Laponite clay in homopolymer and tri-block copolymer matrices

Macromolecule/laponite nanomaterials were studied by DSC and X-ray diffraction techniques. The matrices are poly(ethylene) glycols at various molecular masses and poly(ethylene oxides)-poly(propylene oxides)-poly(ethylene oxides) tri-block copolymers. The latter were tuned by modulating the molecular masses, at constant hydrophilic/hydrophobic ratio, and the hydrophilicity. For all the investigated systems, the enthalpy of melting (ΔH _m) is nearly constant up to a given composition thereafter it increases monotonically reaching the value of the pure macromolecule. We proposed a model to interpret the DSC data. Briefly, it was invoked a mechanism of interaction following which some segments of the adsorbed macromolecule are anchored to the laponite (RD) particles and the remaining segments are radiating away from the surface. The portion of the macromolecule in contact with RD does not contribute to ΔH _m whereas that radiating away from the clay does. Once that the RD surface is saturated, the excess of the macromolecule behaves like the pure one. The proposed model allowed to compute successfully the ΔH _m values. The X-ray diffraction experiments ruled out the polymer intercalation between the silicate sheets.     

A tri-block copolymer templated synthesis of gold nanostructures

Stable ultra-small gold nanoparticles have been synthesized in aqueous phase by using a tri-block copolymer (BMB) as a templating agent consisting of two PEG-methylacrylate chains (B blocks) anchored to a poly(methacrylic) moiety containing a trithiocarbonate unit (M block). The effect of the BMB/Au molar ratios on the final particle size, shape and monodispersity has been investigated. The synthesized nanosols have been characterized by means of Visible Absorption, Small Angle X-ray Scattering (SAXS), and Transmission Electron Microscopy (TEM). Results clearly indicate that the polymer plays a key role in determining the size and shape of gold particles, from fractal-like structures to monodisperse spherical particles with a mean diameter of about 3 nm. The aggregation behavior of these nanostructures has been characterized both in solution (SAXS) as well as on mica substrate (AFM) and has been proven to be driven by the polymer to gold concentration ratio.     

Mechanical hole burning spectroscopy in an SIS tri-block copolymer

We have previously developed a mechanical hole burning spectroscopy (MSHB) technique that promises to be a powerful tool for the investigation of dynamic heterogeneity of polymeric materials. This is because, unlike its dielectric analogue, MSHB can be used to characterize materials having a weak dielectric response, a particular feature of polymeric materials. However, while both mechanical and dielectric hole burning show behaviors that are consistent with dynamic heterogeneity in the materials, it is still unclear what the relationship between the hole properties, for example, frequency and amplitude, and the actual nature of the heterogeneity and particularly the length scale being probed. Here, we provide first evidence that a known length scale can be probed by the MSHB method by using a tri-block copolymer as a “calibration” sample. The heterogeneity of a styrene-isoprene-styrene copolymer was investigated in the vicinity of the order-disorder transition temperature (ODT). It was found that the amplitudes of the mechanical holes gradually decrease as the order-disorder transition is traversed from the region with ordered structures. In the disordered state of the block copolymer, no apparent mechanical holes were detected. In contrast, mechanical holes were burned in the heterogeneous region and the hole amplitude increased as the depth into the ordered structure increased. Hence, the MSHB technique provides a qualitative correlation between the amplitude of the burned holes and the corresponding heterogeneity. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3277–3284, 2007     

Temperature,concentration and salt effect on F68 tri-block copolymer in aqueous solution: Rheological study

The rheology of the aqueous solution of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO?PPO?PEO) triblock copolymer, Pluronic F68 in the presence of KF was studied in the temperature range from 15 to 60°C. The variation of the shear stress according to the shear rate shows that independently from the temperature and concentration, the F68 solutions exhibit a Newtonian behavior. The results show that the Critical Micelle Temperature of Pluronic F68 in a KF aqueous solution decreases with the increase in the salt concentration.     

Wettability of tri-block copolymer coated hydrophobic surfaces Predictions and measurements

Hydrophobic surfaces with adsorbed tri-block copolymers are wetted by oil in spite of the hydrophilic buoy groups of the block copolymer that are present near the surface. The effect of the buoy group length of the adsorbed molecules on the wettability of hydrophobic surfaces is studied by contact angle measurements and by computer modelling.

