微波诱导等离子体热解法合成碳膜包裹的TiO2纳米微晶

微波诱导等离子体热解法合成碳膜包裹的ＴｉＯ２纳米微晶刘洪波（广东石油化工高等专科学校广东茂名５２５０００）洪品杰戴树珊（云南大学化学系云南昆明６５００９１）关键词微波诱导等离子体包裹碳膜ＴｉＯ２纳米微晶中图分类号Ｏ６１４．４１１近年来，对碳膜包裹型材...     

Synthesis and modification of new biodegradable copolymers: Serine/glycolic acid based copolymers

Serine/glycolic acid-based biodegradable polymers have been prepared by ring-opening homopolymerization of 3-(O-benzyl)-L -serinylmorpholine-2,5-dione, and ring-opening copolymerization of the morpholine-2,5-dione derivative and L -lactide/ϵ-caprolactone. The homopolymerization was carried out in the melt at 165°C for 3 min using stannous octanoate as the initiator and continued at lower reaction temperatures (130–150°C) for 48 h, using a molar ratio of monomer and initiator of 1000 yielded a polymer of M_n = 4000. The polymer prepared by homopolymerization of the morpholine-2,5-dione derivative was composed of alternating protected serine and glycolic acid residues. Random copolymers of serine and glycolic acid and L -lactic acid/ϵ-caprolactone were synthesized by copolymerization reaction of 3-(O-benzyl)-L -serinylmorpholine-2,5-dione and lactide or ϵ-caprolactone in the melt at 165°C for 3 min and further reaction at 130°C using stannous octanoate as an initiator. The polymers were deprotected and functionalized through the side chain hydroxyl group of serine residues with an acrylate moiety for applications in injectable drug delivery, cell encapsulation. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1901–1907, 1997     

Comparative reactivity of thiophene and 3,4-(ethylenedioxy)thiophene as terminal electropolymerizable units in bis-heterocycle arylenes

The monomers bis(2-thienyl)-9,9-didecylfluorene, BTDF, and bis(3,4-(ethylenedioxy)thien-2-yl)-9,9-didecylfluorene, BEDOT-DF, have been synthesized and electropolymerized to the corresponding conducting polymers. The potential for the electropolymerization of BTDF was found to be dependent on the solvent composition. In CH₂Cl₂, polymer film deposition is achieved only at potentials higher than 1.3 V vs. Ag/Ag⁺, while in a 30/70 mixture of CH₂Cl₂/CH₃CN the polymerization is efficient at 0.9 V. BEDOT-DF polymerizes at significantly lower potentials and more rapidly than BTDF. The electron-donating alkoxy substituents of the EDOT units lead to stabilization of the cation radical intermediates allowing the electropolymerization to proceed at 0.55 V. The neutral polymers are insoluble in common organic solvents and are stable to 300°C under nitrogen. Upon oxidation, both polymers show two intragap transitions at intermediate doping levels due to the formation of bipolaronic states and the oxidized polymers exhibit conductivities up to 10⁻⁴ S/cm. The redox-stimulated ion transport characteristics, studied by the electrochemical quartz crystal microbalance (EQCM) indicates that the electrolyte anions are the dominant mobile species. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3627–3636, 1997     

The Occurrence and Biological Activity of Tormentic Acid—A Review

This review focuses on the natural sources and pharmacological activity of tormentic acid (TA; 2α,3β,19α-trihydroxyurs-2-en-28-oic acid). The current knowledge of its occurrence in various plant species and families is summarized. Biological activity (e.g., anti-inflammatory, antidiabetic, antihyperlipidemic, hepatoprotective, cardioprotective, neuroprotective, anti-cancer, anti-osteoarthritic, antinociceptive, antioxidative, anti-melanogenic, cytotoxic, antimicrobial, and antiparasitic) confirmed in in vitro and in vivo studies is compiled and described. Biochemical mechanisms affected by TA are indicated. Moreover, issues related to the biotechnological methods of production, effective eluents, and TA derivatives are presented.     

