Cyclohexadepsipeptides from the Filamentous Fungus Acremonium sp. BCC 2629

Seven new cyclohexadepsipeptides, beauvenniatins F, G₁, G₂, G₃, H₁, H₂, and H₃ ( 1 – 7 , resp.), were isolated from cultures of the fungus Acremonium sp. BCC 2629. Their structures were elucidated by extensive spectroscopic analyses. The absolute configurations were addressed by HPLC analyses of their acid hydrolysates. Their biological activities were evaluated against Mycobacterium tuberculosis H37Ra and Plasmodium falciparum K1; the respective MIC and IC₅₀ values were in the micromolar range.     

Competing Knorr and Fischer–Fink pathways to pyrroles in neutral aqueous solution

A proposed chemical model for the prebiogenesis of tetrapyrrole macrocycles relies on the condensation of a 3-alkyl-substituted 2,4-diketone and an α-aminoketone to form a pyrrole equipped for subsequent self-condensation leading to porphyrinogens. The condensation of acyclic reactants can proceed via competing Knorr (desired) and Fischer–Fink (undesired) pathways. Here, the Knorr and Fischer–Fink pathways are quantitated using (1) analogues of those in the proposed prebiotic route wherein the resulting pyrroles are blocked from subsequent condensation, and (2) a set of internal standards for quantitation of crude reaction mixtures by ¹H NMR spectroscopy following extraction into CS₂. The reaction of 1-amino-2-butanone and 3-methyl-2,4-pentanedione at 60 °C in aqueous solution at pH 7 for 24 h afforded the Knorr pyrrole and Fischer–Fink pyrrole in yields of 48% and 7%, respectively. The reaction in hot aqueous acid (pH 4.6, reflux, 30 min) afforded the Knorr pyrrole in diminished yield (22%) relative to that of the Fischer–Fink pyrrole (11%). The Knorr pyrrole (4-ethyl-2,3-dimethylpyrrole) is evanescent whereas the Fischer–Fink pyrrole (2,3,4-trimethyl-5-propanoylpyrrole) is quite stable; hence, rapid analysis of the reaction mixture (vs workup and isolation) is essential for accurate analysis.     

Hamiltonicity of planar graphs with a forbidden minor

Tutte showed that -connected planar graphs are Hamiltonian, but it is well known that -connected planar graphs need not be Hamiltonian. We show that -minor-free -connected planar graphs are Hamiltonian. This does not extend to -minor-free -connected graphs in general, as shown by the Petersen graph, and does not extend to -minor-free -connected planar graphs, as we show by an infinite family of examples.     

[2.2]- and [3.3]Paracyclophane as Bridging Units in Organic Dyads for Visible-Light-Driven Dye-Sensitized Hydrogen Production

Novel donor–acceptor dyads containing [2.2]- and [3.3]paracyclophane (PCP) as the bridging moiety were synthesized and used to effectively fabricate dye-sensitized hydrogen production systems. All the prepared compounds had a phenothiazine and a cyanoacrylic acid/pyridinyl acrylonitrile moiety acting as an electron donor and acceptor, respectively. Although cyclic voltammetry measurements showed similar electron-donating properties among all the synthesized dyads, the lowest absorption energy of the [2.2]PCP moiety was lower than that of the [3.3]PCP one; this was due to its shorter distance between benzene rings, which could effectively drive the charge transfer between the donor and acceptor chromophores. Under visible light (>395 nm), a dyad-loaded photocatalyst in a 0.5 M aqueous glycerol solution generated detectable hydrogen gases. The optimal turnover number and photocurrent order exhibited the same trend as the hydrogen production rate since the suggested number of excited photons played a critical role in hydrogen production.     

Growth of Yb3+-doped KY3F10 concentration gradient crystal fiber by laser-heated pedestal growth (LHPG) technique

Crystal fiber of cubic Yb³⁺-doped KY₃F₁₀ has been grown. Both, mono-doped and concentration gradient fibers were grown by laser-heated pedestal growth (LHPG) method under argon atmosphere. The preparation of feed rod materials under CF₄ atmosphere prior to LHPG is efficient to obtain oxygen-free fluorides. Yb³⁺-doped KY₃F₁₀ crystals have excellent spectroscopic properties, weak self-quenching property and can be expected for solid-state laser application.     

Synthesis and Characterization of the D5h Isomer of the Endohedral Dimetallofullerene Ce2@C80: Two‐Dimensional Circulation of Encapsulated Metal Atoms Inside a Fullerene Cage

Herein we show the synthesis and characterization of the second known Ce₂@C₈₀ isomer. A ¹³C NMR spectroscopic study revealed that the structure of the second isomer has D_5h symmetry. Paramagnetic NMR spectral analysis and theoretical calculation display that the encapsulated Ce atoms circulate two‐dimensionally along a band of ten contiguous hexagons inside a D_5h‐C₈₀ cage, which is in sharp contrast to the three‐dimensional circulation of two Ce atoms in an I_h‐C₈₀ cage. The electronic properties were revealed by means of electrochemical measurements. The D_5h isomer of Ce₂@C₈₀ has a much smaller HOMO–LUMO gap than cluster fullerenes (M₃N@C₈₀, M=Sc, Tm, and Lu) with the same D_5h‐C₈₀ cages. The chemical reactivity was investigated by using disilirane as a chemical probe. The high thermal reactivity toward 1,1,2,2‐tetramesityl‐1,2‐disilirane is consistent with the trends of the redox potentials and the lower LUMO level of the D_5h isomer of Ce₂@C₈₀ compared with that of C₆₀.