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1.
The microphase adsorption–spectral correction (MPASC) technique was applied to the interaction of thioin (TN) with sodium dodecyl sulfate (SDS) at pH 4.56. The synergism mechanism of SDS in solution was analyzed and discussed. The great electrostatic aggregation of TN on SDS obeys Langmuir monolayer adsorption. The property constants of the aggregate were determined and the quantitative determination of the anionic surfactant (AS) in samples was made in the presence of EDTA. Results showed that the large micellar aggregate is (TN–SDS2)31, the adsorption constant of the monomer aggregate is 1.85 × 105 (18°C), and its molar absorptivity is 4.45 × 106 L mol–1 cm–1. For analysis of samples, the recovery is between 94.5 and 111% and the RSD is less than 7.62%. 相似文献
2.
For polystyrene–poly(ethylene oxide) (PS–PEO) diblock copolymers, as micellar dispersions in aqueous medium, the formation of complexes with anionic surfactants, such as sodium dodecylsulfate (SDS) could be confirmed. The number of SDS molecules fixed per EO unit is close to the values reported for the SDS–PEO homopolymer interaction. Advantage of this type of complexation was taken to develop a controlled agglomeration process for SDS stabilized PS and PVC latexes by using as agglomerants ‘hairy’ latexes of PS and PVC that have been synthesized in the presence of PS–PEO block copolymers and that carry therefore a fringe of PEO sequences on their surface. The complexation of SDS by these surface-anchored PEO chains leads to the destabilization of the anionic latex, which has a tendency to precipitate onto the surface of the agglomerant latex. The average particle size and the size distribution of the agglomerated particles were studied as a function of the weight and number ratio of the two types of latexes involved in the agglomeration process, as well as in function of the surface coverage by SDS and PEO respectively. By adjusting these parameters, it was possible to obtain, with an efficiency of almost 100%, latex agglomerates with a monomodal distribution in the size range of 1 to 40 μm. An agglomeration mechanism could be outlined taking into account the complexation capacity and the specific surface of the agglomerating ‘hairy’ latex. To cite this article: P. Peter et al., C. R. Chimie 6 (2003). 相似文献
3.
Maiti S Chatterji PR Nisha CK Manorama SV Aswal VK Goyal PS 《Journal of colloid and interface science》2001,240(2):630-635
Aggregation behavior in aqueous solution of a series of poly (ethylene glycol) (PEG)-based macromonomers with methacryloyl group as the only hydrophobic segment has been investigated using surface tension, steady-state and time-resolved fluorescence spectroscopy using pyrene as a probe, and small-angle neutron scattering techniques. The general formula of these macromonomers is CH2=C(CH3)–CO–O–Em–CH3, where E is the ethylene glycol unit and m=8 (ME8), 18 (ME18), 49 (ME49), and 120 (ME120). The results indicate that a macromonomer with 8 ethylene glycol units forms as an aggregate above a certain critical concentration, which can be defined as critical aggregation concentration. The observed high value of I1/I3 in pyrene emission spectra at the interface of these aggregates and the inability to scatter a neutron beam by these aggregates indicate that the hydrophobic cluster formed by this macromonomer is remarkably solvated. ME18 has a tendency to aggregate but others do not form any hydrophobic cluster. The homopolymerization behaviors of these macromonomers in an aqueous medium at 70°C are consistent with these possibi- lities. 相似文献
4.
The exchange of the original cation present on a Laponite clay (usually Na+) for heavy atoms such as Rb+, Cs+, and Tl+ significantly alters the emission characteristics of some aromatic hydrocarbons (p-terphenyl, naphthalene, pyrene, and biphenyl). The increase of the atomic mass of the cation induces a decrease of the fluorescence emission simultaneous with an increase of the emission in the region of lower energies of the spectra, ascribed to the phosphorescence of those hydrocarbons. Time-resolved experiments for the pyrene–clay system showed a decrease of singlet lifetimes for the heavier atoms. Hydrocarbon aggregates were also detected from both the emission spectra and the time-resolved studies. The “excimer-like” emission showed longer lifetimes (10–25 ns) than the monomolecular hydrocarbons (1–3 ns), as already found for other similar systems. The amount of aggregates increased for the heavier cations due to the smaller surface available on the clay particles. Experiments increasing the amount of Tl+ in samples containing a constant concentration of naphthalene allowed evaluation of the distance between the heavy atoms and the probe on the clay surface. The Perrin model treatment was used and resulted in approximately R0=9.2 Å. 相似文献
5.
