Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Characterization of Primary Amine End-Functionalized Polystyrene and Poly(methyl methacrylate) Synthesized by Living Anionic Polymerization Techniques

The reaction of living anionic polymers with 2,2,5,5-tetramethyl-1-(3-bromopropyl)-1-aza-2,5- disilacyclopentane (1) was investigated using coupled thin layer chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Structures of byproducts as well as the major product were determined. The anionic initiator having a protected primary amine functional group, 2,2,5,5-tetramethyl- 1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane (2), was synthesized using all-glass high-vacuum techniques, which allows the long-term stability of this initiator to be maintained. The use of 2 in the preparation of well-defined aliphatic primary amine R-end-functionalized polystyrene and poly(methyl methacrylate) was investigated. Primary amino R-end-functionalized poly(methyl methacrylate) can be obtained near-quantitatively by reacting 2 with 1,1-diphenylethylene in tetrahydrofuran at room temperature prior to polymerizing methyl methacrylate at -78 °C. When 2 is used to initiate styrene at room temperature in benzene, an additive such as N,N,N',N'- tetramethylethylenediamine is necessary to activate the polymerization. However, although the resulting polymers have narrow molecular weight distributions and well-controlled molecular weights, our mass spectra data suggest that the yield of primary amine α-end-functionalized polystyrene from these syntheses is very low. The majority of the products are methyl α-end-functionalized polystyrene.

Well-Defined Poly(4-vinylbenzocyclobutene): Synthesis by Living Anionic Polymerization and Characterization

Living anionic polymerization of 4-vinylbenzocylobutene was performed in benzene at room temperature using sec-butyllithium as the initiator. Results of the kinetic studies indicated the termination- and transfer-free nature of the polymerization. Homopolymers with predictable molecular weights and narrow molecular weight distributions were produced, excluding the interference of the cyclobutene rings during initiation and propagation. Thermogravimetric analysis of poly(4-vinylbenzocyclobutene) in air showed a small weight gain at ~200 °C, a rapid decomposition at ~455 °C, and a gradual decomposition at ~566 °C. This behavior was attributed to the formation of radicals from the pendent benzocyclobutene functionality through o-quinodimethane intermediates and simultaneous decomposition/cross-linking reactions at high temperature. The living nature of the polymerization was also examined via sequential copolymerization with butadiene to form diblock copolymers.

Opening Remarks for Master Conservationist Presentations

It is a distinct honor for me to help recognize the 2003 Master Conservationists tonight. Tonight's event marks the 20th anniversary of the program sponsored by the Omaha World-Herald and the Institute of Agriculture and Natural Resources at the University of Nebraska-Lincoln.

Opening Comments Before Master Conservationist Presentations

It is a real pleasure to participate in this recognition program honoring the 2004 Master-Conservationists. We are grateful for the partnership with the Omaha World Herald in this unique program. In an effort to keep the program in tune with current developments in soil and waster conservation, a special committee is considering the idea of including conservation easements in the 2005 program. Some members of the committee are in the audience tonight. We appreciate the efforts of members of the Omaha World Herald, Natural Resources Districts, the USDA Natural-Resources Conservation Service and the Institute of Agriculture and Natural Resources in carrying out this program.

Deterministic Solutions for a Step-growth Polymerization

Chain topology, including branch node, chain link and cross-link dynamics that contribute to the number of elastically active strands and junctions, are calculated using purely deterministic derivations. Solutions are not coupled to population density distributions. An eigenzeit transformation assists in the conversion of expressions derived by chemical reaction principles from time to conversion space, yielding transport phenomena type expressions where the rate of change in the molar concentrations of branch nodes with respect to conversion is expressed as functions of the fraction of reactive sites on precursors and reactants. Analogies are hypothesized to exist in cross-linking space that effectively distribute branch nodes with i reacted moieties between cross-links having j bonds extending to the gel. To obtain solutions, reacted sites on nodes or links with finite chain extensions are examined in terms of stoichiometry associated with covalent bonding. Solutions replicate published results based on Miller and Macosko’s recursive procedure and results obtained from truncated weighted sums of population density distributions as suggested by Flory.

