尼罗红为探针对芳醚树枝形聚合物微环境的研究

本工作合成了一系列羧基为外围末端基团的芳醚树枝形聚合物Gn(n=1—4),利用吸收光谱,稳态和时间分辨荧光发射光谱研究了Gn对尼罗红分子的增溶作用和Gn微环境极性.研究结果表明,尼罗红在Gn中的溶解度随代数增加而增大,从G1到G4,尼罗红溶解度相比水中分别增加了3、35、47和215倍.Gn的微环境极性比水低,2-4代芳醚树枝形聚合物具有相似的微环境极性.     

以尼罗红为探针对新型两亲性树枝形聚合物微环境的研究

本工作合成了一系列外围以三缩四乙二醇单甲醚修饰的烷基芳醚骨架两亲性树枝形聚合物Gn(n=0—3),化合物通过了¹H-NMR,IR和MALDI-TOF-MS的表征.利用吸收光谱,稳态和时间分辨荧光光谱研究了水溶液中Gn对尼罗红分子的增溶作用以及Gn内部微环境的极性.研究结果表明,高代数树枝形聚合物Gn对尼罗红具有更好的增溶效果.1—3代树枝形聚合物Gn内部疏水孔腔微环境极性随代数增加而逐渐降低,G1和G2树枝形聚合物具有相似的微环境极性,而由于构象的变化使G3具有更加疏水的微环境.     

荧光猝灭研究芳醚树枝形聚合物构象

本工作分别合成了外围修饰一个芘基团和核心修饰一个芘基团两个系列的芳醚树枝形聚合物Py-Gn-OH和Gn-CH₂-Py(n=1~4)。Py-Gn-OH和Gn-CH₂-Py的发光随代数增加而增强,荧光寿命增加。荧光猝灭实验结果表明,树枝形聚合物Py-Gn-OH和Gn-CH₂-Py的双分子猝灭速率常数均随代数增加而减小,表明树枝形聚合物发生了构象折叠,位于核心和外围的芘基团均被树枝形聚合物骨架包裹,随代数增加树枝形聚合物骨架增大,对芘基团包裹作用增强,导致猝灭剂接近芘基团的位阻增大。Gn-CH₂-Py体系的双分子猝灭速率常数均比相应代数Py-Gn-OH体系略小,说明树枝形聚合物骨架对连接在核心的芘基团的包裹程度比对连接在外围的芘基团略强。本工作为新型功能芳醚树枝形聚合物设计和应用提供了参考。     

芳醚双枝树枝形聚合物体系的设计合成及三重态能量传递和电子转移的研究

树枝形聚合物的结构特点和良好的可修饰性使其在模拟光捕获体系研究中受到广泛重视,本论文设计合成了两个系列的双枝芳醚树枝形聚合物,通过光物理以及光化学方法研究了芳醚树枝形聚合物体系三重态能量传递和三重态电子转移过程:1.设计合成了两个系列的芳醚树枝形聚合物体系.合成了1代到3代外围以二苯酮基团修饰、核心以降冰片二烯基团修饰的双枝芳醚树枝形聚合物([BP-Gn]₂-NBD,n=1-3)及相应的异构化产物([BP-Gn]₂-QC,n=1-3);合成了外围和核心分别修饰二苯酮和萘的双枝芳醚树枝形聚合物([BP-Gn]₂-NA,n=1-4),及相应的给体模型化合物([BP-Gn]₂-BEN,n=1-4),及相应的给体模型化合物([BP-Gn]-2BEN,n=1)4),共16个新化合物.     

PAMAM修饰的六苯并蔻衍生物的合成及其光物理研究

设计合成了外围以0.5、1.5、2.5代聚酰胺-胺(PAMAM)树枝形聚合物修饰的六苯并蔻衍生物HBC-C₆-PAMAM-D_m(m=0.5, 1.5, 2.5), 化合物结构通过了¹HNMR、¹³CNMR、IR和MS的表征.测定了HBC-C₆-PAMAM-D_m在四氢呋喃、乙腈和二氯甲烷中的吸收和荧光发射光谱, 三种溶剂中不同代数的HBC-C₆-PAMAM-D_m均以聚集态形式存在,外围树枝形聚合物骨架与核心HBC发色团的振动耦合作用随代数增加而增强,导致HBC振动能级不均化,引起吸收和荧光光谱发生变化.     

树枝形聚合物修饰双8-羟基喹啉衍生物的合成及稳态光物理性质研究

设计合成了1 3代芳醚骨架树枝形聚合物修饰的双8 羟基喹啉衍生物.对这些化合物在不同溶剂中的荧光光谱研究表明,随着代数的增加,目标树枝形聚合物的荧光量子产率增大,树枝形聚合物对核心发色团具有一定的隔离作用,并且目标分子内可以发生从骨架向核心发色团的能量传递.     