The cation exchange equilibrium in the systems of natural heulandite-binary aqueous solutions of NaCl, NiCl2, CuCl2, ZnCl2, and MnCl2 was studied. The corrected coefficients of the selectivity (k
a
M/Na) and thermodynamic constants (K
M/Na) of the cation exchange of Na+ cations for transition metal cations were determined. The selectivity of the cation exchange on natural heulandite increases in the following order: Ni2+ < Cu2+ < Zn2+ < Na2+ < Mn2+.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1101–1103, May, 1996. 相似文献
6.
R. Fujiyoshi T. Arai M. Katayama 《Journal of Radioanalytical and Nuclear Chemistry》1994,185(1):133-143
Ligand exchange reaction of Zn(II)-acetylacetonate complex (Zn-acac2) with 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid (H2TPPS) has been investigated spectrophotometrically and radiometrically. The exchange reaction was observed by spectral change from H2TPPS to Zn-TPPS or activity of65Zn(acac)2 extracted into the chloroform phase. The 2nd order rate constants (k
2) for the exchange reaction at 70 °C and at pH 7.8 were found to be 32.8±2.3 and 31.2±3.2 M–1·s–1 from the spectrometric and radiotracer experiments, respectively. For the direct complexation of Zn(II) with H2TPPS, a similar 2nd order rate constant (k=32.4±4.7 M–1·s–1) was obtained as that in the ligand exchange reaction. The activation energies (E) for the exchange and the formation of Zn-TPPS were found to be 69.3±0.2 and 69.4±0.2 kJ·mol–1, respectively, in the temperature range from 40 to 70 °C. 相似文献
7.
Thomas Jaffke Reza Hashemi Loucas G. Christophorou Eugen Illenberger 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1992,25(1):77-85
Measurements are reported on the formation of negative ions in O2, O2/Ar and O2/Ne clusters aimed at establishing the mechanisms of anion formation and the role of inelastic electron scattering by the cluster constituents on negative ion formation in clusters. In the case of pure O2 clusters the main anions we detected are of two types: O–(O2)
n0 and (O2)
n
1–
. The yields of O–(O2)
n
showed maxima at 6.3, 8.0 and 14.0 eV and the data suggest O– as their precursor; the maxima at 8 and 14 eV are due to the production of O– via symmetry forbidden dissociative attachment processes in O2 at these energies which become allowed in clusters. The yields of (O2)
n
–
showed a strong maximum at near-zero energy (0.5 eV) and also at 6.3, 8 and 14 eV. With the exception of the near-zero energy resonance, the (O2)
n
–
anions at 6.3, 8 and 14 eV are attributed to nondissociative attachment of near-zero energy secondary electrons to O2 clusters. The slow secondary electrons result predominantly from scattering via the O
2
–
negative ion states of incident electrons with energies in their respective regions. Similar results were obtained for the mixed O2/rare gas clusters except that now a feeble and distinctly structured contribution in the yields of O–(O2)
n
, (O2)
n
–
(and Ar(O2)
n
–
) was observed at energies >10 eV. These anions are believed to have the lowest negative ion states of Ar*– (Ne*–) as their precursors. 相似文献
8.
Bezruchko M. M. Tsventarnyi E. G. Malev V. V. 《Russian Journal of Electrochemistry》2001,37(11):1189-1196
The effect of nature and concentration of supporting-electrolyte cations (Li+, Na+, Cs+, (CH3)4N+, Ca2+, Ba2+) on electroreduction kinetics of PtCl2-
4at a dropping mercury electrode is studied. The electroreduction wave for PtCl2-
4is complicated by a polarographic maximum of first kind followed by a pronounced plateau of limiting current, after which the current passes through a minimum. The electroreduction occurs probably via two different mechanisms and presumably involves the same species, because the charge z
iof discharging species, determined by the Frumkin–Petrii method, remains virtually constant (z
i –1) on both descending (E= –0.6 to –1.0 V vs. SCE) and ascending (–1.3 to –1.6 V) branches of polarization curves and is independent of the nature of the supporting-electrolyte cation. The mechanism is presumably changed by a changed orientation of discharging species relative to the electrode surface. 相似文献
9.
