The biosynthesis of sorbicillinoids in Trichoderma sp. USF-2690: prospect for the existence of a common precursor to sorbicillinol and 5-epihydroxyvertinolide, a new sorbicillinoid member

Biosynthetic feeding studies of [1-¹³C], [2-¹³C], and [1,2-¹³C₂]-labeled sodium acetates into 5-epihydroxyvertinolide, a new sorbicillinoid, gives an incorporation pattern that proves the γ-lactone ring formation associated with a ring cleavage reaction of the precursor, a potential intermediate of sorbicillinol biosynthesis.     

Absolute and convective instabilities of electrostatic ion cyclotron waves excited in an ion beam-plasma system

Experimental results are presented for the observation of the absolute and convective instabilities of the electrostatic ion cyclotron waves excited in an ion beam-plasma system.     

Preparation of Polymeric Ultraviolet Absorbers and Their Effects on the Photodegradation of Polyethylene

Polymeric ultraviolet absorbers were prepared from 2-hydroxy-4-acryloyloxybenzophenone and 2-hydroxy-4-methacryloyloxybenzophenone and their inhibitive effect for photodegradation of polyethylene were examined by measuring mechanical strength, melt index, carbonyl group, and color difference. The polymeric ultraviolet absorbers were superior to the same type of ultraviolet absorber with low molecular weight in many properties, but inferior to Tinuvin, a commercial reagent, which has a different molecular structure. Therefore, within the ultraviolet absorbers examined, molecular structure seems to be a more important factor than molecular weight.     

Universal Reaction Mechanism of Boronic Acids with Diols in Aqueous Solution: Kinetics and the Basic Concept of a Conditional Formation Constant

To establish a detailed reaction mechanism for the condensation between a boronic acid, RB(OH)₂, and a diol, H₂L, in aqueous solution, the acid dissociation constants (${K{{{\rm BL}\hfill \atop {\rm a}\hfill}}}$ ) of boronic acid diol esters (HBLs) were determined based on the well‐established concept of conditional formation constants of metal complexes. The pK_a values of HBLs were 2.30, 2.77, and 2.00 for the reaction systems, 2,4‐difluorophenylboronic acid and chromotropic acid, 3‐nitrophenylboronic acid and alizarin red S, and phenylboronic acid and alizarin red S, respectively. A general and precise reaction mechanism of RB(OH)₂ with H₂L in aqueous solution, which can serve as a universal reaction mechanism for RB(OH)₂ and H₂L, was proposed on the basis of (a) the relative kinetic reactivities of the RB(OH)₂ and its conjugate base, that is, the boronate ion, toward H₂L, and (b) the determined pK_a values of HBLs. The use of the conditional formation constant, K′, based on the main reaction: RB(OH)₂+H₂L ${{\mathop \leftrightarrow \limits ^{K{_{1}}}_{}}}$ RB(L)(OH)^?+H₃O⁺ instead of the binding constant has been proposed for the general reaction of uncomplexed boronic acid species (B′) with uncomplexed diol species (L′) to form boronic acid diol complex species (esters, BL′) in aqueous solution at pH 5–11: B′+L′ ${{\mathop \leftrightarrow \limits ^{K{^\prime}}_{}}}$ BL′. The proposed reaction mechanism explains perfectly the formation of boronic acid diol ester in aqueous solution.     

Electrochemical, HPLC and electrospray ionization mass spectroscopic analyses of peroxycitric acid coexisting with citric acid and hydrogen peroxide in aqueous solution

