Ab initio modelling of crosslinking in polymers. A case of chains with furan rings

A quantum chemical model (Abinitio HF-MO and DFT-B3LYP) of polyfurfuryl alcohol crosslinking is shown. Two pathways were considered: (a) a Diels–Alder (D–A) reaction between a dihydrofuran moiety and a furan ring; (b) the addition reaction of electrophilic specimens on conjugated double bonds. The ability for the formation of D–A adducts (dienes and dienophiles) was investigated by the frontier molecular orbital (FMO) theory. Energy gaps between the FMO's of diene and dienophile structures suggest that the occurrence of the D–A reaction is possible. The results suggest that the carbons of the exo double bonds attached to dihydrofuran rings are the sites most likely to be attacked by electrophilic species, while the C₃ and C₄ atoms display the opposite tendency due to their low HOMO electron densities. Results of a thermochemical approach to these reactions at the MP2 level was in agreement with reactivity modelled by MO predictions.     

Bipyridinophane‐containing conjugated polymers modulated with an intramolecular aromatic C?H/π interaction

Bipyridinophane–fluorene conjugated copolymers have been synthesized via Suzuki and Heck coupling reactions from 5,8‐dibromo‐2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane and suitable fluorene precursors. Poly[2,7‐(9,9‐dihexylfluorene)‐co‐alt‐5,8‐(2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane)] ( P7 ) exhibits large absorption and emission redshifts of 20 and 34 nm, respectively, with respect to its planar reference polymer Poly[2,7‐(9,9‐dihexylfluorene)‐co‐alt‐1,4‐(2,5‐dimethylbenzene)] ( P11 ), which bears the same polymer backbone as P7 . These spectral shifts originate from intramolecular aromatic C? H/π interactions, which are evidenced by ultraviolet–visible and ¹H NMR spectra as well as X‐ray single‐crystal structural analysis. However, the effect of the intramolecular aromatic C? H/π interactions on the spectral shift in poly[9,9‐dihexylfluorene‐2,7‐yleneethynylene‐co‐alt‐5,8‐(2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane)] ( P10 ) is much weaker. Most interestingly, the quenching behaviors of these two conjugated polymers are largely dependent on the polymer backbone. For example, the fluorescence of P7 is efficiently quenched by Cu²⁺, Co²⁺, Ni²⁺, Zn²⁺, Mn²⁺, and Ag⁺ ions. In contrast, only Cu²⁺, Co²⁺, and Ni²⁺ ions can partially quench the fluorescence of P10 , but much less efficiently than the fluorescence of P7 . The static Stern–Volmer quenching constants of Cu²⁺, Co²⁺, and Ni²⁺ ions toward P7 are of the order of 10⁶ M^?1, being 1300, 2500, and 37,300 times larger than those of P10 , respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4154–4164, 2006     

Controlled structure and density of “living” polystyrene brushes on flat silica surfaces

Thin layers of polystyrene were grown from surface-grafted nitroxide initiators via controlled “living” free radical polymerization. The “reactive” Langmuir-Blodgett deposition method allowed an effective control of the initiator layer density leading to PS brushes with different and high grafting density and stretching. The influence of the grafting density on the layer structure was studied. Comparison with theoretical predictions for monodispersed brushes in bad solvent was discussed. The thickness was found to vary linearly with molecular weight and the density dependence was shown using wetting measurements. Special features of controlled radical nitroxide polymerization from a surface were discussed. A direct comparison of the molecular weight and polydispersity between surface and bulk polymers was made by de-grafting the brushes into a toluene/HF solution. Finally, some evidence of a “surface Fischer” effect was shown from re-initiated layers. Received 20 December 2001     

不同方法制备的CO2-3替换磷灰石固溶体晶体化学的FTIR研究

采用不同方法制备了CO2-3替换的磷灰石固溶体,利用FTIR结合XRD对其进行了晶体化学研究,结果表明均相沉淀法制备的碳羟磷灰石(CHAP)属B型替换且替换方式是[CO3·OH]四面体替换[PO4]四面体;固相离子交换法制备的CHAP属A型替换且替换方式是[CO3]三角形配位体替换通道位置的OH-;固相反应法制备的碳氟磷灰石(CFAP)属B型替换,其替换方式是[CO3·F]四面体替换[PO4]四面体;sol-gel法制备的CHAP属AB混合型替换,其Ψ3分裂为Ψ3-1,Ψ3F,Ψ3-4.高斯函数法拟合表明Ψ3F峰是A型替换的Ψ3-2与B型替换的Ψ3-3的叠合.当WCO2-3＜3.34%时,随CO2-3含量增加,A型替换量增大,且当WCO2-3=3.34%时达最大值,当3.34%＜WCO2-3＜7.52%时,随CO2-3含量增加,B型替换量增大,且当WCO2-3= 7.52%时亦到饱和.     