Summary A complex of the formula[Cu2(PEAH2)2(NO3)(H2O)]-(NO3)[PEAH3 = 3,5-bis(N-ethylamido) pyrazole] was synthesized and its crystal structure determined by XRD methods. It consists of a dimeric cation with two bridging pyrazolate groups and a NO
3
–
anion. The geometries of the coordination polyhedra around the copper(II) ions are distorted square pyramidal. The variable temperature (20–300 K) magnetic susceptibility data gave the antiferromagnetic interaction constant as J=-191cm–1, showing that the pyrazole molecule is very effective in transmitting the exchange interaction. 相似文献
10.
In a series of molecular dynamics (MD) runs on (KI)108 clusters, the Born–Mayer–Huggins potential function is employed to study structural, energetic, and kinetic aspects of phase change and the homogeneous nucleation of KI clusters. Melting and freezing are reproducible when clusters are heated and cooled. The melted clusters are not spherical in shape no matter the starting cluster is cubic or spherical. Quenching a melted (KI)108 cluster from 960 K in a bath with temperature range 200–400 K for a time period of 80 ps both nucleation and crystallization are observed. Nucleation rates exceeding 1036 critical nuclei m−3 s−1 are determined at 200, 250, 300, 350, and 400 K. Results are interpreted in terms of the classical theory of nucleation of Turnbull and Fisher and of Buckle. Interfacial free energies of the liquid–solid phase derived from the nucleation rates are 7–10 mJ m−2. This quantity is 0.19 of the heat of transition per unit area from solid to liquid, or about two-thirds of the corresponding ratio which Turnbull proposed for freezing transition. The temperature dependence of σsl(T) of (KI)108 clusters can be expressed as σsl(T)∝T0.34. 相似文献
11.
This report describes the use of a piezoelectric quartz crystal (PQC) sensor to investigate the nonspecific adsorption of fibrinogen (FN) and sodium dodecyl sulfate (SDS) onto a self-assembled monolayer (SAM) of alkanethiols on gold. The change in adsorption mass was monitored in situ by the PQC sensor. A kinetics model was proposed to describe the adsorption of the FN and SDS on the hydrophobic SAM surface. The adsorption kinetics parameters were determined from the responses of the PQC. The adsorption and desorption rate constants of the FN on the SAM surface were estimated to be (6.18 ± 0.53) × 103 M−1 s−1 and (6.74 ± 0.72) × 10−3 s−1, respectively. The rate constants for the adsorption and desorption of SDS on the SAM are (24.3 ± 1.4 M−1 s−1) and (1.52 ± 0.11) × 10−2 s−1, respectively. The adsorption of SDS on the SAM was reversible. The fractional coverage of the FN on the SAM surface was estimated from kinetics analyses to be 42–86% for the FN concentration range 25–400 μg/ml. Over 80% of the FN is irreversibly adsorbed on the SAM surface with respect to dilution of the bulk phase. The fraction of FN reversibly adsorbed increases with the bulk concentration of FN. 相似文献
12.
Xiaoqian Shan Changsheng Liu Yuan Yuan Feng Xu Xinyi Tao Yan Sheng Huanjun Zhou 《Colloids and surfaces. B, Biointerfaces》2009,72(2):303-311
The effect of the PEG-grafted degree in the range of 0–30% on the in vitro macrophage uptake and in vivo biodistribution of poly(ethylene glycol)–poly(lactic acid)–poly(ethylene glycol) (PELE) nanoparticles (NPs) were investigated in this paper. The prepared NPs were characterized in terms of size, zeta potential, hydrophilicity, poly(vinyl alcohol) (PVA) residual on nanoparticles surfaces as well as drug loading. The macrophage uptake and biodistribution including plasma clearance kinetics following intravenous administration in mice of the NPs labeled by 6-coumarin were evaluated. The results showed that, except for the particles size, the hydrophilicity, superficial charges and in vitro phagocytosis amount of NPs are dependent on the PEG content in the copolymers greatly. The higher of the PEG content, the more hydrophilicity and the nearer to neutral surface charge was observed. And the prolonged circulation half-life (t1/2) of the PELE NPs in plasma was also strongly depended on the PEG content with the similar trend. In particular for PELE30 (containing 30% of PEG content) NPs, with the lowest phagocytosis uptake accompanied the highest hydrophilicity and approximately neutral charge, it had the longest half-life in vivo with almost 12-fold longer and accumulation in the reticuloendothelial system organs close to 1/2-fold lower than those of reference PLA. These results demonstrated that the PELE30 NPs with neutral charge and suitable size has a promising potential as a long-circulating oxygen carrier system with desirable biocompatibility and biofunctionality. 相似文献
13.
