Polymorphism and Stretch-Induced Transformations of Sustainable Polyethylene-Like Materials.

Herein we demonstrate that polyethylene-like bioderived, biodegradable, and fully recyclable unbranched aliphatic polyesters, such as PE-2,18, develop hexagonal crystal structures upon quenching from the melt to temperatures <∼50 °C and orthorhombic-like packing at higher quenching temperatures or after isothermal crystallization. Both crystal types are layered. While all-trans CH2 packing characterizes the structure of the orthorhombic-like form, there is significant conformational disorder in the staggered long CH2 sequences of the hexagonal crystals. On heating, the hexagonal crystals transform to the orthorhombic type at ∼60 °C via melt recrystallization, but no change is apparent during heating samples with the orthorhombic form up to the melting point (∼95 °C). The hexagonal structure is of interest not only because it develops under very rapid quenching from the melt but also because under uniaxial tensile deformation it undergoes a stretch-induced transformation to the orthorhombic structure. Compared to deformation of orthorhombic specimens that maintain the same crystal type, such transformation results in larger strains and enhanced strain hardening, thus representing a desired toughening mechanism for this type of polyethylene-like materials.

Hybridization of Wide-Angle X-ray and Neutron Diffraction Techniques in the Crystal Structure Analyses of Synthetic Polymers.

The development in the crystal structure analysis of synthetic polymers using the hybridized combination of wide-angle X-ray and neutron diffraction (WAXD and WAND, respectively) techniques has been reviewed with many case studies performed by the authors. At first, the technical development was reviewed, in which the usage of high-energy synchrotron X-ray source was emphasized for increasing the total number of the observable diffraction peaks, and several examples were introduced. Secondly, the usage of the WAND method was introduced, in which the successful extraction of hydrogen atomic positions was described. The third example is to show the importance for the hybrid combination of these two diffraction methods. The quantitative WAXD data analysis gave the crystal structures of at-poly(vinyl alcohol) (at-PVA) and at-PVA-iodine complex. However, the thus-proposed structure models were found not to reproduce the observed WAND data very much. The reason came from the remarkable difference in the atomic scattering powers of the constituting atomic species between WAXD and WAND phenomena. The introduction of statistical disorder solved this serious problem, which reproduced both of the observed WAXD and WAND data consistently. The more systematic combination of WAXD and WAND methods, or the so-called X-N method, was applied also to the quantitative evaluation of the bonded electron density distribution along the skeletal chains, where the results about polydiacetylene single crystals were presented as the first successful study. Finally, the application of WAND technique in the trace of structural changes induced under the application of external stress or temperature was described. The future perspective is described for the development of structural science of synthetic polymers on the basis of the combined WAXD/WAND techniques.

Synthesis and Cyclization-Induced Charge Transfer of Rectangular Bisterthiophenesiloxanes.

Cyclization-modified terthiophene displays the change of emission behavior from locally excited (LE) to the intramolecular charge transfer (ICT) state. The rectangular bisterthiophenesiloxanes (DSiTh) was successfully prepared by π-π-stacking-aided hydrogen-bonding interactions. Cyclization-induced ICT in DSiTh could be observed, which was confirmed by absorption spectra, fluorescence spectra, and quantum chemistry analysis. The cyclization produces a strong intramolecular electron redistribution of a highly packed π-conjugated terthiophene. Thus, a distinctive variation of the dipole moment and a through-space ICT happen.

Structural Evolution Mechanism of Crystalline Polymers in the Isothermal Melt-Crystallization Process: A Proposition Based on Simultaneous WAXD/SAXS/FTIR Measurements.

