钙催化剂在生物降解脂肪族聚酯合成中的应用

生物降解高分子在环境保护以及组织工程、药物控制释放、骨固定等医药领域有着广泛的应用。特别是以聚丙交酷（PLA）、聚乙交酯（PGA）、聚。一己内酯（PCL）以及它们的共聚物为代表的化学合成生物降解高分子材料，由于具有优异的性能、可以大规模生产、成本较低等优点，得到了人们广泛的关注。作为生物医用材料，对无毒性的要求很严。而现在所用的脂肪族聚酯大都是用金属盐、金属有机化合物等作为催化剂合成出来的，不可避免残留一些催化剂所用的金属元素。研究表明，即使是已经获得美国FDA批准的，现在用得最普遍的辛酸亚锡所残留的锡也可能引起一些细胞毒性。因此对毒性小且活性高的催化剂的研究是非常有意义。钙离子对人体是没有毒性的，因而这几年已引起了人们的兴趣，但文献中报道的钙催化剂，如CaHZ等，催化活性尚不够让人满意。本文对高效的钙催化剂在生物降解脂肪族聚酯中的应用进行详细的研究，得到了一些有意义的结论：1、用EO和PO处理的有机氨钙催化剂（Ca／EO和Ca／PO）聚合了CL和LLA。发现CL聚合速度很快，M／I=650时70℃反应3h后收率已达到90％以上，LLA的聚合速度比CL要慢，M／I=650、70℃反应10h后收率才达到90％以上。以上聚合反应有明显的活性聚合的特点：反应初期Mv和收率和聚合时间呈线性关系；Mv在一定范围内和M／I成线性关系。2、用红外、原子吸收和核磁共振等分析手段阐明了有机氨钙催化剂的结构：结构，而且这两个催化剂的活性中心分别是均是Ca-O键。CL和LLA的开环聚合可能是以配位一插入的机理进行的。3、用C。／PO催化剂聚合LLA时有一定程度的消旋化反应发生，曳NMR研究表明相当于88％的LLA和12％外消旋以共聚。提高反应温度到110℃时比旋光度只有-125℃说明消旋化反应比较严重。4、用C。／PO催化剂先聚合CL再聚合LLA的方法合成了PCL-PLA两嵌段共聚物，并用泊NMR，13C NMR，GPC，DSC，WAXD进行了表征。其绝对和相对分子量可以通过M／I和投料比进行控制。定量碳谱图表明有较严重的消旋化反应发生，相当于84％的LLA和16％外消旋LA共聚。DSC和似XD分析表明，PLA段的分子量小时PLA段不结晶，当PLA段的分子量达到一定程度（3000以上）后PCL一PLA嵌段共聚物有相分离现象发生。5、以各种分子量的PEG为引发剂用氨钙催化剂和开环聚合CL，合成了一系列PCL-PEG-PCL三嵌段共聚物，并用妞NMR，laCNMR，GPC，DSC，做XD进行了表征。聚合物的结构可以通过改变PEG的分子量和CL／PEG投料比来调整。从DSC和wAXD分析可以得出以下几个结论：PCL-PEG-PCL嵌段共聚物有相分离现象发生，形成PCL和PEG微相区域；PEG段的结晶行为受先结晶的PCL段的影响；PCL段的分子量越大PEG段的Tc和Tm越低，其结晶度越低。6、以各种分子量的PEG为引发剂用氨钙催化剂80℃下开环聚合LLA24小时，合成了一系列PLA-PEG-PLA三嵌段共聚物，和别的催化剂比起来温度低得多，反应时间也短得多。可以通过改变PEG的分子量和CL／PEG投料比来调整聚合物的结构。DSC和WAXD分析表明，PLA-PEG-PLA三嵌段共聚物中PEG段的结晶能力受PLA段的影响非常大：当PEG段的分子量很小时（如1000）很难结晶；即使当PEG段的分子量较大时如果PLA段的分子量达到一定程度时PEG段同样也不结晶；而且PLA段的结晶行为受本身分子量的影响比较大，其Tc和伽随着分子量增加有较大的提高。7、合成了MPEG-PLA两嵌段共聚物，发现合成PLA段的分子量大的聚合物比较困难，MPEG-PCL两嵌段共聚物很难合成。DsC和WAXD分析表明，PLA段对MPEG段结晶有一定程度的影响，但是比三嵌段共聚物的影响要小得多。8、用荧光光谱和IHNMR研究了上面合成出的几个样品的胶束行为。发现cmc由大到小的顺序为MPEG（5000）-PLA（5100），PLA（3050）-PEG（4600）-PLA（3050），PCL（2270）-PEG（5000）-PCL（2270），PCL（4600）-PEG（4600）-PCL（4600）。PCL-PEG-PCL三嵌段共聚物在水中形成了具有核一壳结构的胶束。9、以苯甲醇处理的有机氨钙催化剂开环聚合了CL。泊NMR谱图表明得到的聚合物具有苯端基。这一结果为用硝苯基乙醇代替苯甲醇制备催化剂，然后开环聚合CL或LA得到硝基苯端基的脂肪族聚酯打下了实验基础。

