Fluorinated Linkers Enable High-Voltage Pyrrolidinium-based Dicationic Ionic Liquid Electrolytes.

Novel fluorinated, pyrrolidinium-based dicationic ionic liquids (FDILs) as high-performance electrolytes in energy storage devices have been prepared, displaying unprecedented electrochemical stabilities (up to 7 V); thermal stability (up to 370 °C) and ion transport (up to 1.45 mS cm­1). FDILs were designed with a fluorinated ether linker and paired with TFSI/FSI counterions. To comprehensively asess the impact of the fluorinated spacer on their electrochemical, thermal, and physico-chemical properties, a comparison with their non-fluorinated counterparts was conducted. With a specific focus on their application as electrolytes in next-generation high-voltage lithium-ion batteries, the impact of the Li-salt on the characteristics of dicationic ILs was systematically evaluated. The incorporation of a fluorinated linker demonstrates significantly superior properties compared to their non-fluorinated counterparts, presenting a promising alternative towards next-generation high-voltage energy storage systems.

A Living Topochemical Ring-Opening Polymerization of Achiral Amino Acid N-Carboxy-Anhydrides in Single Crystals.

A living topochemical ring-opening polymerization (ROP) of achiral amino-acid N-carboxyanhydrides (NCAs) is reported. Single crystals of the NCAs of α-aminoisobutyric acid (Aib) and 1-aminocyclohexanecarboxylic acid (ACHC) were grown, allowing a ring-opening polymerization macroscopically induced by amines. The single crystals could be polymerized at temperatures from 25-50 °C after physically contacting the amine-based initiator with the crystals. Topochemical polymerization of the crystals was proven by MALDI-ToF MS and XRD, generating polymers with chain lengths of up to 40 units and a complete affixation of the initiating amine at the polymer's head. Due to the proper alignment of the reacting groups in the crystal, longer polymer chains with improved purities can be reached, as chain-transfer is reduced as compared to solution polymerization. Simple purification of the polymers can be achieved by separation of the unreacted NCA via dispersion in acetonitrile. Overall, this method enables the preparation of polymers with higher chain length and purities at mild conditions, finally demonstrating a crystal-based ring opening polymerization.

Formation of Surface Wrinkles in Collapsed Langmuir Films of a Polyhedral Oligomeric Silsesquioxane Containing Diblock Copolymer.

Surface pressure versus mean molecular area isotherms of Langmuir films of a hybrid diblock copolymer of poly(ethylene glycol) (PEG) and poly(methacrylo polyhedral oligomeric silsesquioxane) P(MA-POSS) together with Brewster angle microscopy reveal details of the phase transitions. The formation of a periodic wrinkling pattern in collapsed films is observed by epifluorescence microscopy after applying several compression-expansion cycles above the surface pressure of ≈18 mN/m. The wrinkle formation is reversible upon compression and expansion of the Langmuir films. Two distinct orientations of POSS molecules are assumed in Langmuir films upon compression, vertically for chains close to the water surface and horizontally orientated upper layers with significant amounts of PEG in between them. Thus, the wrinkling forms mainly in the top stiffer MA-POSS blocks above a certain compressional stress. The wrinkles disappear during the Langmuir-Blodgett (LB) transfer. Nevertheless, atomic force microscopy and grazing incidence wide-angle X-ray scattering experiments reveal the formation of highly ordered POSS molecules in LB films.

Crystallization of Poly(ethylene oxide) on the Surface of Aqueous Salt Solutions Studied by Grazing Incidence Wide-Angle X-ray Scattering.

We report the thin layer crystallization of high-molar mass poly(ethylene oxide) (PEO) on a liquid support using a 4 M K2CO3 aqueous solution as a subphase. Because of the Hofmeister effect, PEO does not dissolve and remains at the surface during compression on a Langmuir trough. The transition from the flat pancake conformation upon compression of the spread polymer film to an entangled monolayer results in a plateau region of the Langmuir isotherm. Using grazing incidence wide-angle X-ray scattering, the final crystallization of PEO was observed, and the crystal orientation was determined. The fold surface was (209̅), that is, the helix axis has a tilt angle of 2.9° to the normal vector of the water surface.

Proton conductivity and phase transitions in 1,2,3-triazole.