Time-resolved simultaneous measurements of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) (and FTIR spectra) were performed for various kinds of crystalline polymers in isothermal melt-crystallization processes, from which the common features of the structural evolution process as well as the different behaviors intrinsic to the individual polymer species were extracted. The polymers targeted here were polyethylene, isotactic polypropylene, polyoxymethylene, aliphatic nylon, vinylidene fluoride copolymer, trans-polyisoprene, and poly(alkylene terephthalate). A universal concept of the microscopically viewed structural evolution process in isothermal crystallization may be described as follows: (i) the small domains composed of locally regular but more or less disordered helical chain segments are created in the melt (this important information was obtained by the IR spectral data analysis); (ii) these domains grow larger as the length and number of more regular helical segments increase with time; (iii) the correlation among the domains becomes stronger and they approach each other; and (iv) they merge into the stacked lamellar structure consisting of the regularly arranged crystalline lattices. The inner structure of the domains is different depending on the polymer species, as known from the IR spectral data.

A study of the extraordinarily strong and tough silk produced by bagworms.

Global ecological damage has heightened the demand for silk as 'a structural material made from sustainable resources'. Scientists have earnestly searched for stronger and tougher silks. Bagworm silk might be a promising candidate considering its superior capacity to dangle a heavy weight, summed up by the weights of the larva and its house. However, detailed mechanical and structural studies on bagworm silks have been lacking. Herein, we show the superior potential of the silk produced by Japan's largest bagworm, Eumeta variegata. This bagworm silk is extraordinarily strong and tough, and its tensile deformation behaviour is quite elastic. The outstanding mechanical property is the result of a highly ordered hierarchical structure, which remains unchanged until fracture. Our findings demonstrate how the hierarchical structure of silk proteins plays an important role in the mechanical property of silk fibres.

pH-induced conformational changes in histamine in the solid state.

Histamine is one of the most basic biogenic amino-compounds, which is composed of imidazole and a flexible ethylamine side chain moiety. Histamine is known to take the form of various types of cations, free base, monocation and dication form, where its conformational change is highly sensitively to the pH conditions. The details of these changes are still controversial due to a lack of detailed information on its crystal structures. Thus, in this study, the molecular packing structures of histidine at various pH were analyzed via X-ray diffraction in combination with vibrational spectroscopy and energy calculations. A variety of molecular conformations including the tautomeric phenomenon was found to be intimately related with intra- and intermolecular hydrogen bonds. The role of the hydrogen bonds was studied also to check the possibility of high proton conductivity of histamine, as predicted by computer simulation. Consequently, the thus-predicted proton conductivity was confirmed for the first time experimentally. During the heating process, the conductivity showed the relatively high maximum value of 10-4 S cm-1 at around 60 °C, which is related to the effective proton transfer between the amino NH group of one histamine unit and the imidazole ring of another.

Effect of Elevated Temperatures on the States of Water and Their Correlation with the Proton Conductivity of Nafion.

For the first time, we report the effects of elevated temperatures, from 80 to 100 °C, on the changes in the states of water and ion-water channels and their correlation with the proton conductivity of Nafion NR212, which was investigated using a Fourier transform infrared spectroscopy study. Experimentally, three types of water aggregates, protonated water (H+(H2O) n ), nonprotonated hydrogen (H)-bonded water (H2O···H2O), and non-H-bonded water, were found in Nafion, and the existence of those three types of water was confirmed through ab initio molecular dynamics simulation. We found that the proton conductivity of Nafion increased for up to 80 °C, but from 80 to 100 °C, the conductivity did not increase; rather, all of those elevated temperatures showed identical conductivity values. The proton conductivities at lower relative humidities (RHs) (up to 50%) remained nearly identical for all elevated temperatures (80, 90, and 100 °C); however, from 60% RH (over λ = 4), the conductivity remarkably jumped for all elevated temperatures. The results indicated that the amount of randomly arranged water gradually increased and created more H-bonded water networks in Nafion at above 60% RH. From the deconvolution of the O-H bending band, it was found that the volume fraction f i (i=each deconvoluted band) of H-bonded water for elevated temperatures (>80-100 °C) increased remarkably higher than for 60 °C.

