吡唑和1-甲胺酰基吡唑类化合物的紫外吸收光谱及其应用

研究了吡唑类化合物和1-甲胺酰基吡唑类化合物的紫外吸收光谱.结果表明,3位和5位的取代使吡唑的最大吸收波长红移3～4 nm,而4位的取代能够引起较大的红移(>10 nm).甲胺酰基的引入可使吡唑类化合物的最大吸收波长红移20～26 nm,最大消光系数提高2～3倍.基于此,建立了快速测定吡唑类化合物含量的紫外分光光度法,并测定了长效尿素中3,4-二甲基吡唑磷酸盐(DMPP)的含量为尿素-N的1.15%,1-甲胺酰基-3-甲基吡唑(CMP)在水溶液中水解的半减期在20,25和30℃下分别为48,30和16 h,应用不同提取剂对三种土壤中硝化抑制剂3-甲基吡唑磷酸盐(MPP)的提取率为63.2%～89.2%.     

新型含氧亚甲基和亚胺桥键液晶化合物分子结构与光谱的密度泛函理论研究

采用密度泛函理论方法在B3LYP/6-31G*水平上对6个新型含氧亚甲基和亚胺桥键液晶化合物分子的几何结构进行优化计算,讨论了取代基H,CH3,CH3O,C2H5O,NO2,Cl对分子电荷、前线轨道能量和电子吸收光谱等性质的影响.在此基础上使用含时密度泛函理论方法计算了分子第一激发态的电子垂直跃迁能,得到最大吸收波长λmax.计算表明,取代基的引入导致最大吸收波长红移.     

氢键作用对基于异佛尔酮发光材料的荧光性能的影响

合成了3种基于异佛尔酮的新型单晶荧光材料:3-二丙烯腈基-5,5-二甲基-1-苯乙烯基环己烯(DCDSC)、3-二丙烯腈基-5,5-二甲基-1-(3-羟基苯乙烯基)环己烯(DCDH3C)及3-二丙烯腈基-5,5-二甲基-1-(4-羟基苯乙烯基)环己烯(DCDH4C)。通过氢核磁共振谱和元素分析确定了它们的分子结构。通过单晶X射线衍射获得了3种材料的晶体结构数据。DCDSC、DCDH_3C和DCDH_4C的紫外吸收光谱依序分布在长波区的390,398,424 nm,短波区分布在268,269,283 nm。DCDSC、DCDH3C和DCDH_4C在THF中的最大发射峰分别位于522,549,567 nm。与DCDSC相比,3位羟基取代的DCDH3C的发射波长红移了27 nm,而4位取代羟基的DCDH4C的发射波长红移了45 nm。其主要原因在于DCDSC、DCDH_3C和DCDH_4C存在不同的氢键作用,当然,取代基的类型及位置等也可能对材料的发射波长产生一定作用。     

桥基取代2,7’-(乙烯基)-二-8-羟基喹啉类化合物的密度泛函理论研究

在B3LYP/6-31G(d)水平上对2,7′-(乙烯基)-二-8-羟基喹啉(2,7′-Ethq_2)及其6种桥基取代物的几何结构进行了全优化,探讨了取代基对分子的结构、电荷转移、前线分子轨道能级、能隙等方面的影响.采用含时的密度泛函理论(TD-DFT)研究各分子的气相及液相中的电子光谱,分析光谱的变化规律.结果表明,取代基的电子效应和立体效应对取代物的电子结构和电子光谱有重要影响,取代基重新调整了2,7′-Ethq_2的原子电荷布居,改变了前线分子轨道能隙,导致吸收光谱发生变化.氨基和氰基对2,7′-Ethq_2影响较为显著,吸收波长红移较大.此外溶剂的极性对其电子光谱也有影响,随溶剂极性的增大,硝基取代物的最大吸收波长发生明显的红移,其它取代物的最大吸收波长均发生较小的蓝移.     