1,2,3-Triazole (TR) is a good proton conductor which is tidely related to formation of a hydrogen bond network along the N-HN trajectory and its self-dissociation into diH-1,2,3-triazolium and 1,2,3-triazolate. To gain a deeper understanding, the proton conductivity of TR is measured by impedance spectroscopy (IS) across its melting temperature and an additionally discovered solid-solid phase transition. The orthorhombic high temperature phase and the monoclinic low temperature modification are investigated by polarized optical microscopy, DSC- and WAXS measurements. Furthermore, the diffusion coefficients of TR are determined from IS data and measured by (1)H PFG NMR spectroscopy in the melt which allows for separate evaluation of contributions of proton hopping across the hydrogen bond network and the vehicle mechanism to the proton conductivity where the vehicles are defined as charged species generated by TR self-dissociation. Finally, the degree of dissociation of TR is calculated and the influence of the self-dissociation of TR on the proton conductivity is discussed in the context of the dielectric constant.

Self-organization of poly(ethylene oxide) on the surface of aqueous salt solutions.

It is demonstrated that stable Langmuir films of poly(ethylene oxide) (PEO) can be formed up to surface pressures of 30 mN m(-1) when potassium carbonate K2CO3 is added to the aqueous subphase. Generally, PEO homopolymer cannot stay on the water surface at a surface pressure ≥10 mN m(-1) due to its high water solubility. To prepare stable monolayer films, PEO can be modified with hydrophobic moieties. However, by exploiting the salting out effect by adding certain salts (K2CO3 or MgSO4) into the aqueous subphase, not only very stable films but also unusual self-organization can be achieved by the PEO homopolymer on the surface of the aqueous solution. Thus, a series of OH-terminated PEOs is found to form a stable monolayer at K2CO3 concentrations of 2 M and above in the aqueous subphase, and the stability of the film increases with an increase in K2CO3 concentration. Hysteresis experiments are also carried out. During the phase transition induced by progressive compression, self-organization into well-defined domains with sizes in the micrometer range are observed, and with further compression and holding of the film for 30 min and above the microdomains transform into a crystalline morphology as visualized by Brewster angle microscopy.

1-Ethyl-3-methylimidazolium Acetate as a Reactive Solvent for Elemental Sulfur and Poly(sulfur nitride).

We investigate the reactive dissolution process of poly(sulfur nitride) (SN)x in the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate [EMIm][OAc] in comparison to the process of elemental sulfur in the same IL. It has been known from the literature that during the reaction of S8 with [EMIm][OAc], the respective thione is formed via a radical mechanism. Here, we present new results on the kinetics of the formation of the respective imidazole thione (EMImS) via the hexasulfur dianion [S6]2- and the trisulfur radical anion [S3]•-. We can show that [S6]2- is formed first, which dissociates then to [S3]•-. Also, long-term stable radicals occur, which are necessary side products provided in a reaction scheme. During the reaction of [EMIm][OAc] with (SN)x chains, two further products can be identified, one of which is the corresponding imine. The reactions are followed by time-resolved NMR spectroscopic methods that showed the corresponding product distributions and allowed the assignment of the individual signals. In addition, continuous-wave (CW) EPR and UV/vis spectroscopic measurements show the course of the reactions. Another significant difference in both reactions is the formation of a long-term stable radical in the sulfur-IL system, which remains active over 35 days, while for the (SN)x-IL system, we can determine a radical species only with the spin trap 5,5-dimethyl-1-pyrrolin-N-oxide, which indicates the existence of short-living radicals. Since the molecular dynamics are restricted based on the EPR spectra, these radicals must be large.

Development of Poly(sorbitol adipate)-g-poly(ethylene glycol) Mono Methyl Ether-Based Hydrogel Matrices for Model Drug Release.

