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     

K0.9Li0.1（Ta0.5Nb0.5）O3晶体压电应变系数的测量

用准静态ｄ＿（３３）测量仪和干涉法相结合。测量了Ｋ＿（０．９）Ｌｉ＿（０．１）（Ｔａ＿（０．５）Ｎｂ＿（０．５）Ｎｂ＿（０．５））Ｏ＿３晶体的压电应变系数。结果为：ｄ＿（３３）＝８６．０，ｄ＿（３３）＝一２９．５，ｄ＿（１５）＝１１２．９×１０￣（－１２）Ｃ／Ｎ．     

温度调谐LBO晶体光参量振荡器

本文详细研究０．５３２μｍ激光泵浦、温度调谐Ⅱ型非临界相位匹配ＬＢＯ光参量振荡器。当温度从２０℃升高到２００℃时，其信号波和闲置波的调谐范围分别为１．００２～０．８９８μｍ和１．１３４～１．３０６μｍ。本装置最吸引人之处是本征输出线宽比Ⅰ型情形小一个量级。     

The influence of hard‐segments on two‐phase structure and shape memory properties of PCL‐based segmented polyurethanes

Poly(ε‐caprolactone)‐based segmented polyurethanes (PCLUs) were prepared from poly(ε‐caprolactone) diol, diisocyanates (DI), and 1,4‐butanediol. The DIs used were 4,4′‐diphenylmethane diisocyanate (MDI), 2,4‐toluenediisocyanate (TDI), isophorone diisocyanate (IPDI), and hexamethylene diisocyanate (HDI). Differential scanning calorimetry, small‐angle X‐ray scattering, and dynamic mechanical analysis were employed to characterize the two‐phase structures of all PCLUs. It was found that HDI‐ and MDI‐based PCLUs had higher degree of microphase separation than did IPDI‐ and TDI‐based PCLUs, which was primarily due to the crystallization of HDI‐ and MDI‐based hard‐segments. As a result, the HDI‐based PCLU exhibited the highest recovery force up to 6 MPa and slowest stress relaxation with increasing temperature. Besides, it was found that the partial damage in hard‐segment domains during the sample deformation was responsible for the incomplete shape‐recovery of PCLUs after the first deformation, but the damage did not develop during the subsequent deformation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 557–570, 2007     

Crystallographic report: Crystal structure of tetra(4‐methyl‐5‐imidazole‐carboxyaldehyde)zinc(II) diperchlorate

The central zinc(II) atom in the title complex is tetrahedrally coordinated by four nitrogen atoms derived from 4‐methyl‐5‐imidazolecarboxyaldehyde ligands with Zn? N in the range 2.007(3) to 2.026(4) Å. Copyright © 2003 John Wiley & Sons, Ltd.     

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     

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。     

激光诱导H_2S催化裂解制备H_2的研究

在室温常压静态条件下研究了以Ｖ２Ｏ５／ＴｉＯ２为催化剂，紫外脉冲激光诱导Ｈ２Ｓ催化分解为Ｈ２和Ｓ的反应及其机理。考察了产氢量与激光不同照射条件之间的关系。     

高Q Ba(Zn_(1/3)Ta_(2/3))O_3介质谐振器材料及其在毫米波系统中的应用

叙述了Ｂａ（Ｚｎ１／３Ｔａ２／３）Ｏ３介质谐振器材料的制备、结构、微波性能及典型应用。Ｂａ（Ｚｎ１／３Ｔａ２／３）Ｏ３介质材料介电常数εｒ为２９．５，频率温度系数τ≈０（－５５～＋８５℃），１０ＧＨｚ下最大无载Ｑ值１４７００，在２８ＧＨｚ测得Ｑ值约为４８００。这种材料具有高Ｑ值，特别适用于Ｘ以上波段作为振荡器电路中频率稳定元件。用这种介质谐振器已研制出８ｍｍ介质稳频微带耿氏振荡器，频率稳定度小于１０×１０－６／℃，最大输出功率达１８０ｍＷ。