Ring opening reaction of gem-difluorocyclopropyl ketones with nucleophiles

Syntheses of gem-difluorocyclopropyl ketones (3a–d) and their reactions with nucleophiles are described. Ring opening reactions of 3a,c and d with a methanolate and a thiolate anion took entirely different courses of bond scission of the cyclopropane ring.     

Structural regulation of a peptide-conjugated graft copolymer: a simple model for amyloid formation

The self-assembly of peptides and proteins into beta-sheet-rich high-order structures has attracted much attention as a result of the characteristic nanostructure of these assemblies and because of their association with neurodegenerative diseases. Here we report the structural and conformational properties of a peptide-conjugated graft copolymer, poly(gamma-methyl-L-glutamate) grafted polyallylamine (1) in a water-2,2,2-trifluoroethanol solution as a simple model for amyloid formation. Atomic force microscopy revealed that the globular peptide 1 self-assembles into nonbranching fibrils that are about 4 nm in height under certain conditions. These fibrils are rich in beta-sheets and, similar to authentic amyloid fibrils, bind the amyloidophilic dye Congo red. The secondary and quaternary structures of the peptide 1 can be controlled by manipulating the pH, solution composition, and salt concentration; this indicates that the three-dimensional packing arrangement of peptide chains is the key factor for such fibril formation. Furthermore, the addition of carboxylic acid-terminated poly(ethylene glycol), which interacts with both of amino groups of 1 and hydrophobic PMLG chains, was found to obviously inhibit the alpha-to-beta structural transition for non-assembled peptide 1 and to partially cause a beta-to-alpha structural transition against the 1-assembly in the beta-sheet form. These findings demonstrate that the amyloid fibril formation is not restricted to specific protein sequences but rather is a generic property of peptides. The ability to control the assembled structure of the peptide should provide useful information not only for understanding the amyloid fibril formation, but also for developing novel peptide-based material with well-defined nanostructures.     

Zirconium-mediated intramolecular ester transfer reaction: synthesis of alpha-substituted gamma-aminobutyric acid (GABA) derivatives

[reaction: see text]. The zirconium-mediated intramolecular ester transfer reaction of N-alkenyl carbamate derivatives proceeded to give alpha-substituted gamma-aminobutyric acid (GABA) derivatives in good to excellent yields. Quenching experiments of the reaction mixture with iodine or O2 indicated the presence of a cyclopropane intermediate. The resulting iodide was converted to 2-substituted pyrrolidine-3-carboxylate and/or alpha-alkylidene-gamma-aminobutyric acid derivatives in a stereospecific manner.     

Single-Step N-Terminal Modification of Proteins via a Bio-Inspired Copper(II)-Mediated Aldol Reaction

The chemical modification of proteins is an effective technique for manipulating the properties and functions of proteins, and for creating protein-based materials. The N-terminus is a promising target for single-site modification that provides modified proteins with uniform structures and properties. In this paper, a copper(II)-mediated aldol reaction with 2-pyridinecarboxaldehyde (2-PC) derivatives is proposed as an operationally simple method to selectively modify the N-terminus of peptides and proteins at room temperature and physiological pH. The copper(II) ion activates the N-terminal amino acids by complexation with an imine of the N-terminal amino acid and 2-PCs, realizing the selective formation of the nucleophilic intermediate at the N-terminus. This results in a stable carbon-carbon bond between the 2-PCs and the α-carbon of various N-terminal amino acids. The reaction is applied to four different proteins, including biopharmaceuticals such as filgrastim and trastuzumab. The modified trastuzumab retains the human epidermal growth factor receptor 2 recognition activity.     

Radiation-induced degradation of aqueous 2–chlorophenol assisted by zeolites

Journal of Radioanalytical and Nuclear Chemistry - This study aims to demonstrate that zeolite has the potential to increase the efficiency of radiolysis treatment of aqueous organic pollutants by...     

