色谱灰色数模的建立及其应用研究(Ⅱ)——NLCGM(1,1)模型的建立及芳烃保留行为的预测

色谱保留值与流动相组成间关系的研究一直是色谱工作者关心的课题［１,２］．灰色模型对于处理具有不确定关系的两因素间的关系问题具有独到之处,在容量因子（ｋ）与流动相组成（φ）关系的研究方面已得到了应用［３～８］．传统ＧＭ（１,１）模型将ｋ与φ之间的关...     

灰色模型预测气相色谱法中的保留值

应用灰色理论中的ＧＭ（１,１）模型,对气相色谱法中容量因子ｋ＇和温度倒数１／Ｔ之间的关系进行了研究,求出了许多火炸药组分的ａ和ｕ值,并随机预测了几种火炸药组分的ｋ＇值。结果指出,灰色理论完全适用于对气相色谱保留值问题的研究,方法也完全能应用于实际工作中。     

微分方程演化建模用于色谱保留时间的研究

利用演化算法的自适应、自组织、自学习的特性,设计了遗传程序设计与遗传算法相嵌套的混合演化建模算法,以遗传程序设计优化模型结构,以遗传算法优化模型参数,为化合物的液相色谱容量因子随流动相组成变化关系自动建立微分方程演化模型．通过对７个化合物的建模结果表明,演化模型的拟合和预测精度均明显高于常规的ＧＭ（１,１）模型和改进的ＧＭ（１,１）模型．     

连续型非等时空距灰色模型在液相色谱保留值研究中的应用

本运用灰色理论中的连续型等时空距ＧＭ（１，１）模型，对液相色谱中流动相组成与容量因子间的关系进行了研究，建立了可进行连续预测的数学模型，所建模型与实际情况吻合很好，经检验各模型精度均达到Ｉ级。     

非等时空距灰色模型在液相色谱保留值研究中的应用

本文运用灰色理论中的非等时空距ＧＭ（１，１）模型，对液相色谱中的流动相组成及容量因子的关系进行了研究。所建灰色模型经过检验其精度为Ｉ级。实验结果表明，不仅等时空距灰色模型，而且非等时空距灰色模型，同样适用于色谱保留值的研究。     

稳健灰色模型在色谱保留值研究中的应用

本文提出了具有稳健性的ＧＭ（１，１）灰色模型，并用此模型对８种多环芳烃化合物容量因子与流动相组成间的关系作了研究，建立了其间的稳数学模型，结果表明，稳健ＧＭ（１，１）模型比常规ＧＭ（１，１）模型具有更好的抗干扰性能和受异常点影响小的优点，是一个值得推广的好方法。既丰富了灰色系统理论，又拓宽了灰色理论在分析化学中的应用范围。     

色谱灰色数模的建立及应用研究（Ⅳ）：CGM（1,1,N）模型的 …

应用灰色系统理论，推导出灰色Ｎ参数模型ＣＧＭ（１，１，Ｎ），突破了现有单参数灰色模型的局限性，并用该模型讨论了色谱保留值与分子结构参数间绎烷基苯的同分异构体色谱保留值及疏水性参数进行了预测，经实例验证，其预测精度较单参数灰色模型高，这为溶质保留行为的预测提供了一个实用方法，同时也拓宽了灰色模型的应用范围。     

静态GM（0,6）灰色模型在预测气相色谱保留指数上的应用

本文从麦克雷诺（ＭｃＲｅｙｎｏｌｄｓ）相常数法出发推导了五种标准物质与任意溶质ｉ的色谱保留指数之间的关系符合灰色ＧＭ（０，６）模型，对它们进行了灰色建模。获得了很高的模型精度，并根据模型式预测了涂有不同固定液色谱柱中的溶质ｉ的保留指数。通过预测值与文献值的比较，得到了良好的预测精度。     

灰色理论在液相色谱保留值研究中的应用

本文应用灰色理论中的ＧＭ（１，１）模型，对液相色谱中的Ф和ｋ＇的关系进行了研究，其结果达到用Ｓｃｈｏｅｎｍａｋｅｒｓ公式和卢佩章公式预测及计算ｋ＇的水平。结果指出：灰色理论完全适用于对色谱保留问题的研究，其方法也这无全能满足实际工作中的应用。     

