Spectroscopic characterization of core-based hyperbranched poly(ethyleneimine) and dendritic poly(propyleneimine) as selective uptake devices.

Dendritic polymers have a wide range of potential applications; however, the extensive synthesis and limited availability of bulk quantities of dendrimers restrict their use. Core-based hyperbranched polymers (CBHPs) are, therefore, an attractive alternative to dendrimers for many applications. The selectivity of core-based hyperbranched poly(ethyleneimine), as a host for phenol blue and 2-hydroxy Nile red guests, was investigated using absorption and fluorescence spectroscopies. Research results are compared to those for its dendritic counterpart, poly(propyleneimine). Phenol blue is known to associate near the core in both the CBHPs and dendrimers investigated. The interfering agent, 2-hydroxy Nile red, has also been shown to associate with these polymers; however, this interaction occurs in the outermost branches. In this work, it was found that phenol blue was sequestered in both the CBHPs and dendrimers in the presence of interfering agent, and this association appeared to be the same as that of the polymers with phenol blue alone. Although the presence of 2-hydroxy Nile red did affect the association of phenol blue, there was still considerable association even when 2-hydroxy Nile red was in 10-fold excess. The association of phenol blue with both the CBHPs and dendrimers was stable and robust; however, the association of 2-hydroxy Nile red was relatively weak and unstable.

Spectroscopic investigations of core-based, randomly hyperbranched polymers and comparison with their dendrimeric counterparts.

Randomly hyperbranched polymers containing a core region are a relatively new subclass of materials. In comparison to dendrimeric polymers, there are many similarities, including their proposed applications. Because the core-based hyperbranched polymers can be prepared in a one-pot synthesis, they are an attractive alternative to the dendrimers, which require a laborious multistep process. This research is centered around the comparison of core-based, randomly hyperbranched poly(ethyleneimine) with the dendrimeric poly(propyleneimine) to better understand their host-guest properties. Two sizes of each polymer class were examined, and studies were carried out using the solvatochromic reporter molecule phenol blue. Absorbance and fluorescence measurements (emission and anisotropy) were utilized to determine the location of the fluorophore within the polymer. Results indicate that the phenol blue does associate with both the hyperbranched poly(ethyleneimine) and the dendrmeric poly(propyleneimine), although the association is not the same for the two polymer classes. The loading capacity of both polymer classes was also determined.

Capillary electrophoresis using core-based hyperbranched polyethyleneimine (CHPEI) static-coated capillaries.

With unique 3-D architecture, the application of core-based hyperbranched polyethyleneimine (CHPEI), as a capillary coating in capillary electrophoresis, is demonstrated by manipulation of the electroosmotic mobility (EOF). CHPEI coatings (CHPEI5, M(w) approximately 5000 and CHPEI25, M(w) approximately 25,000) were physically adsorbed onto the inner surface of bare fused-silica capillary (BFS) via electrostatic interaction of the oppositely charged molecules by rinsing the capillaries with different CHPEI aqueous solutions. The EOF values of the coated capillaries were measured over the pH range of 4.0-9.0. At higher pH (pH >6) the coated capillary surface possesses excess negative charges, which causes the reversal of the EOF. The magnitudes of the EOF obtained from the coated capillaries were three-fold lower than that of BFS capillary. Desirable reproducibility of the EOF with % RSD (n = 5) < or = 2 was obtained. Effect of ionic strength, stability of the coating (% RSD = 0.3) and the dependence of the EOF on pH (% RSD = 0.5) were also investigated. The CHPEI-coated capillaries were successfully utilized to separate phenolic compounds, B vitamins, as well as basic drugs and related compounds with reasonable analysis time (< 20 min) and acceptable migration-time repeatability (< 0.7% RSD for intra-capillary and < 2% RSD for inter-capillary).

Encapsulation and quantification of multiple dye guests in unmodified poly(amidoamine) dendrimers as a function of generation.

This work illustrates the remarkable ability of amine-terminated PAMAM dendrimers to entrap multiple guest molecules. While previous encapsulation studies with dendritic polymers demonstrated multi-dye uptake, the dendrimers required extensive synthetic modification. This study utilizes unmodified PAMAM dendrimers to encapsulate multiple phenol blue molecules. Quantitative data on the uptake capacity and robustness of association is presented.

Photodynamic therapy: basic principles and potential uses for the veterinary ophthalmologist.

Photodynamic therapy (PDT) involves the use of photochemical reactions mediated through the interaction of photosensitizing agents, light and oxygen. PDT, while now commonly used in physician ophthalmology and oncology, is uncommonly used for the veterinary ophthalmic patient. It is an emerging new therapy in veterinary ophthalmology for the treatment of periocular tumors. This article reviews the basic principles of PDT to provide the veterinary ophthalmologic community with a succinct reference for this emerging treatment modality in our field.

Spectroscopic investigations of ADMA encapsulated in pyrogallol[4]arene nanocapsules.

