Tailoring new bisphenol a ethoxylated shape memory polyurethanes

Shape memory polyurethanes (SMPUs) have generated great attention because of their unique properties. These properties are result of a particular molecular structure consisting of flexible molecular chains with low glass transition temperatures alternating with hard urethane segments. In this field, bisphenol A (BA) has been used for a long time as chain extender due to the good properties of the obtained SPMU materials. Nevertheless, the high toxicity of this compound has caused a high decrease on its use. For this reason, it has been selected a lower toxicity compound, bisphenol A ethoxylate (BAE). In this work, it is described a new SMPUs based on BAE and the influence of the hard segment on the thermo-mechanical properties and shape memory capacity. For that, both the proportion of the components and the diisocyanate employed (2,4-toluene diisocyanate (TDI), 4,4′-methylene bis(phenylisocyanate) (MDI) or a TDI/MDI mixture) have been modified. Then, depending on the molecular architecture achieved, the polyurethanes present different properties, which were studied by different techniques, such as thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and dynamic-mechanical thermal analysis (DMTA). It has been observed that glass transition temperature (T_g) increases as the hard phase content in the PU samples increases. In addition, T_g-MDI > T_g-MDI-TDI > T_g-TDI, so it is possible to control the T_g of the material, that is, shape memory transition temperature varying the diisocyanate. Finally, the shape memory capacity of the PUs was evaluated by thermo-mechanical analysis (TMA). All the synthesized PUs have shown good shape memory effect with fixation ratios up to 80% and recovery ratios close to 100%.     

氨气/甲烷贫预混旋转湍流火焰稳定性及NO生成

为了研究氨气/甲烷掺混燃气在贫预混旋转湍流状态下的火焰稳定性及NO的排放特性,设计建造了一个可视化的旋转湍流燃烧装置,开展了一系列的实验测量研究。研究表明：随着当量比增大,氨气火焰稳定燃烧的范围有所扩大,但当氨气掺混比大于0.60时火焰出现上下振荡现象,继续增加将导致火焰吹熄;NO的排放水平随当量比增加而提高;但在相同的当量比下,NO的排放随氨气掺混比的增加先升高再下降。此外,分别采用化学反应器网络（CRN）方法和一维层流预混火焰计算方法,对相应的火焰状态进行了数值计算分析,虽然计算结果与实验结果误差较大,但其预测的NO排放特性随氨气掺混比、当量比的变化趋势是一致的,对三者之间误差的来源进行了分析。     

Influence of chemical structure of hardener on mechanical and adhesive properties of epoxy polymers

The mechanical and adhesive properties of epoxy formulations based on diglycidyl ether of bisphenol A cured with various aliphatic amines were evaluated in the glass state. Impact and uniaxial compression tests were used to determine the impact energy, elastic modulus and yield stress, respectively. The adhesion tests were carried out in steel–steel joints using single‐lap shear, T‐peel, and impact adhesive joints geometry. The better mechanical and adhesive behavior of the networks is obtained when exists high flexibility of chain between crosslink and/or high elastic modulus. The 1‐(2‐aminoethyl)piperazine epoxy network presents the best adhesive properties, high flexibility, and the largest impact energy. However, it possesses low elastic modulus and yield stress. Also, exhibits increases in peel strength and impact energy while reductions in lap shear strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Novel Monocyclam Derivatives as HIV Entry Inhibitors: Design,Synthesis, Anti‐HIV Evaluation,and Their Interaction with the CXCR4 Co‐receptor