改进的GM（1,1）模型及其在色谱保留值研究中的应用

由于常规ＧＭ（１，１）模型对批相ＨＰＬＣ中化合物容量因子与流动相组成间非线性关系的线性近似以及常规ＧＭ（１，１）模型建模方法所固的缺点，使得常规ＧＭ（１，１）模型的预测精度难以提高。本文用近代非线性回归分析法对建模方法作了改进，建立了具有更高精度的ＧＭ（１，１）模型，并将其用于多环芳烃容量因子随流动相组成变化关系的建模，获得了满意的结果。     

Synthesis and photophysical properties of dihydroheptacenes: new blue-emitting materials

7,16-Dihydroheptacenes (1-3) substituted at the 6, 8, 15, and 17 positions are synthesized as blue emitters potentially useful in organic light emitting diodes (OLEDs). The photophysical properties of 1-3 (lambda(max) = 424-428 nm, phi(F) = 0.15-0.21, tau(F) = 2.35-2.67 ns in CH2Cl2) are discussed. They are shown to be stable and efficient blue emitters in the solid state (phi(F) = 0.37-0.44). The X-ray crystal structure of 1 is reported.     

On the photochemistry of IONO2: absorption cross section (240-370 nm) and photolysis product yields at 248 nm

The absolute absorption cross section of IONO(2) was measured by the pulsed photolysis at 193 nm of a NO(2)/CF(3)I mixture, followed by time-resolved Fourier transform spectroscopy in the near-UV. The resulting cross section at a temperature of 296 K over the wavelength range from 240 to 370 nm is given by log(10)(sigma(IONO(2))/cm(2) molecule(-1)) = 170.4 - 3.773 lambda + 2.965 x 10(-2)lambda(2)- 1.139 x 10(-4)lambda(3) + 2.144 x 10(-7)lambda(4)- 1.587 x 10(-10)lambda(5), where lambda is in nm; the cross section, with 2sigma uncertainty, ranges from (6.5 +/- 1.9) x 10(-18) cm(2) at 240 nm to (5 +/- 3) x 10(-19) cm(2) at 350 nm, and is significantly lower than a previous measurement [J. C. M?ssinger, D. M. Rowley and R. A. Cox, Atmos. Chem. Phys., 2002, 2, 227]. The photolysis quantum yields for IO and NO(3) production at 248 nm were measured using laser induced fluorescence of IO at 445 nm, and cavity ring-down spectroscopy of NO(3) at 662 nm, yielding phi(IO) 相似文献   

Luminescent Zn and Pd tetranaphthaloporphyrins

Zn and Pd complexes of meso-tetraphenyltetranaphthaloporphyrins (Ph(4)TNP) exhibit strong infrared absorption bands and luminesce in solutions at room temperature. S1 --> S0 fluorescence (lambda(max) = 732 nm, phi = 5.3%) is the predominant emission in the case of ZnPh(4)TNP (1). This emission is in part due to the delayed fluorescence (phi = 1.1%). Phosphorescence (T1 --> S0) of 1 (lambda(max) = 973 nm) is very weak (phi = 0.04%) and occurs with lifetime of about 440 micros in deoxygenated DMF. In the case of PdPh(4)TNP (2), almost no S1 --> S0 fluorescence could be observed, while the main emission detected was T1 --> S0 phosphorescence (lambda(max) = 938 nm). The phosphorescence of 2 occurs with lifetime of about 65 micros and (phi=6.5%) in deoxygenated DMF solution. Metalloporphyrins 1 and 2 are promising near infrared dyes biomedical applications.     

Study of acetone photodissociation over the wavelength range 248-330 nm: evidence of a mechanism involving both the singlet and triplet excited states

Measurements of the acetyl yield from acetone photolysis have been made using laser flash photolysis/laser induced fluorescence. Phi(total)(lambda,p,T) was determined over the ranges: 266 < or = lambda/nm < or = 327.5, 0.3 < or = p/Torr < or = 400 and 218 < or = T/K < or = 295. The acetyl yield was determined relative to that at 248 nm by conversion to OH by reaction with O2. Linear Stern-Volmer plots (1/[OH] vs [M]) describe the data for lambda < 300 nm, but for lambda > 300 nm, nonlinear Stern-Volmer plots were observed. This behavior is interpreted as evidence for dissociation from two excited states of acetone: S1 when the Stern-Volmer plots are linear and both S1 and T1 when Stern-Volmer plots are nonlinear. A model for acetone photolysis is proposed that can adequately describe both the present and literature data. Barriers to dissociation are invoked in order to explain the dependence of pressure quenching of the acetone photolysis yields as a function of wavelength and temperature. This pressure quenching was observed to become more efficient with increasing wavelength, but it was only above approximately 300 nm that a significant T dependence was observed, which became more pronounced at longer wavelengths. This is the first study to observe a T-dependent phi(total)(lambda,p,T). A parametrized expression for phi(total)(lambda,p,T) has been developed and is compared against the recommended literature data by running box model simulations of the atmosphere. These simulations show that acetone photolysis occurs more slowly at the top of the troposphere.     

