Assembling of a Water-Soluble N

We report an unprecedented result of self-aggregation of [Pt(L1 )Cl] (HL1 =1,3-di(5-carboxy-2-pyridyl)benzene) triggered by CO2 in basic aqueous solution. The color of basic aqueous solution containing [Pt(L1 )Cl] changes from yellow to blue-green during the aggregation resulted from a reaction with CO2 in air. Upon CO2 gas bubbling, strong and broad absorption bands of aggregate assigned to the metal-metal-to-ligand charge-transfer transition appeared at 701 and 1152 nm. Recrystallization of [Pt(L1 )Cl] from Na2 CO3 aqueous solution afforded polymorphic crystals of red and blue-green forms. A single X-ray crystallography revealed that the red form of crystal consists of a Pt-Pt stacked dimer bridged by CO3 2- ion and one of the carboxy groups of L1 is deprotonated. An elemental analysis provided evidence that the blue-green crystal is constructed by linear array consisting of the [Pt(L2 )(CO3 )]3- (HL2 =1,3-di(5-carboxylate-2-pyridyl)benzene) units. The formation process of blue-green aggregate in aqueous solution was monitored through a transient absorption spectrum, and the absorption of aggregates involved in the spectral change were examined by a global analysis. A singular value decomposition and kinetic analysis provide that there are four species resulted from the self-assembling reaction in the solution and the maximal degree of aggregation is at least 32-mer.

Elastic and bright assembly-induced luminescent crystals of platinum(II) complexes with near-unity emission quantum yield.

Molecular crystals of Pt(II) complexes with metallophilic interactions can provide bright assembly-induced luminescence with colour tunability. However, the brittleness of many of these crystals makes their application in flexible optical materials difficult. Herein, we have achieved the elastic deformation of crystals of polyhalogenated Pt(II) complexes exhibiting bright assembly-induced luminescence. A crystal of [Pt(bpic)(dFppy)] (Hbpic = 5-bromopicolinic acid, HdFppy = 2-(2,4-difluorophenyl)pyridine) and a co-crystal of [Pt(bpic)(dFppy)] and [Pt(bpic)(ppy)] (Hppy = 2-phenylpyridine) were found to exhibit significant elastic deformation due to their highly anisotropic interaction topologies. While the crystal of [Pt(bpic)(dFppy)] exhibited monomer-based ligand-centred 3ππ* emission with an emission quantum yield of 0.40, the co-crystal exhibited bright, triplet metal-metal-to-ligand charge transfer (3MMLCT) emission owing to Pt⋯Pt interactions, thereby achieving a significantly higher emission quantum yield of 0.94.

Obtainment and confirmation of intergeneric hybrids between marguerite (Argyranthemum frutescens (L.) Sch.Bip.) and two Rhodanthemum species (R. hosmariense (Ball) B. H. Wilcox, K. Bremer & Humphries and R. catananche (Ball) B. H. Wilcox, K. Bremer & Humphries).

Argyranthemum frutescens (L.) Sch.Bip. and Rhodanthemum gayanum (Coss. & Durieu) B. H. Wilcox, K. Bremer & Humphries are capable of hybridization. To expand flower color variation in this intergeneric hybrid group, we performed crosses using A. frutescens as the seed parent and R. hosmariense (Ball) B. H. Wilcox, K. Bremer & Humphries, R. catananche (Ball) B. H. Wilcox, K. Bremer & Humphries as the pollen parent. One plantlet was obtained from each cross between the white to pale pink-flowered A. frutescens and white-flowered R. hosmariense, and from a cross between the pink-flowered A. frutescens and cream to pale yellow-flowered R. catananche, via ovule culture. The cross with R. hosmariense produced an individual with white to pale pink ray florets, and the cross with R. catananche produced an individual with red ray florets. The flower and leaf shape of the progenies was intermediate between the parents, and other morphological traits were also characterized in the same manner. Morphological observations and a cleaved amplified polymorphic sequence marker-based determination, using the internal transcribed spacer region as a target for amplification and the restriction enzyme Afl II, revealed that both individuals are hybrids between A. frutescens and R. hosmariense, R. catananche. To the best of our knowledge, this is the first study to report that crossbreeding between A. frutescens (seed parent) and R. hosmariense, R. catananche (pollen parent) is possible. Moreover, further development of Argyranthemum breeding, especially that of a series of hybrid cultivars with different flower colors, is expected.