OPENING REMARKS - THIRD VERTEBRATE PEST CONFERENCE

To open this Third Vertebrate Pest Conference is a real privilege. It is a pleasure to welcome all of you in attendance, and I know there are others who would like to be meeting with us, but, for one reason or another cannot be. However, we can serve them by taking back the results of discussion and by making available the printed transactions of what is said here. It has been the interest and demand for the proceedings of the two previous conferen- ces which, along with personal contacts many of you have with the sponsoring committee, have gauged the need for continuing these meetings. The National Pest Control Association officers who printed the 1962 proceedings still are supplying copies of that conference. Two reprintings of the 1964 conference have been necessary and repeat orders from several universities indicate that those proceedings have become textbooks for special classes. When Dr. Howard mentioned in opening the first Conference in 1962 that publication of those papers would make a valuable handbook of animal control, he was prophetic, indeed. We are pleased that this has happened, but not surprised, since to many of us in this specialized field, the conferences have provided a unique opportunity to meet colleagues with similar interests, to exchange information on control techniques and to be informed by research workers of problem solving investigations as well as to hear of promising basic research. The development of research is a two-way street and we think these conferences also identify areas of inadequate knowledge, thereby stimulating needed research. We have represented here a number of types of specialists—animal ecologists, public health and transmissible disease experts, control methods specialists, public agency administration and enforcement staffs, agricultural extension people, manufacturing and sale industry representatives, commercial pest control operators, and others—and in addition to improving communications among these professional groups an equally important purpose of these conferences is to improve understanding between them and the general public. Within the term general public are many individuals and also organizations dedicated to appreciation and protection of certain animal forms or animal life in general. Proper concepts of vertebrate pest control do not conflict with such views. It is worth repeating for the record the definition of "vertebrate pest" which has been stated at our previous conferences. "A vertebrate pest is any native or introduced, wild or feral, non-human spe- cies of vertebrate animal that is currently troublesome locally or over a wide area to one or more persons either by being a general nuisance, a health hazard or by destroying food or natural resources. In other words, vertebrate pest status is not an inherent quality or fixed classification but is a circumstantial relationship to man's interests." I believe progress has been made in reducing the misunderstanding and emotion with which vertebrate pest control was formerly treated whenever a necessity for control was stated. If this is true, I likewise believe it is deserved, because control methods and programs have progressed. Control no longer refers only to population reductions by lethal means. We have learned something of alternate control approaches and the necessity for studying the total environment; where reduction of pest animal numbers is the required solution to a problem situation we have a wider choice of more selective, safe and efficient materials. Although increased attention has been given to control methods, research when we take a close look at the severity of animal damage to so many facets of our economy, particularly to agricultural production and public health, we realize it still is pitifully small and slow. The tremendous acceleration of the world's food and health requirements seems to demand expediting vertebrate pest control to effectively neutralize the enormous impact of animal damage to vital resources. The efforts we are making here at problem delineation, idea communication and exchange of methodology could well serve as both nucleus and rough model for a broader application elsewhere. I know we all hope this Third Conference will advance these general objectives, and I think there is no doubt of its value in increasing our own scope of information.

Marine Fungi Aspergillus sydowii and Trichoderma sp Catalyze the Hydrolysis of Benzyl Glycidyl Ether

Whole cells of the marine fungi Aspergillus sydowii Gc12, Penicillium raistrickii Ce16, P. miczynskii Gc5, and Trichoderma sp. Gc1, isolated from marine sponges of the South Atlantic Ocean (Brazil), have been screened for the enzymatic resolution of (+/-)-2-(benzyloxymethyl)oxirane (benzyl glycidyl ether; 1). Whole cells of A. sydowii Gc12 catalyzed the enzymatic hydrolysis of (R,S)-1 to yield (R)-1 with an enantiomeric excess (ee) of 24-46% and 3-(benzyloxy)propane-1,2-diol (2) with ee values < 10%. In contrast, whole cells of Trichoderma sp. Gc1 afforded (S)-1 with ee values up to 60% and yields up to 39%, together with (R)-2 in 25% yield and an ee of 32%. This is the first published example of the hydrolysis of 1 by whole cells of marine fungi isolated from the South Atlantic Ocean. The hydrolases from the two studied fungi exhibited complementary regioselectivity in opening the epoxide ring of racemic 1, with those of A. sydowii Gc12 showing an (S) preference and those of Trichoderma sp. Gc1 presenting an (R) preference for the substrate.

