Langmuir-Blodgett films of fluorinated glycolipids and polymerizable lipids and their phase separating behavior

This paper describes the phase separating behavior of Langmuir monolayers from mixtures of different lipids that (i) either carry already a glycopeptide recognition site or can be easily modified to carry one and (ii) polymerizable lipids. To ensure demixing during compression, we used fluorinated lipids for the biological headgroups and hydrocarbon based lipids as polymerizable lipids. As a representative for a lipid monomer, which can be polymerized in the hydrophilic headgroup, a methacrylic monomer was used. As a monomer, which can be polymerized in the hydrophobic tail, a lipid with a diacetylene unit was used (pentacosadiynoic acid, PDA). The fluorinated lipids were on the one hand a perfluorinated lipid with three chains and on the other hand a partially fluorinated lipid with a T(N)-antigen headgroup. The macroscopic phase separation was observed by Brewster angle microscopy, whereas the phase separation on the nanoscale level was observed by atomic force microscopy. It turned out that all lipid mixtures showed (at least) a partial miscibility of the hydrocarbon compounds in the fluorinated compounds. This is positive for pattern formation, as it allows the formation of small demixed 2D patterned structures during crystallization from the homogeneous phase. For miscibility especially a liquid analogue phase proved to be advantageous. As lipid 3 with three fluorinated lipid chains (very stable monolayer) is miscible with the polymerizable lipids 1 and 2, it was mostly used for further investigations. For all three lipid mixtures, a phase separation on both the micrometer and the nanometer level was observed. The size of the crystalline domains could be controlled not only by varying the surface pressure but also by varying the molar composition of the mixtures. Furthermore, we showed that the binary mixture can be stabilized via UV polymerization. After polymerization and subsequent expansion of the barriers, the locked-in polymerized structures are stable even at low surface pressures (10 mN/m), where the unpolymerized mixture did not show any segregation.     

Microstructure and lateral diffusion in monolayers of polymerizable amphiphiles

Lipid analogue amphiphilic molecules containing polymerizable units were investigated in monolayers at the air/water interface by using film balance measurements, fluorescence microscopy, and photobleaching techniques. The polymerizable groups (diene-, diyne-, and methacrylate units) were introduced into the hydrophobic alkyl chains or into the polar head of the amphiphilic molecules.In the case of the diene- and diyne-containing compounds the polymerizable units are incorporated into the hydrophobic alkyl chains, enabling them to form a two-dimensional network. Due to the free chain flexibility of the monomers the lateral mobility was comparable to that of saturated lipid analogues and decreases upon polymerization proportionally to the dose of UV irradiation. In addition, fluid/solid phase transitions of compounds with polymerizable groups in the hydrophobic part tend to vanish during the formation of the polymers. However, the direct observation of the growth of polymeric crystalline domains can be followed by using diacetylene lipid analogues.In the case of the methacrylate derivatives the polymerizable unit was coupled to the polar part via a flexible spacer. For these systems the characteristics of the monomeric phase transition are retained after polymerization. However, it shows a significant, strong decrease of the in-plane mobility already in the fluid-expanded phase of the polymer. The quantitative measurements of the lateral diffusion in the monolayers can be correlated with fluorescence microscopic images of their structure.     

Development and Evaluation of a New Fluorinated Double-Wall Carbon Nanotube HPLC Stationary Phase

A novel column based on silica-containing immobilized fluorinated double-wall carbon nanotubes (F-DWCNTs) was developed. This F-DWCNT stationary phase was synthesized to combine the analytical performance of carbon nanotubes and the fluorine-based unique selectivity for polar compounds. First, the chromatographic support was coated with DWCNTs in a noncovalent way to preserve the sp² internal nanotube structure. Second, the DWCNT silica particles were functionalized with fluorine atoms via a solution of Br₂ and BrF₃ at room temperature. This F-DWCNT stationary phase was applied for a variety of separations. The solute retention behaviour was particularly studied under isocratic conditions with a high fraction of ACN in the ACN/water (v/v) mobile phase. The retention factors of the solute molecule do not depend linearly on the ACN fraction, but follow a quadratic relationship. This fluorinated stationary phase separated compounds based upon a combination of hydrophobic and polar selective stationary phase interactions. This F-DWCNT appeared to work best when fluorinated or halogenated compounds were encountered. They have longer retention time, better selectivity and work well with high fraction of organic modifiers. This novel stationary phase could thus be a good choice for LC–MS experiments.     

