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1.
A unique photoluminescent phenomenon producing inexplicable, blue emissions [λEx?=?365 nm; λEm?=?460 nm] in the absence of traditional aromatic fluorophores has been observed in a variety of surface functionalized poly(amidoamine) (PAMAM) dendrimers over the past two decades. This emission phenomenon, referred to as non-traditional intrinsic fluorescence (NTIF), originates from the intra-molecular clustering of electron-rich sub-fluorophores (i.e., tertiary amines and/or amido groups) residing in the interior of all PAMAM dendrimers. The intra-molecular clustering of these interior sub-fluorophores is hypothesized to account for the modest but reproducible, blue emissions observed for a variety of dendrimer surface moieties (i.e., –OH, –CO2H, and –NH2). Unexpectedly, a simple, one-step conversion of amine-terminated PAMAM dendrimers to 1-(4-carbomethyoxy) pyrrolidone-terminated dendrimers (4-CMP) was found to produce a 50-fold increase in blue NTIF emission compared to other surface moieties. In an effort to understand this new enhanced emission property, critical nanoscale design parameter (CNDP)-directed quenching experiments were devised to probe the increased NTIF emissions. Was it originating from the interior sub-fluorophoric tertiary amine/amido moieties or from the surface-attached, sub-fluorophoric pyrrolidone amido groups or both? Four generations of 4-CMP PAMAM dendrimers were examined. Two classical quenchers, namely, potassium iodide and acrylamide were selected to probe surface versus interior domains, respectively, as a function of predictable CNDPs associated with generation levels. With increasing dendrimer generation, quencher penetration into the dendrimer interior is impeded due to CNDP-directed generational congestion. Stern-Volmer plots for each quencher, as a function of generation, exhibited appropriate linear or non-linear correlations that corroborated behavior expected for two distinct region-specific emission sites.  相似文献   

2.
Bioapplications of poly(amidoamine) (PAMAM) dendrimers in nanomedicine   总被引:1,自引:0,他引:1  
Poly(amidoamine) (PAMAM) dendrimers are a novel class of spherical, well-designed branching polymers with interior cavities and abundant terminal groups on the surface which can form stable complexes with drugs, plasmid DNA, oligonucleotides, and antibodies. Amine‐terminated PAMAM dendrimers are able to solubilize different families of hydrophobic drugs, but the cationic charges on dendrimer surface may disturb the cell membrane. Therefore, surface modification by PEGylation, acetylation, glycosylation, and amino acid functionalization is a convenient strategy to neutralize the peripheral amine groups and improve dendrimer biocompatibility. Anticancer agents can be either encapsulated in or conjugated to dendrimer and be delivered to the tumor via enhanced permeability and retention (EPR) effect of the nanoparticle and/or with the help of a targeting moiety such as antibody, peptides, vitamins, and hormones. Biodegradability, non-toxicity, non-immunogenicity, and multifunctionality of PAMAM dendrimer are the key factors which facilitate steady increase of its application in drug delivery, gene transfection, tumor therapy, and diagnostics applications with precision and selectivity. This review deals with the major topics of PAMAM dendrimers including structure, synthesis, toxicity, surface modification, and also possible new applications of these spherical polymers in biomedical fields as dendrimer-based nanomedicine.  相似文献   

3.
A fluorescent hybrid cadmium sulphide quantum dots (QDs) dendrimer nanocomposite (DAB-CdS) synthesised in water and stable in aqueous solution is described. The dendrimer, DAB-G5 dendrimer (polypropylenimine tetrahexacontaamine) generation 5, a diaminobutene core with 64 amine terminal primary groups. The maximum of the excitation and emission spectra, Stokes’ shift and the emission full width of half maximum of this nanocomposite are, respectively: 351, 535, 204 and 212 nm. The fluorescence time decay was complex and a four component decay time model originated a good fit (χ = 1.20) with the following lifetimes: τ 1 = 657 ps; τ 2 = 10.0 ns; τ 3 = 59.42 ns; and τ 4 = 265 ns. The fluorescence intensity of the nanocomposite is markedly quenched by the presence of nitromethane with a dynamic Stern-Volmer constant of 25 M−1. The quenching profiles show that about 81% of the CdS QDs are located in the external layer of the dendrimer accessible to the quencher. PARAFAC analysis of the excitation emission matrices (EEM) acquired as function of the nitromethane concentration showed a trilinear data structure with only one linearly independent component describing the quenching which allows robust estimation of the excitation and emission spectra and of the quenching profiles. This water soluble and fluorescent nanocomposite shows a set of favourable properties to its use in sensor applications.  相似文献   

