Optical study and structure modelling of PPI liquid crystalline dendrimer derivatives

Optical study of two families of poly(propylene imine) (PPI) dendrimers (G = 1–5) are reported. The enlarging of the chain number (generations) of the PPI dendrimer leads to the spectra shift to IR region in solvent until 8 and 19 nm for both families, respectively. The theoretical modelling of the dendrimer structure was performed. The geometric characterization of dendrimer structure demonstrates that the preferable free space for encapsulation is periphery of the PPI dendrimer.     

Photophysical property of rhodamine-cored poly(amidoamine) dendrimers: Simultaneous effect of spirolactam ring-opening and PET process on sensing trivalent chromium ion

Two novel poly(amidoamine) (PAMAM) dendrimers, comprising rhodamine B unit in the core and 1-phenyl-3-methyl-5-pyrazolone unit at the periphery, have been synthesized and characterized. Both dendrimers displayed high selectivity and sensitivity towards Cr³⁺ ion. As considering the potential of being applied as fluorescent sensors for Cr³⁺ ion, we studied the complexes formed between the dendrimers and Cr³⁺ ion. Different PAMAM dendrimers had different recognition mechanism towards Cr³⁺ ion. For dendrimer G2, the recognition of Cr³⁺ was mainly due to the ring-opening of spirolactam. However, it significantly depended on the simultaneous effect of ring-opening of spirolactam and photoinduced electron transfer (PET) in the case of dendrimer G3.     

Energy transfer dynamics in wire-type dendrimers having oligophenylene peripheries

Energy transfer and shielding effect are studied in wire-type dendrimers (GnPPV: nth generation dendrimer with poly-(p-phenylenevinylene) backbone; n=1, 2) having oligophenylene light-harvesting (LH) antenna. Following the excitation of the LH-antennae, backbone-polymers in GnPPV give rise to intense photoluminescence (PL) bands. This is due to the presence of highly efficient energy transfer from the LH-antennae to the backbone-polymers. The intensity of backbone-PL increases faster than the decay of the antenna-PL. This result indicates that rapid energy transfer from antenna to backbone takes place utilizing the overlap of wavefunctions in the excited states. In G2PPV having larger LH-antenna, shielding effect against inter-backbone interactions is recognized more effectively than G1PPV. In solid films of GnPPV, red shifts of the backbone-PL bands are observed. This is caused by inter-backbone interactions of the wire-type dendrimers due to aggregation. The extent of the red shift in G2PPV is smaller than that of G1PPV. This result suggests that the larger LH-antenna in G2PPV substantially wraps its backbone-polymer and shields the inter-backbone interactions.     

Determination of non-traditional intrinsic fluorescence (NTIF) emission sites in 1-(4-carbomethoxypyrrolidone)-PAMAM dendrimers using CNDP-based quenching studies

A unique photoluminescent phenomenon producing inexplicable, blue emissions [λ_Ex?=?365 nm; λ_Em?=?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.     

Aggregation of a hydrophobically modified poly(propylene imine) dendrimer

The poly(propylene imine) dendrimer DAB-dendr- (NH2)8 was hydrophobically modified with dodecanoyl end groups. The modified dendrimer was deposited onto mica by adsorption from solution and observed by atomic force microscopy. With the decrease of adsorption time, the modified dendrimer varied from continuous film to scattered islands. For the adsorption time of 20s the dendrimer formed a sub-monolayer thin film that contained many fractal aggregates of fractal dimension 1.80 that were > 1 microm in diameter and no more than 0.8nm thick. After 5 months at 1#1 , the initial fractal aggregates transformed into disks and other less-branched shapes with average heights of the domains of 0.6nm and 0.4nm, respectively. Formation of the fractal aggregates is explained by diffusion-limited aggregation. The slow reorganization of dendrimer molecules in the fractal aggregates occurs at a temperature well above the Tg of the dendrimer.     

Fluorescent properties of novel dendrimer dyes based on thiazole orange

In this paper, polyamidoamine (PAMAM) dendrimers with active amino group of some generations (G=0.5-2) were prepared from commercial aminoacetaldehyde diethyl acetal by the divergent method. After that, thiazole orange (TO) with -COOH was incorporated with dendrimers of G=1 and 2 to afford novel dendrimer-TO dyes. The fluorescent properties studies showed that the fluorescent intensity of the same concentration of dendrimer-TO (G=2) was higher than that of the dendrimer-TO (G=1), and both of them were much stronger than free TO with -COOH. There was a fluorescent enhancement of the dendrimer dyes compared with free dye. The dendrimer dyes were of well-defined chemical structure,with little aggregation and self-quenching as well as good fluorescence properties of good stability, high intensity and sensitivity, which could be used in labeling cancer cells and further in diagnosis and detection of early-stage tumors.     

