Cesar Liberato Petzhold

Aggregation behavior of a new series of ABA triblock copolymers bearing short outer A blocks in B-selective solvent: from free chains to bridged micelles.

A combination of dynamic (DLS) and static (SLS) light scattering measurements was employed to study the self-assembly behavior of a new series of triblock copolymers bearing poly[5-(N,N-diethylamino isoprene)] (PAI) short outer blocks and polystyrene (PS) as the major middle block. Previously, it was verified that PAI outer blocks can be quaternized leading the formation of crew-cut aggregates in water (Riegel, I. C.; Eisenberg, A.; Petzhold, C. L.; Samios, D. Langmuir 2002, 18, 3358). Herein, we focus on the copolymers ability in the nonquaternized version to undergo self-aggregation in dimethylformamide (DMF), a selective solvent for the middle block. Light scattering measurements showed that formation of well-defined flowerlike micelles is likely to occur. Aggregates with a relatively narrow distribution, small average size, and number of aggregation ranging from 21 to 39 chains/micelle were experimentally observed. The results also suggested that approximately 5-6 polymeric units per each short outer block are needed to induce aggregation. The middle block length governs the size of the micelles and influences the number of aggregation of the resultant particles as well. Furthermore, when the polystyrene middle block was particularly long (degree of polymerization DP > 600), dynamic and static light scattering measurements suggested the formation of bridged micelles in an open structure in concentrations as low as 15 mg mL-1.

Influence of 2-hydroxyethyl methacrylate concentration on polymer network of adhesive resin.

PURPOSE To evaluate the effect of variations in 2-hydroxyethyl methacrylate (HEMA) concentrations in an experimental comonomer blend on degree of conversion, water sorption, solubility, and ultimate tensile strength of adhesive resin. MATERIALS AND METHODS The effect of HEMA content (0, 15, 30, and 50%wt - control, G15, G30, and G50 groups, respectively) was tested in an experimental comonomer blend of bis-GMA, bis-EMA, TEG-DMA, and HEMA. The degree of conversion, polymerization rate, ultimate tensile strength, water sorption, and solubility of the adhesive resin blends were determined. RESULTS At 40 s of light activation time, groups G30 and G50 showed a decrease of 30% and 61%, respectively, in degree of conversion compared to control. Water sorption and solubility differed for all groups, and was statistically higher in G50. For ultimate tensile strength, the control and G15 groups showed statistically higher values than the other groups (p < 0.05). CONCLUSION Higher HEMA content increases dental adhesive resin degradation.

Niobium pentoxide as a novel filler for dental adhesive resin.

OBJECTIVES The purpose of this study was to develop an adhesive resin with incorporation of niobium pentoxide and evaluate its properties. METHODS Niobium pentoxide was characterised by X-ray diffraction, surface area, particle size, micro-Raman, scanning electron microscopy and the effectiveness of silanisation process by Fourier Transform Infrared (FTIR). An experimental adhesive resin was formulated with 0, 5, 10 and 20wt% Nb(2)O(5). The formulated adhesive resins were evaluated based on microhardness, degree of conversion, radiopacity and interface (resin/dentine) characterisation by micro-Raman. RESULTS The particles used in this study presented a monoclinic crystalline phase with typical chemical groups and micrometre mean size. Microhardness and radiopacity increased with higher amounts of Nb(2)O(5), and the particles were able to penetrate into the hybrid layers. CONCLUSIONS Therefore, Nb(2)O(5) may be an alternative for polymer-based biomaterials. CLINICAL SIGNIFICANCE Niobium pentoxide could be used to produce adhesive resins with enhanced properties.

Self-assembly of amphiphilic di and triblock copolymers of styrene and quaternized 5-(N,N-diethylamino) isoprene in selective solvents

Self-association of highly asymmetric block copolymers of styrene and quaternized 5-(N,N-diethylamino)isoprene was studied. After quaternization with dimethyl sulfate, the di and triblock copolymers consisted of a long block of polystyrene (PS) with a short poly[5-(N,N,N-diethylmethylammonium)isoprene][methyl sulfate](PAI) block at one or both chain ends, respectively. The aggregates were prepared by first dissolving the copolymers in an organic solvent and then adding water to induce the segregation of the PS chains. Pure DMF, THF or dioxane was used as the organic solvent, as well as DMF/THF mixtures. The critical water content (cwc) and the morphologies were studied as a function of the common solvent, initial copolymer concentration and architecture (di or triblock) by static light scattering and by Transmission Electron Microscopy (TEM), respectively. It was found that both, the cwc and the morphologies of the aggregates are most strongly affected by the nature of the common solvent. Some unexpected behaviors were found for the triblock copolymer. Morphologies of a triblock copolymer in various mixtures of DMF and THF, quenched at determined water contents, were investigated in order to study the degree of morphological control that can be achieved solely as function of the organic solvent composition. Multiple morphologies have been found including equilibrium morphologies and kinetically trapped ones. Finally, the stability of primary micelles prepared in DMF was studied by DLS, upon dilution with DMF and water, and a possible mechanism for the destabilization of the aggregates is proposed.

