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Preparation of polymer nano- and microspheres by vinyl polymerization techniques.

The methodologies and techniques of producing polymer particles (nano- and microspheres) from vinyl monomers are described, with an emphasis on laboratory preparations. Five different techniques are employed in the preparation of polymer micro- and nanoparticles from vinyl monomers. Emulsion polymerization provides particles of about 50-200 nm in diameter, emulsifier free emulsion polymerization produces particles of about 100-1000 nm (0.1-1.0 micron), dispersion polymerization gives particles in the region of 0.3-10 micron, and suspension polymerization leads to the formation of particles of about 20 micron-2 mm. The gap in the 10-20 micron region may be filled by either seeded polymerization or by more elaborately performed suspension polymerization. All of the four techniques mentioned above produce regular, spherical particles. Precipitation polymerization, on the other hand, gives irregularly shaped particles in the range of 0.1-10 micron. An attempt is made to clarify the underlying differences between these techniques and to say how they are practised in the laboratory.

Emulsions↗

Adherence of Candida species to newly polymerized and water-stored denture base polymers.

PURPOSE: The aim of this in vitro study was to examine the adherence of yeasts to newly polymerized and water-stored denture base polymers using four Candida strains with different cell surface hydrophobicities. MATERIALS AND METHODS: Thirty-two autopolymerized denture base polymer specimens were stored in distilled water at 37 degrees C for 7 days and 32 were newly polymerized. Sixteen specimens of each group were pretreated with unstimulated mixed saliva (saliva group), and 16 were pretreated with phosphate-buffered saline ([PBS] PBS group) at 37 degrees C for 1 hour. Hydrophobicity of the newly polymerized and water-stored specimen surfaces was determined by contact angle measurements. C guilliermondii, C albicans, C glabrata, and C tropicalis were grown on tryptic soy agar. They were pretreated either with saliva or PBS and suspended in PBS. Four parallel test specimens were incubated without agitation in each yeast suspension at 37 degrees C for 1 hour, washed, and allowed to dry in air. Adherent cells were fixed, gram stained, and counted from 10 high-power light-microscopy fields of each specimen. RESULTS: Enhanced adherence of yeasts was observed in water-stored test specimens in comparison to newly polymerized test specimens. Salivary pellicle reduced the hydrophobicity of test specimens and the adherence of yeasts. No differences in contact angles of distilled water between newly polymerized and water-stored polymers were observed. CONCLUSION: Yeasts seem to adhere less to newly polymerized than water-stored denture base polymer. This may be due to the release of residual monomer from the newly polymerized material.

Adhesiveness↗

Influence of resin composite polymerization techniques on microleakage and microhardness.

OBJECTIVE: The purpose of this study was to evaluate the marginal microleakage and the extent of polymerization in Class II resin composite restorations prepared with two restorative techniques and two polymerization systems. METHOD AND MATERIALS One hundred twenty Class II cavities were prepared in bovine teeth and randomly divided into four groups: Bulk placement and conventional polymerization (Conv 1); buccolingual increments and conventional polymerization (Conv 3); bulk placement and soft-start polymerization (Soft 1); buccolingual increments and soft-start polymerization (Soft 3). All cavities were restored with the Z100/Single Bond system. After thermocycling, the specimens were immersed in 2% methylene blue solution and then evaluated for microleakage. Half of the samples were embedded in polyester resin and polished. The Knoop microhardness of the restorations was measured. RESULTS: There was no dye penetration in 54.44% of Conv 1, 70.11% of Conv 3, 42.53% of Soft 1, and 63.22% of Soft 3 specimens. There were statistically significant differences in microleakage among groups. There were no statistically significant differences in microhardness among any groups at any depth. CONCLUSION: The incremental placement technique resulted in less microleakage. The soft-start system provided adequate polymerization but could not improve marginal sealing.

Animals↗

The effect of polymerization shrinkage during veneer placement.

