Structural studies of laterally attached liquid crystalline polymers

Abstract

Structural studies of a series of laterally attached side chain liquid crystalline polysiloxanes have been made by X-ray diffraction. All but one exhibit a nematic phase with S_C-like short range ordering. The diffraction has been interpreted in terms of a model in which the mesogenic units form a ‘jacket’ around the polymer backbone. The backbone conformation has been studied by small angle X-ray scattering from oriented samples of mesomorphic solutions and by infrared dichroism measurements on oriented samples of the polymers. In both cases the results were consistent with the mesogens being oriented parallel to the backbone which is consistent with the ‘mesogen jacket’ model.     

The effect of amorphous orientation on the oxygen permeability of polypropylene films

Oxygen permeability measurements have been made on uniaxially and biaxially oriented polypropylene samples. X-ray diffraction pole-figure measurements provided the crystalline orientation functions. These results combined with density and refractive index measurements provided the amorphous orientation functions based on the two-phase model. A good correlation has been found between the amorphous orientation and the oxygen permeability of the samples. © 1993 John Wiley & Sons, Inc.     

Morphology of oriented linear polyethylene: A study by Raman spectroscopy

Measurements have been made of the low-frequency Raman longitudinal acoustic mode (LAM) vibration in oriented linear polyethylenes. The oriented samples were prepared by tensile drawing of both slow-cooled and quenched sheets, and included ultrahigh-modulus materials from draw ratios up to 30. A LAM line is observed clearly in samples of low and intermediate molecular weight up to draw ratios of ca. 15. In all these cases the Raman spectrum has been used to calculate the whole distribution of crystal sizes. This procedure leads to values of the number-average and weight-average crystal size which are in good agreement with crystal size determinations by x-ray diffractometry and gel permeation chromatography on etched samples. At higher draw ratios the peak intensity of the LAM line is diminished. This can be attributed to a change in the distribution of crystal thicknesses, consistent with data from x-ray diffraction and nitric acid etching. Effects due to initial morphology, sample molecular weight, and draw temperature have also been examined.     

Structural study of a smectic C phase of biforked molecules

In the framework of a systematic investigation of the molecular organization in different mesophases exhibited by biforked molecules, we present a structural study of the smectic C phase of a biforked compound containing heptyloxy chains. With a combination of dilatometry measurements and X-ray diffraction on polydomain samples, together with a detailed X-ray investigation on oriented samples, it was possible to describe precisely the packing of the molecules within the smectic C layers. The result is a large tilt of the long aromatic cores of about 50°-60° with respect to the normal to the layer planes, whereas the terminal aliphatic chains are close to the normal to the planes with a small tilt angle of about 20°-30°. For the first time, these two angles have been directly observed on the X-ray patterns of oriented samples.     

Liquid Crystalline Side Chain Polysiloxanes with 4-Cyano- and 4-Alkoxy-Stilbene Mesogenic Units

Abstract

Side chain homo- and copolysiloxanes with 4-cyano- and 4-alkoxy-4′-stilbene mesogens, spaced apart from the backbone by oligomethylene segments of variable lengths, were synthesized via a hydrosilylation coupling reaction of five stilbene-containing α-olefins with four commercial poly(methylhydrosiloxane)s and poly(methyl-hydro-∞-dimethylsiloxane)s. Broad smectic phases were observed for the polysiloxanes with cyanostilbene mesogens, whereas the homologous with alkoxy-terminated stilbenes displayed only narrow mesophases in the high temperature range. Preliminary room tem-perature X-ray diffraction studies on mechanically oriented samples evidenced the occurrence of side chain crystallization, microphase separation and indicated the interdigitated smectic A nature of the mesophases.     

Synthesis, Characterization and X-Ray Diffraction Studies of a New Homologous Series of Cyano-Substituted Mesomorphic Side Chain Polyacrylates

A new series of cyano-substituted mesomorphic side chain polyacrylates has been synthesized. Optical observations, D.S.C. studies and X-ray diffraction on oriented samples show that all polymers possess a partially bilayer S_ad phase. The smectic period has been measured from which it is inferred that the molecular structure of the mesogenic cores (i.e. the presence of pH-systems and antiparallel dipoles) induces a small overlap (d ≊ 1·71). The X-ray patterns show that for the whole series, the third order reflection is the most intense. By inverse Fourier transform, we derive the projection of the electron density profile along the director which we try to explain in terms of the molecular features.     