Michihiro Iijima Yukio Nagasaki 《Journal of polymer science. Part A, Polymer chemistry》2006,44(4):1457-1469
Poly[N‐isopropylacrylamide‐g‐poly(ethylene glycol)]s with a reactive group at the poly(ethylene glycol) (PEG) end were synthesized by the radical copolymerization of N‐isopropylacrylamide with a PEG macromonomer having an acetal group at one end and a methacryloyl group at the other chain end. The temperature dependence of the aqueous solutions of the obtained graft copolymers was estimated by light scattering measurements. The intensity of the light scattering from aqueous polymer solutions increased with increasing temperature. In particular, at temperatures above 40°C, the intensity abruptly increased, indicating a phase separation of the graft copolymer due to the lower critical solution temperature (LCST) of the poly(N‐isopropylacrylamide) segment. No turbidity was observed even above the LCST, and this suggested a nanoscale self‐assembling structure of the graft copolymer. The dynamic light scattering measurements confirmed that the size of the aggregate was in the range of several tens of nanometers. The acetal group at the end of the PEG graft chain was easily converted to the aldehyde group by an acid treatment, which was analyzed by 1H NMR. Such a temperature‐induced nanosphere possessing reactive PEG tethered chains on the surface is promising for new nanobased biomedical materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1457–1469, 2006 相似文献
14.
W. S. Drumond C. G. Mothé S. H. Wang 《Journal of Thermal Analysis and Calorimetry》2006,85(1):173-177
The thermogravimetric analysis (TG) of two series
of tri-block copolymers based on poly(L,L-lactide) (PLLA) and poly(ethyleneglycol) (PEG)
segments, having molar mass of 4000 or 600 g mol–1,
respectively, is reported. The prepared block copolymers presented wide range
of molecular masses (800 to 47500 g mol–1)
and compositions (16 to 80 mass% PEG). The thermal stability increased with
the PLLA and/or PEG segment size and the tri-block copolymers prepared from
PEG 4000 started to decompose at higher temperatures compared to those copolymers
from PEG 600. The copolymers compositions were determined by thermogravimetric
analysis and the results were compared to other traditional quantitative spectroscopic
methods, hydrogen nuclear magnetic resonance spectrometry (1HNMR)
and Fourier transform infrared spectrometry (FTIR). The PEG 4000 copolymer
compositions calculated by TG and by 1HNMR, presented
differences of 1%, demonstrating feasibility of using thermogravimetric analysis
for quantitative purposes. 相似文献
15.
Pamies R Zhu K Kjøniksen AL Knudsen KD Nyström B 《Journal of colloid and interface science》2008,326(1):76-88
Aqueous solutions of a thermoresponsive amphiphilic diblock copolymer, containing poly(N-isopropylacrylamide), in the presence of the anionic sodium dodecyl sulfate (SDS) surfactant can undergo a temperature-induced transition from loose intermicellar clusters to collapsed core–shell nanostructures. The polymer–surfactant mixtures have been characterized with the aid of turbidity, small-angle neutron scattering (SANS), intensity light scattering (ILS), dynamic light scattering (DLS), shear viscosity, and rheo-small angle light scattering (rheo-SALS). In the absence of SDS, compressed intermicellar structures are formed at intermediate temperatures, and at higher temperatures further aggregation is detected. The SANS results disclose a structure peak in the scattered intensity profile at the highest measured temperature. This peak is ascribed to the formation of ordered structures (crystallites). In the presence of a low amount of SDS, a strong collapse of the intermicellar clusters is observed at moderate temperatures, and only a slight renewed interpolymer association is found at higher temperatures because of repulsive electrostatic interactions. Finally, at moderate surfactant concentrations, temperature-induced loose intermicellar clusters are detected but no shrinking was registered in the considered temperature range. At a high level of SDS addition, large polymer–surfactant complexes appear at low temperatures, and these species are compressed at elevated temperatures. The rheo-SALS results show that the transition structures are rather fragile under the influence of shear flow. 相似文献
16.