Polymerization kinetics and reactivity of alternative initiators systems for use in light-activated dental resins

Objectives. The purpose of this study was to evaluate the reactivity and polymerization kinetics behavior of a model dental adhesive resin with water-soluble initiator systems. Methods. A monomer blend based on Bis-GMA, TEGDMA and HEMA was used as a model dental adhesive resin, which was polymerized using a thioxanthone type (QTX) as a photoinitiator. Binary and ternary photoinitiator systems were formulated using 1 mol% of each initiator. The co-initiators used in this study were ethyl 4-dimethylaminobenzoate (EDAB), diphenyliodonium hexafluorophosphate (DPIHFP), 1,3-diethyl-2-thiobarbituric acid (BARB), p-toluenesulfinic acid and sodium salt hydrate (SULF). Absorption spectra of the initiators were measured using a UV-Vis spectrophotometer, and the photon absorption energy (PAE) was calculated. The binary system camphorquinone (CQ)/amine was used as a reference group (control). Twelve groups were tested in triplicate. Fourier-transform infrared spectroscopy (FTIR) was used to investigate the polymerization reaction during the photoactivation period to obtain the degree of conversion (DC) and maximum polymerization rate (R-p(max)) profile of the model resin. Results. In the analyzed absorption profiles, the absorption spectrum of QTX is almost entirely localized in the UV region, whereas that of CQ is in the visible range. With respect to binary systems, CQ + EDAB exhibited higher DC and R-p(max) values. In formulations that contained ternary initiator systems, the group CQ + QTX + EDAB was the only one of the investigated experimental groups that exhibited an R-p(max) value greater than that of CQ + EDAB. The groups QTX + EDAB + DPIHFP and QTX + DPIHFP + SULF exhibited values similar to those of CQ + EDAB with respect to the final DC; however, they also exhibited lower reactivity. Significance. Water-soluble initiator systems should be considered as alternatives to the widely used CQ/amine system in dentin adhesive formulations. (C) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

A comparative study between crack analysis and a mechanical test for assessing the polymerization stress of restorative composites

Objectives. To verify the hypothesis that crack analysis and a mechanical test would rank a series of composites in a similar order with respect to polymerization stress. Also, both tests would show similar relationships between stress and composite elastic modulus and/or shrinkage. Methods. Soda-lime glass discs (2-mm thick) with a central perforation (3.5-mm diameter) received four Vickers indentations 500 mu m from the cavity margin. The indent cracks were measured (500x) prior and 10 min after the cavity was restored with one of six materials (Kalore/KL, Gradia/GR, Ice/IC, Wave/WV, Majesty Flow/MF, and Majesty Posterior/MP). Stresses at the indent site were calculated based on glass fracture toughness and increase in crack length. Stress at the bonded interface was calculated using the equation for an internally pressurized cylinder. The mechanical test used a universal testing machine and glass rods (5-mm diameter) as substrate. An extensometer monitored specimen height (2 mm). Nominal stress was calculated dividing the maximum shrinkage force by the specimen cross-sectional area. Composite elastic modulus was determined by nanoindentation and post-gel shrinkage was measured using strain gages. Data were subjected to one-way ANOVA/Tukey or Kruskal-Wallis/Mann-Whitney tests (alpha: 5%). Results. Both tests grouped the composites in three statistical subsets, with small differences in overlapping between the intermediate subset (MF, WV) and the highest (MP, IC) or the lowest stress materials (KL, GR). Higher stresses were developed by composites with high modulus and/or high shrinkage. Significance. Crack analysis demonstrated to be as effective as the mechanical test to rank composites regarding polymerization stress. (c) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

A comparative evaluation of polymerization stress data obtained with four different mechanical testing systems