The CXCR4 receptor has been shown to interact with the human immunodeficiency virus (HIV) envelope glycoprotein gp120, leading to fusion of viral and cell membranes. Therefore, ligands that can attach to this receptor represent an important class of therapeutic agents against HIV, thus inhibiting the first step in the cycle of viral infection: the virus–cell entry/fusion. Herein we describe the in silico design, synthesis, and biological evaluation of novel monocyclam derivatives as HIV entry inhibitors. In vitro activity testing of these compounds in cell cultures against HIV strains revealed EC₅₀ values in the low micromolar range without cytotoxicity at the concentrations tested. Docking and molecular dynamics simulations were performed to predict the binding interactions between CXCR4 and the novel monocyclam derivatives. A binding mode of these compounds is proposed which is consistent with the main existing site‐directed mutagenesis data on the CXCR4 co‐receptor. Moreover, molecular modeling comparisons were performed between these novel monocyclams, previously reported non‐cyclam compounds from which the monocyclams are derived, and the well‐known AMD3100 bicyclam CXCR4 inhibitors. Our results suggest that these three structurally diverse CXCR4 inhibitors bind to overlapping but not identical amino acid residues in the transmembrane regions of the receptor.     

Performance of selected anion exchange resins for the treatment of a high DOC content surface water

The objective of this study was first to compare the performance of four strong anion exchange resins (AERs) (MIEX from Orica Pty Ltd, DOWEX-11 and DOWEX-MSA from DOW chemical and IRA-938 from Rohm and Haas) for their application in drinking water treatment (natural organic matter (NOM), mineral anions (nitrate, sulfate and bromide) and pesticide removal) using bench-scale experimental procedures on a high DOC content surface water. The efficiency of MIEX for NOM and mineral anions removal was furthermore evaluated using bench-scale dose-response experiments on raw, clarified and post-ozonated waters. NOM removal was assessed using the measurement of dissolved organic carbon (DOC), UV absorbance at 254 nm (UV254) and the use of high-performance size exclusion chromatography with UV (HPSEC/UV) and fluorescence detection (HPSEC/FLUO). The MIEX and IRA938 anionic resins exhibit a faster removal of NOM and mineral anions compared to the DOWEX11 and MSA AERs. All the resins were found to be very effective with similar performances after 30 to 45 min of contact time. As expected, only limited sorption of atrazine and isoproturon (C0=1 microg/L) occurred with MIEX, DOWEX11 and MSA AERs. MIEX resin proved to be very efficient in eliminating NOM of high-molecular weight but also a large part of the smallest UV absorbing organic compounds which were refractory to coagulation/flocculation treatment. Remaining DOC levels after 30 min of contact with MIEX were found similar in raw water, clarified water and even post-ozonated water implying no DOC benefit can be gained by employing conventional treatment prior to MIEX treatment. Removal of bromide (initial concentration 110 microg/L) was also observed and ranged from 30% to 65% for resin dose increasing from 2 to 8 mL/L. T     

Composition of a protein-like fluorophore of dissolved organic matter in coastal wetland and estuarine ecosystems

This study demonstrates the compositional heterogeneity of a protein-like fluorescence emission signal (T-peak; excitation/emission maximum at 280/325 nm) of dissolved organic matter (DOM) samples collected from subtropical river and estuarine environments. Natural water samples were collected from the Florida Coastal Everglades ecosystem. The samples were ultrafiltered and excitation-emission fluorescence matrices were obtained. The T-peak intensity correlated positively with N concentration of the ultrafiltered DOM solution (UDON), although, the low correlation coefficient (r(2)=0.140, p<0.05) suggested the coexistence of proteins with other classes of compounds in the T-peak. As such, the T-peak was unbundled on size exclusion chromatography. The elution curves showed that the T-peak was composed of two compounds with distinct molecular weights (MW) with nominal MWs of about >5 x 10(4) (T(1)) and approximately 7.6 x 10(3) (T(2)) and with varying relative abundance among samples. The T(1)-peak intensity correlated strongly with [UDON] (r(2)=0.516, p<0.001), while T(2)-peak did not, which suggested that the T-peak is composed of a mixture of compounds with different chemical structures and ecological roles, namely proteinaceous materials and presumably phenolic moieties in humic-like substances. Natural source of the latter may include polyphenols leached from senescent plant materials, which are important precursors of humic substances. This idea is supported by the fact that polyphenols, such as gallic acid, an important constituent of hydrolysable tannins, and condensed tannins extracted from red mangrove (Rhizophora mangle) leaves exhibited the fluorescence peak in the close vicinity of the T-peak (260/346 and 275/313 nm, respectively). Based on this study the application of the T-peak as a proxy for [DON] in natural waters may have limitations in coastal zones with significant terrestrial DOM input.     