Ability of Lewis Acids with Shallow σ-Holes to Engage in Chalcogen Bonds in Different Environments

Molecules of the type XYT = Ch (T = C, Si, Ge; Ch = S, Se; X,Y = H, CH₃, Cl, Br, I) contain a σ-hole along the T = Ch bond extension. This hole can engage with the N lone pair of NCH and NCCH₃ so as to form a chalcogen bond. In the case of T = C, these bonds are rather weak, less than 3 kcal/mol, and are slightly weakened in acetone or water. They owe their stability to attractive electrostatic energy, supplemented by dispersion, and a much smaller polarization term. Immersion in solvent reverses the electrostatic interaction to repulsive, while amplifying the polarization energy. The σ-holes are smaller for T = Si and Ge, even negative in many cases. These Lewis acids can nonetheless engage in a weak chalcogen bond. This bond owes its stability to dispersion in the gas phase, but it is polarization that dominates in solution.     

Screening of Potential Anti-Thrombotic Ingredients from Salvia miltiorrhiza in Zebrafish and by Molecular Docking

Background: Danshen (DS), the dry root of Salvia miltiorrhiza Bge., has been used in traditional Chinese medicine (TCM) for many years to promote blood circulation and to inhibit thrombosis. However, the active ingredients responsible for the anti-thrombotic effect and the underlying mechanisms are yet to be fully elucidated. Methods: Molecular docking was used to predict the active ingredients in DS and their potential targets by calculating the scores of docking between DS ingredients and thrombosis-related proteins. Then, a chemical-induced zebrafish thrombosis model was applied to confirm their anti-thrombotic effects. Result: The molecular docking results indicated that compared to the control ligand, higher docking scores were observed for several compounds in DS, among which salvianolic acid B (SAB), lithospermic acid (LA), rosmarinic acid (MA), and luteolin-7-O-β-d-glucoside (LG) could attenuate zebrafish caudal vein thrombosis and recover the decrease in heart red blood cells (RBCs) in a dose-dependent manner. Conclusions: Our study showed that it is possible to screen the potential active components in natural products by combining the molecular docking method and zebrafish in vivo model.     

Structural Requirements of 1-(2-Pyridinyl)-5-pyrazolones for Disproportionation of Boronic Acids

We observed an unusual formation of four-coordinate boron(III) complexes from the reaction of 1-(2-pyridinyl)-5-pyrazolone derivatives with arylboronic acids in the basic media. The exact mechanism is not clear; however, the use of unprotected boronic acid and the presence of a bidentate ligand appeared to be the key structural requirements for the transformation. The results suggest that base-promoted disproportionation of arylboronic acid with the assistance of the [N,O]-bidentate ligation of 1-(2-pyridinyl)-5-pyrazolone should take place and facilitate the formation of pyrazole diarylborinate. Experiments to obtain a deeper understanding of its mechanism are currently underway.     

