Polymerization Mode Research Articles

K-resin based multilayer polymeric mode filter for integrated optics

We demonstrate theoretically as well as experimentally a new type of four layer polymeric waveguide structure which can be used as mode filter. Various optical properties such as refractive index, birefringence and propagation constant of SAN and K-resin are presented. The thin film structure consisting of glass/K-resin/SAN/air is used to act as mode filter. Expressions for the electric field intensity spatial distribution for the structure are used to calculate the intensity profiles to support the observed behavior. The experimental values were in good agreement with the one obtained theoretically.

Architecture of the DNA polymerase B-proliferating cell nuclear antigen (PCNA)-DNA ternary complex

DNA replication in archaea and eukaryotes is executed by family B DNA polymerases, which exhibit full activity when complexed with the DNA clamp, proliferating cell nuclear antigen (PCNA). This replication enzyme consists of the polymerase and exonuclease moieties responsible for DNA synthesis and editing (proofreading), respectively. Because of the editing activity, this enzyme ensures the high fidelity of DNA replication. However, it remains unclear how the PCNA-complexed enzyme temporally switches between the polymerizing and editing modes. Here, we present the three-dimensional structure of the Pyrococcus furiosus DNA polymerase B-PCNA-DNA ternary complex, which is the core component of the replisome, determined by single particle electron microscopy of negatively stained samples. This structural view, representing the complex in the editing mode, revealed the whole domain configuration of the trimeric PCNA ring and the DNA polymerase, including protein-protein and protein-DNA contacts. Notably, besides the authentic DNA polymerase-PCNA interaction through a PCNA-interacting protein (PIP) box, a novel contact was found between DNA polymerase and the PCNA subunit adjacent to that with the PIP contact. This contact appears to be responsible for the configuration of the complex specific for the editing mode. The DNA was located almost at the center of PCNA and exhibited a substantial and particular tilt angle against the PCNA ring plane. The obtained molecular architecture of the complex, including the new contact found in this work, provides clearer insights into the switching mechanism between the two distinct modes, thus highlighting the functional significance of PCNA in the replication process.

ADMET: Metathesis polycondensation

AbstractAlthough it is well known that Acyclic Diene METathesis (ADMET) describes an olefin metathesis polymerization mode that relies on double‐bond substituent interchange of a diolefin, the story behind its discovery is not. The story is divulged here. Olefin metathesis has a rich history dating to the 1950s, but the one particular metathesis mode mentioned, ADMET, has more recent historical roots. ADMET polymerization is easy to do and highlighted here are the particular reaction details for success. Additionally, the most recent advances from the past 5 years are detailed, exemplifying this reaction's wide utility from fundamental structure–property studies to multiple advanced applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Salmonella enterica Response Regulator SsrB Relieves H-NS Silencing by Displacing H-NS Bound in Polymerization Mode and Directly Activates Transcription

The response regulator SsrB activates expression of genes encoded within and outside of a pathogenicity island (SPI-2), which is required for systemic infection of Salmonella. SsrB binds upstream of the sifA, sifB, and sseJ effector genes and directly regulates transcription. SsrB also relieves gene silencing by the nucleoid protein H-NS. Single molecule experiments with magnetic tweezers demonstrated that SsrB displaces H-NS from DNA only when it is bound in a polymerization (stiffening) mode and not when H-NS is bound to DNA in the bridging mode. Thus, in contrast to previous views, the polymerization binding mode of H-NS is the relevant form for counter-silencing by SsrB. Our results reveal that response regulators can directly activate transcription and also relieve H-NS silencing. This study adds to the repertoire of mechanisms by which NarL/FixJ subfamily members regulate transcription. Because SsrB-dependent promoters are diversely organized, additional mechanisms of transcriptional activation at other loci are likely.

Strength of a feldspar ceramic according to the thickness and polymerization mode of the resin cement coating

The aim of this study was to evaluate, in vitro, the biaxial flexural strength (ISO 6872) of a feldspathic ceramic (VM7, Vita Zahnfabrik) coated with a resin cement with different thicknesses and polymerization mode. Control groups consisted in VM7 with and without acid etching with 10% hydrofluoric acid for 1 min. Experimental groups comprised VM7 etched, silanated and coated with Variolink II (Ivoclar Vivadent) cement, that was polymerized through the porcelain in light-cure and dual-cure modes, with thickness ≤150 µm or >150 µm. The specimens (n=15) were subjected to the biaxial flexural strength essay and analyzed fractographically. Parametric (Dunnet, Anova 2-way, Tukey) and non-parametric tests (Weibull) were used to evaluate results. Ceramic disks coated with resin cements of either activation modes and thicknesses exhibited higher flexural strength while the Weibull moduli did not present significant differences for a confidence interval of 95%.