二苯乙烯衍生物的制备及结构-光学性能关系的研究

有机共轭材料由于在电子、非线性光学和发光领域具有广泛应用,引起人们广泛兴趣。苯乙烯衍生物是一类重要的有机共轭化合物。文章采用相转移Wittig反应和钯催化Heck反应合成了三种不同取代基二苯乙烯衍生物。研究了分子结构与电子吸收光谱和材料发光性能关系。同没有取代基的化合物3a相比(电子最大吸收峰波长358 nm),化合物3c中CH₃取代导致电子吸收光谱轻微红移到356 nm,硝基取代的化合物3b呈现出更大的吸收光谱红移现象,电子吸收最大峰红移到388 nm。同时发现：CH₃取代的化合物3c产生荧光发射峰在414 nm,同没有取代基的化合物3a相比,荧光发射强度明显增强;相反具有吸电子NO₂取代基的化合物3b荧光发射峰位于525 nm, 荧光发射强度明显减弱。可见二苯乙烯分子中取代基结构对分子光学性能产生重要影响。这为发光材料的分子设计提供新的思路。     

核糖核酸与甲基紫作用机理及含量测定的研究

研究了在pH 6.0的伯瑞坦-罗比森弱酸性缓冲溶液中,小分子甲基紫与生物大分子核糖核酸之间发生强烈静电缔合相互作用,引起分子光谱红移,吸收值变小。甲基紫在最大吸收波长558 nm处的吸收峰强度显著下降,下降程度与核糖核酸的含量呈线性关系,应用光谱法研究了反应体系酸度、甲基紫用量、反应时间对反应速度的影响,确定了试验最佳条件,提出并建立了测定痕量核糖核酸含量的新方法。线性范围为1.0～8.0 μg·mL-1, 检测限为0.52 μg·mL-1,相关系数r为0.999 9,该法简便,快速,具有较高的选择性和灵敏度,对合成样品中核糖核酸的测定令人满意;初步探讨了反应机理,认为,甲基紫分子与凝聚在RNA分子链上的反离子之间发生静电缔合作用,然后,以协同方式与RNA分子发生键合,使甲基紫三苯环平面结构受到破坏,π-电子叠合程度降低,吸收值降低,最大吸收波长红移。     

给体位置和数目对四苯基乙烯衍生物双光子吸收性质的影响

在杂化密度泛函水平上,利用响应函数方法,计算了一类四苯基乙烯衍生物的双光子吸收性质.考虑了四苯基乙烯上给电子基团的位置和数目对双光子吸收性质的影响.并且,根据实验者采用的分子,通过增加分子的平面性和共轭长度,以及增强给体强度,理论设计了三种分子结构,并计算了它们的双光子吸收性质.结果表明,给体位置和数目对双光子吸收性质有重要影响.位于分子末端的给体取代基能有效提高双光子吸收强度.随着给体数目的增加,双光子吸收波长发生红移.在四苯基乙烯的不同侧位上添加给体取代基对双光子吸收性质的影响有明显差异.与实验者采用的分子相比,理论设计的分子结构双光子吸收截面均明显增大.当三苯胺基代替四苯基乙烯基之后,双光子吸收峰发生较大红移,双光子吸收截面明显增大.     

咪唑[4, 5-f] 1, 10-邻菲罗啉及其2-取代芳基衍生物的电子结构与光谱性质

分别采用B3LYP/6-31G(d)和CIS/6-31G(d)方法对咪唑[4, 5-f] 1, 10-邻菲罗啉(ip)及其8种2-取代芳基衍生物的基态(S0)和单重激发态(S1)的几何构型进行了全优化, 并采用含时的度泛函理论(TD-DFT)计算了上述化合物的电子吸收和电子发射光谱. 分析了取代基对咪唑[4, 5-f] 1, 10-邻菲罗啉的电子结构、前线分子轨道、电离势Ip、电子亲和势EA及电子光谱的影响. 计算结果表明, 取代基使8种取代衍生物前线分子轨道(LUMO-HOMO)能隙降低,导致其最大吸收和发射波长均发生了红移. 化合物1～8的跃迁类型均为分子内电荷转移（ICT）跃迁,且1～4和5～8的电子转移方向刚好相反. 溶剂对其电子光谱也有影响, 振子强度增大, 最大发射波长红移. 另外, 8种取代衍生物的电离势降低, 电子亲和势增大, 化合物1~4易于空穴的注入, 5~8易于电子的注入.     

