Microwave-Accelerated Selective Acylation of (Hydroxyalkyl)phenols Using Acid Chlorides

Highly selective acylation of the alcoholic hydroxy group can be achieved with (hydroxyalkyl)phenols carrying both alcoholic and phenolic hydroxyls by the use of the most common acylating agents, acid chlorides, under microwave irradiation.     

Determination of zinc in marine/lacustrine sediments by graphite furnace atomic absorption spectrometry using Pd/Mg chemical modifier and slurry sampling

Effectiveness of Pd/Mg chemical modifier for the accurate direct determination of zinc in marine/lacustrine sediments by graphite furnace atomic absorption spectrometry (GF-AAS) using slurry samples was evaluated. A calibration curve prepared by aqueous zinc standard solution with addition of Pd/Mg chemical modifier is used to determine the zinc concentration in the sediment. The accuracy of the proposed method was confirmed using Certified Reference Materials, NMIJ CRM 7303-a (lacustrine sediment) from National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology, Japan, and MESS-3 (marine sediment) and PACS-2 (marine sediment) from National Research Council, Canada. The analytical results obtained by employing Pd/Mg modifier are in good agreement with the certified values of all the reference sediment materials. Although for NRC MESS-3 an accurate determination of zinc is achieved even without the chemical modifier, the use of Pd/Mg chemical modifier is recommended as it leads to establishment of a reliable and accurate direct analytical method. One quantitative analysis takes less than 15 minutes after we obtain dried sediment samples, which is several tens of times faster than conventional analytical methods using acid digested sample solutions. The detection limits are 0.13?µg?g^?1 (213.9?nm) and 16?µg?g^?1 (307.6?nm), respectively, in sediment samples, when 40?mg of dried powdered samples are suspended in 20?mL of 0.1?mol?L^?1 nitric acid and a 10?µl portion of the slurry sample is measured. The precision of the proposed method is 8–15% (RSD).     

Single‐Electron‐Transfer (SET)‐Induced Oxidative Biaryl Coupling by Polyalkoxybenzene‐Derived Diaryliodonium(III) Salts

Metal‐free oxidative C? C coupling by using polyalkoxybenzene‐derived diaryliodonium(III) salts as both the oxidant and aryl source has been developed. These salts can induce single‐electron‐transfer (SET) oxidation to yield electron‐rich arenes and subsequently transfer the polyalkoxyphenyl group into in situ generated aromatic radical cations to produce biaryl products. The reaction is promoted by a Lewis acid that activates the iodonium salts. It has been revealed that the reactivity of the salts under acidic conditions is quite different to their known behavior under basic conditions. The reactivity preference of a series of iodonium salts in the SET oxidation and their ligand transfer abilities have been systematically investigated and the results are summarized in this report.     

Diastereo‐ and Regioselective Addition of Thioamide Dianions to Imines and Aziridines: Synthesis of N‐Thioacyl‐1,2‐diamines and N‐Thioacyl‐1,3‐diamines

Addition reactions of thioamide dianions that were derived from N‐arylmethyl thioamides to imines and aziridines were carried out. The reactions of imines gave the addition products of N‐thioacyl‐1,2‐diamines in a highly diastereoselective manner in good‐to‐excellent yields. The diastereomeric purity of these N‐thioacyl‐1,2‐diamines could be enriched by simple recrystallization. The reduction of N‐thioacyl‐1,2‐diamines with LiAlH₄ gave their corresponding 1,2‐diamines in moderate‐to‐good yields with retention of their stereochemistry. The oxidative‐desulfurization/cyclization of an N‐thioacyl‐1,2‐diamine in CuCl₂/O₂ and I₂/pyridine systems gave the cyclized product in moderate yield and the trans isomer was obtained as the sole product. On the other hand, a similar cyclization reaction with antiformin (aq. NaClO) as an oxidant gave the cis isomer as the major product. The reactions of N‐tosylaziridines gave the addition products of N‐thioacyl‐1,3‐diamines with low diastereoselectivity but high regioselectivity and in good‐to‐excellent yields. The use of AlMe₃ as an additive improved the efficiency and regioselectivity of the reaction. The stereochemistry of the obtained products was determined by X‐ray diffraction.     