Synthesis and characterization of a new open-framework fluorinated gallium phosphite with three-dimensional intersecting channels

(C₄N₂H₁₂)[Ga₂F₃(HPO₃)₂(H₂PO₃)] 1 is a new open-framework fluorinated gallium phosphite obtained by mild hydrothermal synthesis using piperazine as template agent and characterized by single crystal X-ray diffraction (XRD), powder XRD, infra-red spectroscopy, inductively coupled plasma, thermogravimetric and elemental analyses. The three-dimensional (3D) anionic framework of compound 1 is constructed from two distinct motifs, a 1D tancoite chain and a single 4-ring (S4R) unit, which contains four intersecting channels running throughout the structure as 8, 12-member rings channels along to the a-axis and 12-member ring channels along the b- and c-axis, respectively. The well-ordered, diprotonated piperazine cations occupy all the channels, and interact with the fluorinated gallium-phosphite framework by strong hydrogen bonds.     

Crystal structure of tetragonal boron related to α-AlB12

Single crystals of the so-called β-tetragonal (or tetragonal II or III) boron modification have been obtained from boron deposits prepared by hydrogen reduction of BBr₃ on tantalum filaments at 1200°C. Chemical analysis of the samples shows that this phase can be regarded as a true modification of pure elemental boron in contrast to α-tetragonal phases which require small amounts of foreign atoms to stabilize their boron framework.The lattice parameters (a = 10.14(1)Å; c = 14.17(1)Å) were obtained and refined from single crystal data. The unit cell contains four chemical units, B₂₁ · 2B₁₂ · B_2.5 resulting in d_c = 2.34 g cm^?3 (d_m = 2.36(2) g cm^?3). The systematic extinctions are compatible with space group P4₁ or P4₃.The structure was determined from 1009 independent reflexions using a model derived from the recently solved structure of α - AlB₁₂ (a = 10.161Å; c = 14.283Å; space group P4₁2₁2 or P4₃2₁2). The final R value (unweighted data) is 9.6%.Basically, the structure of this tetragonal form of boron consists of the same three-dimensional boron skeleton, built upon simple and twinned icosahedra, as that of α-AlB₁₂. However, the defective twinned icosahedral B₁₉ units in α-AlB₁₂ are now completed (B₂₁ units) in the related tetragonal boron. A number of interstitial sites, located at positions different from those occupied by aluminum in α-AlB₁₂, are totally or partially filled by boron atoms and very probably increase the stability of the boron framework.     

Synthesis of a polymerizable metal-ion-chelating lipid for fluid bilayers.

Hydrated lipid structures, such as liposomes, that display tethered metal-ion-chelating groups have proven useful in peptide and protein binding, as well as 2D protein crystallization through molecular recognition of accessible histidine sites in proteins and peptides. Polymerizable metal-ion-chelating lipids bearing a reactive diacetylene group have been described. These interesting compounds can be polymerized in the solid-analogous phase. Here we describe the design of the first polymerizable metal-ion-chelating lipid that can be used in the fluid, i.e., liquid analogous, phase of lipid bilayers. The synthesis of 1-palmitoyl-2-[8-[(E,E)-2',4'-hexadienoyloxy]octanoyl]-sn-glycero-3-N-[11-[N',N'-bis[carboxymethyl]imino]-3,6,9-trioxaundecanoyl] phosphatidylethanolamine (1) is described. The chelator moiety, iminodiacetate (IDA), was linked to the polymerizable phosphatidylethanolamine (PE) with a terminal 2,4-hexadienoyl (sorbyl) group through an oligo(ethylene glycol)-based spacer. Lipid 1-Cu complex is designed to be combined with the corresponding polymerizable matrix lipids (bis-SorbPC) to form functionalized liposomes that can be stabilized by various polymerization methods.     