This study evaluated the relationship of polymerization shrinkage during composite resin veneer placement to direction of the polymerization light source. Fifty maxillary permanent incisors were obtained and divided into five groups of ten. Groups I and II had preparations placed in enamel. Groups III, IV, and V had preparations placed in dentin. In groups I and III, an unfilled bonding resin was placed and polymerized from the facial aspect, followed by placement and polymerization of a hybrid composite resin. Groups II and IV were initially polymerized from the lingual direction. In group V, the unfilled resin and hybrid composite resin were polymerized simultaneously from the facial aspect. Statistical analysis indicated that there was significantly less axial microgap formation during lingual polymerization when the preparation remained in dentin, but demonstrated that there was no statistically significant difference when the preparation remained in enamel.

Analysis of Variance↗

[Study of "living" radical polymerization by FTIR in situ].

Three types of living radical polymerization processes were monitored by means of FTIR spectrometer with handful diamond detector called as Dicomp in situ. It was found that both styrene and styrene/hydroxylpropyl methyacrylate (HPMA) could polymerize according to stable free radical polymerization (SFRP) mechanism in presence of 4-hydroxyl tetramethypiperidiyl-1-oxy(HTEMPO). For styrene/HPMA system, the styrene and HPMA conversion monitored by FTIR were linear with increase of molecular weight, but it gave longer induction period compared with that for St bulk polymerization. It was related to the hydrogen-transfer reaction between the propagating radicals with the end HPMA unit and HTEMPO. Furthermore, This following method in situ could be introduced into monitoring heterogeneous polymerization of styrene during atom transfer radical polymerization (ATRP). The apparent kinetics was found to be about zero order and not 1.0 order, due to propagating on the complex including radicals, CuX and bpy in heterogeneous interface. The polymerization rate will be not related to the St in bulk St phase.

Acrylamides↗

Polymerization efficiency of curing lamps: a universal energy conversion relationship predictive of conversion of resin-based composite.

A universal energy-conversion relationship (ECRu) predictive of conversion of a resin-based composite (RBC) polymerized with any light source has been described. This relationship was derived from an energy conversion relationship for RBC polymerized with a tungsten-halogen lamp and the lamp's efficiency relative to a hypothetical standard lamp. The ECRu was then used to predict conversion throughout RBC polymerized with an LED lamp using the lamp's relative efficiency compared to the standard lamp. The universal energy scale has also been described as predictive of scrape-back lengths for this RBC family when polymerized with any light source. Despite a 31% greater relative efficiency, scrape-back lengths from RBC polymerized using the LED lamp were predicted to be only 6% greater than those polymerized with the tungsten-halogen lamp when RBC is polymerized on an equal energy basis. This result was experimentally verified.

Algorithms↗

Mechanical properties of two orthodontic adhesive materials polymerized with halogen and plasma curing.

OBJECTIVES: The aim of this study is to compare the efficiency of two polymerization techniques (halogen curing--Astralis 7 and plasma curing--Flipo), with two orthodontic adhesive materials (Enlight, a composite resin, and Fuji Ortho LC, a glass ionomer cement). METHODS: The efficiency of the polymerization techniques was shown by two mechanical tests. The hardness test was carried out on the exposed and non-exposed surfaces using 10 x 4 x 3-mm samples, polymerized either by halogen curing (40 seconds) or by plasma curing (5 seconds). The three-point bending tests were carried out on 2 x 2 x 25-mm samples polymerized as above. The samples were kept 1 hr at room temperature, then for 24 hrs in distilled water at 37 degrees C. RESULTS: Whatever the polymerization technique used, the results are similar for hardness and flexion, with the exception of the hardness tests carried out after polymerization with the Flipo light on the surface not directly exposed. CONCLUSION: In orthodontic practice, both polymerization techniques can be used. But a multi-bracket session can be long, and the reduction of time spent in the chair obtained by using plasma lamps seems to make this technique preferable.

Acrylic Resins↗

[Effects of an incremental application technique on the polymerization of two light-activated composite filling materials].

The influence of the use of an incremental technique on the polymerization depth of two light-activated composite resins (hybrid composite resin, microfilled composite resin) was investigated in vitro. Of each of the two materials specimens were produced using variable increments and different polymerization times. Polymerization depth was determined by means of a microhardness tester (Vickers hardness). At the bottom of the cavity hardness values were significantly higher in samples produced in small increments (2 mm) than in samples with thicker layers (3 mm). A polymerization time of 20 s resulted in a significantly poorer polymerization at the bottom of the cavity than longer polymerization times. Hardness values decreased within each layer from the surface to the bottom. Irrespective of the material and the duration of illumination SEM pictures showed the presence of a line in the interface of the layers. The use of incremental technique in class II restorations resulted in differently polymerized zones that are exposed to the varying conditions of the oral cavity.

