激光诱导击穿光谱结合标准加入法定量分析未知样品中铅含量

利用激光诱导击穿光谱结合标准加入法定量分析了铅蓄电池厂含铅污泥中重金属铅元素含量,标准加入法有效避免了外标法与内标法制作标准曲线时基质不同对LIBS检测结果的影响,且样品处理过程简单。实验采用中心波长为1 064 nm的Nd∶YAG脉冲激光器作为激发光源,以高分辨率、宽光谱段的中阶梯光栅光谱仪和增强型电荷耦合器件为谱线分离与探测器件,选取铅的PbⅠ：405.78 nm特征谱线作为分析线,以FeⅠ：404.58 nm特征谱线作为内标线进行结果计算。预实验确定较佳的实验条件后(激光脉冲能量：128.5 mJ,延时：2.5 μs,门宽：3 μs),对铅蓄电池厂的未知铅泥样品中铅元素进行定量分析,结果表明加入铅在0~25 000 mg·kg-1范围内谱线不会产生自吸收,PbⅠ：405.78 nm信号强度与铅加入量呈很好的线性关系,由此确定合适的铅加入量为0~25 000 mg·kg-1。在此基础上配制四个样品,基质均为铅蓄电池厂含铅污泥,加入铅浓度分别为5 000,10 000,15 000,20 000 mg·kg-1,每个样品设置三个平行样,验证实验重复性及可靠性,并与ICP-MS检测结果对比,结果直线外推误差为-14.8%。12个样品单次计算结果误差介于为-24.6%~17.6%之间,含铅量平均值为43 069 mg·kg-1,相对误差为-2.44%。     

基于FBG反射谱特征的修补结构裂纹扩展监测

为了提高飞行器壁板裂纹修补结构的安全性,对基于光纤布拉格光栅(FBG)反射谱特征的航空铝合金修补结构疲劳裂纹扩展长度及角度监测方法进行了研究。修补结构在疲劳载荷的作用下,裂纹发生扩展,其尖端附近会产生不均匀应变场,在其作用下FBG传感器反射谱发生变形,通过检测反射谱变形达到监测裂纹扩展的目的。建立了实验样件的模型,使用有限元方法计算得到不同角度下裂纹扩展到不同长度时的应变分布,使用传输矩阵数值计算方法得到相应的FBG反射谱。提取反射谱的主峰偏移、反射谱面积、次峰峰值和三峰峰值等变形特征,建立并训练人工神经网络(ANN),通过ANN建立反射谱变形特征同裂纹扩展情况的关系,实现了对修补结构裂纹扩展的精确监测,监测裂纹长度误差在0.5 mm之内,角度误差在5°之内。解决了修补结构的裂纹扩展精确监测问题,对提高飞行器安全以及节约维护成本有着重要意义。     