Mesomorphic and structural properties of liquid crystalline side-chain polymethacrylates: from smectic C* to columnar phases

The chiral methacrylate monomers with photosensitive azobenzene group possessing the orthogonal smectic A* and tilted smectic C* (Sm-C*) phases have been synthesised and characterised. The monomers have been used as functional side chains for the design of corresponding polymethacrylates. X-ray diffraction has been applied to elucidate the structure and phase behaviour of liquid-crystalline side-chain polymethacrylates with azobenzene-containing central core, chiral fragments and aliphatic spacers and tails of different length. X-ray patterns of polymethacrylates oriented fibres impose the tilted Sm-C* order as a basic structure of these materials. This is complemented by a regular pattern of small-angle diffuse spots, which implies complex positional order on the local scale and serves as a precursor for the formation of a columnar phase. The increase of the total length of the aliphatic tail and spacer of the side-chain fragments leads to formation of the tilted columnar phase (Col_tilt*) with two-dimensional monoclinic lattice. For the polymer containing 10 methylene units in both, spacer and aliphatic tail, the Col_tilt* precedes the formation of the Sm-C* phase. The observed structural changes are explained as due to coupling between the smectic ordering of the mesogenic side groups and the polymer backbone conformation.     

Structure of gyroid mesophase formed by monodendrons with fluorinated alkyl tails

The structure of a three-dimensional mesophase has been studied by the methods of small-angle X-ray diffraction and reconstruction of electron-density maps of the cubic lattice. In the oriented samples based on monodendrons with partially fluorinated alkyl tails, this mesophase has been shown to coexist with a two-dimensional columnar phase through a wide temperature interval. Epitaxial relationships between (10) planes of the hexagonal lattice and (211) planes of the cubic lattices lead to the ten-point pattern of azimuthal intensity distribution for the first X-ray 211 reflection and to the six-point intensity distribution for the second 220 reflection. The observed 12-point pattern of the 220 reflection is due to the presence of twin “crystallites” of the three-dimensional phase, and their [110] axis is parallel to the axis of cylinders in the columnar phase. The reconstructed electron-density maps show that the regions with increased electron density, which are composed of fluorinated aliphatic tails, form a bicontinuous gyroid structure.     

Ultrastructure studies of polystyrene-based side-chain liquid-crystalline copolymers containing charge transfer groups

A series of new side-chain liquid-crystalline copolymers has been prepared, and the thermal properties of the individual copolymers have been determined. These copolymers are derived from atactic polystyrene and contain both 4-methoxyazobenzene and 4-nitroazobenzene mesogens; these are linked through octyl spacers to the polystyrene backbone. All the copolymers exhibit a smectic phase that has been assigned smectic A on the basis of polarizing microscopy and x-ray diffraction studies. The glass transition temperatures of the polymers exhibit a linear dependence on composition, whereas the clearing temperatures and the associated entropies show significant deviations from such behavior. The smecticisotropic transition temperatures of the copolymers are higher than those of the composition-weighted averages for the corresponding homopolymers, whereas the entropies of transition are lower than expected. X-ray diffraction studies of fiber samples revealed that the director of the mesophase is oriented perpendicular to the fiber axis. The liquid-crystalline polystyrene containing 25 mol % nitro-substituted mesogen shows an unusual S_A-phase WAXS pattern. The copolymers were investigated further by ¹³C CP/MAS NMR spectroscopy, and the observed changes in the spectra are analyzed in terms of chemical composition and local electronic environment. The application of the interrupted decoupling technique revealed that the spacer contains a number of gauche defects. These observations lead us to suggest possible microstructural arrangements in the smectic phase. © 1993 John Wiley & Sons, Inc.     

Structure of the DNA binding cleft of the gene 5 protein from bacteriophage fd.

