Unveiling molecular DOM reactomics and transformation coupled with multifunctional nanocomposites under anaerobic conditions: Tracking potential metabolomics and pathways.

Anaerobic digestion (AD) offers great potential for pollutant removal and bioenergy recovery. However, it faces challenges when using livestock manure (LSM) as a feedstock given its high content of refractory materials (e.g.

Carboiodanation of Arynes: Organoiodine(III) Compounds as Nucleophilic Organometalloids.

Organic iodine(III) compounds represent the most widely used hypervalent halogen compounds in organic synthesis, where they typically perform the role of an electrophile or oxidant to functionalize electron-rich or -nucleophilic organic compounds. In contrast to this convention, we discovered their unique reactivity as organometallic-like nucleophiles toward arynes. Equipped with diverse transferable ligands and supported by a tethered spectator ligand, the organoiodine(III) compounds undergo addition across the electrophilic C-C triple bond of arynes while retaining the trivalency of the iodine center.

Copper-Catalyzed Intramolecular Olefinic C(sp)-H Amidation for the Synthesis of -Alkylidene--lactams.

Herein, we report the copper-catalyzed dehydrogenative C(sp)-N bond formation of 4-pentenamides via nitrogen-centered radicals. This reaction provides a straightforward and efficient preparation method for -alkylidene--lactams. Notably, we could controllably synthesize ,-unsaturated- or ,-saturated--alkylidene--lactams depending on the reaction conditions.

(3R,7S)-12-Hydroxy-jasmonoyl-l-isoleucine is the genuine bioactive stereoisomer of a jasmonate metabolite in Arabidopsis thaliana.

The oxylipin plant hormone (3R,7S)-jasmonoyl-l-isoleucine [or (+)-7-iso-jasmonoyl-l-isoleucine, JA-Ile] is widely recognized as a plant defense hormone against pathogens and chewing insects. The metabolism of JA-Ile into 12-OH-JA-Ile and 12-COOH-JA-Ile is the central mechanism for the inactivation of JA signaling. Recently, 12-OH-JA-Ile was reported to function as a ligand for the JA-Ile co-receptor COI1-JAZ.

Iron-Catalyzed Biomimetic Dimerization of Tryptophan-Containing Peptides.

Biomimetic oxidative dimerization of tryptophan derivatives in aqueous media with oxygen as a bulk oxidant catalyzed by an iron octacarboxy phthalocyanine complex was established. The discovery of the extremely active iron catalyst enables aerobic enzyme-mimetic oxidation to be performed in a flask. This method was applicable to the oxidative dimerization of a wide range of tryptophan derivatives, including various dipeptides and oligopeptides, with remarkable functional-group tolerance without the protection of the amino acid residues.

Thiourea fused γ-amino alcohol organocatalysts for asymmetric Mannich reaction of β-keto active methylene compounds with imines.

Catalytic functionality of new optically active thiourea fused γ-amino alcohols was examined in the asymmetric Mannich reaction of β-keto active methylene compounds with imines to afford chiral Mannich products, β-amino keto compounds, with continuous chiral centers, that are versatile synthetic intermediates for deriving various biologically active compounds. In particular, the thiourea fused γ-amino alcohols showed satisfactory catalytic activity in this reaction and afforded chiral Mannich products in excellent chemical yield (up to 88%) and stereoselectivities (up to  : /93 : 7 dr, up to 99% ee).

New boro amino amide organocatalysts for asymmetric cross aldol reaction of ketones with carbonyl compounds.

Distinct types of new boron fused primary amino amide organocatalysts were designed and synthesized from commercially available amino acids. Their catalytic activities were investigated in asymmetric crossed aldol reaction of ketones with aromatic aldehydes to afford the corresponding chiral -aldol adducts with good chemical yields, moderate diastereoselectivity and good to excellent enantioselectivities (up to 94% yields, up to 90 : 10 dr, up to 94% ee).

Sequential click modification of a lithium-ion endohedral fullerene connecting small molecules through a dieneazide linker.

A versatile method for the chemical modification of a lithium-ion endohedral fullerene (Li@C) to connect various small molecules is described. The designed dieneazide linker enables the facile connection of Li@C with small molecules bearing a terminal alkyne Huisgen annulation and a subsequent Diels-Alder reaction. This strategy significantly expands the diversity of small molecules to be attached by Li@C.