基于遥感信息的常州市热岛效应

以常州市区为研究区域,运用"单窗算法"对TM卫星第6波段进行解译,得到卫星过境时常州市区的地表温度(LST)分布图。结果表明:2006年9月18日卫星过境时常州市城区地表平均温度的热岛强度为3.81K;常州热岛效应的空间分布特征为"一个片区结合多个组团",与城市的发展格局基本一致,表明城市化引起的土地利用/土地覆盖变化是形成热岛效应的主要原因;城市工业用地的地表平均温度极显著高于城区,表明工业生产消耗大量能源而产生的人为热对常州市热岛效应的形成以及热岛强度的增强具有显著影响。

Structural and up-conversion luminescence properties in Tm (3+)/Yb3+-codoped heavy metal oxide-halide glasses

Tm3+/Yb3+-codoped heavy metal oxide-halide glasses have been synthesized by conventional melting and quenching method. Structural properties were obtained based on the Raman spectra, indicating that halide ion has an important influence on the phonon density and maximum phonon energy of host glasses. Intense blue and weak red emissions centered at 477 and 650 nm, corresponding to the transitions (1)G(4) -> H-3(6) and (1)G(4) -> H-3(4), respectively, were observed at room temperature. The possible up-conversion mechanisms are discussed and estimated. With increasing halide content, the up-conversion luminescence intensity and blue luminescence lifetimes of Tm3+ ion increase notably. Our results show that with the substitution of halide ion for oxygen ion, the decrease of phonon density and maximum phonon energy of host glasses both contribute to the enhanced up-conversion emissions. (c) 2005 Elsevier B.V. All rights reserved.

室温下连续波运行Tm:YAP泵浦的Ho:YAG激光器

我们报道了一种以二极管泵浦的 1.94 μm Tm:YAP激光器为泵浦源，常温下在2.1 μm连续运行的Ho:YAG激光器。最大输出功率1.5 W，相应斜率效率为17.9%，二极管到的转换效率为5.6%。

Infrared to visible upconversion fluorescence in Yb,Tm : YAG single crystal

Absorption spectrum from 400 to 2000 run and upconversion fluorescence spectra under 940 nm pumping of YAG single crystal codoped with 5 at.% Yb3+ and 4 at.% Tm3+ were studied at room temperature. The blue upconversion emission centered at 483 nm corresponds to the transition (1)G(4) -> H-3(6), the emission band around 646 nm corresponds to the transition (1)G(4) -> F-3(4) of Tm3+. Energy transfer from Yb3+ to Tm3+ is mainly nonradiative and the transfer efficiency was experimentally assessed. The line strengths, transition probabilities and radiative lifetimes of (1)G(4) level were calculated by using Judd-Ofelt theory. Gain coefficient calculated from spectra shows that the upconversion corresponding with transitions (1)G(4) -> H-3(6) in YAG doped with Yb3+ and Tm3+ is potentially useful for blue light Output. (c) 2006 Elsevier B.V. All rights reserved.