芘和蒽作为荧光探针探测树枝形聚合物微环境

分别以芘和(9-蒽基)甲基三甲基溴化铵(An)作为荧光探针研究了一系列羧基为外围末端基团的芳醚树枝形聚合物Gn(n=1-4)的内部微环境极性及包结情况. 芘荧光I1/I3值在1-3代树枝形聚合物钾盐水溶液中变化不大, 而3到4代有一个陡降, 推测1-3代树枝形聚合物处于相对开放的结构, G4为相对密闭的球形结构, 4代树枝形聚合物表现出更好的包结特性. An在树枝形聚合物G2钾盐水溶液中的荧光光谱结果表明, 树枝形聚合物G2可以包结两个以上的An分子, An分子疏水的蒽环部分位于树枝形聚合物内部孔穴中, 而带正电荷的铵离子靠近树枝形聚合物分子的极性末端.     

激发态分子内质子转移(ESIPT)发色团修饰的树枝形聚合物合成及光物理研究

设计合成了0～4代外围修饰激发态分子内质子转移(ESIPT)发色团的聚酰胺-胺树枝形聚合物G0～G4,化合物结构经过IR,1H NMR,13C NMR和MS表征.稳态光谱研究表明,树枝形聚合物在四氢呋喃溶液中形成了聚集体,发色团酮式发光随着化合物代数增大呈先增加后减小的变化.质子化树枝形聚合物G1-H～G4-H能溶于水,并在水中形成20 nm左右的聚集体,发色团在聚集体疏水区中构象受限,仅发射酮式发光,并且发光强度受树枝形聚合物分子大小的影响.     

树枝形聚合物修饰的双8-羟基喹啉光物理研究

研究了树枝形聚合物修饰的双8-羟基喹啉衍生物(Gn-QMQ, n=1~3)在二氯甲烷和乙腈中的荧光猝灭过程和荧光衰减过程. 随着代数n的增加, 猝灭速率常数减小, 核心双8-羟基喹啉基团荧光寿命增长, 非辐射失活速率常数减小. 研究结果表明, 随着代数的增加, 树枝形骨架对核心基团的位点分离作用增大, 在乙腈中树枝形骨架趋于紧密构象, 具有更强的位点分离作用.     

芳醚树枝形聚合物体系的设计合成及电子转移和三重态能量传递研究

<正>树枝形聚合物是一类具有特殊结构的大分子,通过可控合成,具有光捕获功能的官能团可以精确地分布在树枝形聚合物的核心或外围,甚至可以在支化单元的任何位置,随着代数的增加,官能团数目从核心向外围呈指数增长,树枝形聚合物的这种特殊结构被用来模拟光合作用中的光捕获体系.电子转移和能量传递是光合作用的关键过程,也是光化学研究的重要内容,因此,研究树枝形聚合物体系内的电子转移和能量传递是人工模拟光合作用的一个突破口,是目前相关研究工作的热点之一.本文设计合成了一系列一代到四代的芳醚树枝形聚合物,共24个新化合物,通过稳态、瞬态以及光化学反应的方法研究了芳醚树枝形聚合物体系内电子转移和三重态能量传递过程,得到了一系列有意义的研究结果:     

Unsurpassed cage effect for the photolysis of dibenzyl ketones in water-soluble dendrimers

Amphiphilic water-soluble poly(alkyl aryl ether) dendrimers Gn (n = 1-3) with charge-neutral tetraethylene glycol monomethyl ethers at their periphery were synthesized as microreactors to control the photochemical reactions of dibenzyl ketone derivatives in aqueous solutions. Photophysical studies demonstrated that Gn can encapsulate organic molecules and provide a hydrophobic microenvironment. The product distribution of photolysis of dibenzyl ketone derivatives can be successfully controlled by encapsulating the substrates within dendrimers, and an unsurpassed cage effect of 1.00 is reached in high generation dendrimers, revealing that a thick and compact "shell" was formed at the periphery of the dendrimers. The cage effect is also significantly influenced by the substituent at the para-position of the guest molecules. The higher generation dendrimers exhibit a better confined microenvironment and the aggregates possess more compact cavities to "lock" the guests than the corresponding unimolecular dendrimers. After photolysis, the separation of products can be easily achieved by extracting from the dendrimer solutions and the dendrimers are simply recovered and reused.     

