ABSTRACT
We examine the photophysics of a colloidal suspension of C(60) particles in a micellar solution of Triton X-100 and water, prepared via a new synthesis which allows high-concentration suspensions. The particle sizes are characterized by transmission electron microscopy and dynamic light scattering and found to be somewhat polydisperse in the range of 10-100 nm. The suspension is characterized optically by UV-vis spectroscopy, femtosecond transient absorption spectroscopy, laser flash photolysis, and z-scan. The ground-state absorbance spectrum shows a broad absorbance feature centered near 450 nm which is indicative of colloidal C(60). The transient absorption dynamics, presented for the first time with femtosecond resolution, are very similar to that of thin films of C(60) and indicate a strong quenching of the singlet excited state on short time scales and evidence of little intersystem crossing to a triplet excited state. Laser flash photolysis reveals that a triplet excited-state absorption spectrum, which is essentially identical in shape to that of molecular C(60) solutions, does indeed arise, but with much lower magnitude and somewhat shorter lifetime. Z-scan analysis confirms that the optical response of this material is dominated by nonlinear scattering.
Subject(s)
Fullerenes/chemistry , Octoxynol/chemistry , Surface-Active Agents/chemistry , Water/chemistry , Absorption , Colloids , Lasers , Light , Microscopy, Electron, Transmission , Particle Size , Photolysis , Scattering, Radiation , Soot/chemistry , Suspensions , Time FactorsABSTRACT
Two types of 32 arm star polymers incorporating amphiphilic block copolymer arms have been synthesized and characterized. The first type, stPCL-PEG 32, is composed of a polyamidoamine (PAMAM) dendrimer as the core with radiating arms having poly(epsilon-caprolactone) (PCL) as an inner lipophilic block in the arm and poly(ethylene glycol) (PEG) as an outer hydrophilic block. The second type, stPLA-PEG 32, is similar but with poly(L-lactide) (PLA) as the inner lipophilic block. Characterization with SEC, (1)H NMR, FTIR, and DSC confirmed the structure of the polymers. Micelle formation by both star copolymers was studied by fluorescence spectroscopy. The stPCL-PEG 32 polymer exhibited unimolecular micelle behavior. It was capable of solubilizing hydrophobic molecules, such as pyrene, in aqueous solution, while not displaying a critical micelle concentration. In contrast, the association behavior of stPLA-PEG 32 in aqueous solution was characterized by an apparent critical micelle concentration of ca. 0.01 mg/mL. The hydrophobic anticancer drug etoposide can be encapsulated in the micelles formed from both polymers. Overall, the stPCL-PEG 32 polymer exhibited a higher etoposide loading capacity (up to 7.8 w/w % versus 4.3 w/w % for stPLA-PEG 32) as well as facile release kinetics and is more suitable as a potential drug delivery carrier.
Subject(s)
Drug Carriers/chemical synthesis , Ethylene Glycols/chemical synthesis , Polyesters/chemical synthesis , Polyethylene Glycols/chemical synthesis , Antineoplastic Agents/chemistry , Calorimetry, Differential Scanning , Drug Carriers/chemistry , Ethylene Glycols/chemistry , Etoposide/chemistry , Fluorescent Dyes/chemistry , Hydrophobic and Hydrophilic Interactions , Micelles , Polyesters/chemistry , Polyethylene Glycols/chemistry , Pyrenes/chemistry , Spectrometry, Fluorescence , TemperatureABSTRACT
A star polymer composed of amphiphilic block copolymer arms has been synthesized and characterized. The core of the star polymer is polyamidoamine (PAMAM) dendrimer, the inner block in the arm is lipophilic poly(epsilon-caprolactone) (PCL), and the outer block in the arm is hydrophilic poly(ethylene glycol) (PEG). The star-PCL polymer was synthesized first by ring-opening polymerization of epsilon-caprolactone with a PAMAM-OH dendrimer as initiator. The PEG polymer was then attached to the PCL terminus by an ester-forming reaction. Characterization with SEC, (1)H NMR, FTIR, TGA, and DSC confirmed the star structure of the polymers. The micelle formation of the star copolymer (star-PCL-PEG) was studied by fluorescence spectroscopy. Hydrophobic dyes and drugs can be encapsulated in the micelles. A loading capacity of up to 22% (w/w) was achieved with etoposide, a hydrophobic anticancer drug. A cytotoxicity assay demonstrated that the star-PCL-PEG copolymer is nontoxic in cell culture. This type of block copolymer can be used as a drug delivery carrier.