4.
Solvent-induced aggregation and its effect on the intrinsic emission properties of amine, hydroxy and carboxylate terminated, poly(amidoamine) (PAMAM) dendrimers have been investigated in glycerol, ethylene glycol, methanol, ethylene diamine and water. Altering the solvent medium induces remarkable changes in the intrinsic emission properties of the PAMAM dendrimers at identical concentration. Upon excitation at 370 nm, amine terminated PAMAM dendrimer exhibits an intense emission at 470 nm in glycerol, ethylene glycol as well as glycerol-water mixtures. Conversely, weak luminescence is observed for hydroxy and carboxylate terminated PAMAM dendrimers in the same solvent systems. When the solvent is changed to ethylene diamine, hydroxy terminated PAMAM exhibits intense blue emission at 425 nm. While the emission intensity is varied when the solvent milieu is changed, excited state lifetime values of PAMAM dendrimers remain independent of the solvent used. UV-visible absorption and dynamic light scattering (DLS) experiments confirm the formation of solvent-controlled dendrimer aggregates in the systems. Comparison of the fluorescence and DLS data reveals that the size distribution of the dendrimer aggregates in each solvent system is distinct, which control the intrinsic emission intensity from PAMAM dendrimers. The experimental results suggest that intrinsic emission intensity from PAMAM dendrimers can be regulated by proper selection of solvents at neutral conditions and room temperature.  相似文献   

5.
The curing reaction of glycidyl ether bisphenol A (DGEBA) with n-butyl amine and/or N-methylethylenediamine was monitored by fluorescence spectroscopy. 5-Dimethylaminonaphthalene-1-sulfonamide (DNS) fluorophore was used as a probe and/or label. Fourier transform infrared (FTIR) analysis revealed that the rate constant for the addition reaction of the primary amino group hydrogen of n-butylamine to the epoxide ring is more than four times larger than that arising from a secondary amine. Significant differences have been observed between the fluorescence behavior of the DNS as a probe and label, especially in the system DGEBA–n-butyl amine. Integrated fluorescence intensity for the DNS label, in contrast to the DNS probe, indicates the most important changes in chemical transformations of this reaction mixture (the onset of tertiary amino groups and maximum concentration of secondary amino groups). Similarly, the dependence of the half-bandwidth on the epoxy groups conversion for the DNS label shows these stages of the curing reaction as well. In the system DGEBA–N-methylethylenediamine, the reactivity of the secondary amino group hydrogen is higher than that of the primary amino group. A change in slope of the dependence of integrated fluorescence intensity on epoxy group conversion clearly indicates the gel point and entry of the system into the glassy state. The DNS probe does not sense any of these changes. From the emission spectra of the DNS probe and/or label, the average value <v> = ΣIF (ν)ν/ΣIF (ν) of the emission band position has been correlated with the epoxy group conversion determined by FTIR. Smooth dependencies were obtained in all cases. This enables one to monitor on line and in real time the epoxy group conversion.  相似文献   

6.
A novel fluorescence enhancement-type derivatizing reagent for amino compounds, 6,7-difluoro-1,4-dihydro-1-methyl-4-oxo-3-quinolinecarboxylic acid (FMQC), was developed. FMQC reacts with aliphatic primary amino compounds to afford strong fluorescent derivatives having high photo-and thermo-stabilities. The FMQC derivatives of amino compounds showed 12–159 times higher fluorescence quantum efficiencies than those of FMQC in aqueous and polar organic media. Additionally, the absorption and fluorescence emission wavelength of the derivatives are red-shifted from those of FMQC. These differences in the fluorescence properties between FMQC and the fluorescent derivative enabled the simple and highly sensitive determination of amino compounds without removing any excess unreacted FMQC by using a simple spectrofluorometer as well as HPLC.  相似文献   

