Interaction between sodium dodecylsulfate (SDS) and pluronic L61 in aqueous medium: assessment of the nature and morphology of the formed mixed aggregates by NMR, EPR, SANS and FF-TEM measurements.

The interaction of copolymer L61 i.e., (EO)2(PO)32(EO)2 (where EO and PO are ethylene and propylene oxides, respectively) with surfactant SDS (sodium dodecylsulfate) in relation to their self-aggregation, dynamics and microstructures has been physicochemically studied in detail employing the Nuclear Magnetic Resonance (NMR), Electron Paramagnetic Resonance (EPR), Small-Angle Neutron Scattering (SANS), and Freeze-Fracture Transmission Electron Microscopy (FF-TEM) methods. The NMR self-diffusion study indicated a synergistic interaction between SDS and L61 forming L61-SDS mixed complex aggregates, and deuterium (2H) NMR pointed out the nonspherical nature of these aggregates with increasing [L61]. EPR spectral analysis of the motional parameters of 5-doxyl steraric acid (5-DSA) as a spin probe provided information on the microviscosity of the local environment of the L61-SDS complex aggregates. SANS probed the geometrical aspects of the SDS-L61 assemblies as a function of both [L61] and [SDS]. Progressive evolution of the mixed-aggregate geometries from globular to prolate ellipsoids with axial ratios ranging from 2 to 10 with increasing [L61] was found. Such morphological changes were further corroborated with the results of 2H NMR and FF-TEM measurements. The strategy of the measurements, and data analysis for a concerted conclusion have been presented.

Comparative study on the responses of broiler chicken to hot and humid environment supplemented with different dietary levels and sources of selenium.

Present study was carried out with the objective of investigating the role of green synthesized nano Se (GNS) in growth performance, digestibility of minerals, immunity, stress alleviation, antioxidant status, and body Se content of broiler chicken raised under hot and humid environment with respect to market nano Se (MNS) and inorganic Se. The experimental design was 3 × 3 factorial, in which three levels (0.15, 0.20, and 0.25 ppm) and three sources (inorganic, green nano, and market nano) of Se resulted in nine treatments viz. IS-0.15, GNS-0.15, MNS-0.15, IZ-0.20, GNS-0.20, MNS-0.20, IS-0.25, GNS-0.25, and MNS-0.25 (IS: inorganic Se, GNS: green nano Se, MNS: market nano Se). A total of 432 broiler chicken were divided among nine treatments with six replicates of birds per treatment (8 birds/replicate). Results of present study revealed significantly better growth performance of birds supplemented with 0.25 ppm nano Se. The supplementation of 0.25 ppm nano Se improved the immune response and lymphoid organ development of birds. Significantly higher Se and nitrogen digestibility coefficients, serum antioxidant activity and decline of Heterophil: Lymphocyte ratio and expression of HSP70 gene were observed in birds supplemented with 0.25 ppm Se and nano source of Se compared to inorganic Se. Significantly higher Se concentration in liver and breast muscle and higher serum Se concentration were observed in birds fed 0.25 ppm nano Se. The liver Se concentration was much higher than that of breast muscle. However, the nano Se synthesized by green method in this study did not differ significantly from the chemically synthesized nano Se. It was concluded that 0.25 ppm Se and nano form of Se are superior to lower levels and inorganic form of Se, respectively, in improving the immunity, growth, antioxidant status, and in stress alleviation of broiler chicken. However, GNS is equally efficient as chemically synthesized MNS.

Feeding value of rice distiller's dried grains with solubles as protein supplement in diet of laying hens.

