Modification of the halogen end groups of polystyrene prepared by ATRP

The stabilization modification of the halogen end groups of polystyrene prepared by atom transfer radical polymerization (ATRP) has been attempted. The reaction mechanism adopted is radical chain transfer reaction, and iso-propylbenzene is employed as not only the chain transfer agent but also the solvent. Moreover, Cu⁰ is used as the acceptor of the transformed halogen atom in some experiments. As evidenced by ¹H NMR analysis of the modified products, the halogen end group can really be converted into the much more stable carbon-hydrogen structure. When Cu⁰ is not used, the conversion of the halogen end groups rises rapidly during the early stage and the increase rate slows down after about 8 h reaction. In view of the influence of reaction temperature on the modification, the conversion increases almost exponentially with temperature in the range of 80-100 °C, and the increase rate slows down at higher temperature. ¹H NMR and SEC analyses prove that the modification reaction does not destroy the polymer backbone and the molecular weights remain almost the same as those of the unmodified samples. When Cu⁰ is introduced, the modification reaction proceeds much rapidly, the conversion of the halogen end groups rises almost linearly at the early stage and the nearly complete (>95%) dehalogenation of the polymeric chains is observed after only 12 h reaction. However, the molecular weights rise and the polydispersities become wider after the modification, which implies that the modification is accompanied with the couple termination of the polystyrene radicals besides chain transfer reaction. Furthermore, the couple termination can be restrained at some lower catalyst concentration. Indeed, the modified polymers show improved thermal stability, the initial weight loss temperatures is increased from 196 °C to 378 °C for the linear polystyrene and from 203 °C to 261 °C for the hyperbranched polystyrene.     

LyP-1 peptide-functionalized gold nanoprisms for SERRS imaging and tumor growth suppressing by PTT induced-hyperthermia

The gold nanoprisms (GNPs) have exhibited special plasmonic properties for biomedical applications because of their unique shapes and dimensions. Based on their optical performance, the NIR dye IR780 not only enabled the GNPs-based nanosystem as SERRS nanoparticles for Raman-encoded molecular imaging, but also enhanced the plasmonic photothermal property by laser irradiation. Meanwhile, the GNPs/IR780-Lyp-1 by introduction of tumor-homing peptide segment LyP-1, which presents high affinity to p32 protein, demonstrated the increased enrichment in tumor region and enhanced photothermal therapy efficacy.     

水相中乙醇对胶体泡沫性质的影响

用不同比例的水-乙醇混合物作水相制备了胶体泡沫（CLA）,实验观察并测定了CLA的形态、粒径分布、半衰期、Zeta电位、水相溶液的粘度和水相/油相之间的界面张力等性质.结果表明，水相中加入乙醇会影响CLA的稳定性和粒径大小,但对CLA的Zeta电位影响不大.乙醇对CLA稳定性的影响主要是由于乙醇分子嵌入到界面膜中导致膜的强度变化以及水相粘度发生变化导致CLA粒子间隙的排液过程发生变化.     

Oxidative free radical reactions of enamino esters

Oxidative free radical reactions of enamino esters are described. Electrophilic carbon-centered radicals produced by the cerium(IV) ammonium nitrate (CAN) oxidation of β-dicarbonyl compounds undergo efficient addition to the C-C double bond of enamino esters. This CAN mediated free radical reaction between enamino esters and β-dicarbonyl compounds provides a novel method for the synthesis of highly substituted pyrroles. The direct CAN oxidation of β-enaminocinnamates gave the dimerization products effectively.     

A multifunctional Pasteurella multocida sialyltransferase: a powerful tool for the synthesis of sialoside libraries

A multifunctional sialyltransferase has been cloned from Pasteurella multocida strain P-1059 and expressed in E. coli as a truncated C-terminal His6-tagged recombinant protein (tPm0188Ph). Biochemical studies indicate that the obtained protein is (1) an alpha2,3-sialyltransferase (main function), (2) an alpha2,6-sialyltransferase, (3) an alpha2,3-sialidase, and (4) an alpha2,3-trans-sialidase. The recombinant tPm0188Ph is a powerful tool in the synthesis of structurally diverse sialoside libraries due to its relaxed substrate specificity, high solubility, high expression level, and multifunctionality.     