Structural and lithium intercalation studies of Mn(0.5−x)CaxTi2(PO4)3 phases (0≤x≤0.50)

Materials from the Mn_(0.5−x)Ca_xTi₂(PO₄)₃ (0≤x≤0.50) solid solution were obtained by solid-state reaction in air at 1000 °C. Selected compositions were investigated by powder X-ray diffraction analysis, ³¹P nuclear magnetic resonance (NMR) spectroscopy and electrochemical lithium intercalation. The structure of all samples determined by Rietveld analysis is of the Nasicon type with the R space group. Mn²⁺/Ca²⁺ ions occupy only the M1 sites in the Ti₂(PO₄)₃ framework. The divalent cations are ordered in one of two M1 sites, except for the Mn_0.50Ti₂(PO₄)₃ phase, where a small departure from the ideal order is observed by XRD and ³¹P MAS NMR. The electrochemical behaviour of Mn_0.50Ti₂(PO₄)₃ and Mn_(0.5−x)Ca_xTi₂(PO₄)₃ phases was characterised in Li cells. Two Li ions can be inserted without altering the Ti₂(PO₄)₃ framework. In the 0≤y≤2 range, the OCV curves of Li//Li_yMn_0.50Ti₂(PO₄)₃ cells show two main potential plateaus at 2.90 and 2.50–2.30 V. Comparison between the OCV curves of Li//Li_(1+y)Ti₂(PO₄)₃ and Li//Li_yMn_0.50Ti₂(PO₄)₃ shows that the intercalation occurs first in the unoccupied M1 site of Mn_0.50Ti₂(PO₄)₃ at 2.90 V and then, for compositions y>0.50, at the M2 site (2.50–2.30 V voltage range). The effect of calcium substitution in Mn_0.50Ti₂(PO₄)₃ on the lithium intercalation is also discussed from a structural and kinetic viewpoint. In all systems, the lithium intercalation is associated with a redistribution of the divalent cation over all M1 sites. In the case of Mn_0.50Ti₂(PO₄)₃, the stability of Mn²⁺ either in an octahedral or tetrahedral environment facilitates cationic migration.     

~（23）Na~（39）K分子D~1∏→X~1∑~＋激光感生荧光光谱及强度研究

实验获得了Ａｒ＋激光５１４．５ｎｍ线诱导２３Ｎａ３９Ｋ分子产生的Ｄ１∏→Ｘ１∑＋跃迁荧光谱．通过测量激光感生荧光光谱强度随泵浦功率、热管炉温度及缓冲气压变化规律，详细研究了其跃迁机制．用最小二乘法拟合获得２３Ｎａ３９Ｋ分于Ｘ１∑＋态振动常数．理论计算了各跃迁谱支波长值及Ｆｒａｎｃｋ－Ｃｏｎｄｏｎ因子和光谱强度值，与实验观测值符合得相当好，充分表明本文对激光感生荧光光谱的归属以及对各支谱线振、转量子数的赋值是合理的．     

Spectroscopy of the regenerative soot

The mechanisms and processes of the formation of the regenerative soot in a graphite hollow cathode discharge that produces and emits carbon clusters are presented. Mass spectrometry with a specially designed E×B velocity filter analyzes the entire range of the charged clusters from C ₁ to ∼C ₄₃₀₀. The state of the carbon vapour within the source is evaluated by using the characteristic line emissions from the carbonaceous discharge whose formative mechanisms depend upon the kinetic and potential sputtering of the sooted cathode. The carbonaceous discharge generates atomic and ionic C and its clusters C _m (m≥ 2), noble gas metastable atoms and ions, energetic electrons and photons in the cavity of the graphite hollow cathode. The parameters of soot formation and its recycling depend critically on the discharge parameters, the geometry of the hollow cathode and 3D profile of the cusp magnetic field contours. Received 2nd July 2001 and Received in final form 10 September 2001     

利用莫尔条纹的准正弦特性的三维轮廓术

分析了两个矩形光栅迭合产生的莫尔条纹的光强分布特性，通过选择适当的光栅参数，可得到一个近似的正弦分划板，并把它用于三维面形测量中，实验结果表明，这种方法简单，易于自动处理，有广泛的实用价值。     

Codiameters of 3‐connected 3‐domination critical graphs

A graph G is 3‐domination critical if its domination number γ is 3 and the addition of any edge decreases γ by 1. Let G be a 3‐connected 3‐domination critical graph of order n. In this paper, we show that there is a path of length at least n?2 between any two distinct vertices in G and the lower bound is sharp. © 2002 John Wiley & Sons, Inc. J Graph Theory 39: 76–85, 2002     

Skein related links in 3-manifolds

This paper addresses two problems in the skein theory of homotopy spheres first posed by P. Traczyk. Solutions to both problems are obtained for a large class of manifolds and, since one of the basic techniques used requires the first homology group of the ambient manifold to be torsion free, the extent to which this hypothesis is actually necessary is further explored.