Trialkylsilyl-Protected Functional Initiators for Stereospecific Anionic Polymerization of Methacrylates

Anionic polymerizations of methyl methacrylate with trialkylsilyl-protected lithium benzylamides were conducted in the presence of aluminum compounds such as n-Bu₃Al. When the Me₃Si-protected amide was used, the carbonyl attack took place to some extent to form a methacrylamide derivative with slightly lower initiator efficiency (∼0.9). In the case of i-Pr₃Si-protected amide, the carbonyl addition was completely suppressed. The obtained polymers had narrow molecular weight distribution and carried benzylamino end-group, as revealed by NMR analysis, which is readily accessible for further chemical transformations such as acylation with acryloyl chloride and debenzylation with H₂/Pd-C. Difuntional initiators with protected groups were also examined.     

Anionic Polymerization Chemistry of Epoxides: Electron-Transfer Processes

The reaction of poly(styryl)lithium (PSLi) with styrene oxide (SO) in benzene solution has been investigated. In addition to the functionalized polymer (83.5 wt %) the product mixture consisted of unfunctionalized polymer (9 wt %) and a dimeric product (5.6 wt %). The structure of the dimeric product was determined to be the head-to-head dimer. The regiochemistry of the addition reaction was unselective: 53 mol % addition to the methylene carbon and 47 mol % corresponding to addition to the hindered, methine carbon. Based on the formation of the dimer and the lack of regioselectivity, a pathway involving electron transfer from PSLi to SO was proposed. To further investigate the propensity to react via this electron-transfer mechanism, the SO functionalization of the adduct of PSLi with 1,1-diphenylethylene was investigated as well as the functionalization of PSLi with 1,1-diphenylethylene oxide.     

Functional polymers by living anionic polymerization

The application of living anionic polymerization techniques for the functionalization of polymers and block copolymers is reviewed. The attachment of functional groups to polymeric chains of predetermined lengths and narrow molecular weight distributions is described. Carboxyls, hydroxyls, amines, halogens, double bonds, and many other functional groups can be placed at one or two ends in the center or evenly spaced along polymeric chains. Subsequent transformations of the functional groups further contribute to the versatility of such treatments. General methods based on the use, as terminators, of substituted haloalkanes, as well as the addition of living polymers or their initiators to diphenylethylenes, substituted with appropriate functional groups or molecules, are discussed. Another approach, based on the living polymerization of monomers with protected functional groups, is also discussed. It has been used for the preparation of polymers and copolymers with evenly spaced functional groups. The combination of living anionic polymerization techniques with controlled radical and cationic polymerizations is also described. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2116–2133, 2002     

Anionic polymerization of methyl methacrylate initiated with lithium diphenylamide (Ph2NLi) in the presence of divalent transition metal halide

Anionic polymerization of methyl methacrylate (MMA) in the presence of divalent transition metal halide (MX₂ = FeBr₂, MnCl₂, CoCl₂, NiBr₂) was investigated. Initiating systems with various combinations of MX₂, lithium diphenylamide (Ph₂NLi), and organolithium (RLi, where R = nBu, Me) were effective to giving a high yield of poly(methyl methacrylate)s (PMMAs) at ?78 °C in toluene. The tacticity of the resulting PMMAs was highly dependent on the combination of the reagents used for the generation of the initiating systems within a syndiotactic (rr = 59%) to isotactic (mm = 65%) range. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 31–37, 2004     

吲哚乙酸氧化酶和过氧化物酶关系的同工酶研究

用细胞质雄性不育系小麦（Ａｅ．ｔｒｉｕｎｉｃｉａｌｉｓ）ｃｓ；（Ａｓ．Ｚｈｕｋｏｖｓｋｙｉ）ｃｓ；（Ｔ．ｔｉｍｏｐｈｅｅｖｉ）ｃｓ；（Ａｅ．ｓｐｅｌｔｏｉｄｅｓ）ｃｓ和普通小麦中国春（Ｔ．ａｅｓｔｉｖｕｍ，保持系，ｃｓ）与鄂恩１号（Ｔ．ａｅｓｔｉｖｕｍ）为材料，用Ｄａｖｉｓ和Ｒｅｉｓｆｅｌｄ不连续聚丙烯酰胺垂直板凝胶电泳技术进行吲哚乙酸氧化酶（ＩＡＡ－ｏｘｉａｓｅ）和阴、阳离子过氧化物酶同工酶分析；并用ＳＣ９１０型双波段薄层扫描仪进行扫描，记录其谱带数及强弱．结果表明阳离子过氧化物酶同工酶谱与ＩＡＡ－氧化酶同工酶谱十分相似；而阴离子过氧化物酶酶谱相差甚远．由此表明具有吲哚乙酸氧化酶活性位点的过氧化物酶，应主要是阳离子过氧化物酶．     