The computer model predicts an increase in interfacial free energy with increasing buoy group length for equilibrium adsorption of block copolymer from water. Molecules with large buoy groups occupy more lateral space; therefore the “bare” surface gets more exposed and the anchor groups contribute less to the interfacial free energy which thus increases with the buoy group length.

The calculations showed that the variation of the interaction parameter between solvent and buoy group hardly influences the interfacial free energy. In contrast the interaction parameter between solvent and surface influences the interfacial free energy to a large extent because the oil/surface interactions have a lower energetic value as compared to water/surface interactions and therefore the interfacial free energy is lower than in water. The interfacial free energy varies slightly with increasing buoy group length, depending on the value chosen for the solvent/surface interaction parameter.

Advancing and receding contact angles of hexadecane, sunflower oil and hydrolysate (partly hydrolysed sunflower oil) were measured on hydrophobic surfaces. All oil/water contact angles were small, indicating a hydrophobic apolar surface character. It was found that, for oils with a “good” interaction with the surface (hexadecane and sunflower oil), the contact angle has a minimum value at a certain buoy group length. For hydrolysate (less-strong interaction with the surface) the contact angle decreases monotonically with increasing buoy group length. The results for hexadecane, sunflower oil and hydrolysate are in reasonable agreement with the model predictions. The effect of increasing buoy group length is weak; both decreasing and increasing angles are found, depending on the type of oil used.     

Concentration and solvent induced micellization of F68 tri-block copolymer

The Fourier transform infrared spectroscopy is used to study the binary mixtures of F68/water and F68/p-xylene. The results show that in aqueous solution the wavenumbers of the two bands associated to the O-H and C-O-C vibrations are inversely proportional. This can be explained by the fact that the dehydrated methylene groups approach by the hydrophobic interaction to form hydrophobic cores, which lead to a breakdown of the hydrogen bond between water and C-O-C. The spectrum associated to the binary mixture F68/p-xylene show that F68 exists as nonassociated molecules (unimers) at room temperature. The results of the ternary mixtures of the F68/p-xylene/water show a change in the spectra on the level of the vibrations of the O-H and C-O-C groups which is attributed to the change of structure following the variation of the concentration from unimers to large aggregates.     

Mesoscopic simulation of alkylimidazoline self-aggregation in aqueous solution

A dissipative particle-dynamics method was used to simulate the self-aggregation behavior of 15 alkylimidazoline surfactants of different structures. The effects of concentration and structure of hydrophilic and lipophilic groups of the alkylimidazolines on the configuration and aggregation number (N_agg) of the micelles were also explored. Results show that the concentration of the alkylimidazoline has a significant influence on the configuration of the micelles generated. More specifically, alkylimidazolines of different concentrations are found to generate different structures (spherical, rod-shaped, layered, and interlaced) in aqueous solution. At low (1–10?wt%) and medium (40?wt%) concentrations, the micelles generated in aqueous solution are spherical and rod-shaped, respectively. At higher concentrations (80?wt%), the micelles generated present interlaced shapes with rod-shaped and layered micelles when the length of the lipophilic chain is greater than C₁₃ or the hydrophilic group is H_c. N_agg is strongly dependent on alkylimidazoline concentration and increases as concentration increases. N_agg is also greatly dependent on the structure of the hydrophilic and lipophilic groups present: it increases as the chain length of the lipophilic group increases but decreases as that of the hydrophilic group increases.     

Light scattering and luminescence studies on self-aggregation behavior of amphiphilic copolymer micelles

The self-aggregation behavior of three amphiphilic graft copolymers, oligo(9,9-dihexyl)fluorence-graft-poly(ethylene oxide) (OHF-g-PEO), with different architectures was studied by dynamic and static light scattering (DLS and SLS) in combination with fluorescence spectroscopy and transmission electron microscopy (TEM). The formation of self-assembled polymeric micelles was confirmed by SLS and TEM. DLS and SLS analyses showed that the architecture of graft copolymers has a dramatic effect on critical aggregation concentration (CAC), micelle size distribution, apparent aggregation number (Nagg app), and apparent molecular weight of polymer aggregates (Mw,agg app). An architecture-dependent excimer emission, resulting from the pi-pi stacking of the oligofluorene backbones, was also observed from the photoluminescence spectra of the micelle aqueous solutions, which indicated a strong intermolecular interaction among the polymeric molecules. The excimer emission was further investigated by time-resolved fluorescence spectroscopy.     

