Stereochemistry of cyclobutanone resulted from cycloadditions of t-butylcyanoketene to bicyclo[2.2.1]heptene derivatives, as evidence for a π2s+π2a reaction mode

The stereochemistry of the cyclobutanones 1-7, resulted from the reaction of t-butylcyanoketene with bicyclo[2.2.1]heptene, bicyclo[2.2.1]heptadiene, 1,4 - dihydro - 1,4 - methanonaphthalene, 1,4 - dihydro - 9 - (1 - methylethylidene) - 1,4 - methanonaphthalene, 1,4 - dihydro - 1,4 - epoxynaphthalene, l,4,4a,8b - tetrahydro - 1,4 - methanobiphenylene (l,4,4a,8b) and 1,4,4a,8b - tetrahydro - 1,4 - methanobiphenylene(1,4,4aβ,8bβ) was established as having the cyclobutanone ring exo and the t-Bu group in the configuration. These findings represent a stereochemical argument in favour of a _π2_s + _π2_a reaction mode of t-butylcyanoketene to the above mentioned bicyclo[2.2.1]heptene derivatives. Observations regarding preservation of the original configurations of alkenes as well as the geometrical distorsion of the cyclobutanones are shortly discussed.     

Ruthenium(II) dendrimers containing carbazole-based chromophores as branches

Three new luminescent and redox-active Ru(II) complexes containing novel dendritic polypyridine ligands have been synthesized, and their absorption spectra, luminescence properties (both at room temperature in fluid solution and at 77 K in rigid matrix), and redox behavior have been investigated. The dendritic ligands are made of 1,10-phenanthroline coordinating subunits and of carbazole groups as branching sites. The first and second generation species of this novel class of dendritic ligands (L1 and L2, respectively; see Figure 1 for their structural formulas) have been prepared and employed. The metal dendrimers investigated are [Ru(bpy)(2)(L1)](2+) (1; bpy = 2,2'-bipyridine), [Ru(bpy)(2)(L2)](2+) (2), and [Ru(L1)(3)](2+) (3; see Figure 2). For the sake of completeness and comparison purposes, also the absorption spectra, redox behavior, and luminescence properties of L1 and L2 have been studied, together with the properties of 3,6-di(tert-butyl)carbazole (L0) and [Ru(bpy)(2)(phen)](2+) (4, phen = 1,10-phenanthroline). The absorption spectra of the free dendritic ligands show features which can be assigned to the various subunits (i.e., carbazole and phenanthroline groups) and additional bands at lower energies (at lambda > 300 nm) which are assigned to carbazole-to-phenanthroline charge-transfer (CT) transitions. These latter bands are significantly red-shifted upon acid and/or zinc acetate addition. Both L1 and L2 exhibit relatively intense luminescence at room temperature in fluid solution (lifetimes in the nanosecond time scale, quantum yields of the order of 10(-2)-10(-1)) and at 77 K in rigid matrix (lifetimes in the millisecond time scale). Such a luminescence is assigned to CT states at room temperature and to phenanthroline-centered pi-pi triplet levels at 77 K. The room-temperature luminescence of L1 and L2 is totally quenched by acid or zinc acetate. The metal dendrimers exhibit the typical absorption and luminescence properties of Ru(II) polypyridine complexes. In particular, metal-to-ligand charge-transfer (MLCT) bands dominate the visible absorption spectra, and formally triplet MLCT levels govern the excited-state properties. Excitation spectroscopy evidences that all the light absorbed by the dendritic branches is transferred with unitary efficiency to the luminescent MLCT states in 1-3, showing that the new metal dendrimers can be regarded as efficient light-harvesting antenna systems. All the free ligands and metal dendrimers exhibit a rich redox behavior (except L2 and 3, whose redox behavior was not investigated because of solubility reasons), with clearly attributable reversible carbazole- and metal-centered oxidation and polypyridine-centered reduction processes. The electronic interaction between the carbazole redox-active sites of the dendritic ligands is affected by Ru(II) coordination.     