Subject(s)
Drug Carriers/chemistry , Polymers/chemical synthesis , Animals , Cell Line , Cell Survival , Etoposide/administration & dosage , Micelles , Molecular Conformation , Polyesters , Polyethylene Glycols , Polymers/chemistry , Polymers/therapeutic use , Spectrum Analysis , Surface-Active Agents , SwineABSTRACT
Hydroquinone diphosphate (HQDP) was synthesized and compared to phenyl phosphate (PP) and 1-naphthyl phosphate (NP) as a substrate for alkaline phosphatase (AP) under electrochemical immunoassay (EIA) conditions. Voltammetric and amperometric experiments showed that electrochemical oxidation of hydroquinone (HQ), which is the AP hydrolysis product of HQDP, did not produce electrode passivation, even with repeated biosensor use. In contrast, phenol and 1-naphthol, the hydrolysis products of PP and NP, respectively, were shown to be irreversibly oxidized on the electrode surfaces, and produced rapid electrode passivation, resulting in complete loss of electrode signal. When employed as AP substrate in an iridium oxide based EIA, HQDP produced significantly larger amperometric responses (117 microA/cm2) compared to PP (31 microA/cm2) and NP (27 microA/cm2). The results presented in this paper show that HQDP is an attractive alternative to commonly used AP substrates such as NP and PP. The substrate shows excellent hydrolytic stability, produces larger amperometric responses (than PP or NP), and does not produce sensor passivation.
Subject(s)
Alkaline Phosphatase/analysis , Alkaline Phosphatase/chemistry , Electrochemistry/instrumentation , Electrodes , Hydroquinones/analysis , Hydroquinones/chemistry , Immunoassay/instrumentation , Immunoglobulin G/analysis , Organophosphates/analysis , Organophosphates/chemistry , Electrochemistry/methods , Enzyme Activation , Equipment Failure , Equipment Failure Analysis , Hydrolysis , Immunoassay/methods , Reproducibility of Results , Sensitivity and Specificity , Substrate SpecificityABSTRACT
Novel immunosensors based on antibodies immobilized in electrochemically grown iridium oxide (IrOx) thin film matrices have been developed. Antibody loading in the oxide was evaluated using a non-competitive electrochemical immunoassay for IgG. Anti-IgG loading in the oxide was found to be dependent on the concentration of anti-IgG present in the oxide growth step, with 400 microg/ml anti-IgG producing maximum amperometric responses. To study the potential analytical properties of the matrix, the dose-response behavior of the sensors was determined using optimized alkaline phosphatase-linked IgG immunoassay. Hydroquinone diphosphate (HQDP) was used as enzyme substrate and the oxidation of hydroquinone was detected amperometrically at +420 mV. The sensors displayed a linear dose-response behavior for IgG concentrations between 10 and 200 ng/ml, saturating above 600 ng/ml, and had a low detection limit of 8 ng/ml.Finally, the method was used to produce sensors containing immobilized anti-transferrin. Using a non-optimized electrochemical immunoassay for human transferrin (HT), dose-response behavior was observed for HT concentrations between 100 and 600 ng/ml.The results presented in this paper show that IrOx matrices represent a new method for immunosensor fabrication. The oxide acts as a hydrophilic, highly porous, three-dimensional matrix that can immobilize antibodies and retain their activity. The method is attractive because it offers the potential for high antibody loadings and is suitable for mass production of sensors in an easy and economical manner.