Formulation of benzoporphyrin derivatives in Pluronics

This study investigates the potential of Pluronics for the formulation of tetrapyrrole-based photosensitizers, with a particular focus on B-ring benzoporphyrin derivatives. The B-ring derivatives have a high tendency to aggregate in aqueous solutions, and this poses a significant formulation problem. Pluronics are ABA-type triblock copolymers composed of a central hydrophobic polypropylene oxide section with two hydrophilic polyethylene oxide sections of equal length at either end. Out of a range of different commercially available block copolymers studied, it was found that the longer the hydrophobic block, the better the stabilization of tetrapyrrolic drugs in monomeric form in aqueous suspensions. Of these the best performance was observed in the micelle-forming Pluronic P123. Micelle size determination by laser light scattering confirmed that particle size in stable Pluronic formulations was around 20 nm. Pluronics such as L122 formed emulsions spontaneously without the need for emulsion stabilizers; emulsions were highly stable at ambient temperatures over several days and also highly effective as potential drug delivery agents.     

XPS and wettability characterization of modified poly(lactic acid) and poly(lactic/glycolic acid) films

Poly(lactic acid) (PLA) and poly(lactic/glycolic acid) copolymers (PLGA) are biodegradable drug carriers of great importance, although successful pharmaceutical application requires adjustment of the surface properties of the polymeric drug delivery system to be compatible with the biological environment. For that reason, reduction of the original hydrophobicity of the PLA or PLGA surfaces was performed by applying a hydrophilic polymer poly(ethylene oxide) (PEO) with the aim to improve biocompatibility of the original polymer. PEO-containing surfaces were prepared by incorporation of block copolymeric surfactants, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (Pluronic), into the hydrophobic surface. Films of polymer blends from PLA or PLGA (with lactic/glycolic acid ratios of 75/25 and 50/50) and from Pluronics (PE6800, PE6400, and PE6100) were obtained by the solvent casting method, applying the Pluronics at different concentrations between 1 and 9.1% w/w. Wettability was measured to monitor the change in surface hydrophobicity, while X-ray photoelectron spectroscopy (XPS) was applied to determine the composition and chemical structure of the polymer surface and its change with surface modification. Substantial reduction of surface hydrophobicity was achieved on both the PLA homopolymer and the PLGA copolymers by applying the Pluronics at various concentrations. In accordance with the wettability changes the accumulation of Pluronics in the surface layer was greatly affected by the initial hydrophobicity of the polymer, namely, by the lactide content of the copolymer. The extent of surface modification was also found to be dependent on the type of blended Pluronics. Surface activity of the modifying Pluronic component was interpreted by using the solubility parameters.     

Effects of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymers on structure and stability of liposomal dioleoylphosphatidylethanolamine

The effects caused by poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO; Pluronic) copolymers on the structure and stability of dioleoylphosphatidylethanolamine (DOPE) liposomes were studied by means of turbidity, leakage, and cryo-transmission electron microscopy investigations. The results show that by inclusion of Pluronics in the DOPE dispersion it is possible to stabilize the lamellar Lalpha phase and to produce liposomes that are stable and nonleaky at low pH (pH 5). The stabilizing capacity was observed to depend critically on the molecular composition of the Pluronics. Block copolymers with comparably long PPO and PEO segment lengths, such as F127 and F108, most effectively protected DOPE liposomes prepared at high pH from aggregation and subsequent structural rearrangements induced by acidification. A sufficiently long PPO block was found to be the most decisive parameter in order to obtain adequate coverage of the liposome surface at low Pluronic concentrations. Upon increasing the copolymer concentration, however, Pluronics with comparably short PPO and PEO segment lengths, such as F87 and P85, could also be used to stabilize the DOPE liposomes. Essentially the same trends were observed when the Pluronics were added to preformed DOPE liposomes instead of being included in the preparation mixture. In this case the least effective copolymers failed, however, to completely prevent the DOPE liposomes from releasing encapsulated hydrophilic markers.     

