新型L-氨基酸尾式卟啉及其锌(Ⅱ)配合物的合成与光谱性质

用L-氨基酸和5-[邻-(2-溴乙氧基)苯基]-10,15,20-三苯基卟啉为原料合成了三种新型L-氨基酸尾式卟啉及其锌(Ⅱ)配合物,通过元素分析、红外光谱、紫外光谱、化学分析和质谱等对其进行了结构表征。测试并研究了它们在4 000～400 cm-1范围内的傅里叶变换红外光谱,对主要谱带进行了经验归属。     

The mm-wave dielectric measurements with an electric-field cross-correlation Fourier transform spectrometer

A method for measuring complex permittivity based on an electric-field cross-correlation Fourier transform spectrometer was proposed. Its principle can be extended over the whole microwave region. Two typical solid media, teflon and plexigrass, and a kind of sand were measured in 8mm-wave region by the method. The results show that this method has potentialities to perform accurate permittivity measurements.Supported by Foundation of Specialities Opened to Doctorate Study     

A paradigm shift in rate determining step from single electron transfer between phenylsulfinylacetic acids and iron(III) polypyridyl complexes to nucleophilic attack of water to the produced sulfoxide radical cation: a non‐linear Hammett

Mechanism of oxidative decarboxylation of phenylsulfinylacetic acids (PSAAs) by iron(III) polypyridyl complexes in aqueous acetonitrile medium has been investigated spectrophotometrically. An initial intermediate formation between PSAA and [Fe(NN)₃]³⁺ is confirmed from the observed Michaelis–Menten kinetics and fractional order dependence on PSAA. Significant rate retardation with concentration of [Fe(NN)₃]³⁺ is rationalized on the basis of coordination of a water molecule at the carbon atom adjacent to the ring nitrogen of the metal polypyridyl complexes by nucleophilic attack at higher concentrations. Electron‐withdrawing and electron‐releasing substituents in PSAA facilitate the reaction and Hammett correlation gives an upward ‘V’ shaped curve. The apparent upward curvature is rationalized based on the change in the rate determining step from electron transfer to nucleophilic attack, by changing the substituents from electron‐releasing to electron‐withdrawing groups. Electron‐releasing substituents in PSAA accelerate the electron transfer from PSAA to the complex and also stabilize the intermediate through resonance interaction leading to negative reaction constants (ρ). Conversely, electron‐withdrawing groups, while retarding the electron transfer exert an accelerating effect on the nucleophilic attack of H₂O which leading to low magnitude of ρ⁺ compared to high ρ^? values of electron‐releasing groups. Marcus theory is applied, and a fair agreement is seen with the experimental values. Copyright © 2016 John Wiley & Sons, Ltd.     

面向低强度无线网络信号接收谱参数估计研究

针对以北斗卫星导航信号为代表的亚纳秒级的低强度无线网络信号在定位中难以获取精确时间估计及角度估计,且易受环境噪声影响,使其定位精度不高等难题,本文提出了基于亚纳秒级的低强度无线网络信号接收谱参数估计方法。首先通过抽样方式,将发射信号抽样为多维独立子信号并独立建模,通过构造噪声空间与子信号空间在对应列向量正交化的基础上精确获取TOA估计;随后利用复数域映射,在获取TOA估计基础上采取比对方式精确地获取DOA估计。最后对本文参数估计方法进行了精度分析。测试数据显示：与 PM算法、ESPRIT算法相比,本文技术在TOA及DOA估计上更为精确;同时在信号强度低且背景噪声干扰严重的情况下,本文方法仍可有效的维持参数估计精度。     

铽－甲基吲哚乙酰丙酮三元配合物发光过程研究

测定和分析了ＲＥ．Ｌ１．Ｌ２（ＲＥ＝Ｔｂ（Ⅲ）、Ｇｄ（Ⅲ），Ｌ１＝３Ｍ（３甲基吲哚－１－乙酰基丙酮），Ｌ２＝ＴＰＰＯ、Ｐｈｅｎ、Ｄｉｐｙ）三元配合物的荧光光谱、磷光光谱、磷光寿命及变温荧光光谱等．讨论了Ｔｂ（Ⅲ）与配体之间的能级匹配和Ｌ１与Ｌ２的三重态之间传能的问题，说明了影响这些三元配合物荧光效率的主要因素及其发光过程．     

FTIR－PAS技术在卟啉类化合物中的应用（Ⅳ）──稀土乙酰丙酮－meso－四－（α－萘基）四苯并卟啉配合物的红外光谱

研究了ｍｅｓｏ－四－（α－萘基）四苯并卟啉及其Ｄｙ，Ｈｏ，Ｅｒ，ＴＭ，Ｙｂ，Ｌｕ乙酸丙酮形成的配合物在３６００～２２０ｃｍ－１范围内的傅里叶变换红外光声光谱（ＦＴＩＲ－ＰＡＳ），对主要谱带进行了经验归属。结果表明，四－（ａ－萘基）四苯并卟啉与稀土乙酰丙酮配合物中稀土金属离子配位削弱了乙酰丙酮环上Ｍ—Ｏ键的伸缩振动，使此谱带向低波数位移。金属敏感港带出现在～１５１３，～１３２３～１０９０，１０５３和～２５０ｃｍ－１。     

Mössbauer studies of mixed-valence spin-crossover iron complexes with a hexadentate tripod ligand

The spin-crossover behaviors of mixed-valence iron compounds [Fe^IIH₃L][Fe^IIIL](NO₃)₂ (1) and [Fe^IIH₃L^Me][Fe^IIIL^Me](NO₃)₂ (2) have been investigated by ⁵⁷Fe Mössbauer spectroscopy, where H₃L is a hexadentate N₆ tripod ligand containing three imidazole groups and H₃L^Me is its 2-methylimidazole derivative. Deconvolution analyses of the Mössbauer spectra revealed that a two-step SCO (LS Fe^II–LS Fe^III→HS Fe^II–LS Fe^III→HS Fe^II–HS Fe^III) proceeds in each compound on elevating the temperature. Compound 2 exhibited lower spin-transition temperatures than 1. “Frozen-in effect” was observed below 120 and 50 K for 1 and 2, respectively.     

Vibrational dynamics of the organometallic compound triarylorganoantimony (V) SbPh<Subscript>3</Subscript>[O<Subscript>2</Subscript>CC(OH)Ph<Subscript>2</Subscript>]<Subscript>2</Subscript>

A complete normal coordinate analysis was performed for five-coordinate non-rigid triarylantimony diester SbPh₃(O₂CR)₂, known to be a bioactive molecule, using Wilson G-F matrix method and Urey Bradley force field. The study of vibrational dynamics was performed using the concept of group frequencies and band intensities.      

对Reissner-Nordstrm-anti-de Sitter黑洞Hawking隧穿辐射的研究

在考虑粒子间的自引力相互作用后,首先采用Parikh-Wilczek的半经典隧穿方法对带电粒子与不带电粒子在Reissner-Nordstrm-anti-de Sitter黑洞视界处的隧穿辐射特征进行了研究.其次,推广复路径方法对该黑洞的辐射谱进行研究.两种方法所得的结果都支持Parikh-Wilczek的观点,即黑洞的隧穿率Bekenstein-Hawking熵变有关,真实的辐射谱不是纯热谱.