A feeding trial of 10 weeks duration was undertaken on laying hens (n = 240) to evaluate feeding value of rice distiller's dried grains with soluble (rDDGS) with or without enzyme supplementation (α-amylase, ß-glucanase, xylanase, carboxymethylcellulase, pectinase, proteinase, α-galactosidase, ß-galactosidase, lipase, and phytase), following 4 × 2 factorial design, on egg production, nutrient utilization, and cost economics of egg production. The birds were randomly assigned to eight dietary treatments with 30 birds/treatment. The birds were housed individually in layer cages and each bird was taken as an experimental unit. Eight experimental diets were prepared by incorporating four levels (0, 50, 75, and 100 g/kg) of rDDGS with and without enzyme supplementation. The results revealed a significant (P < 0.01) increase of egg mass, feed intake, egg production, and body weight gain in dietary treatments with up to 75 g rDDGS though the values were statistically similar to the hens fed 100 g rDDGS. Enzyme supplementation resulted in significant (P < 0.01) improvement of egg mass, egg production, feed conversion ratio (FCR) per dozen eggs, FCR per kilogramme egg mass, and net FCR. The significantly (P < 0.01) higher yolk index was observed at 100 g rDDGS level, while shell thickness improved significantly (P < 0.01) up to 75 g rDDGS level. No significant effect of rDDGS inclusion was observed on shape index, albumin index, and Haugh unit. Enzyme supplementation significantly improved the shell thickness and yolk colour of eggs. Nitrogen, calcium, and phosphorus retention and dry matter metabolizability did not show any significant treatment effects. There was significant (P < 0.01) reduction in feed-cost per kilogramme egg mass or per dozen eggs with the increased DDGS levels and dietary enzyme supplementation. It was concluded that rDDGS can be used up to 100 g/kg diet of laying hens along with enzyme supplementation for better productivity of layer hens.

Effect of graded levels of soapnut (Sapindus mukorossi) shell powder on reproductive performance in broiler breeders.

OBJECTIVE: This study investigated the effects of soapnut (Sapindus mukorossi) shell powder (SSP) on serum hormone level, egg quality, semen characteristics and reproductive performance of broiler breeders fed with a maize-soybean meal based diet. METHODS: Ninety six female and twenty four male CARIBRO-VISHAL broiler breeders, 38-week old, were individually caged and randomly allocated to four treatment groups (24 female breeders/treatment and 6 male breeders/treatment): an un-supplemented control (T1) and three groups with 0.0176% SSP (group T2), 0.026% SSP (group T3) and 0.0528% SSP (group T4), to have supplementary saponin at 0, 50, 75, and 150 ppm, respectively, for 42 days. RESULTS: The results indicated that serum (p<0.001) and seminal plasma (p<0.05) testosterone level, semen volume (p<0.001), mass motility (p<0.001), and live spermatozoa count (p<0.001) was increased in groups T3 and T4 compared to T2 and control groups. Compared with control group, total sperm count was increased (p<0.001) and dead spermatozoa count was decreased (p<0.001) in SSP supplemented groups. Supplementation of SSP did not affected the quality of egg lay. Compared with control group, fertility (p<0.01) and hatchability (total eggs set and fertile eggs set) (p<0.001) were significantly improved in SSP supplemented groups with the highest improvement in T3 treatment group. Embryonic death was decreased (p< 0.001) in SSP supplemented groups compared to control; lowest embryonic death was recorded in T3 treatment group. CONCLUSION: Thus, it was concluded that dietary supplementation of 0.026% SSP (saponin equivalent 75 ppm) improved the reproductive performance of broiler breeders.

Dietary supplementation of saponins to improve the quality and oxidative stability of broiler chicken meat.

