Hydrophilic Chain Length Research Articles

Towards high-performance polysulfone membrane: The role of PSF-b-PEG copolymer additive

Polysulfone (PSF) membranes were prepared by nonsolvent-induced phase separation (NIPS) method using PSF-b-PEG copolymer as pore formation additive. The effects of copolymer composition, hydrophilic chain length and copolymer dosage on membrane morphologies, permeability, stability and biocompatibility were systematically discussed in order to determine the role of the additive. The results suggest that the copolymer composition and dosage play an important role in pore formation. The increase of PEG content in the copolymer results in larger pore size and narrower pore size distribution. The modified membranes show average surface pore sizes in the range of 11.4–15.2 nm, which increase by 14–52% compared to that of the pristine PSF membrane. With increase of copolymer dosage, the pore size increases first and then decreases. The hydrophilic chain length has no significant influence on the pore size and size distribution. The results of pure water flux and rejection agree with the variation of pore size. With increasing the copolymer dosage, the static adsorption of protein and platelet to the membrane is suppressed and thus the antifouling ability is improved. The PSF-b-PEG copolymer outperforms the common water soluble additive (i.e. PVP) in terms of the better pore forming ability and membrane stability, implying that the PSF-b-PEG copolymer would be an alternative to PVP in membrane preparation.

Innovative amphiphilic cellulose nanobiostructures: Physicochemical, spectroscopic, morphological, and hydrophilic/lipophilic properties

ABSTRACTThe amphiphilic character of cellulosic copolymers offers the opportunity to employ their derivatives as novel bio-friendly stable amphiphilic agents. It can be speculated that the synthesized nanobiostructures with hydrophilic and hydrophobic segments will have micellar features. Our investigations, for the first time, demonstrate that the amphiphilic nature of the synthesized macromolecules based on hydrophobic cellulose triacetate (CTA) and hydroxyl terminated oligomeric species of CTA (HCTA) by using hydrophilic polyethylene glycol (PEG) with Mn 600 and 2000 D as CTA-g-PEG, 600; CTA-g-PEG, 2000; HCTA-b-PEG, 600; and HCTA-b-PEG, 2000. The characteristic features of the copolymers were determined by XRD, differential scanning calorimeter, 1H NMR, FTIR, GPC, dynamic light scattering measurements, and transmission electron microscopy. In addition, their critical micelle concentrations were evaluated. The obtained results indicated that the hydrophobic blocks make a significant influence on the micellar characteristics of the surfactants. A comparison of the micellar behavior of a hydrophobic species, like pyrene, incorporated in the synthesized systems indicated that the incorporation content of the surfactants is influenced by the hydrophobic and hydrophilic chain lengths. Therefore, it is possible to design the diversity of the surfactants based on various hydrophilic/lipophilic balance.

Self-Assembled PAEEP–PLLA Micelles with Varied Hydrophilic Block Lengths for Tumor Cell Targeting

The properties of hydrophilic shell in micelles significantly affect the interaction between micelles and cells. Compared with frequently used polyethylene glycol (PEG) as the hydrophilic block, polyphosphoesters (PPEs) are superior in functionality, biocompatibility, and degradability. A series of amphiphilic poly(aminoethyl ethylene phosphate)/poly(l-lactide acid) (PAEEP-PLLA) copolymers were synthesized with hydrophilic PAEEP with different chain lengths. The corresponding self-assembled micelles were used for doxorubicin (Dox) entrapment. The length of hydrophilic PAEEP block on the shell affected the structure of micelles. PAEEPm-PLLA168 (m = 130 or 37) polymers formed vesicles, while PAEEPm-PLLA168 (m = 15 or 9) formed large compound micelles (LCMs), suggesting a difference in tumor cell uptake and intracellular trafficking. PAEEP15-PLLA168 polymer showed superiority on cellular uptake amount, intracellular drug release, and cell apoptosis. Lipid rafts and macropinocytosis are the leading endocytic pathways of PAEEP-PLLA micelles. The shape coupling between micelles and cell membrane facilitated cell surface features such as flattened protrusions (membrane protein) and inward-pointing hollows as well as efficient endocytosis. These results suggested that PAEEP-PLLA self-assembled block copolymer micelles may be an excellent drug delivery system for tumor treatment and that the hydrophilic chain length could regulate drug targeting to tumor cells.

