Solid state NMR characterization of formation of poly(ϵ‐caprolactone)/maghnite nanocomposites by in situ polymerization

Results of multinuclear MAS NMR spectroscopy are reported for poly (ε‐caprolactone)/maghnite nanocomposite formation, with ε‐caprolactone in situ polymerized in the presence of maghnite, a proton exchanged montmorillonite clay. Exfoliated and intercalated materials with different maghnite loading in the range 3–15 wt % were investigated. ¹H NMR evidences Brønsted acid hydroxyl groups in the silicate layers and shows that their broad signal at 7.6 ppm present in the parent clay disappears in the nanocomposite material. ²⁷Al MAS NMR results show that beside the hexacoordinated aluminum signal, two additional peaks corresponding to two different tetrahedral Al sites are present in the clay framework. The NMR signal intensity of only one of them was found to be affected in the nanocomposites compared with the parent maghnite, suggesting that these specific aluminum sites are the reactive ones at the initial stages of the polymerization. However almost no changes occurred in the ²⁹Si NMR spectra, confirming that the polymer grafting, as indicated earlier by atomic force microscopy, took place on the aluminum tetracoordinated sites rather than on the silicon sites. A mechanism of maghnite surface catalyzed polymerization of ε‐caprolactone was proposed, involving Brønsted and Lewis acid sites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3060–3068, 2007     

Synthesis of spherical and hemispherical sugar‐containing poly(ornithine) dendrimers

A novel sugar‐containing poly(ornithine) dendrimer is synthesized for possible antigen delivery and related applications. The dendrimer contains an ornithine dendron as interior scaffolding and oligosaccharides on the periphery, which provide an attachment site for a peptide antigen. Maltose or lactose is bound to both hemispherical and spherical poly(ornithine) dendrimer generation 3 (G3) by reductive amination between its reducing end and the peripheral amino group of the dendrimer using a borane‐pyridine complex in a buffer solution at 50 °C. The degree of substitution of sugar is changed by varying the molar ratio of sugar to dendrimer. When the surface of spherical poly(ornithine) dendrimer G3 is modified by binding β‐alanine to the 16 amino groups, highly substituted maltose‐ or lactose‐β‐alanine‐poly(ornithine) dendrimer G3 is obtained in high yield after 7 days of reaction. The structures of these sugar‐containing dendrimers are characterized by NMR and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analyses. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1400–1414, 2004     

Degree bounds for syzygies of invariants

Suppose that G is a linearly reductive group. Good degree bounds for generators of invariant rings were given in (Proc. Amer. Math. Soc. 129 (4) (2001) 955). Here we study minimal free resolutions of invariant rings. For finite linearly reductive groups G it was recently shown in (Adv. Math. 156 (1) (2000) 23, Electron Res. Announc. Amer. Math. Soc. 7 (2001) 5, Adv. Math. 172 (2002) 151) that rings of invariants are generated in degree at most the group order |G|. In characteristic 0 this degree bound is a classical result by Emmy Noether (see Math. Ann. 77 (1916) 89). Given an invariant ring of a finite linearly reductive group G, we prove that the ideal of relations of a minimal set of generators is generated in degree at most ?2|G|.     

The samarium(II)-mediated intermolecular couplings of ketones and β-alkoxyacrylates: a short asymmetric synthesis of an antifungal γ-butyrolactone

The samarium(II) iodide-mediated coupling of ketones with β-alkoxyacrylates gives β-hydroxy-γ-butyrolactones in moderate yield. The process has been applied to the asymmetric synthesis of an antifungal, γ-butyrolactone natural product.     

A Bitangential Interpolation Problem on the Closed Unit Ball for Multipliers of the Arveson Space

We solve a bitangential interpolation problem for contractive multipliers on the Arveson space with an arbitrary interpolating set in the closed unit ball . The solvability criterion is established in terms of positive kernels. The set of all solutions is parametrized by a Redheffer transform. Submitted: February 2, 2002.     

5-(对羧基苯偶氮)-8-羟基喹啉与钍的显色反应及应用

研究了钍与5-(对羧基苯偶氮)-8-羟基喹啉(5-CPAHQ)的显色反应条件:在阳离子表面活性剂十六烷基三甲基溴化铵(CTMAB)存在下,pH4.4-5.4缓冲介质中,形成稳定的橙红色络合物,最大吸收波长为490nm,ε=1.10×105L·mol-1·cm-1,钍在0-9μg/25mL范围内符合比尔定律。用TBP萃淋树脂分离,该方法可用于测定矿石中的微量钍。     

热线法测定气体导热系数实验的探讨与改进

在准静态低气压下测量气体的热传导系数时，理论上在低压强范围内应得到Q^-1低-p^-1线性关系图象，但实验数据所绘出的图象出现明显的非线性．本文着重分析出现非线性的原因，并提出实验改进的方法。     

Inhibitors of biotin biosynthesis as potential herbicides

Isosteric derivatives and analogues of the 7-keto-8-aminopelargonic acid (KAPA), 7,8-diaminopelargonic acid (DAPA) and desthiobiotin (DTB) vitamer intermediates involved in the biosynthetic pathway of biotin were prepared and evaluated as potential herbicides. The most active compound was desmethyl-KAPA which displayed a GR₅₀ (concentration of the active compound that causes a 50% growth inhibition) value of 8 ppm, where values <50 ppm are considered herbicidal. Other KAPA analogs where the terminal Me group was replaced by bulkier substituents such as Et, i-Pr and HOCH₂ showed moderate activity.     

Rapid syntheses of oligo(p-phenyleneethynylene)s via iterative convergent approach

A general and controlled bidirectional growth strategy enable a very rapid and efficient construction of oligo(phenyleneethynylene)s possessing functional groups such as methylthio and thioacetate groups at both ends. The strategy employs only one reaction type with good to moderate yields to grow the conjugated chains. The synthesis is efficient and can give 23 benzene rings and 22 carbon-carbon triple bonds in the conjugated chains. The compounds are fully characterized by ¹H and ¹³C NMR and UV/vis and fluorescence spectroscopy.     

Robust Output Tracking Control of an Uncertain Linear System via a Modified Optimal Linear-Quadratic Method

This study investigates the robust output tracking problem for a class of uncertain linear systems. The uncertainties are assumed to be time invariant and to satisfy the matching conditions. According to the selected nominal parameters, an optimal solution with a prescribed degree of stability is determined. Then, an auxiliary input via the use of an adapting factor, connected to the nominal optimal control, is introduced to guarantee the robustness and prescribed degree of stability for the output tracking control of the uncertain linear systems. This method is very simple and effective and can reject bounded uncertainties imposed on the states. A maglev vehicle model example is given to show its effectiveness.