Sign Response Mechanism of TCA Self-assembled Fluorescence Probe for Cu~(2+) Detection: FRET Evidence by DFT

A new type of self-assembled molecule ON-OFF fluorescence probe for toxic transition metal ions, made up of thiacalix[4]arene, micelle and fluorescence group, has been studied by DFT/TDDFT method combined with experiment spectra. Since the mechanism of the optical quenching signal response of such self-assembled micelle probe has always been a controversial issue of uncertainty, the spatial construction and geometric structures of the functional units of probe in the Cu~(2+) ion detecting process were calculated and the mechanism was investigated by the molecular transition orbital pairs method to explore the origination of ON-OFF fluorescence sign response. The results presented that the signal response mechanism of the micelle probe is ascribed to F?rster resonance energy transfer(FRET) which provides new sights different from most of the conclusions by the related research work reported.     

ERDS-RE''''NYI大数律下自正则的效用

｛Ｘ，Ｘｉ，ｉ≥１｝是ｉ．ｉ．ｄ．ｒ．ｖ′．ｓ．在矩母函数存在的条件下，由古典的Ｅｒｄｏｓ－Ｒéｎｙｉ大数律有ｌｉｍｎ→∞ｍａｘ０≤ｋ≤ｎ∑ｋ＋［ｃｌｏｇｎ］ｉ＝ｋ＋１Ｘｉ［ｃｌｏｇｎ］＝α（ｃ），α（ｃ）为某常数．自正则下ＭｉｋｌóｓＣｓｏｒｇｏ＆ＳｈａｏＱｉｍａｎ（１９９４）在仅要求一阶矩的条件下就得到了：ｌｉｍｎ→∞ｍａｘ０≤ｋ≤ｎ∑ｋ＋［ｃｌｏｇｎ］ｉ＝ｋ＋１Ｘｉ∑ｋ＋［ｃｌｏｇｎ］ｉ＝ｋ＋１（Ｘ２ｉ＋１）＝β（ｃ），β（ｃ）为某常数．众所周知，自正则下人们往往在较弱条件下取得相应结果是因为：分母中的Ｘ能有效抵销分子中Ｘ较大而引起整个分式极限行为的波动．因此，在什么样的条件下，式ｍａｘ０≤ｋ≤ｎ∑ｋ＋［ｃｌｏｇｎ］ｉ＝ｋ＋１Ｘｉ∑ｋ＋［ｃｌｏｇｎ］ｉ＝ｋ＋１Ｘ２ｉ１－β［ｃｌｏｇｎ］β→ｒ（ｃ）成为非常有意思的问题，因为它将依赖于β的大小．本文给出，当０＜β≤１２时，只要Ｅ（Ｘ）≥０，上式就有有限极限．当１２＜β＜１时，则必须在矩母函数存在下，上式才有有限极限．并都求出了其极限表达式．     

A Density Functional Theory Study on Electronic Structure and Second—order Nonlinear Optical Properties of Some Push—Pull Molecules

Time-dependent density-functional theory(TDDFT)has been applied to calculate the electronic structure and second-order nonlinear optical(NLO) properties of some organic molecules.The two-dimensional(2-D)charge transfer charateristics of calculated molecules were studied and compared with corresponding experimental results.All the theoretical results agree well with the measurement.For 2-D molecule with two-fold symmetry,the dominant charge transfer is off-diagonal,while for three-fold symmetry 2-D molecule,the dominant charge transfer is not only between branches and central group but also among branches.     

