Influence of secondary preparative parameters and aging effects on PLGA particle size distribution: a sedimentation field flow fractionation investigation

Poly(lactic-co-glycolic acid) particles in the 200–400-nm size range were formulated through nanoprecipitation and solvent evaporation methods. Different concentrations of the polymer and stabilizer (Pluronic® F 68) were tested in order to identify the best conditions for making poly(lactic-co-glycolic acid) particles of suitable size, stable in time, and to be used as carriers for brain-targeting drugs. The particles with the best characteristics for delivery system design were those formulated by nanoprecipitation with an organic/water phase ratio of 2:30, a polymer concentration of 25 mg/mL, and a surfactant concentration of 0.83 mg/mL; their surface charge was reasonably negative (approximately -27 mV) and the average size of the almost monodisperse population was roughly 250 nm. Particle characterization was obtained through ζ-potential measurements, scanning electron microscope observations, and particle size distribution determinations; the latter achieved by both photon-correlation spectroscopy and sedimentation field flow fractionation. Sedimentation field flow fractionation, which is considered more reliable than photon-correlation spectroscopy in describing the possible particle size distribution modifications, was used to investigate the effects of 3 months of storage at 4 °C had on the lyophilized particles.

The effect of ring nitrogen atoms on the homolytic reactivity of phenolic compounds: understanding the radical-scavenging ability of 5-pyrimidinols

Six substituted 5-pyrimidinols were synthesized, and the thermochemistry and kinetics of their reactions with free radicals were studied and compared to those of equivalently substituted phenols. To assess their potential as hydrogen-atom donors to free radicals, we measured their O-H bond dissociation enthalpies (BDEs) using the radical equilibration electron paramagnetic resonance technique. This revealed that the O-H BDEs in 5-pyrimidinols are, on average, about 2.5 kcal mol(-1) higher than those in equivalently substituted phenols. The results are in good agreement with theoretical predictions, and confirm that substituent effects on the O-H BDE of 5-pyrimidinol are essentially the same as those on the Obond;H BDE in phenol. The kinetics of the reactions of these compounds with peroxyl radicals has been studied by their inhibition of the AIBN-initiated autoxidation of styrene, and with alkyl and alkoxyl radicals by competition kinetics. Despite their larger O-H BDEs, 5-pyrimidinols appear to transfer their phenolic hydrogen-atom to peroxyl radicals as quickly as equivalently substituted phenols, while their reactivity toward alkyl radicals far exceeds that of the corresponding phenols. We suggest that this rate enhancement, which is large in the case of alkyl radical reactions, small in the case of peroxyl radical reactions, and nonexistent in the case of alkoxyl radical reactions, is due to polar effects in the transition states of these atom-transfer reactions. This hypothesis is supported by additional experimental and theoretical results. Despite this higher reactivity of 5-pyrimidinols towards radicals compared to phenols, electrochemical measurements indicate that they are more stable to one-electron oxidation than equivalently substituted phenols. For example, the 5-pyrimidinol analogues of 2,4,6-trimethylphenol and butylated hydroxytoluene (BHT) were found to have oxidation potentials approximately 400 mV higher than their phenolic counterparts, but reacted roughly one order of magnitude faster with alkyl radicals and at about the same rate with peroxyl radicals. The 5-pyrimidinol structure should, therefore, serve as a useful template for the rational design of novel air-stable radical scavengers and chain-breaking antioxidants that are more effective than phenols.     

Sedimentation field flow fractionation of immunoglobulin A coated polystyrene beads. Influence of carrier composition on complex characterization

The amount of immunoglobulin A (IgA) adsorbed on the surface of two different samples of polystyrene (PS) microbeads was evaluated using differential sedimentation field flow fractionation (SdFFF) analyses. For the first time, the SdFFF separations obtained by using, as mobile phase, solutions common to many biochemical procedures and applications have been compared and discussed. Good separation results were achieved in the different carriers, and the SdFFF gave equivalent mass per particle values in all carriers provided that the pH and ionic strength conditions of the eluents were well controlled. The IgA adsorption process onto PS occurred by maintaining unaltered the capacity of the PS-IgA substrate to selectively recognize anti-IgA (aIgA), as proven by elution of the ternary complex PS-IgA-aIgA and from the monitored lack of reaction when the PS-IgA was placed in contact with aIgE.     

Analysis of drugs of forensic interest with capillary zone electrophoresis/time-of-flight mass spectrometry based on the use of non-volatile buffers

The present work is aimed at investigating the influence of the background electrolyte composition and concentration on the separation efficiency and resolution and mass spectrometric detection of illicit drugs in a capillary zone electrophoresis-electrospray ionization-time of flight mass spectrometry (CZE-ESI-TOF MS) system. The effect of phosphate, borate and Tris buffers on the separation and mass spectrometry response of a mixture of 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, methadone, cocaine, morphine, codeine and 6-monoacetylmorphine was studied, in comparison with a reference ammonium formate separation buffer. Inorganic non-volatile borate and Tris buffers proved hardly suitable for capillary electrophoresis-mass spectrometry (CE-MS) analysis, but quite unexpectedly ammonium phosphate buffers showed good separation and ionization performances for all the analytes tested. Applications of this method to real samples of hair from drug addicts are also provided.     