Transformation of Coiled α-Helices into Cross-ß-Sheets Superstructure.

The fibrous silk produced by bees, wasps, ants, or hornets is known to form a four-strand α-helical coiled coil superstructure. We have succeeded in showing the formation of this coiled coil structure not only in natural fibers, but also in artificial films made of regenerated silk of the hornet Vespa simillima xanthoptera using wide- and small-angle X-ray scatterings and polarized Fourier transform infrared spectroscopy. On the basis of time-resolved simultaneous synchrotron X-ray scattering observations for in situ monitoring of the structural changes in regenerated silk material during tensile deformation, we have shown that the application of tensile force under appropriate conditions induces a transition from the coiled α-helices to a cross-ß-sheet superstructure. The four-stranded tertiary superstructure remains unchanged during this process. It has also been shown that the amorphous protein chains in the regenerated silk material are transformed into conventional ß-sheet arrangements with varying orientation.

Infrared Spectroscopy and X-ray Diffraction Characterization of Dimorphic Crystalline Structures of Polyethylenes with Halogens Placed at Equal Distance along the Backbone.

Polyethylenes with halogens placed on each and every 21st, 15th, or ninth backbone carbon display crystallization patterns enabled by the size of the halogen and by changing crystallization kinetics. The different structures have been identified from X-ray patterns combined with a detailed analysis of the infrared spectra of series containing F, Cl, or Br atoms that were either fast or isothermally crystallized from the melt. Under both crystallization modes, all specimens develop layered crystallites that accommodate 5-9 repeating units along the chain's axis. The size of the halogen and intermolecular staggering to maximize packing symmetry are responsible for striking structural differences observed between the series and between the two modes of crystallization. While the small size of the F atom causes a small perturbation to the crystal lattice and the orthorhombic structure is maintained for all members of the series either fast or isothermally crystallized, each Cl or Br-containing system presents dimorphism. Under fast crystallization, Cl and Br containing samples adopt the all-trans conformation (planar Form I), while in slowly crystallized samples gauche conformers set for bonds of the backbone carbons adjacent to the carbon with the halogen due to a close intermolecular staggering of halogens (herringbone Form II). In both forms the methylene sequence between halogens maintains the all-trans conformation. The structural details are extracted from the analysis of the C-halogen stretching region of the IR spectra, and from adherence to the n-alkane behavior of CH2 rocking, CH2 wagging, and C-C stretching progression modes.

Time-Resolved Imaging of the Phase Transition in the Melt-Grown Spherulites of Isotactic Polybutene-1 as Detected by the Two-Dimensional Polarized IR Imaging Technique.

In order to visualize the 2D spatial distribution of the structural change in the phase transition from crystal form II to I of isotactic polybutene-1 spherulite grown from the melt, the time-dependent measurement of the 2D polarized FTIR spectra has been performed. At a melt-isothermal crystallization temperature of 103 °C, the square-shape spherulite appeared from the melt and grew with time. When the isothermal crystallization occurred at 98 °C, the round-shaped spherulite was observed. In both cases, after the temperature jump to an ambient temperature, the 2D images changed clearly in the process of the phase transition from form II to form I, but the spherulite morphology itself was not changed detectably. The polarized IR imaging has revealed the preferential orientation of the crystallites in the spherulite. In the case of the spherulite grown at 103 °C, the ab plane is oriented in parallel to the spherulite plane and the molecular chains stand along the normal to the surface. On the other hand, in the spherulite grown at 98 °C, the chains were found to lie on the spherulite plane preferentially. Such a difference in the crystal orientation in the spherulite is related intimately with the outer shape of the spherulite and also with the growth mechanism of the spherulite. In this way, the polarized 2D IR imaging was found to be quite useful for the in situ detection of the time-dependently changing 2D spatial distribution of the crystallites in the spherulite.

Molecular Orientation Enhancement of Silk by the Hot-Stretching-Induced Transition from α-Helix-HFIP Complex to ß-Sheet.