咪唑[4, 5-f] 1, 10-邻菲罗啉及其2-取代芳基衍生物的电子结构与光谱性质

分别采用B3LYP/6-31G(d)和CIS/6-31G(d)方法对咪唑[4, 5-f] 1, 10-邻菲罗啉(ip)及其8种2-取代芳基衍生物的基态(S0)和单重激发态(S1)的几何构型进行了全优化, 并采用含时的度泛函理论(TD-DFT)计算了上述化合物的电子吸收和电子发射光谱. 分析了取代基对咪唑[4, 5-f] 1, 10-邻菲罗啉的电子结构、前线分子轨道、电离势Ip、电子亲和势EA及电子光谱的影响. 计算结果表明, 取代基使8种取代衍生物前线分子轨道(LUMO-HOMO)能隙降低,导致其最大吸收和发射波长均发生了红移. 化合物1～8的跃迁类型均为分子内电荷转移（ICT）跃迁,且1～4和5～8的电子转移方向刚好相反. 溶剂对其电子光谱也有影响, 振子强度增大, 最大发射波长红移. 另外, 8种取代衍生物的电离势降低, 电子亲和势增大, 化合物1~4易于空穴的注入, 5~8易于电子的注入.     

新型吡唑啉类荧光化合物的合成及光谱分析

吡唑啉衍生物作为荧光增白剂具有优良的性质,已被广泛应用于染料工业。根据Schellhammer化学结构与荧光性的经验,在吡唑啉环的1-位引入苯并噻唑基,3-位引入吲哚基,5-位引入苯基衍生物,设计并合成了六种新的吡唑啉衍生物,并且通过红外光谱、1H NMR谱、质谱和元素分析进行了确证。化合物的荧光性能测定结果显示此类化合物具有良好的荧光性,均可吸收353 nm左右紫外光,最大发射波长在430～443 nm之间,是一类很有发展前途的蓝紫色荧光化合物。荧光最大发射波长和荧光强度与取代基有关,在苯并噻唑上引入6-Br基团,化合物的荧光发射波长发生蓝移,且强度增大;而引入CH₃基团,化合物的荧光发射波长发生红移,且强度降低。取代基和溶剂极性对荧光量子产率的影响较小。荧光相对强度与荧光量子产率没有直接关系。     

Solution absorption and luminescence studies of tetraphenylboron, -carbon, -silicon, -germanium, -tin, -lead, -phosphorus, -arsenic,and -antimony

The lowest absorption band of the tetraphenyl compounds resembles that of the lowest absorption band of benzene with the following difference. In benzene the electronic origin is strictly forbidden, and all intensity is associated with a symmetric progression built on one mode of asymmetric vibration. In the tetraphenyl compounds the intensity associated with the asymmetric vibration is relatively unaffected; however, there is increasing intensity associated with the electronic origin and a symmetric progression built on it along the series

$\text{φ}{}_4\text{Pb}\text{< φ}{}_4\text{Sn}\text{< φ}{}_4\text{Ge}\text{< φ}{}_4\text{Si}\text{< φ}{}_4\text{C}\text{? φ}{}_4\text{B}{}^{\mathrm{?}}\text{< φ}{}_4\text{Sb}{}^{\mathrm{+}}\text{< φ}{}_4\text{As}{}^{\mathrm{+}}\text{< φ}{}_4\text{P}{}^{\mathrm{+}}$

. For the cations it is the electronic origin and the progression built on it that are the primary source of intensity. This effect is attributed to an inductive perturbation. A similar effect is observed in the fluorescence spectrum. In phosphorescence, the relative enhancement of the electronic origin and the progression built on it is far less marked. The phosphorescence emission of φ₄Pb and φ₄Sb⁺ are red shifted from the others by ～0.5 eV, an effect attributed to formation of a triplet excimer. Increasing spin-orbit coupling in the triplet due to a heavy atom effect can be seen in the decreasing phosphorescence lifetime (range 4 sec to 4 msec) and decreasing ratio of $\text{φ}{}_{\mathrm{f}}\text{φ}{}_{\mathrm{p}}$ (fluorescence to phosphorescence quantum yields) in the order

$\text{φ}{}_4\text{C}\text{> φ}{}_4\text{B}\text{> φ}{}_4\text{Si}\text{> φ}{}_4\text{P}{}^{\mathrm{+}}\text{> φ}{}_4\text{Ge}\text{> φ}{}_4\text{As}{}^{\mathrm{+}}\text{> φ}{}_4\text{Sn}$

In all cases nonexponential decay of phosphorescence is observed.     