Polymerization of liposomes composed of diene-containing lipids by radical initiators. II. Polymerization of monodiene-type lipids as liposomes

1-Palmitoyl-2(2,4-octadecadienoyl)-sn-glycero-3-phosphocholine (POPC), a polymerizable lipid that contains one diene group in only a 2-acyl chain, was polymerized as liposome in an aqueous medium. Polymerization was initiated by water-insoluble azobisisobutyronitrile (AIBN), or water-soluble azobis(2-amidinopropane) dihydrochloride (AAPD). AIBN was mixed with monomeric lipids, and the mixture was dispersed in an aqueous medium by sonication to prepare AIBN-containing monomeric lipid liposomes. On the other hand, AAPD was simply added to the liposome suspension. The POPC liposomes were easily polymerized by the addition of AAPD, a water-soluble radical initiator, but few were polymerized by AIBN. The results suggested that the diene group in the 2-acyl chain was in an aqueous phase and, therefore, easily polymerized by a water-soluble radical initiator. The polymerized POPC liposomes were revealed to be more stable than those of monomeric ones because the scattered-light intensity from the polymerized POPC liposome suspension changed a little by the addition of Triton X-100. For only the polymerized ones, the liposome structure was confirmed by TEM after addition of an excess amount of Triton X-100.     

Thermal stability and crystal structure of β-Ba3YB3O9

A new compound, β-Ba₃YB₃O₉, has been attained through solid phase transition from α-Ba₃YB₃O₉ at high temperatures. Differential thermal analysis (DTA) revealed the phase transition at about 1120°C, the melting temperature at about 1253°C. Its crystal structure has been determined from powder X-ray diffraction data. The refinement was carried out using the Rietveld method and the final refinement converged with R_p=10.5% and R_wp=13.7%. This compound belongs to the hexagonal space group R-3, with lattice parameters a=13.0441(1) Å and c=9.5291(1) Å. There are 6 formulas per unit cell and 7 atoms in the asymmetric unit. The structure of β-Ba₃YB₃O₉ is built up from Ba(Y)O₈, BaO₆ and YB₆O₁₈ units formed by one YO₆ octahedron and six BO₃ triangles with shared O atoms.     

Crystal structures of α- and β-EuPrCuS3

The crystal structure of the EuPrCuS₃ complex sulfide synthesized for the first time has been solved by X-ray powder diffraction. Crystals are orthorhombic, space group Pnma. EuPrCuS₃ has two polymorphs: the high-temperature phase of Ba₂MnS₃ structural type with unit cell parameters a = 8.0786(1) Å, b = 4.0288(1) Å, and c = 15.8389(2) Å and the low-temperature phase of BaLaCuS₃-isostructural with unit cell parameters a = 11.0819(2) Å, b = 4.0710(1) Å, and c = 11.4459(3) Å.     

Synthesis and characterization of the variable-composition phase Na1−x Ni1−x Cr1+x (MoO4)3 (0 ≤ x ≤ 0.4) with a NASICON structure

Synthetic conditions are determined for the variable-composition phase Na_1?x Ni_1?x Cr_1+x (MoO₄)₃ (0 ≤ x ≤ 0.4) with a NASICON structure. The unit cell parameters of this phase are derived from X-ray powder diffraction data, and the phase is characterized by IR and Raman spectroscopy.     

Effects of chemical variations on the mesophase behavior of new fluorinated poly(vinylcyclopropane)s

Several new structures of fluorinated polymers poly(1)-poly(9) were prepared by free radical ring opening polymerization of vinylcyclopropane monomers 1-9 containing different fluorinated side groups of the type (CH₂)_n(CF₂)_pF. While in poly(1)-poly(3) p varied from 6 to 10 for a fixed n=2, in poly(4)-poly(6) n increased from 3 to 5 at the given p=8. In poly(7) and poly(8) a phenyl ring was incorporated to elongate the mesogenic side group (n=2; p=6 and 8, respectively), that was further separated from the polymer backbone by a methylene spacer (m=11) in poly(9). Therefore, the effects of various chemical variations of the polymer structure on the mesophase behavior could be assessed. The polymers were in fact co-polymers comprising both 1,5-linear and cyclobutane-ring isomer units. In any case they formed smectic mesophase(s) owing to the special character of the perfluorinated chains. The order and the isotropization temperature (T_i) of the mesophase were enhanced by increasing p, but T_i lowered with increasing n. Extension of the side group by insertion of a phenyl ring improved T_i. Wide angle X-ray diffraction studies clarified the nature of the different smectic phases, the occurrence of which was discussed in terms of the ability of the fluorinated side groups to pack antiparallel in either a partly or fully interdigitated structure. Co-polymers of 3 with a non-mesogenic, not fluorinated co-monomer 10 were also prepared with different chemical compositions. Co-polymerization was found to be another effective means of modifying the mesophase behavior of the poly(vinylcyclopropane)s.     