The constituents of the root and stem of Aristolochia heterophylla Hemsl

Seven new compounds, sodium aristolochate-VII (1), aristolactam-CIV (2), madolin-I (3), -J (4), -K (5), -L (6) and -M (7) together with 71 known compounds were isolated and characterized from the fresh root and stem of Aristolochia heterophylla Hemsl. Their structures were determined by spectral methods. Compound 8 was revised as aromadendrane-4beta, 10beta-diol by spectral data and single-crystal X-ray analysis.     

负载型非晶态Cu/SiO2催化剂的非晶性质

以超细ＳｉＯ２为载体，用ＫＢＨ４还原Ｃｕ＾２＋盐溶液制备了非负载型Ｃｕ和负载型Ｃｕ／ＳｉＯ２催化剂，ＸＲＤ，ＴＥＭ和电子衍射分析结果表明，负载型Ｃｕ／ＳｉＯ２为完全非晶态，而非负载型Ｃｕ中存在着少量晶态Ｃｕ，ＤＳＣ结果表明，非晶态Ｃｕ／ＳｉＯ２的热稳定性明显高于非负载型Ｃｕ，说明超细ＳｉＯ２具有稳定非晶结构的作用，ＸＰＳ结果表明，还原产物中的铜原子呈Ｃｕ状态，ＩＣＰ分析结果表明，样品中的Ｂ含量均低     

Graft copolymerization of methyl acrylate onto potato starch initiated by ceric ammonium nitrate

A study was made of the ceric ammonium nitrate (CAN) initiated graft copolymerization of methyl acrylate (MA) onto potato starch. The variables affecting the graft were investigated. The optimums have been obtained; they are the concentrations of MA, CAN, and nitric acid (HNO₃) (1.08, 5.0 × 10^?3, and 0.081 mol/L, respectively). The reaction temperature is ca. 50°C and the reaction time is 2 h. The molecular weight of grafted poly(methylacrylate) has been determined. On the basis of experimental results, the mechanism of grafting has been explored, a new kinetic equation of the graft copolymerization is established: R_p = Kk_d [STOH] [Ce⁴⁺] + Kk_pk_d/k_t[STOH][M], where K, k_d, k_p, and k_t are constants. The equation fits the results of experiments. © 1993 John Wiley & Sons, Inc.     

Isoochotensine,a New Spirobenzyusoquinoline Alkaloid from: Corydalis Ochotensis Turcz

Separation of the phenolic fraction of Corydalis ochotensis afforded a new spirobenzylisoquinoline alkaloid, isoochotensine ( 1 ) and three known alkaloids, ochotensine ( 3 ), cheilanthifoline ( 7 ), and lienkonine ( 9 ) as their acetyl derivatives together with a known nonphenolic alkaloid, ochotensimine ( 5 ). Their structures were elucidated by the spectral data.     

氧缺位铁酸盐的制备及结构与还原行为的研究

在３５８Ｋ下用２００ｍｌ／ｍｉｎ的空气氧化碱性悬浮液合成了ＭＦｅ_２Ｏ_（４＋δ）（δ≥０，Ｍ＝Ｆｅ、Ｃｏ、Ｎｉ、Ｍｎ），并在５７３Ｋ下用４０ｍｌ／ｍｉｎ的Ｈ_２还原ＭＦｅ_２Ｏ_（４＋δ）制备了氧缺位铁酸盐ＭＦｅ_２Ｏ_（４－δ）（δ＞０）。用ＸＲＤ、Ｍｓｓｂａｕｅｒ谱等测试方法对铁酸盐的结构进行了表征，考察了铁酸盐的组成及第二金属组分（Ｃｏ、Ｎｉ、Ｍｎ）对铁酸盐还原性能的影响。在Ｈ_２还原３ｈ内，铁酸盐氧缺位程度随还原时间增加而增大，晶格常数也相应增大；５ｈ以上，铁酸盐将被还原为ＭＯ－ＦｅＯ或α－Ｆｅ，晶格常数几乎不变。按Ｆｅ、Ｃｏ、Ｎｉ、Ｍｎ顺序，ＭＯ与ＦｅＯ的相互作用能力、ＭＯ－ＦｅＯ固溶体的稳定性及铁酸盐还原为ＭＯ－ＦｅＯ的能力均增强，ＭＯ－ＦｅＯ进一步还原为α－Ｆｅ的能力却减弱。