Judd-Ofelt analysis of spectra and experimental evaluation of laser performance of Tm3+ doped Lu2SiO5 crystal

This paper reports that the TM3+:Lu2SiO5 (Tm:LSO) crystal is grown by Czochralski technique. The room-temperature absorption spectra of Tm:LSO crystal are measured on a b-cut sample with 4 at.% thulium. According to the obtained Judd-Ofelt intensity parameters Omega(2)=9.3155 x 10(-20) cm(2), Omega(4)=8.4103 x 10(-20) cm(2), Omega(6)=1.5908 x 10(-20) cm(2), the fluorescence lifetime is calculated to be 2.03 ms for F-3(4) -> H-3(6) transition, and the integrated emission cross section is 5.81 x 10(-18) cm(2). Room-temperature laser action near 2 mu m under diode pumping is experimentally evaluated in Tm:LSO. An optical-optical conversion efficiency of 9.1% and a slope efficiency of 16.2% are obtained with continuous-wave maximum output power of 0.67 W. The emission wavelengths of Tm:LSO laser are centred around 2.06 mu m with spectral bandwidth of similar to 13.6 nm.

Room-temperature cw and pulsed operation of a diode-end-pumped Tm:YAP laser

We report the continuous-wave and acousto-optical Q-switched operation of a diode-end-pumped Tm:YAP laser. Continuous-wave output power of 3.5 W at 1.99 mu m was obtained under the absorbed pump power of 14 W. Under Q-switched laser operation, the average output power increased from 1.57 W to 2.0 W, with an absorbed pump power of 12.6 W, as the repetition rate increased from 1 kHz to 10 kHz. The maximum Q-switched pulse energy was 1.57 mJ with a repetition rate of 1 kHz. The minimum pulse width was measured to be about 80 ns, corresponding to a peak power of 19.6 kW.

利用窄得-奥菲特理论研究Tm:Lu_2SiO_5晶体的光谱特性

采用丘克拉斯基(Czochralski)技术生长了掺铥硅酸镥(Tm∶Lu2SiO5,Tm∶LSO)晶体;测量了LSO晶体在室温下的非偏振吸收光谱和非偏振荧光光谱;利用窄得-奥菲特(Judd-Ofelt)理论计算了Tm∶LSO晶体的窄得-奥菲特强度参数、振子强度、自发辐射概率、辐射寿命、积分吸收截面和积分发射截面.Tm∶LSO晶体的强度参数为Ω2=9.1355×10-20cm2,Ω4=8.4103×10-20cm2,Ω6=1.5908×10-20cm2;Tm∶LSO晶体在1.9μm附近有明显的发射峰(3F4→3H6跃迁),相应的辐射寿命为2.03 ms,积分发射截面为5.81×10-18cm2,半峰全宽(FWHM)为250 nm.用Tm∶LSO晶体在77 K温度下实现了激光运转.利用792 nm的激光二极管(LD)作为抽运源,获得中心波长为1960 nm的激光输出,抽运阈值为2.13 kW/cm2.

Diode-pumped Q-switched Tm:YAP laser with a pump recycling scheme

We reported on a diode end-pumped AO Q-switched Tm:YAP laser at 1937 nm. The average output power was 3.9 W, with a slope efficiency of 29.4% and optical-optical conversion efficiency of 21.6% at a 5-kHz repetition rate. The temperature dependency of the output power and the pulse width at different repetition rates were investigated in details.

Judd-Oflet analysis of spectrum and laser performance of Ho:YAP crystal end-pumped by 1.91-mu m Tm:YLF laser

The Ho:YAP crystal is grown by the Czochralski technique. The room-temperature polarized absorption spectra of Ho:YAP crystal was measured on a c-cut sample with 1 at% holmium. According to the obtained Judd-Ofelt intensity parameters Omega(2) = 1.42 x 10(-20) cm(2), Omega(4) = 2.92 x 10(-20) cm(2), and Omega(6) = 1.71 x 10(-20) cm(2), this paper calculated the fluorescence lifetime to be 6 ms for I-5(7) -> I-5(8) transition, and the integrated emission cross section to be 2.24 x 10(-18) cm(2). It investigates the room-temperature Ho:YAP laser end-pumped by a 1.91-mu m Tm:YLF laser. The maximum output power was 4.1 W when the incident 1.91-mu m pump power was 14.4W. The slope efficiency is 40.8%, corresponding to an optical-to-optical conversion efficiency of 28.4%. The Ho:YAP output wavelength was centred at 2118 nm with full width at half maximum of about 0.8 nm.