Walks,walls, wetting,and melting

New results concerning the statistics of, in particular,p random walkers on a line whose paths do not cross are reported, extended, and interpreted. A general mechanism yielding phase transitions in one-dimensional or linear systems is recalled and applied to various wetting and melting phenomena in (d=2)-dimensional systems, including fluid films and p×1 commensurate adsorbed phases, in which interfaces and domain walls can be modelled by noncrossing walks. The heuristic concept of an effective force between a walk and a rigid wall, and hence between interfaces and walls and between interfaces, is expounded and applied to wetting in an external field, to the behavior of the two-point correlations of a two-dimensional Ising model belowT _c and in a field, and to the character of commensurate-incommensurate transitions ford=2 (recapturing recent results by various workers). Applications of random walk ideas to three-dimensional problems are illustrated in connection with melting in a lipid membrane model.Based on the Boltzmann Medalist address presented at the 15th IUPAP International Conference on Thermodynamics and Statistical Mechanics, Edinburgh, July 1983.     

Einstein,Podolsky, Rosen,and Shannon

The Einstein–Podolsky–Rosen paradox (1935) is reexamined in the light of Shannons information theory (1984). The EPR argument did not take into account that the observers information was localized, like any other physical object.Dedicated to the memory of James T. Cushing     

Quarks,diquarks, tetraquarks,and pentaquarks

A particle about 50% more massive than a proton, with positive charge, positive strangeness and positive baryon number, has been claimed in several experiments. Such a particle cannot be made from three quarks; its minimal configuration requires four quarks and an antiquark and it became known as a ‘pentaquark’. This article summarizes the evidence and concentrates on the theoretical interest that it has excited into the nature of correlations among quarks and antiquarks in the strong interaction limit of QCD.     

Mesomorphic, dielectric, and optical properties of fluorosubstituted biphenyls, terphenyls, and quaterphenyls

Compounds with moderate and large negative dielectric anisotropy (Δɛ) are very attractive liquid crystal (LC) for vertical alignment mode (VA). Materials with such properties can be achieved by lateral substitution of a polar group into a mesogenic molecule. We synthesized some new LC materials with a negative value of Δɛ, a moderately high birefringence (Δn), and a low viscosity. The mesomorphic and physical behaviour of the novel biphenyls, terphenyls and quaterphenyls fluorosubstituted in the rigid core and also with fluorinated alkyl and alkoxy chains are investigated. The prepared series of four LC compounds are promising for new LC mixtures for various applications. Examples of nematic mixtures with Δɛ∼−3.25 will be presented.     

Black swans,power laws,and dragon-kings: Earthquakes,volcanic eruptions,landslides, wildfires,floods, and SOC models

Extreme events that change global society have been characterized as black swans. The frequency-size distributions of many natural phenomena are often well approximated by power-law (fractal) distributions. An important question is whether the probability of extreme events can be estimated by extrapolating the power-law distributions. Events that exceed these extrapolations have been characterized as dragon-kings. In this paper we consider extreme events for earthquakes, volcanic eruptions, wildfires, landslides and floods. We also consider the extreme event behavior of three models that exhibit self-organized criticality (SOC): the slider-block, forest-fire, and sand-pile models. Since extrapolations using power-laws are widely used in probabilistic hazard assessment, the occurrence of dragon-king events have important practical implications.     

Elements,devices, and methods for fractal communication technology,electronics, and nanotechnology

The numerous results obtained in radio physics using fractal theory, fractional dimension, and fractional operators have been briefly classified taking into account the scaling effects of real radio signals and electromagnetic fields. A universal modeling environment based on a multilayer virtual generalized distributed RLCG element and the method of generalized finite distributed elements for analysis and synthesis of models of fractional objects and processes that possess fractional power dependence of the input impedance on frequency have been proposed. Examples of synthesis of one- and two-dimensional models are given. It is shown that nonlinear, parametrical, and other properties of modeled objects can be taken into consideration by means of the vectors of electrophysical parameters of layers and design factors.