Poly(N-ethylmethacrylamide) thermally-sensitive microgel latexes: effect of the nature of the crosslinker on the polymerization kinetics and physicochemical properties

Thermally-sensitive crosslinked submicronic particles were prepared by an emulsion/precipitation process of N-ethylmethacrylamide (NEMAM), using potassium persulphate as initiator and four different crosslinkers; ethylene glycol dimethacrylate (EGDMA), 1,3-butanediol dimethacrylate (1,3-BDDMA), 1,4-butanediol dimethacrylate (1,4-BDDMA) and tetraethylene glycol dimethacrylate (TEGDMA). At first, polymerization kinetics was studied by NMR, revealing the negligible effect of the crosslinker nature. On the contrary, the water-soluble polymer amounts, the final hydrodynamic particle size, the swelling ability, the electrokinetic properties were found to be dependent upon the nature of crosslinker. The final latexes were found to be narrowly size distributed irrespective of the crosslinker agent’s chemical nature. In this study, the water solubility of the cross-linker was reported to be an important criterion, but other factors, such as diffusion and reactivity, have to be taken into consideration. To cite this article: P. Hazot et al., C. R. Chimie 6 (2003).     

Sugar conformational effects on the photochemistry of thymidylyl(3'-5')thymidine

The synthesis and conformational analysis of 2'-O,5-dimethyluridylyl(3'-5')-2'-O,5-dimethyluridine (1a), the analogue of thymidylyl(3'-5')thymidine (TpT; 1b) in which a methoxy group replaces each 2'-alpha-hydrogen atom, are described. In comparison with TpT, such modification increases the population of the C3'-endo conformer of the sugar ring puckering at the 5'- and 3'-ends from 30 to 75% and from 37 to 66%, respectively. Photolyses of 1a and TpT at 254 nm are qualitatively comparable (the cis-syn cyclobutane pyrimidine dimer and the (6-4) photoproduct are formed), although it is significantly faster in the case of 1a. These results are explained by the increased propensity of the modified dinucleotide to adopt a base-stacked conformation geometry reminiscent of that for TpT.     

Interplay of Charge Transfer, Dimensionality, and Amide Hydrogen Bond Network Adaptability in TCNQF4 Complexes of EDO-TTF-CONH2 and EDT-TTF-CONH2

[EDO-TTF-CONH₂][TCNQF₄], triclinic system, space group P-1, a=8.2479(12) Å, b=12.282(2) Å, c=12.6842(18) Å, α=113.850(17)°, β=106.420(17)°, γ=90.284(19)°, V=1116.8(4) ų; and [EDT-TTF-CONH₂]₂[TCNQF₄], triclinic system, space group P-1, a=6.5858(9) Å, b=11.699(2) Å, c=12.2281(18) Å, α=104.000(19)°, β=93.611(17)°, γ=98.279(19)°, V=899.9(3) ų, whose π-donor molecules, (ethylenedioxo)-carbamoyltetrathiafulvalene and (ethylenedithio)-carbamoyltetrathiafulvalene, respectively, differ solely by the nature of the chalcogen atoms in their outer ethylene dichalcogeno bridge, yet form very different charge-transfer complexes with the same π-acceptor. [EDO-TTF-CONH₂^•+]₂ [TCNQF₄^•−]₂ is a diamagnetic insulating ionic salt with a three-dimensional rock-salt-type structure based on discrete dimers while in the semi-conducting mixed-valence complex, [EDT-TTF-CONH₂]₂^•+[TCNQF₄^•−], the mixed-valence dimers aggregate into infinite chains interspersed within parallel rows of non-interacting radical anions. It is shown how the robust and adaptable supramolecular amide hydrogen bond tweezers-like motifs common to the two solids simply comply to the 3-to-1 dimensionality reduction upon substitution of O for S.     