Hydrogels were prepared by Steglich esterification and by crosslinking pre-synthesized poly(sorbitol adipate)-graft-poly(ethylene glycol) mono methyl ether (PSA-g-mPEG) using different-chain-length-based disuccinyl PEG. PSA and PSA-g-mPEG were investigated for polymer degradation as a function of time at different temperatures. PSA-g-mPEG hydrogels were then evaluated for their most crucial properties of swelling that rendered them suitable for many pharmaceutical and biomedical applications. Hydrogels were also examined for their Sol-Gel content in order to investigate the degree of cross-linking. Physical structural parameters of the hydrogels were theoretically estimated using the modified Flory-Rehner theory to obtain approximate values of polymer volume fraction, the molecular weight between two crosslinks, and the mesh size of the hydrogels. X-ray diffraction was conducted to detect the presence or absence of crystalline regions in the hydrogels. PSA-g-mPEG hydrogels were then extensively examined for higher and lower molecular weight solute release through analysis by fluorescence spectroscopy. Finally, the cytotoxicity of the hydrogels was also investigated using a resazurin reduction assay. Experimental results show that PSA-g-mPEG provides an option as a biocompatible polymer to be used for pharmaceutical applications.

Formation of structured polygonal nanoparticles by phase-separated comb-like polymers.

A simple approach using comb-like polymers that undergo nanophase separation between the polyester backbone and the stearoyl side chains is proposed for the preparation of structured non-spherical nanoparticles from a nanoemulsion. Depending on the degree of esterification of the OH groups of poly(glycerol adipate) differently ordered nanostructures is obtained. A perfect lamellar arrangement is obtained for polymers with a high degree of esterification and leads to spherical nanoparticles with an internal onion-like structure. However, when the degree of esterification is only 20 mol%, polygonal nanoparticles with an internal pseudo-hexagonal structure are obtained. The differences in the nanoparticle shapes are related to the volume fraction of the paraffinic pool.

Langmuir and Langmuir-Blodgett films of multifunctional, amphiphilic polyethers with cholesterol moieties.

Langmuir films of multifunctional, hydrophilic polyethers containing a hydrophobic cholesterol group (Ch) were studied by surface pressure-mean molecular area (π-mmA) measurements and Brewster angle microscopy (BAM). The polyethers were either homopolymers or diblock copolymers of linear poly(glycerol) (lPG), linear poly(glyceryl glycidyl ether) (lPGG), linear poly(ethylene glycol) (lPEG), or hyperbranched poly(glycerol) (hbPG). Surface pressure measurements revealed that the homopolymers lPG and hbPG did not stay at the water surface after spreading and solvent evaporation, in contrast to lPEG. Because of the incorporation of the Ch group in the polymer structure, stable Langmuir films were formed by Ch-lPG(n), Ch-lPGG(n), and Ch-hbPG(n). The Ch-hbPG(n), Ch-lPEG(n), Ch-lPEG(n)-b-lPG(m), Ch-lPEG(n)-b-lPGG(m), and Ch-lPEG(n)-b-hbPG(m) systems showed an extended plateau region assigned to a phase transition involving the Ch groups. Typical hierarchically ordered morphologies of the LB films on hydrophilic substrates were observed for all Ch-initiated polymers. All LB films showed that Ch of the Ch-initiated homopolymers is able to crystallize. This strong tendency of self-aggregation then triggers further dewetting effects of the respective polyether entities. Fingerlike morphologies are observed for Ch-lPEG(69), since the lPEG(69) entity is able to undergo crystallization after transfer onto the silicon substrate.

Synthesis of well-defined graft copolymers by combination of enzymatic polycondensation and "click" chemistry.

Aliphatic polyesters having pendant azide groups were prepared by enzymatic polycondensation in the presence of lipase from Candida antarctica type B (CAL-B). The grafting reaction to the N(3)-functional polyester was carried out quantitatively at room temperature using copper-catalyzed azide-alkyne cycloaddition (CuAAC, "click" reaction) with monoalkyne-functional poly(ethylene oxide) (alkyne-PEO, M(n) = 750 g/mol). Furthermore, both enzymatic polycondensation and "click" reaction were carried out successfully in sequential one-pot reaction. The graft copolymer was surface-active and self-assembled in water. The graft copolymer had a critical aggregation concentration (cac) of 3 × 10(-2) µM in water determined by surface tension measurements. Above cac, the graft copolymer formed single chains and aggregates having a hydrodynamic radius of ∼75 nm. Furthermore, the surface activity of the polymers at the air-water interface was studied by Langmuir trough measurements. The Langmuir isotherm of the graft polymer showed a pseudoplateau resulting from desorption of PEO chains into the subphase upon compression.