A total of 384 broiler chicken of same hatch and uniform body weight were used to assess the role of saponins in meat quality. The soapnut shell powder obtained from Sapindus mukorossi was used as a source of saponins. Following a 4 × 2 factorial design broiler chicken diets were supplemented with four saponin levels (0, 100, 150, 200 mg/kg diet) and each provided for 42 (0-42 day) and 21 days (21-42 day) resulting into eight dietary treatments. The results revealed that dietary saponin supplementation significantly (P < 0.05) and progressively decreased the cholesterol, fat content, and peroxide values (after 30 days of 0 °C storage) of breast and thigh meat. There was a progressive and significant (P < 0.05) increase in the ABTS and DPPH values of broiler chicken meat with increasing dietary saponin levels. However, the effect of dietary saponin level of 150 mg did not differ significantly from 200 mg level. The peroxide values of breast and thigh meat after 30 days of storage and TBARS values of fresh breast and thigh meat as well as after 30 days of storage were significantly (P < 0.05) higher in control group compared to other groups supplemented with different saponin levels which did not differ significantly (P > 0.05) from each other. Further, significantly (P < 0.05) better antioxidant and lipid oxidation status was observed by supplementing saponins for 42 days duration compared to 21 days. Thus, it was concluded that the dietary supplementation of 150 mg saponin/kg diet of broiler chicken for 42 day duration results in better meat quality with better lipid oxidative stability.

Effect of dietary manipulation and vaccination of turkey breeder hens on immunoglobulin levels of yolk, yolk sac and neonate poults.

Two hundred turkey breeder hens and 24 viable toms of 30-35 weeks age of small white variety were distributed into two treatment groups having four replicates of 25 hens and three toms in each treatment. First four replicates were offered a turkey breeder diet (Diet A) (Nutrient requirements of poultry, 1994, National Academic Press, Washington, DC) and the rest four replicates were maintained on a higher plane of nutrition (Diet B) for 8-week duration. After 6 weeks of experimental feeding, two replicates from each treatment groups were vaccinated with ND (R2 B) vaccine. Yolk sac of embryo from birds fed Diet B had a significantly higher (p < .05) IgG, IgM level and HI titre (log 2) than those fed Diet A. HI titre values of embryonic yolk sac from the vaccinated birds fed Diet B were significantly higher (p < .05) than that of the control groups. In addition, HI titre values were significantly higher (p < .05) in the day-old poults of the birds fed Diet B than that of those fed Diet A. There was significantly (p < .01) positive correlation between serum IgG and IgM of the breeder birds and day-old chicks. Similarly, there was significantly (p < .05) positive correlation between yolk IgG and IgM after 1-month experimental feeding and yolk sac IgG and IgM. Positive correlation (p < .05) also existed between yolk sac IgM and day-old chick serum IgM. Furthermore, the HI titres of breeder birds' serum at 14 days post-vaccination were positively correlated with their egg yolk after 10 and 15 days post-vaccination, yolk sac and day-old chicks. Thus, the study envisaged that a higher immunity in neonate poults from turkey breeders maintained on a higher plane of nutrition may be elicited as there was maternal transfer of antibodies from the serum of breeder birds to their offsprings through their yolk sac.

Vesicle to micelle transition in the ternary mixture of L121/SDS/D2O: NMR, EPR and SANS studies.

Subtle changes in the microstructure and dynamics of the triblock copolymer L121, (ethylene oxide)5 (propylene oxide)68 (ethylene oxide)5i.e., E5P68E5, and sodium dodecylsulfate (SDS) system in aqueous medium were investigated using high-resolution nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR) and small-angle neutron scattering (SANS) methods. NMR self-diffusion measurements helped us to understand the nature of binding of SDS with L121, and the formation of their mixed aggregates. These results showed that even at low [SDS] (∼2 mM), the addition of L121 stabilized the dynamics of SDS. Furthermore, the increase in [SDS] resulted in progressive changes in the diffusion behavior of both SDS and L121. 13C chemical shift analysis revealed that preferential binding of L121 occurred on the SDS micelle surface. Deuterium (2H) NMR spin-relaxation data evidenced that the formed mixed aggregates were non-spherical in terms of relaxation rate changes, and slowed the dynamics. The rotational correlation times of mixed aggregates were estimated from EPR analysis. A SANS study indicated the presence of uni- and multi-lamellar vesicles of L121 at low [SDS]. The vesicles transformed to mixed L121-SDS micelles in the presence of a higher [SDS]. This was supported by the measurements of 2H NMR spin-relaxation and EPR rotational correlation times.