Optical spectroscopic investigations of model beta-sheet hairpins in aqueous solution

In this contribution we report optical spectroscopic data on a series of designed beta hairpins previously shown by NMR to contain a substantial population of beta-sheet structure. These models contain a designed hydrophobic cluster and a (D)Pro-Gly sequence to promote formation of a turn geometry. FTIR, electronic and vibrational CD (ECD and VCD) spectra for these small peptides are comparable to expected bandshapes for peptides of high beta-sheet content. The (D)Pro-Gly sequence provides a better turn motif than Asn-Gly as measured by its beta-sheet spectral characteristics. IR and VCD spectra are in qualitative agreement with theoretical simulations based on transfer of parameters from ab initio quantum mechanical force field and intensity computations for the turn and strands. These calculations provide assignments for some distinguishing modes in both IR and VCD spectra. Increased sheet structure can be induced in these hairpins by use of mixed solvent conditions. Thermal denaturation studies reveal that these hairpins undergo very broad unfolding transitions. Guanidine hydrochloride unfolding transitions for the selected hairpin models are similarly broad. However, the "end-states" of temperature and chaotropic denaturation are spectroscopically differentiable.     

Improving the aging resistance of styrene-butadiene-styrene tri-block copolymer modified asphalt by addition of antioxidants

The aging properties of base asphalt and styrene-butadiene-styrene tri-block copolymer (SBS) modified asphalts (PMA) are evaluated using Fourier Transform Infrared (FTIR) spectroscopy. An aging cell fitted to the FTIR microscope was used to continually and directly study the oxidation of the PMA. In particular, Attenuated Total Reflectance, ATR, with a zinc selenide prism was used to quantify the changes in the spectra of the PMA before and after thin film oven test (TFOT). The effect of a small amount (1 wt%) of some modifiers, zinc dialkyldithiophosphate (ZDDP), zinc dibutyl dithiocarbamate (ZDBC) or naphthenoid oil, on the chemical and physical properties of the PMA was studied. The modification extent of the modifiers increases in the order: oil, ZDBC, ZDDP. With the aging of the PMA, carbonyl groups formed and the intensity of the absorption peak at 965 cm⁻¹ (the characteristic peak of SBS) decreased. Antioxidants, ZDDP or ZDBC modified PMA are resistant to the formation of carbonyl to some extent, indicating the improvement of aging resistance of the PMA by the addition of the antioxidants. ZDDP and ZDBC as antioxidants can retard the oxidation of the PMA through the inhibition of peroxides and radical scavenging. Furthermore, ZDDP in a liquid state at room temperature acts as plasticiser, giving rise to a good aging resistance of PMA.     

Synthesis of nanoporous metal oxides through the self-assembly of phloroglucinol-formaldehyde resol and tri-block copolymer

A versatile route to synthesize nanoporous crystalline metal oxides has been developed through the self-assembly of phloroglucinol-formaldehyde resol and tri-block copolymer templates. Materials were characterized by a complementary combination of X-ray diffraction, nitrogen sorption, and transmission electron microscopy. Metal oxides synthesized using this route have remarkably high surface area when compared with the commercial samples. The surface area of metal oxides decreased upon calcination at higher temperatures. However, the surface area was still much higher when compared with the commercial samples. TEM investigation reveals that upon calcination at higher temperature, the size of the crystal increased but the short range order was merely disturbed. The analyses show that the present method is suitable as a direct route to synthesize crystalline nanoporous metal oxides. Hydrogen bonding plays a key role in the preferential arrangement of porous metal-carbon structure in the domain of tri-block copolymer. The nanoporous metal oxides with ordered mesoporous structure, high surface area, and crystalline framework are expected to show significant improvement in catalysis and nano-technology.     

NMR investigations of rotenoids

Extensive NMR studies of major rotenoids have (1) verified the cis B/C ring fusion of rotenone; (2) confirmed the structure of the reduction-dehydration product of rotenone; (3) provided considerable evidence regarding the preferred conformations of rotenoids; (4) revealed an array of long-range couplings; and (5) pointed up analytically useful solvent effects. Incidentally, these studies also allowed assignment of NMR signals for essentially all protons of the major rotenoids in deuterochloroform.     