Interaction between cationic, anionic, and non-ionic surfactants with ABA block copolymer Pluronic PE6200 and with BAB reverse block copolymer Pluronic 25R4

The interaction in aqueous solution between either the normal block copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide): Pluronic PE6200 [(EO)(11)-(PO)(28)-(EO)(11)], or the reverse block copolymer poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide): Pluronic 25R4 [(PO)(19)-(EO)(33)-(PO)(19)] and the surfactants sodium decylsulfate, C(10)OS, decyltrimethyl ammonium bromide, C(10)TAB, and pentaethylene glycol monodecyl ether, C(10)E(5), was investigated and the aggregation behavior of these surfactants with Pluronics was compared. Surface tension measurements show that Pluronics in their non-aggregated state better interact with the anionic surfactant C(10)OS than with cationic and non-ionic ones. The presence of the two Pluronics induces the same lowering of the aggregation number of C(10)OS as shown by fluorescence quenching measurements. The number of polymer chains necessary to bind each C(10)OS aggregate has been estimated to be approximately 6 for PE6200 and approximately 2 for 25R4. Furthermore, this surfactant also induces the same increment in the gyration radius of the polymers as revealed by viscosimetry. Calorimetric results have been reasonably reproduced by applying a simple equilibrium model to the aggregation processes.     

Mixed micelle formation with hydrophobic and hydrophilic Pluronic block copolymers: implications for controlled and targeted drug delivery

Pluronic block copolymers offer affluent phase behavioral characteristics and are extensively investigated for drug delivery applications. Hydrophobic Pluronics produce larger aggregates whereas hydrophilic Pluronics often generate small-sized micelles in aqueous milieu. To overcome the limitations and combine the advantages of different kinds of Pluronics the mixing of such two types of Pluronics is studied here, especially for hydrophobic Pluronic L81 and relatively hydrophilic Pluronic P123. Critical micelle concentration (CMC) of the developed binary mixtures was 0.032 mg/ml as evidenced from pyrene fluorescence spectroscopy and is located in between that of the individual Pluronics. Dynamic light scattering (DLS) showed very small particle sizes (～20 nm) and low polydispersity indices for most of the mixed micelles. Transmission electron microscopy (TEM) demonstrated spherical shape of micelles. Based upon the ratio of hydrophobic and hydrophilic Pluronics, dispersions of varied stability were obtained. With 0.1/1.0 wt.% and 0.5/3.0 wt.% of Pluronic L81/P123, stable dispersions were obtained. Stability was assessed from turbidity measurement, size analysis and clarity of dispersion on standing. Micelles were also found to be stable in bovine serum albumin (BSA) solution. Mixed micelles showed fairly high entrapment efficiency, loading capacity and sustained release profile for aceclofenac (Acl), a model hydrophobe. Presence of salt lowered Acl solubilization in micelles. Thermodynamic parameters for Acl solubilization in mixed micelles revealed high partition coefficient values and spontaneity of drug solubilization. Thus, the developed novel mixed micelles hold promise in controlled and targeted drug delivery owing to their very small size, high entrapment efficiency and stability.     

Interfacial properties of Pluronics and the interactions between Pluronics and cholesterol/DPPC mixed monolayers

Pluronics are triblock copolymers of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) with wide range of hydrophilic-lipophilic balance. In order to investigate the relationship between the chemical structures of Pluronics and the interfacial properties at the air-water interface by monolayer techniques, Pluronics L61, P65, F68, P84, P123, L35, and P105 were selected. Since cholesterol influenced substantially the molecular packing stage and the characteristics of cell membranes, the interactions between Pluronics and model cell membranes in the absence and presence of cholesterol were compared. The results of pi-A isotherms and surface elasticities of Pluronic monolayers indicated that the first and second transition like stage were mainly affected by the numbers of EO and PO monomers, respectively. Pluronics with higher hydrophobicities demonstrated larger surface activities and penetration abilities to dipalmitoylphosphatidylcholine (DPPC) monolayers, which might be due to hydrophobic interactions and van der Waals forces. In the presence of cholesterol, hydrogen bonding effects was supposed to exist between the 3beta-hydroxy group of cholesterol and ether oxygen of PEO chains, which led Pluronic F68, with the longest PEO chain herein, to exhibit significantly higher penetration ability. Our findings proposed a theoretical basis for selection of optimized drug carriers and the starting point for further investigations.     

