Absolute Configuration of 4-Methyl-3-Heptanone and 4-Methyl-3-Heptanol from Mandibular Glands of Virgin Males and Females ofAtta sexdens rubropilosa

(S)-;(+)-4-Methyl-3-heptanone is the principal component in the secretion from the mandibular glands of unmated and mated males and females ofAtta sexdens rubropilosa. In mated and unmated females, it is essentially the only component in the glandular secretion. In unmated males up to 50% of the secretion is a mixture of (3S, 4S)- and (3R, 4S)-4-methyl-3-heptanol. After mating, the amount of alcohol in the males decreases markedly.     

Anticancer Potential of (Pentamethylcyclopentadienyl)chloridoiridium(III) Complexes Bearing κP and κP,κS‐Coordinated Ph2PCH2CH2CH2S(O)xPh (x=0–2) Ligands

Iridium(III) complexes of the type [Ir(η⁵‐C₅Me₅)Cl₂{Ph₂PCH₂CH₂CH₂S(O)_xPh‐κP}] (x=0–2; 1 – 3 ) and [Ir(η⁵‐C₅Me₅)Cl{Ph₂PCH₂CH₂CH₂S(O)_xPh‐κP,κS}][PF₆] (x=0–1; 4 and 5 ) with 3‐(diphenylphosphino)propyl phenyl sulfide, sulfoxide, and sulfone ligands Ph₂PCH₂CH₂CH₂S(O)_xPh were designed, synthesized, and characterized fully, including X‐ray diffraction analyses for complexes 3 and 4 . In vitro studies against human thyroid carcinoma (8505C), submandibular carcinoma (A253), breast adenocarcinoma (MCF‐7), colon adenocarcinoma (SW480), and melanoma (518A2) cell lines provided evidence for the high biological potential of the neutral and cationic iridium(III) complexes. Neutral iridium(III) complex 5 proved to be the most active, with IC₅₀ values up to about 0.1 μM , representing activities of up to one order of magnitude higher than cisplatin. Using 8505C cells, apoptosis was shown to be the main mechanism through which complex 5 exerts its tumoricidal action. The described iridium(III) complexes represent potential leads in the search for novel metal‐based anticancer agents.     

Photoluminescence decay rate of silicon nanoparticles modified with gold nanoislands

We investigated plasmon-assisted enhancement of emission from silicon nanoparticles (ncs-Si) embedded into porous SiO _x matrix in the 500- to 820-nm wavelength range. In the presence in the near-surface region of gold nanoisland film, ncs-Si exhibited up to twofold luminescence enhancement at emission frequencies that correspond to the plasmon resonance frequency of Au nanoparticles. Enhancement of the photoluminescence (PL) intensity was attributed to coupling with the localized surface plasmons (LSPs) excited in Au nanoparticles and to increase in the radiative decay rate of ncs-Si. It has been shown that spontaneous emission decay rate of ncs-Si modified by thin Au film over the wide emission spectral range was accelerated. The emission decay rate distribution was determined by fitting the experimental decay curves to the stretched exponential model. The observed increase of the PL decay rate distribution width for the Au-coated nc-Si-SiO _x sample in comparison with the uncoated one was explained by fluctuations in the surface-plasmon excitation rate.

PACS

78. 67. Bf; 78.55.-m     

Oxidative Stability and Changes in Chemical Composition of Extra Virgin Olive Oils After Short‐Term Deep‐Frying of French Fries

