首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
Optically active dendrimers containing a 1,1'-binaphthyl core and cross-conjugated phenylene dendrons were synthesized and characterized. The chiral optical properties of these phenylene-based dendrimers are different from the previously reported phenyleneethynylene-based dendrimers probably because of the increased steric interaction between the adjacent phenylene units. UV and fluorescence spectroscopic studies demonstrate that the energy harvested by the periphery of the dendrimers can be efficiently transferred to the more conjugated core, generating much enhanced fluorescence signal at higher generation. The fluorescence of these dendrimers can be quenched both efficiently and enantioselectively by chiral amino alcohols. The energy migration and light-harvesting effects of the dendrimers make the higher generation dendrimer more sensitive to fluorescent quenchers than the lower ones. Thus, the dendritic structure provides a signal amplification mechanism. These materials are potentially useful in the enantioselective recognition of chiral organic molecules.  相似文献   

2.
Synthesis and characterization of dendrimers containing thienylbenzene repeating units, red-emitting benzothiadiazole core, and triarylamine peripheries that bear naphthyl units are reported. The relevant dendrimers of different generations are classified as G(nb) (n=1-3), while the tert-butyl dendrimers G(na) with the acceptor alone were also synthesized to serve as control chromophores that avoid donor-acceptor interactions. The resulting dendrimers are capable of harvesting photon energy through efficient energy transfer among donor-acceptor moieties, so that highly luminescent red fluorophores result. Transient fluorescence studies suggest that the energy transfer and its efficiency are approximately unity in all G(a) dendrimers, whereas the rate of energy transfer for the G(b) dendrimers is suppressed, that is, charge transfer from the core to the periphery is a significant quenching pathway. These dendrimers are amorphous in nature with high glass transition temperatures (176-201 degrees C). Electroluminescent devices were fabricated by using the dendrimers as hole-transporting emitters, and the devices exhibit promising red emission parameters.  相似文献   

3.
PAMAM dendrimers of the zeroth to fifth generation (G0-5) have been peripherally modified with phenyl, naphthyl, pyrenyl, and dansyl chromophores. Their fluorescence behaviors are strongly affected by the dendritic architectures at different generations. These dendrimers modified with hydrophobic chromphores can self-organize into vesicular aggregates at the low generations G0-3 in water. The size and aggregation number of these vesicles decrease with increasing generation from G0 to G3. Critical aggregation concentration determined by fluorescence spectroscopy reveals that these aggregates can be favorably formed in the order of G3 > G2 > G1. In contrast to the vesicles made from traditional amphiphilic compounds, these dendrimer-based vesicles are very adhesive due to the H-bonding interaction and entanglement of dendritic branches located in the outer layer. A large number of multivesicle assemblies, i.e., "twins" and "quins" consisting of two and five vesicles, were clearly identifiable with transmission electron (TEM) and atomic force microscopy. For the dendrimers with peripheral pyrenyl chromophores, triangle-like vesicles were observed in water. The hydrophobic interphase thickness of the vesicular bilayer is ca. 2.0-3.2 nm determined by fluorescence resonance energy transfer methods, which agrees well with the thickness directly observed with TEM.  相似文献   

4.
Dendrimer technology has enabled us to build macromolecules with nanosized defined structures. By introducing unsymmetrical patched structures in dendrimers, sophisticated artificial receptors exhibiting nanoscale substrate recognition can be obtained. In this review article, our recent studies on molecular recognition by porphyrin dendrimers with patched structures are summarized. Three topics are presented: (1) oligopeptide-patched dendrimers as a nanoscale receptor of cytochrome c protein; (2) pocket dendrimers as a nanoscale receptor for bimolecular guest accommodation; and (3) energy transfer in unsymmetrical dendrimers. These dendrimers nicely mimic proteins and enzymes, and also act as photofunctional artificial receptors, in which porphyrin’s strong photoabsorption and intense fluorescence signals can respond sensitively to the substrate binding.  相似文献   

5.
Jiang H  Lee SJ  Lin W 《Organic letters》2002,4(13):2149-2152
[structure: see text] New chiral terpyridines containing Frechét-type dendrons have been readily synthesized by coupling dendritic benzyl bromide and 4'-[6-(2,2'-dihydroxy-1,1'-binaphthyl)]-2,2':6'2' '-terpyridine. These chiral dendritic terpyridines were used to efficiently construct high molecular weight hybrid metal-organic dendrimers based on the Ru(II)-bis(terpy) linkage. Preliminary fluorescence measurements show generation-dependent fluorescence quenching behavior of 3,5-dimethoxybenzyl peripherals by the [Ru(terpy)(2)](2+) unit.  相似文献   

