The CeCl3·7H2O-NaI system as promoter in the synthesis of functionalized trisubstituted alkenes via Knoevenagel condensation

The arylidene malonates with two different geminal carboxylate functions, a suitable class of substrates of several synthetic and pharmacological studies, are easily available through Knoevenagel condensation of ethyl tert-butyl malonate and different aromatic aldehydes. The results have increased the potentialities of CeCl₃·7H₂O-NaI system as a type of water-tolerant green Lewis acid promoter for carbon-carbon bond forming procedures.     

Identification (GC and GC-MS) of unsaturated acetates in Elasmopalpus lignosellus and their biological activity (GC-EAD and EAG)

Two insect colonies of Elasmopalpus lignosellus were reared in our laboratory, the first being initiated from pupae obtained from a cornfield in the region of Sete Lagoas, Minas Gerais and the second from a cornfield in the region of Goiania, Goiás. From the two colonies, two extracts were prepared from the pheromone glands of virgin E. lignosellus females. The extract obtained from the first colony was designated as extract 1 while the extract obtained from the second colony was designated as extract 2. Extract 1 was analyzed by gas chromatography-mass spectrometry (GC-MS) with (Z)-9-hexadecenyl acetate [(Z)-9-HDA] and (Z)-11-hexadecenyl acetate [(Z)-11-HDA] being identified and confirmed by the formation of DMDS derivatives. In addition, a third acetate, which could be either (E)-8-hexadecenyl acetate [(E)-8-HDA] or (E)-9-hexadecenyl acetate [(E)-9-HDA] was detected by GC-MS. Extract 2 was analyzed by gas chromatography (GC) and gas chromatography-electroannetography (GC-EAD) revealing the presence of (Z)-11-HDA and (Z)-9-TDA. In addition, the same compounds elicited a response with the E. lignosellus male antenna obtained from the second insect colony. Electroantennography (EAG) screening with the male E. lignosellus antenna (obtained from the second insect colony) was conducted with the 23 possible tetradecenyl acetates (TDA) and 22 hexadecenyl acetates (HDA) as standards. Out of the 23 TDA isomers evaluated, only (Z)-9-TDA elicited a response and out of the 22 HDA [(Z) and (E) isomers gamma2 to delta13] evaluated only (Z)-11-HDA elicited a response. The acetate compositions of two extracts obtained from insects originating from the two states (Minas Gerais and Goiás) of Brazil were different from one another as well as from that obtained from insects in Tifton, GA, USA. The bioactivity data (GC-EAD) of the extract 2 differed from those reported for the Tifton, GA, USA population. These data suggest polymorphism in relation to the insect populations found in Brazil and in the USA. The possibility of the existence of an E. lignosellus sub-species cannot be ruled out.     

Amino Acid Based Epoxy-Poly(Ester Amide)s—A New Class of Functional Biodegradable Polymers: Synthesis and Chemical Transformations

A new class of biodegradable functional polymers – epoxy-poly(ester amide)s (EPEAs), was synthesized for the first time on the basis of naturally occurring α-amino acids, fatty diols and cis- and trans-epoxysuccinic acids. The syntheses were conducted via both solution Active Polycondensation and Interfacial Polycondensation using, accordingly, either activated di-p-nitrophenyl esters or dichlorides of cis- and trans-epoxysuccinic acids as bis-electrophilic monomers. Di-p-toluenesulfonic acid salts of bis-(L-phenylalanine)-1,6-hexylene and bis-(L-leucine)-1,6-hexylene diesters were used in both cases as bis-nucleophilic counter-partners. High-molecular-weight polymers (M_w up to 67.000) with desirable material properties were obtained via solution polycondensation using di-p-nitrophenyl-trans-epoxy succinate. The EPEAs were chemically modified further under mild conditions: oxirane groups along the backbone were reacted with both nucleophilic and electrophilic reagents, and also subjected to thermal and chemical curing. The macromolecular transformations of EPEAs substantially broaden material properties and, hence, the potential to apply amino acid-based biodegradable poly(ester amide)s as absorbable drug carriers and surgical devices.     

U-Closure Operators and Compactness

A notion of compactness with respect to a previously introduced notion of functor induced closure operator is presented and analyzed. Even though this new notion shows very similar properties to compactness with respect to the classical notion of categorical closure operator, in general the two concepts are different. Examples are provided.     

Thermal analysis characterization of PAAm-<Emphasis Type="Italic">co</Emphasis>-MC hydrogels

This paper reports the thermal characterization of polyacrylamide-co-methylcellulose hydrogels and the constituent monomers (acrylamide and methylcellulose). Polymeric materials can be used to produce hydrogels, which can be natural, synthetic, or a mixture. The hydrogels described here were obtained by free radical polymerization, in the presence of N,N′-methylene-bis-acrylamide as a cross-linker agent. Four acrylamide concentrations were used for the synthesis of hydrogels: 3.6, 7.2, 14.7, and 21.7% (w/v). The materials so obtained were analyzed by TG, DTG, DSC, and FT-IR. The TG curves of acrylamide and methylcellulose showed three mass loss events. In DSC curves, the acrylamide exhibited one melting peak at 84.5 °C, and methylcellulose indicated one exothermic event. Nevertheless, acrylamide was considered more stable than methylcellulose. The TG curves of the hydrogels exhibited three mass loss events, and on the DSC curves, three endothermic events were observed. It was verified that the different acrylamide proportions influenced the thermic behavior of hydrogels, and that the authors considered the 7.2% hydrogel a promising drug carrier system. The absorption bands were well defined, confirming the presence of the functional groups in the samples.     

Experimental results on quadratic maps using generalized complex numbers

Summary Some results obtained introducing two-unit generalized complex numbers to determine Mandelbrot and Julia sets for quadratic maps are presented. We also highlight some analogies and differences between classic complex numbers and one of the proposed extensions. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Capanello, Italy, July 4–8, 1994.     

On Equivalent Equilibrium Problems

We give sufficient conditions for the equivalence between two equilibrium problems. In particular we deduce that, under suitable assumptions, an equilibrium problem has an equivalent reformulation as a generalized variational inequality. Such conditions are satisfied when the equilibrium bifunction is lower semicontinuous, coercive and quasiconvex with respect to the second variable. We also show that the equivalent generalized variational inequality inherits the same generalized monotonicity properties of the original nonconvex equilibrium problem.     

Fermi acceleration with memory-dependent excitation

Some scaling properties for a classical particle confined to bounce between two walls, where one wall is fixed and the other one moves in time according to a random signal with a memory length are studied. We have considered two different kinds of collisions of the particle with the moving wall namely: (i) elastic and (ii) inelastic. The dynamics of the model is described in terms of a two-dimensional nonlinear mapping. For the case of elastic collisions, we show that the memory of the stochastic signal affects directly the behaviour of the average velocity of the particle. It then exhibits different slopes for the average velocity at different stages of the series with β≅3/4 for a short time, β≅1 for the average stage and β≅1/2 for a long time, as predicted by the Central Limit Theorem, therefore leading to the Fermi acceleration. The situation where inelastic collisions are taken into account yields a more drastic change, particularly suppressing the Fermi acceleration.