Flexible organic crystals. Understanding the tractable co-existence of elastic and plastic bending.

As an emerging class of flexible materials, mechanically bendable molecular crystals are broadly classified as elastic or plastic. Nevertheless, flexible organic crystals with mutually exclusive elastic and plastic traits, with contrasting structural requirements, co-existing under different stress settings are exceptional; hence, it is imperative to establish the concurring factors that beget this rare occurrence. We report a series of halogen-substituted benzil crystals showing elastic bending (within ∼2.45% strain), followed by elastoplastic deformation under ambient conditions. Under higher stress settings, they display exceptional plastic flexibility that one could bend, twist, or even coil around a capillary tube. X-ray diffraction, microscopy, and computational data reveal the microscopic and macroscopic basis for the exciting co-existence of elastic, elastoplastic, and plastic properties in the crystals. The layered molecular arrangement and the weak dispersive interactions sustaining the interlayer region provide considerable tolerance towards breaking and making upon engaging or releasing the external stress; it enables restoring the original state within the elastic strain. Comparative studies with oxalate compounds, wherein the twisted diketo moiety in benzil was replaced with a rigid and coplanar central oxalate moiety, enabled us to understand the effect of the anisotropy factor on the crystal packing induced by the C[double bond, length as m-dash]O⋯C tetral interactions. The enhanced anisotropy depreciated the elastic domain, making the oxalate crystals more prone to plastic deformation. Three-point bending experiments and the determined Young's moduli further corroborate the co-existence of the elastic and plastic realm and highlight the critical role of the underlying structural elements that determine the elastic to plastic transformation. The work highlights the possible co-existence of orthogonal mechanical characteristics in molecular crystals and further construed the concurrent role of microscopic and macroscopic elements in attaining this exceptional mechanical trait.

Mechanical deformation and multiple thermal restoration of organic crystals: reversible multi-stage shape-changing effect with luminescence-color changes.

Shape-memory materials can be mechanically deformed and subsequently reverse the deformation upon changing the temperature. Shape-memory materials have attracted considerable attention for basic research and industrial applications, and polymer and alloy shape-memory materials have been well studied; however, it is formidably challenging to develop functional shape-memory materials, such as materials with multi-stage and anisotropic shape changes and shape changes accompanied by changes in color and light emission. Here, we found a reversible multi-stage shape-changing effect after mechanical deformation in a molecular crystal induced by multi-step thermal phase transitions with reversible shape changes and luminescence-color changes. Using single-crystal structure and thermal analyses as well as mechanical property measurements, we found that the reversible multi-stage shape-changing effect was achieved by a combination of a twinning deformation and multi-step thermal phase transitions. The changes in the crystal shape and luminescence suggest novel strategies for imparting known shape-memory materials with additional functionalities.

Intergeneric hybridization of marguerite (Argyranthemum frutescens (L.) Sch. Bip.) and Roman chamomile (Chamaemelum nobile (L.) All.) using ovule culture and confirmation of hybridity.