Biodegradable materials — Present situation and future perspectives

Biodegradable polymers constitute a loosely defined family of polymers that are designed to degrade through the action of living organisms. They offer a possible alternative to traditional nonbiodegradable polymers if recycling is impractical or not economical. The main driving force behind this technology is the solid waste problem, particularly with regard to the decreasing availability of landfills, the litter problem and the pollution of marine environment by non-biodegradable plastics. Technologies like composting used for the disposal of food and yard waste are the most suitable for the disposal of biodegradable materials. European Standardisation Committee (CEN), Organic Reclamation and Composting Association (ORCA) and German Institute for Standardisation (DIN) have already defined, at a draft level, the basic requirements for a product to be declared compostable. They are based on: complete biodegradability of the product in a time period compatible with composting, measured through respirometric tests (ASTM D5338-9, ISO/CD14855, etc); disintegration of the material during the fermentation phase; no negative effects on compost quality; checking of laboratory-scale results on pilot/full-scale composting plants. These requirements set forth a common base for a universal marking system to readily identify products to be composted. Thermoplastic starch-based polymers and aliphatic polyesters are the two classes of biodegradable materials with the greatest near-term potential. This paper reviews a great variety of properties, structures and biodegradation behaviour of thermoplastic starch in combination with poly(vinyl alcohol) or some aliphatic polyesters like poly(hydroxybutyrate-co-hydroxyvalerate), poly(lactic acid), poly(ϵ-caprolactone) and poly(butanediyl succinate).     

Synthesis of benzo-fused five- and six-membered heterocycles by palladium-catalyzed cyclocarbonylation

A novel and simple synthetic methodology, based on palladium-catalyzed cyclocarbonylation reaction, is presented for preparing five- and six-membered benzo-fused heterocycles. A mechanism for the process is also proposed and discussed.     

Size sorting of citrate reduced gold nanoparticles by sedimentation field-flow fractionation

Gold nanoparticles (GNPs) have been synthesized through the citrate reduction method; the citrate/gold(III) ratio was changed from 1:1 up to 10:1 and the size of the resulting nanoparticles was measured by sedimentation field-flow fractionation (SdFFF). Experimental data showed that the GNPs size decreases in the ratio range 1:1–3:1 and then increases from 5:1 to 10:1 passing through a plateau region in between, and is almost independent of the precursor solution concentrations. In the zone of minimum diameters the synthetic process does not produce monodispersed GNPs but often multiple distributions, very close in size, are observed as evidenced by the particle size distributions (PSDs) derived from the SdFFF fractograms. UV–vis spectrophotometry, being the most common technique employed in the optical characterization of nanoparticles suspensions, was used throughout this work. A confirmation of the nucleation–aggregation–fragmentation mechanism was inferred from the cross-correlation between UV–vis and SdFFF results.     

Sedimentation field flow fractionation and flow field flow fractionation as tools for studying the aging effects of WO₃ colloids for photoelectrochemical uses

WO₃ colloidal suspensions obtained through a simple sol–gel procedure were subjected to a controlled temperature aging process whose time evolution in terms of particle mass and size distribution was followed by sedimentation field flow fractionation (SdFFF) and flow field flow fractionation (FlFFF). The experiments performed at a temperature of 60 °C showed that in a few hours the initially transparent sol of WO₃ particles, whose size was less than 25 nm, undergoes a progressive size increase allowing nanoparticles to reach a maximum equivalent spherical size of about 130 nm after 5 h. The observed shift in particle size distribution maxima (SdFFF), the broadening of the curves (FlFFF) and the SEM–TEM observations suggest a mixed mechanism of growth-aggregation of initial nanocrystals to form larger particles. The photoelectrochemical properties of thin WO₃ films obtained from the aged suspensions at regular intervals, were tested in a biased photoelectrocatalytic cell with 1 M H₂SO₄ under solar simulated irradiation. The current–voltage polarization curves recorded in the potential range 0–1.8 V (vs. SCE) showed a diminution of the maximum photocurrent from 3.7 mA cm⁻² to 2.8 mA cm⁻² with aging times of 1 h and 5 h, respectively. This loss of performance was mainly attributed to the reduction of the electroactive surface area of the sintered particles as suggested by the satisfactory linear correlation between the integrated photocurrent and the cyclic voltammetry cathodic wave area of the W(VI) → W(V) process measured in the dark.     

Electrospray ionisation tandem mass spectrometric investigation of phenylpropanoids and secoiridoids from solid olive residue

This work is focused on the recovery and structural characterisation of bioactive compounds from SOR (solid olive residue), a low cost and widely available by-product in the Mediterranean basin. In the light of the interesting biological activities attributed both to secoiridoid and phenylpropanoids, the aim of this work was to carry out a systematic tandem mass spectrometric study for the identification and characterisation of these two class of compounds extracted from SOR derived from Coratina, a cultivar widely diffused in the south of Italy. Five phenylpropanoids, in addition to verbascoside, and two new secoiridoids were identified.