Green chemistry for the synthesis of methacrylate-based hydrogels crosslinked through Diels–Alder reaction

This study describes an environmentally friendly and green synthetic approach for the preparation of poly(aminoethylmethacrylate)-based hydrogels crosslinked through Diels–Alder (DA) reaction in water. This “click” reaction offers the possibility of preparing chemically crosslinked hydrogels in the absence of any catalyst, initiator or coupling agent, thus preserving the biocompatibility of the material. The suitable furan diene was obtained by modifying a methacrylate polymer by its reaction with furfural, a first generation compound derived from renewable resources. Methacrylate-based complementary polymeric dienophiles were also prepared by introducing maleimide groups into the structure. The products obtained at different steps were characterized by FTIR, NMR and TGA techniques. The study of the rheological properties of the hydrogels proved the success of this green “click” synthetic strategy confirming the formation of chemically crosslinked networks by the use of the Diels–Alder reaction. Furthermore, SEM studies revealed promising morphological properties of the ensuing hydrogels in terms of biomedical applications.     

Synthesis of New Five Membered Nitrogen Containing Heterocycles Bearing D-Galactose Side Chains

The synthesis of 5-[6′-deoxy-(1′,2′:3′,4′-di-O-isopropylidene-α-D-galactopyranos-6′-yl)]tetrazole and its reaction with acetic anhydride and 1,2:3,4-di-O-isopropylidene-6-O-(4-toluenesulfonyl)-α-D-galactopyranose are described.     

Selective Sulfenylative Desulfonylation or Decarbalkoxylation of α-Sulfonyl Malonates with DABCO or Bu3N: Reactivity and Conformational Analysis

The study on reactivity of several α-substituted α-sulfonyl malonates toward 1,4-diazabicyclo[2.2.2]octane (DABCO) and Bu₃N is described. The reactivity with DABCO revealed the possible competition between decarbalkoxylation and unexpected desulfonylation, depending on the α-substituent, because of sterical hindrance around the electrophilic centers (SO₂ and CO₂R). The derivatives with crowded α-substituents suffer selective desulfonylation, and a novel and efficient desulfonylation method can be proposed. The dependence of the reactivity of α-sulfonyl malonates on the sterical hindrance around the electrophilic centers is confirmed by conformational analysis (Macromodel/MM2? and Mopac/MP3). The carbanionic mechanism is proved because the corresponding protonated, deuterated, and sulfenylated products were obtained by addition of the corresponding electrophilic agents. Bu₃N showed itself to be a novel selective decarbalkoxylation agent for any α-substituted α-sulfonyl malonate.     

Synthesis of bifunctional cyclic carbonates from CO2 catalysed by choline-based systems

Easily prepared choline iodide is an active catalyst for the synthesis of cyclic carbonates through the coupling reaction of CO₂ and epoxides using low pressure (1 MPa), moderate temperature (85 ºC) and green solvents (ethanol and propan-2-ol). The effects of reaction temperature, pressure, reaction time and amount of catalyst used were also investigated. The results showed moderate to high yields and excellent selectivities of cyclic carbonates with vinyl or acrylate groups under mild reaction conditions. The heterogenization of choline over a Merrifield resin gives access to a supported catalyst with good recyclability and reactivity that can be extended to a variety of terminal epoxide substrates.     

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.     

Affinity Matrices of Cratylia mollis Seed Lectins for Isolation of Glycoproteins from Complex Protein Mixtures

This work reports the use of matrices containing Cratylia mollis lectins (Cramoll 1,2,3-Sepharose and Cramoll 3-Sepharose) for isolation of glycoproteins from fetal bovine serum, human colostrum, hen egg white, and human blood plasma. Cramoll 1,2,3-Sepharose was able to bind a glycoprotein from fetal bovine serum which showed the same fetuin electrophoretic profile. The data indicate that this protein adsorbed to the matrix by interaction with Cramoll 3. Cramoll 1,2,3-Sepharose was not efficient to retain glycoproteins from human colostrum or commercial ovalbumin. Cramoll 3-Sepharose bound ovalbumin, and the support retained protein from hen egg white. Protein peaks eluted from the column with 1.0 M NaCl or 0.3 M galactose showed apparent molecular mass of ovalbumin. Two main proteins from blood plasma with apparent molecular mass 67 (similar to albumin) and 50 kDa (similar to fetuin) adsorbed on Cramoll 3-Sepharose and were eluted with 1.0 M NaCl as a single peak. Elution of adsorbed plasma proteins with 0.3 M galactose was less selective than with 1.0 M NaCl as revealed by SDS-PAGE. In conclusion, the Cramoll 1,2,3-Sepharose and Cramoll 3-Sepharose matrices were useful to separate glycoproteins from complex protein mixtures, and the adsorption phenomena was a carbohydrate-dependent event.     

Trapped modes along a periodic array of freely floating obstacles

We consider the coupled problem describing the motion of a linear array of three‐dimensional obstacles floating freely in a homogeneous fluid layer of finite depth. The interaction of time‐harmonic waves with the floating objects is analyzed under the usual assumptions of linear water‐wave theory. Quasi‐periodic boundary conditions and a simplified reduction scheme turn the system into a linear spectral problem for a self‐adjoint operator in Hilbert space. Based upon the operator formulation, we derive a sufficient condition for the nonemptiness of its discrete spectrum. Various examples of obstacles that generate trapped modes are given. Copyright © 2014 John Wiley & Sons, Ltd.     

Penultimate Approximations in Statistics of Extremes and Reliability of Large Coherent Systems

In reliability theory any coherent system can be represented as either a series-parallel or a parallel-series system. Its lifetime can thus be written as the minimum of maxima or the maximum of minima. For large-scale coherent systems it is sensible to assume that the number of system components goes to infinity. Then, the possible non-degenerate extreme value laws either for maxima or for minima are eligible candidates for the system reliability or at least for the finding of adequate lower and upper bounds for the reliability. The identification of the possible limit laws for the system reliability of homogeneous series-parallel (or parallel-series) systems has already been done under different frameworks. However, it is well-known that in most situations such non-degenerate limit laws are better approximated by an adequate penultimate distribution. Dealing with regular and homogeneous parallel-series systems, we assess both theoretically and through Monte-Carlo simulations the gain in accuracy when a penultimate approximation is used instead of the ultimate one.     

Fingerprinting pre-historical symbolic artefacts by a non-destructive methodological approach

Journal of Radioanalytical and Nuclear Chemistry - A contribution to the discussion about Vila Nova de São Pedro (VNSP) as a production centre of symbolic lithic artefacts, the origin of raw...