Enhancing the molecular orientation of the regenerated silk fibroin (RF) up to a level comparable to the native silk is highly challenging. Our novel and promising strategy for the poststretching process is (1) creating at first an α-helix-HFIP complex with a hexagonal packing as an intermediate state and then (2) stretching it at a high temperature to induce the helix-to-sheet structural phase transition. Here we show for the first time the significantly high stretching efficiency of the proposed technique compared with the conventional wet-stretching techniques and the successful achievement of higher crystalline orientation and higher Young's modulus compared even with the native silk. The detailed structural analysis based on the time-resolved simultaneous measurement of stress-strain curve, synchrotron X-ray scatterings, and FTIR has revealed the structural transition mechanism from the hexagonally packed α-helix-HFIP complex to the highly oriented ß-sheet crystalline state as well as the critical level of crystal orientation needed for the helix-to-sheet transition.

Constructing π-Electron-Conjugated Diarylbutadiyne-Based Polydiacetylene under Molecular Framework Controlled by Hydrogen Bond and Side-Chain Substituent Position.

Diarylbutadiyne derivatives are ideal monomers for providing the π-electron-conjugated system of polydiacetylenes (PDAs). The geometrical parameters for diacetylene topochemical polymerization are known. However, control of the molecules under these parameters is yet to be addressed. This work shows that by simply tailoring diarylbutadiyne with amide side-chain substituents, the arrangement of the substituents and the resulting hydrogen bond framework allows formation of π-electron-conjugated PDA.

Molecular assembly of highly symmetric molecules under a hydrogen bond framework controlled by alkyl building blocks: a simple approach to fine-tune nanoscale structures.

To date, molecular assemblies under the contribution of hydrogen bond in combination with weak interactions and their consequent morphologies have been variously reported; however, how the systematic variation of the structure can fine-tune the morphologies has not yet been answered. The present work finds an answer through highly symmetric molecules, i.e. diamine-based benzoxazine dimers. This type of molecule develops unique molecular assemblies with their networks formed by hydrogen bonds at the terminal, while, at the same time, their hydrogen bonded frameworks are further controlled by the hydrophobic segment at the center of the molecule. When this happens, slight differences in hydrophobic alkyl chain lengths (, , and ) bring a significant change to the molecular assemblies, thus resulting in tunable morphologies, i.e. spheres, needles and dendrites. The superimposition between the crystal lattice obtained from X-ray single crystal analysis and the electron diffraction pattern obtained from transmission electron microscopy allows us to identify the molecular alignment from single molecules to self-assembly until the morphologies developed. The present work, for the first time, shows the case of symmetric molecules, where the hydrophobic building block controls the hydrogen bond patterns, leading to the variation of molecular assemblies with tunable morphologies.

Shifting from hydrogen bond network to π-π stacking: a key mechanism for reversible thermochromic sulfonated poly(ether ether ketone).

Sulfonated poly(ether ether ketone) (SPEEK) thin film performs reversible thermochromic property by developing the color to be yellowish at the temperature above 190 °C. The detailed analyses based on temperature-dependent techniques suggest the thermal treatment inducing the shifting of the hydrogen bond network between the sulfonated group and the hydrated water molecules to the π-π stacking among aromatic rings in SPEEK chains. Although it is general that the polymer chain packing is unfavorable at high temperature, the present work shows a good example that when the polymer chains can form specific molecular interaction, such as π-π stacking, even in harsh thermal treatment, a rearrangement will effectively occur, which leads to an external stimuli-responsive property.

Clarification of cross-linkage structure in boric acid doped poly(vinyl alcohol) and its model compound as studied by an organized combination of X-ray single-crystal structure analysis, Raman spectroscopy, and density functional theoretical calculation.