Semen characteristics and biochemical composition of cloacal foam of male Japanese quails (Coturnix coturnix Japonica) fed diet incorporated with selenium.

An attempt was made to investigate the effect of dietary selenium (Se) on physical and cloacal gland size, foam production, biochemical composition of foam and semen biochemical characteristics of male Japanese quail (Coturnix coturnix Japonica). Two hundred twenty-five (225)-day-old male Japanese quail were randomly distributed to three dietary treatment groups for a period of 20 weeks. Each treatment comprised of three replicates, each containing 25 chicks. Three experimental diets were supplemented with 0, 0.5 and 1.0 mg Se/kg (T1 , T2 and T3, respectively), and diet T1 was considered as control. Sodium selenite was used as the source of selenium. All the birds were provided with feed and water ad libitum. Cloacal foam characteristics, that is cloacal gland index and foam weight, were significantly higher in T2 group. However, body weight, frequency of foam discharge and testes weight (left and right) did not differ significantly (p > 0.05). Physical characteristics of semen, that is semen volume and sperm concentration, did not differ (p > 0.05) among the Se-treated groups. The sperm motility, live-dead count and abnormality improved significantly (p < 0.05) in 0.5 mg/Se-supplemented group compared to 0 or 1.0 mg/Se-supplemented groups. Similarly, fertility and hatchability percentages were higher (p < 0.05) in 0.5 mg/Se-supplemented group than in control or 1.0 mg/Se-supplemented counterparts. The biochemical characteristics of foam in terms of total protein, acid phosphatase (ACP) and nitric oxide did not differ (p > 0.05), while the concentration of glucose was higher (p < 0.05) in 0.5 mg/Se-supplemented diet. On the other hand, alkaline phosphatase (ALP), alanine aminotransferase (ALT) and aspartate aminotransferase (AST) were lower (p < 0.05) in 0.5 mg/Se-supplemented group compared to control or 1.0 mg/Se-supplemented groups. From this study, it was concluded that supplementation of 0.5 mg Se/kg diet was beneficial for foam variables, biochemical composition of foam, semen characteristics and fertility in male Japanese quail.

Impact of feeding chromium supplemented flaxseed based diet on fatty acid profile, oxidative stability and other functional properties of broiler chicken meat.

A total of 240 broiler chicken of same hatch with uniform weight were used in a biological experiment with completely randomized design to investigate the effects of incorporating organic chromium (Cr) in flaxseed meal based diet on the fatty acid profile, oxidative stability and functional properties of broiler chicken meat. Five diets were formulated as per the recommendations of BIS (Nutrient requirements for poultry 13: 9863, Bureau of Indian Standards, New Delhi, 1992) in which flaxseed meal was used to replace 10% of soyabean in basal diet and four levels of Cr (0.0, 0.5, 1.0 and 1.5 mg/kg diet) as Cr-picolinate were used. The results revealed that flaxseed feeding significantly increased the percentage of unsaturated fatty acids, including MUFA, PUFA, ω-3, ω-6 fatty acids and ω-3:ω-6 and PUFA:SFA ratios, whereas, significant decline was seen in saturated fatty acids and no effect of Cr was observed on the fatty acid profile of broiler chicken. Flaxseed feeding significantly reduced the cholesterol and fat percentage of meat, whereas, significant progressive reduction was observed with increasing Cr levels. The combination of 10% flaxseed with 1.0 mg Cr/kg diet increased the final pH of broiler meat. The addition of flaxseed significantly reduced water holding capacity, extract release volume and antioxidant potential of broiler meat, whereas, increasing Cr supplementation progressively increased them. Flaxseed feeding significantly increased the drip loss and lipid peroxidation of broiler meat, whereas, Cr supplementation decreased them. It was concluded that inclusion of 10% flaxseed and 1.5 mg Cr/kg diet results in desirable fatty acid profile, oxidative stability and functional properties of broiler chicken meat.

