Difference in micellar properties of sodium dodecyl sulfonate from sodium 4-decyl naphthalene sulfonate in D2O solution studied by 1H NMR relaxation and 2D NOESY

¹H chemical shift changes of sodium 4-decyl naphthalene sulfonate (SDNS) at 313 K show that its critical micellar concentration lies between 0.82 and 0.92 mmol/dm³, which is in the same range as that of the previous study at 298 K. The spin–lattice relaxation time, spin–spin relaxation time and two-dimensional nuclear Overhauser enhancement spectroscopy experiments give information about the structure of the SDNS micelle and the dynamics of the molecules in the micelle. The size of the SDNS micelle remains almost unchanged in the temperature range from 298 to 313 K as deduced by analyzing the self-diffusion coefficient. Special arrangement of the naphthyl rings of SDNS in the micelles affects the packing of these hydrophobic chains. The methylene groups of the alkyl chain nearest the naphthalene groups penetrate into the aromatic region, which results in a more tightly packed hydrophobic micellar core than that of sodium dodecyl sulfonate.     

Unusual volumetric and hydration behavior of the catanionic system sodium undecenoate: sodecyltrimethylammonium bromide

Following the studies on the effect of double bonds in the surfactant hydrophobic tail on the formation of mixed surfactant aggregates, we studied the viscosity and density of the system Sodium 10-undecenoate (SUD)–decyltrimethylammonium bromide (DTAB)–water. We found that the partial molar volume (pmv) and intrinsic viscosity of both, micellised and unmicellised mixtures, are non-ideal, dependent on the mixture composition and related to structural changes in micelles. These phenomena are caused by the presence of the double bond at the distal extreme of the SUD molecule, which has some affinity with water by formation of hydrogen bonds. In particular, as far as we know, this is the first report on non-ideal behavior of the pmv in mixed micelles.     

Application of solid phase peptide synthesis to engineering PEO–peptide block copolymers for drug delivery

This work describes a simple, versatile solid-phase peptide-synthesis (SPPS) method for preparing micelle-forming poly(ethylene oxide)-block-peptide block copolymers for drug delivery. To demonstrate its utility, this SPPS method was used to construct two series of micelle-forming block copolymers (one of constant core-composition and variable length; the other of constant core length and variable composition). The block copolymers were then used to study in detail the effect of size and composition on micellization. The various block copolymers were prepared by a combination of SPPS for the peptide block, followed by solution–phase conjugation of the peptide block with a proprionic acid derivative of poly(ethylene oxide) (PEO) to form the PEO-b-peptide block copolymer. The composition of each block component was characterized by mass spectrometry (MALDI and ES-MS). Block copolymer compositions were characterized by ¹H NMR. All the block copolymers were found to form micelles as judged by transmission electron microscopy (TEM) and light scattering analysis. To demonstrate their potential as drug delivery systems, micelles prepared from one member of the PEO-b-peptide block copolymer series were physically loaded with the anticancer drug doxorubicin (DOX). Micelle static and dynamic stability were found to correlate strongly with micelle core length. In contrast, these same micellization properties appear to be a complex function of core composition, and no clear trends could be identified from among the set of compositionally varying, fixed length block copolymer micelles. We conclude that SPPS can be used to construct biocompatible block copolymers with well-defined core lengths and compositions, which in turn can be used to study and to tailor the behavior of block copolymer micelles.     

Effect of hydrophobic amino acids on the conformational change of decapeptides in micellar environments

A series of peptides containing various hydrophobic amino acids [methionine (Met), leucine (Leu), norleucine (Nle), phenylalanine (Phe), 2-aminooctanoic acid (Aoc), and 2-aminodecanoic acid (Ade)] were synthesized and their conformations were studied using circular dichroism (CD) spectroscopy in different solvents such as water, methanol, and aqueous solution of ammonium tetradecanesulfonate. Peptides containing hydrophobic amino acids with linear side chains formed -sheets in water and methanol. Electrostatic interaction between the charged side chain (lysine) and a micelle consisting of an anionic surfactant, ammonium tetradecanesulfonate, is necessary for the formation of -helices in micellar environments. The conformational transition from -helix to -sheet structure required moderate hydrophobicity and linear side chains. This conformational transition depended on the surfactant concentration.     

