紫外吸收温差光谱特性与化合物的电子跃迁类型

用紫外吸收变温光谱差减法获得化合物的紫外吸收温差光谱（UVSDT）。测量了系列化合物的温差光谱。结果表明,UVSDT具有很强的特征性：n→σ^*电子跃迁的UVSDT单边红移,温差增大峰强度增加、红移增大;n-π^*电子跃迁的UVSDT为正、负两峰、温差增大,正负两峰各自向正、负方向增强;π-π^*电子跃迁的UVSDT为负峰,温差增大,峰强负向增大,峰位不移动。     

不同溶剂中番茄红素的荧光光谱及其特性研究

用970CRT荧光光度计测定了番茄红素在正己烷、乙酸乙酯、四氢呋喃、氯仿、丙酮和苯等6种溶剂中的荧光光谱以及番茄红素在四氢呋喃溶液中不同浓度下的荧光光谱。对所测光谱分析得出:6种溶剂中荧光光谱的最大峰值波长(λmax)分别为542.5 nm5、48.2 nm5、55.0 nm、555.7 nm、556.4 nm和565.7 nm,由于溶剂效应,随溶剂极性由小到大,荧光光谱的最大峰值波长(λmax)逐渐红移,由这些峰值波长计算得出相应的番茄红素分子在6种溶剂中的跃迁能ET分别为220.5 kJ/mol2、18.2 kJ/mol2、15.6 kJ/mol2、15.3 kJ/mol2、14.9 kJ/mol和211.5 kJ/mol,可见跃迁能ET也随溶剂极性增大而降低;当番茄红素在四氢呋喃溶液中的质量浓度低于50μg/ml时,溶液的荧光强度随溶液浓度增加而增大,当质量浓度高于50μg/ml时,由于番茄红素的激发态分子与基态分子相互作用,荧光强度反而减小;在浓度低于80μg/ml的溶液中,番茄红素的荧光光谱除最大峰值外还有三个较小峰值,据此计算得出相应的番茄红素分子的跃迁能分别为E(T1)=278.2 kJ/mol、E(T2)=260.2 kJ/mol和E(T3)=239.3 kJ/mol。     

偶氮连苯三酚试剂的合成及其光谱特性

合成了 2 -羧基苯胺重氮盐和 2 -羟基苯胺重氮盐 ,它们与连苯三酚偶联 ,得到新的偶氮试剂 4 - (2 -羧基苯偶氮 ) -连苯三酚和 4 - (2 -羟基苯偶氮 ) -连苯三酚。研究了偶氮试剂的红外光谱、紫外光谱和荧光光谱特性。     

含偶氮苯的咔唑类光折变化合物的合成与光谱研究

通过重氮化偶联反应制备了一种既含偶氮基团又含咔唑基团的光折变材料,并通过红外、紫外和拉曼光谱对其进行了结构鉴定和分析.     

偶氮染料掺杂高分子薄膜的荧光光谱特性

利用旋涂法制备了新的偶氮染料掺杂薄膜，在室温下测试了该薄膜的吸收光谱，稳态荧光光谱和时间分辨荧光光谱，研究了荧光衰减动力学过程，得到了反式和顺式异构体的激光发单线态（S1）的荧光寿命。     

7-羟基喹啉的双光子荧光光谱特性

利用超快激光脉冲作为激发光源,研究了激发态质子转移有机分子7-羟基喹啉溶液的双光子吸收光谱特性。实验发现在波长为532nm的脉冲激光作用下,该溶液在波长约为380nm和550nm处出现了两个荧光峰,研究证明,峰波长为380nm处的荧光是7-羟基喹啉醇式结构下分子从激发态返回基态时发射的荧光,而峰波长为550nm处的荧光是该溶液的酮式结构分子从激发态返回基态时发射的荧光。     

紫外光区S_2分子激光诱导荧光光谱

利用真空脉冲放电超声射流气体束(H_2S/Ar~3%混合气体)的方法产生了气相S_2分子,并研究了30 400~34 400cm~(-1)范围内S_2分子的时间分辨和基态振动频率分辨的激光诱导荧光光谱,获得了184支谱带的高分辨率(0.1cm~(-1))和低分辨率(0.3cm~(-1))转动光谱。实验观测并归属了S_2分子B_u~(Σ-)-X~3Σ_g~-和B″~3Π_u-X~3Σ_g~-共84支振动跃迁,分析得到了激发态B~3Σ_u~-态ν=0~9和B″~3Π_u态ν=2~12的分子常数以及B~3Σ_u~-态的基态平衡分子构型。由于S_2分子B~3Σ_u~-与B″~3Π_u态之间存在微扰,这两个电子激发态的振动能级间隔、自旋分裂常数和自旋-轨道分裂常数变化不规律,转动跃迁强度和跃迁选择定则存在异常,利用~3Σ-~3Π的齐次微扰哈密顿量定性地对这些异常光谱进行了解释,进一步丰富了S_2分子紫外区低能电子激发态的信息。     