"Bottom-up" self-assembly and "cold crystallization" of butterfly shaped tetrabenzofluorene molecules.

Butterfly-shaped tetrabenzo[a,c,g,i]fluorene (TBF)-based molecules (1 and 2) were designed, synthesized and well characterized using various spectroscopic techniques. The single crystal X-ray structure of 1 shows the presence of intermolecular 3-D π-π stacking interaction and unprecedented "cold crystallization" in polycyclic aromatic molecules. We report for the first time, the "bottom-up" self-assembly of TBF based organic molecules. The supramolecular studies reveal the formation of vesicles and cuboid-shaped nanocrystals in THF-water and toluene solution, respectively.

2-Octyl thiophene based three ring mesogens: solid state (13)C NMR and XRD investigations.

2-Octyl thiophene based three-ring mesogens namely 4-n-alkoxyphenyl 4-(5-n-octyl-2-thienyl)benzoates are synthesized by employing palladium acetate based direct arylation. The alkoxy terminal is varied with even carbons from C2 to C14 and enantiotropic polymesomorphism is noticed for all the homologs. Accordingly, phase sequence consisting of nematic, smectic A, smectic C and smectic B is seen for mesogens with terminal chains C6, C8, C10 and C12 on cooling the isotropic phase. For mesogens with C2, C4, C8 and C10 terminal alkoxy chains, the mesophase assignment from hot-stage optical microscopy and differential scanning calorimetry is further confirmed by variable temperature powder X-ray diffraction measurements. The appearance of smectic B phase is established by noticing sharp and intense peaks in both small-angle and wide-angle regions. For a representative mesogen, i.e. T10, high-resolution solid-state (13)C NMR investigations are carried out in all the phases, viz. nematic, smectic A, smectic C and smectic B phases. The orientational order parameters calculated from (13)C-(1)H dipolar couplings from 2D SAMPI-4 experiments are found to be 0.44, 0.67, 0.73 and 0.79 in nematic, smectic A, smectic C and smectic B mesophases for the center phenyl ring respectively. Remarkably, the thiophene order parameter in all mesophases is found to be higher than that of phenyl rings and is explained by considering the molecular shape, which has a terminal bend. Further, the mesogens are found to be photoemissive in chloroform solution with an emission band at ∼410 nm.

Physicochemical perspectives (aggregation, structure and dynamics) of interaction between pluronic (L31) and surfactant (SDS).

The influence of the water soluble non-ionic tri-block copolymer PEO-PPO-PEO [poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)] i.e., E2P16E2 (L31) on the microstructure and self-aggregation dynamics of the anionic surfactant sodium dodecylsulfate (SDS) in aqueous solution was investigated using cloud point (CP), isothermal titration calorimetry (ITC), high resolution nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), and small-angle neutron scattering (SANS) measurements. CP provided the thermodynamic information on the Gibbs free energy, enthalpy, entropy and heat capacity changes pertaining to the phase separation of the system at elevated temperature. The ITC and NMR self-diffusion measurements helped to understand the nature of the binding isotherms of SDS in the presence of L31 in terms of the formation of mixed aggregates and free SDS micelles in solution. EPR analysis provided the micro-viscosity of the spin probe 5-DSA in terms of rotational correlation time. The SANS study indicated the presence of prolate ellipsoidal mixed aggregates, whose size increased with the increasing addition of L31. At a large [L31], SANS also revealed the progressive decreasing size of the ellipsoidal mixed aggregates of SDS-L31 into nearly globular forms with the increasing SDS addition. Wrapping of the spherical SDS micelles by L31 was also corroborated from (13)C NMR and SANS measurements.

In ovo carbohydrate supplementation modulates growth and immunity-related genes in broiler chickens.

