含有二个聚醚软链段的聚醚聚酯嵌段共聚物的合成及其血液相容性的研究

 本文报道了一类新的具有二种聚醚软链段(PTMGT和PEGT)和一种聚酯硬链段(PET)的混合聚醚-聚酯嵌段共聚物(MPEE)的合成和它的血液相容性,并与具有相同软、硬链段比及相同软链段组成比(PTMGT/PEGT)的二种聚醚聚酯嵌段共聚物(PTMGT-PET和PEGT-PET)的共混物(BPEE)的性质进行了比较,结果表明:(1)聚醚聚酯嵌段共聚物的血液相容性可以通过引入亲水性好的PEGT组分而得到提高;(2)在多数的组成比下,共聚型的MPEE具有比共混型的BPEE优良的血液相容性;(3)特定的组成比:PTMGT/PEGT=60/40(mol),共混型的BPEE:(60/40)呈现最好的血液相容性以及最佳的力学性质。研究中发现材料的微相分离结构同血液相容性有关,细微的相分离结构可导致优良的血液相容性。     

含有二个聚醚软链段的聚醚聚酯嵌段共聚物的合成及其血液相容性的研究

本文报道了一类新的具有二种聚醚软链段(PTMGT和PEGT)和一种聚酯硬链段(PET)的混合聚醚-聚酯嵌段共聚物(MPEE)的合成和它的血液相容性,并与具有相同软、硬链段比及相同软链段组成比(PTMGT/PEGT)的二种聚醚聚酯嵌段共聚物(PTMGT-PET和PEGT-PET)的共混物(BPEE)的性质进行了比较,结果表明:(1)聚醚聚酯嵌段共聚物的血液相容性可以通过引入亲水性好的PEGT组分而得到提高;(2)在多数的组成比下,共聚型的MPEE具有比共混型的BPEE优良的血液相容性;(3)特定的组成比:PTMGT/PEGT=60/40(mol),共混型的BPEE:(60/40)呈现最好的血液相容性以及最佳的力学性质。研究中发现材料的微相分离结构同血液相容性有关,细微的相分离结构可导致优良的血液相容性。     

聚酯-聚酯多嵌段共聚物的合成及其动态力学性能

聚酯-聚醚多嵌段共聚物的动态力学性能谱上有两个T_8,不宜做阻尼材料。本文报道聚对苯二甲酸乙二醇酯(PET)-端羟基聚己二酸乙二醇酯(PEA)共聚物(简称嵌段共聚酯),比聚醚-聚酯多嵌段共聚物有更好的相容性。我们研究了PEA的分子量,间苯二甲酸的用量对嵌段共聚酯的结晶度,以及结晶度对嵌段共聚酯的动态力学性能的影响。     

链段相容性对聚酯-聚醚多嵌段共聚物组成均一性的影响

<正> 由结晶型芳族聚酯为硬链段,无定型脂肪族聚醚为软链段的聚酯-聚醚多嵌段共聚物,是一类性能优良的热塑弹性体,本文研究链段相容性对这类聚合物组成均一性的影响,因此,合成了一系列不同链段结构的聚酯-聚醚多嵌段共聚物。 如硬链为聚对苯二甲酸乙二醇酯(PET)和丁二醇酯(PBT);软链段有聚乙二醇醚(PET)、聚丁二醇醚(PTMG)、聚二醇醚(PPG)和四氢呋喃同环氧丙烷的共聚醚二醇     

硬段含介晶的多嵌段共聚物的合成和研究

通过对-乙酰氧基苯甲酸或对-乙酰胺基苯甲酸和聚酯-聚醚多嵌段共聚物的硬段PET进行酸解反应,和随后的乙酰氧基或乙酰胺基,和羧基间的缩聚反应,分别合成了硬段含介晶的共聚酯-聚醚多嵌段共聚物和聚酯酰胺-聚醚多嵌段共聚物,研究了它们的热致液晶行为。     

聚丙烯与聚酯-聚醚多嵌段共聚物共混的研究

聚丙烯和聚酯-聚醚多嵌段共聚物的熔融共混物是微多相分散体系,其力学性能和软链段的结构有关。DSC和偏光显微镜图分别表明共混物中聚丙烯结晶度以及球晶尺寸随聚酯-聚醚的混入量而变小。聚丙烯和少量聚酯-聚醚多嵌段共聚物共混,可改进聚丙烯的流变性,吸湿性和染色性。     