Strand breakage in poly(C), poly(A), single- and double-stranded DNA induced by nanosecond laser excitation at 193 nm.

Single- and double-stranded calf thymus DNA and two polynucleotides (0.4 mM) were studied in aqueous solution at pH approximately 7 using pulsed, 20 ns laser excitation at 193 nm. Monophotonic ionization of the nucleic acids is suggested from the linear dependences of the concentration of ejected electrons and the number of single- and double-strand breaks (ssb, dsb, respectively) on laser intensity (IL) in the range (0.2-3) x 10(6) W cm-2. The quantum yields of formation of hydrated electrons (phi e-) and ssb and dsb (phi ssb and phi dsb) are therefore independent of IL. In contrast, under 248 nm excitation these quantum yields increase linearly with IL under otherwise comparable conditions. Nevertheless, several effects and mechanistic implications are analogous using lambda exc = 193 and 248 nm. For polycytidylic acid, poly(C), in Ar-saturated solution for example, the efficiency of ssb per radical cation (eta RC = phi ssb/phi e-) is similar to the efficiency of ssb per OH radical (eta OH). For polyadenylic acid, poly(A), and single- and double-stranded DNA eta RC (lambda exc = 193 nm) is significantly smaller than eta OH. The ratio phi ssb (N2O)/phi ssb (Ar) is approximately 2 for poly(C), approximately 4 for poly(A) approximately 10 for DNA; the conversion of hydrated electrons into OH radicals in N2O-saturated solution and smaller eta RC than eta OH values in the case of DNA account for these results. For double-stranded DNA phi dsb does not depend on IL but increases linearly with the dose, indicating an accumulative effect of two ssb to generate one dsb. The critical distance for this event is 60-85 phosphoric acid diester bonds.     

1,2,5-噻二唑衍生物电子结构的紫外光电子能谱研究

首次报导了１,２,５－噻二唑衍生物３－氯－１,２,５－噻二唑（Ａ）和３,４＝二氯－１,２,５－噻二唑（Ｂ）化合物的紫外光电子能谱（ＵＰＳ）,谱带的指认建筑在对谱带形状、相对强度、实验电离能（ＩＰＳ）的分析以对研究分子Ｇａｕｓｓｉａｎ ９４ＳＴ０－６Ｇ从头计算电离能（－ε１）。化合物Ｂ ＵＰＳ谱带的ＩＰＳ比相应的化合物Ａ的ＩＰＳ均你芝归结为Ｂ分子中两个取代Ｃ１原子上电子的拥挤效应。计算的Ｂ的 有量（     

Superstructure-dependent optical and electrical properties of an unusual face-to-face, pi-stacked, one-dimensional assembly of dehydrobenzo[12]annulene in the crystalline state

To develop a novel pi-conjugated molecule-based supramolecular assembly, we designed and synthesized trisdehydrotribenzo[12]annulene ([12]DBA) derivative 2 with three carboxyl groups at the periphery. Recrystallization of 2 from DMSO gave a crystal of the solvate 23 DMSO. Crystallographic analysis revealed, to our surprise, that a face-to-face pi-stacked one-dimensional (1D) assembly of 2 was achieved and that the DMSO molecule played a significant role as a "structure-dominant element" in the crystal. This is the first example of [12]DBA to stack completely orthogonal to the columnar axis. To reveal its superstructure-dependent optical and electrical properties, 2 and its parent molecule 1, which crystallizes in a herringbone fashion, were subjected to fluorescence spectroscopic analysis and charge-carrier mobility measurements in crystalline states. The 1D stacked structure of 2 provides a red-shifted, broadened, weakened fluorescence profile (lambda(max) = 545 nm, phi(F) = 0.01), compared to 1 (lambda(max) = 491 nm, phi(F) = 0.12), due to strong interactions between the p orbitals of the stacked molecules. The charge-carrier mobility of the single crystal of 23 DMSO, as well as 1, was determined by flash photolysis time-resolved microwave conductivity (FP-TRMC) measurements. The single crystal of 23 DMSO revealed significantly-anisotropic charge mobility (sigma(mu) = 1.5x10(-1) cm(2) V(-1) s(-1)) along the columnar axis (crystallographic c axis). This value is 12 times larger than that along the orthogonal axis (the a axis).     