Synthesis and fluorescence properties of new fluorescent, polymerizable, metal-chelating lipids

Liposomes incorporating fluorescent, metal-chelating lipids find applications in molecular recognition of peptides, 2D protein recrystallization, protein targeting, and biological sensing. It would be advantageous to combine the usefulness of polymerizable, metal-chelating lipids and fluorescent lipids. Herein, we report the synthesis and fluorescence properties of several fluorescent, polymerizable, metal-chelating lipids. They have been successfully incorporated into liposomes and then polymerized. These lipids can be used as membrane probes to study the polymerizable liposomes in the unpolymerized state and to investigate lipid redistribution during polymerization. In addition, if a luminescent metal ion (e.g., Eu(3+), Tb(3+), etc.) is used to complex the headgroup, the lipids can probe the membrane interior and exterior simultaneously.     

Ga3(HPO3)4F4(H3DETA) (DETA=diethylenetriamine): A new open-framework fluorinated gallium phosphite with pentameric building unit

Ga₃(HPO₃)₄F₄(H₃DETA) is a new open-framework fluorinated gallium phosphite obtained by mild hydrothermal synthesis using diethylenetriamine as templated agent and characterized by single crystal X-ray diffraction, the powder X-ray diffraction, IR spectroscopy, TGA, ICP and elemental analyses. It crystallizes in the monoclinic space group C2/c, a=12.741(6) Å, b=12.068(6) Å, c=11.988(5) Å, β=94.902(8)^o, V=1836.6(15) Å³, Z=4. The construction of 3D open-framework structure in the title compound may be viewed as the assembly of pentameric building units and HPO₃ groups. The pentameric building unit is the first to be found, which lead to form the three types of channels along a-, b- and c-axes, respectively, in gallium phosphite. The triprotonated DETA cations are inserted within the 10-membered ring channels and interact with anions of the framework via hydrogen bonds.     

EuNdCuS3: Crystal structure of the high-temperature polymorph and properties

The X-ray diffraction structure of the high-temperature polymorph of complex sulfide EuNdCuS₃ is determined. The phase we prepared has an orthorhombic structure with the unit cell parameters a = 8.0648(3) Å, b = 4.0207(1) Å, c = 15.7924(3) Å, space group Pnma, Z = 4, Ba₂MnS₃ type structure. The sample is IR transparent in the range 1800–2800 cm^?1. Thermal expansion coefficient is found to experience jumps, which are characteristic of phase transitions.     

Spatially selected synthesis of LaF3 and Er-doped CaF2 crystals in oxyfluoride glasses by laser-induced crystallization

Oxyfluoride glasses with a small amount of NiO are prepared using a conventional melt quenching technique, and the spatially selected crystallization of LaF₃ and CaF₂ crystals is induced on the glass surface by irradiations of continuous wave lasers with a wavelength of λ=1064 or 1080 nm. Dots and lines including LaF₃ crystals are patterned by heat-assisted (300 °C) laser irradiations (λ=1064 nm) with a power of P=1 W and an irradiation time of 10 s for dots and a scanning speed of S=5 μm/s for lines. Lines consisting of CaF₂ crystals are also patterned in an ErF₃-doped oxyfluoride glass by laser irradiations (λ=1080 nm) with a power of P=1.7 W and a scanning speed of S=2 μm/s, and the incorporation of Er³⁺ ions into CaF₂ crystals is confirmed from micro-photoluminescence spectrum measurements. It is proposed that the lines patterned by laser irradiations in this study are consisted of the composite of LaF₃ or CaF₂ nanocrystals and SiO₂-based oxide glassy phase. It is demonstrated that a combination of Ni²⁺-dopings and laser irradiations is effective in spatially selected local crystallizations of fluorides in oxyfluoride glasses.     