聚醚聚酯嵌段共聚物特性粘数同熔体流动性的关系

聚醚聚酯嵌段共聚物是一类性能优良的热塑弹性体,有关合成方面的研究报道甚多,运用电镜、X线衍射、DSC等技术进行的超结构和形态方面的研究报道亦已不少,但有关流变性方面的研究报道尚少。 本工作研究了不同催化体系所合成的聚醚聚酯嵌段共聚物,发现随催化体系的改变共聚物的熔融指数与溶液特性粘数之间的关系亦发生变化。总结了不同催化体系下两者间的关系,提出了通过经验公式计算简化测试工作的途径;并对此关系式进行了初步探讨。     

从聚酯合成聚酯-聚醚多嵌段共聚物

研究直接以聚酯为原料,合成聚酯-聚醚多嵌段共聚物。研究了反应机理、链段结构对反应的影响以及由此法制备的多嵌段共聚物的链段序列结构。实验结果表明,链段相容性对聚合物法的影响至为重要,链段相容性不仅决定了所得嵌段共聚物的组成均一性,而且还决定了某一链段结构的多嵌段共聚物能否用聚合物法制备。     

聚醚型多嵌段共聚物软链段结晶特性的研究

本文使用虹外光谱及膨胀计等方法,对聚四亚甲基醚二醇类多嵌段共聚物的软链段结晶性进行了研究。在聚醚-聚酯多嵌段共聚物中(PTMEG>60％),其软链段结晶的熔点和结晶速率均随PTMEG含量减少而下降。而在聚醚-聚脲胺酯多嵌段共聚物中,由于N—H和C—O—C之间氢键的作用,即使在低温下,其软链段也难于结晶。此外,高倍拉伸会提高上述二类多嵌段共聚物中软链段结晶的熔点和结晶速率。     

微相分离及链结构对聚酯-聚醚嵌段共聚物分子运动的影响

本文首先研究了成型方法和热处理对聚对苯二甲酸乙二酯与聚氧四亚甲基嵌段共聚物动态力学温度谱的影响,结合应力-应变曲线讨论了微相分离与力学性能的关系。其次,比较了三种不同链结构的聚酯-聚醚嵌段共聚物在不同温控程序下的动态力学温度谱,讨论了链结构对软链段结晶的影响。最后观察了聚氨酯-聚醚嵌段共聚物双重玻璃化转变现象并作了解释。     

Quenching of exciplex and charge-transfer complex fluorescence of poly(N-vinylcarbazole) – benzanthrone system

When benzanthrone (Bt), a weak electron acceptor, is doped into poly(N-vinylcarbazole) (PVCz) solution or film, an excited carbazole chromophore (D*) interacts with Bt to form a new exciplex state, which gives a broad fluorescence band (λ_max = 440 nm) in solution and a new state, which gives broad fluorescence (λ_max = 550 nm) in the film. In order to elucidate the origin of these new states, we have studied the results of experiments for absorption, concentration dependence of the excimer and exciplex fluorescence quenching, both in solution and in the film, and electric field-induced fluorescence quenching in the film. Taking into account that (i) the new state formation in the PVCz film containing small amounts of Bt enhances the photocurrent in the absorption region, where the photon energy is insufficient to excite polymer molecules directly into the conduction state, (ii) the 550 nm fluorescence of the PVCz - Bt system in film is only partly quenched by electric field, (iii) the appearance of structureless tail in the fluorescence excitation spectrum, the charge transfer interaction model of the PVCz - Bt system in film is proposed.     

Photopolymerization of N-substituted phenyl maleimide initiated with N,N-dimethyl-4-toluidine

Several N-phenyl maleimides with different p-substituents have been synthesized from the maleic anhydride and relevant aromatic amine. In the presence of N,N-dimethyl-4-toluidine (DMT), the N-substituted phenyl maleimide (4-XPhMIs) could be polymerized under UV irradiation. It was observed that a new absorption appeared on the UV-Vis spectrum of the mixture solution of 4-XPhMI and DMT, which reveals the formation of charge-transfer complex in the ground state. It was found that the fluorescence of DMT was quenched by 4-XPhMI and the quenching constant of 4-XPhMI, obtained from the Stern–Volmer plot, increases with the electron-deficiency of ethylene double bond of 4-XPhMI. The dynamic quenching of the fluorescence of DMT by 4-XPhMI suggests the formation of exciplex in excited state between DMT and 4-XPhMI. The radicals formed in the systems have been detected by spin-trapping techniques and electron paramagnetic resonance (EPR) spectrometer. Based on all of these results, it has been proposed that the initiation process of the polymerization involves the formation of exciplex and the initial radicals were produced by proton-transfer in the exciplex from DMT to 4-XPhMI. © 1997 John Wiley & Sons, Inc.     