When boric acid (BA) is added to poly(vinyl alcohol) (PVA), a chemical reaction occurs to form the cross-linkages between the amorphous PVA chains. The local structural change caused by this reaction has been clarified concretely from the microscopic level on the basis of the X-ray-analyzed crystal structure, Raman spectra, and ab initio density functional theory using a model compound produced by the reaction between pentanediol (PENT) and boric acid (PENT-BA). The PENT-BA compound was found to take the TT and TG conformations in the methylene segmental parts depending on the stereoregularity of the PENT molecule itself, meso and racemo configurations, respectively. These two conformations give the Raman bands at the different positions. By comparison of the Raman spectra between the PVA-BA and PENT-BA model compounds, the local structures of PVA chains connected to BA molecules have been derived concretely: the syndiotactic PVA parts in the amorphous region form the TG-type ring structure with the 3-coordinate boron atom, where T and G are trans and gauche conformers, respectively. On the other hand, the isotactic PVA part takes the TT conformation when it forms a ring with boron atom. The thus-created rings are hydrogen-bonded to form a dimer, which plays a role as cross-linkage between the neighboring PVA chain segments in the amorphous region.

Polyethylenimine containing benzimidazole branching: a model system providing a balance of hydrogen bond network or chain mobility enhances proton conductivity.

A series of multibenzimidazole functionalized branched polyethylenimine (MPEI) molecules with varied benzimidazole substitution are designed and synthesized to study how hydrogen bonds of benzimidazole can be enhanced through the branching structure of polymer chains. The reduction of H-bonding and the increment of interatomic distance distribution initiate an increase in proton conductivity with temperature as detailed analyses by temperature dependence Fourier transform infrared spectroscopy and radial distribution function calculated from temperature dependence X-ray diffraction technique. MPEIs with a higher benzimidazole substitution form a greater number of hydrogen bonds together with the lowering of chain mobility. In combination with the proton conductivity evaluation, bPEI with 19.7% benzimidazole substitution is a preferable condition since at this condition both hydrogen bond and chain mobility are in good balance and favor the proton transfer resulting in a significant proton conductivity ∼10(-5) S cm(-1) in the case of the pure sample in pellet form and ∼10(-4) S cm(-1) in the case of the blend with PVA in the membrane form measuring at 190 °C under anhydrous condition.

Systematic study of aggregation structure and thermal behavior of a series of unique H-shape alkane molecules.

The H-shape alkanes of various arm lengths have been synthesized successfully through the Grignard reaction. The detailed investigation of these novel compounds may allow us to widen the topological chemistry field furthermore. The molecular form and molecular packing structure in the crystal lattice have been revealed successfully on the basis of X-ray structure analysis as well as the analysis of Raman longitudinal acoustic modes (LAM) sensitive to the alkyl zigzag chain segments. The molecular conformation in the crystal lattice is deformed markedly from the originally imagined H-shape. In the cases of C3HOH to C6HOH, for example, the molecules are packed in a complicated manner and the OH···O hydrogen bonds govern the whole intermolecular interactions mainly. Since the alkyl segmental length is not very long, the conformational change is not very drastic, i.e., the small configurational entropy. Synergic effect of the hydrogen bonds and the small configurational entropy gives the higher melting point as known from the thermal data. On the other hand, in the cases of C10HOH and C12HOH, one of the long alkyl chain arms is found to be bent by 90° so that all of the alky chain segments of planar-zigzag conformation can be packed as closely as possible, and the intermolecular OH···O hydrogen bonds are also formed effectively without any mistake. As a result, the contribution of nonbonded intra- and intermolecular van der Waals interactions between the trans-zigzag alkyl chain segments become major, and the coupling of this enthalpy effect with the larger configurational entropy effect of the molecular shape results in the decrement of the melting point which approaches gradually that of longer n-alkane compound. In this way a sensitive balance between the nonbonded van der Waals interactions, the OH···O hydrogen bonds, as well as the configurational entropy effect gives the characteristic thermal behavior of the H-shape compounds. The thus-newly synthesized H-shape alkane compounds should give us new insight into the packing topology of complicated molecules, leading to the development of new functionality unexpected for normal linear alkane compounds.

