Polyelectrolyte complexes. VI. Polycation structure,polyanion molar mass,and polyion concentration effects on complex nanoparticles based on poly(sodium 2‐acrylamido‐2‐methylpropanesulfonate)

The formation and characterization of some interpolyelectrolyte complex (IPEC) nanoparticles based on poly(sodium 2‐acrylamido‐2‐methylpropanesulfonate) (NaPAMPS), as a function of the polycation structure, polyanion molar mass, and polyion concentration, were followed in this work. Poly(diallyldimethylammonium chloride) and two polycations (PCs) containing (N,N‐dimethyl‐2‐hydroxypropyleneammonium chloride) units in the backbone (PCA₅ and PCA₅D₁) were used as starting polyions. The complex stoichiometry, (n^?/n⁺)_iso, was pointed out by optical density at 500 nm (OD₅₀₀), polyelectrolyte titration, and dynamic light scattering. IPEC nanoparticle sizes were influenced by the polycation structure and polyanion molar mass only before the complex stoichiometry, which was higher for the more hydrophilic polycations (PCA₅ and PCA₅D₁) and for a higher NaPAMPS molar mass, and were almost independent of these factors after that, at a flow rate of the added polyion of about 0.28 mL × (mL PC)^?1 × h^?1. The IPEC nanoparticle sizes remained almost constant for more than 2 weeks, both before and after the complex stoichiometry, at low concentrations of polyions. NIPECs as stable colloidal dispersions with positive charges in excess were prepared at a ratio between charges (n^?/n⁺) of 0.7, and their storage colloidal stability, as a function of the polycation structure and polyion concentration (from 0.8 to ca. 7.8 mmol/L), was demonstrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2495–2505, 2004     

Semiconductor waveguide directional couplers for coherent receivers

Optical waveguide 3-dB couplers integrated on semicondutors have been studied, designed and fabricated, using both bulk and diluted multi-quantum-well InGaAsP/InP-based materials, grown by MOCVD. The device structure is based on the two-mode interference (TMI) principle and is fully compatible for integration with the optoelectronic and electronic components of a coherent receiver. Bulk material couplers provide an output balanced within 0.05 dB per nanometer and an excess loss of 1.4 dB, compared to a straight guide, while coupling loss to a tapered-lensed single mode fibre is 4 dB.Improved coupling efficiency to single-mode fibres is achieved by use of moderately diluted multi-quantum-well waveguides, which include InGaAsP wells and InP barriers: coupling loss to a tapered-lensed single-mode fibre as low as 0.5 dB and excess loss of 1.8 dB are featured. Couplers fabricated with this waveguide structure have a balance sensitivity of 0.03 to 0.04 dB per nanometer.A moderately diluted multi-quantum-well 3-dB coupler has been permanently pigtailed and butt-coupled to a dual balanced PIN photoreceiver. This hybrid assembly was tested in a coherent transmission system at 155 and 622 Mbits^-1 showing sensitivities, for 10^-9 BER, of about-38.0 dBm and-28.8 dBm, respectively.     

Photoinitiated substitution reactions of 2 and 4-pyridinecarbonitrile with cyclopentene

The photoreactions of 4 and 2-pyridinecarbonitrile with cyclopentene carried out in acetone or in acetonitrile solutions lead, respectively, to 4-(2 cyclopentenyl)-pyridine $\text{1}$ and 2-(2 cyclopentenyl)pyridine $\text{2}$. From 2-pyridinecarbonitrile a little amount of ketone $\text{3}$ is obtained.     