BASE RELEASE FROM DNA AND POLYNUCLEOTIDES UPON 193 nm LASER EXCITATION

Release of bases form calf thymus DNA and three polynucleotides, induced by 20 ns excitation at 193 nm in aqueous solution at pH 7, was detected by HPLC. The quantum yields of formation of free bases (phi B) from double-stranded DNA (0.4 mM) are independent of intensity, indicating a one-quantum mechanism of N-glycosidic bond cleavage. The phi B values increase in the order guanine, thymine, adenine, cytosine, the latter being phi C approximately 7 x 10(-4) for double-stranded DNA under Ar and O2. The larger phi B values in N2O-saturated solution, e.g., phi C = 1.2 x 10(-3), are ascribed to additional base release via OH-adduct radicals. The phi B values of homopolynucleotides increase in the order poly(G), poly(A) and poly(C), e.g. phi C = 7 x 10(-3) under Ar, as do the efficiencies for base release per radical cation (eta B). A comparison of the eta B values with the efficiencies of single-strand breakage for poly(C), poly(A) and DNA shows a similar trend; both are markedly larger for pyrimidines than for purines. Pathways to undamaged bases, initiated from base radical cations, are proposed.     

De novo synthesis of stable tetrahydroporphyrinic macrocycles: bacteriochlorins and a tetradehydrocorrin

[structures: see text] Bacteriochlorins (tetrahydroporphyrins) are attractive for diverse photochemical applications owing to their strong absorption in the near-infrared spectral region, as exemplified by the bacterial photosynthetic pigment bacteriochlorophyll a, yet often are labile toward dehydrogenation to give the chlorin. Tetradehydrocorrins (ring-contracted tetrahydroporphyrins) are attractive for studies of catalysis analogous to that of vitamin B12. An eight-step synthesis toward such tetrahydroporphyrinic macrocycles begins with p-tolualdehyde and proceeds to a dihydrodipyrrin-acetal (1) bearing a geminal dimethyl group and a p-tolyl substituent. Self-condensation of 1 in CH3CN containing BF3 x OEt2 at room temperature afforded a readily separable mixture of two free base bacteriochlorins and a free base B,D-tetradehydrocorrin. Each bacteriochlorin contains two geminal dimethyl groups to lock-in the bacteriochlorin hydrogenation level, p-tolyl substituents at opposing (2,12) beta-positions, and the absence (H-BC) or presence (MeO-BC) of a methoxy group at the 5- (meso) position. The B,D-tetradehydrocorrin (TDC) lies equidistant between the hydrogenation levels of corrin and corrole, is enantiomeric, and contains two geminal dimethyl groups, 2,12-di-p-tolyl substituents, and an acetal group at the pyrroline-pyrrole junction. Examination of the effect of the concentrations of 1 (2.5-50 mM) and BF3 x OEt2 (10-500 mM) revealed a different response surface for each of H-BC, MeO-BC, and TDC, enabling relatively selective preparation of a given macrocycle. The highest isolated yield of each was 49, 30, and 66%, respectively. The macrocycles are stable to routine handling in light and air. The bacteriochlorins display characteristic spectral features; for example, H-BC exhibits near-IR absorption (lambda(Qy) = 737 nm, epsilon(Qy) = 130,000 M(-1) cm(-1)) and emission (lambda(em) = 744 nm, phi(f) = 0.14). In summary, this simple entry to stable bacteriochlorins and tetradehydrocorrins should facilitate a wide variety of applications.     

Photophysical properties of anthanthrene-based tunable blue emitters

Anthanthrene (1) derivatives substituted at the 4,10 and 6,12 positions (2-6) were synthesized as promising candidates for organic light emitting diodes (OLEDs). The emission of these compounds can be manipulated in the blue region (lambda(max) = 437-467 nm) through structural modifications. Photophysical and electrochemical properties (phi(F) = 0.20-0.47; tau(F) = 2.97-6.06 ns; HOMO-LUMO energy gap = 2.25-2.56 eV) as well as geometry optimized structures of 1-6 are reported.