Effects of Hydrogen-bonding Interaction and Polarity on Emission Spectrum of Naphthalene-Triethylamine in Mixed Solvent

The effects of the protic and aprotic polar solvents on the emission spectrum of the naphthalene-triethyl-amine system in THF were studied under conditions of steady-state illumination. The fluorescence spectrum of the naphthalene-triethylamine system consists of two emission bands, the fluorescence band of naphthalene (band A, 329 nm) and the emission band of the exciplex(band B, 468 nm). The intensities of both the emission bands decrease with increasing the solvent polarity. The intensity of band B also decreases due to the hy-drogen-bonding interaction between triethylamine and protic solvent, while that of band A increases. It is thus suggested that the quenching of naphthalene fluorescence by triethylamine in THF occurs through the charge transfer and electron transfer reactions. The spectral changes upon the increase of solvent polarity can be explained by the dependences of the equilibrium constant between exciplex and ion-pair and the rate constant for the electron transfer reaction from triethyl.amine to the excited naphthalene on the rel.ative permittivity of solvent. It is shown that the formation of intermolecular hydrogen-bonding between triethylamine and protic solvent suppresses the quenching reaction by the decrease in free amine. Acetonitrile has only a polar effect and trichloroacetic acid only a hydrogen-bonding(or protonation) effect, while alcohols have both the effects. The effects of alcohols could be separated into the effects of solvent polarity and intermolecular hy-drogen-bonding interaction quantitatively.     

Mechanism of Exciplex Decay: The Quantum Yields and the Rate Constants of Radical Ion Formation from Exciplexes with Partial Charge Transfer

The dynamics of exciplex and radical ion formation was studied in donor–acceptor systems with G ^* _et > –0.1 eV. It was shown that the quenching of excited singlet states of aromatic molecules by electron donors in polar solvents led to the formation of radical ions via exciplex dissociation resulting to complete charge separation. Intersystem crossing and internal conversion into the ground state (back electron transfer) compete with this process. The quantum yields and the rate constants of the radical ion formation were measured.     

Quencing of perylene fluorescence by Ag+ ions via exciplex formation

The fluorescence of perylene in alcoholic solution is dynamically quenched by AgClO₄ resulting in a new emission band with its maximum around 480 nm. Analysis of fluorescence decay curves at various emission wavelengths proves the formation of a perylene/Aa⁺ ion exciplex in the quenching reaction.     

PHOTOSTATIONARY FLUORESCENCE EMISSION AND TIME RESOLVED SPECTROSCOPY OF SYMMETRICALLY DISUBSTITUTED ANTHRACENES ON THE meso AND SIDE RINGS: THE UNUSUAL BEHAVIOR OF THE 1,4 DERIVATIVE*

Abstract— Steady state and time resolved fluorescence emission properties of symmetrical dialkoxy-anthracenes (especially substituted on the side rings) 1-X, Y were studied in methylcylohexane. At room temperature, the fluorescence spectra of 1-X, Y show bands in the region of 380–550 nm and quantum yields (φ_F) in the range of 0.2–1. The fluorescence emission decays were found to be single exponential. The determination of the intersystem crossing quantum yields (φ_isc) for the weakly fluorescent compounds (1–1,5, 1–1,8 and 1–2,3) demonstrates that internal conversion is negligible compared with fluorescence emission and intersystem crossing, as previously observed for other anthracene derivatives. The fluorescence emission efficiency of compounds 1-X,Y is controlled by the relative mutual positions of the second triplet T₂ (whose energy varies significantly with substitution) and the first excited singlet S₁ states, respectively. An unusual solvatochromism was found for compound 1–1,4 which has a very weak permanent dipole moment in the ground state. This behavior was assigned to strong changes in the electronic densities between the excited singlet state and the ground state.     