Biosynthetic Conclusions from the Functional Dissection of Oxygenases for Biosynthesis of Actinorhodin and Related Streptomyces Antibiotics

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Highlights? ActVA-ORF5 is a flavin-dependent monooxygenase required for actinorhodin biosynthesis ? ActVA-ORF5 and its three close homologs were functionally dissected ? ActVA-ORF5 and Gra-21 are bifunctional at C-6/C-8, while Med-7 acts only for C-6 ? AlnT exhibits different regiospecificity for oxidation of tricyclic substrates     

Effects of Inorganic Salts on Micellization and Solubilization in an Aqueous Solution of Poly(ethylene oxide)/Poly(propylene oxide)/Poly(ethylene oxide) Triblock Copolymer

The effects of inorganic salts on micellization and solubilization of prednisolone in aqueous solution of poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) triblock copolymer (Pluronic P85) were studied. The effect of inorganic salts on decrease in the cloud point and the critical micelle concentration (cmc) of Pluronic P85 was the order of Na₂HPO₄ > NaH₂PO₄ > NaCl > NaBr. Moreover, it was found that Pluronic P85 forms two kinds of micelles: monomolecular micelles and polymolecular micelles. The polymolecular micelle increased with increasing amount of added inorganic salts. Moreover, solubilization behavior is explained from the standpoint of salting out for prednisolone and association characteristics of Pluronic P85.     

Formation,Expansion, and Interconversion of Metallarings in a Sulfur‐Bridged AuICoIII Coordination System

A novel Au^ICo^III coordination system that is derived from the newly prepared [Co(D ‐nmp)₂]⁻ ( 1 ⁻; D ‐nmp=N‐methyl‐D ‐penicillaminate) and a gold(I) precursor Au^I is reported. Complex 1 ⁻ acts as a sulfur‐donating metallaligand and reacts with the gold(I) precursor to give [Au₂Co₂(D ‐nmp)₄] ( 2 ), which has an eight‐membered Au^I₂Co^III₂ metallaring. Treatment of 2 with [Au₂(dppe)₂]²⁺ (dppe=1,2‐bis(diphenylphosphino)ethane) leads to the formation of [Au₄Co₂(dppe)₂(D ‐nmp)₄]²⁺ ( 3 ²⁺), which consists of an 18‐membered Au^I₄Co^III₂ metallaring that accommodates a tetrahedral anion (BF₄⁻, ClO₄⁻, ReO₄⁻). In solution, the metallaring structure of 3 ²⁺ is readily interconvertible with the nine‐membered Au^I₂Co^III metallaring structure of [Au₂Co(dppe)(D ‐nmp)₂]⁺ ( 4 ⁺); this process depends on external factors, such as solvent, concentration, and nature of the counteranion. These results reveal the lability of the Au S and Au P bonds, which is essential for metallaring expansion and contraction.     

Efficient partial hydrogenation of trichloromethyl to gem-dichloromethyl groups in platinum on carbon-catalyzed system

While gem-dichloromethyl groups can be directly synthesized by the mono-dechlorination of the corresponding trichloromethyl groups, the suppression control of the over-reduction to form chloromethyl or methyl functionalities is quite difficult. We have established the efficient and widely applicable mono-dechlorination method of the trichloromethyl groups to form the corresponding gem-dichloromethyl groups using platinum on carbon in dimethylacetamide as a specific solvent at 25 °C under a hydrogen atmosphere. The mono-dechlorination of the α,α,α-trichloromethylcarbonyl groups smoothly proceeded by the use of platinum on carbon as a catalyst in a highly chemoselective manner, while the efficient mono-dechlorination of the alkyl- and aryl-trichloromethyl groups required the combined use of Bu₃SnH.     

Magnetic resonance force microscopy combined with surface topography

A new method of surface microscopy is proposed, which combines three-dimensional electron spin resonance imaging by magnetic resonance force microscopy (MRFM) and topographic imaging of the sample surface by scanning force microscopy (SFM). In order to demonstrate its potential for the identification of microscale objects, the individual and combined images are used to provide the locations, shapes and spin density distributions of target phantom objects. We report spatial resolution in MRFM of 2.8 x 2.8 x 2.0 microm(3). This could be improved to the theoretical limit of 0.08 x 0.08 x 0.04 microm(3) through reduction of the thermal noise by cooling to cryogenic temperatures approximately 0.5K. We believe that this type of microscopy will become a very useful tool for the investigation of anomalies induced in surfaces by materials buried below the surface.