Development of an Internal Calibration Algorithm for Ultrahigh-Resolution Mass Spectra of Dissolved Organic Matter.

In order to obtain a spectrum with high mass accuracy, an internal calibration of Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) is inevitable. This in turn is critical for subsequent data processing and is generally performed using the commercial instrument software DataAnalysis in the benchmark calibration mode. However, no methodological study has systemically addressed the automated internal calibration of FTICR-MS spectra for dissolved organic matter (DOM) from different sources such as terrestrial and aquatic environments.

New small γ-turn type -primary amino terminal tripeptide organocatalyst for solvent-free asymmetric aldol reaction of various ketones with aldehydes.

New small γ-turn type -primary amino terminal tripeptides were synthesized and their functionality as an organocatalyst was examined in the asymmetric aldol reaction of various ketones with different aromatic aldehydes under solvent-free neat conditions to afford the desired chiral -aldol products in good to excellent chemical yields, diastereoselectivities and enantioselectivities (up to 99%, up to  : /13 : 87 dr, up to 99% ee).

Heterospin frustration in a metal-fullerene-bonded semiconductive antiferromagnet.

Lithium-ion-encapsulated fullerenes (Li@C) are 3D superatoms with rich oxidative states. Here we show a conductive and magnetically frustrated metal-fullerene-bonded framework {[Cu(Li@C)(L)(py)](NTf)(hexane)} (1) (L = 1,2,4,5-tetrakis(methanesulfonamido)benzene, py = pyridine, NTf = bis(trifluoromethane)sulfonamide anion) prepared from redox-active dinuclear metal complex Cu(L)(py) and lithium-ion-encapsulated fullerene salt (Li@C)(NTf). Electron donor Cu(L)(py) bonds to acceptor Li@C via eight Cu‒C bonds.

Direct C-H Carboxylation Forming Polyfunctionalized Aromatic Carboxylic Acids by Combined Brønsted Bases.

CO fixation into electron-deficient aromatic C-H bonds proceeds with the combined Brønsted bases LiO--Bu and LiO--Am/CsF/18-crown-6 (-Am = CEtMe) under a CO atmosphere to afford a variety of polyfunctionalized aromatic carboxylic acids.

Enantiodivergent One-Pot Synthesis of Axially Chiral Biaryls Using Organocatalyst-Mediated Enantioselective Domino Reaction and Central-to-Axial Chirality Conversion.

Enantiodivergent one-pot synthesis of biaryls was developed using a catalytic amount of a single chiral source. A domino organocatalyst-mediated enantioselective Michael reaction and aldol condensation provided centrally chiral dihydronaphthalenes with excellent enantioselectivity, from which an enantiodivergent chirality conversion from central-to-axial chirality was achieved. Both enantiomers of biaryls were obtained with excellent enantioselectivity.

Evidence for an enolate mechanism in the asymmetric Michael reaction of α,β-unsaturated aldehydes and ketones a hybrid system of two secondary amine catalysts.

The key nucleophile was found to be neither an enamine nor an enol, but an enolate in the direct Michael reaction of α,β-unsaturated aldehydes and non-activated ketones catalyzed by two amine catalysts namely diphenylprolinol silyl ether and pyrrolidine. This is a rare example of an enolate from a ketone serving as a key intermediate in the asymmetric organocatalytic reaction involving secondary amine catalysts because the ketone enolates are generally generated using a strong base, and the enamine is a common nucleophile in this type of reaction.

Simple amino silyl ether organocatalyst for asymmetric hetero Diels-Alder reaction of isatins with enones.

New two catalysts component system comprising of a primary β-amino silyl ethers as an organocatalyst and N-protected amino acids as a co-catalyst put together worked as an efficient organocatalyst system in the hetero Diels-Alder reaction of isatins with enones affording the chiral spirooxindole-tetrahydropyranones in good chemical yields and stereoselectivities (up to 94%, up to dr 78:22., up to 85% ee).

Semipinacol rearrangement of a bicyclo[7.2.0]undecane framework into a bicyclo[6.3.0]undecane skeleton: a model study on the biosynthesis of seiridiasteriscane A.

Seiridiasteriscane A is an asteriscane-type sesquiterpenoid bearing a trans-fused bicyclo[6.3.0]undecane skeleton.

Temperature-Dependent Low-Frequency Vibrations of Thiamine Crystal Containing Hydrated Ions.