"Click" synthesis and properties of carborane-appended large dendrimers

Large dendrimers, noted G(n)-3(n+2)cage, containing 3(n+2) o-carborane cluster cages MeC(2)B(10)H(10) at their peripheries (n = number of generation noted G(n)) have been synthesized by Huisgen-type azide alkyne Cu(I)-catalyzed dipolar "click" cycloaddition reactions (CuAAC) between an o-carborane monomeric cluster containing an ethynyl group and arene-centered azido-terminated dendrimers G(n)-3(n+2)N(3) of generations 0, 1, and 2. Attempts to synthesize higher-generation dendrimers of this family yielded insoluble materials. The carborane dendrimers G(0)-9cage, G(1)-27cage, and G(2)-81cage have been characterized by (1)H, (13)C, (11)B NMR, elemental analysis, matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) mass spectroscopy, and size exclusion chromatography (SEC) showing low polydispersities, dynamic light scattering (DLS) showing hydrodynamic diameters of 5.7 nm for the G(1)-27cage and the 12.9 nm for the G(2)-81cage. These dendrimers are extremely robust thermally, with 10% mass loss temperatures of 411 °C for the G(0)-9cage, 371 °C for the G(1)-27cage, and 392 °C for the G(2)-81cage. They all showed a strong absorption in the UV region peaking at 258 nm, whereas emission spectra of low intensities were observed between 280 and 480 nm.     

Ground and excited-state electronic interactions in poly(propylene amine) dendrimers functionalized with naphthyl units: effect of protonation and metal complexation.

We report the absorption spectra and the photophysical properties (fluorescence spectrum, quantum yield, and lifetime) of four dendrimers of the poly(propylene amine) family (POPAMs) functionalized at the periphery with naphthylsulfonamide (hereafter called naphthyl) units. Each dendrimer Gn, where n = 1 to 4 is the generation number, comprises 2n + 1 (i.e., 32 for G4) naphthyl functions in the periphery and 2n + 1--2 (i.e., 30 for G4) tertiary amine units in the branches. All the experiments have been carried out in acetonitrile solutions. Comparison with two reference compounds (N-methyl-naphthalene-2-sulfonamide, A, and N-(3-dimethylamino-propyl)-2-naphthalene-1-sulfonamide, B) has shown that the absorption spectra of the dendrimers are significantly different from those expected from the component units. Furthermore, the intense fluorescence band of the naphthyl unit (lambda max = 343 nm; phi = 0.15, tau = 8.5 ns) is strongly quenched in the dendrimers. The quenching effect increases with increasing generation and is accompanied by the appearance of a weak and broad emission tail at lower energy. Protonation of the amine units of the dendrimers by addition of CF3SO3H (triflic) acid causes a strong increase in the intensity of the naphthyl luminescence and a change in the form of the emission tail. The shapes of the titration curves depend on dendrimer generation, but in any case, the effect of the acid can be fully reversed by successive addition of a base (tributylamine). The results obtained show that in the dendrimers there are interactions (both in the ground and excited states) between naphthyl units as well as between naphthyl units and amine units of the branches; this gives rise to dimer/excimer and charge-transfer/exciplex excited states. Titration with Zn(CF3SO3)2 has the same effect as acid titration, as far as the final emission spectrum is concerned, but a much higher concentration of Zn(CF3SO3)2 has to be used and the shapes of the titration plots are very different. Titration with Co(NO3)2.6H2O causes a much smaller increase in the intensity of the naphthyl fluorescence compared with Zn(CF3SO3)2. The results obtained have shown that protonation and metal coordination can reveal the presence of ground and excited state electronic interactions in functionalized poly(propylene amine) dendrimers, and that the presence of photo-active units in the dendrimers can be useful to reveal some peculiar aspects of the protonation and metal coordination processes.     

Photoresponsive nanocarriers based on PAMAM dendrimers with a o‐nitrobenzyl shell

Gn (n = 3, 4, and 5) poly(amidoamine) (PAMAM) dendrimers were synthesized and peripherally modified with photocleavable o‐nitrobenzyl (NB) groups by reacting o‐nitrobenzaldehyde with the terminal amine groups of PAMAM dendrimers, followed by reducing the imine to amine groups with NaBH₄. The NB‐modified dendrimers, Gn‐NB (n = 3, 4, and 5), were characterized by nuclear magnetic resonance and fourier transform infrared spectroscopy. The results showed that the NB groups were successfully attached on the periphery of the dendrimers with near 100% grafting efficiency. Such a photosensitive NB shell could be cut off on irradiation with 365 nm ultraviolet (UV) light. The encapsulation and release of guest molecules, that is, salicylic acid (SA) and adriamycin (ADR), by Gn‐NB were explored. The encapsulation capability of these dendrimers was found to increase as the guest molecular size was decreased and have dependence on the generation of dendrimers as well. For both of SA and ADR, the average encapsulation numbers per dendrimer decreased in the order of G4‐NB > G5‐NB > G3‐NB, indicating that the fourth generation dendrimer was a better container for the guest molecules. The rate of SA release was found to be greater with UV irradiation than that without, suggesting that the NB‐shelled PAMMAM dendrimers could function as a molecular container/box with photoresponsive characteristics. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 551–557, 2010     

