基于有机羧酸配体的Co(Ⅲ)/Cu(Ⅱ)配合物的合成、结构及表征

在溶剂热条件下,以含卤素有机羧酸3-溴-吡啶-2,6-二甲酸(H₂L)为配体,以硝酸钴、硝酸铜为金属源,合成了两例配合物:[Co(L′)₃](1)和[Cu(L′)₂]_n(2)(HL′=5-溴-吡啶-2-甲酸),通过元素分析(EA)、X射线单晶衍射(SXRD)、X射线粉末衍射(PXRD)、红外光谱(IR)和热重分析(TGA)进行结构表征。X射线单晶衍射结果表明,配体H₂L在反应过程中发生脱羧现象,生成单羧酸配体5-溴-吡啶-2-甲酸。在配合物1中,每个Co(Ⅲ)都位于略微扭曲的八面体几何构型中,不对称单元中含有两个单核单元,单核单元通过C—H…O氢键形成三维超分子结构。配合物2的不对称单元中含有一个Cu(Ⅱ),两个脱质子的L′^-配体,每个Cu(Ⅱ)都是六配位的,位于扭曲的八面体几何构型中。Cu(Ⅱ)由配体连接生成1D链结构,通过C—H…O氢键形成三维超分子结构。此外,研究了两例配合物的热稳定性能。     

Facile synthesis of metal-polyphenol-formaldehyde coordination polymer colloidal nanoparticles with sub-50 nm for T_1-weighted magnetic resonance imaging

Plant polyphenol-based coordination polymers(CPs) with ultra-small particle size and tailorable compositions are highly desired in biomedical applicatio ns,but their synthesis is still challenging due to the sophisticated coordination assembly process and unavoidable self-oxidation polymerization of polyphenol. He rein,a general ligand covalent-modification mediated coordination assembly strategy is proposed for the synthesis of water-dispersible CPs with tunable metal species(e.g., Gd,Cu,Ni,Zn,Fe)and ultra-small diameter(8.6-37.8 nm) using nontoxic plant polyphenol(e.g..tannic acid,gallic acid) as a polymerizable ligand.Polyphenol molecules react with formaldehyde firstly,which can effectively retard the oxidation induced self-polymerization of polyphenol and lead to the formation of metal ions containing CPs colloidal nanoparticles.These ultrafine nanoparticles with stably chelated metal io ns are highly water dispersible and thus advantageous for bioimaging.As an example,ultra-small Gd contained CPs exhibit higher longitudinal relaxivity(r_1=25.5 L mmol ~1 s ~1) value with low r_2/r_1(1.19) than clinically used Magnevist(Gd-DTPA,r_1=3.7 L mmol ~1 s ~1).Due to the enhanced permeability and retention effect,they can be further used as a positive contrast agent for T_1-weighted MR imaging of tumour.     

微珠析相微萃取-石墨炉原子吸收法测定岩石样品中痕量铬

采用二苯碳酰二肼为络合剂,正戊醇为萃取剂,乙醇为助溶剂,建立了微珠析相微萃取-石墨炉原子吸收法测定地质样品中痕量Cr的分析方法。实验详细探讨了微珠析相微萃取的析相条件、石墨炉原子吸收工作参数及共存离子的干扰,优化了体系萃取条件。实验结果表明：微珠析相微萃取既起到了分离富集的作用,在石墨炉升温程序中又起到了基体改进剂的作用;当萃取剂用量为0.2～1.5 mL时,使之与水完全互溶所需助溶剂体积约为水相体积的0.2～0.5倍;方法线性范围为0～10 μg·L-1,检出限为0.057 μg·L-1,相对标准偏差（RSD）为3.3%（c= 2.5 μg·L-1,n=11）;当萃取剂用量为1.5 mL、水相体积15 mL时,与直接溶液进样相比其灵敏度可提高10倍。所建立的方法用于地质标准参考物质AGV-2和G-2中Cr的测定,测定值与参考值具有较好的一致性。     

Synthesis of Halopyrazole Matrine Derivatives and Their Insecticidal and Fungicidal Activities

Matrine is a traditional botanical pesticide with a broad-spectrum biological activity that is widely applied in agriculture. Halopyrazole groups are successfully introduced to the C13 of matrine to synthesize eight new derivatives with a yield of 78–87%. The insecticidal activity results show that the introduction of halopyrazole groups can significantly improve the insecticidal activity of matrine on Plutella xylostella, Mythimna separata and Spodoptera frugiperda with a corrected mortality rate of 100%, which is 25–65% higher than matrine. The fungicidal activity results indicate that derivatives have a high inhibitory effect on Ceratobasidium cornigerum, Cibberella sanbinetti, Gibberrlla zeae and Collectot tichum gloeosporioides. Thereinto, 4-Cl-Pyr-Mat has the best result, with an inhibition rate of 23–33% higher than that of matrine. Therefore, the introduction of halogenated pyrazole groups can improve the agricultural activity of matrine.     

广义双二项风险模型的破产概率和Lundberg不等式

本文将双二项分布风险模型推广到资金利率和通货膨胀率下带干扰的新模型--广义双二项风险模型.然后讨论了盈余过程的性质并利用盈余过程的性质获得了广义双二项风险模型的破产概率和Lundberg不等式,最后就保费额服从混合指数分布的情况进行了分析.     

