Integrated catalytic C-H transformations for one-pot synthesis of 1-arylisoindoles from isoindolines via palladium-catalyzed dehydrogenation followed by C-H arylation

A one-pot conversion of isoindolines to 1-arylisoindoles was established from palladium-catalyzed cascade C-H transformations, that is, the dehydrogenation of isoindolines to give isoindoles, with subsequent C-H arylation of the isoindoles.     

Emergence of self-similarity in football dynamics

The multiplayer dynamics of a football game is analyzed to unveil self-similarities in the time evolution of player and ball positioning. Temporal fluctuations in both the team-turf boundary and the ball location are uncovered to follow the rules of fractional Brownian motion with a Hurst exponent of H ~ 0.7. The persistence time below which self-similarity holds is found to be several tens of seconds, implying a characteristic time scale that governs far-from-equilibrium motion on a playing field.     

Quantum chemical study of the interaction of the short-chain poly(oxyethylene)s CH3(OCH2CH2)mOCH3 (C1EmC1; m = 1 and 2) with a water molecule in the gas phase and in solutions

It is well-known that the role of the oxygen atom of the hydrophilic unit of poly(oxyethylene) (POE) is one of the important factors of the high solubility of POE in water. In the present study, we focused on the hydration of the oxyethylene OCH2CH2O unit of POE, CH3(OCH2CH2)mOCH3 (C1EmC1), and theoretically examined the role of the water molecule on the stability of POE using the short-chain POE, 1,2-dimethoxyethane (DME) CH3(OCH2CH2)OCH3 (C1E1C1) and diglyme CH3(OCH2CH2)2OCH3 (C1E2C1). The relative energies of the important conformers of the model POE with and without a water molecule in the gas phase and the solvent have been calculated by the second-order M?ller-Plesset perturbation (MP2) method using the 6-311G basis set. We found three types of H-bonding of a water molecule with the POE chain for the TTT and the TGT conformers of C1E1C1 and for the TTTTTT, the TGTTGT, and the TGTTG'T conformers of C1E2C1, which are classified into the monodentate and the bidentate H-bonding. The conformers including the gauche form of the OCH2CH2O unit without the intramolecular electrostatic interaction are less stable in energy than the trans conformers in the gas phase for both C1E1C1 and C1E2C1. However, this order in the stability is reversed by the hydration. It is also found that the H-bond between POE and a water molecule is strengthened in the solvent. The stability of the conformers of POE in the gas phase and in the solvent is discussed in detail.     

Rapid determination of five antibiotic residues in swine wastewater by online solid-phase extraction–high performance liquid chromatography–tandem mass spectrometry

A simple and quick online solid-phase extraction (SPE) coupled to liquid chromatography (LC)/tandem mass spectrometry (MS/MS) for the determination of the five antibiotics (florfenicol, FF; lincomycin, LCM; oxytetracyclin, OTC; tylosin, TS; valnemulin, VLM) in swine wastewater has been developed. After filtration, aliquots (100 μl) of wastewater samples were directly injected to a column-switching LC system. Some matrix interference was removed by washing up SPE column with 0.2% formic acid solution and acetonitrile. Antibiotics eluted from SPE column were separated on analytical column by converting switching valve and were detected by MS/MS. Calibration curves using the method of standard addition had very good correlation coefficients (r > 0.99) in the range of 0.1 to 2 ng/ml. The intra-day precision of the method was less than 12% and the inter-day precision was between 6 to 17%. The detection limits were 0.01–0.1 ng/ml. When this method was applied to wastewater samples in swine facilities, four compounds (LCM, OTC, TS, and VLM) were detected.     

Chemical synthesis of human adiponectin(19–107) bearing post-translational glycosylation

Human adiponectin(19–107), which consists of the variable region and the collagenous domain bearing post-translational modifications including glycosylation, was chemically synthesized for the first time. A glycoside of 5-hydroxylysine (Hyl) was incorporated using an α-d-glucopyranosyl-(1→2)-β-d-galactopyranosyl/Hyl-Gly building block in a benzyl-protected form by solid-phase peptide synthesis (SPPS). The molecule was assembled from four segments prepared by SPPS via native chemical ligation (NCL) and thioester methods.     

Crystal Structures of Two-Dimensional Coordination Polymer Fe(Methylpyridine)2Ni(CN)4

Abstract

Two-dimensional coordination polymer compounds FeL₂Ni(CN)₄ (L: 2, 3, or 4-methylpyridine) have been synthesized and characterized by single crystal X-ray diffraction method.     

Synthesis of sphingomyelin carbon analogues as sphingomyelinase inhibitors

The highly efficient and stereocontrolled syntheses of sphingomyelin carbon analogues 1 and 2 were achieved by effectively utilizing Hofmann rearrangement of enantiomerically pure beta-hydroxyamide 7, which was prepared by an asymmetric hydrogenation of alpha-acyl-gamma-butyrolactone 9 and ring opening with NH(3). Intermediary isocyanate 6 was selectively trapped with the vicinal hydroxy group in an intramolecular fashion to produce an oxazolidinone derivative, 5. In the synthesis of a quite polar compound such as 1, a convenient one-pot procedure of the introduction of a benzyloxycarbonyl group into the hydroxy group resulting from the oxazolidinone ring opening is another key point, because, in addition to the efficiency, this protecting group was easily removable by a simple procedure and workup at the final step. Both synthesized compounds 1 and 2 showed moderate inhibitory activity toward sphingomyelinase from B. cereus.     

Determination of thyroid hormones in pharmaceutical preparations,after derivatization with 9-anthroylnitrile,by high-performance liquid chromatography with fluorescence detection

Fast ion-exchange chromatography has been developed and applied to the separation of common inorganic anions. Using a didodecyldimethylammonium bromide (DDAB) coated short (30 mm x 4.6 mm) ODS analytical column (3-microm particle size) and a 5 mM phthalate eluent (pH 7.5) the isocratic separation of nine common anions in 160 s was possible, with the first seven anions, including phosphate, chloride and sulphate, separated within 65 s. Detection was achieved using indirect UV at 279 nm. The high capacity, highly hydrophobic ion-exchange coating demonstrated excellent stability over time, even at elevated temperatures (45 degrees C) and exhibited unusual selectivity for common anions (retention order=fluoride, carbonate, phosphate, chloride, bromate, nitrite, sulphate, bromide and nitrate). The developed chromatography was successfully applied to the rapid analysis of river water and seawater samples.