Photosensitized oxygenation of sulfides within an amphiphilic dendrimer containing a benzophenone core

Photosensitized oxygenation of sulfides within amphiphilic dendrimers, Gn [n(generation) = 1-3], consisting of a benzophenone (BZP) sensitizing core, apolar interior based on n-undecane spacer, and polar dendron exterior based on 2,2-bis(hydroxymethyl)propionic acid, has been investigated in O(2)-saturated methanol. Sulfoxide formation occurring via reaction of O(2) with triplet excited-state sulfide ((3)sulfide), which is formed by a triplet energy transfer (TET) from photoformed (3)BZP to sulfide, was accelerated by the dendric sensitizers, where G2 showed the highest yields of alkylaryl and dialkyl sulfoxides. Laser photolysis studies revealed that enhanced access of sulfide to the (3)BZP core inside the apolar microenvironment accelerates the TET to sulfide, whereas prompt migration of polar sulfoxide to the polar outer shell of the dendrimer suppresses a competitive TET to sulfoxide, thus resulting in effective (3)sulfide formation. Another notable feature of the dendric sensitizer appears in oxygenation of diaryl sulfide, which is promoted by a persulfoxide intermediate formed by photooxygenation of dialkyl sulfide; photoirradiation of a mixture of diethyl sulfide (1a) and diphenyl sulfide (4a) with G2 gave 17-fold higher diphenyl sulfoxide (4b) yield than that obtained with unmodified BZP. The apolar microenvironment within the dendric sensitizer encapsulates a large quantity of 4a, which is oxidized effectively by the persulfoxide of 1a, thus resulting in high 4b yield. The BZP core within the dendric sensitizer is stable even by photoexcitation in protic solvent, suggesting potential utilities of this dendric system for effective and selective photosensitized oxygenation of sulfides.     

Characteristics of organic transformations in a confined dendritic core: studies on the AIBN-initiated reaction of dendrimer cobalt(II) porphyrins with alkynes

Cobalt(II) complexes of poly(aryl ester) dendrimer porphyrins [(m-[Gn]TPP)Co(II)] (generation number n=0-4), in the presence of azobisisobutyronitrile (AIBN) at 60 degrees C, underwent alkenylation with several alkynes at the metal center. A complete inhibition of double-bond migration (secondary transformation) was observed for [(m-[Gn]TPP)Co(II)] (n=3 and 4), which gave [(m-[Gn]TPP)Co(III)-C(=CH(2))R] (n=3 and 4) exclusively. Overall reaction rates for [(m-[Gn]TPP)Co(II)] (n=0-3) were hardly dependent on the size of the dendritic substituents, while a notable retardation was observed for the largest dendrimer, [(m-[G4]TPP)Co(II)]. Mechanistic studies on double-bond migration with pure [(m-[Gn]TPP)Co(III)-C(=CH(2))Bu] (n=0-4) demonstrated that the secondary transformation involves participation of [(m-[Gn]TPP)Co(III)H] (n=0-4), derived from [(m-[Gn]TPP)Co(II)] and AIBN, rather than [(m-[Gn]TPP)Co(II)] alone. Crossover experiments using [(m-[Gn]TPP)Co(III)-C(=CH(2))Bu] (n=2-4), in combination with nondendritic [(m-[G0]TPP)Co(II)] and AIBN, indicated a high level of steric protection of the active center by a robust [G4]-dendritic cage, as suggested by a (1)H NMR pulse relaxation time profile of m-[G4]TPPH(2).     

Dendrimers as photochemical reaction media. Photochemical behavior of unimolecular and bimolecular reactions in water-soluble dendrimers

Synthesis and studies of poly(alkyl aryl ether) dendrimers, possessing carboxylic acid functionalities at their peripheries, are reported. 5-Bromopentyloxy methylisophthalate was utilized as the monomer to O-alkylate the phenolic hydroxyl groups of poly(alkyl aryl ether) dendrimers. Dendrimers of first, second, and third generations, possessing 6, 12, and 24 carboxylic acids, respectively, were thus prepared. These dendrimers were soluble in alkaline aqueous solutions, and the ensuing microenvironmental properties of the aqueous solutions were assessed by pyrene solubilization studies. Upon establishing the presence of nonpolar microenvironments within the dendritic structures, solubilizations of few organic substrates were conducted and their photochemical behaviors were assessed. Specifically, the photolysis of 1-phenyl-3-p-tolyl-propan-2-one and benzoin ethyl ether and photodimerization of acenaphthylene were conducted. These studies revealed that the product distribution and the "cage effect" were more distinct and efficient for the third generation dendrimer, than for the first and second generation dendrimers. The photochemical studies of carboxylic acid functionalized dendrimers were compared to that of hydroxyl group terminated poly(alkyl aryl ether) dendrimers.