The Effects of Salts and Ionic Surfactants on the Micellar Structure of Tri‐Block Copolymer PEO‐PPO‐PEO in Aqueous Solution

The micelles of two poly(ethylene oxide)‐poly(propylene oxide)‐poly(ethylene oxide) (PEO‐PPO‐PEO) block copolymers, P123 and F127 (same mol wt of PPO but different % PEO) in aqueous solution in the absence and presence of salts as well as ionic surfactants were mainly examined by dynamic light scattering (DLS). The study is further supported by cloud point and viscosity measurements. The change in cloud point (CP), as well as the size of micelles in aqueous solution in presence of salts obeys the Hofmeister lyotropic series. Addition of both cationic cetylpyridinium chloride (CPC) and anionic sodium dodecylsulfate (SDS) surfactants in the aqueous solution of P123 show initial decrease of micellar size from 20 nm to nearly 7 nm and then increasing with a double relaxation mode, further in the presence of NaCl this double relaxation mode vanishes. The effect of surfactant on F127, which has much bigger hydrophilic part is different than P123 and have no double relaxation. The relaxation time distributions is obtained using the Laplace inversion routine REPES. Two relaxation modes for P123 are explained on the bases of Pluronic rich mixed micelles containing ionic surfactants and the other smaller, predominantly surfactant rich micelles domains.     

Study of heat of micellization and phase separation for Pluronic aqueous solutions by using a high sensitivity differential scanning calorimetry

Heat of micellization and phase separation temperature (known as cloud point) for the poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (abbreviated by PEO–PPO–PEO) triblock copolymers, the Pluronics F108, F98, F88, F68, F38, P65, and L62, in water are carefully determined by using a high sensitivity differential scanning calorimeter. It is interesting to find out that there exists a maximum heat of micellization for all these Pluronics. In this study, the heat of micellization of all of the Pluronics decreases as the temperature increases, as expected, at high temperature region (low Pluronic concentration region). However, the enthalpy change has a surprisingly positive relationship with temperature at low temperature region (high Pluronic concentration region). The critical micelle temperature consistently decreases as the Pluronic concentration increases. This unexpected behavior of the positive heat capacity changes of Pluronic aqueous solutions at higher concentration region is somewhat related to the variation of water accessible polar (PEO groups) and non-polar (PPO groups) surface areas in the micellization process. Especially, the removal of polar surface area from water may dominate the contribution to the positive heat capacity change upon micellization. In addition, the cloud points of Pluronic solutions are also discussed. The enthalpy–entropy compensation phenomenon for the micellization of Pluronics is discussed, and the enthalpy–entropy compensation temperature is calculated.     

Pluronic L61 accelerates flip-flop and transbilayer doxorubicin permeation

It has recently been found that Pluronics (block copolymers of ethylene oxide, EO, and propylene oxide, PO) favor the permeability and accumulation of anthracycline antibiotics, for example doxorubicin (Dox), in tumor cells. In an effort to understand these results, the interaction of EO(2)/PO(32)/EO(2) (Pluronic L61) with unilamellar egg yolk vesicles (80-100 nm in diameter) was examined. A partition coefficient K(p)=[Pl](membrane)/[Pl](water)=45 was determined. This corresponds to adsorption of about 20 polymer molecules to the surface of each vesicle in a 20 microM polymer solution. Despite this rather weak adsorption, Pluronic has a substantial effect upon the transmembrane permeation rate of Dox and upon the phospholipid flip-flop rate within the bilayers. Thus, the Dox permeation rate increases threefold and the flip-flop rate increases sixfold in 20 microM Pluronic. The two rates increase linearly with the amount of adsorbed polymer. The obvious ability of Pluronics to increase the mobility of membrane components may have important biomedical consequences.     

PE-CPE blends and their graphene oxide nanocomposites with reduced low temperature brittleness

The low-temperature flexibility of polyethylene (PE)–chlorinated polyethylene (CPE) blends and their composites with a small amount of graphene oxide filler was studied. Quantitative height variation in the AFM images, rheological as well as fracture analyses were employed to gain insights into the generation of flexibility in the matrix phase. The semi-crystalline CPE (CPE25) polymer did not induce viscoelastic behavior at temperatures lower than the glass transition temperature of PE, whereas the amorphous CPE (CPE35) had completely different behavior. The samples with CPE35 could not be sufficiently hardened even at ?180 °C and remained too soft for cryosectioning. Therefore, compression, which results in a 30–60 % reduction in length along the cutting direction with no change in the dimension perpendicular to it, was very prominent for both thin section and block face of the sample. The composites had even higher degree of compression due to additional effect of weak filler matrix interactions and as a consequence, the topographical variations led to filler pull out during sectioning. It was also confirmed using the rheological analysis that composites (and blends with 10 % CPE35 content) had phase immiscibility as CPE phase was suspected to concentrate near the graphene oxide phase leading to generation of chlorine-rich phases. The addition of graphene oxide did not lead to reduced flexibility and the composites also retained the modulus similar to pure polymer. The mechanical fracture of the samples also confirmed the flexibility of the CPE containing blends and composites as these samples were still flexible at ?195 °C.     