行列可交换不相关随机变量组列的中心极限定理之收敛速度

（ｘｉｊ）为行列可交换不相关随机变量组列,本文讨论ｓｕｐ│ｐ（ａ＾－１ｎＴｎ〈ｘ）－Φ（ｘ）│→０的速度（其中Ｔｎ＝１／ｎ２ｎΣｉ＝１ｎΣｊ＝１ｘｉｊ,Ｏ＾２ｎ＝ＶａｒＴｎ,Φ（ｘ）为标准正态分布函数）,取得了与Ｕ－统计量情形下相同的结果。     

某些过渡金属钌配合物非线性光学性能的从头算和密度泛函理论研究

实验发现金属钌的某些配合物具有大的非线性光学性能。我们的理论研究表明 金属钌配合物[Ru(NH_3)_4L~DL~A]~(n+) (n = 2，3；L~D，L~A =吡啶衍生物配体) 的非线性光学性能取决于推电子基团L~D的给电子能力以及拉电子基团L~A的受电子 能力，L~D和L~A的推拉电子越强越有利于提高配合物的二阶非线性光学系数β，因 此带正电荷的L~A能大幅度提高β值。虽然增加共轭体系的长度有利于提高β值， 但在Ru的配合中，吡啶环间或吡淀环与苯环间不一定要保持共面也会有大的β值。 DFT和ab initio方法的计算结果对比表明，对于含过渡金属Ru的化合物，在HF水平 上难以得到满意的结论，由从头算有限场方法计算得到的β值偏小，而用TDDFT方 法能得到可与实验值符合较好的结果。     

Theoretical Study of Hydrated Cd~（2＋） Interactions with Guanine

Theoretical study was performed to investigate how the hydration of cadmium ca-tion influences the structure and properties of guanine.The aqueous environment was simulated by both explicit solvent(1-5 water molecules) model and implicit solvent model.For complexes in which Cd2+ attached to the N(7) and O(6) sites of guanine,energy analysis together with the Natural Bonding Orbital(NBO) analysis were performed to elucidate the bonding characteristics in detail.The most stable structures are penta-coordinate complexes without aqua ligand located at the guanine site.Higher number of water ligands corresponds to higher stabilization energies.Average bonding energies of G-Cd increase with the number of water molecules.Bonding energies of water ligands depend on its position in the complexes.The charge distribution of guanine changed with increasing the number of water ligands,which may also influence the base-pairing pattern of guanine.There is positive charge transfer from guanine to aqua ligand as the number of the hydration waters increases.IEFPCM optimization has results comparable to the [CdG(H2O)5]2+ structure 5a.     

一水甲酸锂晶体三阶非线性光学性质理论研究

用含时藕合微扰Hartrre一Fork（CPHF）方法，有限场MP2理方法以及有向气 体方法，首次分别在分子和晶体水平上计算了一水甲酸锂晶体三次谐波极化率，表 明超分子γ(一3ω；ω,ω,ω)数值与超分子链长有线性关系；晶体x（一3ω;ω, ω,ω）计算值主要受到电子相关影响，其次受到基组和局域场影响，在非共振 条件下，频率色散的影响甚小'最后，估算了一水甲酸锂的三次谐波系数．     

尿素分子团簇线性和一阶非线性光学极化率的理论计算

检验分子晶体非线性光学极化率的可加性,对于确认有向气体模型(Oriented-Gas Model) 具有重要的科学意义,对探索新型实用的分子非线性光学材料也有实际的意义。本文对尿素晶体中分子簇非线性光学极化率的可加性做了详尽的理论研究。首次做到了尿素分子最近邻排布团簇的非线性光学极化率的从头算,从而扩展了前人的工作。研究结果有效地确认了有向气体模型。同时,我们还提出了壳层结构模型 (Shell-Structure Model),用以解决有向气体模型中的缺陷,可实现更为有效可靠地计算晶体宏观非线性光学系数。     

声学微结构的微流控声场的改进与优化*

受限于加工工艺,目前多数的声表面波微流控芯片,主要依靠普通的直通道调节细胞流速,从而控制微球在通道中的排列。但其形成的声场通常无法满足低能量、多功能的微流控需要。本文在普通声表面波微流控芯片的基础上,分别在频域和时域内构建声学微结构,并改变微结构阵列中铜柱间距,模拟仿真了微流控芯片输出端的电势,发现其输出端电压得到了明显的改善。当输入电信号频率在0-30MHz时,输出端电势增加约0.25V;在0-1000ns内,输出端电势增加0.015V左右;进而可以探索开发性价比更高的声波微流控芯片,针对病理检测等所存在的问题进行分析优化,提出新的细胞分离等技术。