Lipid-core nanocapsules: mechanism of self-assembly, control of size and loading capacity

Nanotechnology in pharmaceutics has the potential to improve drug efficacy by influencing drug distribution in tissues. Nanocarriers have been developed as drug delivery systems to be administered by different biological routes. To ensure the nanotechnological properties, pre-formulation studies are especially critical in determining the influence of the process parameters on the size and polydispersity of particles. Thus, the objective of this work was to establish the mechanism of self-assembly, by determining the influence of the critical aggregation concentration of the materials in the organic phase on the final average particle size and polydispersity of polymeric lipid-core nanocapsules obtained by interfacial deposition of polymer. Measurements of the surface tension and viscosity of the organic and aqueous phases were correlated with the particle size and the concentration of raw materials. We demonstrated that the lipid-core nanocapsules are formed on the nanoscopic scale as unimodal distributions, if the aggregation state of raw materials in the organic phase tends to infinite dilution. The strategy for controlling the particle size distribution is a valuable tool in producing lipid-core nanocapsule formulations with different loading capacities intended for therapeutics.

2-Hydroxyethyl methacrylate as an inhibitor of matrix metalloproteinase-2

This study evaluated the effect of different concentrations of 2-hydroxyethyl methacrylate (HEMA) on the inhibition of matrix metalloproteinase-2 (MMP-2) in vitro. Mouse gingival explants were cultured overnight in Dulbeccos modified Eagles minimal essential medium, following which the expression of secreted enzymes was analyzed by gelatin zymography and the effects of different amounts of HEMA on enzyme activity were investigated. The gelatinolytic proteinases present in the conditioned media were characterized as being matrix metalloproteinases (MMPs) by means of specific chemical inhibition. The MMPs present in the conditioned media were identified, using immunoprecipitation, as MMP-2. Three major bands were detected in the zymographic assays and were characterized, according to their respective molecular weights, into the following forms of MMP-2: zymogene (72 kDa), intermediate (66 kDa), and active (62 kDa). All forms of MMP-2 were inhibited by HEMA in a dose-dependent manner, implying that MMP-2 may be inhibited by HEMA in vivo.

Symmetrical and Asymmetrical Cyanine Dyes. Synthesis, Spectral Properties, and BSA Association Study

New cyanines were prepared by an efficient and practical route with satisfactory overall yield from low-cost starting materials. The photophysical behavior of the cyanines was investigated using UV-vis and steady-state fluorescence in solution, as well as their association with bovine serum albumin (BSA) in phosphate buffer solution (PBS). No cyanine aggregation was observed in organic solvents or in phosphate buffer solution. The alkyl chain length in the quaternized nitrogen was shown to be fundamental for BSA detection in PBS in these dyes.

Preparation and Evaluation of Dental Resin Luting Agents with Increasing Content of Bisphenol-A Ethoxylated Dimethacrylate

Resin luting agents in which bisphenol-A glycidyl dimethacrylate (Bis-GMA) and/or triethylene glycol dimethacrylate (TEGDMA) are replaced with increasing amounts of bisphenol-A ethoxylated dimethacrylate are prepared. Degree of conversion (DC), diametral tensile strength (DTS), Young’s modulus (YM), Knoop hardness (KHN), film thickness (FT), water sorption (Wsp ), and solubility are evaluated. Regression analyses investigate the substitution of each monomer. The most appreciable differences are detected when TEGDMA is replaced: decreased DC, DTS, and Wsp, and increased YM, KHN, and FT. For substitution of Bis-GMA, the only significant differences are reduced Wsp and increased YM. An ideal formulation of resin cement would make use of the three monomers.

Synthesis and AChE inhibitory activity of new chiral tetrahydroacridine analogues from terpenic cyclanones

This work describes the enantioselective synthesis of a new series of terpenic chiral 9-aminotetrahydroacridine analogues. Several chiral ketones were synthesized from natural monoterpenes in an optically active form and subjected to the cyclodehydration reactions with anthranilonitrile in the presence of BF(3).Et(2)O as catalyst. The 9-aminotetrahydroacridine analogues were tested as acetylcholinesterase (AChE) inhibitors. Based on qualitative structure-activity relationship some trends are suggested.

The effect of sterilization methods on electronspun poly(lactide‐co‐glycolide) and subsequent adhesion efficiency of mesenchymal stem cells

The sterilization of scaffolds is an essential step for tissue engineering in vitro and, mainly, clinical biomaterial use. However, this process can cause changes in the structure and surface of the scaffolds. Therefore, the objective of this study was to investigate the effect of sterilization by ethanol, ultraviolet radiation (UVR) or antimicrobial solution (AMS) on poly(lactide-co-glycolide) (PLGA) scaffolds produced by the electrospinning technique. The properties of nanofibers and the cellular adhesion of mesenchymal stem cells to the scaffolds were analyzed after the treatments. All methods generated sterile scaffolds but showed some kind of damage to the scaffolds. Ethanol and AMS caused changes in the morphology and scaffold dimensions, which were not observed when using the UVR method. However, UVR caused a greater reduction in polymeric molecular weight, which increased proportionally with exposure time of treatment. Nanofibers sterilized with AMS for 1 h and 2 h showed greater cellular adhesion than the other methods, demonstrating their potential as a method for sterilizing PLGA nanofibers.