Thermodynamics of temperature-sensitive polyether-modified poly(acrylic acid) microgels

The temperature-induced structural changes and thermodynamics of ionic microgels based on poly(acrylic acid) (PAA) networks bonded with poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) (Pluronic) copolymers have been studied by small-angle neutron scattering (SANS), ultra-small-angle neutron scattering (USANS), differential scanning calorimetry (DSC), and equilibrium swelling techniques. Aggregation within microgels based on PAA and either the hydrophobic Pluronic L92 (average composition, EO8PO52EO8; PPO content, 80%) or the hydrophilic Pluronic F127 (average composition, EO99PO67EO99; PPO content, 30%) was studied and compared to that in the solutions of the parent Pluronic. The neutron scattering results indicate the formation of micelle-like aggregates within the F127-based microgel particles, while the L92-based microgels formed fractal structures of dense nanoparticles. The microgels exhibit thermodynamically favorable volume phase transitions within certain temperature ranges due to reversible aggregation of the PPO chains, which occurs because of hydrophobic associations. The values of the apparent standard enthalpy of aggregation in the microgel suspensions indicate aggregation of hydrophobic clusters that are more hydrophobic than the un-cross-linked PPO chains in the Pluronic. Differences in the PPO content in Pluronics L92 and F127 result in a higher hydrophobicity of the resulting L92-PAA-EGDMAmicrogels and a larger presence of hydrophobic, densely cross-linked clusters that aggregate into supramolecular structures rather than micelle-like aggregates such as those formed in the F127-PAA-EGDMA microgels.     

Amorphous Calcium Phosphate Based Composites: Effect of Surfactants and Poly(ethylene oxide) on Filler and Composite Properties

The uncontrolled aggregation of amorphous calcium phosphate (ACP) particulate fillers and their uneven distribution within polymer matrices can have adverse effects on the properties of ACP composites. In this article, we assessed the influence of nonionic and anionic surfactants and poly(ethylene oxide) (PEO) introduced during the preparation of ACP on the particle size distribution and compositional properties of ACP. In addition, the mechanical strength of polymeric composites utilizing such fillers with a photo‐activated binary methacrylate resin was evaluated. Zirconia‐hybridized ACP (Zr‐ACP) filler and its corresponding composite served as controls for this study. Surfactant‐ and PEO‐ACPs had an average water content of 16.8% by mass. Introduction of the anionic surfactant reduced the median particle diameter about 45% (4.1 µm versus 7.4 µm for the Zr‐ACP control). In the presence of PEO, however, the d_m increased to 14.1 µm. There was no improvement in the biaxial flexure strength (BFS) in any of the dry composite specimens prepared with the surfactant and/or PEO‐ACPs compared to those formulated with Zr‐ACP. The BFS of wet composite specimens decreased by 50% or more after a month‐long exposure to saline solutions. Other types of surfactants and/or polymers as well as alternative surface modification protocols need to be explored for their potential to provide better dispersion of ACP into the matrix resin and better mechanical performance ACP composites.     

Cellulose Nano Whiskers (CNWs) Loaded-Poly(sodium acrylate) Hydrogels. Part-I. Effect of Low Concentration of CNWs on Water Uptake

In this work, de-watered cellulose pulp(DCP), obtained from a paper mill, have been acid-hydrolyzed to yield cellulose nano-whiskers (CNWs). As revealed from FESEM measurements, these CNW were found to possess a median length of 258.5 nm, diameter of 35.2 nm, and an aspect ratio of 7.3. The CNWs were also characterized by TGA, XRD and FTIR analysis. The CNWs were found to possess a fairly high Crystallinity Index (CI) of 0.925. The addition of cellulose at low concentration range, i.e., from 25 to 125 mg (nearly 1.25 to 6.25 weight percent of polymer sodium acrylate) caused an enhancement in water uptake of resulting hydrogels .The CNWs-loaded poly(SA) hydrogels showed chain relaxation controlled swelling in the medium of pH 7.4 as was confirmed from the swelling exponent ‘n’ values obtained using power function law‥ The second order kinetic model was found to fit well to the kinetic water uptake data. However, all the samples, when prepared in the form of films, did not show any remarkable increase in their mechanical strength.     