6.
The search for a model that can be used to describe the optical excitation migration in dendrimers has attracted great attention. In most cases in a dendrimer the conjugation is disrupted at the branching point; however, the excitation is delocalized. The strength of interactions among neighboring chromophores plays a key role in determining the energy migration mechanism. Conversely, having many identical chromophores held tightly together in an ordered macromolecular architecture will allow for many dipoles to be accessible for optical excitation. Therefore, the relative orientation of dipoles will be important in determining the mechanism of energy migration. Here we report the synthesis and photo-physical investigation of triarylamine-based dendrimers. Two important synthetic steps were utilized in the synthesis. First, we employed diphenylmethyl protective groups on the amines to assist in deprotective hydrogenolysis of the larger structures. Second, highly active catalysts for formation of both di- and triarylamines that are based on a 1:1 ratio of P(t-Bu)3 and Pd(dba)2 improved reaction yields of the C-N bond formation and decreased reaction times The energy migration processes in the dendrimers were investigated utilizing ultrafast time-resolved fluorescence anisotropy measurements. The fluorescence anisotropy of all three dendrimers decayed to a residual value within approximately 100 fs. This fluorescence anisotropy decay showed a general trend in decreasing with increasing dendrimer generation. The residual anisotropy value also showed a gradual decrease with an increase in the dendrimer generation. This fast energy depolarization is discussed through a coherent excitonic mechanism among dipoles oriented in different directions. We believe that the formation of coherent domains leads to fast energy migration extending over a large part of the dendrimer.  相似文献   

7.
The photochemical and photophysical behavior of two dendrimers consisting of a benzophenone core and branches that contain dimethoxybenzene units has been investigated. Such dendrimers can undergo a variety of photochemical and photophysical processes, namely: 1) quenching of the fluorescence and phosphorescence of the dimethoxybenzene units by energy transfer to the benzophenone core (antenna effect), 2) direct and sensitized phosphorescence (and delayed fluorescence) of the benzophenone core, 3) hydrogen abstraction by the triplet excited state of the benzophenone core from solvent molecules, 4) intramolecular hydrogen abstraction by the triplet excited state of the benzophenone core from the dendrimer branches, 5) quenching of the phosphorescence and hydrogen abstraction reaction of the benzophenone core by energy transfer to terbium ions and dioxygen; 6) conversion of the UV light absorbed by the dendrimer branches into visible (Tb3+) or near infrared (O2) emission via the sequence of processes 1) and 5). The results obtained emphasize the great potential of suitably designed dendrimers for a multiple use of light signals.  相似文献   

8.
A dramatic enhancement in fluorescence intensity from 1,1'-bi-2-naphthol (BINOL) to dendritic phenyleneethynylenes containing the BINOL core was observed. The strong fluorescence of the dendrimers allows a very small amount of the chiral materials to be used for sensing. The light harvesting antennas of the dendrimer funnel energy to the center BINOL unit, whose hydroxyl groups upon interaction with a quencher molecule lead to fluorescence quenching. This mechanism makes the dendrimers have much more sensitive fluorescence responses than corresponding small molecule sensors. The fluorescence of these dendrimers can be enantioselectively quenched by chiral amino alcohols. It is observed that the fluorescence lifetime of the generation two dendrimer does not change in the presence of various concentrations of 2-amino-3-phenyl-1-propanol. This demonstrates that the fluorescence quenching is entirely due to static quenching. Thus, formation of nonfluorescent ground-state hydrogen-bond complexes between the dendrimers and amino alcohols is proposed to account for the fluorescent quenching. A linear relationship has been established between the Stern-V?lmer constant of the generation two dendrimer and the enantiomeric composition of 2-amino-3-phenyl-1-propanol. Such enantioselective fluorescent sensors may allow a rapid determination of the enantiomeric composition of chiral molecules and are potentially useful in the combinatorial search of asymmetric catalysts and reagents.  相似文献   