7.
The aim of this study was to investigate the interactions between poly(propylene imine) (PPI) dendrimers and 2′-/3′-O-(N′-methylanthraniloyl)-ATP (Mant-ATP). Mant-ATP was used as a model molecule. Purine and pyrimidine nucleoside analogues are antimetabolites commonly used in therapy for cancer. Drug molecules can complex with dendrimers in two ways: therapeutic agents may be attached in dendrimer interior or bind to functional groups on the surface. Drugs attached to nanoparticles are characterized by improved solubility, pharmacokinetics and stability. Here, we have used poly(propylene imine) dendrimers of the 4th and 5th generations (PPI G4 and PPI G5) with primary amino surface groups partially modified with maltose (PPI-m) or without modification (PPI). We assessed the efficiency of complex formation in relation to dendrimer generation, pH of solution and the type of dendrimer used. A double fluorimetric titration method was used to estimate the binding constant (K b ) and the number of binding centers per molecule of the binding agent (n).  相似文献   

8.
Continuous 295 nm excitation of whey protein bovine apo-α-lactalbumin (apo-bLA) results in an increase of tryptophan fluorescence emission intensity, in a progressive red-shift of tryptophan fluorescence emission, and breakage of disulphide bridges (SS), yielding free thiol groups. The increase in fluorescence emission intensity upon continuous UV-excitation is correlated with the increase in concentration of free thiol groups in apo-bLA. UV-excitation and consequent SS breakage induce conformational changes on apo-bLA molecules, which after prolonged illumination display molten globule spectral features. The rate of tryptophan fluorescence emission intensity increase at 340 nm with excitation time increases with temperature in the interval 9.3–29.9°C. The temperature-dependent 340 nm emission kinetic traces were fitted by a 1st order reaction model. Native apo-bLA molecules with intact SS bonds and low tryptophan emission intensity are gradually converted upon excitation into apo-bLA molecules with disrupted SS, molten-globule-like conformation, high tryptophan emission intensity and red-shifted tryptophan emission. Experimental Ahrrenius activation energy was 21.8 ± 2.3 kJ.mol−1. Data suggests that tryptophan photoionization from the S1 state is the likely pathway leading to photolysis of SS in apo-bLA. Photoionization mechanism(s) of tryptophan in proteins and in solution and the activation energy of tryptophan photoionization from S1 leading to SS disruption in proteins are discussed. The observations present in this paper raise concern regarding UV-light pasteurization of milk products. Though UV-light pasteurization is a faster and cheaper method than traditional thermal denaturation, it may also lead to loss of structure and functionality of milk proteins.  相似文献   

9.
E,E-2,5-bis[2-(3-pyridyl)ethenyl]pyrazine (BPEP) has been prepared by aldol condensation between 2,5-dimethylpyrazine and pyridine-3-carboxaldehyde. It is characterized by IR, 1H NMR, and 13C NMR. The electronic absorption and emission properties of BPEP were studied in different solvents. BPEP displays a slight solvatochromic effect of the absorption and emission spectrum, indicating a small change in dipole moment of BPEP upon excitation. The dye solutions (1 × 10?4 M) in CHCl3, EtOH and dioxane give laser emission in blue region upon excitation by a 337.1 nm nitrogen pulse (λ = 337 nm). The tuning range, gain coefficient (α) and emission cross – section (σe) have been determined. Ground and excited states electronic geometric optimizations were performed using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), respectively. A DFT natural bond analysis complemented the ICT. The simulated maximum absorption and emission wavelengths are in line the observed ones in trend, and are proportionally red-shifted with the increase of the solvent polarity. The stability, hardness and electrophilicity of BPEP in different solvents were correlated with the polarity of the elected solvents. BPEP dye displays fluorescence quenching by colloidal silver nanoparticles (AgNPs). The fluorescence data reveal that radiative and non-radiative energy transfer play a major role in the fluorescence quenching mechanism.  相似文献   