The structure of the gene 5 DNA unwinding protein from bacteriophage fd has been solved to 2.3-A resolution by X-ray diffraction techniques. The molecule contains an extensive cleft region that we have identified as the DNA binding site on the basis of the residues that comprise its surface. The interior of the groove has a rather large number of basic amino acid residues that serve to draw the polynucleotide backbone into the cleft. Arrayed along the external edges of the groove are a number of aromatic amino acid side groups that are in position to stack upon the bases of the DNA and fix it in place. The structure and binding mechanism as we visualize it appear to be fully consistent with evidence provided by physical-chemical studies of the protein in solution.     

Synthetic polypeptide adsorption to Cu-IDA containing lipid films: a model for protein-membrane interactions

Adsorption of synthetic alanine-rich peptides to lipid monolayers was studied by X-ray and neutron reflectivity, grazing incidence X-ray diffraction (GIXD), and circular dichroic spectroscopy. The peptides contained histidine residues to drive adsorption to Langmuir monolayers of lipids with iminodiacetate headgroups loaded with Cu2+. Adsorption was found to be irreversible with respect to bulk peptide concentration. The peptides were partially helical in solution at room temperature, the temperature of the adsorption assays. Comparisons of the rate of binding and the structure of the adsorbed layer were made as a function of the number of histidines (from 0 to 2) and also as a function of the positioning of the histidines along the backbone. For peptides containing two histidines on the same side of the helical backbone, large differences were observed in the structure of the adsorbed layer as a function of the spacing of the histidines. With a spacing of 6 A, there was a substantial increase in helicity upon binding (from 17% to 31%), and the peptides adsorbed to a final density approaching that of a nearly completed monolayer of alpha-helices adsorbed side-on. The thickness of the adsorbed layer (17 +/- 2.5 A) was slightly greater than the diameter of alpha-helices, suggesting that the free, unstructured ends extended into solution. With a spacing of 30 A between histidines, a far weaker increase in helicity upon binding was observed (from 13% to 19%) and a much lower packing density resulted. The thickness of the adsorbed layer (10 +/- 4 A) was smaller, consistent with the ends being bound to the monolayer. Striking differences were observed in the interaction of the two types of peptide with the lipid membrane by GIXD, consistent with binding by two correlated sites only for the case of 6 A spacing. All these results are attributed to differences in spatial correlation between the histidines as a function of separation distance along the backbone for these partially helical peptides. Finally, control over orientation was demonstrated by placing a histidine on an end of the sequence, which resulted in adsorbed peptides oriented perpendicular to the membrane.     

Structural and electro-optical investigations of the smectic phase of chlorine-substituted banana-shaped compounds

Six members of a new homologous series of achiral banana-shaped molecules have been synthesized and studied by optical microscopy, differential scanning calorimetry, NMR spectroscopy and X-ray diffraction. According to X-ray diffraction measurements on oriented samples, four homologues form an XB2 phase behaviour. From electro-optical studies the spontaneous polarization and the tilt angle could be measured. An orientational order parameter of 0.8 was determined by 13C NMR and this is nearly independent of the temperature. NMR investigations also give information about the real conformation of the molecules in the XB2 phase. Dielectric measurements indicate that the rotation around the molecular long axis is clearly hindered because of the packing of the bent molecules within the smectic layers. which exhibits antiferroelectric switching     

Synthesis of a stable radical anion via the one electron reduction of a 1,1-bis-phosphinosulfide alkene derivative

A new type of stable radical ligand featuring a 1,1-bis-phosphinosulfide alkene backbone has been prepared and characterized on the basis of X-ray diffraction, EPR and DFT studies.     

Hexakis(isopropylthio)-1,5-hexadien-3-yne and its fluorescent Ag(I) coordination polymers: assembly of helicates with thioether sites

A new thioether-rich ligand with a conjugated dienyne backbone and its fluorescent Ag(I) coordination networks have been synthesized and characterized by single crystal X-ray diffraction studies, which reveal that the supramolecular architectures of the networks contain assembled helicates with thioether sites.     