9.
A fundamental understanding of multivalency can have a profound influence on bottom-up nanofabrication. For this purpose, three different types of ferrocenyl (Fc) functionalized dendrimers of generations 1-5 with various spacer groups were adsorbed at self-assembled monolayers (SAMs) of heptathioether-functionalized beta-cyclodextrin (betaCD) on gold. The dendrimers formed kinetically stable supramolecular assemblies at the betaCD host surface having up to eight multivalent supramolecular interactions, but could be efficiently removed from the host surface by electrochemical oxidation of the Fc end groups. Dendrimer desorption and re-adsorption could be repeated a number of times without significant decomposition of the system. The stoichiometries of the dendrimers at the surface were determined using cyclic voltammetry (CV). These were quantitatively confirmed for the lower generations by surface plasmon resonance (SPR) titrations of the dendrimers to the betaCD SAM. Measuring CV and SPR simultaneously gave crucial mechanistic information on the electrochemically induced desorption of the dendrimers from the host surface. The redox-active dendrimers effectively blocked the host surface for binding other molecules, e.g. adamantyl-functionalized dendrimers, but electrochemically induced release of the blocking layer revealed the host surface to which the adamantyl dendrimers could then bind.  相似文献   

10.
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.  相似文献   

11.
Hydroxyl group terminated poly(propyl ether imine) dendrimers of 1 to 5 generations absorb in the region of 260-340 nm, in MeOH and aqueous solutions. Excitation of a solution of the dendrimers at 330 nm led to an emission at approximately 390 nm. The emission intensities increased under acidic pH and in more viscous solvents. The presence of air did not affect the emission profiles, as also aging of a dendrimer solution for prolonged periods. Lifetime measurements show at least two species responsible for the emission. Anions perchlorate, periodate, nitrite, and pyridinium methyliodide quenched the fluorescence efficiently, among several anions tested.  相似文献   

12.
The synthesis and photophysical characterization of a series of free base porphyrin-containing polyamide dendrimers terminated with anthraquinone groups (FbP-Ga-AQ(n)(), a = 1-3, n = 12, 36, 108) are described. Substantial quenching (58-75%) of the porphyrin fluorescence of FbP-Ga-AQ(n)() is observed when compared to the analogous ethyl-terminated dendrimers (FbP-Ga-Et(n)()) in steady-state fluorescence experiments and is attributed to intramolecular electron transfer. Time-resolved fluorescence experiments were fit to 2-3 exponentials, indicating multiple orientations for electron transfer, consistent with the flexible nature of these dendrimers.  相似文献   

13.
Lin YH  Wu HH  Wong KT  Hsieh CC  Lin YC  Chou PT 《Organic letters》2008,10(15):3211-3214
Covalent linkage of dendritic carbazole-based donors and 1,3,4-oxdiazole-based acceptors renders novel bipolar dendrimers that can efficiently facilitate the photoinduced electron transfer (PET) process. Photodynamic studies indicated that the PET rate of bipolar dendrimers DA1 and DA2 can be modulated by the number of acceptors presented in the molecule.  相似文献   

14.
Different generations of carboxyl-terminated poly(aryl ether) dendrimers bearing a diphenylanthracene core were designed and synthesized. It is interesting to see that not only two-generation dendrimers but also one-generation dendrimers can be fabricated into thin films by self-deposition. Fluorescence spectra indicate that increasing the generation number of a dendrimer can effectively control the quenching of the fluorescence. Moreover, the fluorescence property of the diphenylanthracene core of the dendrimers in a solid film is quite similar to that of one in a solution, which is important for designing light-emitting materials.  相似文献   

15.
The photochemical properties of a series of newly synthesized dendrimers, 4-6, having a 2-(2'-hydroxyphenyl)benzoxazole (HBO) core, were studied in benzene. The fluorescence quantum yields (Phi(f)) were determined to be 0.022, 0.030, and 0.038 for 4, 5, and 6, respectively, increasing in higher generation dendrimers. With transient absorption spectroscopy, the quantum yields of the isomerization from the (E)-keto form ((1)K(E)*) to the (Z)-keto form ((1)K(Z)) (Phi(E)(-->)(Z)) and those of intersystem crossing (Phi(isc)) can be estimated. Whereas Phi(E)(-->)(Z) values decreased in higher generation dendrimers, Phi(isc) values were almost the same among 4-6. The quantum yields of nonradiative decay (Phi(nr)) increased in higher generation dendrimers. The dendrimer structure also affected the reverse tautomerization process.  相似文献   