Liquid-crystalline dendrimer Cu(II) complexes and Cu(0) nanoclusters based on the Cu(II) complexes: An electron paramagnetic resonance investigation

New nanostructured materials, namely, the liquid-crystalline copper(II) complexes that contain poly(propylene imine) dendrimer ligands of the first (ligand 1) and second (ligand 2) generations and which have a columnar mesophase and different copper contents (x = Cu/L), are investigated by EPR spectroscopy. The influence of water molecules and nitrate counterions on the magnetic properties of complex 2 (x = 7.3) is studied. It is demonstrated that water molecules can extract some of the copper ions from dendrimer complexes and form hexaaqua copper complexes with free ions. The dimer spectra of fully hydrated complex 2 (x = 7.3) are observed at temperatures T < 10 K. For this complex, the structure is identified and the distance between the copper ions is determined. It is shown that the nitrate counterion plays the role of a bridge between the hexaaqua copper(II) complex and the dendrimer copper(II) complex. The temperature-induced valence tautomerism attended by electron transport is revealed for the first time in blue dendrimer complexes 1 (x = 1.9) with a dimer structure. The activation energy for electron transport is estimated to be 0.35 meV. The coordination of the copper ion site (NO₄) and the structural arrangement of green complexes 1 (x = 1.9) in the columnar mesophase are determined. Complexes of this type form linear chains in which nitrate counterions serve as bridges between copper centers. It is revealed that green complexes 1 (x = 1.9) dissolved in isotropic inert solvents can be oriented in the magnetic field (B ₀ = 8000 G). The degree of orientation of these complexes is rather high (S _z = 0.76) and close to that of systems with a complete ordering (S _z = 1) in the magnetic field. Copper(0) nanoclusters prepared by reduction of complex 2 (x = 7.3) in two reducing agents (NaBH₄, N₂H₄ · H₂O) are examined. A model is proposed for a possible location of Cu(0) nanoclusters in a dendrimer matrix.     

Binding Properties of Water-Soluble Carbosilane Dendrimers

Dendrimers have been proposed as new carriers for drug delivery. They have distinctive characteristics, such as uniform and controlled size, monodispersity and modifiable surface group functionality, which make them extremely useful for biomedical applications. In this study, the binding capacity of water-soluble carbosilane dendrimers was examined. A double fluorimetric titration method with 1-anilinonaphthalene-8-sulphonic acid (ANS) was used to estimate the binding constant and the number of binding centers per dendrimer molecule. The data obtained suggest that ANS interacts non-covalently with the dendrimers. Second generation dendrimers have an open, asymmetric structure that allows them to encapsulate ANS. The ability of the polymers to interact with DNA was assessed by an ethidium bromide (EB) displacement assay. All the dendrimers studied bound to DNA in competition with EB, though the strength of binding varied. Dendrimer interactions with a protein (BSA) were tested using fluorescence quenchers. The dendrimers caused no conformation change in the protein, indicating that interactions between carbosilane dendrimers and BSA are weak and occur preferentially at the protein surface.     

Deformability of poly(amidoamine) dendrimers

Experimental data indicates that poly(amidoamine) (PAMAM) dendrimers flatten when in contact with a substrate, i.e. they are no longer spherical, but resemble flat disks. In order to better understand the deformation behavior of these branched polymers, a series of atomistic molecular dynamics simulations is performed. The resulting flattened dendrimer conformations are compared to atomic force microscopy (AFM) images of individual dendrimers at air/mica and water/mica interfaces. The ability of the polymers to deform is investigated as a function of dendrimer generation (2-5) and the required energies are calculated. Our modeling results show good agreement with the experimental AFM images, namely that dendrimers are highly flexible and capable of forming multiple interaction sites between most of their branch ends and the substrate. The deformation energy scales with dendrimer generation and does not indicate an increase in stiffness between generations 2 and 5 due to steric effects.PACS: 81.07.Nb Molecular nanostructures - 82.20.Wt Computational modeling; simulation - 68.37.Ps Atomic force microscopy (AFM)     

Development of TREN dendrimers over mesoporous SBA-15 for CO2 adsorption

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.     

Counterion distribution and many-body interaction in charged dendrimer solutions

Coarse-grained molecular dynamics simulations are performed to study the structural formation, counterion distribution and effective interaction on charged dendrimers in an aqueous solution. In particular, the many-body effects in triplet systems are clarified. The conformation of a dendrimer molecule depends on the size of counterions, and the counterion distribution can be scaled by the gyration radius of a dendrimer molecule. Two-body and three-body interactions have been numerically investigated, and the results indicate both similarities and differences between dendrimer solutions and other soft colloidal systems, such as star polymer solutions.     

Effect of solvent-controlled aggregation on the intrinsic emission properties of PAMAM dendrimers

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.     