垂直水声通信中的伪随机序列精确定时算法*

针对垂直水声通信中时变多普勒引起的定时偏差问题,研究一种基于伪随机序列的迭代定时估计及补偿算法。该方法利用伪随机序列作为同步信号,分三步估计时变多普勒：采用低复杂度的模糊函数法粗补偿接收信号内的平均多普勒;通过迭代插值法实现残留时变多普勒的精确估计及补偿;利用基于信道相关函数的相位信息,纠正均衡后信号的偏转相位。为实现高阶海试数据的有效解调,采用基于伪随机序列均方误差的多通道加权合并方式,获得空间分集增益。仿真及海试数据处理结果证明所提方法具有良好的时变多普勒估计及补偿性能,同时对30个通道内的1024QAM数据进行合并处理,在500 m的通信距离下,误码率为0.04,信道容量达到7.6 bits/symbol。与传统数据帧结构相比,无需使用线性调频信号,可以提高有效数据传输率。     

脉冲软X光辐射三种材料的喷射冲量实验研究

 在强光一号脉冲加速器上进行了国内首次的实验室软X光辐射三种材料的喷射冲量研究。结果表明，在能量为(0.2～0.33)keV、平均脉宽为39ns左右的X光辐射下，对灰漆、白漆和硬铝，在能注量分别为(92～152)J/cm²、(115～136)J/cm²和(163～192)J/cm²时，它们的冲量耦合系数分别为(0.61～0.80)Pa·s/(J·cm^-2)、(0.58～0.97)Pa·s/(J·cm^-2)和(0.61～0.84)Pa·s/(J·cm^-2)。     

磁场中多原子极性晶体中体极化子的基态能量

研究磁场中多原子极性晶体中体极化子的性质,采用线性组合算符法,分别导出强,弱耦合情形下体极化子的基态能量。     

高反射膜激光零几率损伤阈值的实验研究

在确定光学薄膜激光损伤阈值的实验数据处理过程中,发现一些样品的数据点分布偏离直线型式。对此,用国际标准规定的零几率来确定损伤阈值的同时,对测试数据点采用了不同的非直线拟合,也得到一个零几率损伤阈值。比较两者差异,并与实验测试结果对照,发现这些样品采用非直线拟合得出的零几率损伤阈值与实际情况更接近一些。     

掺杂聚苯乙烯制备研究

讨论了惯性约束聚变研究中采用化学及物理手段在聚苯乙烯（PS）材料掺杂卤素、硅、氘等非金属元素以及铁、铬、钛等金属元素的原理和方法。利用硅烷偶联剂对氧化物表面进行了预处理,采用本体聚合的方式将氧化物掺杂在PS网络之中,简述了它们在ICF中的应用。     

热处理条件对PVA薄膜阻氢性能的影响

采用XRD测定了PVA薄膜在不同热处理条件下的结晶度,并用自行设计的渗氢系数测量系统研究了在不同热处理条件下的PVA薄膜阻氢性能的变化规律。结果表明,PVA薄膜的热处理温度越高,其结晶度越高,越有利于提高PVA薄膜的阻氢性能,但热处理温度宜选择在180℃以下,以防止PVA薄膜热降解,另一方面,在PVA的玻璃化转变温度以下进行热处理同样能够提高PVA薄膜的阻氢性能,而醇解度较低的PVA薄膜在玻璃化转变温度以下经热处理后的阻氢性能提高的幅度较大。     

三氧化二铝-聚苯乙烯复合微球的制备

以Al2O3-PS复合材料为原料,采用乳液微封装法制备出掺杂Al2O3的PS空心微球。三相溶液分别是两个水相：蒸馏水（W1相）、5wt%PVA水溶液（W2相）和3wt%Al2O3-PS溶液（O相,苯和三氯甲烷混合物作溶剂）。所得微球表面粗糙度低于50nm。