一种卟啉-螺吡喃化合物的合成及其离子响应行为研究

合成了一种卟啉-螺吡喃化合物,并对其结构进行详细表征。在此基础上,通过紫外光谱研究了其光致异构与离子响应特征,并提出了一种解释卟啉环与螺吡喃之间耦合行为的新机制。研究结果表明,金属离子会诱导合成的卟啉-螺吡喃分子产生新的构象,从而影响螺吡喃的光致异构。此外,随着离子半径以及亲电能力的不同,卟啉-螺吡喃衍生物的光学特性也产生明显差异。这种卟啉-螺吡喃化合物为构建新型离子探针提供了一种思路。     

Trans-cis Photoisomerization of 1-Methyl-4-(4′-hydroxystyryl)pyridinium in inclusion complexes ofβ-cyclodextrin and its derivatives

The effects of -cyclodextrin (-CyD), heptakis(2,6-di-O-methyl)--cyclodextrin (DMCyD) and heptakis(2,3,6-tri-O-methyl)--cyclodextrin (TMCyD) ontrans-cis photoisomerization of 1-ethyl-4-(4-hydroxystyryl)pyridinium (POH) have been studied in aqueous solutions. The ratio of [cis]/[trans] for POH in the photostationary state at pH 8.54 was remarkably reduced by the presence of CyD or DMCyD. The reduction of the [cis]/[trans] ratio in the photostationary state was explained in terms of the shift of the equilibrium of POH ₊ ^trans PO _trans + H^– toward PO _trans formation. The binding constants of CyD and DMCyD for PO _trans were 2.00- and 1.36-fold larger than those for POH ₊ ^trans , respectively. The binding constants of TMCyD for both species are much smaller than those of CyD and DMCyD. This result indicates that PO _trans , which has a betain structure, forms stable complexes with CyD and DMCyD with its hydrophobic parts inside and the charged parts outside the CyD cavities.     

Fluorinated Azobenzenes Switchable with Red Light

Molecular photoswitches triggered with red or NIR light are optimal for photomodulation of complex biological systems, including efficient penetration of the human body for therapeutic purposes (“therapeutic window”). Yet, they are rarely reported, and even more rarely functional under aqueous conditions. In this work, fluorinated azobenzenes are shown to exhibit efficient E→Z photoisomerization with red light (PSS_660nm >75 % Z) upon conjugation with unsaturated substituents. Initially demonstrated for aldehyde groups, this effect was also observed in a more complex structure by incorporating the chromophore into a cyclic dipeptide with propensity for self-assembly. Under physiological conditions, the latter molecule formed a supramolecular material that reversibly changed its viscosity upon irradiation with red light. Our observation can lead to design of new photopharmacology agents or phototriggered materials for in vivo use.     

A Photo-Responsive Organogel Based on Pyrene-Substituted Acylhydrazone Derivative

A new simple pyrene-substituted acylhydrazone derivative, 4-(3,4-dioctyloxy) phenyl-1-pyrene acylhydrazone (PAH-8), was designed and synthesized. The PAH-8 can form thermo-reversible organogel in DMSO, and shows gelation-induced enhanced fluorescence emission. Xerogel exhibits ribbon-like fibrous aggregates with widths of 0.5-1 μm. The PAH-8 organogel indicates photo-responsive behaviors due to the trans-cis isomerizations of -C=N- bond upon exposure to visible or UV light. Upon visible light irradiation, the partial trans-cis isomerization of the -C=N- bond causes the fiber morphology to disappear, resulting in gel-sol transition, whereas the PAH-8 organogel exhibits few photoisomerizations from trans to cis transition without breakage of the gel state upon UV light irradiation.     