To introduce useful characteristics such as fragrance into Argyranthemum frutescens (L.) and to expand the variation, we conducted crosses using A. frutescens as the seed parent and Chamaemelum nobile (L.) All. as the pollen parent. All the tested cross combinations between the three strains of A. frutescens and one strain of C. nobile produced embryos, and healthy plants were obtained by ovule culture. The obtained plantlets had a white ray floret, and the leaf shape was intermediate to those of the parents. The individuals obtained from this cross were subjected to two methods to determine hybridity: flow cytometry analyses and cleaved amplified polymorphic sequence (CAPS) markers. For the CAPS marker, we selected the internal transcribed spacer (ITS) region, which is highly variable among the genera, as the region to be amplified. We selected restriction enzymes BmgT120 I and Afl II, which selectively cut common sequences in the genus Argyranthemum, based on the sequence analysis of one parent strain each of A. frutescens and C. nobile and alignment with known sequences of related species. Flow cytometry analyses and CAPS markers revealed that the individuals obtained from the cross between A. frutescens and C. nobile are intergeneric hybrids. In addition, these established methods were capable of quickly and reliably identifying hybrids between A. frutescens and C. nobile. This report shows for the first time that crossbreeding between A. frutescens (seed parent) and C. nobile (pollen parent) is possible, and further development of Argyranthemum breeding, such as the expansion of variation by intergeneric crosses, is expected.

A superelastochromic crystal.

Chromism-color changes by external stimuli-has been intensively studied to develop smart materials because of easily detectability of the stimuli by eye or common spectroscopy as color changes. Luminescent chromism has particularly attracted research interest because of its high sensitivity. The color changes typically proceed in a one-way, two-state cycle, i.e. a stimulus-induced state will restore the initial state by another stimuli. Chromic systems showing instant, biphasic color switching and spontaneous reversibility will have wider practical applicability. Here we report luminescent chromism having such characteristics shown by mechanically controllable phase transitions in a luminescent organosuperelastic crystal. In mechanochromic luminescence, superelasticity-diffusion-less plastic deformation with spontaneous shape recoverability-enables real-time, reversible, and stepless control of the abundance ratio of biphasic color emissions via a single-crystal-to-single-crystal transformation by controlling a single stimulus, force stress. The unique chromic system, referred to as superelastochromism, holds potential for realizing informative molecule-based mechanical sensing.

Photoluminescent Ferroelastic Molecular Crystals.

Ferroelasticity has been reported for several types of molecular crystals, which show mechanical-stress-induced shape change under twinning and/or spontaneous formation of strain. Aiming to create materials that exhibit both ferroelasticity and light-emission characteristics, we discovered the first examples of ferroelastic luminescent organometallic crystals. Crystals of arylgold(I)(N-heterocyclic carbene)(NHC) complexes bend upon exposure to anisotropic mechanical stress. X-ray diffraction analyses and stress-strain measurements on these ferroelastic crystals confirmed typical ferroelastic behavior, mechanical twinning, and the spontaneous build-up of strain. A comparison with single-crystal structures of related gold-NHC complexes that do not show ferroelasticity shed light on the structural origins of the ferroelastic behavior.

A Multidirectional Superelastic Organic Crystal by Versatile Ferroelastical Manipulation.

Mechanical twinning changes atomic, molecular, and crystal orientations along with directions of the anisotropic properties of the crystalline materials while maintaining single crystallinity in each domain. However, such deformability has been less studied in brittle organic crystals despite their remarkable anisotropic functions. Herein we demonstrate a direction-dependent mechanical twinning that shows superelasticity in one direction and ferroelasticity in two other directions in a single crystal of 1,3-bis(4-methoxyphenyl)urea. The crystal can undergo stepwise twinning and ferroelastically forms various shapes with multiple domains oriented in different directions, thereby affording a crystal that shows superelasticity in multiple directions. This adaptability and shape recoverability in a ferroelastic and superelastic single crystal under ambient conditions are of great importance in future applications of organic crystals as mechanical materials, such as in soft robotics.

Effects of single ingestion of rice cracker and cooked rice with high resistant starch on postprandial glucose and insulin responses in healthy adults: two randomized, single-blind, cross-over trials.