Microhardness of dual-polymerized resin cement around a translucent fiber post in the intraradicular environment

Aim:In this study, we evaluated the effect of photopolymerization on Vickers microhardness of dual-polymerized resin cement at three locations when a translucent quartz fiber post was used.Materials and Methods:Single-rooted bovine teeth received quartz fiber post systems (length: 12 mm) using a dual-polymerized resin cement. In Group 1, the posts were cemented but not photopolymerized, and in Group 2, the posts were both cemented and photopolymerized. After cementation, approximately 1.5-mm thick sections were obtained (two cervical, two middle, and two apical) for regional microhardness evaluations.Statistical Analysis:Statistical analyses were performed using the SPSS software (ver. 11.0 for Windows; SPSS, Inc., Chicago, IL, USA). Microhardness (kg/mm2) data were submitted to two-way analysis of variance (two-way ANOVA) and repeated measures with microhardness values as the dependent variable and polymerization status (two levels: with and without) and root region (three levels: cervical, middle, and apical) as independent variables. Multiple comparisons were made using Dunnett's T3 post-hoc test. P values of <0.05 were considered to indicate statistical significance in all tests.Results:Photopolymerization did not significantly change the microhardness values when compared with no photopolymerization. Microhardness values also showed no significant difference between the three regions in the root canals in both groups.Conclusions:The mode of polymerization of the cement tested in combination with the translucent quartz fiber post system did not affect the microhardness of the cement at the cervical, middle, or apical regions of the root.

Postoperative sensitivity in Class V composite restorations: Comparing soft start vs. constant curing modes of LED

Background:One of the major disadvantages associated with using composites is polymerization shrinkage; stresses are generated at the margins, and if these stresses exceed the bond strength, microleakage occurs at the tooth restoration interface which causes ingress of cariogenic bacteria, post-operative sensitivity, and secondary caries. LED offers several curing modes: constant cure, ramped cure, and soft start cure. It is claimed that soft start polymerization mode produces less polymerization shrinkage and consequently less postoperative sensitivity.Objective:To compare the postoperative sensitivity in Class V composite restorations using soft start and constant LED curing modes.Materials and Methods:Using the appropriate burrs cavity was prepared and filled with composite Z 100(3M-ESPE) using a incremental technique. Each increment of 2 mm was cured either with soft start or constant cure. All patients were evaluated at day 2 for postoperative sensitivity.Results and Discussion:Out of 124 restorations that were placed, only three restorations presented with postoperative sensitivity, each one being in mild, moderate, and severe categories, respectively. No relationship was seen between the sensitivity and tooth type. There was no statistically significant difference in postoperative sensitivity in either of the treatment modalities (constant or soft start).Conclusion:We conclude that restorations placed with the soft start curing technique did not show significant changes in postoperative sensitivity when compared to the constant curing technique.

Shade and polymerization mode influence on conversion of dual-cured cements

Shade and polymerization mode influence on conversion of dual-cured cements

Contemporary curing profiles: Study of effectiveness of cure and polymerization shrinkage of composite resins: An in vitro study

Aims:This study was undertaken to determine the effect of step-curing, ramp curing, single intensity on the effectiveness of cure and polymerization shrinkage of composite resin. The influence of filler loading on the effectiveness of cure and polymerization shrinkage of composite resin was investigated.Materials and Methods:In this study, a total of 80 specimens divided into four groups were used. Group I – specimens cured with the step-cure mode. Group II – specimens cured with single high intensity. Group III – specimens cured with the ramp-cure mode. Group IV – specimens cured with single low intensity. Each group had two subgroups based on the composite resins used for making the specimen. The effectiveness of cure was determined from surface hardness values obtained from Rockwell hardness testing. A mathematical volumetric method was used to assess the volumetric shrinkage.Results:Group III showed the best effectiveness of cure followed by group I and II. Group IV showed the least. Polymerization shrinkage was highest with group III and group II, were as was lowest for group I and IV. Charisma showed better effectiveness of cure and low polymerization shrinkage compared to Durafill VS.Conclusion:This study emphasizes on the fact that, the soft–start polymerization modes (step curing and ramp curing) should be preferentially used over the conventional single (high or low light) intensities to cure composite resins, as its use results in optimal properties.