Insights into the luminescent properties of anionic cyclometalated iridium(III) complexes with ligands derived from natural products

In the search of remarkable anionic electroluminescent semiconductors to be applied in energy conversion devices such as Light Emitting Electrochemical Cells, we report the electronic, photophysical, and charge injection/transfer properties of a series of cyclometalated iridium(III) complexes through a DFT/TD‐DFT procedure. The proposed semiconductors involve bidentated ligands based on natural products (salicylic acid and boldine), and phenylpyridine and phenylpyrazole as the cyclometalating units. The proposed compounds emit in the range of 446 to 571 nm, where the boldine based compounds have red‐shifted emissions compared to their analogs with salicylic acid. Blue phosphors were obtained by the use of phenylpyrazole units; however, the ligand field is weak in these cases compared to the ligand field exerted by the phenylpyridine ligands. The latter allows the accessibility to the radiationless states for emitters below 495 nm as a result of the increased stability of the metal centered excited states; consequently, the luminescent quantum yield could be decreased. Conversely, the semiconductors with phenylpyridine units show a restricted accessibility to radiationless processes, which could result in emitters with a high luminescent quantum yield and low non‐radiative constants. Finally, the proposed anionic semiconductors show a better balance between hole/electron transfer rate compared to related cationic Ir(III) complexes; while, the easier hole‐electron injection is favored for semiconductors with salicylic acid and phenylpyridine units.     

Adsorption of anionic dye by anionic surfactant modified chitosan beads: Influence of hydrophobic tail and ionic head-group

In this paper, how chitosan hydrogel beads were modified by anionic surfactants (SDS, SDOS, SDBS, AOT, and DTM-12) and then used for the adsorption and removal of an anionic dye (congo red) from aqueous solutions were described. The effect of surfactant concentration, surfactant ionic head-group, and surfactant hydrophobic tail were investigated in detail. The result revealed the modified CS beads all had the obviously higher adsorption capacity than CS beads. Compared to the ionic head-group, the hydrophobic tail of the surfactant plays more important role in the adsorption, and a high adsorption capacity was observed for CS/AOT beads and CS/DTM-12 beads (both with two hydrophobic tails). The Sips isotherm model showed a good fit with the equilibrium experimental data, and the values of the heterogeneity factor (n) indicated heterogeneous adsorption. The adsorption kinetics analysis indicated that the pseudo-second-order rate model could better describe the adsorption process than the pseudo-first-order rate model.     

Development of a Cross‐Conjugated Vinylogous [4+2] Anionic Annulation and Application to the Total Synthesis of Natural Antibiotic (±)‐ABX

The cross‐conjugated vinylogous [4+2] anionic annulation has been newly developed, the cascade process of which has a high preference for regiochemical control and chemoselectivity, giving rise to exclusively Michael‐type adducts in moderate to high yields (up to 94 %, 35 examples). By making use of this approach as a key operation, the first total synthesis of natural antibiotic ABX, in racemic form, has been successfully achieved in a concise 7‐step sequence with an overall yield of about 20 %.     

Anionic Aliovalent Substitution from Structure Models of ZnS: Novel Defect Diamond-like Halopnictide Infrared Nonlinear Optical Materials with Wide Band Gaps and Large SHG Effects

To design pnictide nonlinear optical materials with wide band gap and large second-harmonic generation, the heavy halogen I was introduced into pnictides through anionic aliovalent substitution with diamond-like ZnS as templates. Thus, four excellent halopnictide-based infrared nonlinear optical crystals, M^II₃PnI₃ (M^II=Zn, Cd; Pn=P, As), were obtained. They all exhibited defect diamond-like structures with highly parallel-oriented [M^IIPnI₃] mixed-anionic tetrahedral groups, leading to excellent physical properties including wide band gaps (2.38–2.85 eV), large second harmonic generation responses (2.7–5.1×AgGaS₂), high laser-induced damage thresholds (5.5–10.7×AgGaS₂), and good IR transparency. In particular, Cd₃PI₃ and Cd₃AsI₃ achieved phase-matching (Δn=0.035 and 0.031) that their template β-ZnS could not do. Anionic aliovalent substitution provides a feasible strategy to design novel promising halopnictide IR NLO materials.