Tether‐Directed Bisfunctionalization Reactions of C60 and C70

Four easily isolable regio‐ and stereoselective bis‐adducts of C₆₀ and C₇₀, as well as a new C₇₀‐dumbbell derivative, have been synthesized by using two different bismalonate tethered moieties. The derivatives that possess relatively long‐tethered moieties show highly symmetric addition patterns, as evidenced by spectroscopic measurements, whereas the derivatives possessing the shorter‐tethered moiety exhibit interesting addition patterns on C₆₀ and C₇₀.     

Guidelines for dynamics‐based parameterization of one‐dimensional cellular automata rule spaces

As paradigmatic complex systems, various studies have been done in the context of one‐dimensional cellular automata (CA) on the definition of parameters directly obtained from their transition rule, aiming at the help they might provide to forecasting CA dynamic behavior. Out of the analysis of the most important parameters available for this end, as well as others evaluated by us, a set of guidelines is proposed that should be followed when defining a parameter of that kind. Based upon the guidelines, a critique of those parameters is made, which leads to a set of five that jointly provide a good forecasting set; two of them were drawn from the literature and three are new ones defined according to the guidelines. By using them as a heuristic in the evolutionary search for CA of a predefined computational behavior, good results have been obtained, exemplified herein by the evolutionary search for CA that perform the Synchronization Task. © 2001 John Wiley & Sons, Inc.     

Cationic photopolymerization of tetrahydrofuran: A mechanistic study on the use of a sulfonium salt–phenothiazine initiation system

The kinetics aspects of the photoinitiated polymerization of tetrahydrofuran with triphenylsulfonium hexafluoroarsenate and sensitized by phenothiazine was studied under visible‐light irradiation. A photosensitizer mechanism was proposed involving electron transfer from phenothiazine to the triphenylsulfonium salt, forming a cation radical, the true precursor of the polymerization. An initial complex in the ground state between the phenothiazine and the triphenylsulfonium was formed prior to the excitation, and this complex actually activated the photopolymerization rate. The polymerization conversion presented an S‐shaped curve, suggesting an induction period caused by the existence of two pathways responsible for the beginning of the polymerization. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 46–55, 2001     

A Pharmacokinetic Study of Mix-160 by LC-MS/MS: Oral Bioavailability of a Dosage Form of Citroflavonoids Mixture

This study was performed to evaluate and compare the pharmacokinetic parameters between two dosage formulations of hesperidin and naringenin: mixture and tablet. Our objective was to determine that the flavonoid tablet does not significantly modify the pharmacokinetic parameters compared with the mixture. For this study, we administered 161 mg/kg of either mixture (Mix-160) or tablet composed of hesperidin and by intragastric administration. Blood microsamples were collected from tail vein up to 24 h. Serum flavonoid extraction was performed by solid phase extraction and analyzed by LC-MS/MS of triple quadrupole (QqQ). Serum concentration vs. time plot showed that data fitted for a first-order model. The pharmacokinetic parameters were calculated by a noncompartmental model. The results showed that the absorption constant is higher than the elimination constant. The first concentration was found at five minutes, and minimal concentration at 24 h after administration, suggesting a enterohepatic recirculation phenomena and regulation of liver cytochromes’ activity. We did not find meaningful differences between the pharmacokinetic parameters of both samples. We concluded that tablet form did not interfere with the bioavailability of hesperidin and naringenin, and it could be a suitable candidate for developing a drug product.     

Hydrothermal CO2 Reduction by Glucose as Reducing Agent and Metals and Metal Oxides as Catalysts

High-temperature water reactions to reduce carbon dioxide were carried out by using an organic reductant and a series of metals and metal oxides as catalysts, as well as activated carbon (C). As CO₂ source, sodium bicarbonate and ammonium carbamate were used. Glucose was the reductant. Cu, Ni, Pd/C 5%, Ru/C 5%, C, Fe₂O₃ and Fe₃O₄ were the catalysts tested. The products of CO₂ reduction were formic acid and other subproducts from sugar hydrolysis such as acetic acid and lactic acid. Reactions with sodium bicarbonate reached higher yields of formic acid in comparison to ammonium carbamate reactions. Higher yields of formic acid (53% and 52%) were obtained by using C and Fe₃O₄ as catalysts and sodium bicarbonate as carbon source. Reactions with ammonium carbamate achieved a yield of formic acid up to 25% by using Fe₃O₄ as catalyst. The origin of the carbon that forms formic acid was investigated by using NaH¹³CO₃ as carbon source. Depending on the catalyst, the fraction of formic acid coming from the reduction of the isotope of sodium bicarbonate varied from 32 to 81%. This fraction decreased in the following order: Pd/C 5% > Ru/C 5% > Ni > Cu > C ≈ Fe₂O₃ > Fe₃O₄.     

Interpretation of seasonal variation of metals and abiotic properties in a tropical lake using multivariate analysis and MINTEQA2 program.

The hydrological cycle of Lake Ipê and the principal parameters that could affect its abiotic parameters and its metal (Fe, Mn, and Cd) concentrations were investigated. A detailed study of seasonal variations using Principal Components Analysis (PCA) for the most relevant metals (Fe, Mn and Cd) was performed, assisted by the MINTEQA2 geochemical equilibrium program using 15 water abiotic parameters. The abiotic variables and metals in the lake were governed by the hydrological regimen of the Parana River and by the occurrence of occasional flood pulses and rainfall. The occurrence of cadmium is a concern; its presence could be due to industrial or agricultural activities or even to a natural geochemical process.     

Surgical and chemical castration induce differential histological response in prostate lobes of Mongolian gerbil

The present study describes the short-term alterations in the prostate ventral and dorsal lobe of the adult Mongolian gerbil, in response to two different androgen suppression approaches. Groups (n=6) of 16-week-old gerbils were maintained intact or subjected, either to the bilateral surgical castration 1 week previously or to daily subcutaneous injections of Flutamide (10mg/kg body weight) for 7 days. The main microscopic features of both prostate lobes in these groups were compared using conventional paraffin tissue sections, measurements of acinar epithelial height and stereological data of main gland components (acini, collagen fibers and fibromuscular stroma). Marked alterations were observed in the basement membrane of the ventral lobe after both surgical and chemical castration, such as an increase in thickness and collagen staining. A low degree of epithelial atrophy was detected in the dorsal lobe following both androgen suppression approaches in comparison with that found in the ventral lobe, indicating that this lobe is not so responsive to testosterone ablation induced by castration or Flutamide treatment, at least insofar as secretory activity is concerned. However, the dorsal lobe exhibited marked stromal modification, such as an increase in collagen fibers following castration and an increase in fibromuscular stroma following Flutamide-treatment. Thus, the histological and quantitative data indicates a differential short-term response of the prostate dorsal lobe to surgical castration and Flutamide therapy, suggesting the existence of lobe-specific mechanisms for stromal remodeling.     

Statistical mechanical modelling of chemical reactions in complex systems: the kinetics of the Haem carbon monoxide binding–unbinding reaction in Myoglobin

The free energy profile and the (classical) kinetics of chemical reactions in (soft) condensed phase may be well modelled theoretically by means of molecular dynamics simulations, the perturbed matrix method (PMM) and statistical mechanics, as we provided in previous articles. In this paper, we describe the theoretical framework, discussing thoroughly its crucial points, and apply the model to an important biochemical reaction: the Haem carbon monoxide binding–unbinding reaction in Myoglobin, specifically investigating the reaction step involving the carbon–iron chemical bond formation (disruption) which is of particular biochemical interest.