Thermodynamic Properties of the First-Generation Hybrid Dendrimer with “Carbosilane Core/Phenylene Shell” Structure

The molar heat capacity of the first-generation hybrid dendrimer with a “carbosilane core/phenylene shell” structure was measured for the first time in the temperature range T = 6–600 K using a precise adiabatic vacuum calorimeter and DSC. In the above temperature interval, the glass transition of the studied compound was observed, and its thermodynamic characteristics were determined. The standard thermodynamic functions (the enthalpy, the entropy, and the Gibbs energy) of the hybrid dendrimer were calculated over the range from T = 0 to 600 K using the experimentally determined heat capacity. The standard entropy of formation of the investigated dendrimer was evaluated at T = 298.15 K. The obtained thermodynamic properties of the studied hybrid dendrimer were compared and discussed with the literature data for some of the first-generation organosilicon and pyridylphenylene dendrimers.     

One-, two- and three-photon spectroscopy of π-conjugated dendrimers: cooperative enhancement and coherent domains

We use wavelength tunable femtosecond pulses to measure intrinsic (simultaneous) two-photon absorption (2PA) and three-photon absorption (3PA) molecular cross section in two series of π-conjugated dendrimers built of identical 4,4′-bis(diphenylamino) stilbene (BDPAS) and 4,4′-bis(diphenylamino) distyrylbenzene (BDPADSB) repeat units. Record large 2PA cross sections, σ₂=10⁻⁴⁶ cm⁴ s are obtained for the largest second-generation BDPAS-based dendrimer, as well as zeroth-generation 4-arm BDPADSB-based dendrimer. In both series, maximum 2PA cross section increases nonlinearly with the number of π-electrons, whereas for higher generations this dependence turns to linear one. 3PA cross section also increases nonlinearly with the size of the system in the series of BDPAS-based molecules, amounting a record large value, σ₃=10⁻⁷⁹ cm⁶ s², for the largest, second-generation dendrimer. We interpret these results in terms of direct inter-branch conjugation, which facilitates cooperative enhancement of the nonlinear-optical response. We propose a simple model which allows us to determine the effective size of coherent domains (extent of conjugation), which, in turn, determines the optimum dendrimer size for most efficient nonlinear response.     

The instant-direct-templating synthesis of phenyl-functionalized HOM-type mesoporous silica materials

Two kinds of novel phenyl-functionalized mesoporous silica materials have fabricated for the first time by an instant-direct-templating method using poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) and tetraethyl orthosilicate as surfactant template and precursor, respectively. Samples were characterized by Fourier transform infrared spectroscopy, small-angle X-ray diffraction, thermogravimetric analysis, N₂ adsorption-desorption, scanning electron micrography and transmission electron micrography. The results show that phenyl groups are attached covalently to the pore wall of mesoporous materials after modification. The functionalized materials still preserve a desirable ordered hexagonal P6mm and cubic Ia3d mesophase structure, respectively, have high specific surface area, large pore volume and narrow pore size distribution.     

Quantitative assessment of surface functionality effects on microglial uptake and retention of PAMAM dendrimers

Dendrimers are a promising class of polymeric nanoparticles for delivery of therapeutics and diagnostics. Polyamidoamine (PAMAM) dendrimers have shown significant efficacy in many animal models, with performance dependent on surface functionalities. Understanding the effects of end groups on biological interactions is critical for rational design of dendrimer-mediated therapies. In this study, we quantify the cellular trafficking kinetics (endocytosis and exocytosis) of generation 4 neutral (D4-OH), cationic (D4-NH₂), anionic (D3.5-COOH), and generation 6 neutral (D6-OH) PAMAM dendrimers to investigate the nanoscale effects of surface functionality and size on cellular interactions. Resting and LPS-activated microglia were studied due to their central roles in dendrimer therapies for central nervous system disorders. D4-OH exhibits greater cellular uptake and lower retention than the larger D6-OH. D4-OH and D3.5-COOH exhibit similar trafficking kinetics, while D4-NH₂ exhibits significant membrane interactions, resulting in faster cell association but lower internalization. Cationic charge may also enhance vesicular escape for greater cellular retention and preferential partitioning to nuclei. LPS activation further improves uptake of dendrimers, with smaller and cationic dendrimers experiencing the greatest increases in uptake compared to resting microglia. These studies have implications for the dependence of trafficking pathway on dendrimer properties and inform the design of dendrimer constructs tailored to specific therapeutic needs. Cationic dendrimers are ideal for delivering genetic materials to nuclei, but toxicity may be a limiting factor. Smaller, neutral dendrimers are best suited for delivering high levels of therapeutics in acute neuroinflammation, while larger or cationic dendrimers provide robust retention for sustained release of therapeutics in longer-term diseases.     