Synergistic solubilization of low-brominated diphenyl ether mixtures in nonionic surfactant micelles

The present study investigated the co-solubilization of three representative low-brominated diphenyl ethers (low-BDEs) in nonionic surfactant micelles. Co-solubilization effects were quantified in terms of molar solubilization ratio (MSR), micelle–water partition coefficient (log Km), extent of synergism/inhibition (RΔMSR), first stepwise association constant (K1), the average number of solute molecules per micelle (SM), excess Gibbs energy (ΔG0 excess), and interaction parameter (ω/RT). The solubilities of low-BDEs during co-solubilization were increased (i.e., synergism) in all of the surfactants tested, relative to their respective solubilities during solubilization. In each surfactant system, synergism was weaker for BDE-15/BDE-28 than that for BDE-15/BDE-47 because BDE-15 and BDE-28 may be partitioned more uniformly in the micelle core than BDE-47, which increased the possibility of their competition. Unexpectedly, BDE-28 and BDE-47 with similar log Kow values demonstrated enhanced co-solubility. This phenomenon was attributed to the positive electrostatic potentials of bromines (computed by Gaussian program) on BDE-28 and BDE-47 which may provide additional attractions to oxygen atoms of the hydrophilic chains. The synergism observed for BDE-15/BDE-28 and BDE-15/BDE-47 was stronger in the Brij35 system than that in Brij58 and Brij78 systems, suggesting that a surfactant with lower aggregation number and/or longer hydrophilic chain length can avoid the competition between solutes for the micelle core. This study may improve the understanding of multi-solutes interactions in surfactant micelles.

Controlled Synthesis of PCL/PVP Copolymer by RAFT Method and Its Hydrophilic Block-Dependent Micellar Behaviors

A range of poly(ε-caprolactone)/poly(N-vinyl-2-pyrrolidone) amphiphilic block copolymers with well-defined hydrophilic chain length were synthesized by the living/controlled reversible addition fragmentation chain transfer polymerization method. The composition and structure of the targeted resultants were characterized with 1H NMR, 13C NMR, FT-IR spectroscopy and gel permeation chromatography. The various block copolymers were successfully employed to fabricate the spherical micelle with core-shell morphological structure. The poly(N-vinyl-2-pyrrolidone) block-dependent characteristics of the copolymeric micelles were investigated by fluorescence spectroscopy dynamic light scattering, and transmission electron microscopy. The solubilization of the hydrophobic ibuprofen as a model drug in the micelle solution was also explored. It was found that the drug loading contents are related to the micellar morphology structure determined by hydrophilic chain length in the copolymer.

Reorganization of self-assembled supramolecular materials controlled by hydrogen bonding and hydrophilic-lipophilic balance.

Supramolecular assembly to form a large variety of nanostructures has received increasing attention for diverse applications, in particular biomedical applications involving drug delivery, bioimaging, therapy and regenerative medicine. Meanwhile, the modulation of morphology and structure of nanoassemblies is a still big challenge. Herein, we report a series of supramolecular structures (BP-KLVFFG-PEG, BKP) and elucidate that their morphological transformation process is modulated by H-bonding, π-π interactions and hydrophilic/lipophilic balance (HLB). Our studies reveal that the hydrophobic and π-π interactions initially drive the self-assembly of BKP into nanoparticles in J-type aggregates in water, and the H-bonding interactions further induce an in situ spontaneous morphology transformation into nanofibers. The conversion rate is related to the length of the hydrophilic chains. The nanofibers are maintained by β-sheet H-bonds with parallel structure. Our results provide insight into the relationship between molecular structures and morphological transformations of self-assembled nanomaterials, which will guide the design of complex self-assembled materials in biological conditions.