10.
The phenomenon of excited state twisted intramolecular charge transfer (TICT) process in N,N-dimethylaminonaphthyl-(acrylo)-nitrile (DMANAN) has been reported on the basis of steady-state absorption and fluorescence spectroscopy in combination with quantum chemical calculations. The absorption and fluorescence characteristics of DMANAN in solvents of different polarity reveal the presence of a single species in the ground state which forms the intramolecular charge transfer state upon photoexcitation. The observed dual fluorescence is assigned to a high-energy emission from the locally excited or the Franck-Condon state and the red-shifted emission from the charge transfer (CT) state. In polar protic solvents, hydrogen-bonding interaction on CT emission has been established from the linear dependency of the position of the low-energy emission maxima on hydrogen-bonding parameter (α). The experimental findings have been correlated with the theoretical results based on TICT model obtained at density functional theory (DFT) level. The theoretical potential energy surface for the first excited state along both the donor and acceptor twist coordinates in the gas phase obtained by time dependent density functional theory (TDDFT) method and in polar solvent by time dependent density functional theory-polarized continuum model (TDDFT-PCM) method predicts well the experimental spectral properties.  相似文献   

11.
Novel pyrazoly 1,3,4-oxadiazole derivatives were synthesized and characterized by 1H NMR, IR, HRMS and X-ray diffraction analysis. UV–vis absorption and fluorescence properties of these compounds in different solutions showed that the maximum absorption wavelength was not significantly changed in different solvents; however, maximal emission wavelength was red-shifted with the increase of solvent polarity. Absorption λmax and emission λmax was less correlated with substituent groups on aryl rings.  相似文献   

12.
A donor-acceptor compound based on Rhodanineacetic acid-pyrene derivative (RAAP), which emits weak yellow-green fluorescence in the methanol solution, was investigated. RAAP nanoparticles with a mean diameter of 50–60 nm were prepared by a simple reprecipitation method without surfactants. The observation of RAAP nanoparticles were undertaken through SEM and TEM method. The emission spectra of RAAP nanoparticles are red-shifted (Δ λem = 86 nm) to red region and the intensity is 40-fold higher than that in the methanol solution. Both the J-aggregation and aggregation-induced intramolecular planarization are considered to be the probable mechanism of strong emission for RAAP nanoparticles. The excellent sensibility toward organic vapor which profits from its fluorescence switching behavior is well demonstrated by vapor experiment.  相似文献   

13.
Steady state and time resolved fluorescence quenching behaviors of meso-Tetrakis (pentafluorophenyl) porphyrin (H2F20TPP) in presence of different aliphatic and aromatic amines have been executed in homogeneous dichloromethane (DCM) solution. At room temperature in DCM, free base (H2F20TPP) shows fluorescence with two distinct peaks at 640 and 711 nm and natural lifetime τ f = 9.8 ns which are very similar to that of meso-tetraphenyl porphyrin (TPP). Unlike TPP, addition of both aliphatic and aromatic amines to a solution containing H2F20TPP results in an efficient decrease in fluorescence intensity without altering the shape and peak position of fluorescence emission. Upon addition of amines there was no change in optical absorption spectra of H2F20TPP. The fluorescence quenching rate constants ranged from 1 × 109 to 4 × 109 s−1, which are one order below to the diffusion control limit, and temperature dependent quenching rate constants yield the activation energies which are found to be order of 0.1 eV. Femto second transient absorption studies reveal the existence of amine cation radical and porphyrin anion radicals with very short decay time (15 ps). The fluorescence quenching reaction follows Stern–Volmer kinetics. Steady state and time-resolved data are interpreted within general kinetic scheme of Marcus semi-classical model which attributes bimolecular electron transfer process between amines and the lowest excited singlet state of H2F20TPP. Calculated internal reorganization energies are found to be in between 0.04 and 0.22 ev. Variation of electron transfer rate as function of free energy change (∆G0) points the ET reactions in the present systems are in Marcus normal region. This is the first example of reductive fluorescence quenching of free base neutral porphyrins in homogeneous organic solvent ever known.  相似文献   