Novel (n + 1 + 1) cycloaddition reactions; the formation of cyclic tetraphosphonium dications with four linked phosphorus atoms and an organic backbone

In the presence of SnCl(2), a novel cycloaddition of two moles of R'PCl(2) (R' = Et or Ph) to a diphosphane has been achieved, forming a cyclic dication with four linked phosphorus atoms and an organic backbone; two of these species have been characterised by single-crystal X-ray diffraction, and the mechanism of the reaction has been established.     

The use of 2D diffractometry data for oriented samples in the choice of a unit cell

An approach for the substantiated choice of the indexing procedure of a diffraction pattern is described. The technique is based on a combined use of powder X-ray diffraction data in Bragg–Brentano schemes and 2D GIXD of mainly oriented polycrystalline samples.     

The electron microscope characterization of the fine structure of nylon 6: II. On the rearrangement of the structure during cold-drawing

The transmission electron microscope (TEM) visualization of the supermolecular structure of cold-drawn, oriented nylon 6 bulk material (bristles) by stained ultra-thin sections is reported. For evaluating the electron micrographs optical diffraction (OD) has been applied in comparison with small angle X-ray scattering (SAXS). The deformation of the spherulites was followed by polarization microscopy. In addition, investigations were carried out on commercial nylon 6 fibres. As the main result a transverse structure was revealed within the drawn samples at draw ratios between =4 and 4.5, consisting of mosaic crystals which show some lateral alignment. The structure is described by a modified layer lattice model. While the long period may increase slightly during drawing, the crystallite thickness remains almost constant. Fibres with =3.4 show a similarly oriented structure though the lateral alignment of the crystals is not so pronounced.     

Sandwich layer structure of a novel polyimide with methylene spacing groups in biphenyl side chain

The aggregation structure of a novel polyimide (PI-6) with six methylene flexible spacing groups in biphenyl side chain was investigated using polarized optical microscope (POM), wide/small-angle X-ray diffraction (WAXD/SAXD) and molecular simulation approach. Depending on increasing temperature, the sandwich layer aggregation structure of PI-6 was developed from the thermo reversible gel. The backbones are lamellar stacking with 11.5 Å thickness. The side chains are randomly packed into the backbone lamellar intervals and the width of this layer for both backbone and side chain is about 23.1 Å which is consistent with the simulation data.     

Catalytic activity of phosphorus and steam modified HZSM-5 and the theoretical selection of phosphorus grafting model

The modification of HZSM-5 zeolite with phosphorus and steam has been studied. Results show that 1% phosphorus and steam modified HZSM-5 has the highest catalytic activity for n-heptane. Physicochemical and catalytic properties of 1% phosphorus and steam modified HZSM-5 zeolites have been investigated. The X-ray diffraction （XRD） results exhibit that there is considerable variation in the relative intensity of the individual diffraction peaks. The acidity of the samples decreases with an increase in the steaming temperature, which is determined by the IR of adsorbed pyridine and temperature programmed desorption （TPD） of ammonia. The oxidation state of phosphorus shown by XPS is ＋5, and a model for surface structure modification is proposed. The nitrogen adsorption isotherm for all samples is a combination of type I and type IV, all hysteresis loops resemble the H4-type. The density functional and cluster model methods have been invoked to select the phosphorus grafting model, and it was found that the phosphorus grafting model were more probable in the form of the terminal oxygen coordinating with aluminum.     

Real-time X-ray scattering study during heating of oriented injection-molded polyethylene

Highly oriented linear polyethylene was prepared by elongational flow injection molding. The changes in crystal orientation were investigated as a function of temperature by real-time wide-angle X-ray diffraction. Additionally, the influence of molecular weight upon the microstructure and the changes in orientation, during heating near the melting point, and after cooling have been examined. A shish-kebab structure is inferred for the high molecular weight samples (M_w≥10⁵) from SAXS observations, while for samples with M_w<10⁵ only an oriented lamellar structure is found. Consequently, a higher thermal stability is shown by the higher molecular weight samples. Furthermore, a recovery of crystal orientation on rapid cooling of the samples from the melt is only observed for samples with M_w≥10⁵. The results are discussed in terms of a preferential recrystallization of chain-folded lamellae, on cooling, onto the shish fibrils which survive at high temperature.