Cyclodextrin polyrotaxanes assembled from a molecular construction kit in aqueous solution

We describe a molecular construction kit in which amphiphilic polymers and functionalized cyclodextrins are arranged into sophisticated molecular architectures in aqueous solution without the need to perform chemical reactions. Therefore, these systems are highly biocompatible and show programmable lifetimes. The kinetic stabilities of our polyrotaxane structures are tunable using sterically demanding groups that hinder dissociation. These cyclodextrin‐based polymer systems are applicable in principle for the detection of analytes at the level of single molecules. These systems may also serve well in targeted drug delivery and gene transfection. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6333–6341, 2009     

Excitation wavelength dependence of solvation dynamics in a supramolecular assembly: PEO-PPO-PEO triblock copolymer and SDS

The triblock copolymer (PEO)20-(PPO)70-(PEO)20 (P123) forms a supramolecular aggregate with sodium dodecyl sulfate (SDS). The solvation dynamics and anisotropy decay of coumarin 480 (C480) in different regions of a P123-SDS aggregate are studied through variation of the excitation wavelength (lambdaex) using femtosecond upconversion. In a P123 micelle, because of the drastic differences in polarity between the hydrophilic corona region (PEO block) and the hydrophobic PPO core, C480 exhibits a pronounced red edge excitation shift (REES) of emission maximum by 24 nm. In the P123-SDS aggregate, SDS penetrates the core of the P123 micelle. This increases the polarity of the core and reduces the difference in the polarity between the core and the corona region. In a P123-SDS aggregate, the REES is much smaller (5 nm) which suggests a reduced difference between the core and the corona. Solvation dynamics in a P123 micelle displays a bulklike ultrafast component (<0.3 and 1 ps) in the PEO corona region, a 200 ps component arising from dynamics of polymer segments, and a very long component (5000 or 3000 ps) due to the highly restricted PPO core. In a P123-SDS aggregate, at lambdaex = 375 and 405 nm, the solvation dynamics is found to be faster than that in P123 micelle. In this case, the component (3000 ps) arising from the core region is faster than that (5000 ps) in P123 micelle. In both P123 micelle and P123-SDS aggregate, the relative contribution of the core region decreases and that of the corona region increases with an increase in lambdaex. At lambdaex = 435 nm, which probes the hydrophilic corona, the solvation dynamics for both P123 micelle and P123-SDS aggregate are almost similar.     

NMR investigations of polymer electrets

1H NMR investigations were performed on thin films of poly(vinylidene fluoride) (PVDF) and polyamide 11 (PA 11). The variation of the angle between the static magnetic B_o-field and preferred directions given by drawing and poling leads to characteristic dependences of T_20ff, which can be discussed in terms of Legendre polynomials of the orientational distribution functions of crystallographic c- and b-axis. A good c-axis alignment can be realized by uniaxial drawing. The tendency for b-axis to orient towards the direction of the applied electric field via the orientation of the electric dipoles is evident. The b-axis alignment can be “switched” periodically.     

Alpha-cyclodextrin-induced self-assembly of a double-hydrophilic block copolymer in aqueous solution

Double-hydrophilic poly(ethylene oxide)-b-poly(acrylic acid) (PEO-b-PAA) self-assembled into nanostructures in basic solution upon the addition of alpha-cyclodextrin (alpha-CD) as a result of the complexation between alpha-CD and PEO. The nanostructures produced were spherical in shape as observed by transmission electron microscopy (TEM) and possessed radii that were much larger than that of a single stretched polymeric chain. The ratio of Rg/Rh (where Rg is the z-average radius of gyration and Rh is the hydrodynamic radius) obtained from laser light scattering (LLS) was approximately approximately 1.0, and the aggregation number was approximately 4100. The zeta-potential of complex particle was -45 mV, suggesting that the particle possessed a stable negatively charged surface, attributed to ionized PAA segments. The above results suggested that the nanostructures formed in the PEO-b-PAA/alpha-CD solution at high pH were likely to be spherical vesicles.     

Proton NMR studies of a polybenzimidazole in solution

Molecular aggregation of poly(4,4′-diphenyl ether-5,5′-bibenzimidazole)(PBI) in solution has been studied by high resolution proton NMR. PBI and model compounds have been synthesized, purified, and characterized. Proton resonances in the NMR spectrum of PBI are assigned by comparison with the proton resonances of the model compounds. Spectra are studied by total line-shape analysis, assuming each absorption curve to be Lorentzian. For PBI in N,N-dimethylacetamide (DMAc), the resonance due to the proton of a hydroxyl group formed by proton exchange between the imino group of PBI and the carbonyl group of DMAc is observed. The activation energy for the proton exchange, obtained from Arrhenius plots of the temperature dependence of the chemical shifts of the hydroxyl proton and the imino proton, was found to increase in the order corresponding to dissociation energy of the N? H···O?C hydrogen bond. The chemical shifts in the NMR spectra of PBI-DMAc solutions on the addition of LiCl are strongly dependent on the polymer-salt ratio; and thereby the coordination position of LiCl to PBI is tentatively identified, assuming a pseudocontact LiCl-induced shift. The dependence of the chemical shifts of protons in PBI on the dielectric constant of the solvent is demonstrated by using polar solvents of varying dielectric constant, such as N-methylpyrrolidone, dimethylsulfoxide, and formic acid. The viscosity of the PBI-DMAc solutions is reported at various temperatures and concentrations of LiCl. The results from viscometry are explicable in terms of the NMR observations.     