CAROTENOID TRIPLET STATE AND CHLOROPHYLL FLUORESCENCE QUENCHING IN CHLOROPLASTS AND SUBCHLOROPLAST PARTICLES

Abstract— Absorption changes attributed to the triplet state of carotenoids and to primary electron donors (P-700. P-680)^: and fluorescence quenching at several wavelengths have been measured with a single apparatus. following flash excitation with a dye or a ruby laser. Spinach chloroplasts as well as subchloroplast particles enriched in Photosystem-1 (F₁), Photosystem-2 (F₁) or the light-harvesting Chl a/h (F_III) have been examined at temperatures varying between 5 and 294 K.
The triplet state of carotenoids has been identified on the basis of its difference spectrum (having a peak at 515 nm) and decay kinetics (⋍ 7 µs at low temperature; accelerated by O₂ at 294 K). It is formed in all of the materials studied. The quantum yield of carotenoid triplet formation in chloroplasts increases at low temperature, but less than the fluorescence yield.
In most cases the fluorescence quenching recovers approximately with the same kinetics as the decay of the carotenoid triplets. The fluorescence recovery is, however, significantly faster for chloroplasts at 730 nm. Fluorescence quenching occurs in all types of materials. The ratio of fluorescence quenching to the concentration of carotenoid triplets varies with the material, being maximum in chloroplasts and minimum in F_m particles.
We conclude that the formation of the carotenoid triplet state is not limited to a few sites in the chloroplast and that a carotenoid triplet is a quencher of chlorophyll fluorescence. A detailed comparison of carotenoid triplets and fluorescence quenching gives some information concerning the organization of the pigments in the photosynthetic apparatus.     

水溶液中芘的荧光被核酸碱基猝灭的研究

众所周知,稠环芳烃是一类具有致癌性的物质.虽然对其致癌机理的认识尚未形成一致的看法,但一般都认为同稠环芳烃与DNA,蛋白质等生物活性物质的相互作用有关.因为致癌物后的致癌作用最终都是通过损伤细胞中的DNA而实现的.     

RESONANCE RAMAN SPECTRUM OF THE EXCITED 21Ag STATE OF ß-CAROTENE

Abstract— Resonance Raman (RR) bands assignable to the 2¹A_g excited state of ß-carotene are recorded using picosecond time-resolved resonance Raman (PTR³) spectroscopy. The RR spectrum contains bands in both the C-C (1204 cm^?1, 1243 cm^?1, and 1282 cm^?1) and C=C (1777 cm^?1) stretching regions. The time-dependent intensities of these RR features, measured with ? 30 ps. resolution, are found (i) to closely correlate with picosecond transient absorption (PTA) data recorded at 575 nm on the same sample and (ii) inversely correlate with the time-dependent intensities of RR bands assigned to the 1¹A_g ground state. Both of these observations support the assignment of these four RR features to the 2¹A_g excited state. These results remove uncertainties associated with earlier experiments in which excited-state RR scattering from (3-carotene was not observed in spite of predicted trends emanating from studies of shorter polyene compounds. The observed C=C band position also agrees with a recent report of this feature.     

THE ENERGETICS OF ELECTRON-TRANSFER REACTIONS OF CHLOROPHYLL AND OTHER COMPOUNDS*

Abstract— Quite often the primary photochemical reaction of an excited state molecule is transfer of an electron to or from another molecule in its ground state. Rates of such reactions are closely dependent on differences between ground and excited state redox potentials of the reagents. The solvent also plays an important role in stabilizing ion pairs formed by the electron transfer. This Review discusses experimental data relating rates to electrochemical energy parameters in the context of a scheme which portrays the energy and electron transactions in a unified manner. Three consequences of reaction of a singlet excited state are distinguished: (S1) quenching without detectable products, (S2) exciplex fluorescence, (S3) transient radical ion production, and energetically necessary conditions are derived for each. Similarly, four kinds of reactions involving the triplet state are distinguished, which depend on the relation between the energy of the triplet state and that of the ion pair states: (TI) rapid quenching, (T2) slow quenching, (T3) accelerated intersystem crossing and (T4) generation by reaction between radical ions of like spin. The last may be followed by electrochemiluminescence. Classes of compounds for which data are available include chlorophylls, porphyrins and a few other molecules of biological interest, aromatic hydrocarbons and their derivatives, heterocyclic systems, carbonyl compounds, dyes, and complexes of Ru and U. A Table compiling median or selected values of ground and excited state electrochemical potentials of chlorophylls, some porphyrins, and a few other compounds is presented.