Rice with double mutation of starch synthase IIIa and branching enzyme IIb (ss3a/be2b) has much higher amounts of apparent amylose and resistant starch (RS) than usual varieties. In this study, we conducted two randomized, single-blind, crossover trials to investigate the effect of single ingestion of two processed foods composed of ss3a/be2b mutant rice on postprandial blood glucose and insulin response in healthy adults, compared to those of usual cultivar. In trial 1, of ingestion of rice crackers, the incremental area under the curves of glucose (IAUCglc) and insulin (IAUCins) in RS group was significantly lower than in the control group. In trial 2, of the ingestion of cooked rice, IAUCglc in the RS group was significantly lower than in the control group. These results showed that the ss3a/be2b-mutant rice cracker and cooked rice having high RS can attenuate postprandial blood glucose and insulin response.

Shape Rememorization of an Organosuperelastic Crystal through Superelasticity-Ferroelasticity Interconversion.

As altering permanent shapes without loss of material function is of practical importance for material molding, especially for elastic materials, shape-rememorization ability would enhance the utility of elastic crystalline materials. Since diffusionless plastic deformability can preserve the crystallinity of materials, the interconversion of diffusionless mechanical deformability between superelasticity and ferroelasticity could enable shape rememorization of superelastic single crystals. This study demonstrates the shape rememorization of an organosuperelastic single crystal of 1,4-dicyanobenzene through time-reversible interconversion of superelasticity-ferroelasticity relaxation by holding the mechanically twinned crystal without heating. The shape-rememorization ability of the organosuperelastic crystal indicates the compatibility of superelasticity (antiferroelasticity) and ferroelasticity as well as the intrinsic workability of organic crystalline materials capable of recovering their crystal functions under mild conditions.

Superplasticity in an organic crystal.

Superplasticity, which enables processing on hard-to-work solids, has been recognized only in metallic solids. While metallic materials and plastics (polymer solids) essentially possess high plastic workability, functional crystalline solids present difficulties in molding. Organic crystals especially are fragile, in the common view, and they are far from the stage of materials development. From the viewpoint of practical application; however, organic crystals are especially attractive because they are composed of ubiquitous elements and often exhibit higher performance than metallic materials. Thus, finding superplastic deformation of organic crystals, especially in a single-crystal-to-single-crystal manner, will pave the way for their material applications. This study confirmed superplasticity in a crystal of a simple organic compound: N,N-dimethyl-4-nitroaniline. The crystal exhibits single-crystal-to-single-crystal superplastic deformation without heating. This finding of "organosuperplasticity" will contribute to the future design of functional solids that do not lose their crystalline quality in molding.

KRIT1 mutations in three Japanese pedigrees with hereditary cavernous malformation.

Cerebral cavernous malformation is a neurovascular abnormality that can cause seizures, focal neurological deficits and intracerebral hemorrhage. Familial forms of this condition are characterized by de novo formation of multiple lesions and are autosomal-dominantly inherited via CCM1/KRIT1, CCM2/MGC4607 and CCM3/PDCD10 mutations. We identified three truncating mutations in KRIT1 from three Japanese families with CCMs: a novel frameshift mutation, a known frameshift mutation and a known splice-site mutation that had not been previously analyzed for aberrant splicing.

Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates.

Functions of clusters in nano or sub-nano scale significantly depend on not only kinds of their components but also arrangements, or symmetry, of their components. Therefore, the arrangements in the clusters have been precisely characterized, especially for metal complexes. Contrary to this, characterizations of molecular arrangements in supramolecular clusters composed of organic molecules are limited to a few cases. This is because construction of the supramolecular clusters, especially obtaining a series of the supramolecular clusters, is difficult due to low stability of non-covalent bonds compare to covalent bonds. From this viewpoint, utilization of organic salts is one of the most useful strategies. A series of the supramolecules could be constructed by combinations of a specific organic molecule with various counter ions. Especially, primary ammonium carboxylates are suitable as typical examples of supramolecules because various kinds of carboxylic acids and primary amines are commercially available, and it is easy to change their combinations. Previously, it was demonstrated that primary ammonium triphenylacetates using various kinds of primary amines specifically construct supramolecular clusters, which are composed of four ammoniums and four triphenylacetates assembled by charge-assisted hydrogen bonds, in crystals obtained from non-polar solvents. This study demonstrates an application of the specific construction of the supramolecular clusters as a strategy to conduct systematical symmetric study for clarification of correlations between molecular arrangements in supramolecules and kinds and numbers of their components. In the same way with binary salts composed of triphenylacetates and one kind of primary ammoniums, ternary organic salts composed of triphenylacetates and two kinds of ammoniums construct the supramolecular clusters, affording a series of the supramolecular clusters with various kinds and numbers of the components.

