Functional liquid-crystalline assemblies: self-organized soft materials

In the 21st century, soft materials will become more important as functional materials because of their dynamic nature. Although soft materials are not as highly durable as hard materials, such as metals, ceramics, and engineering plastics, they can respond well to stimuli and the environment. The introduction of order into soft materials induces new dynamic functions. Liquid crystals are ordered soft materials consisting of self-organized molecules and can potentially be used as new functional materials for electron, ion, or molecular transporting, sensory, catalytic, optical, and bio-active materials. For this functionalization, unconventional materials design is required. Herein, we describe new approaches to the functionalization of liquid crystals and show how the design of liquid crystals formed by supramolecular assembly and nano-segregation leads to the formation of a variety of new self-organized functional materials.     

A new carbon—phosphorous bond forming reaction and synthesis of aminoalkylphosphonic acid derivatives

A new carbon—phosphorous bond forming reaction, that is, the reaction of α-methoxyurethanes with trialkyl phosphites in the presence of Lewis acid catalysts was studied on twelve examples.     

Solvent-induced polymorphism of three-dimensional hydrogen-bonded networks of hexakis(4-carbamoylphenyl)benzene

The crystal structures for three types of three-dimensional (3-D) hydrogen-bonded networks of hexakis(4-carbamoylphenyl)benzene (1), the network morphologies of which depend greatly on crystallization conditions, have been determined. When this compound is crystallized from hot DMSO, the resulting crystals, 1.12DMSO (orthorhombic, Pca2(1)), showed a 3-D hydrogen-bonded porous network (type A) via 1-D catemer chains as a hydrogen-bonding motif of six primary amide groups. The type A network creates chambers surrounded by six molecules of 1 and channels along the c axis to give the highest porosity among the network polymorphs of 1 investigated here. Crystallization from a boiling mixture of n-PrOH and water gave 1.6n-PrOH (monoclinic, P2(1)/c), which exhibits another type of 3-D hydrogen-bonded porous network (type B) via cyclic dimers as another hydrogen-bonding motif of six primary amide groups. The type B network leads to triangle-like channels along the a axis having a cross section of ca. 9.2 x 9.7 x 9.7 A (including van der Waals radii). The crystal structure of 1.H(2)O (monoclinic, P2(1)/c), which was produced under hydrothermal conditions, showed a nonporous 3-D hydrogen-bonded network chain of amide groups (type C) composed of a mixed hydrogen bonding motif of helical catemer chains/cyclic dimer/catemer. Solvent-induced topological isomerism of these 3-D hydrogen-bonded networks of 1 arises from (i) the guest inclusion ability based on a radially functionalized hexagonal structure of 1, (ii) the correlation between the hydrogen bond donor ability of the syn and anti protons of the primary amide group in host 1 and the hydrogen bond acceptor ability of the oxygen atoms of 1 and guest solvents, and (iii) the polarity of the bulk crystallization solvents.     

Dependence of chiral recognition on the degree of substitution of cellulose benzoate

A series of cellulose benzoates with different degrees of substitution (DS) were prepared by aminolysis under homogeneous conditions. Using them as a stationary phase, the dependence of the chromatographic chiral recognition of cellulose benzoate (CB) on its DS was studied under normal phase conditions. For most enantiomeric pairs, chiral recognition decreased along with the decrease in DS. However, some enantiomeric pairs were resolved only by CBs carrying unsubstituted hydroxyl groups. Many of the compounds were quite strongly retained by cellulose benzoate with a DS of 2.8. A study of the retention behaviors of simple achiral compounds led us to the conclusion that the change in the retention behaviors by introducing free hydroxyl groups into tribenzoate is not caused by hydrogen bonding including the hydroxyl groups, but by a specific unidentified change.     

Frequency Dependence of ESR in Pristine Trans-Polyacetylene: Line Width

We measured a frequency dependence of ESR line width in (CH)x and (CD)x at frequencies 5～9,500 MHz. From a detailed analysis we could independently deduce 1-D diffusion rate of electron spin (neutral soliton) D_‖ /c_‖ ², and the trapped spin concentration C between 200 and 340 K.     