Chemistry of Spontaneous Alkylation of Methimazole with 1,2-Dichloroethane

Spontaneous S-alkylation of methimazole (1) with 1,2-dichloroethane (DCE) into 1,2-bis[(1-methyl-1H-imidazole-2-yl)thio]ethane (2), that we have described recently, opened the question about its formation pathway(s). Results of the synthetic, NMR spectroscopic, crystallographic and computational studies suggest that, under given conditions, 2 is obtained by direct attack of 1 on the chloroethyl derivative 2-[(chloroethyl)thio]-1-methyl-1H-imidazole (3), rather than through the isolated stable thiiranium ion isomer, i.e., 7-methyl-2H, 3H, 7H-imidazo[2,1-b]thiazol-4-ium chloride (4a, orthorhombic, space group Pnma), or in analogy with similar reactions, through postulated, but unproven intermediate thiiranium ion 5. Furthermore, in the reaction with 1, 4a prefers isomerization to the N-chloroethyl derivative, 1-chloroethyl-2,3-dihydro-3-methyl-1H-imidazole-2-thione (7), rather than alkylation to 2, while 7 further reacts with 1 to form 3-methyl-1-[(1-methyl-imidazole-2-yl)thioethyl]-1H-imidazole-2-thione (8, monoclinic, space group P 2₁/c). Additionally, during the isomerization of 3, the postulated intermediate thiiranium ion 5 was not detected by chromatographic and spectroscopic methods, nor by trapping with AgBF₄. However, trapping resulted in the formation of the silver complex of compound 3, i.e., bis-{2-[(chloroethyl)thio]-1-methyl-1H-imidazole}-silver(I)tetrafluoroborate (6_, monoclinic, space group P 2₁/c), which cyclized upon heating at 80 °C to 7-methyl-2H, 3H, 7H-imidazo[2,1-b]thiazol-4-ium tetrafluoroborate (4b, monoclinic, space group P 2₁/c). Finally, we observed thermal isomerization of both 2 and 2,3-dihydro-3-methyl-1-[(1-methyl-1H-imidazole-2-yl)thioethyl]-1H-imidazole-2-thione (8), into 1,2-bis(2,3-dihydro-3-methyl-1H-imidazole-2-thione-1-yl)ethane (9), which confirmed their structures.     

Dietary Flavonoids: Cardioprotective Potential with Antioxidant Effects and Their Pharmacokinetic,Toxicological and Therapeutic Concerns

Flavonoids comprise a large group of structurally diverse polyphenolic compounds of plant origin and are abundantly found in human diet such as fruits, vegetables, grains, tea, dairy products, red wine, etc. Major classes of flavonoids include flavonols, flavones, flavanones, flavanols, anthocyanidins, isoflavones, and chalcones. Owing to their potential health benefits and medicinal significance, flavonoids are now considered as an indispensable component in a variety of medicinal, pharmaceutical, nutraceutical, and cosmetic preparations. Moreover, flavonoids play a significant role in preventing cardiovascular diseases (CVDs), which could be mainly due to their antioxidant, antiatherogenic, and antithrombotic effects. Epidemiological and in vitro/in vivo evidence of antioxidant effects supports the cardioprotective function of dietary flavonoids. Further, the inhibition of LDL oxidation and platelet aggregation following regular consumption of food containing flavonoids and moderate consumption of red wine might protect against atherosclerosis and thrombosis. One study suggests that daily intake of 100 mg of flavonoids through the diet may reduce the risk of developing morbidity and mortality due to coronary heart disease (CHD) by approximately 10%. This review summarizes dietary flavonoids with their sources and potential health implications in CVDs including various redox-active cardioprotective (molecular) mechanisms with antioxidant effects. Pharmacokinetic (oral bioavailability, drug metabolism), toxicological, and therapeutic aspects of dietary flavonoids are also addressed herein with future directions for the discovery and development of useful drug candidates/therapeutic molecules.     

Cyanovinylation of Aldehydes: Organocatalytic Multicomponent Synthesis of Conjugated Cyanomethyl Vinyl Ethers

A novel organocatalytic multicomponent cyanovinylation of aldehydes was designed for the synthesis of conjugated cyanomethyl vinyl ethers. The reaction was implemented for the synthesis of a 3-substituted 3-(cyanomethoxy)acrylates, using aldehydes as substrates, acetone cyanohydrin as the cyanide anion source, and methyl propiolate as the source of the vinyl component. The multicomponent reaction is catalyzed by N-methyl morpholine (2.5 mol%) to deliver the 3-(cyanomethoxy)acrylates in excellent yields and with preponderance of the E-isomer. The multicomponent reaction manifold is highly tolerant to the structure and composition of the aldehyde (aliphatic, aromatic, heteroaromatics), and it is instrumentally simple (one batch, open atmospheres), economic (2.5 mol% catalyst, stoichiometric reagents), environmentally friendly (no toxic waste), and sustainable (easy scalability).