Probabilistic approach and size effect in brittle materials under multiaxial stress states

Summary The problem of evaluating the strength of brittle materials demands a statitistical approach owing to the considerable dispersion shown by these materials, particularly if subject to stress states in which the tensile component is predominant. For this purpose, the Weibull theory can be conveniently applied, which is based on the concept of the weakest link in a chain allowing the determination of both the failure probability of a model under certain loading conditions and the corresponding mean strength.In the present work the Weibull theory is applied, by means of of the Stanley's approach, to the case of multiaxial stress states in order to deal with some problems not thoroughly investigated so far, among which the effect of the shear stresses on the flexural strength and the indirect evaluation of the tensile strength by means of the Brazilian test.In conclusion, the theory is applied to assess the difference between the tensile strength values obtained by means of different tests. The results achieved are then compared with experimental data.

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Sommario Il problema della resistenza dei materiali fragili richiede un approccio statistico a causa della forte dispersione propria di questi materiali, in particolare se soggetti a uno stato tensionale prevalentemente di trazione. A questo scopo può essere applicata la teoria di Weibull, basata sul concetto dell'anello più debole di una catena, che consente di determinare la probabilità di crisi di un modello per una determinata condizione di carico e la corrispondente resistenza media.In questo lavoro la teoria di Weibull viene applicata al caso degli stati di tensione pluriassiali con l'approccio di Stanley, allo scopo di indagare su alcuni problemi non ancora affrontati per questa via, tra cui l'influenza delle tensioni tangenziali sulla resistenza a flessione e la determinazione indiretta della resistenza a trazione mediante prova Brasiliana.A conclusione, la teoria viene impiegata per valutare la differenza tra i valori di resistenza a trazione ottenibili con diversi tipi di prova. I risultati vengono posti a confronto con dati sperimentali.

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Signification of fundamental symbols used P _f probability of failure - applied stress - _u location parameter - ₀ scale parameter - m shape parameter (Weibull modulus) - (z) Gamma function - V total volume of the model - unit volume - _f mean tensile strength in flexure - _b mean indirect tensile strength (Brazilian test) - _t mean direct tensile strength - _tv mean direct tensile strength of unit volume - _c mean cylindrical compressive strength. Some results of this work were presented at the following meetings:- 10th National Meeting of A.I.A.S., Associazione Italiana per l'Analisi delle Sollecitazioni, Cosenza (Italy), September 22–25, 1982;- 4th I.C.A.S.P., International Conference on Applications of Statistics and Probability in Soil and Structural Engineering, Firenze (Italy), June 13–17, 1983.This work was supported by the C.N.R.     

The use of liquid chromatography-atmospheric pressure chemical ionization mass spectrometry to explore the in vitro metabolism of cyanoalkyl piperidine derivatives

A LC/MS method using atmospheric pressure chemical ionization, positive ion mode and full scan to measure the in vitro metabolic stability of cyanoalkyl functionalized compounds with the human liver microsomes was employed. Percentage metabolism examined for the five cyanoalkyl piperidines revealed the optimal chain length and positioning of these functions to produce the most metabolically stable compound. The 4-cyanomethyl piperidine derivative was the most stable compound with 15% metabolism after 15 min incubation with human liver microsomes. In general, the major metabolites formed from the cyanoalkyl piperidine derivatives were due to oxidation of the cyanoalkyl chain or the piperidine fragment, resulting in a M+16 ion. However, the 2-cyanomethyl piperidine derivative exhibited an interesting biotransformation pathway with unusual metabolite peaks corresponding to M+5, M-11 and M+21 ions. Data-dependent MS/MS scanning was used to generate daughter ion spectra from the parent compound and its metabolite peaks. Based on the fragmentation analysis, a carboxylic acid, aldehyde and oxidative metabolite of the carboxylic acid structure have been proposed for M+5, M-11 and M+21 ions, respectively.     

An expeditious synthesis of tailed tren-capped porphyrins

[structure: see text] A one-pot two-step versatile synthesis of tailed tren-capped porphyrins has been achieved. The two resulting ligands demonstrate that this expeditious method can be applied to various axial bases to obtain highly functionalized macromolecules attractive for heme modeling purposes. Dioxygen binding of the pyridine-tailed iron complex is reported as a direct application.     