16.
The synthesis, cytotoxicity, and behavior in cell culture of a new set of first- (G1) and second-generation (G2) dendrimers is reported. The surface functionality of these dendrimers has been varied to see whether structure/toxicity relations can be observed. The outermost functional groups are amines that are decorated either with protons, tert-butoxycarbonyl (Boc) or benzyloxycarbonyl (Cbz) protecting groups, Boc-protected or unprotected natural amino acid residues, ethylenediamine ligands, and/or dansyl fluorescence labels. The cytotoxicity was determined in vitro in concentration-dependent assays using the human MCF-7 breast cancer cell line. Cellular uptake and intracellular distribution was monitored by confocal fluorescence microscopy after internalization of the dansyl-labeled dendrimers by HeLa cells.  相似文献   

17.
Multiporphyrin dendrimers are among the most promising architectures to mimic the oxygenic light-harvesting complex because of their structural similarities and synthetic convenience. The overall geometries of dendrimers are determined by the core structure, the type of dendron, and the number of generations of interior repeating units. The rigid core and bulky volume of exterior porphyrin units in multiporphyrin dendrimers give rise to well-ordered three-dimensional structures. As the number of generations of interior repeating units increases, however, the overall structures of dendrimers become disordered and randomized due to the flexibility of the repeating units. To reveal the relationship between molecular structure and processes of excitation-energy migration in multiporphyrin dendrimers, we calculated the molecular structure and measured the time-resolved transient absorption and fluorescence anisotropy decays for various hexaarylbenzene-anchored polyester zinc(II) porphyrin dendrimers along with three types of porphyrin dendrons as references. We found that the congested two-branched type dendrimers exhibit more efficient energy migration processes than one- or three-branched type dendrimers because of multiple energy migration pathways, and the three-dimensional packing efficiency of dendrimers strongly depends on the type of dendrons.  相似文献   

18.
Two series of phosphorus dendrimers functionalized by maleimide derivatives are synthesized, as well as three new monomeric maleimide derivatives, of which two are characterized by X-ray diffraction. The first series of phosphorus dendrimers possesses maleimide derivatives as end groups (6-48, from generation 0 to generation 3). The second series of dendrimers possesses a single copy of the same maleimide derivative linked "off-center" to a cyclotriphosphazene core, leading to dissymmetrical dendrimers; this series is synthesized from generation 0 to generation 2. The fluorescence properties of both series of dendrimers and of monomers are studied, affording new information. First, the presence of labile hydrogen extinguishes the fluorescence. Second, the grafting of the fluorophore(s) directly to the core affords highly fluorescent compounds. Finally, an original influence of the branches possessing phosphorhydrazone linkages toward the fluorescence properties is shown.  相似文献   

19.
Quantitative evaluation of F?rster-type fluorescence resonance energy transfer (FRET) was undertaken by statistical investigations on perylene-cored anthracene dendrimers.  相似文献   

20.
Selectively deuterated, dodecyloxy substituted stilbenoid dendrimers of the first and second generation were synthesized by a convergent synthesis, using the Wittig-Horner reaction. The photochemistry and the fluorescence in the different crystalline and liquid crystalline phases were investigated. Molecules deuterated at the alpha-position of the alkoxy chains were used to study the photoreactions in the neat phases by 1H NMR. Reactions of the double bonds are exclusively observed in the liquid crystal phases. No photoreactions occur in the crystalline state. The mobility of the dendrimers was studied by means of 2H solid-state NMR spectroscopy. The onset of the photochemistry for dendrimer 1 [all-(E)-1,3,5-tris[2-(3,4,5-tridodecyloxyphenyl)ethenyl]benzene] corresponds to the increasing mobility at the Cr/LC transition. The first generation dendrimers still show large angle motion, whereas dendrimers of the second generation 2 [all-(E)-1,3,5-tris(2-[3,5-bis[2-(3,4,5-tridodecyloxyphenyl)ethenyl]phenyl]ethenyl)benzene] are restricted to librational motions. Photochemical conversion and fluorescence quenching for first and second generation dendrimers 1 and 2 increase with increasing molecular motion and reach a maximum in the isotropic phase.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号