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51.
Ana A. C. Pacheco Arnaldo F. da Silva Filho Kristoffer Kortsen Magnus W. D. Hanson-Heine Vincenzo Taresco Jonathan D. Hirst Muriel Lansalot Franck D'Agosto Steven M. Howdle 《Chemical science》2021,12(3):1016
Reversible addition–fragmentation chain transfer (RAFT) dispersion polymerisation of methyl methacrylate (MMA) is performed in supercritical carbon dioxide (scCO2) with 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) present as chain transfer agent (CTA) and surprisingly shows good control over PMMA molecular weight. Kinetic studies of the polymerisation in scCO2 also confirm these data. By contrast, only poor control of MMA polymerisation is obtained in toluene solution, as would be expected for this CTA which is better suited for acrylates. In this regard, we select a range of CTAs and use them to determine the parameters that must be considered for good control in dispersion polymerisation in scCO2. A thorough investigation of the nucleation stage during the dispersion polymerisation reveals an unexpected “in situ two-stage” mechanism that strongly determines how the CTA works. Finally, using a novel computational solvation model, we identify a correlation between polymerisation control and degree of solubility of the CTAs. All of this ultimately gives rise to a simple, elegant and counterintuitive guideline to select the best CTA for RAFT dispersion polymerisation in scCO2.RAFT dispersion polymerisation of methyl methacrylate is performed in scCO2 with 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) present as chain transfer agent (CTA) and surprisingly shows good control over PMMA molecular weight. 相似文献
52.
Ronaldo Santos da Silva Maria Inês Basso Bernardi Antonio Carlos Hernandes 《Journal of Sol-Gel Science and Technology》2007,42(2):173-179
In this work, we have studied the influence of the pH on the synthesis and structural properties of the Ba0.77Ca0.23TiO3 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, Ba0.77Ca0.23TiO3 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. 相似文献
53.
Summary In a series of hexacoordinated nickel(II) complexes, prepared from thio-, sulphinyl, and carbonyl derivatives of pyridine and pyrimidine, the endocyclic N-atom was always the preferred basic site; the sulphinyl O-atom was also a donor centre, forming 5-membered heterocycles, whereas the carbonyl O-atom did not bond to the metal. Alkylthio derivatives did not react, unlike thiolate anions, which form N, S-bonded 4-membered rings. On the other and 2,2-bis(pyridyl)ketone bonded exclusively through the N-atoms, forming 6-membered cycles. 相似文献
54.
55.
The quenching of the fluorescence of three anthropogenic fulvic acids (FA) provoked by Cu(II) (pH 6.0), Fe(III) (pH 4.0) and UO22+ (pH 3.5), was analyzed by a non-linear method and by Stern-Volmer plots. The FA samples were extracted from composted sewage sludges (csFA), composted municipal wastes (mwFA) and composted livestock wastes (lsFA). Synchronous-scan fluorescence (SyF) spectra were collected as a function of metal ion concentration. Spectral data were treated by a self-modeling mixture analysis method (SIMPLISMA) to detect the SyF spectral band with the strongest quenching and to calculate the corresponding quenching profile. The analysis of these profiles by a non-linear method allowed the estimation of conditional stability constants (K) and of the percentage of non-complexing fluorophores. The same quantitative information was obtained by the modified Stern-Volmer equation taking into account the existence of fluorophores that do not participate in the complexation. Good agreement was found between the results of the two procedures. The log K calculated by the non-linear method were (standard deviation in parenthesis): csFA, Cu(II), 4.22 (5); Fe(III), 5.0 (1); UO22+, 5.2 (2); mwFA, Cu(II), 4.21 (3); Fe(III), 5.6 (2); UO22+, 4.7 (3); lsFA, Cu(II), 4.51 (8); Fe(III), 5.5 (2); UO22+, 3.6 (2). 相似文献
56.
Armando J.L. Pombeiro Christopher J. Pickett Raymond L. Richards 《Journal of organometallic chemistry》1982,224(3):285-294
The isocyanide complexes trans-[ReCl(CNR)(dppe)2] (R Me, But, C6H4CH3-4, C6H4CH3-2, C6H4Cl-4, C6H4OCH3-4 and C6H3Cl2-2,6; dppe Ph2PCH2CH2PPh2) have been prepared by isocyanide displacement of dinitrogen from the parent complex trans-[ReCl(N2)(ddpe)2]. Their redox properties have been studied by cyclic voltammetry and are interpreted on the basis of the electronic properties and the geometry of the ligating isocyanides which are believed to be bent in these complexes, appearing to exhibit ligand parameter (PL) values ca. +0.3 V higher than those which would be expected for linear geometry. A very high polarisability (B ? 3.4) is observed for the {ReCl(dppe)2} site. 相似文献
57.