14.
Eu3+-, Tb3+- and Er3+-cored dendrimer complexes were prepared by self-assembly of three fluorinated dendrons, each with a carboxylate anion focal point, around the lanthanide ion. Energy transfer from the peripheral fluorinated phenyl moieties of the dendrons to the lanthanide cation was evidenced spectroscopically for Eu3+- and Tb3+-cored dendrimer complexes in solution. The excitation of perfluorinated aromatic groups was found to decay with ca. 0.7 ns and a longer decay time 10-13 ns was related to the coordination at the Ln3+ focal point. Luminescence from the lanthanide core decays with lifetime in the range 1-1.5 ms over a wide concentration range (μM-mM), similar to the luminescence decay time of the corresponding acetate ion complexes in D2O. The main quenching mechanism of the lanthanide emission appears to be due to vibrations among surrounding C-H bonds of the intermediate shell of the flexible dendrimer scaffold. Antenna effect and energy harvesting from the surface of the dendrimer and transfer to the core was the main mechanism for luminescecnce in the dendrimer complexes with lanthanide cations.  相似文献   

15.
Commercial glass fibers have been subjected to different activation treatments under neutral and acidic conditions to achieve different coating degrees when silanized with -aminopropyltriethoxisi lane (APES). A fluorescent sulfonamide (PSA) was formed between the amine residue and a fluorescent probe, pyrenesulfonyl chloride (PSC). Reflectance UV–Vis spectra of the pyrene-doped fibres show that pyrene is present in the form of preassociated dimers when the coating degree is low. Emission and excitation fluorescence spectra reveal the existence of a charge transfer ground-state complex with exciplex emission at 460–515 nm and absorption red-shifted with respect to the S0 S1 transition. Lifetime measurements yield three lifetimes, which are assigned to dimer, exciplex, and monomer emission. From the photophysical data it is concluded that the fibers with the highest silane content have an open structure with the highest fraction of isolated fluorescent moieties.  相似文献   

16.
Room-temperature electronic absorption, fluorescence, and low-temperature (77 K) phosphorescence spectra of a series of indolecarboxylic acids have been measured in predominantly aqueous solutions at pH 1.2, 7.0, 12.5, and in 5 N NaOH. The 1La and 1Lb π, π 1 states have been assigned to the electronic transitions for all the compounds under study. The quenching of fluorescence, the appearance of a new fluorescence emission band, red-shifted by 40 nm, in very alkaline media, and the disappearance of the indole carboxylate short-wavelength band have been attributed to the formation of an excited singlet-state indolate carboxylate (dianion) stabilized by hydrogen bonding with the solvent. The existence of two successive excited singlet-state prototropic equilibria is discussed.  相似文献   

17.
A series of amino silicones with different amino values were synthesized and adsorbed onto surfaces of cotton fibers and cellulose substrates. The film morphology, hydrophobic properties and surface composition of the silicones are investigated and characterized by field emission scanning electron microscope (FESEM), atomic force microscope (AFM), contact angle measurement, X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance infrared (ATR-IR). The results of the experiments indicate that the amino silicone can form a hydrophobic film on both cotton fibers and cellulose substrates and reduce the surface roughness significantly. Furthermore, the roughness becomes smaller with an increase in the amino value. All these results suggest that the orientation of amino silicone molecule is with the amino functional groups of amino silicone molecule adsorbed onto the cellulose interface while the main polymer chains and the hydrophobic Si-CH3 groups extend toward the air.  相似文献   