Crystallization of Poly(ethylene)s with Regular Phosphoester Defects Studied at the Air-Water Interface.

Poly(ethylene) (PE) is a commonly used semi-crystalline polymer which, due to the lack of polar groups in the repeating unit, is not able to form Langmuir or Langmuir-Blodgett (LB) films. This problem can be solved using PEs with hydrophilic groups arranged at regular distances within the polymer backbone. With acyclic diene metathesis (ADMET) polymerization, a tool for precise addition of polar groups after a certain interval of methylene sequence is available. In this study, we demonstrate the formation of Langmuir/LB films from two different PEs with regular phosphoester groups, acting as crystallization defects in the main chain. After spreading the polymers from chloroform solution on the water surface of a Langmuir trough and solvent evaporation, the surface pressure is recorded during compression under isothermal condition. These π-A isotherms, surface pressure π vs. mean area per repeat unit A, show a plateau zone at surface pressures of ~ (6 to 8) mN/m, attributed to the formation of crystalline domains of the PEs as confirmed by Brewster angle and epifluorescence microscopy. PE with ethoxy phosphoester defects (Ethoxy-PPE) forms circular shape domains, whereas Methyl-PPE-co-decadiene with methyl phosphoester defects and two different methylene sequences between the defects exhibits a film-like morphology. The domains/films are examined by atomic force microscopy after transferring them to a solid support. The thickness of the domains/films is found in the range from ~ (2.4 to 3.2) nm depending on the transfer pressure. A necessity of chain tilt in the crystalline domains is also confirmed. Grazing incidence X-ray scattering measurements in LB films show a single Bragg reflection at a scattering vector qxy position of ~ 15.1 nm-1 known from crystalline PE samples.

Comparison of the monolayer formation of fluorinated and nonfluorinated amphiphilic block copolymers at the air-water interface.

Series of fluorinated amphiphilic diblock copolymers poly(ethylene oxide)-b-poly(heptafluorobutyl methacrylate) (PEO-b-PHFBMA) and nonfluorinated analogue copolymers poly(ethylene oxide)-b-poly(n-butyl methacrylate) (PEO-b-PBMA) with different lengths of hydrophobic blocks were synthesized. Their interface properties at the air-water interface were investigated using surface pressure and X-ray reflectivity (XR) measurements on the Langmuir trough. The fluorinated species have shown a distinct transition from flat-lying to standing side chains, whereas the nonfluorinated ones have no indication for a significant amount of flat-lying side chains. The water surface is covered by a single layer, which is proved by XR measurements of PEO-b-PHFBMA. The obtained thickness and electron density can be related to the hydrophobic part of the copolymer by a simple consistency check: The total numbers of electrons from the fit of the XR curve should agree with the numbers of electrons in the corresponding block.

Chain Tilt and Crystallization of Ethylene Oxide Oligomers with Midchain Defects.

Many text books and publications do not focus on the necessity of chain tilting in crystalline lamellae of oligomers and polymers, a fundamental aspect of their crystallization already discussed by Flory. Herein we investigate the chain tilt of ethylene oxide oligomers (EOs) containing various midchain defects by WAXS, SAXS and solid state 13C MAS NMR spectroscopy. At low temperatures, one out of the two EO chains of EO9-meta-EO9 and EO11-TR-EO11 containing a 1,3-disubstituted benzene or a 1,4-disubstituted 1,2,3-triazole defect in central position of the oligomer chain forms crystals and the other EO chain as well as the defect remain in the amorphous phase. The aromatic midchain defect of these two oligomers can be incorporated into the crystalline lamella upon heating below Tm. Then, the adjoining amorphous EO chain crosses from the lamellae to the amorphous regions at an angle ξ, which is preordained by the substitution pattern of the aromatic defect, revealing that the chain tilt angle ranges between 36° ≤ ϕ ≤ 60°.

Contact angle, WAXS, and SAXS analysis of poly(beta-hydroxybutyrate) and poly(ethylene glycol) block copolymers obtained via Azotobacter vinelandii UWD.