Preparation and Surface Activities of Modified Soy Protein–Dextrin Surfactants

AbstractA series of polymeric surfactants has been prepared through the reaction of soy protein with polyethoxylated stearyl ethers of various hydrophilic chain lengths. These surfactants exhibited surface activity, evaluated using surface tension, foaming, and wetting power that was superior to that of traditional surfactants containing only one hydrophobic moiety and one hydrophilic head group. Changing the ethoxylate (EO) group length had a significant effect on the surface activity. Increasing the EO group length decreased the critical micelle concentration (CMC) and increased the surface tension at the CMC (γCMC). The good surface properties of these polysaccharide/protein‐type surfactants suggest that they could be used as emulsifiers to prepare oil‐in‐water emulsions displaying good stability.

Preparation and in vitro antimicrobial activity of silver-bearing degradable polymeric nanoparticles of polyphosphoester-block-poly(L-lactide).

The development of well-defined polymeric nanoparticles (NPs) as delivery carriers for antimicrobials targeting human infectious diseases requires rational design of the polymer template, an efficient synthetic approach, and fundamental understanding of the developed NPs, e.g., drug loading/release, particle stability, and other characteristics. Herein, we developed and evaluated the in vitro antimicrobial activity of silver-bearing, fully biodegradable and functional polymeric NPs. A series of degradable polymeric nanoparticles (dNPs), composed of phosphoester and L-lactide and designed specifically for silver loading into the hydrophilic shell and/or the hydrophobic core, were prepared as potential delivery carriers for three different types of silver-based antimicrobials-silver acetate or one of two silver carbene complexes (SCCs). Silver-loading capacities of the dNPs were not influenced by the hydrophilic block chain length, loading site (i.e., core or shell), or type of silver compound, but optimization of the silver feed ratio was crucial to maximize the silver loading capacity of dNPs, up to ca. 12% (w/w). The release kinetics of silver-bearing dNPs revealed 50% release at ca. 2.5-5.5 h depending on the type of silver compound. In addition, we undertook a comprehensive evaluation of the rates of hydrolytic or enzymatic degradability and performed structural characterization of the degradation products. Interestingly, packaging of the SCCs in the dNP-based delivery system improved minimum inhibitory concentrations up to 70%, compared with the SCCs alone, as measured in vitro against 10 contemporary epidemic strains of Staphylococcus aureus and eight uropathogenic strains of Escherichia coli. We conclude that these dNP-based delivery systems may be beneficial for direct epithelial treatment and/or prevention of ubiquitous bacterial infections, including those of the skin and urinary tract.

Preparation of Associative Polyurethane Thickener and Its Thickening Mechanism Research

Associative polyurethane (PU) thickener has been synthesized by preparing the prepolymer with the reaction of polyethylene glycol (PEG) and isophorone diisocyanate (IPDI), which then end‐capping with long‐chain alkanol. The synthesis process, as well as hydrophilic chain length, theoretical molecular weight, solvent ratio, and thickener percentages, has been researched. The results shows that it reaches the upmost thickening effect when the theoretical molecular weight is under 20000, soft‐segment length is under 4000, solvent ratio is 1 : 1, and thickener percentages are controlled at 10%. Furthermore, thickening mechanism of PU thickener has been analyzed detailedly through the measurement of the critical micelle concentration (CMC) of PU thickener and analysis of the influence of PU thickener on the particle size and morphology of PU dispersions. It has been observed from the scanning electron microscopy (SEM) that the PU aqueous dispersions produce a certain degree of flocculation when the PU thickener was added, and this flocculation structure has been proved to be a thixotropic structure through the characterization of the change of particle size before and after the thickener is introduced into the PU aqueous dispersions. The CMC measurement results present that the thickening effect will be apparent when the concentration is controlled in a low range.

Synthesis and characterization of waterborne polyurethane thickeners based on hyperbranched polyester

Octahydroxyl-terminated and hexadecahydroxyl-terminated hyperbranched polyesters (HPE-8 and HPE-16) were synthesized from 2,2-dimethylol propionic acid and 1,4-butanediol. The hyperbranched waterborne polyurethane (HWPU) thickeners containing different branching structure and length of hydrophilic chain were prepared with hexamethylene diisocyanate, polyethylene glycol (PEG), cetyl alcohol, and HPE. The structures of HPE and HWPU were characterized by Fourier transform infrared spectra and nuclear magnetic resonance (1H NMR and 13C NMR). The rheological properties of polyurethane emulsion thickened by HWPU were measured using Brookfield LVDV-III rheometer, and the effects of HPE structure and PEG molecular weight on the thickening property of HWPU were studied. The results showed that HWPU with HPE branching number of 8 and PEG molecular weight of 4000 exhibited an excellent thickening effect in the aqueous polyurethane emulsion.