Composite Resins↗

The role of residual monomer in PMMA powder and methods of polymerization in the finding of residual monomer in poly(methylmethacrylate) denture base.

The amount of residual monomer in methylmethacrylate resins used for denture bases is directly dependent on the polymerization procedure chosen. Residual monomer in PMMA powder has not yet been fully clarified. The aim of this study was to determine the amount of residual monomer in some PMMA powders used for denture bases. The study included determination of the amount of residual monomer in specimens polymerized by various methods of polymerization, attempting to test the interrelationship between the finding of residual monomer in PMMA powder and the respective group of heath-cured resin specimens. Materials from the group of poly(methylmethacrylate) resins type I, class 1 (1--Biocryl R, Galenika, Belgrade-Zemun, and 2--Major Base R, Major Dental Industry, Torino) were used in the study. Experimental specimens were divided into two groups: (1) original PMMA powders; and (2) polymerized specimens obtained by two short curing cycles (a--fractional, classical, heterogeneous polymerization; b--using the Prestherm, Bego device) and three long-curing cycles of polymerization (a--14 h at 70 degrees C; b--7 h at 70 degrees C and 3 h at 100 degrees C; and c--14 h at 70 degrees C and 3 h at 100 degrees C). By 2 g of each powder/specimen were extracted with methanol for residual monomer to be demonstrated by a modified method of gas chromatography on a device manufactured by Perkin Elmer Co. (Norwalk, Conn., USA). Original PMMA powders contained a high but varying percentage of residual monomer. Polymerized specimens had significantly lower values of residual monomer as compared to PMMA powders.(ABSTRACT TRUNCATED AT 250 WORDS)

Denture Bases↗

Biophysical characteristics of hemoglobin intramolecularly cross-linked and polymerized.

Hemoglobin modified by intramolecular cross-linking with 2-nor-2-formylpyridoxal 5'-phosphate (NFPLP) has potential application as an oxygen-carrying plasma expander with improved vascular retention time (threefold) and oxygen-transporting properties compared to native hemoglobin. Under some conditions a further prolongation is required. In this study polymerization of the purified modified hemoglobin (HbNFPLP) with glutaraldehyde was investigated. The influence of the degree of polymerization on the iso-oncotic concentration and the viscosity of the polymerized Hb-NFPLP (polyHbNFPLP) was investigated with three products polymerized to an increasing extent. Exchange transfusions in rats followed by gel filtration analyses of plasma samples provided information on the vascular retention time of four separate polymer fractions (i.e., monomers, dimers, trimers/tetramers, and polymers). The vascular retention time of these fractions correlated with their size. For lightly and highly polymerized HbNFPLP we found fivefold and sevenfold increases, respectively, compared to the retention time for native hemoglobin. This finding and the different shapes of the clearance curves suggested a different clearance mechanism from the vascular system for the monomer and polymer fractions. By polymerizing HbNFPLP the oxygen affinity was enhanced (oxygen half-saturation pressure shifted from 45 to 22 mm Hg), and it appeared to be independent of the degree of polymerization. Because hemoglobin was undetectable in the urine of the rats after the exchange transfusions, no accumulation of polyHbNFPLP will occur in the tubules of the kidney.(ABSTRACT TRUNCATED AT 250 WORDS)

Colloids↗

Ketotifen inhibits PAF-induced actin polymerization in a human eosinophilic leukaemia cell line, EoL-1.