Objectives. The null hypothesis was that mechanical testing systems used to determine polymerization stress (sigma(pol)) would rank a series of composites similarly. Methods. Two series of composites were tested in the following systems: universal testing machine (UTM) using glass rods as bonding substrate, UTM/acrylic rods, "low compliance device", and single cantilever device ("Bioman"). One series had five experimental composites containing BisGMA:TEGDMA in equimolar concentrations and 60, 65, 70, 75 or 80 wt% of filler. The other series had five commercial composites: Filtek Z250 (3M ESPE), Filtek A110 (3M ESPE), Tetric Ceram (Ivoclar), Heliomolar (Ivoclar) and Point 4 (Kerr). Specimen geometry, dimensions and curing conditions were similar in all systems. sigma(pol) was monitored for 10 min. Volumetric shrinkage (VS) was measured in a mercury dilatometer and elastic modulus (E) was determined by three-point bending. Shrinkage rate was used as a measure of reaction kinetics. ANOVA/Tukey test was performed for each variable, separately for each series. Results. For the experimental composites, sigma(pol) decreased with filler content in all systems, following the variation in VS. For commercial materials, sigma(pol) did not vary in the UTM/acrylic system and showed very few similarities in rankings in the others tests system. Also, no clear relationships were observed between sigma(pol) and VS or E. Significance. The testing systems showed a good agreement for the experimental composites, but very few similarities for the commercial composites. Therefore, comparison of polymerization stress results from different devices must be done carefully. (c) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

The influence of "C-factor" and light activation technique on polymerization contraction forces of resin composite

Objectives: This study evaluated the influence of the cavity configuration factor ("C-Factor") and light activation technique on polymerization contraction forces of a Bis-GMA-based composite resin (Charisma, Heraeus Kulzer). Material and Methods: Three different pairs of steel moving bases were connected to a universal testing machine (Emic DL 500): groups A and B - 2x2 mm (CF=0.33), groups C and D - 3x2 mm (CF=0.66), groups E and F - 6x2 mm (CF=1.5). After adjustment of the height between the pair of bases so that the resin had a volume of 12 mm(3) in all groups, the material was inserted and polymerized by two different methods: pulse delay (100 mW/cm(2) for 5 s, 40 s interval, 600 mW/cm(2) for 20 s) and continuous pulse (600 mW/cm(2) for 20 s). Each configuration was light cured with both techniques. Tensions generated during polymerization were recorded by 120 s. The values were expressed in curves (Force(N) x Time(s)) and averages compared by statistical analysis (ANOVA and Tukey's test, p<0.05). Results: For the 2x2 and 3x2 bases, with a reduced C-Factor, significant differences were found between the light curing methods. For 6x2 base, with high C-Factor, the light curing method did not influence the contraction forces of the composite resin. Conclusions: Pulse delay technique can determine less stress on tooth/restoration interface of adhesive restorations only when a reduced C-Factor is present.

Characterization of depolymerized residues from extremely low acid hydrolysis (ELA) of sugarcane bagasse cellulose: Effects of degree of polymerization, crystallinity and crystallite size on thermal decomposition

Sugarcane bagasse cellulose was subjected to the extremely low acid (ELA) hydrolysis in 0.07% H2SO4 at 190, 210 and 225 degrees C for various times. The cellulose residues from this process were characterized by TGA, XRD, GPC, FIR and SEM. A kinetic study of thermal decomposition of the residues was also carried out, using the ASTM and Kissinger methods. The thermal studies revealed that residues of cellulose hydrolyzed at 190, 210 and 225 degrees C for 80,40 and 8 min have initial decomposition temperature and activation energy for the main decomposition step similar to those of Avicel PH-101. XRD studies confirmed this finding by showing that these cellulose residues are similar to Avicel in crystallinity index and crystallite size in relation to the 110 and 200 planes. FTIR spectra revealed no significant changes in the cellulose chemical structure and analysis of SEM micrographs demonstrated that the particle size of the cellulose residues hydrolyzed at 190 and 210 degrees C were similar to that of Avicel. (C) 2011 Elsevier B.V. All rights reserved.