Evidence for Superconductivity in Nb2SC0.90 Carbosulfide

Abstract

Evidence for bulk superconductivity in Nb₂SC_0.90 carbosulfide is presented. Diamagnetic volume fraction of Nb₂SC_0.90 was precisely determined with low applied magnetic fields which were corrected by 6N lead rod as an internal standard. Based on magnetic field dependence of magnetic moment at several constant temperature's below T_C = 5 K, Nb₂SC_0.90 is found to be a type II superconductor with relatively high H _C2 and low H_C1.     

Mirror Observation of Finger Action Enhances Activity in Anterior Intraparietal Sulcus: A Functional Magnetic Resonance Imaging Study

Mirror therapy can be used to promote recovery from paralysis in patients with post-stroke hemiplegia, There are a lot of reports that mirror-image observation of the unilateral moving hand enhanced the excitability of the primary motor area (M1) ipsilateral to the moving hand in healthy subjects. but the neural mechanisms underlying its therapeutic effects are currently unclear. To investigate this issue, we used functional magnetic resonance imaging to measure activity in brain regions related to visual information processing during mirror image movement observation. Thirteen healthy subjects performed a finger-thumb opposition task with the left and right hands separately, with or without access to mirror observation. In the mirror condition, one hand was reflected in a mirror placed above the abdomen in the MRI scanner. In the masked mirror condition, subjects performed the same task but with the mirror obscured. In both conditions, the other hand was held at rest behind the mirror. A between-task comparison (mirror versus masked mirror) revealed significant activation in the ipsilateral hemisphere in the anterior intraparietal sulcus (aIP) while performing all tasks, regardless of which hand was used. The right aIP was significantly activated while moving the right hand. In contrast, in the left aIP, a small number of voxels showed a tendency toward activation during both left and right hand movement. The enhancement of ipsilateral aIP activity by the mirror image observation of finger action suggests that bimodal aIP neurons can be activated by visual information. We propose that activation in the M1 ipsilateral to the moving hand can be induced by information passing through the ventral premotor area from the aIP.     

Mechanical Properties and Intermolecular Interactions in Molecular Composites Composed of Wholly Aromatic Polyamide and Poly-(Amide-Imide)

Poly(p-phenylene-3,4′-oxydiphenylene terephthalamide) (PPOT) and poly(4,4′-oxydiphenylene-4-carbonamidephthalimide-N-yl) (PAI) are compatible. Molecular composites were prepared by solution blending and subsequently solvent casting. The glass transition temperature of the composite increased with increasing fraction of PPOT. Intermolecular interactions between the two components increase due to formation of hydrogen bonds between the amide linkages of the component polymers. The elastic modulus of the composite was always higher than the modulus predicted on the basis of the additivity. Similar deviations from additivity were observed for the bulk density. These desirable results arise from an increase of the packing density of molecules due to the additional hydrogen bonding also shown by the infrared spectra.     

Simultaneous manifestation of metallic conductivity and single-molecule magnetism in a layered molecule-based compound

Single-molecule magnets (SMMs) show superparamagnetic behaviour below blocking temperature at the molecular scale, so they exhibit large magnetic density compared to the conventional magnets. Combining SMMs and molecular conductors in one compound will bring about new physical phenomena, however, the synergetic effects between them still remain unexplored. Here we present a layered molecule-based compound, β′′-(BEDO-TTF)₄ [Co(pdms)₂]·3H₂O (BO4), (BEDO-TTF (BO) and H₂pdms are bis(ethylenedioxy)tetrathiafulvalene and 1,2-bis(methanesulfonamido)benzene, respectively), which was synthesized by using an electrochemical approach and studied by using crystal X-ray diffraction. This compound simultaneously exhibited metallic conductivity and SMM behaviour up to 11 K for the first time. The highest electrical conductivity was 400–650 S cm⁻¹ at 6.5 K, which is the highest among those reported so far for conducting SMM materials. Furthermore, antiferromagnetic ordering occurred below 6.5 K, along with a decrease in conductivity, and the angle-independent negative magnetoresistance suggested an effective electron correlation between the conducting BO and Co(pdms)₂ SMM layers (d–π interactions). The strong magnetic anisotropy and two-dimensional conducting plane play key roles in the low-temperature antiferromagnetic semiconducting state. BO4 is the first compound exhibiting antiferromagnetic ordering among SMMs mediated by π-electrons, demonstrating the synergetic effects between SMMs and molecular conductors.

A metallic single-molecule magnet was synthesised demonstrating simultaneous metallic conduction and excellent SMM properties at the same temperature range for the first time, with potential applications in molecule-based quantum spintronics.