Synthesis of non-agglomerated Ba<Subscript>0.77</Subscript>Ca<Subscript>0.23</Subscript>TiO<Subscript>3</Subscript> nanopowders by a modified polymeric precursor method

In this work, we have studied the influence of the pH on the synthesis and structural properties of the Ba_0.77Ca_0.23TiO₃ nanopowders synthesized by a modified polymeric precursor method, in order to achieve non-agglomerated powders. Synthesis, morphology, thermal reactions, crystallite and average particle size of the synthesized powders were investigated through thermal analysis (DTA/TG), X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and Infrared spectroscopy. In summary, Ba_0.77Ca_0.23TiO₃ nanopowders were synthesized for the first time at a relative low temperature (500 °C). It was also found that the alkalinity and acidity of the solution presented a great influence on the powder properties. The best results were obtained from solutions with pH = 8.5 and 11 whose nanopowders presented weakly agglomerate, with homogeneous particle size and a narrow size distribution (30–40 nm). This behavior could be explained based on the FT-IR results in which it was possible to see the increased of the chelation in higher pHs.     

Reactivity of DNA guanyl radicals with phenolate anions

Guanine bases are the most easily oxidized sites in DNA. Electron-deficient guanine species are major intermediates produced in DNA by the direct effect of ionizing radiation (ionization of the DNA itself) because of preferential hole migration within DNA to guanine bases. By using thiocyanate ions to modify the indirect effect (ionization of the solvent), we are able to produce these single-electron-oxidized guanine radical species in dilute aqueous solutions of plasmid DNA where the direct effect is negligible. The guanyl radical species produce stable modified guanine products. They can be detected in the plasmid by converting them to strand breaks after incubation with a DNA repair enzyme. If a phenol is present during irradiation, the yield of modified guanines is decreased. The mechanism is reduction of the guanine radical species by the phenol. It is possible to derive a rate constant for the reaction of the phenol with the guanyl radical. The pH dependence shows that phenolate anions are more reactive than their conjugate acids, although the difference for guanyl radicals is smaller than with other single-electron-oxidizing agents. At physiological pH values, the reduction of a guanyl radical entails the transfer of a proton in addition to the electron. The relatively small dependence of the rate constant on the driving force implies that the electron cannot be transferred before the proton. These results emphasize the potential importance of acidic tyrosine residues and the intimate involvement of protons in DNA repair.     

Synthesis of Glycosylrifamycins,a new type of semisynthetic rifamycins

Glycosylrifamycins, a new type of semisynthetic rifamycin derivatives, can be easily obtained by reaction of 3-(2-aminoethylthio)rifamycin SV ( 2 ) with a glycosyl compound carrying a coupling group, such as isothicyanate or carboxy. We prepared O-acetylated and free glucopyranosyl and arabinopyranosyl derivatives of rifamycin S and SV (see 3–10 ). Additionally, derivatives with D -saccharo-1,4-lactone and with shikimic acid were obtained (see 11–15 ). Glycosylrifamycins show an interesting inhibitory power on Gram-positive bacteria (Table).     

Chemistry for Beginners. Women Authors and Illustrators of Early Chemistry Textbooks

Before women could participate directly in the creation of scientific knowledge, they worked privately as translators, illustrators, and authors of science books. In the early nineteenth century, Jane Marcet in Britain, and later Almira Lincoln Phelps in the U.S., recognized the need for experimental training of beginners and, to compensate for the lack of experiments, produced meaningful drawings for their textbooks. By using a fresh narrative, a pleasing style, and beautiful drawings of their own, they wrote chemistries for the beginners that were both instructional and entertaining. Engraved in the tradition of the nineteenth century illustration, Jane Marcets Conversations on Chemistry and Almira Lincoln Phelps Chemistry for Beginners, originally written for the education of women, were immensely successful and lasted longer than many of the more specialized contemporary works.     

A comparative analysis of various gradient methods for geometry optimization at the ab initio SCF-MO level

Various techniques, already suggested for improving the computational efficiency of the force relaxation method, have been applied here in conjunction with the variable metric algorithms suggested by Murtagh and Sargent and by Fletcher. Various tests have been performed to assess the computational efficiency of the resulting minimization procedures. In addition, procedures where the steps are defined in terms of a parabolic fitting of the forces in approximated normal coordinates have been tested. In all cases the forces are computed analytically.