Ultrabright AIEdots with tunable narrow emission for multiplexed fluorescence imaging

AIEgen doped fluorescent nanodots (AIEdots) have attracted lots of attention, due to their superior characteristics as fluorescent probes, such as excellent photostability, large Stokes shift, high brightness and tunable emission. Unfortunately, most of the currently available AIEdots exhibit broad emission bandwidth, which limits their applications in multiplexed fluorescence imaging and detection. In this work, the strategy of designing and fabricating narrow emissive AIEdots (NE-AIEdots) with tunable wavelengths was presented by constructing a light-harvesting system with high energy transfer efficiency. Efficient intra-particle energy transfer from highly doped AIEgens, serving as the light-harvesting antenna, to the lightly doped narrow emissive fluorophore, resulted in high brightness and narrow emission. The emission band of NE-AIEdots with the full-width-at-half-maximum varied from 18 to 36 nm was 3–6.3 times narrower than that of traditional AIEdots. The single-particle brightness of NE-AIEdots was over 5-times that of commercial quantum dots under the same excitation and collection conditions. Taking advantage of the superior performance of these NE-AIEdots, multiplexed fluorescence imaging of lymph nodes in living mice was realized, which supported the future applications of NE-AIEdots for in vivo multiplexed labeling and clinical surgery.

AIEdots with high brightness and narrow emission bandwidth were developed for multiplexed in vitro and in vivo fluorescence imaging.     

金属超材料TEM-TE11高功率微波模式转换器

利用高折射率的金属超材料作为移相器,设计了一种紧凑型高功率微波TEM-TE11模式转换器。通过研究同轴扇形金属栅格超材料的传输特性,得到高折射率的全金属超材料。采用CST Microwave Studio 软件对金属超材料TEM-TE11模式转换器进行了数值模拟,结果显示：该转换器在1.56 GHz附近转换效率大于96%,相对带宽约4%,功率容量不低于2 GW,系统纵向长度仅0.42个波长。将所设计的模式转换器结合L波段磁绝缘线振荡器开展了一体化设计,在器件输出口得到了TE11模高功率微波输出。     

跌落冲击载荷下焊锡接点金属间化合物层的动态开裂

跌落冲击载荷作用下,含铅焊锡接点与无铅焊锡接点的破坏模式明显不同,而导致这种差异的原因目前尚不明朗.论文提出了一种可用于模拟焊锡接点在跌落冲击载荷下破坏行为的有限元模型,此模型中,金属间化合物(IMC)与焊料间的界面采用粘性区模型(CZM)来模拟其损伤开裂过程,而IMC层内的破坏程度则通过计算其能量释放率来判断.通过对板级封装跌落冲击过程的数值模拟发现,与无铅焊锡接点(Sn3.5Ag)相比,含铅焊锡接点(Sn37Pb)与IMC间的CZM层更容易发生损伤破坏,而该层的开裂会减小IMC层的应力,即降低了其内部的开裂驱动力,从而缓解了IMC层裂纹的起始和扩展.     

家鸽头部的磁性物质

磁铁矿可以在很多生物组织中被发现,国外研究者同样在家鸽上喙皮肤组织中发现了规则分布的超顺磁磁铁矿颗粒。他们应用透射电子显微镜确认了这些小磁铁矿晶体为尺寸在1—5 nm 的聚集体,集中存在于皮下组织中。这些超顺磁粒子聚集体又形成直径为1—3 μm的粒子束,分布在大细胞之间的长形结构中,并且与神经组织紧密相连。应用光学显微镜和电子显微镜,国外研究者也对家鸽上喙传入三叉神经末梢的次细胞组织进行了研究。这些神经末梢组织直径大约5 μm,内部包含着聚集成束的超顺磁磁铁矿颗粒。大约10到15个粒子束存在于一个神经末梢中,沿着细胞膜排列。每一个超顺磁粒子束包埋在一个纤维杯中,口朝向细胞表面,通过纤维组织,这些粒子束粘附在细胞表面上。除了超顺磁颗粒,非晶态铁磷酸盐也被发现,它们沿着神经末梢的纤维中心分布。解剖特征表明,这些神经末端可以探测很小的地磁场强度的变化,考虑到以超顺磁磁铁矿颗粒为基础的“磁接收器”理论,他们还给出了几个“磁接收器”的模型。     

激光沉积修复BT20合金的显微组织和力学性能

针对BT20钛合金锻件当量孔损伤进行激光沉积修复试验,考察了修复试样的组织和力学特点。修复区与基材之间形成了致密冶金结合,Al,Zr,Mo,V合金元素由锻件基体到激光修复区均匀分布,无宏观偏析,硬度分布从基材到修复区依次提高。热影响区组织是由基材的双态组织过渡到网篮组织;修复区组织为粗大的原始柱状晶,晶粒内为/网篮组织,晶内片层取向随机, 宽0.4~0.5 m。修复过程中发现,激光加工工艺参数选择不当、坡度过大等原因会造成修复区组织形成气孔和熔合不良等缺陷,但是通过优化工艺参数可以获得无缺陷修复试样。修复试样的室温静拉伸结果表明,试样的抗拉强度接近锻件基体强度,但修复件的韧性比锻件稍有提高。