稀土尾矿砂放射性活度的测量与计算分析

准确测量并计算稀土尾矿砂的放射性活度浓度及其变化规律对制定相应的豁免标准和日后的处理处置具有重要的意义。根据选取的特征 射线,分析对比平衡与非平衡状态下铀系、钍系、锕系三个天然衰变系的总活度浓度,结合衰变链的一般动力学方程,计算总放射性活度与每个核素的放射性活度,并研究钍系各核素在平衡被不同程度破坏的情况下随时间的变化规律。结果显示,按照非平衡情况下计算得出的总α 和总β 放射性活度浓度比平衡情况下的更接近实际测量结果,此外,钍系核素在平衡被破坏后的放射性活度随时间变化情况与母体和228Ra 的初始放射性活度浓度有关,若228Ra 小于232Th,则总放射性活度在60 a再次平衡后达到最大值,为10 倍的母体活度;若228Ra 大于232Th,则总放射性活度在3.82 a 出现最大值,为4.57 倍母体活度与5.25 倍第一子体228Ra 的初始活度浓度之和。因此,可知稀土尾矿砂放射性活度已经遭到破坏,其总活度浓度应该采用非平衡情况下的几个特征核素的活度浓度共同计算得到,并且需计算分析其随时间变化出现的最大值,以此来确定是否超过相关法规标准。It is of great significance to measure and calculate rare earth tailing radioactivity for the development of appropriate standards and exemption disposal. The total activity concentration of the three natural decay series (uranium series, thorium series, actinium series) was analyzed under the equilibrium and disequilibrium state according to the selected characteristic  γ-rays. At the same time, we calculated the total activity concentration and the radioactivity for each radionuclide based on the general kinetic equations of decay chain and studied the trend of each radionuclide of thorium-series under different degrees of disequilibrium with time. The results demonstrated that the total radioactivity of and calculated in disequilibrium state was more closed to the actual measurement results compared to that in equilibrium state. In addition, the activity changes with time of thorium series in disequilibrium state are related to the initial activity concentration of the mother nuclide and 228Ra. If the activity concentration of 228Ra is less than that of 232Th, the total activity peak will be 10 times to maternal activity and appear after 60 a when the thorium series become balance again. If the activity concentration of 228Ra is greater than that of 232Th, the maximum total activity will appear in 3.82 a, and will be the sum of 4.57 times of the initial activity concentration of the mother nuclide and 5.25 times of the initial activity concentration of the first daughter 228Ra. Therefore, the rare earth tailings have been in disequilibrium state, and its total activity concentration should be determined based on the activity concentration of several  feature radionuclides. In addition, the maximum value of the activity concentration is profitable to judge whether the activity concentration is fit with relevant regulations and standards.     

硅胶键合膦的制备及其对铑络合物催化1-辛烯氢甲酰化反应的影响

以硅胶为载体, 采用键合接枝法将2-(二苯膦基)乙基三乙氧基硅烷(DPPES)共价键合于硅胶表面, 制备了性能优良的硅胶键合型膦配体(以SiO₂(PPh₂)表示). 以SiO₂(PPh₂)为配体, Rh(acac)(CO)₂ (acac:乙酰丙酮)为催化前体, 负载铑膦络合物催化剂(SiO₂(PPh₂)/Rh)在1-辛烯氢甲酰化反应中原位生成. 对生成的负载型催化剂和硅胶键合型膦配体进行了傅里叶变换红外(FTIR)光谱表征, 考察了膦/铑摩尔浓度比([P]/[Rh])、温度等因素对铑催化的长链1-辛烯氢甲酰化反应的影响. 结果表明, 膦/铑摩尔浓度比的增加能显著提高反应的成醛选择性, 降低铑的流失. 在[P]/[Rh]=12、363 K、2.0 MPa、1.5 h 的温和反应条件下, 1-辛烯转化率和成醛选择性分别可达98.4%和95.3%, 其催化活性与DPPES或三苯基膦(TPP)作配体时的均相铑催化相近. 催化剂循环4 次后, 反应活性无明显下降, 1-辛烯转化率均在97.0%左右, 经电感耦合等离子体原子发射光谱(ICP-AES)检测,有机相中铑流失低于0.1%.     

常压微等离子体阳极与离子溶液界面的电荷转移反应

常压微等离子体电极是一种有望取代常用贵金属电极用于电化学反应的气体电极. 然而目前关于微等离子体阳极与离子溶液界面反应的研究及其用于金属电沉积的报道还较少. 本文使用常压微等离子体作为阳极, 通过紫外-可见吸收光谱监测阳极电解液中亚铁氰化钾被氧化生成的铁氰化钾的含量, 发现铁氰化钾的含量随放电时间的延长而增加, 并且其增加的速率与放电电流成比例. 在放电结束后, 随着放置时间的延长铁氰化钾的含量继续升高, 其升高的速率与放电时间的长短有关. 放电结束后铁氰化钾含量的增加速率远小于放电时的增加速率. 实验结果表明微等离子体电极可以作为气体阳极在等离子体和液体界面进行电荷传输, 并引发电化学反应, 同时在放电的过程中产生了氧化活性物质. 在饱和硫酸铜溶液中, 使用微等离子体阳极可以在不锈钢阴极上进行铜的电沉积, 电流效率达到90%.     