Mono- and Di-valent Salts as Modifiers of PEO-PPO-PEO Block Copolymer Interactions with Silica Nanoparticles in Aqueous Dispersions

Colloidal stabilization of nanoparticle dispersions is central to applications including coatings, mineral extraction, and dispersion of oil spills in oceanic environments, which often involves oil-mineral-aggregates (OMAs). We have an ongoing interest in the modulation of amphiphile micellization and adsorption behavior in aqueous colloidal dispersions in the presence of various additives. Here we evaluate the effect of added salts CaCl₂, MgCl₂, and NaCl on the micellization and adsorption behavior of the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer Pluronic P105 (EO₃₇PO₅₆EO₃₇). In 0.10 wt% silica nanoparticle (10.6 nm average diameter) dispersion, adsorbed block copolymer layer formation begins at a critical surface micelle concentration (csmc) of 0.02 wt%, well below the critical micellization concentration of Pluronic P105 in water. Dye solubilization experiments demonstrate an increase in the csmc upon addition of each salt. Each added salt reaches a level of maximum effectiveness in its ability to disfavor Pluronic P105 adsorption at the silica surface. These peak levels occur at concentrations of 0.005, 0.03, and 0.05 M for CaCl₂, MgCl₂, and NaCl, respectively, in the presence of 0.10 wt% silica nanoparticles. We explain these results in the context of an electrostatic displacer mechanism and discuss possible connections to OMA-dispersant formation.     

Surface modification of cellulose nanowhiskers for application in thermosetting epoxy polymers

Cellulose nanowhiskers (CNWs) were chemically modified with dodecenyl succinic anhydride to obtain hydrophobic CNWs called DCNWs. Surface modification was confirmed by infrared spectroscopy, transmission electron microscopy, and X-ray diffraction. The surface substitution degree determined by X-ray photoelectron spectroscopy was 0.30. Nanocomposites were prepared by incorporating different amounts of DCNWs pre-dispersed in a small amount of acetone into an epoxy matrix. Scanning electron microscope demonstrated that DCNWs dispersed well in the epoxy matrix. A strong interaction was proved between the DCNWs and epoxy matrix, as results of which the nanocomposites exhibited an obvious increase in T _g by about 30 °C, simultaneous increases in tensile strength, Young’s modulus, and strain at break; and an improvement in the hydrothermal properties. Compared with the neat epoxy, the nanocomposite containing 3.5 wt% of DCNWs exhibited an increase in tensile strength by 82 %, Young’s modulus by 21 %, and a strain at break by 198 %.     

二元Pluronic嵌段共聚物相互作用

用I2探针增溶分光光度法考察二元Pluronic两亲嵌段共聚物在水溶液中的胶束化行为,实验结果表明,对于分子PPO嵌段长度相近的P94/L92和F108/L92二元混合体系,这些分子在全部浓度比例范围内都发生相互作用,生成了混合胶束,由于这些分子的PEO嵌段长度不等,随着具有较短PEO嵌段的L92分子加入,P94/L92和F108/L92混合胶束外壳的EO基团数减少导致水化度降低。对于分子PPO嵌段长度不等的P94/L64二元混合体系,当溶液体当中L64的质量分数wL64<0.4时,由于P94/L64混合预胶束的形成,使P94分子在较高浓度时才生成单组分胶束,当wL64>0.4后,溶液中生成了P94/L64混合胶束,温度升高促进了胶束化行为。     

Calorimetric and Scattering Studies on Micellization of Pluronics in Aqueous Solutions: Effect of the Size of Hydrophilic PEO End Blocks,Temperature, and Added Salt

Micellar behavior of five ethylene oxide–propylene oxide (EO–PO) triblock copolymers, called Pluronics, with similar molecular weights of middle block PPO (～2250 g/mol) and varied percentages of poly(ethylene oxide) (10%, 40%, 50%, 70%, and 80%, referred to as L81, P84, P85, F87, and F88, respectively) was examined by thermal (isothermal titration calorimetry and high-sensitivity differential scanning calorimetry), spectral (UV–vis), and dynamic light scattering (DLS) techniques. Micellization was decreased with increasing hydrophilicity of copolymer but induced in the presence of salt. Critical micelle temperatures (CMTs) of copolymers at different concentrations, with and without sodium chloride, are reported. Viscosity and DLS results reveal that highly hydrophilic copolymers (F87 and F88) did not show significant change in micelle size even at temperatures close to cloud point, whereas micelle growth and sphere-to-rod transition occurred for P84 and P85. Surface tension of solutions in water and salt also show enhanced surface activity and salt-induced micellization. The CMTs for different systems using different methods are compared.     