We aimed at investigating oxidative stability and changes in fatty acid and tocopherol composition of extra virgin olive oil (EVOO) in comparison with refined seed oils during short‐term deep‐frying of French fries, and changes in the composition of the French fries deep‐fried in EVOO. EVOO samples from Spain, Brazil, and Portugal, and refined seed oils of soybean and sunflower were studied. Oil samples were used for deep‐frying of French fries at 180 °C, for up to 75 min of successive frying. Tocopherol and fatty acid composition were determined in fresh and spent vegetable oils. Tocopherol, fatty acid, and volatile composition (by SPME–GC–MS) were also determined in French fries deep‐fried in EVOO. Oil oxidation was monitored by peroxide, acid, and p‐anisidine values, and by Rancimat after deep‐frying. Differential scanning calorimetry (DSC) analysis was used as a proxy of the quality of the spent oils. EVOOs presented the lowest degree of oleic and linoleic acids losses, low formation of free fatty acids and carbonyl compounds, and were highly stable after deep‐frying. In addition, oleic acid, tocopherols, and flavor compounds were transferred from EVOO into the French fries. In conclusion, EVOOs were more stable than refined seed oils during short‐term deep‐frying of French fries and also contributed to enhance the nutritional value, and possibly improve the flavor, of the fries prepared in EVOO.     

Engraftment of Prevascularized,Tissue Engineered Constructs in a Novel Rabbit Segmental Bone Defect Model

The gold standard treatment of large segmental bone defects is autologous bone transfer, which suffers from low availability and additional morbidity. Tissue engineered bone able to engraft orthotopically and a suitable animal model for pre-clinical testing are direly needed. This study aimed to evaluate engraftment of tissue-engineered bone with different prevascularization strategies in a novel segmental defect model in the rabbit humerus. Decellularized bone matrix (Tutobone) seeded with bone marrow mesenchymal stromal cells was used directly orthotopically or combined with a vessel and inserted immediately (1-step) or only after six weeks of subcutaneous “incubation” (2-step). After 12 weeks, histological and radiological assessment was performed. Variable callus formation was observed. No bone formation or remodeling of the graft through TRAP positive osteoclasts could be detected. Instead, a variable amount of necrotic tissue formed. Although necrotic area correlated significantly with amount of vessels and the 2-step strategy had significantly more vessels than the 1-step strategy, no significant reduction of necrotic area was found. In conclusion, the animal model developed here represents a highly challenging situation, for which a suitable engineered bone graft with better prevascularization, better resorbability and higher osteogenicity has yet to be developed.     

Leachability of degradation products from hard chairside reline resins in artificial saliva: Effect of water‐bath post‐polymerization treatment

The effect of a post‐polymerization treatment on the leaching of methacrylic acid (MA) and benzoic acid (BA) from the reline resins [Kooliner (K), New Truliner (N), Ufi Gel hard (U), and Tokuso Rebase Fast (T)] was evaluated. Specimens of each material were divided into two groups: Group C (control) – left untreated; Group WB (water‐bath) – immersion in water at 55 ± 1°C for 10 min. Specimens were placed in artificial saliva at 37 ± 1°C and, after 1‐, 3‐, 5‐, 24‐h and 3‐, 7‐, 14‐, and 30‐day intervals, aliquots were removed and analyzed using high performance liquid chromatography. Data were analyzed by using Wilcoxon, Mann–Whitney or Kruskal–Wallis tests (α = 0.05). At 1 h, the concentration of MA released from U control specimens was higher than those of the other ones, and decreased after 3 h. WB specimens released lower amounts of MA than control specimens only for material U, at the 1‐ and 3‐h periods. For all control specimens, concentrations of leached BA progressively decreased within 5 h and from 24 h to the end. WB specimens released significantly lower amounts of BA than did the control groups. The highest concentration of MA was leached from control specimens of Ufi Gel hard. Water‐bath post‐polymerization treatment caused a significant reduction in elution of BA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Characterization of a water-based paint for corrosion protection

