Alternating conjugated and transannular chromophores: tunable property of fluorene-paracyclophane copolymers via transannular pi-pi interaction

[structure-see text]A series of fluorene-dithia[3.3]paracyclophane copolymers was synthesized by Suzuki coupling reactions of suitable precursors. Transannular pi-pi interactions altered the electronic and optical properties of the polymer backbone significantly. A large red shift in the emission spectrum of the unsubstituted polymer was accompanied by enhanced photoluminescence (PL) efficiency. Substitution in the cyclophane unit resulted in PL quenching.     

Limit theorems for sums of dependent random variables

Summary In Lai and Stout [7] the upper half of the law of the iterated logarithm (LIL) is established for sums of strongly dependent stationary Gaussian random variables. Herein, the upper half of the LIL is established for strongly dependent random variables {X _i} which are however not necessarily Gaussian. Applications are made to multiplicative random variables and to f(Z _i ) where the Z _i are strongly dependent Gaussian. A maximal inequality and a Marcinkiewicz-Zygmund type strong law are established for sums of strongly dependent random variables X _i satisfying a moment condition of the form E¦S _a,n ¦^pg(n), where , generalizing the work of Serfling [13, 14].Research supported by the National Science Foundation under grant NSF-MCS-78-09179Research supported by the National Science Foundation under grant NSF-MCS-78-04014     

Doeblin's big limit theorem

Doeblin regarded his paper(²) as his hardest work. The big limit is that ofP(ⁿ)(x, E) asn tends to infinity, in a measurable non-topologized space. An exposition of part one of this paper was published in Ref. 1. This is the exposition of part two, which contains some reparation as well as clarification.Doeblin's great contributions to probability theory were remembered at a conference 50 Years after Doeblin: Developments in the Theory of Markov Chains, Markov Processes and Sums of Random Variables held at Blaubeuren. Germany November 2–7, 1991. Professor Chung contributed this article to further celebrate this occasion. The editor thanks him.     

有机质谱学在中药鱼腥草研究中的应用

研究了中药鱼腥草的挥发性物质和鱼腥草注射液的有效成分。用CC／MS方法鉴定了鱼腥草挥发性物质和鱼腥草注射液有效成分的化学组成，从二者中共鉴定出48个化合物。研究结果表明：二者中的化学组成基本相同。主要成分有：2-十一烷酮(甲基正壬酮)、癸酰乙醛(鱼腥草素)、苯甲醛、薄荷醇、冰片乙酸酯、2-十一烯醛、正十一烷醇、葵酸、δ-瑟林烯、肉豆蔻醚、斯巴醇、石竹烯氧化物、二苯胺及十六酸。占优势的化合物为甲基正壬酮，它在鱼腥草的挥发性物质中和鱼腥草注射液的有效成分中分别占9．8％和9．2％。作为鱼腥草中的特有物质癸酰乙醛(鱼腥草素)，在鱼腥草的挥发性物质中和鱼腥草注射液的有效成分中分别占5．1％和2．6％。本文还讨论了甲基正壬酮和癸酰乙醛结构的确定。     

[K_2(TNR)(H_2O)]_n的制备、分子结构和热分解机理

2,4,6-三硝基间苯二酚(斯蒂芬酸)及其盐类,如斯蒂芬酸铅、斯蒂芬酸钡等是常用的含能材料犤1犦,但斯蒂芬酸铅盐及钡盐在爆炸后产生重金属污染,对使用人员的健康及环境都产生危害。同时,斯蒂芬酸铅盐和钡盐存在一些缺陷,如斯蒂芬酸铅对静电敏感、生产不安全等,这就要求人们寻求新的产品来代替它们。近年来钾含能配合物以其低毒性、良好的安定性引起了火工药剂专家和研究人员的重视犤2～9犦,成为了含能材料行业一个重要研究方向。因此,我们选择了斯蒂芬酸与氢氧化钾反应制备了斯蒂芬酸钾,并就其晶体结构及热分解机理进行了研究。1实验部分1.1仪…     

Electronic spectroscopy, photophysical properties, and emission quenching studies of an oxidatively robust perfluorinated platinum porphyrin