Reducing the incompatibility between two-step adhesives and resin composite luting cements.

To determine whether the adverse interaction between a two-step/acidic etch-and-rinse adhesive (One-Step Plus [OS], Bisco) and chemically cured resin luting cement [Variolink II, Ivoclar Vivadent] can improve adhesive coupling by reducing the dentin permeability with an oxalate desensitizer (BisBlock, Bisco). After exposing dentin on the occlusal surfaces of human third molars, bonding was performed on either oxalate treated (BB) or nontreated (NB) demineralized dentin. A resin luting cement was placed in the format of a crown following the light-curing mode (only with the base syringe [LC]) or the chemically curing mode (mixture of base and catalyst syringes [CC]). The activation of the LC or CC cements was either immediately [IM], meaning soon after the placement of LC and the initial set of CC cement (5 min), or after a delay of 20 min [DP] for both modes of polymerization. Five teeth were assigned to each experimental condition. Teeth were sectioned to obtain sticks with a cross-sectional area of 0.95 mm2, which were tested using the microtensile bond strength test soon after the specified periods of polymerization. The bond strength values of each adhesive were analyzed by three-way repeated measures ANOVA and Tukey's tests (α = 0.05). Fractographic analysis of the specimens was performed using SEM. The delayed polymerization (for both LC and CC cements) produced low bond strength values compared to IM activation. When the BB was employed, the bond strength values of the CC cement was approximately doubled, while the BB did not affect the bond strength of the LC cement. Bond strength values of LC cements were higher than CC. The use of BB significantly improved the bond strength of CC cement only. The morphological observations confirmed the bond strength results. A myriad of voids could be detected in the luting cement side when BB was not applied, except for the immediately light-cured group. The use of an oxalate desensitizer (BisBlock) reduced the incompatibility between a two-step etch-and rinse adhesive and chemically cured resin cements and light-cured systems in the delayed polymerization mode.

Three Mechanisms of Asymmetric Polymerization of Phenylacetylenes Having an l-Amino Ether Residue and Two Hydroxy Groups

Three novel chiral phenylacetylenes having an octyloxyethanolamine residue derived from a l-aminoalcohol and two hydroxymethyl groups were synthesized and polymerized by two achiral catalysts ((nbd)Rh+[η6-(C6H5)B−(C6H5)3] and [Rh(nbd)Cl]2/triethylamine (TEA)) and a chiral catalytic system ([Rh(nbd)Cl]2/(S)- or (R)-phenylethylamine ((S)- or (R)-PEA)). All of the resulting polymers showed Cotton effects at wavelengths around 430 nm. This observation indicated that they had an excess of one-handed helical backbones. Positive and negative Cotton effects were observed for the polymers having an l-valinol residue produced by using (S)- and (R)-PEA as a cocatalyst, respectively, although the monomers had the same chirality. The two polymers having an l-alaninol or l-phenylalaninol residues obtained by using (S)- and (R)-PEA as a cocatalyst showed CD absorptions with identical signs. Therefore, we found that the chiral monomer having an l-valinol residue was suitable for both modes of asymmetric polymerization, t...

Antioxidant capacity of potato chips and snapshot trends in acrylamide content in potato chips and cereals on the Canadian market

The concentration of acrylamide was measured in selected varieties of five brands of potato chips and breakfast cereals over a 5-year period. Most of the products were purchased in one locality in Canada. Samples were analysed by an isotope dilution (13C3) acrylamide method. They were extracted with water, partitioned with dichloromethane, filtered through a 5 kDa centrifuge filter, cleaned-up on HLB Oasis polymeric and Accucat mixed mode anion and cation exchange SPE columns, and analysed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The acrylamide concentration in potato chips varied from 106 to 4630 ng g−1, while values in cereals varied from 50 to 347 ng g−1. Wide variations were observed between brands, within brands over time, and between lots of the same brand. A subset of potato chip samples was analysed for in vitro antioxidant activity. No relationship was found between antioxidative capacity of potato chips and their acrylamide content.