Light-induced Photoswitching of 4-(Phenylazo)benzoic Acid on Au(111)

Photochromic molecules can undergo a reversible conversion between two isomeric forms upon exposure to external stimuli such as electromagnetic radiation. A significant physical transformation accompanying the photoisomerization process defines them as photoswitches, with potential applications in various molecular electronic devices. As such, a detailed understanding of the photoisomerization process on surfaces and the influence of the local chemical environment on switching efficiency is essential. Herein, we use scanning tunneling microscopy to observe the photoisomerization of 4-(phenylazo)benzoic acid (PABA) assembled on Au(111) in kinetically constrained metastable states guided by pulse deposition. Photoswitching is observed at low molecular density and is absent in tight-packed islands. Furthermore, switching events were noted in PABA molecules coadsorbed in a host octanethiol monolayer, suggesting an influence of the surrounding chemical environment on photoswitching efficiency.     

紫外光辐照对偶氮苯光谱特性的影响

采用紫外可见吸收、稳态荧光光谱和荧光衰减测量技术,观察了4-硝基-4'-氨基偶氮苯(NAA)在氯仿溶液中的光致变色现象及分子的跃迁能级和能级寿命。结果表明:NAA分子的顺反异构化反应并非一级反应;分子处于反式异构体和顺式异构体的跃迁能分别为255.6,240.2 kJ/mol;分子处于反式异构体的能级寿命为0.02 ns,处于顺式异构体的能级寿命为3.54 ns。顺反异构体的含量、NAA分子之间及NAA分子与溶剂分子之间的相互作用影响NAA分子激发态的能级寿命。     

一代树状碳硅烷液晶的光化学研究－－端基含12个4－丁氧基氮苯介晶基元

研究了新的含12个丁氧基偶氮苯介晶基元的五代树状碳硅烷液晶D1及偶氮苯介 晶基元化合物M5在氯仿、四氢呋喃、N，N－二甲基甲酰胺、乙醇和苯等溶剂中的量 子产率、反－顺光异构化、光回复异构、反／顺异构组分比、热回复异构及活化能 。D1和M5的光致变色速率常数为10~(-1)s~(-1)，而含同一偶氮基元的光致变色液 晶聚硅氧烷的光致变色速率常数为10~(-8)s~(-1)，因此，液晶树状物D1的光响应 速度比后者快10~7倍。     

Theoretical Study on Photoisomerization of 2-Methylfuran to 3-Methylfuran

1 INTRODUCTION 2-Methylfuran belongs to the basic heteroaromatic compounds relevant to many fields of modern che- mistry, ranging from the study of natural products and biologically active substances to the develop- ment of building blocks for organic synthesis and conducting polymers[1]. Since the photochemistry ofR-furan was gradually recognized in 1960s[2～7], lots of interest has been aroused. Herein we only study one branch of photoche- mistry of R-furan: the isomerization of 2-methy…     

Effect of structural variation within cationic azo-surfactant upon photoresponsive function in aqueous solution

The cationic azo-surfactants possessing different spacers and tail alkyl chain lengths have been synthesized by azocoupling ofp-alkylaniline orop-ethoxyaniline with phenol, followed by alkylation and quaternalization with dibromoalkane and trimethylamine, respectively. These surfactants showed a good solubility in water. A reversibletrans-cis isomerization of the azosurfactants by photoirradiation was assessed by UV-Vis absorption spectra. Due to a difference in HLB between thetrans- andcis-surfactants, the observed critical micelle concentration (CMC) values and the electric conductivity of the surfactant solution at above the CMC were significantly affected by the photoinducedtrans-cis isomerization. The azo-surfactants bearing moderate alkyl chain lengths such as surfactants 6 (R₂=C₂H₄, R₃=C₄H₉) and 9 (R₂=C₄H₈, R₃=C₂H₅) were found to be effective to achieve large CMC changes (3.6 mmol/L for 6 and 5.9 mmol/L for 9) by UV-light irradiation. The replacement of the tail chain species also affected the photoresponsive function. The surfactant 12, possessingp-ethoxy group as the tail chain, was found to form a stable micelle aggregation as compared with the structurally related surfactant 10 having ethyl unit as its tail group, but it exhibited a large CMC change (5.3 mmol/L) by UV-light irradiation.