SDS胶束对孔雀绿褪色反应的影响

研究了十二烷基硫酸钠（SDS）表而活性剂胶束和预胶束对孔雀绿褪色可逆反应的影响，建立了1－1型可逆反应的胶束催化模型和预胶束催化模型，获得了胶束相中正逆反应的速率常数和预胶束的平均聚集数．结果表明，SDS胶束和预胶束对正反应有禁阻作用，而对逆反应有催化作用．     

荧光探针法研究PEO-PPO嵌段共聚物胶束的特性

利用十六烷基罗丹明Ｂ作为主要荧光探针，研究了水溶性嵌段共聚物Ｐｌｕｒｏｎｉｃ Ｆ－６８在水溶液中的胶束化行为，研究表明，Ｐｌｕｒｏｎｉｃ－Ｆ－６８形成胶束的监界胶束浓度与温度有极大关系，随温度的升高，其ＣＭＣ值急剧下降，并且温度对胶束的性质也有很大，影响温度升高可导致胶束的微观粘度增大，表现出很强的负粘－温效应，并发现引起这种负粘－温效应的主要原因是Ｐｌｕｒｏｎｉｃ Ｆ－６８分子中聚环氧乙烷（ＰＥ     

Hydrolysis of cephanone in the micelles with different charges

The hydrolysis of cephanone in water and micelles with different charges was studied by UV-vis absorption spectroscopy. The change of pH with the hydrolysis of cephanone was determined. The mechanism of the hydrolysis and the effect of the acidity of the media on the hydrolysis were studied. The results show that the hydrolysis rate of cephanone increases with the acidity. Compared with water, SDS micelles accelerate this hydrolysis, whereas CTAB and Triton X-100 micelles suppress it. The effects of the micelles with different charges on the hydrolysis are explained by the proton concentration of the micro-environment where cephanone exists and by the charge density of the polar group of the cephanone molecules.     

Interaction of sodium cholate with dioctadecyldimethylammonium chloride vesicles in aqueous dispersion

Mixtures of dioctadecyldimethylammonium chloride (DODAC) cationic vesicle dispersions with aqueous micelle solutions of the anionic sodium cholate (NaC) were investigated by differential scanning calorimetry, DSC, turbidity and light scattering. Within the concentration range investigated (constant 1.0 mM DODAC and varying NaC concentration up to 4 mM), vesicle → micelle → aggregate transitions were observed. The turbidity of DODAC/NaC/water depends on time and NaC/DODAB molar concentration ratio R. At equilibrium, turbidity initially decreases smoothly with R to a low value (owing to the vesicle–micelle transition) when R = 0.5–0.8 and then increases steeply to a high value (owing to the micelle–aggregate transition) when R = 0.9–1.0. DSC thermograms exhibit a single and sharp endothermic peak at T_m ≈ 49 °C, characteristic of the melting temperature of neat DODAC vesicles in water. Upon addition of NaC, T_m initially decreases to vanish around R = 0.5, and the main transition peak broadens as R increases. For R > 1.0 two new (endo- and exothermic) peaks appear at lower temperatures indicating the formation of large aggregates since the dispersion is turbid. All samples are non-birefringent. Dynamic light scattering (DLS) data indicate that both DODAC and DODAC/NaC dispersions are highly polydisperse, and that the mean size of the aggregates tends to decrease as R increases.     

Fluorescence Probe Studies of Ionic Micelles in Concentrated Salt Solutions

We have investigated the effect of salt concentration and temperature on the average aggregation number and micro-polarity of the interior of micelles of sodium dodecyl sulfate (SDS). sodium tetradecyl sulfate (STDS) and lithium dodecyl sulfate (LiDS). The transient fluorescence decay of micelle-solubilized pyrene has been measured and analyzed. An exponent weighted average aggregation number <n>_e was obtained by this technique. For SDS and STDS in NaCl solution, <n>_e increases as the temperature is lowered or salt concentration is increased <n>_e increased from ～ 50 to ～ 250 over [NaCl] = 0 to 0.8 M. Due to the strong counterion binding of lithium in the micellar solution, the LiDS micelle is much, smaller and does not increase appreciabily even at [LiCl] =0.8 M. From the fluorescence spectrum fine structure of pyrene and the fluorescence decay of the monomer and excimer, we can understand the local polarity and the water penetration to the interior of the micelle upon addition of salts and with changing temperature. The interior of the micelle becomes more nonpolar as the salt concentration is increased and the temperature is lowered. A complete kinetic analysis of the time–dependence of the fluorescence is given. The kinetic analysis is in agreement with the results reached by fluorescence spectral analysis.