.

A total synthesis of the novel silphinane sesquiterpene alcohol (+/-)-cameroonanol (6-OH) from bicyclic enone 10 was accomplished by conjugate addition of crotylsilane, photochemical hydrobromination, intramolecular alkylation, and hydride reduction. The stereoisomers cameroonan-7beta-ol (18-OH) and 9-epicamerooonanols (19 and 20) were separated from isomer mixtures and the 9-desmethylcameroonanols (21-OH and 22-OH) were obtained by similar means. Solvolysis of 6-OMs and 18-OMs effected skeletal rearrangements to (+/-)-silphiperfol-6-ene (5), (+/-)-prenopsanol (7) and (+/-)-nopsanol (8), and (+/-)-silphiperfolan-7beta-ol (9) in parallel with biogenetic schemes proposed for these naturally occurring sesquiterpenes. The nor analogues 21-OMs and 22-OMs underwent solvolytic rearrangments to a similar set of nor products. The increase in solvolytic rates for the 7beta-mesylates 18-OMs and 22-OMs in comparison to the 7alpha epimers is attributed to concerted antiperiplanar Wagner-Meerwein rearrangements to the prenopsyl and norprenopsyl carbocations. Further analysis of the kinetic data and comparisons with solvolysis rates for the structurally related silphin-1beta-yl and silphin-1alpha-yl mesylates (28 and 29) are presented. The rearrangements observed afford chemical precedent for the biogenetic pathways in the literature for these silphinane sesquiterpenes.

Chromatography, High Pressure Liquid↗
PubMed2005

Synthesis of 2,3-dihydro-3-hydroxy-2-hydroxylalkylbenzofurans from epoxy aldehydes. One-step syntheses of brosimacutin G, vaginidiol, vaginol, smyrindiol, xanthoarnol, and Avicenol A. Biomimetic syntheses of angelicin and psoralen.

We have developed two practical one-step syntheses of 2,3-dihydro-3-hydroxy-2-hydroxyalkylbenzofurans from readily available optically pure alpha,beta-epoxy aldehydes. Electron-deficient resorcinols react with epoxy aldehydes using either Cs2CO3 in DMF or KOH/CaCl2 in MeOH to give adducts 13, 16, 18, 20, 21, and brosimacutin G (6t). Grignard reagents prepared by low-temperature halogen-metal exchange of acetoxy iodocoumarins 35d and 40 and acetoxy bromonaphthalene 41 add to epoxy aldehyde (S)-26 to complete the first syntheses of vaginidiol (7c), vaginol (7t), smyrindiol (8c), xanthoarnol (8t), and avicenol A (9t). Acid-catalyzed fragmentation of vaginidiol or vaginol provides angelicin, while that of smyrindiol or xanthoarnol affords psoralen. In both cases, the trans isomers fragment only twice as fast as the cis isomers, possibly through the intermediacy of a common benzylic cation. This may have implications for the biosynthesis of angelicin and psoralen.

Aldehydes↗
PubMed2004

A novel biomimetic route to the 3-acyl-5-hydroxy-3-pyrrolin-2-one and 3-acyl-3,4-epoxy-5-hydroxypyrrolidin-2-one ring systems.

Modified Moffat oxidation of alcohols 17, 22, and 25 afforded aldehydes that underwent intramolecular aldol reactions on treatment with a NaOH solution to yield 4-pyrrolin-2-ones 16, 23, and 26. Oxidation with DMDO at -40 degrees C provided 3-acyl-5-hydroxy-3-pyrrolin-2-ones 18, 24, and 27 with the ring system of oteromycin (3), UCS1025A (5), and related natural products. Further oxidation of 18 yielded 3-acyl-3,4-epoxy-5-hydroxy-pyrrolidin-2-one 19 with the ring system of fusarin C (1) and epolactaene (2). Dehydration of 18 afforded 20 with the talaroconvolutin A (4) ring system.

Molecular Conformation↗