Corrosion of steel rebars in reinforced concrete is one of the major problems in the construction industry. Carbonation reactions of concrete with carbon dioxide and, mainly, the chloride salts action are the main causes responsible for concrete degradation. Protective coatings help to improve the durability of concrete structures by acting as a physical barrier against the corrosion agents. Waterborne paints are usually used for concrete protection rather than solvent-based paints since they are less pollutant. The aim of this work is to investigate the influence of the pore size and porosity on the permeability of the paints films toward sodium chloride. Three characterization methods from membrane science were implemented to characterize paint coatings. The time-lag method was used to determine the permeability toward the sodium chloride and toward helium and argon, these for approximately 100% relative humidity. From the seven waterborne paints formulated, only one was found to be suitable for surface protection of reinforced concrete, since its permeability toward NaCl was smaller than 10⁻¹⁴ m² s⁻¹, the threshold value required by National Laboratory of Civil Engineering (LNEC) in Portugal. For the formulated paints, it was observed that the average pore size correlates well with the permeability toward sodium chloride. This is an important result since obtaining the permeability toward sodium chloride of corrosion protective paints is very time consuming, while the average pore size can be obtained in a much shorter time.     

IR-change and colour changes of long-oil air drying alkyd paints as a result of UV irradiation

In this study the formation of photo-oxidative species was studied by monitoring the changes in the FT-IR spectra and colour changes. To stabilize long-oil air drying alkyd paint, separate and synergistic influence of two stabilizers were used Uvasorb^®S28 as the UV-absorber and Uvasorb^®HA29 as the stabilizer which inhibits the degradation of some groups. In the presence of UV radiation (450 h, λ > 300 nm), the alkyd paint undergoes photodegradation with gradual change of its colour. The photochemical degradation of the alkyd paint is associated with an increase in the hydroxyl content and broadening of the absorption in the carbonyl region. Analysis of the colour changes in alkyd surface during photodegradation was carried out by measuring CIEL*a*b* colour components (L*, a*, b* and ΔE*). Overall, ΔE* colour change correlates well with photodegradation of alkyd paint by relative increase of the concentration of carbonyl and hydroxyl groups determinated by FT-IR measurements.     

Effect of amine-terminated butadiene-acrylonitrile/clay combinations on the structure and properties of epoxy nanocomposites

The effect of the clay content and the method of its combination with amine-terminated butadiene-acrylonitrile (ATBN) on the structure and behavior of epoxy was studied. In the case of the simultaneous addition of both components, the increasing clay content had a very small effect on the size of the reaction-induced phase separation-formed particles at 5% rubber content due to predominant elimination of two major clay effects, i.e., the nucleation due to phase separation and the kinetics. As a result, both the time window between the onset of phase separation and vitrification and the viscosity at the cloud point did not change significantly. The minor change in the particle size/clay content dependences with different curing temperatures indicates that the balance between the two clay effects shifted. The corresponding study of the mechanical behavior indicated that the best balanced mechanical properties were obtained at certain clay/ATBN ratios, and thus, there was synergy between the components. Similar mechanical parameters were obtained for the application of both components in the form of ATBN/montmorillonite intercalate. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Refractory Alkali-Free Cristobalite Glass-Ceramics: Activated Reaction Sinter-Crystallization Synthesis and Properties

A new approach for the synthesis of chemically stabilized β-cristobalite-like glass-ceramic materials is developed. It is based on an activated reaction sinter-crystallization process of compacted powder mixtures at relatively low temperatures (1400–1450°C) and short heat treatment times. To facilitate homogeneous dopant distribution and thus the formation of a high content of β_x-cristobalite-like phases, possessing a very low thermal expansion coefficient, the batch components are introduced in a chemically, mechanically, or thermally preactivated form. In this way, the high-temperature glass premelting usually employed in the “classical” synthesis of glass-ceramics is avoided. Using different, mutually complementary techniques of analysis it is revealed that optimal refractory properties are achieved with glass-ceramics containing α_x- and β_x-cristobalite solid solutions with close values of the lattice parameters. In this case, the transformation between these two cristobalite-like solid solutions proceeds instead by a first-order displacive transition, by a process exhibiting features characteristic for both a suppressed first-order phase change and a second-order λ-type phase transitions. The refractory properties of the glass-ceramic materials thus synthesized and the possibility to use various forming techniques open many fields for their application.