Use of an environmental specimen bank for evaluating the impact of the Prestige oil spill on the levels of trace elements in two species of Fucus on the coast of Galicia (NW Spain)

In the present study we investigated possible contamination by trace elements due to the oil slick caused by the shipwreck of the Prestige oil tanker, in two species of brown macroalgae (Fucus vesiculosus and Fucus ceranoides) collected from the coastal area most severely affected by the spill (Galicia, NW Spain). The oil slick apparently did not cause significant increases in the concentrations of the trace elements studied, except vanadium. It appears that the magnitude of terrestrial inputs to coastal waters is sufficiently high to mask the inputs of trace elements from the fuel. The observed exception of V suggests that bioaccumulation of this element by the two species of Fucus may be used to indicate exposure to petrochemical products similar to the Prestige fuel. The findings of the study are another example of the importance of the existence of Environmental Specimen Banks for studies of this type.     

Persistent, bioaccumulative and toxic substances in fish: human health considerations

Fish are important dietary items that provide essential nutrients. Fish however, bioaccumulate monomethyl mercury (MMHg) and organo-halogenated pollutants (OHP) that are persistent bioaccumulative and toxic substances (PBTS). Unlike man-made OHP, MMHg is mainly of natural origin but background concentrations of aquatic systems are determined by the environmental Hg-methylating potential. Industrial activities can modulate environmental discharges and fish bioaccumulation of PBTS. Fish and seafood consumption are associated with human body load of PBTS, but farming practices that utilize fishmeal increase the terrestrial food chain resulting in farm-animal accumulation of PBTS. These substances are neurotoxic and endocrine active that can impact humans and wild life, but chemical characteristics of MMHg and OHP modulate interactions with animal tissues. MMHg is protein reactive with a faster metabolism (months) than OHP that are stored and slowly (years) metabolized in fat tissues. Except for brain-Hg, neither Hg nor OHP in tissues are markers of toxic effects; however, deficits in neurobehavioral test-scores of children have been shown in some fish-eating populations. These deficits are transient and within normal range, and are not prodromes of neurological diseases. Although population studies show that consumption of fish at current levels of contamination do not explain neurological disorders, endocrine activity remains controversial. Understanding risk of hazard caused by fish-PBTS consumption requires a wide range of expertise. We discuss chemical, toxic, metabolic, and ecological characteristics associated with PBTS in fish. There are proven health outcome derived from fish consumption, while risk of exposure to avoidable PBTS is a chance that can be minimized by societal actions.     

Influence of the character of NOM on the ozonation of MIB and geosmin

Tastes and odours (T&Os) are a major concern in drinking water as they are not efficiently removed by conventional water treatment. Ozonation has been effective for their destruction in some studies. However, the natural organic matter (NOM) in waters can affect the ozonation process and subsequently affect the destruction of T&Os. Five NOM fractions were isolated and ozonated in synthetic waters. The fraction containing the more highly coloured, higher molecular weight compounds exhibited the highest ozone (O3) demand, whereas the low aromatic fraction exhibited the lowest O3 demand. The character of the NOM fractions influenced the ozonation of MIB and geosmin. The destruction of MIB and geosmin was significantly higher in the fraction with the highest colour and UV/visible absorbance at all O3 doses. The destruction of the compounds in the other fractions showed the same trends, increasing MIB and geosmin destruction with increasing UV/visible absorbing character of the NOM. MIB was also ozonated in two real waters. with results showing a competing effect between NOM concentration and NOM character. The O3 reaction time was shown to be important for the destruction of both compounds.