Pyrogallol[4]arenes form stable hydrogen-bonded nanocapsules that have unique properties that may make them suitable for diverse applications, such as catalysts and molecular transporters. Little is known about the behavior of the interior of these new materials in solution, and by using the solvent-dependent properties of 1-(9-anthryl)-3-(4-dimethylaniline) propane (ADMA), the inner phase properties of the hexamers are investigated. Steady-state and dynamic spectrofluorometric results are in agreement, are consistent with solid-state studies, and indicate that the majority of ADMA is sequestered in an extended conformation with the crystallization solvent. The conformational flexibility of ADMA is attributed to lower capsule occupancies ( approximately 50%, i.e., 1 molecule per 2 capsules, one occupied and one empty) relative to our previous study with pyrene butyric acid (occupancy of 150%, i.e., 1.5 molecules per capsule) in which the probe was restricted within a nanocapsule. The nature of the encapsulated ADMA complexes are found to change with time, as there is either fluorophore leaching from the capsule or endo-exo-capsule solvent exchange. However, the choice of crystallizing solvent (ethyl acetate or acetonitrile) and PgC(n) alkyl tail (C(6) or C(10)) does not influence experimental outcomes. These research findings give a better understanding of the encapsulation versatility of these unique supramolecular assemblies and the protective nanopockets that can exist for guest molecules.

Contrasting solvent and capping ligand effects directing the photochemistry of uranyl(VI) Schiff base complexes.

Photolysis of the uranyl(VI) Schiff base complex UO2(tBu4-salphen)(THF) (1a) with cobaltocene in THF affords [Cp2Co][UO2(tBu4-salphen)(OH)] (2) in high yield while irradiation in toluene yields no reaction. Electronic emission spectra of 1a reveal a large Stokes' shift in toluene similar to that observed in the free ligand, while in THF the structural rearrangement responsible for this shift is blocked. Instead, the ligand-centered excited state is redirected to the uranyl(VI) center by way of energy transfer, thus generating 2 from the intramolecular activation of a coordinated THF molecule.

Spectroscopic characterization of poly(amidoamine) dendrimers as selective uptake devices: Phenol blue versus Nile red.

Selectivity of amine-terminated poly(amidoamine) (PAMAM-AT) dendrimers as host molecules for phenol blue and Nile red guests was investigated using absorption and fluorescence spectroscopies. Phenol blue has been known to associate near the core in the PAMAM-AT dendrimers. Nile red has also been shown to associate with this dendrimer family; however, this occurs in the outermost branches. Concentration ratios and generational dependencies were investigated. It was found that phenol blue was sequestered in the PAMAM-AT dendrimers in the presence of the interfering Nile red, and this association appeared to be the same as that of PAMAM-AT with phenol blue alone. As the concentration of Nile red increased relative to the concentration of phenol blue, the desired association of phenol blue became increasingly hindered. While the presence of Nile red did affect association, phenol blue still had considerable association even when Nile red was in ten-fold excess. The association of phenol blue with PAMAM-AT was stable and robust; however, Nile red's association was relatively weak and unstable.

Fluorescent guest molecules report ordered inner phase of host capsules in solution.

Despite recent strides in the synthesis of elaborate nanometer-scale molecular hosts, the internal structure of these self-assembled cages remains ill characterized. We used fluorescent probe molecules, pyrene butyric acid (PBA), as guests in C-hexylpyrogallol[4]arene capsules to relay information about the chemical environment on the interior of the assemblies. Spectroscopic and single-crystal x-ray diffraction studies show that, in both solution and the solid state, the host can encapsulate two PBA guests and keep them well separated through specific interactions with the capsule walls.

Optimization of micellar liquid chromatographic separation of polycyclic aromatic hydrocarbons with the addition of second organic additive.

The micellar liquid chromatographic (MLC) separations of polycyclic aromatic hydrocarbons (PAHs) were optimized for three micellar systems, cetyltrimethylammonium chloride (CTAC), dodecyltrimethylammonium chloride (DTAC), and sodium dodecylsulfate (SDS), with 1-pentanol as the only organic additive. A difference in the separation was observed between CTAC and SDS/DTAC. Under each optimized separation conditions, CTAC-modified mobile phase provides the least desirable separation, which is attributed to its longer carbon tail (C16 vs. C12). In addition to 1-pentanol, the main organic additive, a second organic additive (3% 1-propanol) in the micelle-modified mobile phase was found to enhance the resolution of PAH chromatographic peaks. However, the extent of the enhancement varies for the different micellar systems, with the greatest resolution improvement seen for CTAC, and little effect for shorter-tail SDS and DTAC. This study shows the potential use of second organic additive (1-propanol), to the main nonpolar additive (1-pentanol), in facilitating the MLC separation of larger nonpolar compounds.

High-performance liquid chromatographic separation of polycyclic aromatic hydrocarbons using pyridinium chloride as a selective fluorescence quencher to aid detection.

The first use of pyridinium chloride (PC), as a selective fluorescence quenching agent of alternant polycyclic aromatic hydrocarbons (PAHs), under HPLC separation conditions is reported. PC was found to be superior to nitromethane, the only reported PAH selective quencher used in HPLC. The mobile phase addition of 0.03 M PC greatly simplifies the observed fluorescence-detected chromatograms for complex PAH mixtures, facilitating PAH identification. Stern-Volmer quenching constants (K(sv)) for PAHs were calculated from the chromatograms obtained under isocratic and gradient conditions and found to be similar. The K(sv) values were shown to be useful in establishing peak purity.