Crystal growth, spectroscopic characterization, and laser performance of Tm:LiLuF4 crystal

The National Science Foundation of China(Grant No. 60578044).

探索一种监测典型草原草场退化的新方法--结合群落样方调查资料和卫星遥感数据（TM）

大范围、实时、准确地监测典型草原地区草场退化或健康状况对于草原生态系统的保育、农牧业的可持续性发展具有非常重要的意义。比起传统的群落学研究方法，遥感技术对于监测大尺度的植被状况具有无可争议的优越性，并且已经被广泛引入监测植被覆盖变化的研究中。本项研究系统地分析、综述了过去用非遥感手段对放牧和草场退化的关注和研究，介绍了遥感技术应用于植被研究的理论基础、主要途径（植被指数）、有关领域的研究进展。特别是本文提出草场退化状况或整体健康状况可以由基干相互独立的层面表示，而过去监测植被变化主要依赖的NDVI等植被指数只能监测草原植被的个别层面（总量层）。 本文以草场放牧退化比较典型的内蒙古锡林河流域为研究对象，在进行了大量的野外样方调查的基础上，提出一种结合群落样方调查和遥感技术的监测草场健康状况的新方法。本文引入主成份分析方法（PCA），从包含12个反映群落各方面信息的变量中提取出3个有特定生态学意义的主成份，并进一步对其进行分析组合，得出一个能比较敏感、全面反映群落健康状况的新指标-草场健康指数（GHI）。 从6波段的植被光谱反射数据中比较理想地提取出2个主成份：可见光因子和红外光因子。表征群落总量、放牧退化的主成份和GHI与样方光谱反射值有相当的相关性，由此得到GHI与可光、红外光因子的回归模型。 应用此模型到卫星遥感数据（TM），得到GHI影像，并与同一数据的NDVI影像作对比研究，发现GHI在反映放牧等人为干扰对草原植被的影响效应方面比NDVI有明显的优点。此外，GHI影像对植被分布格局，特别是斑块结构有更好的显示效果。应用GHI到历史TM数据，对所研究地域的植被覆盖变化、农牧业的变迁模式等进行了定性研究。研究还发现有较长放牧史的过度放牧区的植被类型没有沿牧压梯度的规律性分布，而是呈随机斑块分布模式。

彗星电泳检测~(12)C~(6+)离子束辐照人类肝L02细胞的DNA损伤效应

以传能线密度为30keV/μm的12C6+离子束辐照人类肝L02细胞,利用彗星电泳技术检测了以DNA链断裂为生物终点的DNA辐射损伤效应。CASP软件分析彗星图像,主要检测尾部DNA(TDNA%)、彗星全长(CL)、尾长(TL)、尾矩(TM)和Olive尾矩(OTM)等指标,SPSS11.5软件进行统计学分析,绘制并拟合TM-剂量曲线。结果显示,辐照以剂量依赖的方式引起L02细胞彗星图像各指标的增大,且TM值与剂量线性正相关。说明12C6+离子束对DNA有较强的致损伤效应,且与剂量正相关。研究为正确评价重离子对人体正常组织的辐射风险及危害提供了一定的基础数据和依据。

Analysis of spatio-temporal dynamic pattern and driving forces of urban land in China in 1990s using TM images and GIS

China has witnessed fast urban growth in the recent decade. This study analyzes spatio-temporal characteristics of urban expansion in China using satellite images and regionalization methods. Landsat TM images at three time periods, 1990/1991, 1995/1996, and 1999/2000, are interpreted to get 1:100000 vector land use datasets. The study calculates the urban land percentage and urban land expansion index of every 1 km(2) cell throughout China. The study divides China into 27 urban regions to conceive dynamic patterns of urban land changes. Urban development was achieving momentum in the western region, expanding more noticeably than in the previous five years, and seeing an increased growth percentage. Land use dynamic changes reflect the strong impacts of economic growth environments and macro-urban development policies. The paper helps to distinguish the influences of newly market-oriented forces from traditional administrative controls on China's urban expansion. (c) 2005 Elsevier Ltd. All rights reserved.