Current Trends in Health Insurance Systems: OECD Countries vs. Japan.

Over the past few decades, the longest extension in life expectancy in the world has been observed in Japan. However, the sophistication of medical care and the expansion of the aging society, leads to continuous increase in health-care costs. Medical expenses as a part of gross domestic product (GDP) in Japan are exceeding the current Organization for Economic Co-operation and Development (OECD) average, challenging the universally, equally provided low cost health care existing in the past. A universal health insurance system is becoming a common system currently in developed countries, currently a similar system is being introduced in the United States. Medical care in Japan is under a social insurance system, but the injection of public funds for medical costs becomes very expensive for the Japanese society. In spite of some urgently decided measures to cover the high cost of advanced medical treatment, declining birthrate and aging population and the tendency to reduce hospital and outpatients' visits numbers and shorten hospital stays, medical expenses of Japan continue to be increasing.

Current trends in health insurance systems: OECD countries vs. Japan.

Over the past few decades, the longest extension in life expectancy in the world has been observed in Japan. However, the sophistication of medical care and the expansion of the aging society, leads to continuous increase in health-care costs. Medical expenses as a part of gross domestic product (GDP) in Japan are exceeding the current Organization for Economic Co-operation and Development (OECD) average, challenging the universally, equally provided low cost health care existing in the past. A universal health insurance system is becoming a common system currently in developed countries, currently a similar system is being introduced in the United States. Medical care in Japan is under a social insurance system, but the injection of public funds for medical costs becomes very expensive for the Japanese society. In spite of some urgently decided measures to cover the high cost of advanced medical treatment, declining birthrate and aging population and the tendency to reduce hospital and outpatients' visits numbers and shorten hospital stays, medical expenses of Japan continue to be increasing.

Characterization of supramolecular hidden chirality of hydrogen-bonded networks by advanced graph set analysis.

Supramolecular hidden chirality of hydrogen-bonded (HB) networks of primary ammonium carboxylates was exposed by advanced graph set analysis from a symmetric viewpoint in topology. The ring-type HB (R-HB) networks are topologically regarded as faces, and therefore exhibit prochirality and positional isomerism due to substituents attached on the faces. To describe the symmetric properties of the faces, additional symbols, Re (right-handed or clockwise), Si (left-handed or anticlockwise), and m (mirror), were proposed. According to the symbols, various kinds of faces were classified based on the symmetry. This symmetry consideration of the faces enables us to precisely evaluate supramolecular chirality, especially its handedness, of 0D-cubic, 1D-ladder and 2D-sheet HB networks that are composed of the faces. The 1D-ladder and 2D-sheet HB networks generate chirality by accumulating the chiral faces in 1D and 2D manners, respectively, whereas 0D-cubic HB networks generate chirality based on combinations of eight kinds of faces, similar to the chirality of dice.

Gastric cancer progression may involve a shift in HLA-E profile from an intact heterodimer to ß2-microglobulin-free monomer.