Micellization in aqueous solution of an ethylene oxide-propylene oxide triblock copolymer, investigated with 1H NMR spectroscopy, pulsed-field gradient NMR, and NMR relaxation

(1)H nuclear magnetic resonance (NMR) spectroscopy has been applied to study the temperature and concentration-induced micellization of a poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) triblock copolymer, Pluronic P105, in D(2)O solutions in the temperature range from 5 to 45 degrees C and the concentration range from 0.01 to 15% (w/v). The intrinsic probes, the chemical shift, and the half-height width of the PO CH(3) signal are very sensitive to the local environment and can be used to characterize the temperature and concentration-dependent aggregation process. When the temperature approaches the critical micellization temperature or the polymer concentration reaches the critical micellization concentration, the chemical shift of the PO CH(3) signal moves toward lower ppm values and the half-height width of the PO CH(3) signal shows a sudden increase. It indicates that the methyl groups are experiencing a progressively less polar environment and transferring from water to the hydrophobic micellar core. The hydrodynamic radius of the unimers and the micelles are determined as be 1.8 and 5.0 nm by means of pulsed-field gradient spin-echo (PGSE) NMR. They were independent of temperature and concentration. The drastic shortening of spin-lattice relaxation time T(1) for the PO CH(3)/CH(2) protons in the transition region suggested that the PPO blocks are located in a "liquid-like" micellar core, whereas the exponential increase of T(1) for the PEO CH(2) protons implied that the PEO blocks are still keeping in contact with surrounding water. Thermodynamics analysis according to a closed association model shows that the micellization process is entropy-driven and has an endothermic micellization enthalpy.     

NMR studies of block copolymer micelles

Block copolymers dissolved in selective solvent often self-assemble. We review the use of NMR to study this process and to characterize the aggregates formed. We stress the need to consider the polydispersity of the polymers and the fact that the increase in NMR relaxation rates observed upon aggregation can be assigned to contributions from the block copolymer micelle tumbling.     

Lactic acid in solution: investigations of lactic acid self-aggregation and hydrogen bonding interactions with water and methanol using vibrational absorption and vibrational circular dichroism spectroscopies

The infrared vibrational absorption (VA) and vibrational circular dichroism (VCD) spectral features of L-(+)-lactic acid (LA) in CDCl3 solution are concentration dependent, showing evidence of oligomerization with increasing concentrations. To understand the observed spectra, geometry optimizations, vibrational frequencies, and VA and VCD intensities were evaluated for (LA)n with n=1-4 using density functional theory calculations at the B3LYP6-311++G(d,p), B3LYP/cc-pVTZ, and in some cases, B3LYP/aug-cc-pVTZ levels of theory. Comparisons with the experimental spectra indicate that the lowest energy LA dimer (AA), formed by two C Double Bond O...HO hydrogen bonds, is one of the dominating species in solution at room temperature. Possible contributions from the LA trimer and tetramer are also discussed. To model the VA and VCD spectra of LA in water and in methanol, both implicit polarizable continuum model and explicit hydrogen bonding considerations were used. For explicit hydrogen bonding, geometry optimizations of the AA-(water)n and AA-(methanol)n complexes, with n=2,4,6, were performed, and the corresponding VA and VCD spectra were simulated. Comparisons of the calculated and experimental VA and VCD spectra in the range of 1000-1800 cm(-1) show that AA-(water)n with n=6 best reproduces the experimental spectra in water. On the other hand, AA-(methanol)n with n=2 reproduces well the experimental results taken in methanol solution. In addition, we found evidence of chirality transfer, i.e., some vibrational bands of the achiral water subunits gain VCD strength upon complexation with the chiral LA solute. The study is the first to use VCD spectroscopy to probe the structures of LA aggregates and hydrogen bonding solvation clusters in the solution phase.