荧光光谱及其成像技术在光活检中的应用

分析了人体组织自体荧光的主要物质来源和荧光特性,同时总结了国内外常见的第二代新型光敏剂及其临床应用情况。在此基础上,全面比较了各种应用于早期肿瘤光活检的荧光光谱及其成像技术,并重点讨论了这些技术的基本原理和临床应用现状,以及它们今后的发展方向。     

橙黄Ⅱ薄层光谱电化学的动力学研究

本文推导了单电势跃计时吸收光谱实验中，在扩散控制条件下，平行入射电极上吸光度随时间变化关系式。研究了橙黄Ⅱ在二氧化锡电极上的电化学行为，采用单电势跃计时吸收谱法和单电势跃开路弛豫计时吸收谱法测定了橙黄Ⅱ的扩散系数和其中间产物１．２－萘醌的随后化学反应表观速率常数。     

激发态分子内质子转移分子2-羟基-1-萘甲醛半碳酰腙的光谱特性

通过考察2-羟基-1-萘甲醛半碳酰腙(HNLSC)在不同极性溶剂中的吸收光谱和荧光光谱,详细研究了HNLSC分子在不同溶剂及酸、碱条件下的不同构型,证实了HNLSC具有典型的ESIPT特性。在非极性溶剂中分子主要以分子内氢键的闭式构型存在,这种闭式构型使分子具有ESIPT特性,在环己烷溶剂和高酸度极性溶剂中分子均表现出～415nm的正常荧光和～435nm处的反常ESIPT荧光。在极性质子溶剂中,因溶质和溶剂之间形成了分子间的氢键以及进一步去质子化,HNLSC形成了基态的溶剂化开式构型和离子构型,在吸收光谱中表现出～395nm的离子构型特征吸收。开式构型和离子构型阻断了分子内质子转移途径,因而在荧光光谱中仅表现出一个特征峰。实验进一步通过三乙胺和稀硫酸调节溶液体系的极性和酸度环境,证明在不同溶剂极性和酸度环境下,HNLSC分子不仅存在萘环上羟基变化引起的多种互变异构体间的转化平衡,同时存在—CHN—NH—CO—NH2结构域的烯醇式和酮式结构的相互转化。     

稀土夹心双酞菁铽的荧光特性研究

利用稳态荧光光谱和时间分辨光谱方法研究了稀土夹心双酞菁铽衍生物(TbPcPc^*)氯仿溶液的荧光特性,分析了激发波长、溶液浓度对荧光特性的影响。TbPcPc^*氯仿溶液在707nm处有一强的荧光发射峰,它对应于电子从激发态S₁向基态S₀的跃迁。当使用500nm的光激发时,电子吸收能量发生向激发态S₁的跃迁以及到更高能级的混合跃迁,当电子从这些能级再跃迁到基态时主要发射525,707nm的荧光。Tb-PcPc^*氯仿溶液在707nm处的荧光发射峰具有两个衰减过程,短寿命的衰减为分子单体所产生,而长寿命的衰减为聚集体所产生。随着浓度的降低,单体所占比例增加,其对应的寿命组分比例也相应的增加。     

酮类甲醛荧光探针的合成及其光学性质

设计合成了两种化合物4-氨基4-（4-甲氧基苯基）-3-丁烯-2-酮（1b）和4-氨基-4-（1,3-亚甲二氧基苯基-5-基）-3-丁烯-2-酮（2b）,测试了其在不同甲醛含量下的紫外吸收光谱及单光子荧光光谱。当含有100 μmol/L和5 μmol/L的甲醛时,化合物1b和2b的紫外吸收峰强度分别达到其最大值。在单光子荧光方面,化合物1b的荧光发射峰位置在384 nm,与紫外吸收峰相比红移50 nm。化合物2b的荧光发射峰呈现出双峰形状,其发射峰位置分别在384 nm及411 nm左右。当加入15 μmol/L的甲醛时,化合物2b的411 nm处的荧光发射峰明显增强,两峰的重叠程度降低,可作为检测甲醛的特征变化。以上数据表明,化合物1b和2b不仅能够对微量甲醛产生响应,也可作为一种理想平台为更进一步拓宽化合物1b和2b在监测生物体系中甲醛荧光生物成像上的应用奠定理论基础。     

Structure and Luminescent Properties of the 4-Arylidene-2-Aryl-5-Oxazolones(Azlactones)In Solution and Crystalline State