Synthesis of a norbornene monomer having cyclic carbonate moiety based on CO2 fixation and its transition metal-catalyzed polymerizations

A norbornene monomer bearing cyclic carbonate moiety (NB-CC) was successfully synthesized from the corresponding precursor having epoxy moiety by its reaction with carbon dioxide under atmospheric pressure, which was efficiently catalyzed by lithium bromide. NB-CC underwent the ring-opening metathesis polymerization (ROMP) catalyzed by a ruthenium carbene complex to give the corresponding poly(norbornene), of which side chain inherited the cyclic carbonate moiety from the monomer without any deterioration. The same ROMP system was applicable to the copolymerization of NB-CC and 5-butyl-2-norbornene (BNB), which afforded the corresponding copolymer with a composition ratio same as a feed ratio. In addition, by using a catalytic system consisted of palladium (II) acetate/tricyclohexylphosphine/triphenylcarbenium tetrakis(pentafluorophenyl)borate, the copolymerization of NB-CC and BNC proceeded successfully in a vinyl addition polymerization mode to give the corresponding poly(norbornene) having CC moiety in the side chain. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3896–3902, 2010

Two Modes of Interaction of the Single-stranded DNA-binding Protein of Bacteriophage T7 with the DNA Polymerase-Thioredoxin Complex

The DNA polymerase encoded by bacteriophage T7 has low processivity. Escherichia coli thioredoxin binds to a segment of 76 residues in the thumb subdomain of the polymerase and increases the processivity. The binding of thioredoxin leads to the formation of two basic loops, loops A and B, located within the thioredoxin-binding domain (TBD). Both loops interact with the acidic C terminus of the T7 helicase. A relatively weak electrostatic mode involves the C-terminal tail of the helicase and the TBD, whereas a high affinity interaction that does not involve the C-terminal tail occurs when the polymerase is in a polymerization mode. T7 gene 2.5 single-stranded DNA-binding protein (gp2.5) also has an acidic C-terminal tail. gp2.5 also has two modes of interaction with the polymerase, but both involve the C-terminal tail of gp2.5. An electrostatic interaction requires the basic residues in loops A and B, and gp2.5 binds to both loops with similar affinity as measured by surface plasmon resonance. When the polymerase is in a polymerization mode, the C terminus of gene 2.5 protein interacts with the polymerase in regions outside the TBD. gp2.5 increases the processivity of the polymerase-helicase complex during leading strand synthesis. When loop B of the TBD is altered, abortive DNA products are observed during leading strand synthesis. Loop B appears to play an important role in communication with the helicase and gp2.5, whereas loop A plays a stabilizing role in these interactions.

Dual-curing, self-adhesive resin cement: influence of the polymerization modes on the degree of conversion and microhardness

during 20 seconds while for GR3 the same intensity was used but the irradiation time was 40 seconds. The GR2 followed the same polymerization mode of the GR1 but a ceramic disk was applied as a light barrier. For the last group, only the chemical polymerization was carried out. The DC and VMH were measured immediately after the irradiation time and again after 24 hours. Dual-polymerization (light and chemical polymerization) showed higher DC and VMH than the chemical polymerization (dark cure). The presence of a ceramic disk did not affect the DC but reduced the VMH. Increasing the exposure to light, the DC remained almost constant whereas the VMH raised slightly indicating that the VMH is quite dependent on the incident energy. Additionally, the powder/liquid portions of the cement were also characterized. The TG showed that the solid fraction was constituted of 96% of inorganic matter and 4% of vinyl-silane, a coupling agent. Regarding the liquid part, it was found that 84% was related to the mixture of monomers. The SEM revealed that the size particle of the inorganic fillers were between 400and 11.000 nm. Factors such as energy density, size and distribution of inorganic fillers and the low effectiveness of the chemical cure contributed to the low values of the DC and VMH.

Fabrication and optical properties of Alq 3 doped PMMA microsphere arrays templated by ZnO inverse opal structure

PMMA microsphere arrays are fabricated by a double replicating method with common used polystyrene colloidal crystal template. High quality ZnO inverse opals formed by electrodeposition play the key role between the PMMA microsphere arrays and polystyrene colloidal crystals. The electrodeposition method has advantage on fabricating IO structures with high solid fraction. After the subsequently in-situ polymerization of MMA in the voids of ZnO inverse opals, the ZnO is removed by hydrochloric acid solution. Microsphere arrays fabricated by PMMA or PMMA doped with Alq 3 are prepared. Reflection stop bands are detected from the formed PMMA microsphere arrays. Solid fraction from 37% to 50% of the PMMA arrays can be formed by different in-situ polymerization modes of MMA. The photoluminescence of Alq 3 in the PMMA spheres is partly suppressed at the wavelength of the photonic stop band induced by PMMA arrays.