This study investigated and correlated physical properties and cell interactions of copolymers obtained by a poly(ethylene glycol) (PEG)-modulated fermentation of Azotobacter vinelandii UWD. PEGs with molecular weights of 400 and 3400 Da and di(ethylene glycol) (DEG) were used to modulate the bacterial synthesis of poly(beta-hydroxybutyrate) (PHB). The PHB crystallinity was determined by wide-angle X-ray scattering (WAXS). Small-angle X-ray scattering (SAXS) showed that lamellar distances decreased between the PHB and the PHB modulated with PEG or DEG. Furthermore, the contact angle of water on the PHB/PEG polymer surfaces decreased when compared to that of PHB. The significant decrease of the contact angle and corresponding increase in surface tension, as well as significant decrease in cell adhesion, suggest the presence of hydrophilic PEG and DEG within the hydrophobic surface.

Formation of 2D spherulites in Langmuir films of amphiphilic T-shaped liquid crystals.

Langmuir films of facial T-shaped amphiphilic liquid crystals were studied at the air-water interface. The liquid crystals were composed of three incompatible segments: a central rigid rodlike p-terphenyl (TP) group, two flexible hydrophobic n-alkyl terminal chains of identical length linked through ether bonds, and one hydrophilic lateral chain of three ethylene oxide units with a carboxyl end group. In order to determine the influence of the alkyl chain length on the characteristics of condensed films three TPs having n-alkyl chains with eight (TP8/3), ten (TP10/3) or 16 (TP16/3) carbon atoms were investigated. Surface pressure - mean molecular area isotherms revealed clear differences. TP8/3 and TP10/3 exhibit an extended plateau region where a phase transition from monolayer to multilayer takes place. On the other hand, the TP16/3 isotherm showed a distinct maximum ('spike') corresponding to a surprising surface crystallization process which is reported for the first time for a Langmuir film of a liquid crystal. Brewster angle microscopy clearly confirmed these differences: TP8/3 and TP10/3 formed circular domains with liquid crystalline order, while TP16/3 formed well-defined two-dimensional polycrystalline spherulites which are fractured after further compression. The film thickness determined by X-ray reflectivity measurements correlated with a multilayer formation for TP10/3. The morphology of Langmuir-Blodgett (LB) films transferred onto silicon wafers and studied by atomic force microscopy also confirmed the striking different behavior (multilayer formation vs. 2D crystallization) of the TPs under investigation.

Modification of a reverse microemulsion with a fluorinated triblock copolymer.

A w/o microemulsion consisting of n-decane, AOT, and water with a droplet volume fraction Phi=0.2 and a molar ratio of water to AOT omega=40 has been used as a model system to investigate the effect of added amphiphilic triblock copolymers on structure and conductivity of the system. Structure of the system is determined by small-angle X-ray scattering. Conductivity is measured in a wide frequency and temperature range. The pure microemulsion displays the known phenomenon of conductivity increase with temperature at the percolation temperature T(p). Droplets are found to decrease in size in the same temperature range. The triblock copolymer poly(perfluorohexylethyl methacrylate)-b-poly(ethylene oxide)-b-poly(perfluorohexylethyl methacrylate) has been added to the microemulsion such that the number of polymers per droplet z is between 0.5 and 2. The polymer dissolves in the microemulsion and is located in the droplet. Microemulsion droplets deform continuously from spherical to prolate ellipsoidal shape with increasing polymer content. Furthermore, a strong shift of T(p) to higher T with increasing polymer content is observed. For z > or = 1.5 DeltaT(p) is nearly constant. Besides the confinement effect the specific interaction of the polymer blocks with the surfactant layer are of importance.

Langmuir monolayers and Langmuir-Blodgett films of 1-acyl-1,2,4-triazoles.