Junhong Qian Yufang Xu Xuhong Qian Jiaobing Wang Shenyi Zhang 《Journal of photochemistry and photobiology. A, Chemistry》2008,200(2-3):402-409
Two fluorescent molecular sensors CS1 and CS2 were designed and synthesized to probe the aggregate behavior of anionic surfactant SDS. CS1 was based on the photo-induced electron transfer (PET) mechanism, while CS2 was founded on the intramolecular charge transfer (ICT) mechanism. The photophysical properties of CS1–2 in anionic surfactant sodium dodecyl sulfate (SDS) solution were studied by fluorescence and UV–vis methods. The experimental results show that significant absorption and emission spectral responses of CS1 were observed with the addition of SDS: the absorbance and fluorescence intensity decreased first and then increased. The plot of fluorescence intensity of CS1 versus SDS concentration showed two break points, which might be ascribed to the critical micellar concentration (cmc) and the formation of premicelle (cac) aggregate, respectively. But the solution’s color of CS2 changed from yellow to red with increasing SDS concentrations. The large red-shift in both absorption (50 nm) and emission (55 nm) spectra of CS2 was resulted from the protonation of the electron accepting moiety (NC nitrogen), which enhanced the “push–pull” interaction of the ICT fluorophore. This was facilitated by the increase of local H+ concentration around SDS premicelle and micelle. As a consequence, pKa values of CS1 and CS2 were elevated in SDS micelle. 相似文献
17.
Sergey P. Tunik Ivan S. Podkorytov Brian T. Heaton Jonathan A. Iggo Jeyagowry Sampanthar 《Journal of organometallic chemistry》1998,550(1-2)
Multinuclear NMR data (13C, 31P, 13C–{31P}, 13C–{103Rh} and 31P–{103Rh}) for a series of mono- and di-substituted derivatives of Rh6(CO)16 containing neutral two electron donor ligands [Rh6(CO)15L, (L=NCMe, py, cyclooctene, PPh3, P(OPh)3,1/2(μ2,η1:η1-dppe)); Rh6(CO)14(LL), (LL=cis-CH2=CMe-CMe=CH2, dppm, dppe, (P(OPh)3)2)] are reported; these data show that the solid state structure is maintained in solution. Detailed assignments of the 13CO NMR spectra of Rh6(CO)15(PPh3) and Rh6(CO)14(dppm) clusters have been made on the basis 13C–{103Rh} double resonance measurements and the specific stereochemical features of the observed long range couplings in these clusters have been studied. The stereochemical dependence of 3J(P–C) for terminal carbonyl ligands is discussed and the values of 3J(P–C) are found to be mainly dependent on the bond angles in the P–Rh–Rh–C fragment; these data enable the fine structure of the complex multiplets in the 13C–{1H} and 31P–{1H} NMR spectra of Rh6(CO)14 (dppm) to be simulated. Variable temperature 13C–{1H} NMR measurements on Rh6(CO)15(PPh3) reveal the carbonyl ligands in this complex to be fluxional. The fluxional process involves exchange of all the CO ligands except the two terminal CO's associated with the rhodium trans to the substituted rhodium and can be explained by a simple oscillation of the PPh3 on the substituted rhodium atom aided by concomitant exchange of the unique terminal CO on this rhodium with adjacent μ3-CO's. 相似文献
18.