The highly electron-deficient, beta-octafluorinated meso-tetrakis(pentafluorophenyl)-porphyrin (H(2)F(28)TPP) was metalated with platinum to afford the oxidatively robust luminophore [PtF(28)TPP], and its X-ray structure shows that the porphyrin core exists in a slightly saddle-shaped conformation. The absorption spectrum of [PtF(28)TPP] in CH(2)Cl(2) displays a near-UV Soret band (B) at 383 nm (epsilon = 2.85 x 10(5) dm(3) mol(-1) cm(-1)) and two visible Q(1,0) and Q(0,0) bands at 501 (epsilon = 1.45 x 10(4) dm(3) mol(-1) cm(-1)) and 533 (epsilon = 1.36 x 10(4) dm(3) mol(-1) cm(-1)) nm, respectively. These absorption bands of [PtF(28)TPP] are blue-shifted from those in [PtF(20)TPP] (390, 504, and 538 nm, respectively) and [PtTPP] (401, 509, and 539 nm, respectively). Excitation of [PtF(28)TPP] (complex concentration = 1.5 x 10(-6) mol dm(-3)) in dichloromethane at the Soret or Q(1,0) or Q(0,0) band gave a phosphorescence with peak maximum at 650 nm (lifetime = 5.8 micros) and a weak shoulder at 712 nm. Both the emission lifetime and quantum yield vary with solvent polarity, and plots of tau versus E(K) and Phi versus E(K) (where E(K) is the empirical solvent polarity parameter based on the hypsochromic shift of the longest wavelength absorption of the [Mo(CO)(4)[(C(5)H(4)N)HC[double bond]NCH(2)C(6)H(5)]] complex with increasing solvent polarity; see: Kamlet, M. J.; Abboud, J. L. M.; Taft, R. W. Prog. Phys. Org. Chem. 1981, 13, pp 485-630) show linear correlation, indicating that the emission is sensitive to the local environment/medium. Electrochemical studies on [PtF(28)TPP] by cyclic voltammetry showed no porphyrin-centered oxidation at potential < or = 1.5 V versus Ag/AgNO(3), demonstrating that [PtF(28)TPP] is more resistant toward oxidation than [PtF(20)TPP] (E(1/2) = 1.33 V) and [PtTPP] (E(1/2) = 0.97 V). The porphyrin-centered reduction of [PtF(28)TPP] occurs at -0.75 and -1.18 V, which is anodically shifted from those at -1.06 and -1.55 V in [PtF(20)TPP], and -1.51 V in [PtTPP], respectively. The excited-state reduction potential of [PtF(28)TPP] is estimated to be 1.49 V versus Ag/AgNO(3). Over 97% of the emission intensity of [PtF(28)TPP] was retained after irradiation with a high power mercury arc lamp (500 W) for 14 h, compared to 90% and 12% for [PtF(20)TPP] and [PtTPP], respectively; hence, [PtF(28)TPP] exhibits superior photostability. Quenching of the emission of [PtF(28)TPP] by oxygen, alcohol, catechol, and butylamine reveals that [PtF(28)TPP] is an oxidatively robust material with medium-sensitive photoluminescence properties.     

对氟苯酚-H_2O_2-HRP体系酶联荧光免疫分析研究ⅢF~--Al-酸性铬蓝K荧光熄灭法测定人血清中乙肝E抗原

建立了一种检测人血清中乙肝Ｅ抗原的新荧光光度法．通过酶促反应：对氟苯酚＋Ｈ２Ｏ２ＨＲＰ→苯酚＋Ｆ－＋Ｈ２Ｏ与Ａｌ－酸性铬蓝Ｋ荧光体系相偶合，测定辣根过氧化物酶（ＨＲＰ）及其标记物．测定ＨＲＰ的线性范围为０．１９～３１ｍＵ／ｍＬ，检出限为０．０４ｍＵ／ｍＬ．     

稀土钒磷酸盐荧光粉的共沉淀法合成及光致发光

以稀土、钒的氯化物为原料，以氨水、双氧水和磷酸氢二铵溶液作复合沉淀剂，采用共沉淀工艺合成了YP1-xVxO4：RE^3 (RE=Sm，Eu，Dy，Tm，Er)荧光粉。利用XRD，SEM，紫外以及真空紫外激发下的发射光谱对其进行表征，并探讨其实际应用的可能性。结果表明，共沉淀法合成的稀土钒磷酸盐荧光粉颗粒形貌规则、均一；YP0.2V0.8O4：Eu^3 荧光粉发射主峰位于619．5nm，是现有PDP商品(Y，Gd)BO3：Eu^3 荧光粉的良好替代品；发射橙红光的YP0.4V0.6O4：Sm^3 荧光粉是价格低廉的稀土三基色灯用Y2O3：Eu^3 红粉的替代品；Dy^3 ,Tm^3 共掺杂YP0.4V0.6O4可直接得到发白光的二基色灯用荧光粉。     

Crystal Radii and Their Application on the Study of Electronic Structures of LaX(X=N,P,As,Sb)

以Ｐｈｉｌｉｐｓ－ＶａｎＶｅｃｈｔｅｎ理论和晶体光学性质为基础，计算了ＬａＸ（Ｘ＝Ｎ，Ｐ，Ａｓ，Ｓｂ）晶体的离子半径（单位：ｎｍ）：（Ｌａ：Ｎ）为（０．１４１４，０．１２３６），（Ｌａ：Ｐ）为（０．１５１８，０．１４８９），（Ｌａ：Ａｓ）为（０．１５３６，０．１５２６），（Ｌａ：Ｓｂ）为（０．１５８６，０．１６５１）．用ＬＭＴＯ－ＡＳＡ方法对ＬａＸ系列晶体的能带结构进行了计算．所得到的能隙是：ＬａＮ为２．３０ｅＶ，ＬａＰ为２．０５ｅＶ，ＬａＡｓ为１．６６ｅＶ，ＬａＳｂ为１．３４ｅＶ．与实验结果相符．这也证明了作者得到的半径的合理性．     

酚氧桥联铜钴异双核配合物的密度泛函研究

用密度泛函方法,在ROB3LYP/SDD//ROB3LYP/LanL2MB水平上,对酚氧桥联CuⅡ-CoⅡ异双核配合物CuCo(TS)(H2O),进行了理论计算.优化得到了它的单、三重态的平衡几何构型,计算了它们的谐振动频率.结果表明,该配合物分子的三重态比单重态稳定;电子自旋布居高度集中在Co(6)及其周围的配体原子上,而Cu（1）则没有发现电子自旋布居; 体系中存在较强的自旋离域效应.体系的前线分子轨道主要由Co(6)的d轨道和配体原子的p轨道组成,这有利于配体原子与Co(6)之间的电子转移.计算结果与实验符合得很好.