Self-assembly behavior of a linear-star supramolecular amphiphile based on host-guest complexation.

A star polymer, β-cyclodextrin-poly(l-lactide) (β-CD-PLLA), and a linear polymer, azobenzene-poly(ethylene glycol) (Azo-PEG), could self-assemble into a supramolecular amphiphilic copolymer (β-CD-PLLA@Azo-PEG) based on the host-guest interaction between β-CD and azobenzene moieties. This linear-star supramolecular amphiphilic copolymer further self-assembled into a variety of morphologies, including sphere-like micelle, carambola-like micelle, naan-like micelle, shuttle-like lamellae, tube-like fiber, and random curled-up lamellae, by tuning the length of hydrophilic or hydrophobic chains. The variation of morphology was closely related to the topological structure and block ratio of the supramolecular amphiphiles. These self-assembly structures could disassemble upon an ultraviolet (UV) light irradiation.

Asymmetric vesicle constructed by AB/CB diblock copolymer mixture and its behavior: a Monte Carlo study.

Asymmetric vesicles constructed from AB/CB diblock copolymer mixture in a selective solvent for A and C blocks are studied using Monte Carlo simulation. The effects of the mixed ratio of the two diblock copolymers, the solution pH, and the hydrophilic chain length on the distributions of hydrophilic blocks on the surfaces of asymmetric vesicles are studied systematically. The simulation results show that asymmetric vesicle, in which the inner and outer surfaces are constructed from different hydrophilic blocks, can be obtained from AB/CB diblock copolymer mixture. The formation of ABC or CBA three-layer asymmetric vesicle depends on the composition of the mixture, the chain length of hydrophilic block, and the solution pH. The hydrophilic block with the same charge (induced by the solution pH), or longer chain length, or lower content in the mixture is more likely to distribute on the outer surface of the vesicle. Moreover, the transition from ABC to CBA three-layer asymmetric vesicle in which blocks C are charged can occur by adjusting the composition of the mixture. On the other hand, the investigations of the interfacial energy density of asymmetric vesicles elucidate the distribution regularity of hydrophilic blocks. When the hydrophilic chain lengths are equal, the difference between the outer and inner interfacial energies is the main factor that determines the asymmetric vesicle structures; that is, the distributions of different hydrophilic blocks on asymmetric vesicles always tend to gain the largest difference between the outer and inner interfacial energies. However, when the hydrophilic chain lengths are different, the chain conformational entropy becomes the main driving force for determining the distribution of hydrophilic blocks on asymmetric vesicles.

Effect of the alkyl chain length of a hydrophobic ionic liquid (IL) as an oil phase on the phase behavior and the microstructure of H2O/IL/nonionic polyoxyethylene surfactant ternary systems

The use of hydrophobic ionic liquids (ILs) as oil phases to formulate a H2O-in-IL (W/IL) microemulsion is of great significance to enzyme catalysis. In this report, we present the essential influence of the alkyl chain length of ILs on the phase behavior and the microstructure of H2O/IL/CnEm (polyoxyethylene alkyl ether) ternary systems. The ILs are [C4mim][PF6] (1-butyl-3-methylimidazolium hexafluorophosphate) and [C8mim][PF6] (1-octyl-3-methylimidazolium hexafluorophosphate). For a given nonionic surfactant, the alkyl chain length of ILs has an influence on the water solubilization capacity. The difference in the capacity, however, narrows and even disappears upon significant increase of the hydrophilic chain length of CnEm. FTIR spectroscopy and UV-Vis spectroscopy confirm the existence of bulk water in both [C4mim][PF6]- and [C8mim][PF6]-based C12E23-stabilized W/IL microemulsions. The catalytic activity of laccase hosted in the W/IL microemulsion and the dynamic light scattering measurement reveal that under the same conditions, the water droplet size dispersed in [C4mim][PF6] is larger than that in [C8mim][PF6]. To establish the newly developed W/IL microemulsion as an effective medium for laccase, a control study is presented, demonstrating that the W/IL microemulsion is superior to the pure ILs for the expression of the catalytic activity of laccase.