一氧化碳的发现与燃素说的终结

考察一氧化碳的发现过程可知,这不仅是一种化学物质的发现史,也是燃素说的兴衰史。笃信燃素说的英国科学家普里斯特利首先在实验室制取并研究了它,称之为重可燃空气。相信氧化学说的英国化学家克鲁克香克用实验证明了它是一氧化碳,使当时的科学家大都皈依氧化学说,从而终结了燃素说。这段历史让人们认识到创新的理论思维对于科学研究的重要意义。     

新型氧钒(IV)席夫碱配合物［VO(dtbsal-met)(phen)和VO(naph-met)(phen)］的合成及其抗肿瘤活性

以L-蛋氨酸（met）, 1,10-邻菲啰啉（phen）和3,5-二叔丁基水杨醛（dbsal）［或2-羟基-1-萘醛（naph）］为原料,经胺醛缩合反应合成了两个新型的氧钒(IV)席夫碱配合物［VO(dtbsal-met)(phen)（1）和VO(naph-met)(phen)（2）］,其结构经IR, HR-ESI-MS,摩尔电导和X-射线单晶衍射表征。1（CCDC：1 429 158）和2（CCDC：1 429 159）分别属单斜晶系和三斜晶系。用MTT法研究了1和2对人肺腺癌细胞（A549）和人源肝癌细胞（HepG2）的体外抗肿瘤活性。结果表明：1和2对A549和HepG2均表现出一定的抑制活性。     

Synthesis and Secondary Conformations of Homochiral β-Oligopeptides Containing Aryl Side Chains

A series of novel homochiral β-oligopeptides bearing aryl side chains was designed and synthesized from (S)-β-phenyl-β-amino acid derivatives by solution-phase methods. By means of circular dichroism(CD), Fourier- transform infrared spectrometry(FTIR), powder X^-ray diffraction analysis(XRD) and density functional theory(DFT) calculations, we suggest that dipeptide P-2 and tripeptide P-3 adopt random coil-like conformations, pentapeptide P-5 and hexapeptide P-6 adopt stable 12-helix conformations in both solution and solid-state. Meanwhile, tetrapeptide P-4 adopt random coil-like conformation in solution and adopt 12-helix conformation in solid state.     

Effect of Polyhedral Oligomeric Silsesquioxane and Sorbitol on Properties of Isotactic Polypropylene

Isotactic polypropylene(iPP) was modified by the introduction of polyhedral oligomeric silsesquio- xanes(POSS) and 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol(DMDBS). Chemical combination of (3-mercapto)- propyl-heptaisobutyl POSS with DMDBS(POSS-DMDBS), and physical mixing of DMDBS with octaisobutyl POSS (iso-POSS/DMDBS) or trisilanolisobutyl POSS(tri-POSS/DMDBS) were applied respectively to modifying iPP, and the effects of POSS and DMDBS on crystallization, rheological and mechanical properties of iPP were systematically investigated. The results indicate that iso-POSS/DMDBS and tri-POSS/DMDBS were more effective than POSS-DMDBS on the improvement of the crystallization behavior of iPP due to the higher crystallization temperature, while the crystallinity of iPP containing POSS-DMDBS was enhanced, approximately approached to that of iPP containing tri-POSS/DMDBS. The tensile strength of iPP with POSS-DMDBS was significantly increased from 34 MPa to 40 MPa, as high as that of iPP with iso-POSS/DMDBS. The different effects caused by the specific interaction between POSS and DMDBS could possibly be applied in the modification of iPP.     

近红外宽带全方向反射镜的设计

研究了一维光子晶体的全方向反射镜.用传输矩阵法分析了影响全反镜全方向反射带带宽和位置的因素.利用带隙展宽理论,构建异质结构光子晶体,设计得到了近红外宽带全反射镜.比较发现,Te/SiO2构成的一维异质结构全向带反射特性优于TiO2/SiO2构成的一维异质结构,该反射镜TE偏振波的全方向反射带分布在近红外波段1 001 ～ 2999 nm范围内,TM偏振波的全向反射带分布在1001 ～2323 nm波段范围内,获得的反射率高于98;,而薄膜层数只需要20层.