Low-frequency vibrations of crystalline molecules are very sensitive to the local environment in which the molecules, for example, hydrated ions captured in crystals, find themselves. We present low-temperature X-ray crystallographic measurements on the harvested thiamine crystal containing hydrated ions and its temperature-dependent terahertz spectra and synchrotron infrared microspectra. It is found from the X-ray structure that the hydrated ions and hydration water are in a similar environment to liquid, although those are captured in crystals.

Synthesis of Stoichiometric SrTiO and Its Carrier Doping from Air-Stable Bimetallic Complexes.

We demonstrate the synthesis of perovskite oxide SrTiO with ideal cation stoichiometry and homogeneous La doping using air-stable Sr-Ti and La-Ti bimetallic peroxo complexes with a 1:1 cation ratio. Phase-pure SrTiO, LaTiO, and LaTiO were successfully synthesized by thermal decomposition of those complexes. La-doped SrTiO was obtained by mixing the Sr-Ti and La-Ti complexes in an acid solution, followed by thermal decomposition.

Simple primary β-amino alcohols as organocatalysts for the asymmetric Michael addition of β-keto esters to nitroalkenes.

Simple primary β-amino alcohols act as an efficient organocatalysts in the asymmetric Michael addition of β-keto esters with nitroalkenes affording highly pure chiral Michael adducts. Also, both enantiomers of the adducts were obtained, depending on the specific catalyst used and reaction temperature.

Stereocontrolled Total Synthesis of (-)-Isocelorbicol and Its Elaboration to Natural Dihydro-β-agarofuran Esters.

The first total synthesis of four naturally occurring dihydro-β-agarofuran esters has been accomplished via a highly stereocontrolled 14-step access to their common core triol, (-)-isocelorbicol. A semipinacol rearrangement of an epoxy alcohol to install a quaternary carbon, diastereoselective conjugate reduction of a spirocyclic butenolide for the establishment of a methyl-bearing chiral center, and ring-closing metathesis to construct the decalin ring system were exploited as the key steps for the high-yielding synthesis of (-)-isocelorbicol.

Cocrystals of Li encapsulated fullerenes and Tb(iii) double-decker single molecule magnet in a quasi-kagome lattice.

Cocrystallization of a lithium ion encapsulated fullerene Li@C with a terbium(iii) phthalocyaninato porphyrinato double-decker single-molecule magnet [Tb(Pc)(OEP)] is reported. The cocrystal, containing PF as a counter anion, packs in a quasi-kagome lattice, which leads to intermolecular ferromagnetic interactions as well as the modulation of the single-molecule magnet (SMM) properties.

Development and Application of a High-Precision Algorithm for Nontarget Identification of Organohalogens Based on Ultrahigh-Resolution Mass Spectrometry.

Brominated and/or chlorinated organic compounds (referred to as organohalogens) are frequently detected in natural and engineered environments. However, ultrahigh-resolution mass spectrometry (UHR-MS)-based nontargeted identification of organohalogens remains challenging because of the coexistence of a vast number of halogenated and nonhalogenated organic molecules. In this study, a new algorithm, namely, the NOMDBP code, was developed to simultaneously identify organohalogens and non-organohalogens from the UHR-MS spectra of natural and engineered waters.

Self-assembly of photoresponsive azo-containing phospholipids with a polar group as the tail.

Vesicles or micelles prepared from amphiphiles with azobenzene (Az) moieties and long alkyl chains have attracted much attention in drug delivery systems. To induce release behavior from smart carriers - photoisomerization of the Az groups, UV light exposure is typically used, but it can damage DNA and hardly penetrates cells. In this paper, Az-containing phospholipids without long alkyl tails were designed and synthesized; in these compounds, the end group of the Az moiety was substituted with a -NO and -OCH group (abbreviated N6 and M6, respectively).

Data on synthesis and characterization of new p-nitro stilbene Schiff bases derivatives as an electrochemical DNA potential spacer.

The structural investigation of synthesized compounds can be carried out by various spectroscopic techniques. It is an important prospect in order to elucidate the structure of the desired products before being further utilized. The preparation of new p-nitro stilbene Schiff base derivatives as an electrochemical DNA potential spacer was synthesized using (E)-4-(4-nitrostyryl)aniline from Heck reaction with aldehydes in ethanolic solution.