Synthesis of Organic/Inorganic Polyhedral Oligomeric Silsesquioxane-Containing Block Copolymers via Reversible Addition–Fragmentation Chain Transfer Polymerization and Their Self-Assembly in Aqueous Solution

Polyhedral oligomeric silsesquioxane (POSS)-containing homopolymers (PHEMAPOSS) with a high degree of polymerization (DP) were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. PHEMAPOSS was used as a macro-RAFT agent to construct a series of amphiphilic diblock copolymers, PHEMPOSS-b-PMAA (poly (methyl methacrylate)), which possessed a different length of hydrophilic chains. The self-assembly behavior of PHEMPOSS-b-PMAA in aqueous solution was studied by transmission electron microscopy (TEM), atomic force microscopy (AFM), and dynamic light scattering (DLS), respectively. The results showed that PHEMAPOSS45-b-PMAA523 forms typical core–shell spherical micelles where the hydrophobic PHEMAPOSS blocks as the core and hydrophilic PMAA blocks as the shell. With increasing PMAA chain length, PHEMAPOSS45-b-PMAA1173 with a longer PMAA chain self-assembled into irregular aggregates with POSS moieties dispersed in the aggregates. On the other hand, PHEMAPOSS45-b-PMAA308 with ...

Self-Assembly Behaviors of Heterogemini Surfactant in Aqueous Solution Investigated by Dissipative Particle Dynamics

As a preliminary study, self-assembly behaviors of heterogemini surfactant in aqueous solution are explored tentatively by means of dissipative particle dynamics simulation. Five kinds of heterogemini molecules are involved, and a variety of novel morphologies have been obtained. Results based on detailed comparisons among themselves and with traditional symmetric gemini surfactant show the proportion of hydrophilic to hydrophobic chain lengths in one monomer is the most important, more difference between proportions in the two monomers can induce more diverse self-assembly morphologies. The second important is the hydrophilic chain length, in which a small change can lead to obvious difference in self-assembly behaviors. While the length of hydrophobic chain has a less important influence, only the concentration for self-assembly morphologies appearing can be affected by its change. The microscopic morphology of heterogemini surfactant in its self-assembly structure can be embodied through its radius of gyration. Our simulation results can undoubtedly provide a theoretical guide to further research towards self-assembly behaviors of heterogemini surfactants and practical applications of these matters.

Wetting and rheological characteristics of hydrophobic organic pigments in water in the presence of non-ionic surfactants

Wettability and rheological characteristics of highly hydrophobic organic pigments were determined in the absence and presence of surfactants. Two widely used pigments, carbon black (CB) and copper phthalocyanine blue (CuPc), were selected as model pigments. As wetting and dispersing agents, a range of non-ionic nonylphenol ethoxylated (NPE) surfactants with varying hydrophilic chain length was used in the tests. Wetting properties of the pigment powders were investigated by the contact angle measurements based on capillary rise method. Rheology experiments were carried out by a controlled shear stress rheometer. Rheological properties of pigment suspensions were determined by applying common rheological models to shear stress (τ) versus shear rate (γ) plots. The experimental results demonstrated that, highly ethoxylated surfactants were more efficient than less ethoxylated surfactants in reducing contact angle of pigment powders. Finally, it was inferred that CB and CuPc suspensions behaved virtually as Bingham plastic and shear thickening (dilatant) type suspensions, respectively.

Impact of amphiphilic triblock copolymers on stability and permeability of phospholipid/polymer hybrid vesicles

This Letter seeks to understand the impact of ABA amphiphilic copolymers on liposomes concerning their stability, bilayer permeability and bilayer phase transition. Results show that the hybrid vesicles have substantially increased shelf stability, resistance against rupture and fusion, and unique permeation behavior. Discussion is carried out on the possible mechanisms associated with bilayer structural changes, which the hydrophobic B block of the copolymer serves as a spacer and fills the voids between the lipids and the hydrophilic A block provides ‘arms’ in the aqueous phase. A longer hydrophilic chain length provided enhanced vesicle stability relative to a shorter chain length.