A study was undertaken to investigate the role of in ovo administrated carbohydrates on the expression pattern of growth and immune-related genes. In ovo injections (n = 400) were carried out on the 14th day of incubation into the yolk sac/amnion of the broiler chicken embryos. Expression of growth-related genes: chicken growth hormone (cGH), insulin-like growth factor-I & II (IGF-I & II) and mucin were studied in hepatic and jejunum tissues of late-term embryo and early post-hatch chicks. Expression of candidate immune genes: Interleukin-2, 6, 10 and 12 (IL-2, IL-6, IL-10 and IL-12), Tumour necrosis factor-alpha (TNF-α) and Interferon gamma (IFN-γ) were studied in peripheral blood monocyte cells of in ovo-injected and control birds following antigenic stimulation with sheep RBC (SRBC) or mitogen concanavalin A (Con-A). Glucose injection significantly increased the expression of IGF-II gene during embryonic period and both cGH and IGF-II in early post-hatch period, while ribose-injected chicks had higher expression of IGF-II gene during embryonic stage. Enhanced mucin gene expression was also observed in fructose-injected chicks during embryonic age. Glucose-injected chicks had higher expression of IL-6 or IL-10, while those injected with fructose or ribose had higher expression of IL-2, IL-12 and IFN gamma. It is concluded that in ovo supplementation of carbohydrates might help in improving the growth of late-term embryos and chicks. In ovo glucose could modulate humoral-related immunity, while fructose or ribose might help in improving the cellular immunity in broiler chickens.

Micellization and related behavior of sodium dodecylsulfate in mixed binary solvent media of tetrahydrofuran (Tf) and formamide (Fa) with water: a detailed physicochemical investigation.

The detailed aggregation behavior of sodiumdodecyl sulfate (SDS) in tetrahydrofuran (Tf)-water (W) and formamide (Fa)-water (W) media at varied volume percent compositions has been investigated. Surface tension (ST), conductance (Cond), viscosity (Visc), isothermal titration calorimetry (ITC), nuclear magnetic resonance (NMR) and small angle neutron scattering (SANS) were used in this study. The presence of nonaqueous solvents affected the critical micelle concentration (CMC) of SDS, the counter-ion binding of the micelle, the energetics of the air/water interfacial adsorption and micellization of the amphiphiles in the bulk, the ion-association (ion-pair, triple-ion, quadruple, etc. between Na(+) and DS(-) ions) as well as the weakly soluble (aggregation less) amphiphile solution. Tf has been observed to produce a "dead zone" or "non-micelle formation zone" in the mixed Tf-W domain of 10-40 vol%. Fa influenced the SDS aggregation up to 70 vol%, at higher proportions (below the Krafft temperature (K(T))), instead of the micelle, "randomly arranged globular assembly" (RAGA) was formed. The correlation of the standard free energy of micellization (ΔG(m)(0)) with different solvent parameters (1) dielectric constant (ε), (2) viscosity (η0), (3) Reichardt parameter (E(T)(30)), (4) Gordon parameter (G), and (5) Hansen-Hildebrand hydrogen bonding parameter (δ(h)) has been attempted. It has been found that δ(h) produced a master correlation between ΔG(m)(0) and δ(h) for different binary mixtures such as Tf-W, Fa-W, Ml-W and Dn-W.

Qualitative toxicity assessment of silver nanoparticles on the fresh water bacterial isolates and consortium at low level of exposure concentration.