18.
General and versatile methods for the functionalization of superparamagnetic, silica-coated, maghemite nanoparticles by surface amino and/or carboxyl groups have been established. The nanoparticles were synthesized using co-precipitation from aqueous solutions and coated with a thin layer of silica using the hydrolysis and condensation of tetraethoxysilane (TEOS). For the amino functionalization, 3-(2-aminoethylamino)propylmethyldimethoxysilane (APMS) was grafted onto the nanoparticle surfaces in their aqueous suspensions. The grafting process was followed by measurements of the ζ-potential and a determination of the concentration of the surface amino groups with conductometric titrations. The surface concentration of the amino groups could be varied by increasing the amount of APMS in the grafting process up to approximately 2.3 –NH2 groups per nm2. The carboxyl functionalization was obtained in two ways: (i) by a ring-opening linker elongation reaction of the surface amines at the functionalized nanoparticles with succinic anhydride (SA) in non-aqueous medium, and (ii) by reacting the APMS and SA first, followed by grafting of the carboxyl-terminated reagent onto the nanoparticle surfaces. Using the first method, the SA only reacted with the terminal primary amino groups (–NH2) of the surface-grafted APMS molecules. Infra-red spectroscopy (ATR FTIR) and mass spectrometry (HRMS) showed that the second method enables the bonding of up to two SA molecules per one APMS molecule, since the SA reacted with both the primary (–NH2) and secondary amino (–NH–) groups of the APMS molecule. When using both methods, the ratio between the surface amino and carboxyl groups can be controlled.  相似文献   

19.
In this paper, a simple synthesis method of small-size( about 50 nm in diameter), high magnetic and fluorescent bi-functional silica composite nanoparticles were developed, in which water-soluble Fe3O4 magnetic nanoparticlels (MNs) and CdTe quantum dots (QDs) were directly incorporated into a silica shell by reverse microemulsion method. The high luminescent QDs can be used as luminescent marker, while the high magnetic MNs allow the manipulation of the bi-functional silica composite nanoparticles by external magnetic field. Poly (dimethyldiallyl ammonium chloride) was used to balance the electrostatic repulsion between CdTe QDs and silica intermediates to enhance the fluorescence intensity of MNs-QDs/SiO2 composite nanoparticles. The optical property, magnetic property, size characterization of the bi-functional composite nanoparticles were studied by UV-Vis and PL emission spectra, VSM, TEM, SEM. The stabilities toward time, pH and ionic strength and the effect of MNs on the fluorescence properties of bi-functional silica composite nanoparticles were also studied in detail. By modifying the surface of MNs-QDs/SiO2 composite nanoparticles with amino and methylphosphonate groups, biologically functionalized and monodisperse MNs-QDs/SiO2composite nanoparticles can be obtained. In this work, bi-functional composite nanoparticles were conjugated with FITC labeled goat anti-rabbit IgG, to generate novel fluorescent-magnetic-biotargeting tri-functional composite nanoparticles, which can be used in a number of biomedical application.  相似文献   

20.
Mesoporous SBA-15 was synthesized using rice husk ash (RHA) as the silica source and their defective Si-OH groups were grafted with tris(2-aminoethyl) amine (TREN) dendrimers generation through step-wise growth technique. The X-ray diffraction (XRD) and nitrogen adsorption/desorption results of parent SBA-15 obtained from RHA, suggests its resemblance with SBA-15 synthesized using conventional silica sources. Furthermore, the nitrogen adsorption/desorption results of SBA-15/TREN dendrimer generations (G1-G3) illustrates the growth of dendrimer inside the mesopores of SBA-15 and their CO2 adsorption capacity was determined at 25 °C. The maximum CO2 adsorption capacity of 5-6 and 7-8 wt% over second and third dendrimer generation was observed which is discernibly higher than the reported melamine and PAMAM dendrimers. The experimental CO2 adsorption capacity was found to be less than theoretically calculated CO2 adsorption capacity due to inter and intra molecular amidation as result of steric hindrance during the dendrimer growth. These SBA-15/TREN dendrimer generations also exhibit thermal stability up to 350 °C and CO2 adsorption capacity remains unaltered upon seven consecutive runs.  相似文献   

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