Study on synthesis and thickening property of hyperbranched waterborne polyurethane

A series of hyperbranched waterborne polyurethanes (HWPU-4, HWPU-6 and HWPU-12) containing hydrophobic end groups were prepared by the hyperbranched core and the polyurethane prepolymer. The core was polyol including pentaerythritol (PE-4), hyperbranched polyester with six hydroxyl end groups (HPE-6) and hyperbranched polyester with 12 hydroxyl end groups (HPE-12). The polyurethane prepolymer was synthesized by hexamethylene diisocyanate (HDI), polyethylene glycol (PEG) and hexadecanol. The structures of the hyperbranched cores and HWPUs were characterized by Fourier transform infrared spectra (FTIR), nuclear magnetic resonance spectra (1H NMR and 13C NMR) and gel permeation chromatography (GPC). The influences of HWPU content and structure on its thickening property were studied by the measurement of rotary viscosity. The results showed that the thickening effect of HWPU enhanced with the increase of HWPU content in the aqueous polyurethane emulsion. The thickening effect of HWPU-6 was superior to that of HWPU-4 and HWPU-12 with the same length of hydrophilic chain. In addition, the thickening effect of HWPU with the same core was related to the length of hydrophilic chain and the relative content of hydrophobic end groups.

Interactions between Pluronics (F127 and F68) and Bile Salts (NaTDC) in the Aqueous Phase and the Interface of Oil-in-Water Emulsions

Pluronics are being introduced in food research in order to delay lipid digestion, with the length of hydrophilic and hydrophobic chains playing an important role in the rate of such a process. Since bile salts play a crucial role in the lipid digestion process, the aim of this work is to analyze the interactions between Pluronic F127 or F68 and the bile salt NaTDC when the latter is added at physiological concentrations. These interactions are studied at the Pluronic-covered oil-water interface and in the aqueous phase of Pluronic-stabilized emulsions. This work has been carried out with techniques such as differential scanning calorimetry, interfacial tension, dilatational rheology, and scanning electron microscopy. As a result, Pluronic F127 was shown to be more resistant to displacement by bile salt than F68 at the oil-water interface due to the larger steric hindrance and interfacial coverage provided. In addition, Pluronics have the ability to compete for the oil-water interface and interact in the bulk with the bile salt. Concretely, Pluronic F127 seems to interact with more molecules of bile salt in the bulk, thus hindering their adsorption onto the oil-water interface. As a conclusion, Pluronic F127 affects to a larger extent the ability of bile salt to promote the further cascade of lipolysis in the presence of lipase owing to a combination of interfacial and bulk events.

Effect of fixed aqueous layer thickness of polymeric stabilizers on zeta potential and stability of aripiprazole nanosuspensions

The aim of this study was to evaluate the effect of the thickness of adsorbed polymer layer (also known as Fixed Aqueous Layer Thickness, FALT) of polymeric stabilizers on zeta potential and stability of nanoparticles in a suspension. Aripiprazole, a poorly water soluble drug was used as a model drug to evaluate rationale for increased FALT and to understand the effect of hydrophilicity and hydrophobicity of polymeric stabilizers on FALT of aripiprazole nanosuspensions. The nanosuspensions were prepared by media milling and Pluronic F68, Pluronic F127, Hydroxypropyl methylcellulose (HPMC) and Hydroxypropyl cellulose (HPC) were used as polymeric stabilizers. The particle size (immediately after preparation and after 1 week of storage at 25°C) and zeta potential of aripiprazole nanosuspensions were determined. For Pluronics, FALT was determined theoretically whereas for HPMC and HPC it was calculated as Debye Huckel parameter from the zeta potential dependence on the ionic strength. An increase in FALT resulted in reduced zeta potential. With an increase in FALT of polymers used, the stability of nanosuspensions showed improvement. Furthermore, a linear correlation was shown to exist between the FALT and length of hydrophilic chains in Pluronics.