Microscopic Fourier Transform Infrared Characterization on Two Types of Spherulite with Polymorphic Crystals in Poly(heptamethylene terephthalate).

FTIR microspectrometry with in situ temperature variation and IR-peak-mapping capability, and POM characterization were used to study the crystal distribution in dual spherulites in poly(heptamethylene terephthalate). By tracing the crystalline IR bands of the α-crystal and ß-crystal to get the crystal distribution, the techniques resolve that the ringed and ringless spherulites comprise α- and ß-crystals, respectively. In addition, temperature-dependent IR analyses on the spots related to the two crystals also reveal the α- and ß-crystals melt at 98 and 104 °C, respectively. The ringed and ringless spherulites were proven to be correlated with the α- and ß-crystal forms, respectively.

Relationship between morphological change and crystalline phase transitions of polyethylene-poly(ethylene oxide) diblock copolymers. 3. Dependence of morphological transition phenomena on the PE/PEO segmental lengths and its possible origins.

By measurement of the small-angle and wide-angle X-ray scatterings and infrared and Raman spectra and thermal data, microphase separation phenomena have been investigated for a series of polyethylene-poly(ethylene oxide) diblock copolymer (PE-b-PEO) in both the heating and cooling processes and compared with the structural changes occurring inside the PE and PEO domains. The complicated morphological changes between lamella, perforated lamella, gyroid, cylinder, and sphere phases were detected for the copolymer with relatively short PE segments. The orthorhombic crystalline structure of PE was kept unchanged in the lamella-to-gyroid transition. When the PE orthorhombic phase transformed to the pseudohexagonal or rotator phase, the gyroid morphology changed to the cylinder. On the other hand, the diblock copolymer with relatively long PE segment was found to show only the lamellar morphology, in which the order-disorder structural transition between the orthorhombic and pseudohexagonal phases occurred in the PE crystal region. As a possibility, the large difference in morphological change between the copolymers with short and long PE segments has been ascribed to the difference in thermal mobility of PE segments, which is controlled by the conformation of chains and their packing mode, i.e., an extended chain or a folded chain. The extended chains may move thermally and actively along the interfacial boundary in addition to the librational motion around the chain axis, resulting in a variety of morphological changes, whereas the thermal motion of the folded chains may be suppressed because of the geometrical constraint and does not cause such a large-scale morphological change from the lamellar structure. This concept, a thermal activity and geometrical constraint, is considered to be quite important in the interpretation of complicated morphological changes observed for many crystalline-amorphous and crystalline-crystalline diblock copolymers when viewed from the molecular level.

Crystal structures of n-alkane with three functional groups in the middle and at both ends.

We synthesized a linear alkane, K35DA, with a main-chain carbon number n = 33 and three functional groups, a carbonyl group in the middle and carboxyl groups at both ends, and studied influences of the functional groups as well as chain length on morphologies of samples prepared by solution-grown and bulk crystallization methods (SG-K35DA and BK-K35DA) from differential scanning calorimetry (DSC), X-ray diffraction, and IR absorption measurements. Data analyses reveal that at room temperature an orthorhombic crystal of type P2(1)2(1)2(1), together with a considerable amount of amorphous fraction, is predominantly realized in BK-K35DA due to the van der Waals force between neighboring long methylene sequences, whereas a monoclinic type of crystal belonging to the same space group (P2(1)/c) as reported for linear dicarboxylic acid crystals with odd carbon numbers is coexistent for SG-K35DA. The crystalline structures appear to be distorted with increasing temperature, as the dipole-dipole interaction between the carbonyl groups tends to be weakened, and both orthorhombic and monoclinic crystals undergo the solid-solid phase transition to the hexagonal crystalline structure at a temperature about 10 K below their respective T(m)s, which can be regarded as a new example of the Brill transition.