New Architecture of Liquid‐Crystalline Polymers from Fluorinated Vinylcyclopropanes

A new class of fluorinated polymers was prepared by radical ring‐opening homopolymerization of vinylcyclopropane monomers with a perfluorinated (CF₂)_nF chain (n = 6, 8, or 10). The polymers were in fact copolymers composed of 1,5‐linear and cyclobutane isomer units, the relative content of which depended on n. Surprisingly, they formed liquid‐crystalline mesophases (SmB_d and/or SmA_d), which was attributed to phase separation of the incompatible fluorocarbon and hydrocarbon components of the repeat unit.     

Phases containing tungsten in Cu(1) positions

A tetragonal (123) phase of composition CdBa₂Cu₂WO₈ with the complete and selective substitution of tungsten atoms for copper in the Cu(1) positions is synthesized from CdWO₄ and BaCuO₂ at 800°C in flowing oxygen. The percentage of the (123) phase in the sample is at least 90%; the unit cell parameters are a = b = 0.4151(3) nm, c = 1.2537(8) nm. The X-ray diffraction pattern shows a superstructure with all three of the unit cell parameters being doubled.     

Crystal structure of α-AlB12

The crystal structure of α-AlB₁₂ (tetragonal; a = 10.158(2) Å, c = 14.270(5) Å, space group P4₁2₁2 or P4₃2₁2) has been determined by the single-crystal X-ray diffraction method. It was solved by the Fourier technique initially based on a partial B₁₂ icosahedral structure, which was inferred from crystal chemical considerations. Refinement was made with the aid of a full-matrix least-squares program leading to a final R value of 3.0%. The structure is based on a three-dimensional framework consisting of B₁₂ icosahedra, B₁₉ units, and single B atoms; the B₁₉ unit is a twinned icosahedron with a triangular composition plane and a vacant apex on each side. The chemical unit is Al_3.2·2B₁₂·B·B₁₉ and its number in the unit cell is 4. The Al atoms are distributed statistically over five sites in the boron framework. The occupancies of the sites are 72, 49, 24, 15, and 2%, respectively.     

Evidence of network demixing in GeS2-Ga2S3 chalcogenide glasses: A phase transformation study

The information of phase transformation is attained by in situ XRD experiments leading to the knowledge of topological threshold in GeS₂-Ga₂S₃ glasses. The turning point of phase transformation behavior is demonstrated to be glasses containing 14-15 mol% Ga₂S₃. To interpret it a network demixing model is further improved and proposed for the structure of these ternary or quasi-binary chalcogenide glasses. For the nearest-neighbor coordination environment of glass with a transitional composition of 85.7 mol% (6/7) GeS₂·14.3 mol% (1/7) Ga₂S₃, six-coordinated [S₃Ga-X-GaS₃] units (X=S or None) are well isolated by the [GeS₄] structures, which contributes to the decreasing of precipitation of Ga₂S₃ crystals in (100−x)GeS₂-xGa₂S₃ (x≤14.3) glasses corresponding to the experimental evidence of the phase transformation behavior. This scenario of intermediate-range structural order, firstly, includes the arrangement of structural units which is consistent with and provides an atomistic explanation of the compositional evolution of phase transformation behavior in these glasses.     

A mass spectral study of some symmetric and unsymmetric sulfides,disulfanes, and trisulfanes

The low-resolution mass spectra of 13 trifluoromethyl and/or methyl sulfur-containing compounds (CF₃S_nCF₃, CF₃S_nCH₃, CH₃S_nCH₃, CF₃S_mCl, and CH₃S_mCl; n = 1, 2, 3; m = 1, 2) are reported and discussed. There is a considerable similarity between the fragmentation pattern of compounds with the same terminal groups. However, with a fluorinated and a non-fluorinated methyl group, the major fragmentation products produced are similar to those for the dimethyl compounds.