Silver nanoparticles (AgNPs) pose a high risk of exposure to the natural environment owing to their extensive usage in various consumer products. In the present study we attempted to understand the harmful effect of AgNPs at environmentally relevant low concentration levels (≤1ppm) towards two different freshwater bacterial isolates and their consortium. The standard plate count assay suggested that the AgNPs were toxic towards the fresh water bacterial isolates as well as the consortium, though toxicity was significantly reduced for the cells in the consortium. The oxidative stress assessment and membrane permeability studies corroborated with the toxicity data. The detailed electron microscopic studies suggested the cell degrading potential of the AgNPs, and the FT-IR studies confirmed the involvement of the surface groups in the toxic effects. No significant ion leaching from the AgNPs was observed at the applied concentration levels signifying the dominant role of the particle size, and size distribution in bacterial toxicity. The reduced toxicity for the cells in the consortium than the individual isolates has major significance in further studies on the ecotoxicity of the AgNPs.

Nanocarriers of solid lipid from micelles of amino acids surfactants coated with polymer nanoparticles.

Polymer nanoparticle coated micelle assemblies of lauryl ester of tyrosine (LET) act as potential nanocarriers for the model solid lipid stearyl alcohol. The coating is afforded by a simple methodology of heterophase polymerization reaction of styrene or the mixture of styrene and butyl acrylate at a mole ratio of 0.8:0.2 in the presence of 200 mM LET in water. On the contrary, the polymer nanoparticles produced under similar conditions in the presence of a structurally similar surfactant, lauryl ester of phenyl alanine (LEP), failed to act as nanocarrier. The micelle templates of LET and LEP favored polymerization under controlled conditions as observed from the near monodisperse distribution of molecular weight and size of the polymers. The particle size distribution of poly(styrene) (PS) and poly(styrene-co-butyl acryalte) (PS-co-PBA) nanoparticles from LET was smaller at 24 and 20 nm in comparison to those from LEP. The encapsulation efficiency of polymer nanoparticles from LET surfactant is explained on the basis of difference in the coating of micelle assemblies, which we believe must be arising due to difference in the solubilization site of the monomers in the surfactant micelles before polymerization reaction. The solubilization of the model monomer, benzene at different regions, varying between shell and core of LET and LEP micelles is established from (1)H nuclear magnetic resonance spectra. The evidence for the coating of micelle assemblies from surface tension measurements and the encapsulation of stearyl alcohol in the polymer nanoparticle dispersions from LET drawn from transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analysis is discussed.

pH-responsive aggregation states of chiral polymerizable amphiphiles from L-tyrosine and L-phenyl alanine in water.

Sodium salts of maleamic acid derivatives of lauryl ester of tyrosine (MTNa) and phenyl alanine (MPNa) in water exhibited strong pH-responsive behaviors of viscosity and specific conductivity that originate from the concentration and pH dependence of their aggregation states. The aggregates were characterized by a novel spin-probe-partitioning electron paramagnetic resonance (SPPEPR) method and dynamic light scattering (DLS). Results of high-precision fitting of the second-harmonic EPR spectra of the small spin probe di-tert-butyl nitroxide (DTBN) in these aggregates together with viscosity, conductivity, and DLS showed that, at pH ~ 7.54, MTNa formed micelles and MPNa vesicles and MTNa exhibited a pH-induced micelle to vesicle transition as pH was lowered toward 6. MTNa, at pH ~ 7.54, formed small micelles at low concentrations that transformed to long worm-like micelles for concentrations ≥ 0.05 M, accompanied by a 30-fold increase in solution viscosity. The hydrodynamic radii from DLS confirmed the presence of small micellar aggregates of radius ~ 2 nm in MTNa at pH ~ 7.54 at the lower concentrations, with coexisting micelles (~2 nm) and vesicles (~50 nm) at pH near 6.5, vesicles (radii ~ 70 nm) at pH near 6, and large vesicles (85 nm) in MPNa at pH ~ 7.60. Both MTNa and MPNa precipitated upon reduction of pH below 6 and below 7, respectively. The rate of transfer of DTBN between the aqueous phase and the aggregate was calculated from the high-field Lorentzian linewidths of the electron paramagnetic resonance (EPR) spectra. The activation energy for the transfer determined from the temperature dependence of the rate of transfer is 12.7 kJ/mol for MTNa vesicles (pH ~ 6) and 20.6 ± 1.3 kJ/mol for MPNa (pH ~ 7.60). The pH-induced transformations were reversible.