Mohamed A. S. Goher Franz A. Mautner Thomas C. W. Mak Morsy A. M. Abu-Youssef 《Monatshefte für Chemie / Chemical Monthly》2003,134(12):1519-1527
Summary. Three new complexes, namely [(nicotinic acid)2H]+I–, [(2-amino-6-methylpyridine)H]+ (NO3)–, and the 1:1 complex between 1-isoquinoline carboxylic acid (zwitter ion form) and L-ascorbic acid were synthesized. The IR spectra revealed different types of hydrogen bonds in these compounds. The X-ray structure determination has shown the first compound to consist of a packing of [(nicotinic acid)2H]+ cations and I– anions. In the dimeric cation the two nicotinic acid molecules (zwitter ions) are connected through hydrogen bonds (O–HO). Each dimer is further engaged in other hydrogen bonds with adjacent dimers giving 2D layers. The I– ion is located at the inversion center. In the second compound the cation and anion are connected via hydrogen bonds formed between oxygen atoms of the NO3
– anion and NH and NH2 of the cation generating a layer structure. All atoms are coplanar on mirror planes. In the 1:1 complex the two molecules are connected through hydrogen bonds formed between the two oxygen atoms of the carboxylate group of 1-isoquinoline carboxylic acid (zwitter ion) and the oxygen atoms of the two adjacent hydrogen groups of the L-ascorbic acid molecule. These complex molecules are engaged in other hydrogen bonds with each other forming a 2D system normal to the long b-axis of the unit cell. 相似文献
19.
Zhu Hai-Liang Tong Ye-Xiang Chen Xiao-Ming Ren Chun-Xia 《Transition Metal Chemistry》2001,26(4-5):528-531
Two 2-terephthalate (tp) bridged complexes, [Cu2(tp)(pren)4](ClO4)2 (pren = 1,3-diaminopropane) (1) and [Ni2(tp)(pren)4(Him)2](ClO4)2 (Him = imidazole) (2), have been synthesized and characterized by X-ray single-crystal structural analysis. In the discrete dinuclear [Cu2(tp)(pren)4]2+ cation of complex (1), each CuII atom has a square-pyramidal geometry, being coordinated by four nitrogen atoms (avg. 2.031 Å) from two pren ligands at the basal plane and one oxygen atom [2.259(3) Å] from a bis-monodentate tp group at the axial position. In the discrete dinuclear [Ni2(tp)(pren)4(Him)2]2+ cation of complex (2), each NiII center is coordinated by five nitrogen atoms [Ni—N 2.069(3)–2.109(2) Å] from one Him group and two pren groups, and completed by one oxygen atom [Ni—O 2.138(3) Å] from a bis-monodentate tp group to furnish a distorted octahedron. Magnetic susceptibility studies show that the pair of metal atoms, although being separated by >11.5 Å, exhibit weak intramolecular antiferromagnetic interactions in complexes (1) (g = 2.07 and J = –3.4 cm–1) and (2) (g = 2.10 and J = –0.7 cm–1). The electrochemical behaviors of the complexes have also been studied by cyclic voltammogram processes. 相似文献
20.
Mohamed A. S. Goher Franz A. Mautner Thomas C. W. Mak Morsy A. M. Abu-Youssef 《Monatshefte für Chemie / Chemical Monthly》2003,15(3):1519-1527
Three new complexes, namely [(nicotinic acid)2H]+I–, [(2-amino-6-methylpyridine)H]+ (NO3)–, and the 1:1 complex between 1-isoquinoline carboxylic acid (zwitter ion form) and L-ascorbic acid were synthesized. The IR spectra revealed different types of hydrogen bonds in these compounds. The X-ray structure determination has shown the first compound to consist of a packing of [(nicotinic acid)2H]+ cations and I– anions. In the dimeric cation the two nicotinic acid molecules (zwitter ions) are connected through hydrogen bonds (O–HO). Each dimer is further engaged in other hydrogen bonds with adjacent dimers giving 2D layers. The I– ion is located at the inversion center. In the second compound the cation and anion are connected via hydrogen bonds formed between oxygen atoms of the NO3 – anion and NH and NH2 of the cation generating a layer structure. All atoms are coplanar on mirror planes. In the 1:1 complex the two molecules are connected through hydrogen bonds formed between the two oxygen atoms of the carboxylate group of 1-isoquinoline carboxylic acid (zwitter ion) and the oxygen atoms of the two adjacent hydrogen groups of the L-ascorbic acid molecule. These complex molecules are engaged in other hydrogen bonds with each other forming a 2D system normal to the long b-axis of the unit cell. 相似文献