The inhibitory effect of ketotifen on platelet activating factor (PAF)-induced actin polymerization in a human eosinophilic leukaemia cell line, EoL-1, was examined by flow cytometry with the use of reagents specific for the filamentous form of actin (F-actin). Actin polymerization has been considered to be essential for locomotion of cells, chemotaxis and chemokinesis, and thus it reflects the chemotactic reaction of EoL-1 cells stimulated by PAF. Unstimulated EoL-1 cells showed little PAF-induced actin polymerization, whereas EoL-1 cells cultured for 9 days with the supernatant of a human ATL cell line, HIL-3 (HIL-3 sup), showed marked actin polymerization when stimulated with PAF. The actin polymerization in EoL-1 cells induced by PAF was seen in a dose-dependent manner at concentrations of 10(-10) M to 10(-6) M of PAF, and the maximum effect was seen at 10(-7) M of PAF. CV-3988, a specific antagonist of PAF, inhibited 80% of the actin polymerization in EoL-1 cells induced by PAF at a concentration of 10(-5) M. Ketotifen inhibited up to 40% of the PAF-induced actin polymerization of EoL-1 cells in a dose-dependent manner at concentrations of 10(-9) M to 10(-5) M. These results suggest that ketotifen may play an important role in the prevention of eosinophil-induced inflammation in allergic disorders by inhibiting PAF-induced chemotaxis of eosinophils.

Actins↗

n-Butyl 2-cyanoacrylate--substitute for IBCA in interventional neuroradiology: histopathologic and polymerization time studies.

Despite the development of new alternative embolic agents, the endovascular treatment of brain arteriovenous malformations continues to frequently require the use of cyanoacrylic glue, especially in situations where particulate or sclerosing agents are ineffective, such as when flow is very rapid or fistulous. Because isobutyl 2-cyanoacrylate (IBCA), the most commonly used embolic glue, is no longer available or manufactured, a real need exists for an alternative fast polymerizing agent. In vivo and in vitro studies were performed to compare IBCA with n-butyl 2-cyanoacrylate (NBCA, supplied as Histoacryl Blue), a tissue adhesive approved for surgical use in some countries. Polymerization times in static plasma were compared, and the effect of the addition of iophendylate oil or glacial acetic acid on polymerization was assessed. Polymerization times in vivo were compared after intraarterial injection into the internal carotid artery in pigs using a standardized technique. The histopathologic reactions to each glue in the embolized pig rete were assessed and compared over a period of 0-60 days after embolization. Our results show that while NBCA polymerization is demonstrably faster than IBCA in vitro, intraarterial injections of each glue show no significant difference in polymerization times. Like IBCA, NBCA polymerization can be predictably prolonged by the addition of oil or glacial acetic acid, though the effect is less for NBCA. Histopathologic reactions were similar, with acute vasculitis observed, becoming chronic and granulomatous after about 1 month. Both glues showed frequent foci of extravascular extrusion through the embolized rete and recanalization of previously occluded embolized vessels. We conclude that NBCA has clinical and biologic behaviors similar to IBCA, and therefore should be an acceptable alternative to IBCA for intravascular use.

Animals↗

Actin polymerization. The mechanism of action of cytochalasin D.

Fluorescence changes using actin covalently labeled with N-(1-pyrenyl)iodoacetamide have been used to determine the effect of cytochalasin D on actin polymerization. A mechanism for the effect of cytochalasin D on actin polymerization is presented, which explains the experimental observation of a cytochalasin D-induced increase in the initial rate of polymerization and a decrease in the final extent of the reaction. Central to this mechanism is the Mg2+-dependent formation of cytochalasin D-induced dimers. The dimers serve as nuclei to enhance the polymerization rate. Binding of Mg2+ to a low affinity site on the dimer induces a conformational change which can be observed as a rapid fluorescence increase. A subsequent time-dependent fluorescence decrease observed prior to polymerization appears to represent ATP hydrolysis resulting in dissociation of the dimer and release of actin monomers containing ADP. We postulate that a slow rate of exchange of ATP for bound ADP relative to hydrolysis results in the accumulation of monomers containing ADP. As these monomers have a high critical concentration, the final extent of polymerization is reduced dramatically. The Mg2+ dependence of the final extent of polymerization in the presence of cytochalasin D is also explained in the context of this mechanism.

Actins↗

Activity of rheumatoid factors of different molecular sizes: comparison of autologous monomeric and polymeric monoclonal IgA rheumatoid factors.