High-Yield Synthesis of Gold Microplates Using Amphiphilic Block Copolymers: Are Lyotropic Liquid Crystals Required?

Summary : High-yield synthesis of gold microplates is achieved through autoreduction of hydrogen tetrachloroaureate (III) hydrate (HAuCl₄ · 3H₂O) in aqueous solutions of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer (Pluronic L64, EO₁₃PO₃₀EO₁₃) at ambient conditions, in the absence of added energy, reductant, or other surfactants. The formation by the amphiphilic block copolymer of lyotropic liquid crystals (e.g., ordered cylindrical/hexagonal or lamellar phases) is not required for templating the formation of such microplates.     

Adsolubilization of 2-naphthol into adsorbed layers of triblock PEO-PPO-PEO copolymers on hydrophobic silica particles

Adsolubilization of 2-naphthol into an adsorbed layer of triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, Pluronics) copolymers on hydrophobically modified silica particles has been investigated. Four kinds of Pluronics (P103, P105, P123, and F108) were employed in order to understand the effect of the hydrophobicity of the surfactants on the adsolubilization. The amount of the Pluronics adsorbed of the maximum/saturation adsorption level was increased with a decrease in the HLB value, suggesting that the more hydrophobic Pluronics (P103 and P123) adsorb preferentially onto the hydrophobic silica surface over the more hydrophilic Pluronics (P105 and F108). The greater adsorbed amount of the more hydrophobic surfactants resulted in a greater amount of 2-naphthol adsolubilized into the adsorbed Pluronics layers. In the case of simultaneous addition of the Pluronics and 2-naphthol, the amount adsolubilized into the adsorbed P123 and P103 layers increased in their low-surfactant-concentration regime, reached a maximum, and then decreased with a further increase in the Pluronics concentration. On the other hand, for both the P105 and F108 copolymers, a decrease in the adsolubilized amount was not observed over the whole range of copolymer concentration investigated. This difference is attributed to a difference in the hydrophobicity of the micellar aggregates in solution and of the adsorbed layers on the hydrophobic surface. When 2-naphthol was added after replacement of the Pluronics supernatant by a surfactant-free solution, the final decrease in the adsolubilization was insignificant for all the Pluronics. Indeed, the maximum amount of adsolubilization was comparable to the corresponding amount obtained in the case of simultaneous addition.     

Liquid crystalline mesophases of pluronics (L64, P65, and P123) and transition metal nitrate salts ([M(H2O)6](NO3)2)

The triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) copolymers, Pluronics (L64, P65, and P123), form liquid crystalline (LC) mesophases with transition metal nitrate salts (TMS), [M(H(2)O)(n)](NO(3))(2), in the presence and absence of free water in the media. In this assembly process, M-OH(2) plays an important role as observed in a TMS:C(n)EO(m) (C(n)EO(m) is oligo(ethylene oxide) nonionic surfactants) system. The structure of the LC mesophases and interactions of the metal ion-nitrate ion and metal ion-Pluronic were investigated using microscopy (POM), diffraction (XRD), and spectroscopy (FTIR and micro-Raman) techniques. The TMS:L64 system requires a shear force for mesophase ordering to be observed using X-ray diffraction. However, TMS:P65 and TMS:P123 form well structured LC mesophases. Depending on the salt/Pluronic mole ratio, hexagonal LC mesophases are observed in the TMS:P65 systems and cubic and tetragonal LC mesophases in the TMS:P123 systems. The LC mesophase in the water/salt/Pluronic system is sensitive to the concentration of free (H(2)O) and coordinated water (M-OH(2)) molecules and demonstrates structural changes. As the free water is evaporated from the H(2)O:TMS:Pluronic LC mesophase (ternary mixture), the nitrate ion remains free in the media. However, complete evaporation of the free water molecules enforces the coordination of the nitrate ion to the metal ion in all TMS:Pluronic systems.