Ana?C.?F.?RibeiroEmail author Victor?M.?M.?Lobo Artur?J.?M.?Valente Eduarda?F.?G.?Azevedo M.??da?G.?Miguel H.?D.?Burrows 《Colloid and polymer science》2004,283(3):277-283
Differential mutual diffusion coefficients of n-alkyltrimethylammonium bromides [CH3(CH2)n–1N(CH3)3Br, CnTAB] (n=10, 12, 14, 16) have been measured in aqueous solutions at 298.15 K using a conductimetric cell and an automatic apparatus to follow diffusion. The cell is based on an open-ended capillary, and the technique follows the diffusion process by measuring the resistance of a solution inside the capillaries at various times. The electrical conductances of those solutions have also been measured to calculate the critical micellar concentration (cmc). Thermodynamic analysis of the data suggests that the free ion concentration decreases at concentrations above the cmc, in agreement with theoretical predictions. The obtained values of the micellization parameters were used to model the mutual diffusion coefficients of CnTAB aqueous solutions. 相似文献
58.
R. M. Mingote P. J. S. Barbeira Z. Rocha 《Journal of Radioanalytical and Nuclear Chemistry》2006,269(2):475-479
Summary The present work proposes a methodology for a rapid determina-tion of the tritium content in urine. The urine is treated with
active carbon and tritium is determined by liquid scintillation counting. Different kinds of active carbon were experimented
for the metabolites removal from urine samples. The counting efficiency was calculated by a quench curve using yellow food
dye as a quenching agent. It was obtained a procedure which maintained a good reproducibility, low uncertainty and detection
limit of 7 Bq/l (10 ml of urine, 120 minutes of counting time and efficiency of 23.9%). 相似文献
59.
M. A. V. Ribeiro da Silva C. P. F. Santos M. J. S. Monte C. A. D. Sousa 《Journal of Thermal Analysis and Calorimetry》2006,83(3):533-539
The
standard (p0=0.1
MPa) molar enthalpies of formation, ΔfHm0, for
crystalline phthalimides: phthalimide, N-ethylphthalimide
and N-propylphthalimide were derived from
the standard molar enthalpies of combustion, in oxygen, at the temperature
298.15 K, measured by static bomb-combustion calorimetry, as, respectively,
– (318.0±1.7), – (350.1±2.7) and – (377.3±2.2)
kJ mol–1. The standard molar enthalpies of
sublimation, ΔcrgHm0, at T=298.15
K were derived by the Clausius-Clapeyron equation, from the temperature dependence
of the vapour pressures for phthalimide, as (106.9±1.2) kJ mol–1
and from high temperature Calvet microcalorimetry for phthalimide, N-ethylphthalimide and N-propylphthalimide
as, respectively, (106.3±1.3), (91.0±1.2) and (98.2±1.4)
kJ mol–1.
The derived standard molar enthalpies of formation,
in the gaseous state, are analysed in terms of enthalpic increments and interpreted
in terms of molecular structure. 相似文献
60.
DellaGreca M Iesce MR Previtera L Temussi F Zarrelli A Mattia CA Puliti R 《The Journal of organic chemistry》2002,67(25):9011-9015
Androst-4-ene-3,17-dione (1) and 17alpha-methyltestosterone (2) are dimerized in the solid-state by UV radiation. These substances were selected by a search in the CSD among the steroid enones presenting in the crystalline state an intermolecular short contact between a hydrogen alpha to a carbonyl group and the oxygen of an enone system. Dimerization occurs by transfer of the hydrogen to the oxygen and connection between the two involved carbons. Androst-4-ene-3,17-dione (1) affords dimer 3 and trimer 4, both formed by connection of the C-16 of a molecule with the C-3 of a near one. Irradiation of 17alpha-methyltestosterone (2) gives the isomeric trienones 5 and 6. These compounds are reasonably formed by dehydration of unisolated intermediate products 7 and/or 8 obtained by coupling of two molecules through a linkage between the C-2 and the C-3' carbons. The formation mechanisms of the photoproducts are satisfactory explained on the basis of the molecular arrangement of the monomers in the crystal state. Modeling of the dimeric molecules was done using molecular mechanics calculations. A single-crystal X-ray of the dimer of androst-4-ene-3,17-dione confirms the structural interpretation of spectral data. The conformer found in the solid-state agrees well with the results of molecular mechanics calculations. 相似文献