Differences in rheumatoid factor (RF) activity among the molecular species of IgA were investigated with the use of monomeric and polymeric monoclonal IgA RF paraprotein from the serum of a patient (PS) with idiopathic hyperviscosity syndrome. After fractionation by gel chromatography in acidic buffer, RF activity as determined by latex fixation and solid-phase radioimmunoassay (RIA) specific for IgA RF was confined to the high m.w. (greater than 7S) fractions. However, after adsorption into polystyrene wells, fractions containing monomeric (7S) IgA, as well as those containing polymeric IgA, bound 125I-labeled heat-aggregated human IgG. These observations were confirmed after further purification of the IgA fractions by passage through a protein A-Sepharose CL-4B column followed by precipitation of the IgA proteins with ammonium sulfate at 50% saturation. After "cross-linkage" by a hybridoma anti-human alpha-chain antibody, the activity of the monomeric IgA preparation in the IgA RF RIA approached that of the polymeric IgA preparation. Gel filtration studies verified that this activity was not due to contamination by polymeric IgA RF. Further, classic RF specificity was confirmed for both the monomeric and polymeric IgA RF by reaction with human Fc-coated but not Fab-coated wells. A control monomeric IgA myeloma protein and normal serum IgA did not react in the RF RIA when analyzed in the presence or absence of the hybridoma anti-alpha-chain antibody. Moreover, the activity of the polymeric IgA RF preparation from patient PS in the RIA was minimally influenced by the hybridoma antibody. These results indicate that IgA RF can coexist in both polymeric and monomeric forms, demonstrate that monomeric IgA RF may escape detection by previously described RIA techniques, and suggest an approach for its detection.

Animals↗

Polymerization of ADP-actin and ATP-actin under sonication and characteristics of the ATP-actin equilibrium polymer.

Polymerization under sonication has been developed as a new method to study the rapid polymerization of actin with a large number of elongating sites. The theory proposed assumes that filaments under sonication are maintained at a constant length by the constant input of energy. The data obtained for the reversible polymerization of ADP-actin under sonication have been successfully analyzed according to the proposed model and, therefore, validate the model. The results obtained for the polymerization of ATP-actin under sonication demonstrate the involvement of ATP hydrolysis in the polymerization process. At high actin concentration, polymerization was fast enough, as compared to ATP hydrolysis on the F-actin, to obtain completion of the reversible polymerization of ATP-actin before significant hydrolysis of ATP occurred. A critical concentration of 3 microM was determined as the ratio of the dissociation and association rate constants for the interaction of ATP-actin with the ATP filament ends in 1 mM MgCl2, 0.2 mM ATP. The plot of the rate of elongation of filaments versus actin monomer concentration exhibited an upward deviation at high actin concentration that is consistent with this result. The fact that F-actin at steady state is more stable than the ATP-F-actin polymer at equilibrium suggests that the interaction between ADP-actin and ATP-actin subunits at the end of the ATP-capped filament is much stronger than the interaction between two ATP-actin subunits.

Actins↗

Ca2+ control of actin filament length. Effects of macrophage gelsolin on actin polymerization.

Gelsolin complexes with calcium (gelsolin-Ca2+) binds to the ends of actin filaments to which monomers add preferentially during elongation. It forms a stable complex with actin in a low ionic strength solution which does not normally favor the polymerization of actin. Gelsolin-Ca2+ increases the rate of nucleation of actin which precedes polymerization, but decreases the rate of elongation of the filaments. The final average length of filaments formed in the presence of gelsolin-Ca2+ is shorter and the equilibrium monomer concentration increases relative to actin polymerized in the absence of gelsolin-Ca2+. Gelsolin-Ca2+ also increases the number of actin filaments because the magnitude of the increase in monomer concentration is disproportionately small compared with the reduction in polymer length. In these respects, the population of actin filaments formed during polymerization in the presence of gelsolin-Ca2+ is similar to that resulting from the action of gelsolin on previously assembled actin filaments (Yin, H. L., Zaner, K. S., and Stossel, T. P. (1980) J. Biol. Chem. 255, 9494-9500). The calcium-dependent shortening of ects, the population of actin filaments formed during polymerization in the presence of gelsolin-Ca2+ is similar to that resulting from the action of gelsolin on previously assembled actin filaments (Yin, H. L., Zaner, K. S., and Stossel, T. P. (1980) J. Biol. Chem. 255, 9494-9500). The calcium-dependent shortening of ects, the population of actin filaments formed during polymerization in the presence of gelsolin-Ca2+ is similar to that resulting from the action of gelsolin on previously assembled actin filaments (Yin, H. L., Zaner, K. S., and Stossel, T. P. (1980) J. Biol. Chem. 255, 9494-9500). The calcium-dependent shortening of actin filaments is the primary mechanism for the dissolution of an actin gel by gelsolin. Therefore, the ability of gelsolin to produce short filaments irrespective of the initial state of assembly of the actin offers flexibility for controlling the network structure of the cytoplasm in which either the monomeric or polymeric form of actin molecules might predominate at different times.