A novel amperometric hydrogen peroxide biosensor based on pyrrole-PAMAM dendrimer modified gold electrode

Horseradish peroxidase (HRP) was immobilized into an electrochemically prepared copolymer of pyrrole–PAMAM (PAMAM; polyamidoamine) dendrimers for the construction of amperometric hydrogen peroxide biosensor. First, second, and third generation amidoamine–pyrrole dendrons having branched amine periphery and focal pyrrole functionality were synthesized via divergent pathway. Pyrrole dendrimers were covalently attached onto the electrode surface and polymerized by electrochemical copolymerization with pyrrole monomer. The synthesized dendrimers and copolymers have been characterized by FTIR-ATR and NMR. These copolymers have been utilized as conducting films for amperometric hydrogen peroxide sensing. The HRP retains its bioactivity after immobilization into the dendronized pyrrole-copolymers. Amperometric response was measured as a function of concentration of hydrogen peroxide, at fixed potential of +0.35 V vs. Ag/AgCl in a phosphate buffered saline (pH 7.5). The effect of pH and temperature of the medium, storage, and reusability properties were investigated. The results indicate an efficient immobilization of enzyme onto the PAMAM type dendrimer modified surface containing pyrrole monomer, which leads to high enzyme loading, and increased lifetime stability of the electrode.     

Basicity of trifluoromethylsulfonylformamidines. DFT and FTIR study and NBO analysis

The effect of the electron–acceptor substituent CF₃SO₂ at the imine nitrogen atom on the basicity and the electron distribution in N,N‐alkylformamidines ( 1 , 2 , 3 , 4 , 5 ) was studied experimentally by the FTIR spectroscopy and theoretically at the DFT (B3LYP/6‐311+G(d,p)) level of theory, including the natural bond orbital (NBO) analysis. The calculated proton affinities of the imine nitrogen atom and the sulfonyl oxygen (PA_N′ and PA_O) depend on the atomic charges, the C?N′ and N′―S bond polarity and on the energy of interaction of the amine nitrogen and the oxygen lone pairs with antibonding π* and σ*‐orbitals. The basicity of the imine nitrogen atom is increased with the increase of the electron‐donating power of the substituent at the amine nitrogen atom due to stronger interaction n_N → π*_C?N′, but is decreased for the electron‐withdrawing groups MeSO₂ and CF₃SO₂ at the imine nitrogen atom in spite of the increase of this conjugation. Protonation of ( 1 , 2 , 3 , 4 , 5 ) in CH₂Cl₂ solution in the presence of CF₃SO₃H occurs at the imine nitrogen atom, while the formation of hydrogen bonds with 4‐fluorophenol takes place at the sulfonyl oxygen atom, whose basicity is lower than that of N,N′‐dimethylmethanesulfonamide but higher than of N,N′‐dimethyltrifluoromethanesulfonamide. Copyright © 2015 John Wiley & Sons, Ltd.     

Imaging {Au0-PAMAM} Gold-dendrimer Nanocomposites in Cells

Dendrimer nanocomposites (DNC) are hybrid nanoparticles formed by the dispersion and immobilization of guest atoms or small clusters in dendritic polymer matrices. They have a great potential in biomedical applications due to their controlled composition, predetermined size, shape and variable surface functionalities. In this work, d=5–25nm spherical nanoparticles composed of gold and poly(amidoamine) (PAMAM) dendrimers have been selected to demonstrate this nanoparticle based concept. {Au(0)_n-PAMAM} gold dendrimer nanocomposites with a well-defined size were synthesized and imaged by transmission electron microscopy both in vitro and in vivo. DNC have also the potential to be used for imaging and drug delivery vehicles either by utilizing bioactive guests or through the incorporation of radioactive isotopes, such as Au-198.     

金属钴树状高分子与DNA相互作用的光谱法研究

通过氯化钴、乙二醛和第五代树状高分子反应合成了金属钴树状高分子配合物。并以亚甲基蓝为荧光探针,通过紫外-可见光谱、荧光光谱和同步荧光方法研究了金属钴树状高分子配合物与鲱鱼精DNA(hsDNA)的相互作用。结果显示,此配合物与hsDNA作用时,其紫外吸收产生明显增色效应,荧光强度增强。NaCl不同程度抑制金属钴树状高分子与hsDNA的结合。配合物也以竞争方式抑制亚甲基蓝与hsDNA作用,而亚甲基蓝可以插入金属钴树状高分子配合物的内部。这些结果证明,配合物主要通过与hsDNA链上带负电荷的磷酸基静电相吸形式结合而堆积在双螺旋hsDNA分子表面,减弱了结合位点附近亚甲基蓝分子与hsDNA的静电作用,而钠离子中和了hsDNA上磷酸基团上的负电荷,削弱了该配合物与hsDNA的静电结合。