We successfully determined the molecular structure of peroxycitric acid (PCA) coexisting in the aqueous equilibrium mixture with citric acid (CA; 1,2,3-tricarboxylic-2-hydroxy propane) and hydrogen peroxide (H₂O₂) by a combined use of reversed-phase HPLC (RP-HPLC), potentiometric, hydrodynamic chronocoulometric (HCC) and electrospray ionization mass spectroscopic (ESI-MS) methods. Firstly, the RP-HPLC was employed to separate CA, PCA and H₂O₂ coexisting in the equilibrium mixture and the concentration of CA consumed (ΔC_CA) in the formation of PCA that was evidenced to be fairly stable during the RP-HPLC measurement was quantitatively measured based on the standard calibration curve of CA. Secondly, the total oxidant concentration (C_Ox) corresponding to peroxycarboxylic (–COOOH) group in PCA in the equilibrium mixture was determined using potentiometric measurement. The ratio of C_Ox/ΔC_CA was found to be 1.07, which indicates that only one –COOH group in CA molecule is oxidized to the corresponding –COOOH group in PCA molecule. Thirdly, using the HCC technique the diffusion coefficient of PCA, which could be electroreduced at a more positive potential by 1.0 V than the coexisting H₂O₂, was independently measured as 0.3 × 10⁻⁵ cm² s⁻¹ and at the same time, by considering ΔC_CA as the concentration of PCA, the number of electrons (n) required for the reduction of PCA was determined to be 2. The result obtained from RP-HPLC and HCC, i.e., n = 2 which is equivalent to one –COOOH group in PCA, is in agreement with that obtained from the combination of RP-HPLC and potentiometric measurements. Finally, the structure of PCA was proposed to contain one –COOOH group with a molecular mass of 208 confirmed by negative ion ESI-MS method. A probable molecular structure of PCA was discussed.     

Water electrolysis: an excellent approach for the removal of water from ionic liquids

An electrochemical system based on platinum cathode and glassy carbon anode was assembled for a successful removal of water from ionic liquids via the water electrolysis strategy.     

Electrodeposition of platinum nanoparticles in a room-temperature ionic liquid

The electrochemistry of the [PtCl(6)](2-)-[PtCl(4)](2-)-Pt redox system on a glassy carbon (GC) electrode in a room-temperature ionic liquid (RTIL) [i.e., N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEMEBF(4))] has been examined. The two-step four-electron reduction of [PtCl(6)](2-) to Pt, i.e., reduction of [PtCl(6)](2-) to [PtCl(4)](2-) and further reduction of [PtCl(4)](2-) to Pt, occurs separately in this RTIL in contrast to the one-step four-electron reduction of [PtCl(6)](2-) to Pt in aqueous media. The cathodic and anodic peaks corresponding to the [PtCl(6)](2-)/[PtCl(4)](2-) redox couple were observed at ca. -1.1 and 0.6 V vs a Pt wire quasi-reference electrode, respectively, while those observed at -2.8 and -0.5 V were found to correspond to the [PtCl(4)](2-)/Pt redox couple. The disproportionation reaction of the two-electron reduction product of [PtCl(6)](2-) (i.e., [PtCl(4)](2-)) to [PtCl(6)](2-) and Pt metal was also found to occur significantly. The electrodeposition of Pt nanoparticles could be carried out on a GC electrode in DEMEBF(4) containing [PtCl(6)](2-) by holding the potential at -3.5 or -2.0 V. At -3.5 V, the four-electron reduction of [PtCl(6)](2-) to Pt can take place, while at -2.0 V the two-electron reduction of [PtCl(6)](2-) to [PtCl(4)](2-) occurs. The results obtained demonstrate that the electrodeposition of Pt at -3.5 V may occur via a series of reductions of [PtCl(6)](2-) to [PtCl(4)](2-) and further [PtCl(4)](2-) to Pt and at -2.0 V via a disproportionation reaction of [PtCl(4)](2-) to [PtCl(6)](2-) and Pt. Furthermore, the deposition potential of Pt nanoparticles was found to largely influence their size and morphology as well as the relative ratio of Pt(110) and Pt(100) crystalline orientation domains. The sizes of the Pt nanoparticles prepared by holding the electrode potential at -2.0 and -3.5 V are almost the same, in the range of ca. 1-2 nm. These small nanoparticles are "grown" to form bigger particles with different morphologies: In the case of the deposition at -2.0 V, the GC electrode surface is totally, relatively compactly covered with Pt particles of relatively uniform size of ca. 10-50 nm. On the other hand, in the case of the electrodeposition at -3.5 V, small particles of ca. 50-100 nm and the grown-up particles of ca. 100-200 nm cover the GC surface irregularly and coarsely. Interestingly, the Pt nanoparticles prepared by holding the potential at -2.0 and -3.5 V are relatively enriched in Pt(100) and Pt(110) facets, respectively.