Actins↗

Variation in fetal hemoglobin parameters and predicted hemoglobin S polymerization in sickle cell children in the first two years of life: Parisian Prospective Study on Sickle Cell Disease.

Intracellular hemoglobin S (HbS) polymerization is most likely to be the primary determinant of the clinical and biologic manifestations of sickle cell disease (SCD). Fetal hemoglobin (HbF) does not enter the HbS polymer and its intracellular expression in sickle erythrocytes inhibits polymerization. HbF levels, high at birth but decreasing thereafter, protect the newborn from the clinical manifestations of this hemoglobinopathy. We have measured the sequential changes in HbF, F reticulocytes, and F cells in the first 2 years of life in 25 children with SCD and compared the results with those obtained in 30 normal children (AA). We have also calculated HbF per F cell (F/F cell), the preferential survival of F cells versus non-F cells, as measured by the ratio F cells versus F reticulocytes (FC/FR) and polymer tendency at 40% and 70% oxygen saturation. HbF levels decreased from about 80.4% +/- 4.0% at birth to 9.2% +/- 2.9% at 24 months. During this time, we observed a regular decrease of the F reticulocytes and the F cells. The kinetics of the decline of F/F cell was comparable with the decline of HbF, rapid from birth (mean, 27.0 +/- 3.6 pg) to 12 months of age (mean, 8.5 +/- 1.5 pg) and then slower from 12 to 24 months of age (mean, 6.2 +/- 1.0 pg) in the SCD children. In the AA children, the decrease in HbF, due to changes in both numbers of F cells and F/F cell, was more precipitous, reaching steady-state levels by 10 months of age. Calculated values for mean polymer tendency in the F-cell population showed that polymerization should begin to occur at 40% oxygen saturation at about 3 months and increase progressively with age, whereas polymerization at 70% oxygen saturation would not occur until about 24 months. These values correspond to HbF levels of 50.8% +/- 10.8% and 9.2% +/- 2.9%, respectively, and F/F cell levels of 15.6 +/- 4.5 pg and 6.2 +/- 1.0 pg, respectively. In the non--F-cell population, polymerization was expected at birth at both oxygen saturation values. Three individuals had significantly greater predicted polymerization tendency than the remainder of the group because of early decreases in HbF. These individuals in particular, the remainder of the cohort, as well as other recruited newborns, will be studied prospectively to ascertain the relationship among hematologic parameters, which determine polymerization tendency and the various clinical manifestations of SCD.

Anemia, Sickle Cell↗

Both isoforms of skeletal muscle subfragment 1 (S1A1 and S1A2) can induce actin polymerization with equal speed in the absence of ATP.

The ability of myosin subfragment 1 to induce actin polymerization was reinvestigated using the DNase I inhibition assay, by electron microscopy after negative staining, cosedimentation, measurement of viscosity and the fluorescence increase of pyrenyl-labeled actin. Using these techniques we demonstrate that rabbit skeletal muscle myosin subfragment 1 containing either the alkali light chain 1 (S1A1) or the alkali light chain 2 (S1A2) is able to promote actin polymerization even in the absence of divalent cations or salt. In the presence of ATP the rate of induction of actin polymerization by S1A2 is slower than by A1A1. In contrast, in the absence of free ATP, both subfragment 1 variants exhibit equal ability to induce actin polymerization. Evidence is given that the slower rate of induction of actin polymerization by S1A2 in the presence of free ATP is due to a slower rate of ATP-hydrolysis by S1A2 and thus to a slower rate of ATP depletion. We therefore assume that the formation of rigor type complexes involving the subfragment 1 heavy chain is necessary for the induction of actin polymerization. The ability of subfragment 1 to induce actin polymerization is retarded by a synthetic heavy chain mimetic peptide which inhibits its actin binding or after proteolytic cleavage of the subfragment 1 heavy chain by trypsin.

Actins↗