Thiophene 1-oxides. V. Comparison of the crystal structures and thiophene ring aromaticity of 2,5-diphenylthiophene,its sulfoxide and sulfone

The detailed preparation of 2,5-diphenylthiophene 1-oxide (2) is reported as well as the comparative study of the crystal structures of 2,5-diphenylthiophene, 1 , its sulfoxide 2 and sulfone 3 obtained by X-ray diffraction. This work represents the first experimental study of a complete heterocyclic series, including a thiophene derivative, and the corresponding sulfoxide and sulfone. On the basis of the geometrical parameters, the first unequivocal experimental parameters obtained for a thiophene 1-oxide derivative, we have also examined the evolution of the aromatic character of the thiophene ring when oxidizing the sulfur atom to the sulfoxide and the sulfone. Paolini's bond orders and Julg and Francois's aromaticity indices have also been calculated for the three compounds and compared to those previously calculated for related thiophene derivatives by semi-empirical or ab initio methods [6], [7]. All the data examined showed that, in spite of its non planarity, the thiophene ring of 2,5-diphenylthiophene 1-oxide 2 could still exhibit some de localization of its p electrons indicating a certain degree of aromaticity lower than in thiophene 1 but higher than in the sulfone 3 .     

Study of non-covalent complexation between catechin derivatives and peptides by electrospray ionization mass spectrometry

The recent development of electrospray ionization mass spectrometry (ESI-MS) has allowed its use to study molecular interactions driven by non-covalent forces. ESI-MS has been used to detect non-covalent complexes between proteins and metals, ligands and peptides and interactions involving DNA, RNA, oligonucleotides and drugs. Surprisingly, the study of the interaction between polyphenolic molecules and peptides/proteins is still an area where ESI-MS has not benefited. With regard to the important influence of these interactions in the biological and food domains, ESI-MS was applied to the detection and the characterization of soluble polyphenol-peptide complexes formed in model solution. The ability to observe and monitor the weak interactions involved in such macromolecular complexation phenomena was demonstrated for monomeric and dimeric flavonoid molecules (catechin-derived compounds) largely encountered in plants and plant derived products. Intact non-covalent polyphenol-peptide complexes were observed by ESI-MS using different experimental conditions. Utilizing mild ESI interface conditions allowed the detection of 1 : 1 polyphenol-peptide complexes in all tested solutions and 2 : 1 complexes for the dimers and galloylated polyphenols (flavanols). These results show that there is a preferential interaction between polymerized and/or galloylated polyphenols and peptide compared with that between monomeric polyphenols and peptides. Thus, ESI-MS shows potential for the study of small polyphenolic molecule-peptide interactions and determination of stoichiometry.     

European intercomparison study for the determination of fumonisins in maize

Fumonisins are mycotoxins occurring largely in maize and maize products, which cause animal diseases, such as equine leukoencephalomalacia and porcine pulmonary edema, and may also induce liver cancer on experimental rats. The European Commission Standards, Measurements and Testing (SMT, formerly BCR) Programme, has sponsored a project to improve analytical methodologies for the determination of the two major fumonisins (fumonisin B1 and fumonisin B2) in maize materials. The project involved the following steps: i) the preparation of a blank and a maize material contaminated with fumonisins Bl and B2; ii) a preliminary study of the -irradiation conditions for sterilization; iii) homogeneity and stability studies of the maize materials; iv) an intercomparison study for fumonisins analysis in the above materials with the involvement of 24 European laboratories, most of which have national or international responsibilities for foodstuff and/or feedstuff quality control. Results of the intercomparison study are presented together with the homogeneity and stability data relevant to the maize materials.     

Synthesis of the TT pyrimidine (6-4) pyrimidone photoproduct-thio analogue phosphoramidite building block

The phosphoramidite building block synthesis of the thio analogue at the 5,6-dihydropyrimidine C5 position of the thymidylyl(3'-5')thymidine (6-4) photoproduct 1 is presented. This compound was readily obtained from the appropriately protected dinucleotide P-methyl-5'-O-dimethoxytritylthymidilyl(3' --> 5')-4-thiothymidine 2 after irradiation at 366 nm, then S-sulfenylmethylation of the thiol function of the resulting (6-4) adduct, and phosphitylation of the 3'-hydroxyl group.