Experimental and theoretical evaluations have proven that very low fluorescence quantum yields of azlactones in solution are not caused by an efficient inter system crossing from S₁*(ππ) to T*(nπ) states, but rather from solvation and steric effects, that result in non-planarity of the molecular system. High fluorescence quantum yields in the solid state are attributed to the planarity of the azlactone molecule upon packing into the crystal lattice. Supporting evidence was found upon observation of the excited state proton transfer (ESIPT) bands of fluorescence emissions of o-hydroxyarylidene derivatives. The photoinstability of azlactones in liquid states are attributed to photochemical E-Z isomerization and cleavage of the hetero ring α to the carbonyl group.     

Fluorescence Study of Excited-State Relaxation Processes of 2-Pyridyl-5-Aryloxazoles

Anomalously high fluorescence spectrum Stokes' shifts of 2(4-pyridyl)-5-(4-methylphenyl)oxazole, 2(4-pyridyl)-5-(4-methoxyphenyl)oxazole, 2(4-pyridyl)-5-(4-N,N-dimethylaminophenyl)oxazole have been found. The fluorescence spectra of the compounds studied are shifted to longer wavelengths as the solvent dielectric constant increases. The dipole moments of these compounds increase by 3–4 times upon excitation. The fluorescence spectra of the compounds investigated are shifted to shorter wavelengths, and the fluorescence quantum yields increase as the temperature decreases. The fluorescence rate constant of 2(4-pyridyl)-5-(4-N,N-dimethylaminophenyl)oxazole changes slightly as the temperature decreases from 293 K (relaxed state) to 114 K (mainly nonrelaxed state). It was concluded that the anomalously high fluorescence Stokes' shift of 2-pyridyl-5-aryloxazole derivatives is caused by solvent orientation relaxation.     

中高端苏酒的紫外荧光特性对比研究

针对苏酒中最具代表性的国缘系列和洋河蓝色经典系列两种中高端白酒进行研究,得出三维荧光光谱图,并对两种白酒的各自独有的荧光特征加以分析。发现国缘白酒在280～400 nm激发波长范围内具有明显的荧光特征,包含一个主要的荧光峰;洋河蓝色经典白酒在200～450 nm激发波长范围内包含5个明显的荧光峰。两个系列白酒在激发波长310～350 nm内具有明显的荧光特征,此范围内的有机化合物为主要的呈香呈味物质,对苏酒的口感香型起决定性作用。该研究成果对改善苏酒勾兑工艺,提高苏酒品质提供了科学的参考依据和量化标准。     

Study of the Interaction of Fangchinoline with Human Serum Albumin by Fluorescence and UV Spectroscopic Method

The interaction of fangchinoline with human serum albumin (HSA) was studied by use of fluorescence quenching spectra, synchronous fluorescence spectra, and ultraviolet spectra. It was shown that fangchinoline has a strong ability to quench the fluorescence of HSA. The Stern‐Volmer curves based on the quenching of the fluorescence of HSA by fangchinoline indicated that the quenching mechanism of fangchinoline on HSA was static quenching and non‐radiation energy transfer. Based on the Förster theory of non‐radiation energy transfer, the binding distances (r) and the binding constants (K _A) between fangchinoline and HSA were found. The thermodynamic parameters obtained revealed that the interaction between fangchinoline and HSA was mainly driven by hydrophobic force. The conformational changes of HSA were investigated by use of synchronous fluorescence. The result indicates that an ionic electrostatic interaction between fangchinoline and HSA could not be excluded.     

Fluorescence and Laser Emission from Coumarin-Acridine Orange Mixtures

The sensitized fluorescence and laser emissions of dye mixtures; (I) coumarin 102 (donor) and acridine orange (acceptor) and (II) coumarin 47 (donor) and acridine orange (acceptor) with Hg-lamp and N₂ laser, have been measured as a function of dye concentration and of the pump power (N₂ laser). Acridine orange which does not lase by itself on excitation with N₂ laser, lases efficiently in the presence of 7-amino-coumarins via singlet-singlet energy transfer. Energy transfer rate constants and critical distances have been estimated from fluorescence intensity and lifetime measurements. The performance of energy transfer dye lasers (ETDLs) are discussed in terms of spectral characteristics of the dyes and their penetration depths.     

Mass Spectrum of Naturally Abundant Ethyldigermane

A complete mass spectral fragmentation pattern of naturally abundant ethyldigermane is presented. The base peak occurs at m/e 148 in the Ge₂H_×=0←5 ⁺ region and not in the parent region. Three metastable peaks are observed at m/e 52.70, m/e 59.36, and m/e 125.63 respectively.