TRNA nucleotidyltransferases: ancient catalysts with an unusual mechanism of polymerization.

RNA polymerases are important enzymes involved in the realization of the genetic information encoded in the genome. Thereby, DNA sequences are used as templates to synthesize all types of RNA. Besides these classical polymerases, there exists another group of RNA polymerizing enzymes that do not depend on nucleic acid templates. Among those, tRNA nucleotidyltransferases show remarkable and unique features. These enzymes add the nucleotide triplet C-C-A to the 3'-end of tRNAs at an astonishing fidelity and are described as "CCA-adding enzymes". During this incorporation of exactly three nucleotides, the enzymes have to switch from CTP to ATP specificity. How these tasks are fulfilled by rather simple and small enzymes without the help of a nucleic acid template is a fascinating research area. Surprising results of biochemical and structural studies allow scientists to understand at least some of the mechanistic principles of the unique polymerization mode of these highly unusual enzymes.

Effect of homogeneity of methanol/water/monomer mixture on the mode of polymerization of MMA: Soap-free emulsion polymerization versus dispersion polymerization

The soap-free emulsion polymerization of methyl methacrylate (MMA) was carried out with varying amount of methanol in the aqueous medium. As methanol content increased, the phase of polymerization mixture (methanol/water/monomer) changed from heterogeneous to homogeneous state and the transition occurred at 30 wt% methanol. In order to identify the mechanism of the polymerization in heterogeneous and homogeneous mixture, the properties of the prepared PMMA particles were analyzed in terms of the effects of methanol content on the conversion at 1 h, initiator concentration and polymerization temperature. With the heterogeneous mixture in the range of 0–20 wt% methanol, the polymerization product and polymerization behavior resembled those typically observed in the soap-free emulsion polymerization. On the other hand, the characteristics of the polymerization products were similar to those typically obtained in the dispersion polymerization under the homogeneous mixture ranging 40–60 wt% methanol. Thus, the homogeneity in the aqueous methanol mixture can be a critical factor in determining the polymerization modes between the soap-free emulsion and dispersion polymerization.

Effect of curing mode on bond strength of self‐adhesive resin luting cements to dentin

In this study, the in vitro bond strength of dual-curing resin cements to indirect composite restorations when the cement was either light polymerized or allowed to only autopolymerize was evaluated. Occlusal dentin surfaces of 56 extracted human third molars were flattened to expose coronal dentin. Teeth were assigned to eight groups (n = 7) according to resin cement products and polymerization modes: conventional cement (Panavia F 2.0; Kuraray Medical) and self-adhesive cements [RelyX Unicem (3M ESPE), BisCem (Bisco), and G-Cem (GC Corp.)]. Cements were applied to prepolymerized resin discs (2-mm-thick Sinfony; 3M ESPE), which were subsequently bonded to the prepared dentin surfaces. The restored teeth were either light-polymerized through the overlying composite according to manufacturers' instructions or were allowed to only self-cure. After 24 h, the teeth and restorations were sectioned to obtain multiple bonded beams (1.0 mm(2)) and tested in tension at a crosshead speed of 0.5 mm/min until failure. Data (MPa) were analyzed by two-way ANOVA and Tukey test (alpha = 0.05). Light activation of some cement systems (G-Cem and Panavia F 2.0) increased the bond strength, while the curing mode did not affect the bond strength for some (RelyX Unicem and BisCem). The bond strength in the autopolymerized mode varied among products. In general, the use of self-adhesive resin cements did not provide significantly higher bond strengths than that of a conventional material, and two self-adhesive cements yielded significantly lower bond values (regardless of cure mode) than the other products.

New cyclic tetrameric and square-grid polymeric modes of supramolecular self-assembly of zinc tetra(4-pyridyl)porphyrin

New supramolecular assembly patterns of zinc tetra(4-pyridyl)porphyrin into discrete (0D) cyclic tetrameric oligomers and polymeric 2D square-grids by self-coordination have been revealed.