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     

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).     

A computer program for searching the best model for describing different experimental systems

An algorithm for searching the best polynomial analytical function for describing different experimental systems is presented. It is based

1. (1)on the generation of all possible analytical functions of a given order, with a given number of terms and with a given number of independent variables, and

2. (2)on the calculation of the parameters of all selected functions using the linear regression method.

To show the ability of the program two different examples are given:

1. (1) searching the best univariate polynomial model, and

2. (2) modelling of the stability of a two-component mixture as a function of three factors.

Determination of metal concentration in fat supplements for swine nutrition by atomic absorption spectroscopy

The presence of some essential and toxic metals in fat supplements for swine diet was investigated. Collected samples represented a relevant production of the Italian industry. In particular, some samples were enriched with antioxidants or waste cooking oils. The method for the determination of Ca, Cu, Cd, Fe, Mg, Mn, Ni, Pb, and Zn in fat samples was developed by means of a certified reference material (CRM 186) and a representative fatty sample (RFS). All samples were digested in closed vessels in a microwave oven and then analyzed by flame atomic absorption or graphite furnace atomic absorption spectrometry. The entire analytical method provided a satisfactory repeatability and reproducibility confirmed by agreement between the experimental recovery data obtained for the CRM 186 sample and, with the method of standard additions, for the RFS material. The samples generally showed a small amount of metals compared with the recommended daily intake for the essential elements. On the other hand, some samples contained a significant concentration, from an analytical point of view, of Cd, Ni, and Pb. Principal component analysis (PCA) was applied to inspect the experimental data obtained from samples analysis. Basically no differences were detected in terms of metal concentration among the fat supplements analyzed.     

Nucleic acid analysis using an expanded genetic alphabet to quench fluorescence

Organic chemistry has made possible the synthesis of molecules that expand on Nature's genetic alphabet. Using the previously described nonstandard DNA base pair constructed from isoguanine and 5-methylisocytosine, we report a highly specific and sensitive method that allows for the fast and specific quantitation of genetic sequences in a closed tube format. During PCR amplification, enzymatic site-specific incorporation of a quencher covalently linked to isoguanine allows for the simultaneous detection and identification of multiple targets. The specificity of method is then established by analysis of thermal denaturation or melting of the amplicons. The appropriate functions of all reactions are further verified by incorporation of an independent target into the reaction mixture. We report that the method is sensitive down to the single copy level, and specificity is demonstrated by multiplexed end-point genotypic analysis of four targets simultaneously using four separate fluorescent reporters. The method is general enough for quantitative and qualitative analysis of both RNA and DNA using previously developed primer sets. Though the method described employs the commonly used PCR, the enzymatic incorporation of reporter groups into DNA site-specifically should find broad utility throughout molecular biology.     

Styrene copolymers as pollutant adsorbents : Safe sampling volume determination

The determination of safe sampling volumes of benzene and acetone on air samplers filled with Porapak Q, Chromosorb 101, 102 and 103 is described. Two direct methods are employed; one method is based on frontal chromatography, while the second one is a concentration method followed by thermal desorption. The results are compared to those determined by the indirect pulse chromatographic method. The safe sampling volumes determined by the direct methods were in accordance. The indirect method gives slightly different values; however, this procedure is carried out at "infinite dilution". The effect of the pollutant concentration on the safe sampling volumes was also examined. The values decrease with increasing pollutant concentration.     

Different Pathways in the Base-Promoted Isomerization of Benzyl Oxiranyl Ethers

The base-promoted isomerization of benzyl oxiranyl ethers was investigated. In particular it was shown that the reaction may proceed toward two main regioisomeric products: a benzyl vinyl ether or a 2-aryl-3-(hydroxyalkyl)oxetane, depending on subtle variations in the substitution on the phenyl ring. Disubstituted oxetanes were obtained in a stereoselective manner, thus providing a good entry to this class of synthetically useful compounds.     

Alkyl 2-(2-benzoyl-2-ethoxycarbonyl-1-ethenyl)amino-3-dimethylaminopropenoates in the synthesis of heterocyclic systems

Alkyl 2-(2-benzoyl-2-ethoxycarbonyl-1-ethenyl)amino-3-dimethylaminopropenoates 4a,b were prepared. They react with C-nucleophiles such a 2-pyridinylacetonitrile 5 and methyl-2-quinolinylacetate 8, cyclohexane-1,3-dione 10 and its derivatives 12 and 14, resorcinol derivative 16 , 2-naphtol 18, 2-pyranone derivatives 20 and 22, and 4-hydroxypyridin-2(1H)-one 24, to form substituted amino derivatives of quinolizine 6, benzo[c]quinolizine 9, tetrahydrobenzopyran-2-one 11, 13, 15 , naphto[2,1-b]pyran-3-one 19 , pyranopyranones 21, 23, and pyrano[3,2-c]pyridine 25.