Poly(acrylate‐b‐styrene‐b‐isobutylene‐b‐styrene‐b‐acrylate) Block Copolymers via Carbocationic and Atom Transfer Radical Polymerizations

A series of polyacrylate‐polystyrene‐polyisobutylene‐polystyrene‐polyacrylate (X‐PS‐PIB‐PS‐X) pentablock terpolymers (X=poly(methyl acrylate) (PMA), poly(butyl acrylate) (PBA), or poly(methyl methacrylate) (PMMA)) was prepared from poly (styrene‐b‐isobutylene‐b‐styrene) (PS‐PIB‐PS) block copolymers (BCPs) using either a Cu(I)Cl/1,1,4,7,7‐pentamethyldiethylenetriamine (PMDETA) or Cu(I)Cl/tris[2‐(dimethylamino)ethyl]amine (Me₆TREN) catalyst system. The PS‐PIB‐PS BCPs were prepared by quasiliving carbocationic polymerization of isobutylene using a difunctional initiator, followed by the sequential addition of styrene, and were used as macroinitiators for the atom transfer radical polymerization (ATRP) of methyl acrylate (MA), n‐butyl acrylate (BA), or methyl methacrylate (MMA). The ATRP of MA and BA proceeded in a controlled fashion using either a Cu(I)Cl/PMDETA or Cu(I)Cl/Me₆TREN catalyst system, as evidenced by a linear increase in molecular weight with conversion and low PDIs. The polymerization of MMA was less controlled. ¹H‐NMR spectroscopy was used to elucidate pentablock copolymer structure and composition. The thermal stabilities of the pentablock copolymers were slightly less than the PS‐PIB‐PS macroinitiators due to the presence of polyacrylate or polymethacrylate outer block segments. DSC analysis of the pentablock copolymers showed a plurality of glass transition temperatures, indicating a phase separated material.     

Al2O3/K2O-containing non-stoichiometric lithium disilicate-based glasses

The crystallisation kinetics of experimental glasses in 3 different systems: (A) Li₂O–SiO₂, (B) Li₂O–Al₂O₃–SiO₂ and (C) Li₂O–K₂O–Al₂O₃–SiO₂ were studied under non-isothermal conditions. The DTA results revealed a stronger tendency to crystallisation of binary compositions in comparison to the ternary and quaternary compositions comprising Al₂O₃ and K₂O which present the lower crystallisation, i.e. the crystallisation propensity follows the trend A > B > C. The devitrification process in the Li₂O–SiO₂ and Li₂O–Al₂O₃–SiO₂ systems began earlier and the rate was higher in comparison to that of glasses in the quaternary Li₂O–K₂O–Al₂O₃–SiO₂ system. Thus, addition of Al₂O₃ and K₂O to glasses of Li₂O–SiO₂ system was demonstrated to promote glass stability against crystallisation. However, the activation energy for crystallisation was shown to depend also on the SiO₂/Li₂O ratio with the binary system showing a decreasing trend with increasing SiO₂/Li₂O ratio, while the opposite tendency was being observed for compositions with added Al₂O₃ and K₂O.     

A close analysis of metal-enhanced fluorescence of tryptophan induced by silver nanoparticles: wavelength emission dependence

In the last few years, silver nanoparticles have been proposed as a promising alternative for the label-free detection of proteins via metal-enhanced fluorescence. Generally, the aromatic amino acid tryptophan is most frequently used in this type of studies, because the intrinsic fluorescence of proteins is usually dominated by tryptophan emissions. In the present study, we evaluated the fluorescence behavior of tryptophan in the presence of a silver colloid with nanoparticles of 100 nm in diameter. The results showed that a nanoparticles concentration of 32 mg L^?1 induced maximum fluorescence enhancement. However, the metal-enhanced fluorescence was dependent on the emission wavelength of tryptophan, and this phenomenon was closely related to the metal surface reabsorption process (inner filter effect), suggesting that the plasmon resonance reabsorption effect should be taken into account in analyses involving protein studies by metal-enhanced fluorescence.     

Simple Reduction of Heteroaromatic Esters to Alcohols Using a Sodium Borohydride–Methanol System

Some heteroaromatic esters were reduced to the corresponding alcohols by using a sodium borohydride–methanol system. The reduction was completed within 0.15–2.0 h in refluxing THF. The alcohol products were isolated after aqueous workup in moderate to excellent yield (48–97%).     

Sonochemical Formation of Iodohydrin and Epoxide from Cyclohexene

Ultrasonic irradiation substantially improves the reaction of cyclohexene with I₂ in aqueous dioxane in the presence of Cu(OAc)₂ · H₂O to generate the expected iodohydrin in high yield. The product undergoes cyclization to the epoxide by biphasic treatment with either Na₂CO₃ or KOH in a sonication‐sensitive step.     