New 1-acyl-1,2,4-triazoles (ATs) with different n-alkyl chain lengths from C2 to C18 were synthesized. ATs with long n-alkyl chains (C12 and larger) are non-charged amphiphilic molecules with a polar triazole head group. The Langmuir isotherms of ATs at the air-water interface with 12 (DoT-C12), 14 (MyT-C14), 16 (PaT-C16) and 18 (StT-C18) carbon atoms in their n-alkyl chains were studied using surface pressure-mean molecular area (pi-mmA) measurements. Characteristic for the Langmuir isotherms of PaT-C16 and StT-C-18 was the first sharp increase of the surface pressure at a mmA value of approximately 20A(2) marking a transition of the ATs from the gaseous state with n-alkyl chains already oriented perpendicular to the water surface to a condensed state. The collapse of the monolayers occurred between 20 and 36mNm(-1) with a typical 'spike' in the isotherms of MyT-C14, PaT-C16 and StT-C18 which can be assigned to the buckling and subsequent folding of the monolayer. After the collapse point a pseudo-plateau region of slightly increasing surface pressure appeared for all ATs from C12 to C18 indicating a trilayer formation by the roll-over mechanism for MyT-C14, PaT-C16 and StT-C18. Upon further compression the final collapse occurred at pi values between 59 and 67mNm(-1). From reversibility studies it was found that the Langmuir isotherms of the ATs were irreversible. The morphology of Langmuir-Blodgett films of ATs transferred onto silicon wafers was studied by atomic force microscopy.

Hierarchical organization of poly(ethylene oxide)-block-poly(isobutylene) and hydrophobically modified Fe(2)O(3) nanoparticles at the air/water interface and on solid supports.

Langmuir monolayers and Langmuir-Blodgett (LB) film morphologies of block copolymers and hydrophobically modified iron oxide nanoparticles were studied by surface pressure-mean molecular area (pi-mmA) measurements and by tapping mode atomic force microscopy (AFM). The amphiphilic diblock copolymers consisted of a hydrophilic poly(ethylene oxide) (PEO) block and a hydrophobic poly(isobutylene) (PIB) block. The pi-mmA isotherm of PEO(97)-b-PIB(37) (the subscripts refer to the respective degrees of polymerization) at the air/water interface had an extended plateau reflecting the extension of PEO chains into the water subphase at a surface pressure of 10 mN.m(-1), which is absent for the more hydrophobic PEO(19)-b-PIB(130). Iron oxide (Fe(2)O(3)) nanoparticles capped with oleic acid ligands as the shell were dispersed in the amphiphilic block copolymers at the air/water interface to prevent macroscopic aggregation of the particles. When the nanoparticles were mixed with PEO(97)-b-PIB(37), using a particle to polymer chain ratio of 1:100, macroscopic aggregation of the nanoparticles was not observed, and the pi-mmA isotherm was dominated by PEO(97)-b-PIB(37). Monolayers of block copolymers were transferred at different surface pressures from the air/water interface to hydrophilic silicon substrates using the Langmuir-Blodgett technique. The AFM images of PEO(97)-b-PIB(37) LB films depicted not only the typical finger-like morphology of the crystallized PEO blocks but also PIB blocks arranged in vertical columns growing perpendicular to the substrate surface. The columns are characteristic for PEO(19)-b-PIB(130) LB films after transfer at high surface pressures and can be assigned to a mesomorphic PIB phase with ordered chains. Finally, it was observed that small clusters of a few Fe(2)O(3) nanoparticles occupy the top of PIB phases after compression and transfer of the block copolymer nanoparticle mixtures to solid supports.

Influence of amphiphilic block copolymer induced changes in membrane ion conductance on the reversal of multidrug resistance.

Block copolymers are able to reverse multidrug resistance (MDR) of tumor cells by a yet unknown mechanism. The drug efflux system's direct and indirect inhibition mediated by polymer P-glycoprotein (Pgp) interactions or adenosine triphosphate (ATP) depletion, respectively, may be involved in MDR reversal as well as damage to the membrane barrier caused by polymer insertion into the membrane. To test the latter hypothesis, cellular drug accumulation was monitored in the presence of both overexpressed fluorescently labeled Pgp and different block copolymers. Therefore, a new triblock copolymer (poly(ethylene oxide)- block-poly(hexafluoropropylene oxide)- block-poly(ethylene oxide)) was designed and synthesized by combined polymerization and polymer analogous reaction. Its administration induced drug uptake, whereas control cells with high Pgp expression levels showed no drug accumulation. Drug uptake was even more pronounced in the presence of another triblock copolymer: (poly(perfluorohexylethyl methacrylate)- block-poly(ethylene oxide)- block-poly(perfluorohexylethyl methacrylate). The latter polymer's lack of ionophoric activity suggests that ion transport facilitation by polymers is not a determinative factor for MDR reversal.