Phenotypic expression of human leukocyte antigen (HLA)-E on the surface of tumor lesions includes intact heterodimer [HLA-E heavy chain and ß2-microglobulin (ß2m)] and ß2m-free monomer. Anti-HLA-E monoclonal antibodies (mAbs), MEM-E/02 or 3D12 bind to the peptide sequences in ß2m-free HLA-E, which is common and shared with HLA-Ia monomers. A newly developed monospecific anti-HLA-E mAb (TFL-033) recognizes HLA-E-restricted peptide sequences on α1 and α2 helices away from ß2-m-site. Tumor progression may involve shedding of ß2-m from HLA-E or overexpression of ß2m-free monomers. There is a need to identify and distinguish the different phenotypic expression of HLA-E, particularly the intact heterodimer from the ß2m-free monomer on the surface of tumor lesions. Because of the unique peptide-binding affinities of the mAbs, it is hypothesized that TFL-033 and MEM-E/02 may distinguish the phenotypic expressions of cell surface HLA-E during stages of tumor progression. Only TFL-033 stained diffusely the cytoplasm of normal mucosa. The incidence and intensity of TFL-033 staining of the cell surface in early stages, poorly or undifferentiated and non-nodal lesions and in diffuse carcinoma is greater than that of MEM-E/02. Whereas MEM-E/02 stained terminal stages, adenocarcinoma and lymph node metastatic lesions intensely, either owing to increased expression of ß2m-free HLA-E with tumor progression or owing to expression of HLA-Ia molecules. Our study evaluates the relative diagnostic potential of HLA-E-monospecific TFL-033 and the HLA-Ia-reactive MEM-E/02 for determining the specific distribution and immunodiagnosis of different phenotypic expression HLA-E in tumor lesions, and the structural and functional alterations undergone by HLA-E during tumor progression.

Spinal cord stimulation and intrathecal baclofen therapy: combined neuromodulation for treatment of advanced complex regional pain syndrome.

OBJECTIVE: Spinal cord stimulation (SCS) is one of the widely used procedures for the treatment of complex regional pain syndrome (CRPS). However, complete pain relief is rarely achieved, and the SCS effect diminishes over time. Recently intrathecal baclofen (ITB) therapy is reported to be a modality for treating fixed dystonia related to CRPS. Other reports have suggested that ITB therapy can enhance the effect of SCS in patients with neuropathic pain. We report the effectiveness of combined SCS and ITB therapy, focusing on the role of ITB therapy as an adjunctive therapy for controlling symptoms of advanced CRPS. METHODS: Five affected extremities of 4 patients with CRPS (2 male; mean age, 32.5 years) refractory to conservative treatment were evaluated retrospectively. Three patients underwent SCS implantation first, with ITB pumps being implanted a few years later. Bolus ITB injection was administered under temporary percutaneous SCS in 1 patient. Pain intensity was evaluated using the visual analogue scale (VAS) before and after ITB administration. RESULTS: Pain relief of more than 50% was observed in the upper extremity of 1 patient and one of more than 30% was observed in 2 patients. The mean pain reduction rate in all 4 patients was 28.9% before and 43.8% after treatment. All patients, including those without any improvements in VAS score, showed decreased postural abnormalities after combined SCS and ITB therapy. Improvement in postural abnormalities, such as fixed dystonia or paroxysmal tremor-like movements, resulted in overall pain relief by reducing pain fluctuations. CONCLUSIONS: Combined SCS and ITB neuromodulation decreases pain intensity in refractory CRPS cases or improves associated abnormal dystonic posture and movement disorders and reduces pain fluctuations.

Linkage control between molecular and supramolecular chirality in 21-helical hydrogen-bonded networks using achiral components.

Chiral molecules preferentially form one-handed supramolecular assemblies that reflect the absolute configuration of the molecules. Under specific conditions, however, the opposite-handed supramolecular assemblies are also obtained because of flexibility in the bond length and reversibility of non-covalent interactions. The mechanism of the handedness selectivity or switching phenomenon remains ambiguous, and most phenomena are observed by chance. Here we demonstrate the construction of chiral hydrogen-bonded twofold helical assemblies with controlled handedness in the crystalline state based on crystallographic studies. Detailed investigation of the obtained crystal structures enabled us to clarify the mechanism, and the handedness of the supramolecular chirality was successfully controlled by exploiting achiral factors. This study clearly reveals a connection between molecular chirality and supramolecular chirality in the crystalline state.