Three new polyketide-terpenoid hybrids from Penicillium sp

Three novel hybrid polyketide-terpenoid metabolites were isolated from a Penicillium minioluteum strain. Their structures were determined by NMR spectroscopic analyses and X-ray crystallography. The proposed biosynthetic pathway including a unique retro-Claisen migration of methyl carbonate correlates the three compounds with berkeleydione and berkeleytrione.     

Synthesis of vanadium oxide nanotubes via an ultrasonic method

Vanadium oxide nanotubes were synthesized using V₂O₅ powder as the precursor and hexadecylamine as the structure-directing template using a sol-gel reaction method followed by a one-step hydrothermal treatment. The effect of ultrasonics on the formation of nanotubes is reported. The structure and morphology of the nanotubes were investigated by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The inner and outer diameters of the nanotubes varied from 20 to 40 nm and 80 to 100 nm, respectively. The nanotubes measured several micrometers in length.     

Estimation of sedimentation rates using 210Pb and 210Po at the coastal water of Sabah, Malaysia

Sediment cores were obtained from Teluk Brunei, Sipitang, Teluk Kimanis, Kota Kinabalu and Kuala Penyu at the coastal water of Sabah and analyzed for ²¹⁰Pb and ²¹⁰Po to estimate the sedimentation rates. The calculated sedimentation rates of ²¹⁰Pb and ²¹⁰Po varied from 0.003 to 0.049 cm/y and 0.74 to 8.77 cm/y, respectively. The highest sedimentation rates were determined for ²¹⁰Pb and ²¹⁰Po at stations located at Sipitang (mean: 0.027 cm/y) and Teluk Kimanis (mean: 5.53 cm/y), respectively. The sedimentation rate estimated for ²¹⁰Pb is not fully reliable because the activity of ²²⁶Ra was higher than that of ²¹⁰Pb and bioturbation was active at the sampling stations.     

Ketene-forming eliminations from aryl bis(4'-chlorophenyl)acetates promoted by R2NH-R2NH2+ in aqueous MeCN. Change of mechanism

Elimination reactions of (4'-ClC6H4)2CHCO2C6H3-2-X-4-NO2 promoted by R2NH-R2NH2+ in 70 mol% MeCN (aq.) have been studied kinetically. The reactions are second-order and exhibit Br?nsted beta = 0.44-0.86 and /beta(lg)/ = 0.41-0.71. The Br?nsted beta decreased with a poorer leaving group and /beta(lg)/ increased with a weaker base. The results are consistent with an E2 mechanism. When X=H, the reaction proceeded by the concurrent E2 and Elcb mechanism.     

Rate Acceleration in Nucleophilic Alkylation of Carbonyl Compounds with a New Template Containing Two Metallic Centers

Two aluminum centers aligned in the same direction capture carbonyl groups in such a way that efficient alkyl transfer becomes possible from aluminum to the carbon atom. This occurs via a favorable cyclic six-membered transition state ( 1 ). Carbonyl compounds can now be alkylated with otherwise less reactive alkylmetal species.     

Highly enantioselective conjugate addition of nitroalkanes to alkylidenemalonates using efficient phase-transfer catalysis of N-spiro chiral ammonium bromides

Highly enantioselective conjugate addition of nitroalkanes to alkylidenemalonates has been accomplished for the first time by the utilization of efficient phase-transfer catalysis of N-spiro C2-symmetric chiral quaternary ammonium bromide 1. For instance, simple mixing of nitropropane (2, R1 = Et), diisopropyl benzylidienemalonate (3, R2 = Ph), Cs2CO3 (1 equiv), and (S,S)-1 (1 mol %) in toluene at 0 degrees C for 2.5 h gave rise to the desired conjugate addition product 4 (R1 = Et, R2 = Ph) quantitatively (anti/syn = 86:14) with 97% ee (anti isomer). The applicability of this procedure has been demonstrated with other representative alkylidenemalonates and nitroalkanes. Since 4 can be readily transformed into the corresponding gamma-amino acid hydrochloride 5 without loss of diastereo- and enantioselectivity, the present method provides a new and practical access to various optically active gamma-amino acid derivatives.     

Separation of positional isomers of mono-poly(ethylene glycol)-modified octreotides by reversed-phase high-performance liquid chromatography

The purpose of this study was to develop a reversed-phase high-performance liquid chromatographic method (RP-HPLC) for separating each positional isomer from low- to high-molecular-weight mono-PEGylated octreotides prepared by polyethylene glycol (PEG) derivatives with various molecular weights (2, 5, or 20 kDa). In the gradient elution using acetonitrile and 10 mM phosphate buffer at pH 7.0 on a Phenomenex Gemini C-18 column (250 mm × 4.6 mm id, 5 μm), each positional isomer of the mono-PEGylated octreotides was completely resolved with good resolution (PEG-2K: 7.6, PEG-5K: 6.6, and PEG-20K: 3.1). The optimal RP-HPLC condition also resolved the degradation products of mono-PEG-octreotide isomers in thermal stability studies at 55 °C and enzymatic stability studies with trypsin. In conclusion, the developed RP-HPLC method will be valuable for studying the effect of PEGylation site and the attached PEG size on the physicochemical and pharmacological properties of PEGylated octreotides.     

Duplex‐forming Oligonucleotide of Triazole‐linked RNA

An oligonucleotide of triazole‐linked RNA (^TLRNA) was synthesized by performing consecutive copper‐catalyzed azide‐alkyne cycloaddition reactions for elongation. The reaction conditions that had been optimized for the synthesis of 3‐mer ^TLRNA were found to be inappropriate for longer oligonucleotides, and the conditions were reoptimized for the solid‐phase synthesis of an 11‐mer ^TLRNA oligonucleotide. Duplex formation of the 11‐mer ^TLRNA oligonucleotide was examined with the complementary oligonucleotide of natural RNA to reveal the effects of the 2′‐OH groups on the duplex stability.     

Unveiling Latent Photoreactivity of Imines

Unlike carbonyl compounds, it has long been common understanding that excited imines show virtually no photoreactivity, and hence their properties and potential utility in chemical science remain largely unexplored. Now, a strategy is presented for eliciting latent photoreactivity of imines based on the introduction of a donor–acceptor (D‐A) structure to extend the lifetime of their photoexcited states. A series of spectroscopic analyses and density functional theory calculations reveal unique photophysical properties of the D‐A‐type imines. Furthermore, the reactivity of the D‐A‐type imines is demonstrated by using them as a photoredox catalyst for atom‐transfer radical addition. These findings illuminate a previously neglected chemical space in the field of photochemistry, which will be exploited by taking advantage of the inherent structural modularity of imines.