Fiber Post Cementation Strategies: Effect of Mechanical Cycling on Push-out Bond Strength and Cement Polymerization Stress

Purpose: To evaluate the effect of mechanical cycling and cementation strategies on the push-out bond strength between fiber posts and root dentin and the polymerization stresses produced using three resin cements. Materials and Methods: Eighty bovine mandibular teeth were sectioned to a length of 16 mm, prepared to 12 mm, and embedded in self-curing acrylic resin. The specimens were then distributed into 8 groups (n = 10): Gr1 - Scotchbond Multi Purpose + RelyX ARC; Gr2 - Scotchbond Multi Purpose + RelyX ARC + mechanical cycling; Gr3 - AdheSE + Multilink Automix; Gr4 - AdheSE + Multilink Automix + mechanical cycling; Gr5 - phosphoric acid + RelyX U100 (self-adhesive cement); Gr6 - phosphoric acid+ RelyX U100 + mechanical cycling; Gr7 - RelyX U100; Gr8 - RelyX U100 + mechanical cycling. The values obtained from the push-out bond strength test were submitted to two-way ANOVA and Tukey's test (p = 0.05), while the values obtained from the polymerization stress test were subjected to one-way ANOVA and Tukey's test (alpha = 0.05). Results: Mechanical cycling did not affect the bond strength values (p = 0.236), while cementation strategies affected the push-out bond strength (p < 0.001). Luting with RelyX U100 and Scotch Bond Multi Purpose + RelyX ARC yielded higher push-out bond strength values. The polymerization stress results were affected by the factor "cement" (p = 0.0104): the self-adhesive cement RelyX U100 exhibited the lowest values, RelyX ARC resulted in the highest values, while Multi link Automix presented values statistically similar to the other two cements. Conclusion: The self-adhesive cement appears to be a good alternative for luting fiber posts due to the high push-out bond strengths and lower polymerization stress values.

Steam reforming of ethanol for hydrogen production on Co/CeO²-ZRO² catalysts prepared by polymerization method

Catalysts containing 10%Co supported on CexZr1-xO2 (0 < x < 1) were applied to ethanol steam reforming reactions. The catalysts were characterized by Raman spectroscopy, XANES-H-2 and DRS-UV-Vis. The catalytic tests were conducted at 673, 773 and 873 K, with molar ratios of H2O:ethanol = 3:1. The ethanol conversion and H-2 selectivity were temperature dependent and the association of CeO2 with ZrO2 in the support led to show a low formation of CO, due to the higher mobility of oxygen. (C) 2012 Elsevier B.V. All rights reserved.

Supracerebellar transtentorial approach-resection of the tentorium instead of an opening-to provide broad exposure of the mediobasal temporal lobe: anatomical aspects and surgical applications Clinical article

Object. The aim of this study was to describe the surgical anatomy of the mediobasal aspect of the temporal lobe and the supracerebellar transtentorial (SCTT) approach performed not with an opening, but with the resection of the tentorium, as an alternative route for the neurosurgical management of vascular and tumoral lesions arising from this region. Methods. Cadaveric specimens were used to illustrate the surgical anatomy of the mediobasal region of the temporal lobe. Demographic aspects, characteristics of lesions, clinical presentation, surgical results, follow-up findings, and outcomes were retrospectively reviewed for patients referred to receive the SCTT approach with tentorial resection. Results. Ten patients (83%) were female and 2 (17%) were male. Their ages ranged from 6 to 59 years (mean 34.5 +/- 15.8 years). All lesions (3 posterior cerebral artery aneurysms, 3 arteriovenous malformations, 3 cavernous malformations, and 3 tumors) were completely excluded or resected. After a mean follow-up period of 143 months (range 10-240 months), the mean postoperative Glasgow Outcome Scale score was 4.9. Conclusions. Knowledge of the surgical anatomy provides improvement for microsurgical approaches. The evolution from a small opening to a resection of the tentorium absolutely changed the exposure of the mediobasal aspect of the temporal lobe. The SCTT approach with tentorial resection is an excellent alternative route to the posterior part of mediobasal aspect of the temporal lobe, and it was enough to achieve the best neurosurgical management of tumoral and vascular lesions located in this area. (http://thejns.org/doi/abs/10.3171/2011.12.JNS111256)