Unprecedented relationship between the size of spherical chiral micellar aggregates and their specific optical rotations.

Transmission electron microscopy (TEM) images and fluorescence quenching methods indicated that lauryl ester of L-phenylalanine (LEP) and lauryl ester of L-tyrosine (LET) form spherical chiral micelles in the 50-200 mM range and their size increases with concentration. The number of molecules present in these spherical chiral aggregates varied from 80 to 160 for LEP and 80-100 for LET. The specific optical rotation, representing circular birefringence, for LEP at 405 nm and 32 °C is found to increase linearly from 37 deg cc g(-1) dm(-1) for an isolated molecule to 56 deg cc g(-1) dm(-1) for ∼200 nm size aggregate. A similar trend was found for temperatures up to 70 °C and at other visible wavelengths. A linear relation between specific optical rotation and the size of aggregate is also observed for LET. Circular dichroism, as measured in both the visible and infrared wavelength regions, however did not reveal any concentration dependent changes. The unique sensitivity uncovered for specific optical rotation as a function of the size of spherical chiral aggregates is unprecedented and opens new areas of enquiry for physical chemists.

Formation of self-aggregated structures of different types in water of chiral polymerizable amphiphiles from L-tyrosine and L-phenylalanine.

Sodium salts of maleamic acid derivatives from lauryl esters of L-tyrosine (MTNa) and L-phenylalanine (MPNa) were synthesized and characterized. The aggregated structures of MTNa and MPNa in water were investigated, employing several independent methods. MPNa showed secondary aggregated structures in contrast to MTNa at concentrations of >1 × 10(-3) M. The results from dynamic light scattering, transmittance, conductivity, and viscosity measurements suggested the formation of aggregated structures of different types in MTNa and MPNa solutions. The measured fluorescence anisotropy (r) at 0.180 of the fluoroprobe, 1,6-diphenyl-1,3,5-hexatriene (DPH), and the d spacing of 38 Å from small-angle X-ray diffraction (SAXD) experiments confirmed the bilayer structures in MPNa. Scanning electron microscope (SEM) images provided the morphological features. The emulsion produced using MPNa solution was more stable. The confocal fluorescence microscopy image of the emulsion from MPNa confirmed the entrapment of water-soluble dye, rhodamine. The models of MTNa and MPNa molecules and the aggregated structures are presented.

Amphiphile behavior in mixed solvent media I: self-aggregation and ion association of sodium dodecylsulfate in 1,4-dioxane-water and methanol-water media.

Mixed aquo-organic solvents are used in chemical, industrial, and pharmaceutical processes along with amphiphilic materials. Their fundamental studies with reference to bulk and interfacial phenomena are thus considered to be important, but such detailed studies are limited. In this work, the interfacial adsorption of sodium dodecylsulfate (SDS, C12H25SO4(-)Na(+)) in dioxane-water (Dn-W) and methanol-water (Ml-W) media in extensive mixing ratios along with its bulk behavior have been investigated. The solvent-composition-dependent properties have been identified, and their quantifications have been attempted. The SDS micellization has been assessed in terms of different solvent parameters, and the possible formation of an ion pair and triple ion of the colloidal electrolyte, C12H25SO4(-)Na(+) in the Dn-W medium has been correlated and quantified. In the Ml-W medium at a high volume percent of Ml, the SDS amphiphile formed special associated species instead of ion association. The formation of self-assembly and the energetics of SDS in the mixed solvent media have been determined and assessed using conductometry, calorimetry, tensiometry, viscometry, NMR, and DLS methods. The detailed study undertaken herein with respect to the behavior of SDS in the mixed aquo-organic solvent media (Dn-W and Ml-W) is a new kind of endeavor.