Thermal and photochemical effects on the structure,morphology, thermal and optical properties of PVA/Ni0.04Zn0.96O and PVA/Fe0.03Zn0.97O nanocomposite films

Ni_0.04Zn_0.96O and Fe_0.03Zn_0.97O with average diameter of 23 and 19 nm, respectively, have been synthesized by a modified sol–gel method to be used in the preparation of (100 − x)/x poly(vinyl alcohol)/oxide nanocomposite films, with x = 0, 1, 3 and 5 (in wt.%). A 125 W-Hg vapor lamp with emission above 254 nmwas used to irradiate PVA/Ni_0.04Zn_0.96O and PVA/Fe_0.03Zn_0.97O films. The effect on their structural, thermal, morphological and optical properties was studied by TG, DSC, DRX, AFM, UV–vis and PL spectrophotometry. The Ni_0.04Zn_0.96O addition on PVA films decreases the thermal stability of the polymer in inert and in oxidative atmosphere. In contrast, the Fe_0.03Zn_0.97O presence in the PVA films seems to increase the thermal stability of the polymer. The characteristic peak of the crystalline phase of PVA and wurtzite phase of the zinc oxide were identified through X-ray diffraction in both films. The crystallinity of the PVA film increases with UV irradiation and with the presence of Ni_0.04Zn_0.96O and Fe_0.03Zn_0.97O. The roughness of the PVA film was not modified by the addition of the doped oxides; however, it increases after UV irradiation, more significantly in the films containing the oxides. The PVA film exhibits absorption around 280 nm characteristic of π–π^∗ transitions related to carbonyl groups from residuals acetate, while the 95/05 PVA/Ni_0.04Zn_0.96O and 95/05 PVA/Fe_0.03Zn_0.97O nanocomposite films show absorption at the visible region which is characteristics of the band gap reduction of the doped oxides. The photoluminescence of PVA was modified by the presence of the oxides in the film. These nanocomposite films are interesting due to their thermal, mechanical (flexible) properties and low cost of production. In addition they are also able to exhibit peculiar optical properties showing potential to be used in photonic devices, gas sensors and organic solar cell applications.     

Radiolabeling of low molecular weight d-galactose-based glycodendrimer with technetium-99m and biodistribution studies

Glycodendrimers are neoglycoconjugates that can be considered as bioisosters of glycoproteins, since they can mimic the multivalent interactions of lectin-carbohydrate. The ability of glycodendrimers to present multivalent interactions with lectins as compared to a monovalent ligand is referred to as “cluster effect”. It is expected that, because of the cluster effect, glycodendrimers would result in a better association with lectins than mono-carbohydrate anchored systems. Radioisotopes are useful to evaluate biodistribution of molecules. This study is important to obtain information about molecule–receptor interactions. Indeed, such study can provide an exquisite tool to evaluate the affinity of certain molecules to specific areas in the body, leading to the development of new radiopharmaceuticals and/or drug delivery systems. Herein, we describe a d-galactose coated low molecular weight PAMAM G0 dendrimer that was successfully radiolabeled with technetium-99m. Biodistribution studies and scintigraphic images were performed in healthy mice. It was observed high liver uptake which was significantly reduced in blocking studies, indicating hepatic specificity. Therefore, low molecular weight glycodendrimer can be considered as useful platform for selective targeting of drugs to the liver and to assess hepatic function.     

The Effect of Biomass Immobilization Support Material and Bed Porosity on Hydrogen Production in an Upflow Anaerobic Packed-Bed Bioreactor

The aim of this study was to investigate the effect of the support material used for biomass attachment and bed porosity on the potential generation of hydrogen gas in an anaerobic bioreactor treating low-strength wastewater. For this purpose, an upflow anaerobic packed-bed (UAPB) reactor fed with sucrose-based synthetic wastewater was used. Three reactors with various support materials (expanded clay, vegetal coal, and low-density polyethylene) were operated for hydraulic retention time (HRT) of 0.5 and 2 h. Based on the results obtained, three further reactors were operated with low-density polyethylene as a material support using various bed porosities (91, 75, and 50 %) for an HRT of 0.5 h. The UAPB reactor was found to be a feasible technology for hydrogen production, reaching a maximum substrate-based hydrogen yield of 7 mol H₂ mol^?1 sucrose for an HRT of 0.5 h. The type of support material used did not affect hydrogen production or the microbial population inside the reactor. Increasing the bed porosity to 91 % provided a continuous and cyclic production of hydrogen, whereas the lower bed porosities resulted in a reduced time of hydrogen production due to biomass accumulation, which resulted in a decreasing working volume.