Partial crystalline transformation of solvated cellulose IIII crystals, reproduced by theoretical calculations

In hot-water molecular dynamics simulation at 370 K, four cellulose III_I crystal models, with different lattice planes and dimensions, exhibited partial crystalline transformations of (1 ?1 0) chain sheets, in which hydroxymethyl groups were irreversibly rotated from gt into tg conformations, accompanied by hydrogen-bond exchange from the original O3–O6 to cellulose-I-like O2–O6 bonds. The final hydrogen-bond exchange ratio was about 95 % for some of the crystal models after 50 ns simulation. The corrugated (1 ?1 0) chain sheet was converted to a cellulose-I-like flat chain sheet with a slightly right-handed twist. The 3D structures of the three types of isolated chain sheet models were optimized using density functional theory calculations to compare their stabilities without crystal packing forces. The cellulose Iβ (1 0 0) models were more stable than the cellulose III_I (1 ?1 0) models. The optimized structure of cellulose III_I (1 0 0) models deviated largely from the initial sheet form. It was proposed to the crystalline transformation from cellulose III_I to Iβ that conversion of the chain sheet structure first take place, followed by sliding of the chain sheet along the fiber axis.     

Synthesis and Characterization of Aminoporphyrin‐End‐Functionalized Poly(N‐isopropylacrylamide) with Photodynamic and Thermoresponsive Effects

The novel aminoporphyrin‐end‐functionalized poly(N‐isopropylacrylamide) (PNIPAM) polymer H₂N‐TPP‐PNIPAM (TPP=5,10,15,20‐tetraphenyl‐21H,23H‐porphyrin) behaves as a multifunctional platform that displays a photodynamic effect, thermosensitivity, and fluorescence properties. The polymer was designed by using an asymmetrical aminoporphyrin (i.e., H₂N‐TPP‐Cl) as the initiator for the atom‐transfer radical polymerization of N‐isopropylacrylamide (NIPAM). The polydispersity index (PDI) obtained by gel‐permeation chromatography indicated that the molecular‐weight distribution was narrow (1.09<PDI<1.27). The lower critical solution temperatures of H₂N‐TPP‐PNIPAM showed a decreasing trend as the molecular weight was increased as a result of the incorporation of the porphyrin group at the end of the chain. The fluorescence spectra revealed the luminescent properties of the materials. The results of confocal laser scanning microscopy showed that the polymer could enter the cytoplasm through endocytosis. In addition, the multifunctional platform exhibited low toxicity against normal cells (L929) and cancer cells (Hela) and enhanced photodynamic activity towards HeLa cells, without significant necrocytosis towards L929 cells; as a result this material may be useful in the future for practical photodynamic therapy.     

Extended ensemble molecular dynamics study of cellulose I–ethylenediamine complex crystal models: atomistic picture of desorption behaviors of ethylenediamine

Cellulose - Cellulose I crystals swell on exposure to ethylenediamine (EDA) molecules to form a cellulose I–EDA complex, and successive extraction of EDA molecules converts the complex...     

Cellulose-synthesizing machinery in bacteria

Cellulose - Cellulose is produced by all plants and a number of other organisms, including bacteria. The most representative cellulose-producing bacterial species is Gluconacetobacter xylinus, an...     

Practical Synthesis of 2-Iodosobenzoic Acid (IBA) without Contamination by Hazardous 2-Iodoxybenzoic Acid (IBX) under Mild Conditions

We report a convenient and practical method for the preparation of nonexplosive cyclic hypervalent iodine(III) oxidants as efficient organocatalysts and reagents for various reactions using Oxone^® in aqueous solution under mild conditions at room temperature. The thus obtained 2-iodosobenzoic acids (IBAs) could be used as precursors of other cyclic organoiodine(III) derivatives by the solvolytic derivatization of the hydroxy group under mild conditions of 80 °C or lower temperature. These sequential procedures are highly reliable to selectively afford cyclic hypervalent iodine compounds in excellent yields without contamination by hazardous pentavalent iodine(III) compound.