Quantum chemical study of several monocyclic complex β‐lactam C‐3, C‐4, and N‐derivatives,and β‐ring model molecules

A quantum chemical study of several complex monocyclic 4‐benzoyl‐4‐phenyl‐β‐lactam derivatives was carried out using cyclobutane, azetidine, 2‐azetidinone, 1‐methyl‐2‐azetidinone, and 3‐methyl‐2‐azetidinone as model compounds. The optimum geometry was obtained for the different conformations. The planarity of the ring was discussed in terms of the influence of the substituents on the amide resonance. To better analyze the amide resonance and the activity of the β‐lactam ring, a vibrational study was also carried out. To examine the influence of solvent polarity on the carbonyl bands, the Fourier transform–infrared (FT‐IR) spectra of the β‐lactam monocyclic derivatives were recorded in CCl₄, C₆H₆, and CHCl₃ solutions. The normal vibrations of the β‐lactam ring in the model compounds were characterized and used in the analysis of the β‐ring of more complex derivatives. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

The organocatalytic enantioselective [3+2] cycloaddition reaction of α,β-unsaturated aldehydes with azomethine ylides applied to the asymmetric synthesis of densely substituted pyrroloisoquinolines

The synthesis of densely functionalized pyrrolo[2,1-a]isoquinolines was accomplished using the organocatalytic [3+2] cycloaddition between enals and azomethine ylides under iminium catalysis developed in our group some years ago as the key step. The cycloaddition proceeds smoothly yielding the corresponding pyrrolidine as a single endo diastereoisomer with enantiopurity in the range of 94–96% and further manipulations of the obtained cycloadducts using high yielding reaction protocols and a final mesylation/intramolecular N-alkylation sequence allowed the synthesis of target compounds in which the integrity of all stereocenters installed during the first step is maintained.     

High‐performance liquid chromatographic separations of stereoisomers of chiral basic agrochemicals with polysaccharide‐based chiral columns and polar organic mobile phases

The separation of the stereoisomers of 23 chiral basic agrochemicals was studied on six different polysaccharide‐based chiral columns in high‐performance liquid chromatography with various polar organic mobile phases. Along with the successful separation of analyte stereoisomers, emphasis was placed on the effect of the chiral selector and mobile phase composition on the elution order of stereoisomers. The interesting phenomenon of reversal of enantiomer/stereoisomer elution order function of the polysaccharide backbone (cellulose or amylose), type of derivative (carbamate or benzoate), nature, and position of the substituent(s) in the phenylcarbamate moiety (methyl or chloro) and the nature of the mobile phase was observed. For several of the analytes containing two chiral centers all four stereoisomers were resolved with at least one chiral selector/mobile phase combination.     

Application of chitosan matrix for delivery of rutin

Chitosan matrices are an alternative material to the food industry, due to its ability to release bioactive compounds through interconnected cavities. Chitosan is a biomaterial of excellence, because it shows unique features, such as biocompatibility, non-toxicity, bactericidal action and the ability to associate with other compounds. Thus, this study aimed the development of chitosan matrices incorporated with rutin, as well as the evaluation of rutin release. Chitosan matrices with rutin were prepared by the coacervation method in alkaline solution and subsequently characterized through FT-IR, TG-DSC, X-ray diffraction, SEM and further submitted to rutin release assay. Results show the effectiveness in the incorporation of rutin into the polymeric matrix. The polymeric matrix with rutin can quickly release it, which provides a wide range of applications, such as carrier of rutin as a micronutrient food additive.     

Dimer form of 1,3-dimethyluracil studied by the AM1 semiempirical method

A study of the dimer form of 1,3-dimethyluracil was carried out. The optimum geometric parameters in the monomeric and dimeric forms were obtained using the AM 1 semiempirical method. The results were compared with those reported by X-ray diffraction. The energies in the dimer formation and in the intramolecular C? H···O interaction were calculated. Electronic density maps in two and three dimensions were drawn. Several calculated thermodynamic parameters are discussed. © 1994 John Wiley & Sons, Inc.     

Cluster emission and chemical reactions in oxygen and nitrogen ices induced by fast heavy-ion impact

Two ices, O2 and a mixture of O2 and N2, are bombarded by 252Cf fission fragments (FF) (approximately 65 MeV at target surface); the emitted positive and negative secondary ions are analyzed by time-of-flight mass spectrometry (TOF-SIMS). These studies shall enlighten sputtering from planetary and interstellar ices. Three temperature regions in the 28-42-K range are analyzed: (1) before N2 sublimation, in which hybrid chemical species are formed, (2) before O2 sublimation, in which the TOF mass spectrum is dominated by low-mass (O2)p cluster ions and (3) after O2 sublimation, in which (N2)p or (O2)p cluster ions are practically inexistent. In the first region, four hybrid ion series are observed: NOn-1+, N2On-2(+/-), and N4On-4(-). In the second region, two positive and negative ion series are identified: (O2)pO(+/-) and (O2)pO2(+/-). Their yield distributions are fitted by the sum of two decreasing exponentials, whose decay constants are the same for all series. It is observed that the cluster ion desorption from solid oxygen is very similar to that of other frozen gases, but its yield distribution oscillates with a three- or six-atom periodicity, suggesting O3 or 3O2 units in the cluster structure, respectively.     

Abnormal heating of low-energy electrons in low-pressure capacitively coupled discharges

In low-pressure capacitively coupled plasmas, high-energy electrons are collisionlessly heated by large rf fields in the sheaths while low-energy electrons are confined in the bulk plasma by the ambipolar potential. Low-energy electrons are typically inefficiently heated due to their low collisionality and the weak rf electric field present in the bulk. It is shown, however, that as a result of the nonlinear interaction between the electron motion and the weak rf field present in the bulk, low-energy electrons can be efficiently heated. Electrons in the bulk that bounce inside the electrostatic potential well with a frequency equal to the rf excitation frequency are efficiently heated by the coherent interaction with the rf field. This resonant collisionless heating can be very efficient and manifest itself as a plateau in the electron energy probability function.